CN111469400B - Preparation method of 3D printing polyimide part - Google Patents
Preparation method of 3D printing polyimide part Download PDFInfo
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- CN111469400B CN111469400B CN202010304000.6A CN202010304000A CN111469400B CN 111469400 B CN111469400 B CN 111469400B CN 202010304000 A CN202010304000 A CN 202010304000A CN 111469400 B CN111469400 B CN 111469400B
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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
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
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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
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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
- B29C64/307—Handling of material to be used in additive manufacturing
- B29C64/314—Preparation
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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
- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
- B29C71/02—Thermal after-treatment
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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
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
Abstract
The invention provides a preparation method of a 3D printing polyimide product, and relates to the technical field of 3D printing. The preparation method of the 3D printing polyimide product provided by the invention comprises the following steps: extruding the polyamide solution to obtain an uncured wire; precuring the uncured wire by using an auxiliary solvent to obtain a solid wire; forming a printed pre-cured piece from the solid wire under the control of the three-dimensional platform; carrying out heat treatment on the printed pre-cured piece to obtain a 3D printed polyimide piece; the polyamide solution comprises 5-60% by mass and 0.1-50000 Pa & s of viscosity; the auxiliary solvent comprises water, alcohol solvent, nitrogen-containing solvent, sulfur-containing solvent, ketone solvent and furan solvent. The preparation method provided by the invention can realize the rapid pre-curing molding of the low-concentration polyimide ink which is not easy to print and mold, and can keep the shape stability and the size accuracy of a 3D printed polyimide workpiece for a long time.
Description
Technical Field
The invention relates to the technical field of 3D printing, in particular to a preparation method of a 3D printed polyimide product.
Background
Polyimide has excellent comprehensive performance and is widely applied to the fields of aerospace, automobile manufacturing, microelectronics, photosensitive resin, self-lubricating materials and the like. The aromatic polyimide itself has a rigid molecular chain which gives excellent properties to the material and also causes processing problems such as insolubility and difficult melting. At present, a mould pressing method is mainly adopted for forming and processing a polyimide three-dimensional part, the polyimide part prepared by the method has good mechanical properties, but the forming precision is very limited, and a mould is manufactured for parts with irregular or complex shapes at high cost.
The 3D printing technology is a method for stacking materials layer by layer through digital file introduction and is characterized by high forming precision and unchanged processing cost along with the complexity of parts, and is particularly suitable for processing and forming polyimide complex three-dimensional workpieces. However, the extrusion printing of a low-concentration (mass percentage concentration less than or equal to 5%) polyimide solution is very difficult, and the printed product has the defects of collapse, size deformation and the like in the natural placing or heat treatment process, so that the shape stability and the size accuracy cannot be maintained for a long time.
Disclosure of Invention
In view of this, the invention aims to provide a preparation method of a 3D printed polyimide product. The preparation method provided by the invention realizes the extrusion printing of the polyamide solution with low concentration, and the obtained 3D printed polyimide product can keep the shape stability and the size accuracy for a long time.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a 3D printing polyimide product, which comprises the following steps:
extruding the polyamide solution to obtain an uncured wire;
precuring the uncured wire by using an auxiliary solvent to obtain a solid wire;
forming a printed pre-cured piece from the solid wire under the control of the three-dimensional platform;
carrying out heat treatment on the printed pre-cured piece to obtain a polyimide piece;
the polyamide solution comprises 5-60% by mass and 0.1-50000 Pa & s of viscosity;
the auxiliary solvent comprises one or more of water, an alcohol solvent, a nitrogen-containing solvent, a sulfur-containing solvent, a ketone solvent and a furan solvent.
Preferably, the nitrogen-containing solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylcaprolactam, N-methyl-2-pyrrolidone and 1, 3-dimethylimidazolidinone.
Preferably, the sulfur-containing solvent comprises dimethyl sulfoxide and/or sulfolane.
Preferably, the pre-curing mode comprises one or more of spraying, soaking and atmosphere humidifying.
Preferably, the temperature of the pre-curing is 20-40 ℃, and the time is 3-60 min.
Preferably, the heat treatment mode is constant temperature heat treatment or gradient temperature rise heat treatment.
Preferably, the temperature of the constant-temperature heat treatment is 100-400 ℃, and the time is 6-12 h.
Preferably, the gradient temperature-raising heat treatment includes sequentially performing a first temperature raising to a temperature of the first heat treatment for a first heat preservation, a second temperature raising to a temperature of the second heat treatment for a second heat preservation, a third temperature raising to a temperature of the third heat treatment for a third heat preservation, and a fourth temperature raising to a temperature of the fourth heat treatment for a fourth heat preservation;
the temperature of the first heat treatment is 80-120 ℃, and the first heat preservation time is 1-3 h;
the temperature of the second heat treatment is 180-230 ℃, and the second heat preservation time is 0.5-1.5 h;
the temperature of the third heat treatment is 280-320 ℃, and the third heat preservation time is 0.5-1.5 h;
the temperature of the fourth heat treatment is 340-360 ℃, and the fourth heat preservation time is 0.5-1.5 h.
Preferably, the heating rates of the first heating, the second heating, the third heating and the fourth heating are independently 2-4 ℃/min.
Preferably, the polyamide solution comprises a polyamide acid solution and/or a polyimide solution.
For polyimide ink with low solid content (i.e., high organic solvent content), because of the large amount of solvent, the ink is not solid at normal temperature, and is easy to extrude, but the printed material cannot maintain its shape for a long time. According to the preparation method provided by the invention, the wire is pre-cured by the auxiliary solvent, the rapid pre-curing molding of the low-concentration polyimide ink which is not easy to print and mold can be realized without a complex device, the structure retentivity of the obtained printed pre-cured piece is excellent, the shape stability and the size accuracy of the printed pre-cured piece can be kept in the heat treatment process, and the shape stability and the size accuracy can be kept for a long time. The preparation method provided by the invention further realizes the preparation and additive manufacturing molding of all polyimide materials, expands the molding mode of the polyimide materials, is a new breakthrough of the advanced molding technology of the additive manufacturing of the polyimide, and has potential application value and wide development prospect.
Drawings
FIG. 1 is a schematic diagram of the pre-curing mode of an auxiliary solvent;
FIG. 2 is a schematic diagram of the auxiliary solvent pre-cure principle;
FIG. 3 is a schematic view of an apparatus used to prepare 3D printed polyimide articles;
FIG. 4 is a process flow diagram for preparing a 3D printed polyimide article;
fig. 5 is a full physical representation of the printed pre-cured article prepared in example 1 before and after heat treatment and a cross-sectional microscopic view of a single filament before and after heat treatment of the printed pre-cured article.
Detailed Description
The invention provides a preparation method of a 3D printing polyimide product, which comprises the following steps:
extruding the polyamide solution to obtain an uncured wire;
sequentially carrying out pre-curing and 3D printing on the uncured wire by using an auxiliary solvent to obtain a solid wire;
forming a printed pre-cured piece from the solid wire under the control of the three-dimensional platform;
carrying out heat treatment on the printed pre-cured piece to obtain a 3D printed polyimide piece;
the polyamide solution comprises 5-60% by mass and 0.1-50000 Pa & s of viscosity;
the auxiliary solvent comprises one or more of water, an alcohol solvent, a nitrogen-containing solvent, a sulfur-containing solvent, a ketone solvent and a furan solvent.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
The method comprises the steps of extruding a polyamide solution to obtain an uncured wire; the polyamide solution comprises 5-60% by mass and has a viscosity of 0.1-50000 Pa-s.
In the present invention, the polyamide solution includes a polyamide acid solution or a polyimide solution. In the invention, the mass percentage of the polyamide solution is more preferably 10-55%, more preferably 20-50%, and most preferably 20-30%; the viscosity of the polyamide solution is more preferably 0.2 to 10000 pas, more preferably 5 to 1000 pas, and most preferably 10 to 200 pas. In the present invention, the solvent in the polyamide solution preferably includes one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethylpyrrolidone and polyvinylpyrrolidone, Dimethylsulfoxide (DMSO), and tetrahydrofuran, more preferably N, N-dimethylformamide, Dimethylsulfoxide (DMSO), or N-methyl-2-pyrrolidone, and most preferably N, N-dimethylformamide.
In the present invention, the extrusion is preferably performed in a direct writing 3D printer.
After obtaining an uncured wire, precuring the uncured wire by using an auxiliary solvent to obtain a solid wire; the auxiliary solvent comprises one or more of water, an alcohol solvent, a nitrogen-containing solvent, a sulfur-containing solvent, a ketone solvent and a furan solvent.
In the present invention, the water preferably includes one or more of deionized water, tap water, fresh water and seawater, more preferably includes deionized water, tap water, fresh water and/or seawater, and most preferably deionized water. In the present invention, the alcohol solvent preferably includes one or more of methanol, ethanol, propanol, ethylene glycol and glycerol, more preferably includes methanol, ethanol, propanol, ethylene glycol or glycerol, and most preferably ethylene glycol or ethanol. In the present invention, the nitrogen-containing solvent preferably includes one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylcaprolactam, N-methyl-2-pyrrolidone, and 1, 3-dimethylimidazolidinone, and more preferably includes N, N-dimethylformamide, N-dimethylacetamide, N-methylcaprolactam, N-methyl-2-pyrrolidone, or 1, 3-dimethylimidazolidinone. In the present invention, the sulfur-containing solvent preferably includes dimethyl sulfoxide and/or sulfolane. In the present invention, the ketone solvent preferably includes acetone. In the present invention, the furan-based solvent preferably includes tetrahydrofuran. In the present invention, when the auxiliary solvent includes two or more mixed solvents, the ratio of the different solvents used in the present invention is not particularly limited, and may be any ratio. In the embodiment of the present invention, when the auxiliary solvent is a mixed solvent, the auxiliary solvent is preferably a mixed solvent of deionized water and absolute ethyl alcohol (the volume ratio of deionized water to absolute ethyl alcohol is 1:1), or a mixed solvent of deionized water and N-N dimethylformamide (the volume ratio of deionized water to N-N dimethylformamide is 5:1), or a mixed solvent of deionized water, ethylene glycol and N-N dimethylacetamide (the volume ratio of deionized water, ethylene glycol and N-N dimethylacetamide is 10:5: 2).
The invention uses the auxiliary solvent to exchange with the organic solvent in the polyamide solution, uses the volatile solvent to replace the solvent which is difficult to volatilize, solidifies the surface layer of the uncured wire, keeps part of the organic solvent inside, and continuously permeates outwards, so that the organic solvent in the obtained uncured wire maintains proper content, thereby the low-concentration polymer solution can be solidified and molded. In the invention, the auxiliary solution plays a role in solvent exchange and shape fixing, and reduces the volume shrinkage of the polyimide ink caused by volatilization of a large amount of solvent in the heat treatment process. For polyimide inks with low solids content (i.e., high organic solvent content), extrusion is easy, and the printed article cannot retain its shape for a long time. Because of containing a large amount of solvent, the state is not solid at normal temperature, and the shape stability and the dimensional accuracy can be maintained only after partial solvent is exchanged by external means (auxiliary solvent matched with methods such as spraying, soaking, atmosphere humidifying and the like).
In the present invention, the pre-curing preferably includes one or more of spraying, soaking and humidifying. In the present invention, when the manner of the pre-curing is one manner, it more preferably includes soaking; when the pre-curing mode is two or more, the pre-curing mode more preferably comprises spraying first and then soaking, or humidifying first and then spraying and finally soaking. In the invention, the pre-curing process is to expose the uncured wire to an auxiliary solvent, cure the surface layer of the uncured wire by controlling the environmental temperature and the exposure time, and continuously permeate the organic solvent remained inside the uncured wire to the outside, so that the content of the organic solvent in the wire is maintained at a proper value (namely the content of the polyamide solution in percentage by mass is 70-90%).
In the present invention, a schematic diagram of an apparatus for pre-curing a printing wire by spraying, soaking, and humidifying in an atmosphere is shown in fig. 1, and an arrow indicates a flow direction of an auxiliary solvent. In the invention, the device for pre-curing in a spraying mode comprises a solvent tank, a large-hole spray head (simplified description of the spraying device), an auxiliary solvent and the uncured wire, wherein the large-hole spray head is positioned at the periphery of the solvent tank, and the auxiliary solvent forms a continuous liquid flow through the large-hole spray head and is sprayed to each surface of the uncured wire, so that the uncured wire is pre-cured. In the invention, the device for pre-curing in a soaking mode comprises a solvent tank, an auxiliary solvent and an uncured wire, wherein in the pre-curing process, the auxiliary solvent directly immerses the uncured wire so as to pre-cure the uncured wire. In the invention, the device for pre-curing by adopting the atmosphere humidifying mode comprises a solvent tank, a micropore spray head (simplified description of a gasification device), an auxiliary solvent and an uncured wire rod, wherein the micropore spray head is positioned at the periphery of the solvent tank, the auxiliary solvent is gasified through the micropore spray head, and the gasified auxiliary solvent is contacted with each surface of the uncured wire rod in a certain space volume, so that the uncured wire rod is pre-cured.
In the invention, the schematic diagram of the device for preparing the printed pre-cured part by pre-curing in a soaking mode is shown in fig. 3, and the device comprises a base, a column casing vertical to the base, three-dimensional working platforms arranged on the side wall of the column casing and the surface of the base, an object stage fixed by the three-dimensional platforms and an extrusion needle cylinder; and a solvent groove is fixed on the surface of the objective table. In the present invention, the solvent tank is used to contain an auxiliary solvent. In the invention, a polyamide solution extrudes a wire into a solvent tank through an extrusion needle cylinder, the wire is pre-cured through an auxiliary solvent contained in the wire, and then a printing pre-cured piece is formed under the control of a three-dimensional platform.
In the invention, when the precuring is carried out by adopting a spraying mode, the spraying temperature is preferably 20-40 ℃, and in the embodiment of the invention, the spraying is preferably carried out at room temperature; the spraying time is preferably 10-30 min, and more preferably 15-25 min; the speed and the dosage of the auxiliary solvent for spraying are not particularly limited, and all the outer surfaces of the uncured wire rods can be coated.
In the invention, when the pre-curing is carried out by adopting a soaking mode, the soaking temperature is preferably 20-40 ℃, and in the embodiment of the invention, the soaking is preferably carried out at room temperature; the soaking time is preferably 3-30 min, and more preferably 5-15 min. The amount of the auxiliary solvent used in the present invention is not particularly limited, and the uncured wire rod can be immersed.
In the invention, when the precuring is carried out by adopting an atmosphere humidifying mode, the temperature of the atmosphere humidifying is preferably 20-40 ℃; the time for humidifying the atmosphere is preferably 30-60 min, and more preferably 35-55 min. In the present invention, the volume of the space in which the atmosphere humidification is performed is not limited, and a certain humidity (i.e., a relative humidity of 70 to 90%) may be maintained.
In the present invention, the schematic diagram of the pre-curing of the uncured wire with the auxiliary solvent is shown in fig. 2, and includes extruding the wire, pre-curing the wire, and wire (the wire is shown in cross section in fig. 2); the extruded wire is formed by extruding a polyamide solution, and the solvent in the wire is uniformly distributed; the surface of the wire rod is contacted with the auxiliary solvent in the pre-curing process, because the polyamic acid or the polyimide is not dissolved in water, alcohol and other good solvents, when the auxiliary solvent is exchanged with the organic solvent in the polyamide solution, the surface layer of the wire rod starts to be cured, the external auxiliary solvent continuously permeates into the inner layer along with the extension of the curing time, meanwhile, the organic solvent reserved in the inner layer continuously permeates into the surface layer, and a dynamically-changed middle layer is formed between the surface layer and the inner layer of the wire rod. When the content of the organic solvent in the wire rod maintains a proper value (namely the mass percentage of the polyamide solution is 70-90%), the auxiliary solvent is removed, the organic solvent in the inner layer continuously permeates into the surface layer, so that the middle layer continuously moves towards the outer layer, the balance is finally achieved, and the solvent in the wire rod is uniformly redistributed, so that the solidified wire rod is obtained.
After the solid wire is obtained, the solid wire forms a printing precuring piece under the control of the three-dimensional platform.
The specific operation of forming the printing pre-cured piece by the solid wire under the control of the three-dimensional platform is not particularly limited, and the operation of obtaining the printing pre-cured piece by the control of the three-dimensional platform known by the person skilled in the art can be adopted.
After the printing precured piece is obtained, the printing precured piece is subjected to heat treatment to obtain a 3D printing polyimide product.
In the present invention, the heat treatment is preferably a constant temperature heat treatment or a gradient temperature rise heat treatment. In the invention, the temperature of the constant-temperature heat treatment is preferably 100-400 ℃, more preferably 150-350 ℃, and the time is preferably 6-12 hours, more preferably 8-10 hours. The method can completely volatilize the solvent by utilizing constant-temperature heat treatment, thereby keeping the shape stability and the size accuracy of the 3D printed polyimide product.
In the present invention, the gradient temperature-increasing heat treatment preferably includes sequentially performing a first temperature increase to a temperature of the first heat treatment for a first heat preservation, a second temperature increase to a temperature of the second heat treatment for a second heat preservation, a third temperature increase to a temperature of the third heat treatment for a third heat preservation, and a fourth temperature increase to a temperature of the fourth heat treatment for a fourth heat preservation; in the invention, the temperature of the first heat treatment is preferably 80-120 ℃, more preferably 100 ℃, and the first heat preservation time is preferably 1-3 h, more preferably 2 h; the temperature of the second heat treatment is preferably 180-230 ℃, more preferably 200 ℃, and the second heat preservation time is preferably 0.5-1.5 h, more preferably 1 h; the temperature of the third heat treatment is preferably 280-320 ℃, more preferably 300 ℃, and the third heat preservation time is preferably 0.5-1.5 h, more preferably 1 h; the temperature of the fourth heat treatment is preferably 340-360 ℃, more preferably 350 ℃, and the fourth heat preservation time is preferably 0.5-1.5 h, more preferably 1 h. In the present invention, the heating rates of the first heating, the second heating, the third heating and the fourth heating are independently preferably 2 to 4 ℃/min, more preferably 2 to 3 ℃/min, and most preferably 2 ℃/min. According to the invention, by utilizing gradient heating heat, on one hand, the shape stability and the size accuracy of a 3D printed polyimide part can be kept, and on the other hand, the polyamide acid can be fully imidized to generate polyimide, so that a foundation is laid for obtaining a polyimide part with excellent comprehensive performance.
The apparatus used for the heat treatment is not particularly limited, and a heat treatment apparatus well known to those skilled in the art may be used; in the embodiments of the present invention, the heat treatment is preferably performed in an oven. The atmosphere for the heat treatment is not particularly limited, and a heat treatment atmosphere known to those skilled in the art may be used, specifically, air, a protective atmosphere or vacuum conditions; the protective inert atmosphere preferably comprises nitrogen or argon; the pressure of the heat treatment is preferably 80kPa to 100kPa, more preferably 85kPa to 95kPa, and most preferably 90 kPa.
Compared with the ultraviolet curing forming mode, the auxiliary solvent curing forming method has the advantage that the auxiliary solvent mode can avoid great damage to human health caused by long-time exposure to the ultraviolet irradiation environment.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. 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.
Example 1
The preparation method comprises the steps of adopting the device shown in figure 3 and the process flow shown in figure 4, placing a polyamic acid solution (with the mass percentage content of 20% and the viscosity of 10 Pa.s) in an extrusion needle cylinder for extrusion, extruding a wire rod into a solvent tank, spraying deionized water onto each surface of the wire rod in a spraying mode for 20min, and precuring the uncured wire rod at room temperature to obtain a solid wire rod; forming a printed pre-cured piece from the solid wire under the control of the three-dimensional platform;
and under the condition that the pressure is 90kPa, placing the printed pre-cured piece in an oven to perform gradient heating treatment at a constant heating rate of 2 ℃/min, heating to 100 ℃, then preserving heat for 2h, heating to 200 ℃, then preserving heat for 1h, heating to 300 ℃, then preserving heat for 1h, heating to 350 ℃, and then preserving heat for 1h to obtain the 3D printed polyimide piece.
Fig. 5 shows a real object image of the printed pre-cured object before and after heat treatment and a cross-sectional microscopic image of a single filament before and after heat treatment. As can be seen from FIG. 5, the diameter of the single filament before the heat treatment was 529.5 + -3 μm, the diameter of the single filament after the heat treatment was 481.5 + -3 μm, and the shrinkage was only 9%, indicating that the preparation method provided by the present invention can maintain the shape stability and dimensional accuracy.
Example 2
The preparation method comprises the steps of adopting the device shown in fig. 3 and the process flow shown in fig. 4, placing a polyamic acid solution (with the mass percentage content of 50% and the viscosity of 10000Pa · s) in an extrusion needle cylinder for extrusion, extruding a wire into deionized water contained in a solvent tank, soaking for 5min at room temperature, and precuring the uncured wire to obtain a solid wire; forming a printed pre-cured piece from the solid wire under the control of the three-dimensional platform;
and under the condition that the pressure is 90kPa, placing the printed pre-cured piece in an oven to perform gradient heating treatment at a constant heating rate of 2 ℃/min, heating to 100 ℃, then preserving heat for 2h, heating to 200 ℃, then preserving heat for 1h, heating to 300 ℃, then preserving heat for 1h, heating to 350 ℃, and then preserving heat for 1h to obtain the 3D printed polyimide piece.
The diameter of a single wire of the printed pre-cured part prepared in this example is 510 ± 3 μm, the diameter of a single wire of a 3D printed polyimide part is 468 ± 3 μm, and the shrinkage rate is 8.2%, which indicates that the preparation method provided by the present invention can maintain shape stability and dimensional accuracy.
Example 3
The method is characterized by adopting the device shown in FIG. 3 and the process flow shown in FIG. 4, placing a polyamic acid solution (with the mass percentage of 10% and the viscosity of 0.2Pa · s) in an extrusion needle cylinder for extrusion, extruding a wire rod into a solvent tank, gasifying deionized water in an atmosphere humidifying manner, permeating the deionized water to the surface of the wire rod, and precuring the uncured wire rod to obtain a solid wire rod after the temperature is kept for 45min at room temperature; forming a printed pre-cured piece from the solid wire under the control of the three-dimensional platform;
and under the condition that the pressure is 90kPa, placing the printed pre-cured piece in an oven to perform gradient heating treatment at a constant heating rate of 2 ℃/min, heating to 100 ℃, then preserving heat for 2h, heating to 200 ℃, then preserving heat for 1h, heating to 300 ℃, then preserving heat for 1h, heating to 350 ℃, and then preserving heat for 1h to obtain the 3D printed polyimide piece.
The diameter of the single wire of the printing pre-cured part prepared in this example is 545 +/-5 μm, the diameter of the single wire of the 3D printing polyimide part is 492 +/-4 μm, and the shrinkage rate is 9.7%, which shows that the preparation method provided by the present invention can maintain the shape stability and the dimensional accuracy.
Example 4
A 3D printed polyimide article was prepared as in example 1, except that the polyamic acid solution was 20% by mass and had a viscosity of 10Pa · s; the auxiliary solvent is a mixed solvent of deionized water and absolute ethyl alcohol in a volume ratio of 1: 1.
The diameter of the single wire of the printing pre-cured part prepared in this embodiment is 505 ± 3 μm, the diameter of the single wire of the 3D printing polyimide part is 465 ± 3 μm, and the shrinkage rate is 7.9%, which indicates that the preparation method provided by the present invention can maintain the shape stability and the dimensional accuracy.
Example 5
A 3D printed polyimide article was prepared as in example 1, except that the polyamic acid solution was 20% by mass and had a viscosity of 10Pa · s; the auxiliary solvent is a mixed solvent of deionized water, ethylene glycol and N-N dimethylformamide with the volume ratio of 10:5: 2.
The diameter of a single wire of the printed pre-cured part prepared in this example is 502 ± 3 μm, the diameter of a single wire of a 3D printed polyimide part is 466 ± 3 μm, and the shrinkage rate is 7.2%, which indicates that the preparation method provided by the present invention can maintain shape stability and dimensional accuracy.
Example 6
The preparation method comprises the steps of adopting the device shown in the figure 3 and the process flow shown in the figure 4, placing a polyamic acid solution (with the mass percentage of 30% and the viscosity of 200 Pa.s) in an extrusion needle cylinder for extrusion, extruding a wire into a mixed solvent of deionized water and N-N dimethylformamide with the volume ratio of 5:1, soaking for 15min at room temperature, and precuring the uncured wire to obtain a solid wire; forming a printed pre-cured piece from the solid wire under the control of the three-dimensional platform;
and (3) under the air condition, placing the printed pre-cured piece in a drying oven at the temperature of 150 ℃ for constant-temperature heat treatment for 6h to obtain a 3D printed polyimide piece.
The diameter of the single filament of the printed pre-cured piece prepared in this example is 513 ± 3 μm, the diameter of the single filament of the 3D printed polyimide piece is 470 ± 4 μm, and the shrinkage rate is 8.4%, which indicates that the preparation method provided by the present invention can maintain the shape stability and dimensional accuracy.
The 3D printing polyimide prepared by the invention can keep shape stability and size accuracy for a long time.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (3)
1. A preparation method of a 3D printed polyimide product comprises the following steps:
extruding the polyamide solution to obtain an uncured wire;
precuring the uncured wire by using an auxiliary solvent to obtain a solid wire;
forming a printed pre-cured piece from the solid wire under the control of the three-dimensional platform;
carrying out heat treatment on the printed pre-cured piece to obtain a 3D printed polyimide piece;
the polyamide solution comprises 20-30% by mass and has a viscosity of 0.2-1000 pas;
the heat treatment mode is constant temperature heat treatment or gradient temperature rise heat treatment; the temperature of the constant-temperature heat treatment is 100-400 ℃, and the time is 6-12 hours; the gradient heating treatment comprises the steps of sequentially carrying out first heating to the temperature of the first heat treatment for first heat preservation, second heating to the temperature of the second heat treatment for second heat preservation, third heating to the temperature of the third heat treatment for third heat preservation and fourth heating to the temperature of the fourth heat treatment for fourth heat preservation;
the temperature of the first heat treatment is 80-120 ℃, and the first heat preservation time is 1-3 h;
the temperature of the second heat treatment is 180-230 ℃, and the second heat preservation time is 0.5-1.5 h;
the temperature of the third heat treatment is 280-320 ℃, and the third heat preservation time is 0.5-1.5 h;
the temperature of the fourth heat treatment is 340-360 ℃, and the fourth heat preservation time is 0.5-1.5 h;
the heating rates of the first heating, the second heating, the third heating and the fourth heating are independently 2-4 ℃/min;
the auxiliary solvent comprises one or more of water, an alcohol solvent, a nitrogen-containing solvent, a sulfur-containing solvent, a ketone solvent and a furan solvent; the pre-curing mode comprises one or more of spraying, soaking and atmosphere humidifying; the temperature of the pre-curing is 20-40 ℃, and the time is 3-60 min; the polyamide solution is a polyamide acid solution and/or a polyimide solution.
2. The method according to claim 1, wherein the nitrogen-containing solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylcaprolactam, N-methyl-2-pyrrolidone, and 1, 3-dimethylimidazolidinone.
3. The method of claim 1, wherein the sulfur-containing solvent comprises dimethyl sulfoxide and/or sulfolane.
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