CN108030957A - A kind of gel rubber material and preparation method and application for 3D printing artificial cartilage - Google Patents

A kind of gel rubber material and preparation method and application for 3D printing artificial cartilage Download PDF

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CN108030957A
CN108030957A CN201711471026.4A CN201711471026A CN108030957A CN 108030957 A CN108030957 A CN 108030957A CN 201711471026 A CN201711471026 A CN 201711471026A CN 108030957 A CN108030957 A CN 108030957A
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printing
rubber material
gel rubber
cartilage
preparation
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陈庆
曾军堂
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Chengdu New Keli Chemical Science Co Ltd
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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
    • A61L27/14Macromolecular materials
    • A61L27/20Polysaccharides
    • 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
    • A61L27/52Hydrogels or hydrocolloids
    • 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
    • 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
    • B33Y40/00Auxiliary operations or equipment, e.g. for material handling
    • 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
    • B33Y70/00Materials specially adapted for 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
    • A61L2400/06Flowable or injectable implant compositions
    • 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
    • A61L2430/06Materials or treatment for tissue regeneration for cartilage reconstruction, e.g. meniscus

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

The invention belongs to 3D printing field of material technology, there is provided a kind of gel rubber material and preparation method and application for 3D printing artificial cartilage.Hydroxyapatite, aluminium hydroxide, potassium methyl silicate, alginic acid salt powder are first uniformly mixed by this method, are then dried in vacuo and fine gtinding, add glycerine and calcium stearate carries out gradation modulation, you can cream gel cartilage material is made;Then gel rubber material is subjected to 3D printing shaping, is conserved in further water, you can cartilaginous tissue is made.Compared with conventional method, the adhesion strength of 3D printing cartilage gel rubber material prepared by the present invention is high, plasticity is good, and quality of materials is superior, and the biocompatibility and good surface activity of obtained cartilage finished product, intensity are high, precision is higher and surface quality is good, effect stability, and whole preparation process is simple, it is of low cost, it is time-consuming shorter, it is adapted to promote the use of.

Description

A kind of gel rubber material and preparation method and application for 3D printing artificial cartilage
Technical field
The invention belongs to 3D printing field of material technology, there is provided a kind of gel rubber material for 3D printing artificial cartilage and Preparation method and application method.
Background technology
One kind of 3D printing technique, i.e. RP technique, based on being a kind of digital model file, with powdered gold Belong to or plastics etc. can jointing material, come the technology of constructed object by way of successively printing.Past, it was often in mold manufacturing, work The fields such as industry design are used for modeling, are now increasingly used for the direct manufacture of some products, particularly some high values should The parts formed with having had using the printing of this technology.In recent years, particularly in medical domain, including craniomaxillofacial surgery, Progressively applied and developed in the operation such as dentistry, orthopaedics.
Application of the 3D printing technique at present in Orthopedic Clinical has:Mould is made, is conducive to preoperative planning;Surgery assistor The application of tool;Personalized customization prosthese.Wherein personalized customization prosthese is most common application, is mainly used for tissue engineering bracket Material, according to designed by for different human body tissue and the specific function of substituting tissue and possess.Tissue engineering bracket material includes: The tissue stent material of bone, cartilage, blood vessel, nerve, skin etc., the traditional cartilage of moment effectively solution is being repaired for cartilaginous tissue It is ineffective during reparation, donor is limited, immunological rejection, without self growth ability the problems such as, and utilize 3D printing technique Over time and space it is accurate, deposit different types of biomaterial on demand, while arbitrarily complicated bracket is manufactured, The parameters such as porosity, the pore size of stent can be effectively formulated, promote cell Proliferation and regeneration.
Artificial bone cartilage material can be divided into two classes, i.e., biodegradable and non-biodegradation type.The spy of non-biodegradable material Point is high mechanical strength(Wear-resisting, resistance to tired work(, indeformable etc., biologically inert(It is acid and alkali-resistance, ageing-resistant, non-degradable), but there are secondary Operation, therefore degradable material or degraded and the combination of non-degradable material are the Main ways of development.It is currently available to make cartilage The 3D printing technique that tissue makes has fusion stacking shaping, stereolithography, precinct laser sintering and 3DP technologies, wherein molten It is prevailing technology to melt deposition modeling, and mainly by Filamentous heat-fusible materials heating and melting, while three-dimensional nozzle is in computer Under control, according to section profile information, by material selectivity apply on the table, a layer cross section is formed after quick cooling. After the completion of one formable layer, machine operation platform declines a next layer of height (i.e. lift height) reshaping, until being formed whole real Figure modelling, raw material are usually hot shortness's macromolecule.Since preferable cartilage material should have biocompatibility and surface-active, bone Conductibility and osteoinductive, suitable aperture and porosity and mechanical strength and plasticity, therefore hydroxy phosphorus Calx and gel Material etc. is ideal raw material, but such functional material is difficult to be molded by hot melt adhesion, is caused to 3D printing shaping Greatly perplex.Therefore the raw material of 3D printing cartilage and the research of technique are increasingly valued by people.
At present one has been achieved in 3D printing bone material technology, the especially preparation of cartilage material and application aspect both at home and abroad Determine effect.Wherein Chen Kai et al. has invented a kind of multi-gradient bionic joint cartilage material preparation process based on 3D printing(In State's invention number of patent application 201510752927.5), preparing material includes:Modified ultra-high molecular weight polyethylene for 3D printing Material, dichromic acid oxidation solution, graft esterification solution, polyglycol solution, three kinds of bionic joint cartilage materials, preparation process For:1) porous ultra-high molecular weight polyethylene is prepared using 3D printing technique;2) in the porous ultra-high molecular weight polyethylene table of 3D printing Face is crosslinked PVA/HA composite hydrogel bionic cartilage materials;3 samples are crosslinked PVA/HA-PAA compound water congealings again through esterification treatment Glue bionic cartilage material;4) sample esterification treatment and cross-linked PVA hydrogel bionic cartilage material again;So as to obtain with multilayer The bionic joint cartilage material of gradient-structure.In addition, Li Bofa understands a kind of Bone Defect Repari bioceramic material based on 3D printing (Chinese invention patent application number 201610247006.8), it is made of bata-tricalcium phosphate, hydroxyapatite and polylactic acid, structure is Three-dimensional mesh structure, its preparation method are:Polylactic acid is dissolved in chloroform and is configured to solution, by bata-tricalcium phosphate, hydroxyl Apatite, which is added to the solution and stirs to stable homogeneous, is made composite mortar, and composite mortar is added the printing of 3D printing equipment, will The presoma of the bioceramic material of printing, which vacuumizes, makes chloroform fully volatilize, and obtains product.
As it can be seen that the finished product cartilage in existing 3D printing technique is undesirable in terms of precision and surface quality, hot conditions meeting The chemical composition of raw material is destroyed, since temperature is very big for the influence of fusion stacking molding effect, finished product effect is not sufficiently stable, Short time consumption is longer and cost is higher, while in conventional fused glass pellet technique, some functional materials are difficult to realize heat Bonding forming, can adversely affect cartilage material using during bonding agent.
The content of the invention
For such case, it is proposed that a kind of gel rubber material and preparation method for 3D printing artificial cartilage and should With.Technology point is will to be ground after hydroxyapatite, aluminium hydroxide, potassium methyl silicate, the drying of alginic acid salt powder, then pass through glycerine Modulation, forms the cartilage material that paste is suitable for 3D printing.3D printer extrusion paste layer upon layer shape is utilized during use Into blank cartilaginous tissue, then cartilaginous tissue is conserved in water, by aluminium hydroxide therein, potassium methyl silicate, with hydroxyl Phosphorus stone crystallisation solidification, forms the cartilaginous tissue with good strength.
To achieve the above object, concrete technical scheme of the present invention is as follows:
The preparation method of a kind of gel rubber material for 3D printing artificial cartilage, first by hydroxyapatite, aluminium hydroxide, methyl silicon Sour potassium, alginic acid salt powder are uniformly mixed, and are then dried in vacuo and fine gtinding, add glycerine and calcium stearate is divided Secondary modulation, you can cream gel cartilage material is made, preparation comprises the following steps that:
(1)By weight, by 73~83 parts by weight of hydroxyapatite, 2~4 parts by weight of aluminium hydroxide, 3~5 weight of potassium methyl silicate Part, the mixing of 12~18 parts by weight of alginic acid salt powder are measured, is placed in vacuum drying chamber, drying at a certain temperature is after a certain period of time Take out, be then ground using fine grinding machine, obtain mixed-powder;
(2)By step(1)The mixed-powder of gained is modulated by glycerine, and adds the calcium stearate of certain part by weight, system Into the cream gel cartilage material for being suitable for 3D printing;Wherein, 30~45 parts by weight of mixed-powder, glycerine 15-20 parts by weight, 1~2 parts by weight of calcium stearate.
Preferably, step(1)The hydroxyapatite is voluminous powder, can be hexagonal crystal system or monoclinic system, and particle diameter is 300~800 μm, calcium-phosphorus ratio is 1.6~1.7, and proportion is 3.05~3.18g/cm3
Preferably, step(1)The alginic acid salt powder is white or light yellow, can be calcium alginate, potassium alginate or sea At least one of mosanom, powder diameter are 200~400 μm.
Preferably, step(1)The vacuum drying temperature is 80~90 DEG C, and the time is 8~12h.
Preferably, step(1)The particle diameter of mixed-powder after the fine gtinding is 100~300nm.
Preferably, step(2)In the paste modulated process, glycerine should be divided into 3~5 additions, during each modulation Between be 60~90min, mixing speed during modulation is 300~500r/min.
A kind of application process of gel rubber material for 3D printing artificial cartilage, first by gel rubber material carry out 3D printing into Type, then conserves in water, you can cartilaginous tissue is made, specific application process is:
(1)Gel rubber material is added to the feed inlet of 3D printer, paste is extruded by nozzle and layer upon layer formation blank is soft Bone tissue;
(2)Blank cartilaginous tissue is placed in water maintenance, by aluminium hydroxide, potassium methyl silicate, is consolidated with hydroxylapatite crystal Change, form the cartilaginous tissue with good strength.
Preferably, the jet diameters of the 3D printer are 0.2~0.4mm, and XY axis printing precision is 0.01~0.02mm, Z axis printing precision is 0.002~0.003mm, and floor height precision is 0.05~0.08mm, and printing linear velocity is 30~80mm/s.
Preferably, the environment temperature of the maintenance processes is 20~30 DEG C, and relative humidity is 70~90%, curing time 4 ~6h.
3D printing cartilage gel rubber material prepared by the method for the present invention, by matching somebody with somebody in phosphorus lime and in alginic acid salt powder Hydrogen manufacturing aluminium oxide, potassium methyl silicate, with crystallisation solidification during water curing after 3D printing, effectively avoid using bonding agent to cartilage material Influence.With excellent biocompatibility, preferable material has been opened up in the application of medical field for 3D printing.
The present invention provides a kind of gel rubber material and preparation method and application method for 3D printing artificial cartilage, with showing There is technology to compare, its protrude the characteristics of and excellent effect be:
1. the self-adhesion knotting strength of 3D printing cartilage gel rubber material prepared by the present invention is high, plasticity is good, can have without binding agent Effectiveness is prepared in the printing of cartilaginous tissue, and quality of materials is superior.
2. the biocompatibility and good surface activity of the 3D printing cartilage of the preparation of the present invention, can be used safely in human body.
3. the intensity of the 3D printing cartilaginous tissue of the preparation of the present invention is high, precision is higher and surface quality is good, finished product effect Stablize.
4. the preparation process of the present invention is simple, of low cost, time-consuming shorter, it is adapted to promote the use of.
Embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention Scope be only limitted to following example.Without departing from the idea of the above method of the present invention, according to ordinary skill The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
The preparation process of 3D printing cartilage gel rubber material is:
By the calcium alginate powder of the hydroxyapatite powder of 78kg, the aluminium hydroxide of 3kg, the potassium methyl silicate of 4kg and 15kg Mixing, is placed in vacuum drying chamber, is taken out at 85 DEG C after dry 10h, is then ground, ground using fine grinding machine To the mixed-powder that particle diameter is 100~300nm;Then the mixed-powder of 38kg is taken, is modulated by the glycerine for adding 15kg, And the calcium stearate of 1kg is added, it is made the cream gel cartilage material for being suitable for 3D printing, in modulated process, glycerine is divided into 4 Secondary addition, each modulation time are 80min, and mixing speed during modulation is 400r/min;
The application process of 3D printing cartilage gel rubber material is:
Gel rubber material is added to the feed inlet of 3D printer, the jet diameters of 3D printer are 0.3mm, and XY axis printing precision is 0.01mm, Z axis printing precision are 0.002mm, and floor height precision is 0.06mm, and printing linear velocity is 60mm/s, is extruded by nozzle Paste and layer upon layer form blank cartilaginous tissue, are then placed in water blank cartilaginous tissue, environment temperature be 25 DEG C, Relative humidity conserves 5h under conditions of being 80%, by aluminium hydroxide, potassium methyl silicate, cures with hydroxylapatite crystal, is formed Cartilaginous tissue with good strength.
Embodiment 2
The preparation process of 3D printing cartilage gel rubber material is:
By the potassium alginate powder of the hydroxyapatite powder of 81kg, the aluminium hydroxide of 2kg, the potassium methyl silicate of 3kg and 14kg Mixing, is placed in vacuum drying chamber, is taken out at 80 DEG C after dry 12h, is then ground, ground using fine grinding machine To the mixed-powder that particle diameter is 100~300nm;Then the mixed-powder of 30kg is taken, is modulated by the glycerine for adding 18kg, And the calcium stearate of 2kg is added, it is made the cream gel cartilage material for being suitable for 3D printing, in modulated process, glycerine is divided into 3 Secondary addition, each modulation time are 60min, and mixing speed during modulation is 500r/min;
The application process of 3D printing cartilage gel rubber material is:
Gel rubber material is added to the feed inlet of 3D printer, the jet diameters of 3D printer are 0.2mm, and XY axis printing precision is 0.01mm, Z axis printing precision are 0.002mm, and floor height precision is 0.05mm, and printing linear velocity is 30mm/s, is extruded by nozzle Paste and layer upon layer form blank cartilaginous tissue, are then placed in water blank cartilaginous tissue, environment temperature be 20 DEG C, Relative humidity conserves 6h under conditions of being 70%, by aluminium hydroxide, potassium methyl silicate, cures with hydroxylapatite crystal, is formed Cartilaginous tissue with good strength.
Embodiment 3
The preparation process of 3D printing cartilage gel rubber material is:
By the sodium alginate powder of the hydroxyapatite powder of 74kg, the aluminium hydroxide of 4kg, the potassium methyl silicate of 5kg and 17kg Mixing, is placed in vacuum drying chamber, is taken out at 90 DEG C after dry 8h, is then ground, ground using fine grinding machine To the mixed-powder that particle diameter is 100~300nm;Then the mixed-powder of 45kg is taken, is modulated by the glycerine for adding 15kg, And the calcium stearate of 2kg is added, it is made the cream gel cartilage material for being suitable for 3D printing, in modulated process, glycerine is divided into 5 Secondary addition, each modulation time are 90min, and mixing speed during modulation is 300r/min;
The application process of 3D printing cartilage gel rubber material is:
Gel rubber material is added to the feed inlet of 3D printer, the jet diameters of 3D printer are 0.4mm, and XY axis printing precision is 0.02mm, Z axis printing precision are 0.003mm, and floor height precision is 0.08mm, and printing linear velocity is 80mm/s, is extruded by nozzle Paste and layer upon layer form blank cartilaginous tissue, are then placed in water blank cartilaginous tissue, environment temperature be 30 DEG C, Relative humidity conserves 4h under conditions of being 90%, by aluminium hydroxide, potassium methyl silicate, cures with hydroxylapatite crystal, is formed Cartilaginous tissue with good strength.
Embodiment 4
The preparation process of 3D printing cartilage gel rubber material is:
By the calcium alginate powder of the hydroxyapatite powder of 79kg, the aluminium hydroxide of 2kg, the potassium methyl silicate of 4kg and 13kg Mixing, is placed in vacuum drying chamber, is taken out at 82 DEG C after dry 11h, is then ground, ground using fine grinding machine To the mixed-powder that particle diameter is 100~300nm;Then the mixed-powder of 34kg is taken, is modulated by the glycerine for adding 15kg, And the calcium stearate of 1kg is added, it is made the cream gel cartilage material for being suitable for 3D printing, in modulated process, glycerine is divided into 3 Secondary addition, each modulation time are 80min, and mixing speed during modulation is 450r/min;
The application process of 3D printing cartilage gel rubber material is:
Gel rubber material is added to the feed inlet of 3D printer, the jet diameters of 3D printer are 0.3mm, and XY axis printing precision is 0.02mm, Z axis printing precision are 0.002mm, and floor height precision is 0.07mm, and printing linear velocity is 60mm/s, is extruded by nozzle Paste and layer upon layer form blank cartilaginous tissue, are then placed in water blank cartilaginous tissue, environment temperature be 23 DEG C, Relative humidity conserves 5h under conditions of being 74%, by aluminium hydroxide, potassium methyl silicate, cures with hydroxylapatite crystal, is formed Cartilaginous tissue with good strength.
Embodiment 5
The preparation process of 3D printing cartilage gel rubber material is:
By the potassium alginate powder of the hydroxyapatite powder of 75kg, the aluminium hydroxide of 4kg, the potassium methyl silicate of 4kg and 17kg Mixing, is placed in vacuum drying chamber, is taken out at 86 DEG C after dry 10h, is then ground, ground using fine grinding machine To the mixed-powder that particle diameter is 100~300nm;Then the mixed-powder of 42kg is taken, is modulated by the glycerine for adding 17kg, And the calcium stearate of 1kg is added, it is made the cream gel cartilage material for being suitable for 3D printing, in modulated process, glycerine is divided into 5 Secondary addition, each modulation time are 70min, and mixing speed during modulation is 350r/min;
The application process of 3D printing cartilage gel rubber material is:
Gel rubber material is added to the feed inlet of 3D printer, the jet diameters of 3D printer are 0.4mm, and XY axis printing precision is 0.02mm, Z axis printing precision are 0.002mm, and floor height precision is 0.07mm, and printing linear velocity is 60mm/s, is extruded by nozzle Paste and layer upon layer form blank cartilaginous tissue, are then placed in water blank cartilaginous tissue, environment temperature be 28 DEG C, Relative humidity conserves 6h under conditions of being 75%, by aluminium hydroxide, potassium methyl silicate, cures with hydroxylapatite crystal, is formed Cartilaginous tissue with good strength.
Embodiment 6
The preparation process of 3D printing cartilage gel rubber material is:
By the sodium alginate powder of the hydroxyapatite powder of 80kg, the aluminium hydroxide of 3kg, the potassium methyl silicate of 4kg and 13kg Mixing, is placed in vacuum drying chamber, is taken out at 88 DEG C after dry 10h, is then ground, ground using fine grinding machine To the mixed-powder that particle diameter is 100~300nm;Then the mixed-powder of 40kg is taken, is modulated by the glycerine for adding 18kg, And the calcium stearate of 2kg is added, it is made the cream gel cartilage material for being suitable for 3D printing, in modulated process, glycerine is divided into 4 Secondary addition, each modulation time are 80min, and mixing speed during modulation is 400r/min;
The application process of 3D printing cartilage gel rubber material is:
Gel rubber material is added to the feed inlet of 3D printer, the jet diameters of 3D printer are 0.3mm, and XY axis printing precision is 0.02mm, Z axis printing precision are 0.002mm, and floor height precision is 0.06mm, and printing linear velocity is 60mm/s, is extruded by nozzle Paste and layer upon layer form blank cartilaginous tissue, are then placed in water blank cartilaginous tissue, environment temperature be 26 DEG C, Relative humidity conserves 5h under conditions of being 75%, by aluminium hydroxide, potassium methyl silicate, cures with hydroxylapatite crystal, is formed Cartilaginous tissue with good strength.

Claims (10)

1. the preparation method of a kind of gel rubber material for 3D printing artificial cartilage, it is characterised in that first by hydroxyapatite, hydrogen Aluminium oxide, potassium methyl silicate, alginic acid salt powder are uniformly mixed, and are then dried in vacuo and fine gtinding, add glycerine and Calcium stearate carries out gradation modulation, you can cream gel cartilage material is made, preparation comprises the following steps that:
(1)By weight, by 73~83 parts by weight of hydroxyapatite, 2~4 parts by weight of aluminium hydroxide, 3~5 weight of potassium methyl silicate Part, the mixing of 12~18 parts by weight of alginic acid salt powder are measured, is placed in vacuum drying chamber, drying at a certain temperature is after a certain period of time Take out, be then ground using fine grinding machine, obtain mixed-powder;
(2)By step(1)The mixed-powder of gained is modulated by glycerine, and adds the calcium stearate of certain part by weight, system Into the cream gel cartilage material for being suitable for 3D printing;Wherein, 30~45 parts by weight of mixed-powder, glycerine 15-20 parts by weight, 1~2 parts by weight of calcium stearate.
A kind of 2. preparation method of gel rubber material for 3D printing artificial cartilage according to claim 1, it is characterised in that: Step(1)The hydroxyapatite is voluminous powder, is hexagonal crystal system or monoclinic system, and particle diameter is 300~800 μm, calcium-phosphorus ratio For 1.6~1.7, proportion is 3.05~3.18g/cm3
A kind of 3. preparation method of gel rubber material for 3D printing artificial cartilage according to claim 1, it is characterised in that: Step(1)The alginic acid salt powder is white or light yellow, is at least one in calcium alginate, potassium alginate or sodium alginate Kind, powder diameter is 200~400 μm.
A kind of 4. preparation method of gel rubber material for 3D printing artificial cartilage according to claim 1, it is characterised in that: Step(1)The vacuum drying temperature is 80~90 DEG C, and the time is 8~12h.
A kind of 5. preparation method of gel rubber material for 3D printing artificial cartilage according to claim 1, it is characterised in that: Step(1)The particle diameter of mixed-powder after the fine gtinding is 100~300nm.
A kind of 6. preparation method of gel rubber material for 3D printing artificial cartilage according to claim 1, it is characterised in that: Step(2)In the paste modulated process, glycerine is divided into 3~5 additions, and each modulation time is 60~90min, modulation When mixing speed be 300~500r/min.
7. the gel rubber material for the 3D printing cartilage that any one of claim 1~6 preparation method is prepared.
8. the application process of a kind of gel rubber material for 3D printing artificial cartilage, it is characterised in that first carry out gel rubber material 3D printing is molded, and is then conserved in water, you can cartilaginous tissue is made, specific application process is:
(1)Gel rubber material is added to the feed inlet of 3D printer, paste is extruded by nozzle and layer upon layer formation blank is soft Bone tissue;
(2)Blank cartilaginous tissue is placed in water maintenance, by aluminium hydroxide, potassium methyl silicate, is consolidated with hydroxylapatite crystal Change, form the cartilaginous tissue with good strength;
The gel material for the 3D printing cartilage that the gel rubber material is prepared for any one of claim 1~6 preparation method Material.
A kind of 9. application process of gel rubber material for 3D printing artificial cartilage according to claim 8, it is characterised in that: The jet diameters of the 3D printer are 0.2~0.4mm, and XY axis printing precision is 0.01~0.02mm, and Z axis printing precision is 0.002~0.003mm, floor height precision are 0.05~0.08mm, and printing linear velocity is 30~80mm/s.
10. a kind of application process of gel rubber material for 3D printing artificial cartilage, its feature exist according to claim 8 In:The environment temperature of maintenance processes is 20~30 DEG C in the water, and relative humidity is 70~90%, and curing time is 4~6h.
CN201711471026.4A 2017-12-29 2017-12-29 A kind of gel rubber material and preparation method and application for 3D printing artificial cartilage Withdrawn CN108030957A (en)

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CN111068105A (en) * 2020-01-14 2020-04-28 山东建筑大学 Preparation method of porous artificial cartilage with bioactivity based on 3D printing

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