CN108527839B - 3D printing method and 3D printer for crystalline polymer - Google Patents
3D printing method and 3D printer for crystalline polymer Download PDFInfo
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- CN108527839B CN108527839B CN201711260124.3A CN201711260124A CN108527839B CN 108527839 B CN108527839 B CN 108527839B CN 201711260124 A CN201711260124 A CN 201711260124A CN 108527839 B CN108527839 B CN 108527839B
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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
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/16—Cooling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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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
- 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
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/16—Cooling
- B29C2035/1658—Cooling using gas
Abstract
The invention provides a 3D printing method of a crystalline polymer, which comprises the steps of heating a printing head, melting a first crystalline polymer in the printing head, driving the printing head to print in a single layer to obtain a molten printing pattern layer, cooling the molten printing pattern layer to form a solid printing pattern layer containing an amorphous region, repeating the operation on the top of the cooled printing pattern layer until obtaining a printing workpiece consisting of a plurality of layers of vertically stacked printing pattern layers, wherein at least one printing pattern layer forms a printing pattern layer unit; and carrying out heat treatment on each printing pattern layer unit in the printing process. The 3D printing method of the crystalline polymer obtains the printing workpiece with good toughness and good dimensional stability by a method of printing and heat treatment. The invention also provides a 3D printer.
Description
Technical Field
The invention belongs to the technical field of rapid forming, and particularly relates to a 3D printing method and a 3D printer for a crystalline polymer.
Background
With the rapid development of 3D printing technology, 3D printing technology has been widely applied in many fields. The 3D printing is a rapid forming technology, and the working process is as follows: the model is built through computer software, and then the built three-dimensional model is divided into sections layer by layer, so that the printer is guided to print layer by layer, and thin layers are stacked until a solid object is formed.
Printable polymers are classified into crystalline polymers and amorphous polymers, wherein amorphous polymers are amorphous polymers, and crystalline polymers exist in both crystalline and amorphous states because crystalline polymers cannot be completely crystallized. According to the forming principle of fused Deposition modeling (fdm), in order to achieve effective bonding between layers, mutual diffusion of molecular dimensions must be achieved between printing layers, so as to achieve fusion between printing layers. In achieving the mutual fusing of the printed layers, the heat supplied by the printer must either melt the polymer of the crystalline polymer or bring the polymer in the amorphous state to the viscous state.
In the prior art, the temperature of a forming chamber is generally increased, namely the temperature of a printed layer is increased to compensate heat, so that effective fusion between layers is realized. However, this design is difficult to implement because the high temperature of the forming chamber poses a great challenge to the design of the moving mechanism and the circuit system therein, and the reliability and the life span of the system are reduced. Meanwhile, at a high forming chamber temperature, the crystallinity of the printed workpiece is high, so that the printed workpiece has high brittleness and low toughness.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: aiming at the technical defects that the reliability and the service life of a system are reduced due to high temperature of a forming chamber in the prior art, a 3D printing method and 3D printing equipment for a crystalline polymer are provided.
To solve the above technical problem, in one aspect, an embodiment of the present invention provides a method for 3D printing of a crystalline polymer, including:
heating a print head to melt a first crystalline polymer within the print head;
driving a printing head to perform single-layer printing to obtain a molten printing pattern layer, and cooling the molten printing pattern layer to form a solid printing pattern layer containing an amorphous region;
repeating the operation on the top of the cooled printing pattern layer until a printing workpiece consisting of a plurality of printing pattern layers which are stacked up and down is obtained;
at least one printing pattern layer constitutes a printing pattern layer unit;
and carrying out heat treatment on each printing pattern layer unit in the printing process.
Optionally, the print pattern layer unit is an amorphous polymer.
Optionally, the temperature of the heat treatment is within the glass transition region of the amorphous polymer.
Optionally, the temperature of the heat treatment is greater than the glass transition temperature of the amorphous polymer and the temperature of the heat treatment is less than the crystallization temperature of the amorphous polymer.
Optionally, the thickness of the printing pattern layer unit is less than 2 mm.
Optionally, the print pattern layer unit is a second crystalline polymer containing an amorphous region.
Optionally, the first crystalline polymer is one or more of polyetheretherketone and composites thereof, nylon and composites thereof, polyethylene terephthalate and composites thereof.
On the other hand, the embodiment of the invention further provides a 3D printer, which includes a moving platform, a printing head, a printing platform, a cooling device, a printing head heating device, and a printing pattern layer heating device, wherein the printing head heating device is disposed at an upper end of the printing head, the printing head heating device is connected between the printing head and the moving platform, the moving platform is used for driving the printing head to move on the printing platform according to a preset printing track, the cooling device is disposed above the printing platform and is used for cooling a printing pattern layer formed on the printing platform, and the printing pattern layer heating device is disposed above the printing platform and is used for heating the cooled printing pattern layer formed on the printing platform.
Optionally, the heating means comprises one or more combinations of air heating, infrared heating and laser heating.
Optionally, the printing pattern layer heating device and the cooling device are rotatably connected to two sides of the printing head, and the printing pattern layer heating device and the cooling device are located at the same height.
In the 3D printing method of crystalline polymer provided by the embodiment of the present invention, the melted printing pattern layer is cooled to form a solid printing pattern layer containing amorphous polymer, that is, the melted printing pattern layer is rapidly cooled to make it less than or less than completely crystallized, so as to form a solid printing pattern layer containing amorphous regions. Therefore, compared with the printing pattern layer of the crystalline-state combination, when single-layer printing is carried out on the top of the cooled printing pattern layer, the heat provided by the printing head does not need to destroy the crystal structure and melt the crystalline-state polymer, and the interlayer combination can be realized only by enabling the amorphous-state polymer of the cooled printing pattern layer to be in a viscous flow state, so that the energy required for realizing the interlayer combination of the printing pattern layer is greatly reduced, and the temperature and the printing time in the printing head are also greatly reduced. The obtained printed workpiece has greatly reduced crystallinity and enhanced toughness. In addition, each printing pattern layer unit formed in the printing process is subjected to heat treatment, so that the internal stress among the multiple layers of printing pattern layers in the printing pattern layer units and the internal stress in each printing pattern layer can be timely released in the printing process, the deformation of the workpiece caused by the accumulation of the internal stress in the workpiece printing process is avoided, the dimensional stability of the printed workpiece is improved, and the printed workpiece is not easy to warp or crack.
According to the 3D printer provided by the embodiment of the invention, a closed high-temperature forming chamber is not required to be arranged, and the temperature of the printing head is not required to be increased, so that the abrasion of high temperature to a moving mechanism and a circuit design in the 3D printer is reduced, the service life of the 3D printer is prolonged, the energy consumption of 3D printing is reduced, and the manufacturing cost of the 3D printer is reduced.
Drawings
Fig. 1 is a schematic diagram of a 3D printer provided by a first embodiment of the invention in a printing state;
fig. 2 is a schematic diagram of a 3D printer provided in a first embodiment of the present invention in a heat treatment state.
The reference numerals in the specification are as follows:
1. a print head;
2. a printing platform;
3. a cooling device;
4. a print head heating device;
5. a printing pattern layer heating device;
6. a control system;
7. printing a workpiece;
8. a crystalline polymer.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a 3D printing method of a crystalline polymer, which comprises the steps of heating a printing head, melting a first crystalline polymer in the printing head, driving the printing head to print a single layer to obtain a molten printing pattern layer, cooling the molten printing pattern layer to form a solid printing pattern layer containing an amorphous region, repeating the operation on the top of the cooled printing pattern layer until a printing workpiece consisting of a plurality of layers of printing pattern layers which are stacked up and down is obtained, wherein at least one printing pattern layer constitutes a printing pattern layer unit; and carrying out heat treatment on each printing pattern layer unit in the printing process.
When the print pattern layer unit includes a plurality of print pattern layers, the plurality of print pattern layers are stacked one on another.
In an embodiment, the 3D printing method for the crystalline polymer further includes obtaining a 3D model of the printing workpiece, and the printing head performs single-layer printing based on the 3D model to obtain the printing workpiece which is adapted to the 3D model and is composed of multiple printing pattern layers stacked up and down.
In one embodiment, the cooling rate during cooling is such that the temperature is relatively high that the molten crystalline polymer is less than fully crystalline to form an amorphous polymer, thereby rendering the print pattern layer unit a solid amorphous polymer. When each printing pattern layer is cooled to be solid amorphous polymer, compared with the corresponding crystalline polymer, the structure of crystals does not need to be damaged, the energy required by the combination of the printing pattern layers is reduced, and the printing workpiece with good interlayer bonding force is easily obtained, so that the quality of the whole printing workpiece can be improved.
However, in other embodiments, the cooling rate and cooling temperature during cooling causes the molten crystalline polymer to less than fully crystallize, thereby forming the cooled print pattern layer as a second crystalline polymer comprising amorphous regions.
Therefore, it is possible to obtain printed workpieces containing different degrees of crystallinity by changing the cooling speed and the cooling temperature of the cooling device.
In one embodiment, when the print pattern layers constituting the print pattern layer unit are all amorphous polymers, i.e. the print pattern layer unit is an amorphous polymer, the temperature of the heat treatment is within the glass transition region of the amorphous polymer. Therefore, the activity degree in the molecular chain segment is increased, secondary crystallization is avoided, the internal stress is released, and the dimensional accuracy of the printed workpiece is ensured. Wherein the glass transition region is located between the glassy state and the elastomeric state. Since the transition from the glassy state to the highly elastic state of an amorphous polymer occurs in a temperature range, the glass transition temperature is generally referred to as a specific value in this temperature range. Thus, the glass transition region is the temperature range between the glassy and high elastic states of the amorphous polymer, including the glass transition temperature. The temperature of the heat treatment can also be higher than the glass transition temperature of the amorphous polymer and lower than the crystallization temperature of the amorphous polymer, and the heat treatment temperature is properly increased while the crystallization does not occur in the heat treatment process, so that the dimensional accuracy of the printed workpiece is not affected.
In one embodiment, the print pattern layer unit is a solid second crystalline polymer containing an amorphous region. The temperature of the heat treatment at this time is within the glass transition region of the second crystalline polymer, and may be greater than the glass transition temperature of the second crystalline polymer and less than the crystallization temperature of the second crystalline polymer, so that the heat treatment temperature may be ensured to be below the crystallization temperature of the second crystalline polymer, thereby ensuring that crystallization does not occur during the heat treatment.
The heat treatment method of the above embodiment can actively move the molecular chain segment in the polymer, and can also avoid the technical problems of deformation due to crystallization and reduction in toughness of the workpiece. The internal stress between a plurality of printing pattern layers and the internal stress in each printing pattern layer can be effectively eliminated in time, the accumulation of the internal stress in the printing process is avoided, and the dimensional stability of the printed workpiece is ensured.
In order to avoid the influence of deformation possibly caused in the heat treatment process on the printed workpiece, the thickness of the printing pattern layer unit subjected to the heat treatment is less than 2 mm. Thus, the molecular conformation transition is insufficient to deform the multilayer printed pattern layer in the Z-direction when internal stresses are removed, thereby ensuring that the printed pattern layer unit does not deform during the heat treatment process. The mode of printing and heat treatment simultaneously can ensure that no accumulated internal stress exists in the obtained printed workpiece, and the heat treatment can not generate adverse effect on the shape precision of the printed workpiece.
When the thickness of the printing pattern layer unit is larger than 2mm, the internal stress is accumulated more, and the printing pattern layer unit is deformed to a certain degree by the transformation of molecular conformation in the heat treatment process, so that the shape precision of the whole printing workpiece is influenced.
In one embodiment, the first crystalline polymer is one or more of polyetheretherketone and composites thereof, nylon and composites thereof, polyethylene terephthalate and composites thereof. When it is desired to print a print workpiece to obtain crystalline polymers having different degrees of crystallinity, the rate and temperature of cooling is adaptively adjusted to ensure that the first crystalline polymer does not crystallize, or does not crystallize throughout, during cooling, thereby forming a second crystalline polymer having a different degree of crystallinity.
In order to ensure that the cooling effect and the heat treatment effect are not influenced by each other, the heat treatment can be carried out on a plurality of printing pattern layers after the plurality of printing pattern layers are obtained by printing and cooling, the internal stress of the plurality of printing pattern layers is eliminated, the printing and cooling are continued, or the heat treatment can be carried out on the printing pattern layer every time the printing pattern layer is formed, so that the printing steps of printing, cooling and heat treatment are formed, the interlayer binding force of the printed workpiece is improved, the quality of the printed workpiece is improved, and the subsequent treatment steps of the printed workpiece are greatly simplified.
First embodiment
The first embodiment of the present invention also provides a 3D printer implementing the 3D printing method of a crystalline polymer of the above embodiment, as shown in fig. 1 and 2, the printing apparatus includes a moving platform (not shown), a printing head 1, a printing platform 2, a cooling device 3, a printing head heating device 4 and a printing pattern layer heating device 5, wherein the printing head heating device 4 is arranged at the upper end of the printing head 1, and the printing head heating device 4 is connected between the printing head 1 and the moving platform, the moving platform is used for driving the printing head 1 to move on the printing platform 2 according to a preset printing track, the cooling device 3 is disposed above the printing platform 2 and is used for cooling a printing pattern layer formed on the printing platform 2, the printing pattern layer heating device 5 is disposed above the printing platform and is used for heating the cooled printing pattern layer formed on the printing platform 2. The print head heating device 4 is used to melt the crystalline polymer 8 so that the print head 1 forms a molten print pattern layer on the print platform 2. A plurality of the print pattern layers are stacked one on top of another to form a print workpiece 7.
In the embodiment shown in fig. 1, the cooling device 3 may eject cooling air to the print pattern layer formed on the printing table 2.
However, in other embodiments, the cooling device 3 may eject a rare gas such as cooling nitrogen gas to the print pattern layer formed on the printing stage 2.
In the embodiment shown in fig. 1 and 2, the print pattern layer heating device 5 may eject heated air to the cooled print pattern layer formed on the printing platform 2.
However, in other embodiments, the print pattern layer heating device 5 may also be an infrared heating device or a laser heating device or a combination of both.
In this embodiment, the printing pattern layer heating device 5 and the cooling device 3 are rotatably connected to two sides of the printing head 1, and the printing pattern layer heating device 5 and the cooling device 3 are located at the same height. The rotating cooling device 3 can ensure that the cooling medium sprayed by the cooling device 3 completely covers the printing pattern layer formed on the printing platform 2 during cooling, and the rotating printing pattern layer heating device 5 can ensure that the hot air sprayed during heat treatment can completely cover the printing pattern layer formed on the printing platform 2, so that the quality of the printed workpiece can be ensured to be uniform and stable.
The 3D printer shown in fig. 1 and 2 further includes a control system 6, where the control system 6 includes a print head heating device control unit, a cooling device control unit, and a print pattern layer heating device control unit, and the print head heating device control unit is configured to control a temperature in the print head 1, so that the temperature of the first polymer can be adjusted according to different timings of the first polymer to melt the first polymer. The cooling device control unit is used for controlling the speed of spraying cooling air by the cooling device 3 and the temperature of the cooling air, and the printing pattern layer heating device control unit is used for controlling the speed and the temperature of spraying hot air to the printing pattern layer unit by the printing pattern layer heating device 5.
Second embodiment
The second embodiment of the invention provides a 3D printing method of a crystalline polymer, and a 3D model of a printed workpiece is obtained through self-modeling or 3D scanning. And importing the 3D model of the printed workpiece into slicing software to perform slicing operation, and transmitting the generated code to the 3D printer. The print head is heated with a print head heating device to melt the crystalline polymer (polyetheretherketone) within the print head. And the moving platform drives the printing head to print a single layer on the printing platform to obtain a molten printing pattern layer, and starts the cooling system to spray cooling air to the molten printing pattern layer formed on the printing platform so that the molten crystalline polymer is less than or less than completely crystallized to form a solid printing pattern layer containing an amorphous region. And repeating the printing and cooling steps on the top of the cooled printing pattern layer until a printing workpiece consisting of a plurality of layers of printing pattern layers which are stacked up and down is obtained. In this embodiment, the thickness of each print pattern layer is 0.3mm, and in the printing process, after each two print pattern layers are formed, the two formed print pattern layers are subjected to heat treatment.
However, in other embodiments, when the thickness of each print pattern layer is small, the multi-layer print pattern layer may be heat-treated after forming two or more print pattern layers as long as the thickness of the heat-treated multi-layer print pattern layer is less than 2mm, or may be heat-treated every time a print pattern layer is formed.
In the 3D printing method of crystalline polymer provided in the above embodiment, the melted printing pattern layer is cooled to form a solid printing pattern layer containing amorphous polymer, that is, the melted printing pattern layer is rapidly cooled to make it less than or less than completely crystallized, so as to form a solid printing pattern layer containing amorphous regions. Therefore, compared with the printing pattern layer of the crystalline-state combination, when single-layer printing is carried out on the top of the cooled printing pattern layer, the heat provided by the printing head does not need to destroy the crystal structure and melt the crystalline-state polymer, and the interlayer combination can be realized only by enabling the amorphous-state polymer of the cooled printing pattern layer to be in a viscous flow state, so that the energy required for realizing the interlayer combination of the printing pattern layer is greatly reduced, and the temperature and the printing time in the printing head are also greatly reduced. The obtained printed workpiece has greatly reduced crystallinity and enhanced toughness. In addition, each printing pattern layer unit formed in the printing process is subjected to heat treatment, so that the internal stress among the multiple layers of printing pattern layers in the printing pattern layer units and the internal stress in each printing pattern layer can be timely released in the printing process, the deformation of the workpiece caused by the accumulation of the internal stress in the workpiece printing process is avoided, the dimensional stability of the printed workpiece is improved, and the printed workpiece is not easy to warp or crack.
The 3D printer that above-mentioned embodiment provided need not set up confined high temperature forming chamber, also need not improve the temperature that beats printer head to reduced the wearing and tearing of high temperature to the motion and circuit design in the 3D printer, prolonged the life of 3D printer, reduced the energy consumption that 3D printed, reduced the manufacturing cost of 3D printer.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (6)
1. A method of 3D printing of a crystalline polymer, comprising:
heating a print head to melt a first crystalline polymer within the print head;
driving a printing head to perform single-layer printing to obtain a molten printing pattern layer, and cooling the molten printing pattern layer to form a solid printing pattern layer containing an amorphous region;
repeating the operation on the top of the cooled printing pattern layer until a printing workpiece consisting of a plurality of printing pattern layers which are stacked up and down is obtained;
at least one printing pattern layer constitutes a printing pattern layer unit;
carrying out heat treatment on each printing pattern layer unit in the printing process; wherein
The printing pattern layer unit is amorphous polymer; the temperature of the heat treatment is in the glass transition region of the amorphous polymer, or the temperature of the heat treatment is higher than the glass transition temperature of the amorphous polymer, and the temperature of the heat treatment is lower than the crystallization temperature of the amorphous polymer; alternatively, the first and second electrodes may be,
the printing pattern layer unit is a second crystalline polymer containing an amorphous region; the temperature of the heat treatment is within the glass transition region of the second crystalline polymer, or the temperature of the heat treatment is greater than the glass transition temperature of the second crystalline polymer and less than the crystallization temperature of the second crystalline polymer.
2. The method for 3D printing of crystalline polymer according to claim 1 wherein the thickness of the print pattern layer unit is less than 2 mm.
3. The method for 3D printing of a crystalline polymer according to claim 1, wherein the first crystalline polymer is one or more of polyetheretherketone and composites thereof, nylon and composites thereof, polyethylene terephthalate and composites thereof.
4. A3D printer using the 3D printing method of the crystalline polymer according to any one of claims 1 to 3, it is characterized by comprising a motion platform, a printing head, a printing platform, a cooling device, a printing head heating device and a printing pattern layer heating device, wherein the printing head heating device is arranged at the upper end of the printing head, the printing head heating device is connected between the printing head and the moving platform, the moving platform is used for driving the printing head to move on the printing platform according to a preset printing track, the cooling device is arranged above the printing platform and is used for cooling a printing pattern layer formed on the printing platform, the printing pattern layer heating device is arranged above the printing platform and used for heating the cooled printing pattern layer formed on the printing platform.
5. The 3D printer of claim 4, wherein the heating device comprises one or more combinations of air heating, infrared heating, and laser heating.
6. The 3D printer according to claim 4, wherein the print pattern layer heating means and the cooling means are rotatably connected to both sides of the print head, and the print pattern layer heating means and the cooling means are located at the same height.
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| US20220227040A1 (en) * | 2019-05-31 | 2022-07-21 | Evolve Additive Solutions, Inc. | Selective deposition-based additive manufacturing device and method of printing 3d parts with semi-crystalline materials |
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