CN113103576B - 3D printing method for ordered gradient porous material - Google Patents
3D printing method for ordered gradient porous material Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/188—Processes of additive manufacturing involving additional operations performed on the added layers, e.g. smoothing, grinding or thickness control
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/30—Auxiliary operations or equipment
- B29C64/379—Handling of additively manufactured objects, e.g. using robots
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/40—Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof
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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
- B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
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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
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
- B33Y40/20—Post-treatment, e.g. curing, coating or polishing
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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
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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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
- B33Y80/00—Products made by additive manufacturing
Abstract
The invention relates to the technical field of additive manufacturing, in particular to a 3D printing system and method for ordered gradient porous materials, and aims to solve the problem that printing of anisotropic gradient porous materials in an extrusion single channel cannot be realized in traditional 3D printing. The system comprises the following parts: the device comprises a three-dimensional forming motion module, a digital ultrasonic auxiliary manufacturing system, a controllable air pressure material conveying module and a computer control system. The method comprises the following steps: preparation of printing material containing sacrificial template particles, ultrasonic auxiliary additive manufacturing and post-treatment. The gradient distribution of the oriented pore structure in the single extruded filament from inside to outside in the 3D printing can be realized, and the unique mechanical property and physical property of the filament have great application potential in the fields of tissue engineering and machinery.
Description
Technical Field
The invention relates to the technical field of additive manufacturing, in particular to a 3D printing method for a directional ordered gradient porous material.
Background
The natural organism can greatly reduce the density thereof by constructing a porous structure, and simultaneously can keep excellent mechanical properties (namely light weight, high strength, shock absorption and the like) such as high-efficiency heat insulation, long-range liquid transmission and the like. For example, the hollow and porous hair structure of the polar bear has extremely strong heat preservation and insulation performance; the porous structure of the plant rod diameter provides capillary force for the directional transmission of water from bottom to top; the gradient porous structure of the bone tissue from inside to outside has the characteristics of light weight and high strength. By simulating the ordered porous structure of the biological material, the method is expected to provide important inspiration and help for developing artificial materials with bionic porous structures and excellent performance.
However, the current traditional porous material preparation technology (direct template method, emulsion template method, foaming method, etc.) can only realize uniform and random distribution of void structures, and cannot meet the preparation requirements of people for bionic ordered porous structures, such as the distribution of cancellous bone and compact bone inside bone tissue from inside to outside, and the actual gradient distribution mode that the pore diameter and the porosity are gradually reduced from inside to outside is a specific expression that the cancellous bone with large pore diameter, high porosity and low mechanical property is gradually graded to the compact bone with small pore diameter, low porosity and high mechanical property. The corresponding bone tissue porous structure is repeatedly carved, which is beneficial to obtaining superior mechanical property and physiological characteristic.
The ultrasonic-assisted manufacturing technology is beneficial to promoting the dispersion sacrificial template particles in the matrix material to present a certain concentrated gradient ordered distribution mode, and based on the principle, an ultrasonic-assisted field is added on the basis of the extrusion type 3D printing process to promote the gradient ordered distribution of the dispersion-enhanced phase.
The invention has the following remarkable advantages: 1. the pore density and the pore size in the extrusion single channel gradually decrease from inside to outside and present gradient distribution; 2. the pore gradient mode is adjustable and controllable; 3. the preparation method is simple and easy to operate, and the material has wide application range.
Disclosure of Invention
Aiming at the defect of lacking a technical means for engineering a biological inspired gradient ordered porous material in the prior art, the invention provides a 3D printing system and method for ordered gradient porous materials. The 3D printing system is firstly oriented to the ordered gradient porous material, and the 3D printing method is provided for the ordered gradient porous material.
In order to solve the technical problems, the technical scheme of the invention is as follows:
3D printing system towards ordered gradient porous material, characterized by, includes:
the three-dimensional molding manufacturing module is used for extruding a material system containing the gradient ordered sacrificial template particles from the material extruding module, and then controlling the material extruding module to move in X, Y, Z three-dimensional space, so that the single-channel cumulative molding of the extrusion containing the gradient ordered sacrificial template particles is realized;
the digital ultrasonic auxiliary system is used for assisting the material extrusion module with the ultrasonic auxiliary system to promote the sacrificial template particles in the matrix material to present ordered distribution in a certain mode;
the controllable air pressure conveying module is used for controlling the output of compressed air so as to adjust the extrusion time, the extrusion speed and the extrusion amount of the material system in the material extrusion module;
the computer control system is used for predefining a three-dimensional model containing a printing program, and transmitting the structural characteristics of the printable model to the three-dimensional forming and manufacturing module, the digital ultrasonic auxiliary system and the controllable air pressure material conveying module in a three-dimensional motion code mode so that the three-dimensional forming and manufacturing module can obtain the moving track of the output material extrusion module, the digital ultrasonic auxiliary system can obtain the transverse vibration amplitude and frequency of the output material extrusion module, and the controllable air pressure material conveying module can obtain the material extrusion time, the extrusion speed and the extrusion amount of the output material extrusion module;
further, the three-dimensional modeling manufacturing module comprises:
the material extrusion module is arranged in the middle of the three-dimensional motion hardware system and is directly connected with the digital ultrasonic auxiliary system, the controllable air pressure material conveying module and the computer control system;
a three-dimensional motion hardware system for controlling motion within a space of a material extrusion module.
Further, the material extrusion module comprises:
the mechanical motion device is directly connected with the three-dimensional motion hardware system, receives a motion signal output by the three-dimensional motion hardware system and controls the spatial motion of the material extrusion module;
the material extruding cylinder is directly connected with the controllable air pressure conveying module, receives an air pressure signal of the controllable air pressure conveying module and realizes the timed, fixed-point and quantitative output of a material system;
the transverse vibration structure is directly connected with the digital ultrasonic auxiliary system, receives a mechanical vibration signal output by the digital ultrasonic auxiliary system and prompts the material extrusion cylinder to vibrate transversely, slightly and at high frequency;
further, the digital ultrasound-assisted system comprises:
an ultrasonic generator;
an ultrasonic transducer;
the ultrasonic amplitude transformer is directly connected with a transverse vibration structure in the three-dimensional motion hardware system, converts a mechanical vibration signal with smaller amplitude output by the ultrasonic transducer into a mechanical vibration signal with larger amplitude, transmits the mechanical vibration signal to the material extrusion module, and further controls the distribution of sacrificial template particles in the material system;
further, controllable atmospheric pressure defeated material module includes:
a compressed air supply device capable of producing an adjustable flow of said output air supply;
the compressed air source access part is connected with the compressed air source equipment at one end, and the other end of the compressed air source access part can be communicated with the material extrusion cylinder to control the extrusion of a material system;
further, the computer control system comprises:
an additive assembly to provide the print space and to provide movable three-dimensional coordinate parameters for the three-dimensional forming fabrication module;
the pre-defining module is used for setting the appearance parameters of the integrally formed printing body, the compressed air source parameters and the ultrasonic auxiliary parameters in the process of constructing the printing body;
and the printing program outputs printing information to each execution module based on the three-dimensional coordinate parameters, the shape parameters, the air source parameters and the ultrasonic auxiliary parameters.
Stated additionally, a method of 3D printing facing ordered gradient porous material, comprising:
s101, material preparation
Matrix material: printing the slurry by a precursor of a polymer base or a ceramic base;
sacrificial template particles: pore-forming agent, polyvinyl alcohol fiber, sugar and the like can be used as particles of the sacrificial template;
wherein the matrix material is a precursor printing slurry of one of a ceramic matrix or a polymer matrix;
wherein the ceramic matrix material is prepared from 49-65vol% of calcium phosphate cement and 35-51vol% of NaH2PO4Solution (0.2-0.5 ml/g);
wherein the polymer matrix material consists of 41-70vol% of polylactic acid and 30-59vol% of dichloromethane;
wherein the viscosity of the matrix material is 3000-100000 cP;
the sacrificial template particles are easily removable materials (easy to dissolve, melt/decompose), such as rod-shaped sodium glutamate crystals, sugar particles, salt particles, iodine particles, polyvinyl alcohol fibers and common ceramic pore-forming agents (starch, carbon powder, ammonium bicarbonate, polymethyl methacrylate microspheres and polystyrene microspheres), and can be removed through post-treatment processes (heating, soaking and the like);
wherein the sacrificial template particles are divided into two types in the aspect of geometrical characteristics, including sphere-like and rod-like, wherein the particle size range of the sphere-like particles is 5-200 mu m; the diameter range of the rod-like particles is 5-150 mu m, and the length-diameter ratio is 10-30;
the size of the sacrificial template particles can be divided into a plurality of specifications and can also be the same specification;
mixing 10-70vol% of sacrificial template particles with a matrix material, and uniformly stirring for later use;
s102, additive manufacturing of the gradient ordered reinforced material specifically comprises the following steps:
step 1, constructing a three-dimensional model, namely establishing a related three-dimensional model based on a predefined geometric model of a gradient ordered reinforcing material and an ordered gradient distribution mode of internal sacrificial template particles, and then performing discretization treatment on the three-dimensional model;
and 4, performing additive forming on the gradient ordered reinforced material, and controlling the distribution mode of sacrificial template particles in the material system in real time according to the motion code of the three-dimensional forming manufacturing module, the air source control signal of the controllable air pressure material conveying module and the vibration signal of the digital ultrasonic auxiliary system obtained in the step 2. A material system containing a rich distribution of sacrificial template particles is deposited on the shaping platform.
Wherein the output vibration frequency of the digital ultrasonic auxiliary system is 20-130 KHz;
s103, a post-processing step, namely removing the sacrificial template particles in the printing body according to respective characteristics, and then performing post-processing (curing, sintering and the like) on the formed sample.
Wherein, the removing condition of the sacrificial template particles needs to be dissolved/melted/decomposed and the like according to the physical characteristics of the sacrificial template;
wherein, the post-treatment of the forming sample piece is divided into two parts: if the matrix material is a polymer matrix, placing the formed sample in a vacuum drying oven at 40-60 ℃ for 5-24 h; if the matrix material is a ceramic-based material, placing the formed sample piece into a sintering furnace, wherein the heating speed is 3-15 ℃/min, and the sintering temperature is set to be Tm-15 ℃ and Tm (material melting temperature) and Tm +50 ℃;
the invention has the following beneficial effects:
on the first hand, based on extrusion type 3D printing, 3D printing of a novel porous material is developed, and gradient distribution of pore diameter and pore density is realized in an extrusion single channel;
in a second aspect, the 3D printing system and method provided by the present invention have rich adjustability, the pore size of the material can be adjusted according to the particle size of the sacrificial template, wherein the digitized ultrasound-assisted system can adjust the gradient distribution pattern of pore size and pore density in the single-channel porous material;
in a third aspect, if the sacrificial template particles used by the system and the method provided by the invention are rod-shaped materials, under the action of a digital ultrasonic auxiliary system and post-treatment, the gradient distribution of pore diameter and pores can be realized, and the fibrous pores are directionally distributed along the moving direction of the extrusion head;
in the fourth aspect, the invention can not only realize the gradient distribution of the pore diameter and the pore density in the radial direction, but also realize the control of the uniform degree of the pore diameter and the pore density in the extrusion single-channel axial direction to the gradient degree. If the sacrificial template is a rod-shaped sacrificial template particle, the gradient distribution of disordered holes and ordered holes can be realized.
In a fifth aspect, the 3D printing system and method provided by the invention have a wide range of material applications, and are not only suitable for polymers, but also suitable for ceramic materials and the like.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Fig. 1 is a schematic diagram of the system configuration of the present invention.
FIG. 2 is a radial gradient porous material formed when the sacrificial mold is substantially spherical-like particles of various sizes according to the present invention.
FIG. 3 is a graph of the distribution of radial and axial porosity achieved by tuning the digitized ultrasound-assisted system described in the present invention.
FIG. 4 is a radial gradient ordered porous material formed when the sacrificial mold is substantially rod-like particles of various sizes.
FIG. 5 is a distribution pattern of radial and axial disorder-order porous structures achieved by tuning the digitized ultrasound-assisted system described in the present invention.
The reference numerals in the figures denote:
the device comprises a three-dimensional forming manufacturing module 1, a digital ultrasonic auxiliary system 2, a controllable air pressure material conveying module 3 and a computer control system 4;
a material extrusion module 11, a three-dimensional motion hardware system 12;
a mechanical movement device 111, a material extrusion cylinder 112, a transverse vibration structure 113;
an ultrasonic generator 21, an ultrasonic transducer 22 and an ultrasonic amplitude transformer 23;
a compressed air source device 31 and a compressed air source access part 32.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The present invention is to solve the technical problem that no effective technical means for ordered gradient porous material in practical engineering application is provided in the prior art, and a specific technical solution is shown in fig. 1, and a 3D printing system for ordered gradient porous material includes: the three-dimensional molding manufacturing module 1 is used for extruding a material system containing gradient ordered sacrificial template particles from a material extruding module, and then controlling the material extruding module to move in X, Y, Z three-dimensional space, so that the single-channel cumulative molding of the material system containing gradient ordered sacrificial template particles is realized;
the digital ultrasonic auxiliary system 2 is used for assisting the material extrusion module 11 with an ultrasonic auxiliary system to promote the sacrificial template particles in the matrix material to present ordered distribution in a certain mode;
the controllable air pressure material conveying module 3 is used for controlling the output of compressed air so as to adjust the extrusion time, the extrusion speed and the extrusion amount of the material system in the material extrusion module 11;
the computer control system 4 is used for predefining a three-dimensional model containing a printing program, and transmitting the structural characteristics of the printable model to the three-dimensional molding manufacturing module 1, the digital ultrasonic auxiliary system 2 and the controllable air pressure material conveying module 3 in a three-dimensional motion code mode, so that the three-dimensional molding manufacturing module can obtain the moving track of the output material extrusion module 11, the digital ultrasonic auxiliary system 2 can obtain the transverse vibration amplitude and frequency of the output material extrusion module 11, and the controllable air pressure material conveying module 3 can obtain the material extrusion time, the extrusion speed and the extrusion amount of the output material extrusion module 11;
further, the three-dimensional shape forming manufacturing module 1 includes:
the material extrusion module 11 is arranged in the middle of the three-dimensional motion hardware system and is directly connected with the digital ultrasonic auxiliary system 2, the controllable air pressure material conveying module 3 and the computer control system 4;
a three-dimensional motion hardware system 12 for controlling motion within the space of the material extrusion module 11.
Further, the material extrusion module 11 includes:
the mechanical motion device 111 is directly connected with the three-dimensional motion hardware system, receives a motion signal output by the three-dimensional motion hardware system, and controls the spatial motion of the material extrusion module 11;
the material extruding cylinder 112 is directly connected with the controllable air pressure conveying module, receives an air pressure signal of the controllable air pressure conveying module and realizes the timed, fixed-point and quantitative output of a material system;
the transverse vibration structure 113 is directly connected with the digital ultrasonic auxiliary system, receives a mechanical vibration signal output by the digital ultrasonic auxiliary system and promotes the material extrusion cylinder to vibrate transversely, slightly and at high frequency;
further, the digital ultrasound-assisted system 2 includes:
an ultrasonic generator 21;
an ultrasonic transducer 22;
the ultrasonic amplitude transformer 23 is directly connected with a transverse vibration structure in the three-dimensional motion hardware system, converts a mechanical vibration signal with smaller amplitude output by the ultrasonic transducer into a mechanical vibration signal with larger amplitude, transmits the mechanical vibration signal to the material extrusion module 11, and further controls the distribution of sacrificial template particles in the material system;
further, controllable pneumatic conveying module 3 includes:
a compressed air supply device 31 capable of producing an adjustable flow of said output air supply;
a compressed air source access part 32, one end of which is connected to the compressed air source device 31, and the other end of which can be communicated to the material extruding cylinder 112, so as to control the extrusion of the material system;
further, the computer control system 4 includes:
an additive assembly to provide the printing space and moveable three-dimensional coordinate parameters for the three-dimensional forming fabrication module 1;
the pre-defining module is used for setting the appearance parameters of the integrally formed printing body, the compressed air source parameters and the ultrasonic auxiliary parameters in the process of constructing the printing body;
and the printing program outputs printing information to each execution module based on the three-dimensional coordinate parameters, the shape parameters, the air source parameters and the ultrasonic auxiliary parameters.
The 3D printing method facing the ordered gradient porous material comprises the following steps:
s101, material preparation
Matrix material: printing the slurry by a precursor of a polymer base or a ceramic base;
sacrificial template particles: pore-forming agent, polyvinyl alcohol fiber, sugar and the like can be used as particles of the sacrificial template;
wherein the matrix material is a precursor printing slurry of one of a ceramic matrix or a polymer matrix;
wherein the ceramic matrix material is prepared from 49-65vol% of calcium phosphate cement and 35-51vol% of NaH2PO4Solution (0.2-0.5 ml/g);
wherein the polymer matrix material consists of 41-70vol% of polylactic acid and 30-59vol% of dichloromethane;
wherein the viscosity of the matrix material is 3000-100000 cP;
the sacrificial template particles are easily removable materials (easy to dissolve, melt/decompose), such as rod-shaped sodium glutamate crystals, sugar particles, salt particles, iodine particles, polyvinyl alcohol fibers and common ceramic pore-forming agents (starch, carbon powder, ammonium bicarbonate, polymethyl methacrylate microspheres and polystyrene microspheres), and can be removed through post-treatment processes (heating, soaking and the like);
wherein the sacrificial template particles are divided into two types in the aspect of geometrical characteristics, including sphere-like and rod-like, wherein the particle size range of the sphere-like particles is 5-200 mu m; the diameter range of the rod-like particles is 5-150 mu m, and the length-diameter ratio is 10-30;
the size of the sacrificial template particles can be divided into a plurality of specifications and can also be the same specification;
mixing 10-70vol% of sacrificial template particles with a matrix material, and uniformly stirring for later use;
s102, additive manufacturing of the gradient ordered reinforced material specifically comprises the following steps:
step 1, constructing a three-dimensional model, namely establishing a related three-dimensional model based on a predefined geometric model of a gradient ordered reinforcing material and an ordered gradient distribution mode of internal sacrificial template particles, and then performing discretization treatment on the three-dimensional model;
and 4, performing additive forming on the gradient ordered reinforced material, and controlling the distribution mode of sacrificial template particles in the material system in real time according to the motion code of the three-dimensional forming manufacturing module 1, the air source control signal of the controllable air pressure material conveying module 3 and the vibration signal of the digital ultrasonic auxiliary system 2 obtained in the step 2. A material system containing a rich distribution of sacrificial template particles is deposited on the shaping platform.
Wherein the output vibration frequency of the digital ultrasonic auxiliary system 2 is 20-130 KHz;
s103, a post-processing step, namely removing the sacrificial template particles in the printing body according to respective characteristics, and then performing post-processing (curing, sintering and the like) on the formed sample.
Wherein, the removing condition of the sacrificial template particles needs to be dissolved/melted/decomposed and the like according to the physical characteristics of the sacrificial template;
wherein, the post-treatment of the forming sample piece is divided into two parts: if the matrix material is a polymer matrix, placing the formed sample in a vacuum drying oven at 40-60 ℃ for 5-24 h; if the matrix material is a ceramic-based material, placing the formed sample piece into a sintering furnace, wherein the heating speed is 3-15 ℃/min, and the sintering temperature is set to be Tm-15 ℃ and Tm (material melting temperature) and Tm +50 ℃;
a first, more preferred embodiment of the method of the present application is as follows:
preparing a matrix material: 65vol% of powdered calcium phosphate cement and 35vol% of NaH2PO4The solution (0.3 ml/g) is mixed evenly; reinforcing phase particles: uniformly mixing polymethyl methacrylate microspheres (PMMA, 15-100 mu m) with three specifications in equal amount; adding the sacrificial template particles into the matrix material for three times, and uniformly mixing for later use;
establishing a related three-dimensional model based on a predefined geometric model of the gradient ordered reinforcing material and an ordered gradient distribution mode of internal sacrificial template particles, and then carrying out discretization treatment on the three-dimensional model;
determining a motion code of a three-dimensional motion assembly in a three-dimensional molding manufacturing module 1, an air source control signal of a controllable air pressure material conveying module 3 and a vibration signal of a digital ultrasonic auxiliary system 2 in a 3D printing system based on a gradient ordered distribution mode of sacrificial template particles in a predefined material model;
loading the composite material system doped with PMMA microspheres into a material extrusion cylinder of a material extrusion module 11, and switching on a controllable air pressure material conveying module;
and controlling the distribution mode of PMMA microspheres in the composite material system in real time according to the obtained motion code of the three-dimensional forming manufacturing module 1, the air source control signal of the controllable air pressure material conveying module 3 and the vibration signal (the vibration frequency is 40 KHz) of the digital ultrasonic auxiliary system 2 (as shown in figures 2-3). And depositing the composite material system containing the PMMA microsphere distribution mode on a forming platform.
And (3) carrying out post-treatment on the 3D printed body, placing the printed body in a drying oven at 60 ℃, taking out the printed body after 24h, and removing PMMA microsphere particles serving as materials. And then, the printed body is placed in a high-temperature electric furnace, and is calcined for 3 hours at the temperature of 600 ℃, so that the bionic bone structure with rich pore structures is realized.
A more preferred second embodiment of the method of the present application is as follows:
preparing a matrix material: 50vol% of powdered calcium phosphate cement and 50vol% of NaH2PO4Solution (0.5 ml/g)Mixing uniformly; reinforcing phase particles: selecting rod-shaped sodium glutamate crystal particles with two specifications as pore-forming agents (the length-diameter ratio is 25, and the diameter is 5-10 mu m); adding the rod-shaped sodium glutamate crystal particles into a matrix material for three times, and uniformly mixing for later use;
establishing a related three-dimensional model based on a predefined geometric model of the gradient ordered reinforcing material and an ordered gradient distribution mode of internal sacrificial template particles, and then carrying out discretization treatment on the three-dimensional model;
determining a motion code of a three-dimensional motion assembly in a three-dimensional molding manufacturing module 1, an air source control signal of a controllable air pressure material conveying module 3 and a vibration signal of a digital ultrasonic auxiliary system 2 in a 3D printing system based on a gradient ordered distribution mode of sacrificial template particles in a predefined material model;
loading the composite material system doped with the rod-shaped sodium glutamate crystal particles into a material extrusion cylinder of a material extrusion module 11, and switching on a controllable air pressure material conveying module 3;
and controlling the distribution mode of the rod-shaped sodium glutamate crystal particles in the composite material system in real time according to the obtained motion code of the three-dimensional forming manufacturing module 1, the air source control signal of the controllable air pressure material conveying module 3 and the vibration signal (the vibration frequency is 30 KHz) of the digital ultrasonic auxiliary system 2 (as shown in figures 4-5). And depositing a composite material system containing a distribution mode of rod-shaped sodium glutamate crystal particles on a forming platform.
And (3) post-processing the 3D printing body, namely placing the printing body in deionized water, taking out the printing body after 72 hours, and removing the rod-shaped sodium glutamate crystal particles in the material. And then, the printed body is placed in a high-temperature electric furnace, and is calcined for 3 hours at the temperature of 600 ℃, so that the bionic bone structure with rich pore structures is realized.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (3)
1. The 3D printing method facing the ordered gradient porous material is characterized in that the used 3D printing system facing the ordered gradient porous material comprises the following steps:
the three-dimensional forming manufacturing module (1) is used for extruding a material system containing gradient ordered sacrificial template particles from the material extruding module (11), and then controlling the material extruding module (11) to move in X, Y, Z three-dimensional space to realize the accumulation forming of the extruded single channel containing gradient ordered sacrificial template particles;
the digital ultrasonic auxiliary system (2) is used for assisting the ultrasonic auxiliary system in the material extrusion module (11) to promote the sacrificial template particles in the matrix material to present a certain mode of ordered distribution;
the controllable air pressure conveying module (3) is used for controlling the output of compressed air so as to adjust the extrusion time, the extrusion speed and the extrusion amount of a material system in the material extrusion module (11);
the computer control system (4) is used for predefining a three-dimensional model containing a printing program, transmitting the structural characteristics of the printable model to the three-dimensional forming and manufacturing module (1), the digital ultrasonic auxiliary system (2) and the controllable air pressure material conveying module (3) in a three-dimensional motion code mode, so that the three-dimensional forming and manufacturing module (1) can obtain the moving track of the output material extrusion module (11), the digital ultrasonic auxiliary system (2) can obtain the transverse vibration amplitude and frequency of the output material extrusion module, and the controllable air pressure material conveying module (3) can obtain the material extrusion time, the extrusion speed and the extrusion amount of the output material extrusion module;
the three-dimensional forming and manufacturing module (1) comprises:
the material extrusion module (11) is arranged in the middle of the three-dimensional motion hardware system and is directly connected with the digital ultrasonic auxiliary system (2), the controllable air pressure material conveying module (3) and the computer control system (4);
a three-dimensional motion hardware system (12) for controlling motion within the space of the material extrusion module;
the material extrusion module (11) comprises:
the mechanical motion device (111) is directly connected with the three-dimensional motion hardware system (12), receives a motion signal output by the three-dimensional motion hardware system (12), and controls the spatial motion of the material extrusion module;
the material extruding cylinder (112) is directly connected with the controllable air pressure conveying module (3) and receives an air pressure signal of the controllable air pressure conveying module (3) to realize the timed, fixed-point and quantitative output of a material system;
the transverse vibration structure (113) is directly connected with the digital ultrasonic auxiliary system (2) and receives a mechanical vibration signal output by the digital ultrasonic auxiliary system (2) to promote the material extrusion cylinder to vibrate transversely, slightly and at high frequency;
the digitized ultrasound-assisted system (2) comprises:
an ultrasonic generator (21);
an ultrasonic transducer (22);
the ultrasonic amplitude transformer (23) is directly connected with a transverse vibration structure in the three-dimensional motion hardware system (12), converts a mechanical vibration signal with smaller amplitude output by the ultrasonic transducer into a mechanical vibration signal with larger amplitude, transmits the mechanical vibration signal to the material extrusion module, and further controls the distribution of sacrificial template particles in the material system;
controllable atmospheric pressure defeated material module (3) includes:
a compressed air source device (31) capable of producing an output air source of adjustable flow;
a compressed air source access part (32), one end of which is connected to a compressed air source device (31), and the other end of which can be communicated to the material extrusion cylinder (112) for controlling the extrusion of the material system;
the computer control system (4) comprises:
an additive assembly to provide a print space and moveable three-dimensional coordinate parameters for a three-dimensional forming fabrication module (1);
the pre-defining module is used for setting the appearance parameters of the integrally formed printing body, the compressed air source parameters and the ultrasonic auxiliary parameters in the process of constructing the printing body;
the printing program outputs printing information to each execution module based on the three-dimensional coordinate parameters, the appearance parameters, the air source parameters and the ultrasonic auxiliary parameters;
the 3D printing method facing the ordered gradient porous material comprises the following steps:
s101, material preparation
Matrix material: printing the slurry by a precursor of a polymer base or a ceramic base;
sacrificial template particles: one selected from rod-shaped sodium glutamate crystal, sugar particle, salt particle, iodine particle, polyvinyl alcohol fiber, starch, carbon powder, ammonium bicarbonate, polymethyl methacrylate microsphere and polystyrene microsphere;
wherein the viscosity of the matrix material is 3000-100000 cP;
wherein the sacrificial template particles are divided into two types in the aspect of geometrical characteristics, including sphere-like and rod-like, wherein the particle size range of the sphere-like particles is 5-200 mu m; the diameter range of the rod-like particles is 5-150 mu m, and the length-diameter ratio is 10-30;
wherein the size of the sacrificial template particles is in multiple specifications or in the same specification;
mixing 10-70vol% of sacrificial template particles with a matrix material, and uniformly stirring for later use;
s102, additive manufacturing of the gradient ordered reinforced material specifically comprises the following steps:
step 1, constructing a three-dimensional model, namely establishing a related three-dimensional model based on a predefined geometric model of a gradient ordered reinforcing material and an ordered gradient distribution mode of internal sacrificial template particles, and then performing discretization treatment on the three-dimensional model;
step 2, movement programming of the gradient ordered reinforced material, and determining a movement code of a three-dimensional movement assembly in a three-dimensional forming manufacturing module, an air source control signal of a controllable air pressure conveying module and a vibration signal of a digital ultrasonic auxiliary system in a 3D printing system based on a gradient ordered distribution mode of sacrificial template particles in a predefined material model;
step 3, loading the material system doped with the sacrificial template particles into a material extrusion cylinder of a material extrusion module, and switching on a controllable air pressure material conveying module;
step 4, performing additive forming on the gradient ordered reinforced material, controlling the distribution mode of sacrificial template particles in the material system in real time according to the motion code of the three-dimensional forming manufacturing module, the air source control signal of the controllable air pressure material conveying module and the vibration signal of the digital ultrasonic auxiliary system obtained in the step 2, and depositing the material system containing abundant sacrificial template particle distribution on a forming platform;
wherein the output vibration frequency of the digital ultrasonic auxiliary system is 20-130 KHz;
s103, a post-processing step, namely dissolving, melting or decomposing the sacrificial template particles in the printing body according to the physical characteristics of the sacrificial template, and then solidifying or sintering the formed sample;
wherein, the post-treatment of the forming sample piece is divided into two conditions: if the matrix material is a polymer matrix, placing the formed sample in a vacuum drying oven at 40-60 ℃ for 5-24 h; if the matrix material is a ceramic-based material, the formed sample piece is placed into a sintering furnace, the temperature rise speed is 3-15 ℃/min, and the sintering temperature is set to be Tm-15 ℃ and T +50 ℃.
2. 3D printing method facing ordered gradient porous material according to claim 1, characterized in that ceramic based matrix material is composed of 49-65vol% calcium phosphate cement and 35-51vol% NaH2PO4Composition of solution, in which NaH2PO4The concentration of the solution is 0.2-0.5 g/ml.
3. The 3D printing method facing ordered gradient porous material of claim 1, wherein the polymer-based matrix material consists of 41-70vol% polylactic acid and 30-59vol% dichloromethane.
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