CN101884574B - Method and device for preparing three-dimensional porous support for tissue engineering - Google Patents
Method and device for preparing three-dimensional porous support for tissue engineering Download PDFInfo
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- CN101884574B CN101884574B CN2010102106182A CN201010210618A CN101884574B CN 101884574 B CN101884574 B CN 101884574B CN 2010102106182 A CN2010102106182 A CN 2010102106182A CN 201010210618 A CN201010210618 A CN 201010210618A CN 101884574 B CN101884574 B CN 101884574B
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Abstract
The invention discloses a method and device for preparing a three-dimensional porous support for tissue engineering. The preparation method comprises the following steps of: 1, slicing and layering a support according to a certain thickness firstly to obtain two-dimensional cross section information of each layer of the support; 2, preparing a first layer slice of the support by using a three-dimensional inkjet printing spray head under the control of CAD software, dibbling microcapsule particles on the first layer slice of the support by using a bio-microcapsule preparation nozzle, and stacking the microcapsule particles to form gaps required by a support design; 3, moving the three-dimensional inkjet printing spray head and the bio-microcapsule preparation nozzle for the height of one layer slice of the support to finish the forming preparation of a second layer of the support; and 4, repeating the method layer by layer until the three-dimensional porous support is prepared. The device for preparing the three-dimensional porous support is suitable for the preparation method, and comprises a three-dimensional inkjet printing forming machine, a jetting device, a bio-microcapsule dibbling device and a control system.
Description
Technical field
The invention belongs to biomedical engineering and advanced manufacturing technology field, be specially a kind of method for preparing and equipment of three-dimensional porous support for tissue engineering.
Background technology
In recent years, along with cytobiology, molecular biology and biomaterial are learned advancing by leaps and bounds of research, organizational project has also obtained very big progress as an emerging cross discipline in its research and application facet.The ultimate principle of tissue engineering and method are to have good biocompatibility and in vivo progressively on the tissue engineered porous scaffold of degraded and absorbed with planting at the normal tissue cell of In vitro culture, amplification; Form the cell-scaffold complex; Cell is bred on support, is broken up; With the sick position of decreasing of this complex implanting to human body tissue, continue propagation justacrine extracellular matrix in vivo then, be accompanied by the progressively degraded of material; Form new tissue or the organ that adapts with self function and form, repair sick purpose of decreasing tissue or organ thereby reach.This method will make the damaged treatment of histoorgan get into the New Times that organ is made from organ transplantation.
One of key technology of organizational project is biomaterial is processed the support with given shape and pore structure.The effect of support is the migration and the growth (tissue conductivity) of guiding surrounding tissue cell, or for the growth of planting cell in the support loose structure provides a suitable substrate, guarantees the sticking of cell, increment, differentiation function and migration.In order to satisfy these requirements of cell, select suitable material preparation support extremely important, but also should notice that the support course of processing maybe be to the influence of its adaptability generation simultaneously.
In organizational project, use and more be and particular organization or the organ three-dimensional porous rack with complicated shape of coupling earlier, thereby the technology of preparing that research and development have a three-dimensional porous rack of complicated shape is one of key issue that presses in the Tissue Engineering Study solution.The control of position, tissue engineering bracket mesopore, pore size and the height of porosity also are the key issues in the porous support research.
In existing support method for preparing; The specific fiber surface of fiber gluing method is long-pending big, can be prepared into the difform glutinous each other network of fibers that connects, and is used for the tubular bracket of tissue regeneration such as blood vessel, intestinal; But when if the 3D shape of support is complicated, this technology can not be dealt with problems.Utilize solvent to record that can to make porosity nearly 93% with the particle leaching technology, and the porous support that communicates of hole.Porosity can be regulated through changing the salt consumption, and pore size also can be realized and the irrelevant control of porosity through changing the salt particle size.But (support of thickness＜2mm) can not directly be constructed three-dimensional rack, and can not control the position of hole for wafer that this method can only be used to approach and film material.Particle pore method is simple, the suitability is wide, porosity and hole dimension are prone to independent regulation; It is a method in common; Also obtained extensive use; But this method often need be used organic solvent when pore, and residual organic solvent is understood the toxigenicity effect external in the support, and brings out inflammatory reaction in vivo.The gas foaming method can avoid preparation during support with an organic solvent, this method combines with the particle leaching technology, then can make the porous support of continuous open-celled structure, but that the weak point of this method is a hole in the support is uncontrollable.
Bio-microcapsule, how with physical-chemical processes such as solvent evaporated method, phase separation method, interface sedimentation and spray drying methods, and chemical method preparations such as polymerization, emulsion process.With the microcapsule of method for preparing, need or use the violent destructive organic solvent of reaction under hot conditions usually, the prepared microcapsule particle size distribution is wide, is difficult to satisfy keep the active requirement of biological substance in the biological support, needs screening to filter.Electrostatic method is through the prepared in reaction microcapsule between the electric field intermediate ion type material, though manufacture process is relatively gentleer, production scale is little, and the microcapsule particle diameter of producing can not satisfy actual instructions for use often more than 200 μ m.The microcapsule manufacturing technology of relevant micron order size rarely has report both at home and abroad; Bnenedetti etc. utilize supercritical object technology to make the microcapsule of particle diameter less than 20 μ m; But it is harsh that supercritical object technology requires experimental apparatus, experimental situation and fluidic character, can't realize industrialization.The bag cell sodium alginate micro gel capsule that Dalian Inst of Chemicophysics, Chinese Academy of Sciences's biomedical material engineering group is made, its average diameter is about 240 μ m, and particle diameter is bigger equally, can not satisfy actual instructions for use.
Summary of the invention
Deficiency to prior art; The technical problem that quasi-solution of the present invention is determined is; A kind of method for preparing and equipment of three-dimensional porous support for tissue engineering are provided, and the prepared three-dimensional porous rack of this method for preparing and equipment has and defective tissue or the same complicated contour structures of organ, and the hole of support is controlled; Do not pollute, be suitable for industrializing implementation; This equipment is applicable to method for preparing of the present invention, and is simple in structure.Be convenient to the industrialization manufacturing.
The technical scheme that the present invention solves said method for preparing technical problem is, designs a kind of method for preparing of three-dimensional porous support for tissue engineering, and this method for preparing adopts following steps based on three-dimensional inkjet printing methods and bio-microcapsule dibbling method:
(1) at first goes out the pattern of support, according to the technological requirement of product, support is pressed the certain thickness slicing delamination then, obtain the two-dimensional section information of each layer of support by the three-dimensional CAD software design;
(2) under the CAD control of software; Three-dimensional ink jet printing head is along X axle and Y direction operation; Accomplish the printing campaign that support ground floor cross section information sets; And spray liquid polymer according to this cross section information, make liquid polymer directly or under the irradiation of uviol lamp, be bonded to first synusia of support; Under the control of computer, bio-microcapsule prepares nozzle dibbling microcapsule granule on first synusia of support, microcapsule granule is piled up formed the hole that support Design requires, and makes the following one deck support of the microcapsule granule of accumulation as support simultaneously; Described liquid polymer comprises close-burning biodegradable high molecular polymer or photocuring biodegradable high molecular polymer;
(3) under the control of computer; Making three-dimensional ink jet printing head and bio-microcapsule prepare nozzle moves along Z-direction; The height of a synusia of traversing carriage; Adopt the method the same to accomplish the shaping preparation of the support second layer, make the second layer of support and its ground floor be bonded to an integral body simultaneously, and make bio-microcapsule pile up the hole that forms designing requirement with (2) step;
(4) repetition (2) and (3) one step process successively carry out according to the two-dimensional section information of said each layer of support, until making described three-dimensional porous support for tissue engineering successively.
The technical scheme that the present invention solves said preparation equipment and technology problem is; Design a kind of preparation equipment of three-dimensional porous support for tissue engineering; It is characterized in that this preparation equipment is applicable to method for preparing of the present invention, comprises three-dimensional inkjet printing forming machine, injection apparatus, bio-microcapsule dibbling device and control system; Described three-dimensional inkjet printing forming machine comprise base plate, gantry support, shaping platform, X to drive mechanism, X to the slide block of precision linear module, Y to drive mechanism, Y to the slide block of precision linear module, Z to drive mechanism and Z slide block to the precision linear module; Said gantry support vertically is installed on the base plate; The shaping platform is installed in Y on the slide block of precision linear module; X is fixed on the gantry support to drive mechanism, and Z is fixed on X on the slide block of precision linear module to drive mechanism, and Y directly is fixed on the base plate to drive mechanism;
Said injection apparatus mainly comprises printing head, material-storing box and feed pipe; Printing head is installed in Z on the slide block of precision linear module, and material-storing box is fixed on the described gantry support, is connected through feed pipe between printing head and the material-storing box;
Said bio-microcapsule dibbling device mainly comprises bio-microcapsule nozzle, capsule control valve and capsule storage box; The bio-microcapsule nozzle is installed in Z on the slide block of precision linear module, and the capsule storage box is installed in the top of capsule dibbling device, and links to each other with capsule control valve as the bio-microcapsule memory device; Described printing head and bio-microcapsule nozzle are installed in Z on the slide block of precision linear module;
Described control system comprises control device and computer; Control device is connected with computer through the general extension groove.
Compared with prior art; Method for preparing of the present invention combines with the ingenious of bio-microcapsule method for preparing based on three-dimensional inkjet printing methods; Prepared three-dimensional porous rack has and defective tissue or the same complicated contour structures of organ; And the aperture position and the pore size of support are controlled, do not pollute, and are suitable for industrializing implementation; The present invention prepares equipment and designs according to method for preparing of the present invention; Prepared three-dimensional porous support for tissue engineering has defective tissue or the same complex appearance structure of organ with human body or animal; The porosity of support is not less than 60%, generally can reach 95%, and has continuous pore structure; Both can satisfy the different product designing requirement, be convenient to the industrializing implementation manufacturing again.
Description of drawings
Fig. 1 is the process chart of a kind of embodiment of method for preparing of three-dimensional porous support for tissue engineering of the present invention;
Fig. 2 is the population structure sketch map of a kind of embodiment of preparation equipment of three-dimensional porous support for tissue engineering of the present invention.
The specific embodiment
The present invention is described further with its accompanying drawing below in conjunction with embodiment, but application claim of the present invention is not subject to these embodiment.
The method for preparing of the three-dimensional porous support for tissue engineering (abbreviation support) of the present invention's design (being called for short method for preparing, referring to Fig. 1) is based on the combination of three-dimensional inkjet printing methods and bio-microcapsule dibbling method.Adopt following steps:
(1) at first goes out the pattern of support, according to the technological requirement of product, support is pressed the certain thickness slicing delamination then, obtain the two-dimensional section information of each layer of support by the three-dimensional CAD software design;
(2) under the CAD control of software; Three-dimensional ink jet printing head is along X axle and Y direction operation; Accomplish the printing campaign that support ground floor cross section information sets; And spray liquid polymer according to this cross section information, make liquid polymer directly or under the irradiation of uviol lamp, be bonded to first synusia of support; Under the control of computer, bio-microcapsule prepares nozzle dibbling microcapsule granule on first synusia of support, microcapsule granule is piled up formed the hole that support Design requires, and makes the following one deck support of the microcapsule granule of accumulation as support simultaneously; Described liquid polymer comprises close-burning biodegradable high molecular polymer or photocuring biodegradable high molecular polymer;
(3) under the control of computer; Making three-dimensional ink jet printing head and bio-microcapsule prepare nozzle moves along Z-direction; The height of a synusia of traversing carriage; Adopt the method the same to accomplish the shaping preparation of the support second layer, make the second layer of support and its ground floor be bonded to an integral body simultaneously, and make bio-microcapsule pile up the hole that forms designing requirement with (2) step;
(4) repetition (2) and (3) one step process successively carry out according to the two-dimensional section information of said each layer of support, until making described three-dimensional porous support for tissue engineering successively.
Three-dimensional porous rack of the present invention has complex appearance structure the link to each other pore structure controlled with hole, and hole or aperture size can obtain adjustment through the size of adjustment bio-microcapsule and the numbers of particles of dibbling.Said bio-microcapsule is that enzyme, protein and bioactive substances such as hormone and even cell are encapsulated in the selective permeation film, the spherical microsphere of formation.Be encapsulated in bioactive substance in the bio-microcapsule and can regulate and control the growth and the cell function of tissue.Bio-microcapsule of the present invention is the encapsulation object of bioactive substance, and required backing material when being again three-dimensional inkjet printing need not the specialized designs supporting construction, thereby can make the support volume little, and preparation is simple.The microcapsule that volume is little has that to be beneficial to dead space in oxygen and nutraceutical supply, the capsule little and be convenient to the advantages such as input of support small-bore.The present invention selects for use or the bio-microcapsule particle grain size for preparing is 10～20 μ m, and support aperture controllable size is 10～800 μ m, is generally 200～400 μ m.
The support of the present invention's design, its profile stock both can have been selected for use and have close-burning biodegradable high molecular polymer, like gelatin, albumin, chitin, chitosan and polylactic-co-glycolic acid (PLGA) etc.; Also can select photocuring biodegradable high molecular polymer for use, like unsaturated polyphosphate (UPPE) etc.In the method for preparing of the present invention, if the contoured cradle stock is selected for use when having close-burning biodegradable high molecular polymer, shaping (being configured as the contoured cradle synusia) can directly bond in described (2) step preparation process; And if the contoured cradle stock is when adopting photocuring biodegradable high molecular polymer; Then in described (2) step preparation process; Need to use photocuring light source (embodiment is the 1000W uviol lamp) irradiation certain hour (embodiment is 1s), so that contoured cradle stock solidified forming is the contoured cradle synusia.
The present invention has designed preparation equipment (the abbreviation equipment of said three-dimensional porous support for tissue engineering simultaneously; Referring to Fig. 1,2); It is characterized in that this preparation equipment is applicable to method for preparing of the present invention, comprise three-dimensional inkjet printing forming machine 1, injection apparatus 2, bio-microcapsule dibbling device 3 and control system; Described three-dimensional inkjet printing forming machine comprise base plate 11, gantry support 12, shaping platform 13, X to drive mechanism 14, X to the slide block 15 of precision linear module, Y to drive mechanism 16, Y to the slide block 17 of precision linear module, Z to drive mechanism 18 and Z slide block 19 to the precision linear module; Said gantry support 12 vertically is installed on the base plate 11, and shaping platform 13 is installed in Y on the slide block 17 of precision linear module, and shaping platform 13 is moved along the Y direction; X is fixed on the gantry support 12 to drive mechanism 14, and Z is fixed on X on the slide block 15 of precision linear module to drive mechanism 18, and Y directly is fixed on the base plate 11 to drive mechanism 16; Described X constitutes by servomotor and precision linear module to drive mechanism 18 to drive mechanism 16 and Z to drive mechanism 14, Y; Described X is that employing line slideway and ball-screw be the structure of executive component to precision linear module and Z to the precision linear module to precision linear module, Y;
Said injection apparatus 2 mainly comprises printing head 21, material-storing box 22 and feed pipe 23; Printing head 21 is installed in Z on the slide block 19 of precision linear module, can move along X, Z direction, and material-storing box 22 is fixed on the described gantry support 12, is connected through feed pipe 23 between printing head 21 and the material-storing box 22; The injection apparatus 2 main jet printings of accomplishing contoured cradle structure 7;
Said bio-microcapsule dibbling device (being called for short the dibbling device) 3 mainly comprises bio-microcapsule nozzle 31, capsule control valve 32 and capsule storage box 33; Bio-microcapsule nozzle 31 is installed in Z on the slide block 19 of precision linear module, and capsule storage box 33 is installed in the top of capsule dibbling device 3, and links to each other with capsule control valve 32 as the bio-microcapsule memory device; The 3 main preparations of accomplishing brace aperture structure 8 of capsule dibbling device;
Described control system comprises control device 4 and computer 5; Control device 4 is connected with computer 5 through the general extension groove of computer 5;
Said control device 4 is control centres of equipment, and embodiment is the switch board that is made up of each discrete device; Computer 5 mainly is responsible for providing the concrete control algolithm of control system; The work such as processing of the collection of the setting of the management of control system, program relevant parameter, the demonstration of system mode, control system data, various switching signal and feedback signal, and accomplish the output of control signal by control device 4.
The further characteristic that the present invention prepares equipment is; Between printing head 21 and bio-microcapsule nozzle 31, photocuring light source 6 is installed; Photocuring light source 6 is connected with control device 4 through the light source control line, and control device 4 is directly controlled the switch of photocuring light source 6 according to control information.Photocuring light source 6 and control thereof itself are prior aries.The equipment of this structure is applicable to that said contoured cradle stock selects the situation of photocuring biodegradable high molecular polymer for use.
Use bio-microcapsule dibbling device in method for preparing of the present invention and the preparation equipment, in order to accomplish the shaping manufacturing of brace aperture.Described bio-microcapsule dibbling device is through the switch of computer control capsule control valve, to satisfy the needs of brace aperture to the microcapsule number.When making brace aperture, computer is controlled the folding of microcapsule control valve according to information command.During unlatching; Microcapsule falls in the cavity of bio-microcapsule dibbling equipment; And arrival capsule nozzle place; Again under the control of computer, the capsule nozzle of dibbling device combine three-dimensional ink jet printing head by the product design requirement successively the dibbling bio-microcapsule on the shaping platform, accomplish the manufacturing of said support.Because dibbling equipment and three-dimensional ink jet printing head all are controlled, thereby the complex appearance structure of support and hole, aperture all are controlled.Method of the present invention is or/and the bio-microcapsule of equipment preparation is technological based on little spray and dibbling, and prepared microcapsule particle diameter can be controlled in 10～20 μ m.This microcapsule size can satisfy the active requirement of maintenance biological substance in the used in tissue engineering support fully.
The present invention does not address part and is applicable to prior art.
Provide specific embodiment of the present invention below:
Embodiment 1
With unsaturated polyphosphate (UPPE) material preparation length is 50mm bone tissue engineer three-dimensional porous rack.The biological capsule particle grain size is 20 μ m, and the support number of slices is 2500.
At first use the three-dimensional CAD software design to go out the three-dimensional entity model (referring to Fig. 1) of support, then according to the product design technological requirement, it is carried out slicing delamination by certain thickness, form a series of two dimension slicings, the slice thickness of each layer is 20 μ m.Computer 5 is controlled each controlling organization respectively according to the two dimension shaping information of each layer and is done coordination exercise.Particularly, during the preparation beginning, computer 5 passes to control device 4 to the two dimension shaping information of ground floor; Capsule control valve 32 in the bio-microcapsule dibbling device 3 is opened valve under the control of control device 4, capsule is fallen bio-microcapsule nozzle 31, and control device 4 drives printing head 21 and bio-microcapsule nozzle 31; Printing head 21 is ejected into degradable polymer solution on the shaping platform 13 according to this layer shaping information; Control device 4 control photocuring light sources 6 with its rapid curing, form contoured cradle structural region 7 subsequently; When printing head 21 sprays degradable polymer solution; Biological capsule nozzle 31 dibbling capsule grain diameter one by one is the biological capsule of 20 μ m, forms brace aperture structural region 8, and bio-microcapsule is again as required supporting construction simultaneously; Z is to the coordination exercise of drive mechanism 18 work realization printing heads 21 and biological capsule nozzle 31, and Y moves to the position of drive mechanism 16 control shaping platforms 13.Then, the computer 5 handles shaping information of one deck down pass to control device 4, and control device 4 drives printing heads 21 and accomplishes the preparation of the second layer with biological capsule nozzle 31 as printing ground floor.So repeatedly, printing from level to level and bonding, thus prepare three-dimensional porous rack fast.Under certain conditions, the biological capsule degraded forms brace aperture, can obtain the controlled three-dimensional rack of hole.Prepared three-dimensional porous rack aperture 200～800 μ m, porosity 80%.
Embodiment 2
Basic identical with embodiment 1, different is that the biological capsule particle grain size is 18 μ m, and has added the pharmaceutically active molecule in the capsule, support aperture 200～400 μ m of preparation, porosity 90%.
Embodiment 3
Basic identical with embodiment 1, different is that the biological capsule particle grain size is 15 μ m, and has added the pharmaceutically active molecule in the capsule, support aperture 100～300 μ m of preparation, porosity 85%.
Embodiment 4
Basic identical with embodiment 1, different is that the biological capsule particle grain size is 12 μ m, support aperture 50～200 μ m of preparation, porosity 90%.
Basic identical with embodiment 1, different is that the biological capsule particle grain size is 10 μ m, and has added the pharmaceutically active molecule in the capsule, support aperture 10～100 μ m of preparation, porosity 93%.
Embodiment 6
Basic identical with embodiment 1, different is that the stock of manufacturing contoured cradle is selected for use and had close-burning biodegradable high molecular polymer, need not use light curing light source 6 and control system thereof at this moment, directly is bonded to contoured cradle.The manufacturing of brace aperture can with embodiment 1,2,3,4 or 5 in any is identical.
Claims (4)
1. the method for preparing of a three-dimensional porous support for tissue engineering, this method for preparing adopt following steps based on three-dimensional inkjet printing methods and bio-microcapsule dibbling method:
(1) at first goes out the pattern of support, according to the technological requirement of product, support is pressed the certain thickness slicing delamination then, obtain the two-dimensional section information of each layer of support by the three-dimensional CAD software design;
(2) under the CAD control of software; Three-dimensional ink jet printing head is along X axle and Y direction operation; Accomplish the printing campaign that support ground floor cross section information sets; And spray liquid polymer according to this cross section information, make liquid polymer directly or under the irradiation of uviol lamp, be bonded to first synusia of support; Under the control of computer, bio-microcapsule prepares nozzle dibbling microcapsule granule on first synusia of support, microcapsule granule is piled up formed the hole that support Design requires, and makes the following one deck support of the microcapsule granule of accumulation as support simultaneously; Described liquid polymer comprises close-burning biodegradable high molecular polymer or photocuring biodegradable high molecular polymer;
(3) under the control of computer; Making three-dimensional ink jet printing head and bio-microcapsule prepare nozzle moves along Z-direction; The height of a synusia of traversing carriage; Adopt the method the same to accomplish the shaping of the support second layer, make the second layer of support and its ground floor be bonded to an integral body simultaneously, and make bio-microcapsule pile up the hole that forms designing requirement with (2) step;
(4) repetition (2) and (3) one step process successively carry out according to the two-dimensional section information of said each layer of support, until making described three-dimensional porous support for tissue engineering successively.
2. the method for preparing of three-dimensional porous support for tissue engineering according to claim 1 is characterized in that described close-burning biodegradable high molecular polymer is gelatin, albumin, chitin, chitosan or polylactic-co-glycolic acid; Described photocuring biodegradable high molecular polymer is a unsaturated polyphosphate.
3. the preparation equipment of a three-dimensional porous support for tissue engineering is characterized in that this preparation equipment is applicable to the described method for preparing of claim 1, comprises three-dimensional inkjet printing forming machine, injection apparatus, bio-microcapsule dibbling device and control system; Described three-dimensional inkjet printing forming machine comprise base plate, gantry support, shaping platform, X to drive mechanism, X to the slide block of precision linear module, Y to drive mechanism, Y to the slide block of precision linear module, Z to drive mechanism and Z slide block to the precision linear module; Said gantry support vertically is installed on the base plate; The shaping platform is installed in Y on the slide block of precision linear module; X is fixed on the gantry support to drive mechanism, and Z is fixed on X on the slide block of precision linear module to drive mechanism, and Y directly is fixed on the base plate to drive mechanism;
Said injection apparatus mainly comprises printing head, material-storing box and feed pipe; Printing head is installed in Z on the slide block of precision linear module, and material-storing box is fixed on the described gantry support, is connected through feed pipe between printing head and the material-storing box;
Said bio-microcapsule dibbling device mainly comprises bio-microcapsule nozzle, capsule control valve and capsule storage box; The bio-microcapsule nozzle is installed in Z on the slide block of precision linear module, and the capsule storage box is installed in the top of capsule dibbling device, and links to each other with capsule control valve as the bio-microcapsule memory device; Described printing head and bio-microcapsule nozzle are installed in Z on the slide block of precision linear module;
Described control system comprises control device and computer; Control device is connected with computer through the general extension groove.
4. the preparation equipment of three-dimensional porous support for tissue engineering according to claim 3; It is characterized in that between said printing head and bio-microcapsule nozzle, the photocuring light source being installed; The photocuring light source is connected with control device through the light source control line, and control device is directly controlled the switch of photocuring light source according to control information.
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2010
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101032430A (en) * | 2007-04-13 | 2007-09-12 | 中国人民解放军第三军医大学第一附属医院 | Method for preparing integrated frame fabrication of cartilage of tissue-engineered bone having function interface |
| CN201092148Y (en) * | 2007-08-22 | 2008-07-30 | 西安理工大学 | Ink-jet stamping shaper with printing head capable of carrying out three-dimensional motion |
Non-Patent Citations (1)
| Title |
|---|
| 牛旭锋，等.微囊化壳聚糖/纳米羟基磷灰石/胶原/聚乳酸复合材料.《复合材料学报》.2009,第26卷(第2期),143-147. * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104742372A (en) * | 2015-04-02 | 2015-07-01 | 共享装备有限公司 | 3D printing equipment based on FDM |
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| CN101884574A (en) | 2010-11-17 |
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