CN109371501B - Plant fiber composite wire with shape memory function for 3D printing and preparation method thereof - Google Patents

Plant fiber composite wire with shape memory function for 3D printing and preparation method thereof Download PDF

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CN109371501B
CN109371501B CN201811296113.5A CN201811296113A CN109371501B CN 109371501 B CN109371501 B CN 109371501B CN 201811296113 A CN201811296113 A CN 201811296113A CN 109371501 B CN109371501 B CN 109371501B
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plant fiber
printing
composite wire
fiber composite
shape memory
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CN109371501A (en
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许民
毕红杰
郭蕊
任泽春
贾鑫
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Northeast Forestry University
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances

Abstract

The invention belongs to the technical field of 3D printing, and particularly relates to a plant fiber composite wire with a shape memory function for 3D printing and a preparation method thereof. The plant fiber composite wire comprises plant fiber powder, TPU, a modifier and a lubricant. The preparation steps are as follows: the plant fiber composite wire rod for fused deposition type 3D printing is prepared by the steps of fully mixing plant fiber powder, TPU, a modifier and a lubricant, performing melt extrusion on the obtained material through a parallel double-screw extruder, crushing the obtained material into granules, putting the granules into a single-screw extruder, melting the granules at a certain temperature, and obtaining the plant fiber composite wire rod for fused deposition type 3D printing at a certain traction speed. The invention solves the problem of higher cost of the thermoplastic polyurethane elastomer as the material for 3D printing, not only reduces the material cost, but also improves the interface compatibility between the TPU and the plant fiber powder by modifying the TPU and the plant fiber powder, so that the prepared composite wire has stronger toughness and shape memory recovery performance.

Description

Plant fiber composite wire with shape memory function for 3D printing and preparation method thereof
Technical Field
The invention belongs to the technical field of 3D printing, and particularly relates to a plant fiber composite wire with a shape memory function for 3D printing and a preparation method thereof.
Background
Currently, the importance of 3D printing technology has been verified and widely used in the industry. Among the 3D printing technologies, Fused Deposition Modeling (FDM) is the most common technology, and has a simple device structure, a low price, and a convenient operation process, and the printing process is to melt a thermoplastic filament material from a heating nozzle and extrude the thermoplastic filament material according to a designed track to construct a three-dimensional entity.
Based on the FDM technical characteristics, the technology can print various thermoplastic materials and composite materials thereof, but can manufacture soft body structure finished products with any complex shapes less. Obviously, more novel composite materials capable of being used for 3D printing are provided, so that the composite material has a great market prospect and has an important value for solving the material bottleneck of 3D printing.
Shape memory polymer materials (SMPs) are stimuli responsive materials that change from a temporary shape to an initial shape in response to an external stimulus, such as temperature, light, an electric field, a magnetic field, a ph, etc. The unique shape memory effect, deformability and deformable structure of SMP have shown great application potential and practical value in many fields. On the basis of the elastomer, the elastomer polymer essentially has good shape memory effect and has larger recoverability and processability, wherein the thermoplastic polyurethane elastomer (TPU) is a soft 3D printing material, and a unique shape memory property is endowed by a special microphase separation structure generated between incompatible soft and hard segments in a molecular chain. However, TPU is costly, which limits its applications.
Disclosure of Invention
In order to solve the problem that the thermoplastic polyurethane elastomer is high in cost as a material for 3D printing, the invention provides a plant fiber composite wire with a shape memory function for 3D printing and a preparation method thereof.
The technical scheme of the invention is as follows:
a plant fiber composite wire with a shape memory function for 3D printing comprises the following components in parts by mass: 5-45 parts of plant fiber powder, 55-95 parts of TPU and 0.5-2 parts of lubricant.
Further, the composite wire further comprises the following components in parts by mass: 1-20 parts of a modifier.
A preparation method of a plant fiber composite wire with a shape memory function for 3D printing comprises the following steps: the plant fiber composite wire rod for fused deposition type 3D printing is prepared by the steps of fully mixing plant fiber powder, TPU, a modifier and a lubricant, performing melt extrusion on the obtained material through a co-rotating parallel double-screw extruder, crushing the obtained material into granules, putting the granules into a single-screw extruder, melting the granules at a certain temperature, and obtaining the plant fiber composite wire rod for fused deposition type 3D printing at a certain traction speed.
Further, the plant fiber powder, the TPU and the modifier are dried before mixing, wherein the plant fiber powder and the TPU are dried for 12 hours at 103 ℃, and the modifier is dried for 2 hours at 60 ℃.
Further, the plant fiber powder is one or a combination of more of wood powder, bamboo powder, straw powder, fruit shell powder or bran powder, and the particle size of the plant fiber powder is 80-200 meshes.
Further, the Shore hardness of the TPU is 80-98A.
Further, the modifier is maleic anhydride grafted ethylene propylene diene monomer or maleic anhydride grafted polyolefin elastomer.
Further, the lubricant is one or a combination of more of stearic acid and salts thereof, polyethylene wax, polypropylene wax, oxidized polyethylene wax or paraffin wax.
Furthermore, the temperature of a machine barrel of the co-rotating parallel double-screw extruder is 160-195 ℃, and the temperature of the die is 180-200 ℃.
Further, the particle size of the granules is 2-8 mm, the temperature of a charging barrel of the single-screw extruder is 160-195 ℃, the temperature of the die is 180-200 ℃, the speed of the main machine is set to be 25-40 Hz, and the traction speed is set to be 15-30 Hz.
The invention has the beneficial effects that:
according to the invention, the thermoplastic polyurethane elastomer (TPU) and the waste plant fiber powder of industry and agriculture, such as wood powder, bamboo powder, straw powder, fruit shell powder or bran powder, are used as main raw materials to prepare the plant fiber composite wire for 3D printing, so that the material cost can be reduced, the utilization rate of plant fiber waste materials can be improved, the energy can be saved, the degradation performance of printing materials can be improved, and the environmental pollution can be reduced.
The preparation method provided by the invention modifies the TPU and the plant fiber powder, improves the interface compatibility between the TPU and the plant fiber powder, and enables the prepared composite wire to have stronger toughness and shape memory recovery performance. The tearing elongation of the unmodified TPU-based plant fiber composite wire is about 200 percent, and can exceed 500 percent after modification. And the components with specific contents are matched with each other, so that the prepared TPU-based plant fiber composite wire has excellent colorability, soft touch, weather resistance, wear resistance, temperature resistance and processability, and is widely suitable for home and abroad FDM type 3D printers.
And thirdly, a finished product prepared by 3D printing of the TPU-based plant fiber composite wire has high strength, high toughness and strong shape memory performance, has natural wood texture, can reduce consumption of forest resources and petroleum resources, and is more environment-friendly, efficient and energy-saving.
The TPU-based plant fiber composite wire and the preparation method thereof provided by the invention have important meanings for expanding the application field of 3D printing composite materials and realizing the intellectualization and functionality of non-contact and remote driving materials. The intelligent composite material has great application prospect in the fields of aerospace deformation structures, biomedical equipment, intelligent textile industry, electronic devices, temperature indication and the like.
Drawings
Fig. 1 is a diagram showing the shape memory recovery effect of a 3D printed article prepared in example 11;
fig. 2 is a thermally induced shape memory effect display diagram of a 3D printed character model prepared in example 12;
in the figure, (a) shows a designed model, (b) shows an original shape, (c) shows a temporary shape, (d) shows a state of recovery of the human model after 2min, (e) shows a state of recovery of the human model after 20min, and (f) shows a state of complete recovery of the model shape after 40 min.
Detailed Description
The technical solutions of the present invention are further described below with reference to the following examples, but the present invention is not limited thereto, and any modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Example 1
A plant fiber composite wire with a shape memory function for 3D printing comprises the following components in parts by mass: 5-45 parts of plant fiber powder, 55-95 parts of TPU and 0.5-2 parts of lubricant.
Example 2
A plant fiber composite wire with a shape memory function for 3D printing comprises the following components in parts by mass: 5-45 parts of plant fiber powder, 55-95 parts of TPU, 1-20 parts of modifier and 0.5-2 parts of lubricant.
Example 3
A preparation method of a plant fiber composite wire with a shape memory function for 3D printing comprises the following steps: fully mixing 5-45 parts of plant fiber powder, 55-95 parts of TPU, 1-20 parts of modifier and 0.5-2 parts of lubricant to obtain a material, performing melt extrusion through a co-rotating parallel double-screw extruder, then crushing the material into granules, putting the granules into a single-screw extruder, melting the granules at a certain temperature, and obtaining the plant fiber composite wire for melt deposition type 3D printing at a certain traction speed.
Example 4
A preparation method of a plant fiber composite wire with a shape memory function for 3D printing comprises the following steps: fully mixing 5-45 parts of plant fiber powder, 55-95 parts of TPU, 1-20 parts of modifier and 0.5-2 parts of lubricant to obtain a material, performing melt extrusion by a co-rotating parallel double-screw extruder, and then crushing the material into granules, wherein the temperature of a machine barrel of the co-rotating parallel double-screw extruder is 160-195 ℃, the temperature of a die is 180-200 ℃, and the particle size of the granules is 2-8 mm; and putting the granules into a single-screw extruder, wherein the temperature of a charging barrel of the single-screw extruder is 160-195 ℃, the temperature of the die is 180-200 ℃, the speed of a host is set to be 25-40 Hz, and the traction speed is set to be 15-30 Hz, so that the plant fiber composite wire for fused deposition type 3D printing is obtained.
Example 5
A preparation method of a plant fiber composite wire with a shape memory function for 3D printing comprises the following steps: fully mixing 5-45 parts of plant fiber powder, 55-95 parts of TPU and 0.5-2 parts of lubricant to obtain a material, melting and extruding the material through a co-rotating parallel double-screw extruder, and then crushing the material into granules, wherein the temperature of a machine barrel of the co-rotating parallel double-screw extruder is 160-195 ℃, the temperature of a die is 180-200 ℃, and the particle size of the granules is 2-8 mm; and putting the granules into a single-screw extruder, wherein the temperature of a charging barrel of the single-screw extruder is 160-195 ℃, the temperature of the die is 180-200 ℃, the speed of a host is set to be 25-40 Hz, and the traction speed is set to be 15-30 Hz, so that the plant fiber composite wire for fused deposition type 3D printing is obtained.
The embodiment modifies the TPU and the plant fiber powder, improves the interface compatibility between the TPU and the plant fiber powder, and enables the prepared composite wire to have stronger toughness and shape memory recovery performance.
Example 6
A preparation method of a plant fiber composite wire with a shape memory function for 3D printing comprises the following steps:
drying the peach wood powder with the particle size of 100 meshes and TPU with the Shore hardness of 80-98A for 12 hours at 103 ℃, and mixing 10 parts by mass of the peach wood powder, 60 parts by mass of the TPU and 0.5 part by mass of wetting agent polyethylene wax in a high-speed mixer for 5-15 minutes;
secondly, melting and granulating the mixed materials through a co-rotating parallel double-screw extruder, wherein the barrel temperature of the co-rotating parallel double-screw extruder is 170 ℃, the die temperature is 185 ℃, and the melt is extruded and cooled, and is crushed for 8-15 minutes by a crusher to prepare granules with the particle size of 2-8 mm;
(III) placing the granules into a single-screw extruder, wherein the temperature of a material cylinder of the single-screw extruder is as follows: 1170 ℃ and 185 ℃ of a die; the host machine speed is set to be 25Hz, the traction speed is set to be 15Hz, and the plant fiber composite wire for fused deposition type 3D printing is obtained.
Example 7
A preparation method of a plant fiber composite wire with a shape memory function for 3D printing comprises the following steps:
firstly, drying 100-mesh peach wood powder and TPU with Shore hardness of 80-98A at 103 ℃ for 12h, drying a modifier, namely maleic anhydride grafted ethylene propylene diene monomer rubber at 60 ℃ for 2h, and mixing 10 parts by mass of peach wood powder, 60 parts by mass of TPU, 5 parts by mass of maleic anhydride grafted ethylene propylene diene monomer rubber and 0.5 part by mass of wetting agent, namely polyethylene wax in a high-speed mixer for 5-15 minutes;
secondly, melting and granulating the mixed materials through a co-rotating parallel double-screw extruder, wherein the barrel temperature of the co-rotating parallel double-screw extruder is 170 ℃, the die temperature is 185 ℃, and the melt is extruded and cooled, and is crushed for 8-15 minutes by a crusher to prepare granules with the particle size of 2-8 mm;
(III) placing the granules into a single-screw extruder, wherein the temperature of a material cylinder of the single-screw extruder is as follows: 170 ℃ and 185 ℃ of die temperature; the host machine speed is set to be 25Hz, the traction speed is set to be 15Hz, and the plant fiber composite wire for fused deposition type 3D printing is obtained.
Example 8
A preparation method of a plant fiber composite wire with a shape memory function for 3D printing comprises the following steps:
drying 100-mesh bamboo powder and TPU with Shore hardness of 80-98A at 103 ℃ for 12h, drying a modifier, namely maleic anhydride grafted ethylene propylene diene monomer rubber at 60 ℃ for 2h, and mixing 20 parts by mass of bamboo powder, 70 parts by mass of TPU, 10 parts by mass of maleic anhydride grafted ethylene propylene diene monomer rubber and 1 part by mass of a wetting agent, namely polypropylene wax, in a high-speed mixer for 5-15 minutes;
secondly, melting and granulating the mixed materials through a co-rotating parallel double-screw extruder, wherein the barrel temperature of the co-rotating parallel double-screw extruder is 180 ℃, the die temperature is 190 ℃, and the melt is extruded and cooled, and is crushed for 8-15 minutes by a crusher to prepare granules with the particle size of 2-8 mm;
(III) placing the granules into a single-screw extruder, wherein the temperature of a material cylinder of the single-screw extruder is as follows: the temperature of the die is 190 ℃; the host machine speed is set to be 30Hz, the traction speed is set to be 20Hz, and the plant fiber composite wire for fused deposition type 3D printing is obtained.
Example 9
A preparation method of a plant fiber composite wire with a shape memory function for 3D printing comprises the following steps:
drying 100-mesh straw powder and TPU with Shore hardness of 80-98A at 103 ℃ for 12 hours, drying a modifier, namely a maleic anhydride grafted polyolefin elastomer at 60 ℃ for 2 hours, and mixing 30 parts by mass of the straw powder, 80 parts by mass of the TPU, 15 parts by mass of the maleic anhydride grafted polyolefin elastomer and 1.5 parts by mass of a wetting agent, namely oxidized polyethylene wax in a high-speed mixer for 5-15 minutes;
secondly, melting and granulating the mixed materials through a co-rotating parallel double-screw extruder, wherein the barrel temperature of the co-rotating parallel double-screw extruder is 190 ℃, the die temperature is 195 ℃, and the melt is extruded and cooled, and is crushed for 8-15 minutes by a crusher to prepare granules with the particle size of 2-8 mm;
(III) placing the granules into a single-screw extruder, wherein the temperature of a material cylinder of the single-screw extruder is as follows: the temperature of the die is 195 ℃; the host machine speed is set to be 35Hz, the traction speed is set to be 25Hz, and the plant fiber composite wire for fused deposition type 3D printing is obtained.
Example 10
A preparation method of a plant fiber composite wire with a shape memory function for 3D printing comprises the following steps:
drying 150-mesh fruit shell powder and TPU with Shore hardness of 80-98A at 103 ℃ for 12 hours, drying a modifier, namely a maleic anhydride grafted polyolefin elastomer at 60 ℃ for 2 hours, and mixing 40 parts by mass of straw powder, 90 parts by mass of TPU, 20 parts by mass of maleic anhydride grafted polyolefin elastomer and 2 parts by mass of wetting agent, namely stearic acid and salts thereof in a high-speed mixer for 5-15 minutes;
secondly, melting and granulating the mixed materials through a co-rotating parallel double-screw extruder, wherein the barrel temperature of the co-rotating parallel double-screw extruder is 195 ℃, the die temperature is 200 ℃, and the melt is extruded and cooled, and is crushed for 8-15 minutes by a crusher to prepare granules with the particle size of 2-8 mm;
(III) placing the granules into a single-screw extruder, wherein the temperature of a material cylinder of the single-screw extruder is as follows: 195 ℃ and the temperature of a die is 200 ℃; the host machine speed is set to be 40Hz, the traction speed is set to be 30Hz, and the plant fiber composite wire for fused deposition type 3D printing is obtained.
The plant fiber composite wires for 3D printing prepared in examples 6 to 10 were respectively tested for tensile strength and elongation at break, and the results are shown in table 1:
TABLE 1
Categories Tensile Strength (MPa) Tear elongation (%)
Example 6 14.97±1.85 205.25±20.11
Example 7 15.33±1.88. 451.74±25.72
Example 8 15.92±0.63 591.16±26.29
Example 9 15.43±1.66 540.06±33.29
Example 10 12.24±1.39 520.91±32.85
As can be seen from the data in Table 1, the elongation at break of the unmodified TPU-based plant fiber composite wire of example 6 is 205.25 + -20.11%, while the elongation at break of the modified composite wires of examples 7-10 is more than 2 times that of the unmodified composite wire and is 591.16 + -26.29% at the maximum. This fully demonstrates that the modification treatment of the TPU and the plant fiber according to the present invention can improve the interfacial compatibility between the TPU and the plant fiber, thereby greatly enhancing the toughness of the composite wire.
Example 11
Taking the plant fiber composite wire prepared in the embodiment 7 as a printing material, printing by using an FDM printer to obtain a 3D printed product, wherein the printing temperature is 200-230 ℃, recording the initial shape and the initial angle of a test piece after 3D printing, and heating the test piece for 0.5-2 hours at the temperature of 30-80 ℃; after bending the test piece into a temporary shape, placing the test piece at the temperature of minus 20 to minus 30 ℃ for 8 to 12 hours and fixing the temporary shape. And (3) placing the test piece at the temperature of 30-80 ℃, and monitoring the shape recovery process of the test piece. As a result, as shown in FIG. 1, the 3D product can completely recover the original shape within 20-30 min.
Example 12
Taking the plant fiber composite wire prepared in the embodiment 7 as a printing material, printing by using an FDM (fused deposition modeling) printer to obtain a 3D printed character model product, wherein the printing temperature is 200-230 ℃, recording the initial shape and the initial angle of a test piece after 3D printing, and heating the test piece for 0.5-2 hours at the temperature of 30-80 ℃; after bending the test piece into a temporary shape, placing the test piece at the temperature of minus 20 to minus 30 ℃ for 8 to 12 hours and fixing the temporary shape. And (3) placing the test piece at the temperature of 30-80 ℃, and monitoring the shape recovery process of the test piece. As a result, as shown in FIG. 2, the 3D product can completely recover the original shape within 30-40 min.

Claims (8)

1. The plant fiber composite wire with the shape memory function for 3D printing is characterized by comprising the following components in parts by mass: 20 parts of plant fiber powder, 70 parts of TPU, 10 parts of modifier maleic anhydride grafted ethylene propylene diene monomer rubber and 1 part of lubricant.
2. The preparation method of the plant fiber composite wire for 3D printing with the shape memory function, which is characterized by comprising the following steps of: the plant fiber composite wire rod for fused deposition type 3D printing is prepared by the steps of fully mixing plant fiber powder, TPU, a modifier and a lubricant, performing melt extrusion on the obtained material through a co-rotating parallel double-screw extruder, crushing the obtained material into granules, putting the granules into a single-screw extruder, melting the granules at a certain temperature, and obtaining the plant fiber composite wire rod for fused deposition type 3D printing at a certain traction speed.
3. The preparation method of the plant fiber composite wire for 3D printing with the shape memory function according to claim 2, wherein the plant fiber powder, the TPU and the modifier are dried before being mixed, wherein the plant fiber powder and the TPU are dried at 103 ℃ for 12 hours, and the modifier is dried at 60 ℃ for 2 hours.
4. The preparation method of the plant fiber composite wire for 3D printing with the shape memory function according to claim 3, wherein the plant fiber powder is one or a combination of wood powder, bamboo powder, straw powder, fruit shell powder or bran powder, and the particle size of the plant fiber powder is 80-200 meshes.
5. The preparation method of the plant fiber composite wire for 3D printing with the shape memory function according to claim 4, wherein the Shore hardness of the TPU is 80-98A.
6. The method for preparing the plant fiber composite wire for 3D printing with the shape memory function according to claim 5, wherein the lubricant is one or a combination of stearic acid and salts thereof, polyethylene wax, polypropylene wax, oxidized polyethylene wax or paraffin wax.
7. The method for preparing the plant fiber composite wire for 3D printing with the shape memory function according to claim 6, wherein the cylinder temperature of the co-rotating parallel twin-screw extruder is 160-195 ℃, and the die temperature is 180-200 ℃.
8. The method for preparing the plant fiber composite wire for 3D printing with the shape memory function according to claim 7, wherein the particle size of the granules is 2-8 mm, the temperature of a cylinder of the single screw extruder is 160-195 ℃, the temperature of a die is 180-200 ℃, the speed of a main engine is 25-40 Hz, and the traction speed is 15-30 Hz.
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