Biomass biomorphic composite material as well as preparation method and application thereof

Abstract

The invention discloses a biomass biomorphic composite material as well as a preparation method and application thereof, and relates to the technical field of 3D printing consumables, the biomass biomorphic composite material comprises the following components in parts by weight: 97-99.5 parts of a thermoplastic polymer and 0.5-3 parts of biomass charcoal; the preparation method provided by the invention is simple to operate, the materials are environment-friendly and easy to obtain, the viscosity after melting is relatively low, the melt fluidity is good, a nozzle of a printer cannot be blocked, the popularization is convenient, and meanwhile, the prepared biomass biomorphic composite material has excellent heat-conducting property and good mechanical property and is suitable for industrial production. The method has a wide application prospect in the field of additive manufacturing based on thermal management application.

Description

Technical Field

[0001] The present invention relates to the technical field of 3D printing consumables, and in particular to a biomass composite material and a preparation method and use thereof. Background Art

[0002] 3D printing technology, also known as Additive Manufacturing, is becoming increasingly important in modern life. It provides highly adaptable solutions for medical, consumer products and other fields through personalized customization. In the manufacturing industry, 3D printing accelerates the product development cycle, reduces the cost of prototyping, and supports the manufacture of complex structures, promoting innovation in aerospace and architectural design; its distributed manufacturing model makes production more localized, reduces transportation and inventory costs, and improves supply chain efficiency. In addition, 3D printing has also played an important role in education, scientific research and artistic creation, helping students understand complex concepts, assisting scientific research, and expanding the creative space of artists. 3D printing's efficient use of materials and sustainable development characteristics have further promoted the development of environmental protection and circular economy. 3D printing technology is profoundly changing people's lives and promoting innovation and progress in various fields.

[0003] In 3D printing, fused deposition modeling (FDM) is widely used due to its advantages such as low equipment cost, easy availability of materials, simple operation, and support for a variety of thermoplastic materials such as PLA and ABS. However, single thermoplastic filaments have disadvantages in 3D printing, such as insufficient strength and rigidity, limited heat resistance, and easy warping and deformation, which limit their application in high-performance fields. In addition, single materials usually lack special properties, such as conductivity, wear resistance, or chemical corrosion resistance, and are difficult to meet multifunctional requirements. Therefore, composite filaments came into being, providing a wider range of application possibilities for 3D printing.

[0004] In recent years, biochar has shown great advantages in the preparation of composite 3D printing filaments due to its low cost, renewable and environmentally friendly characteristics. The porous structure and high specific surface area of ​​biochar can enhance interfacial bonding and improve the mechanical properties and stability of the filament. In addition, the high specific surface area and unique carbon structure of biochar enable it to efficiently absorb and convert light energy, improving the photothermal response ability of the filament. These characteristics help to enhance the thermal uniformity of the material during the printing process and reduce warping and shrinkage deformation. In addition, the high thermal conductivity of biochar can improve the heat transfer of the polymer matrix and increase the bonding strength between the printed layers, thereby improving the stability and mechanical properties of the final product, making it more competitive in smart responsive materials and functional printing applications. Summary of the invention

[0005] The technical problem to be solved by the present invention is to provide a biomass legacy composite material, a preparation method thereof and use thereof as a 3D printing consumable. The preparation method provided is simple to operate, the material is environmentally friendly and easy to obtain, and the viscosity after melting is low, the melt fluidity is good, and it will not cause clogging of the printer nozzle, which is easy to promote. At the same time, the prepared biomass legacy composite material has excellent thermal conductivity and good mechanical properties, and has broad application prospects in the field of additive manufacturing based on thermal management applications.

[0006] The technical problem to be solved by the present invention is achieved by adopting the following technical solutions:

[0007] The first object of the present invention is to provide a biomass waste composite material, comprising the following components in parts by weight: 97 to 99.5 parts of a thermoplastic polymer and 0.5 to 3 parts of biomass charcoal.

[0008] The second object of the present invention is to provide a method for preparing a biomass composite material, comprising the following steps:

[0009] (1) melt-blending the biochar and the thermoplastic polymer, cooling and shearing the mixture into masterbatch by a pelletizer;

[0010] (2) The masterbatch is melt-extruded through an extruder to obtain a biomass-based composite material.

[0011] The third object of the present invention is to provide the use of the biomass legacy composite material as a 3D printing consumable.

[0012] The beneficial effects of the present invention are:

[0013] 1. The biomass charcoal used in the present invention is renewable and conforms to the concept of sustainable manufacturing, making the prepared composite material more environmentally friendly and improving the biodegradability of the composite material.

[0014] 2. The present invention adopts thermoplastic polymers with good processing performance, excellent mechanical properties and wear resistance and oil resistance, and biomass charcoal with high specific surface area and unique carbon structure as raw materials to prepare biomass residual composite materials with high photothermal response ability. When used as 3D printing consumables, it shows good processability and printing smoothness.

[0015] 3. The present invention ensures that the biochar is evenly dispersed in the thermoplastic polymer through vacuum melt blending, effectively improving the thermal conductivity of the consumables and not easily clogging the print head.

[0016] 4. The preparation method provided by the present invention is simple to operate, the raw materials are easily available, and it is easy to promote. It is suitable for large-scale industrial production. Therefore, it has broad application prospects in the field of additive manufacturing based on photothermal response applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is a SEM image of the bamboo chip biochar prepared in Example 1 of the present invention;

[0018] Figure 2 This is the XRD pattern of the bamboo chip biochar prepared in Example 1 of the present invention;

[0019] Figure 3 This is a SEM image of the 3D printing consumables prepared in Example 1 of the present invention;

[0020] Figure 4 This is a particle size distribution diagram of the bamboo charcoal biochar prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0021] In order to make the technical means, creative features, objectives and effects achieved by the present invention easy to understand, the present invention is further described below in conjunction with specific embodiments and diagrams.

[0022] The invention provides a biomass waste composite material, comprising the following components in parts by weight: 97 to 99.5 parts of a thermoplastic polymer and 0.5 to 3 parts of biomass charcoal.

[0023] Furthermore, the raw materials for preparing the biochar include, but are not limited to, one or more of bamboo chips, rice husks, straw, wood chips, and sawdust. Common agricultural waste, forestry waste, industrial waste, urban solid waste, etc. can be used to prepare biochar, but the type of raw materials will affect the morphology of the biochar, including the appearance, surface morphology, and microstructure.

[0024] Furthermore, the particle size of the biochar is 10 to 50 μm. Micron-scale biochar is conducive to improving the uniformity and fluidity of the composite material, thereby improving the progress and surface quality of 3D printing, while reducing the possibility of clogging of the 3D printing nozzle, ensuring a smooth printing process.

[0025] Furthermore, the thermoplastic polymer is a thermoplastic polymer known in the art, including but not limited to one or more of thermoplastic polyurethane (TPU), polyester, polyamide, polyethylene, polypropylene, and polystyrene. Thermoplastic polymers are used because they have excellent flexibility, wear resistance, tear resistance, easy processability, resilience, environmental protection, etc., are suitable for printing of complex geometric shapes, and are ideal for preparing 3D printed composite wires. In some specific embodiments, the thermoplastic polymer is TPU. TPU has good mechanical properties and mechanical properties, and is wear-resistant and oil-resistant. Preferably, the hardness of the TPU is 85 to 98A. TPU of this hardness has a good balance between flexibility and rigidity, is easy to extrude and mold in 3D printing, and is suitable for printing of complex geometric shapes.

[0026] The present invention provides a method for preparing a biomass composite material, comprising the following steps:

[0027] (1) melt-blending the biochar and the thermoplastic polymer, cooling and shearing the mixture into masterbatch by a pelletizer;

[0028] (2) The masterbatch is melt-extruded through an extruder to obtain a biomass-based composite material.

[0029] The biomass charcoal in the present invention can be prepared by pyrolysis, and the obtained biomass charcoal is ground to reduce the particle size.

[0030] Furthermore, the biochar and the thermoplastic polymer are dried separately before use, and the drying method includes vacuum drying, airflow drying, microwave drying, etc. The purpose of drying is to remove moisture. Moisture will cause the biochar particles to agglomerate, and drying will help the biochar to be evenly dispersed as a filler; and in subsequent processing, the evaporation of moisture will produce bubbles or pores, affecting the performance of the material. Drying can not only avoid bubbles but also ensure the stability of processing conditions and reduce equipment clogging.

[0031] Furthermore, the melt blending is performed in a vacuum environment. The vacuum environment can effectively remove bubbles and volatiles in the material, reduce pores and defects in the finished product; and melt blending under vacuum conditions can avoid agglomeration and uneven dispersion of fillers, making the materials more evenly mixed; in addition, the vacuum environment can reduce external impurity contamination, ensure the purity of the material, and obtain high-quality 3D printing composite wire.

[0032] Furthermore, the melt blending is carried out at a temperature of 180 to 185° C. and for a time of 5 to 10 minutes.

[0033] Furthermore, the extruder is a single-screw extruder, and the extrusion temperature is set as follows: zone one temperature 25-35°C, zone two temperature 175-185°C, zone three temperature 165-175°C, zone four temperature 135-145°C; the inner diameter of the extrusion die is 1.8-2.1 mm, and the screw speed is 25-40 rpm / min.

[0034] The above-mentioned process parameters of melt blending and melt extrusion are set for TPU. When other types of thermoplastic polymers are used, corresponding process parameters of melt blending and melt extrusion can be set according to their physical properties.

[0035] The present invention also provides the use of the biomass legacy composite material as a 3D printing consumable.

[0036] Furthermore, the 3D printing is FDM type 3D printing. Using the biomass legacy composite material of the present invention as FDM type 3D printing consumables will not cause the printer nozzle to be blocked, and also has excellent thermal conductivity and good mechanical properties.

[0037] The TPU particles in the following examples and comparative examples were purchased from Dongguan Dingyu New Materials Co., Ltd.

[0038] Example 1

[0039] (1) The bamboo chips were placed in a vacuum drying oven at 60 °C and dried for 6 h. Then they were transferred to a tubular furnace and heated to 800 °C at a heating rate of 5 °C / min under a nitrogen atmosphere for 60 min. After being taken out, they were ground and passed through a 400-mesh sieve to obtain bamboo chip biochar.

[0040] (2) The TPU particles and bamboo biochar were dried in a vacuum drying oven at 60°C for 6 h, respectively. 99.5 parts of the dried TPU particles and 0.5 parts of the bamboo biochar were weighed and added into a double cone mixer, and melt-blended for 6 min at 183°C in a vacuum environment. The resulting blend was cooled and pelletized by a pelletizer to obtain a masterbatch.

[0041] (3) The masterbatch is melt-extruded through a multi-stage 3D printing consumables extrusion device to obtain 3D printing consumables with a diameter of 1.75±0.05mm, and rolled into bundles. The operating parameters of the single screw extruder in the multi-stage 3D printing consumables extrusion device are: the temperature of the first zone is 25°C, the temperature of the second zone is 185°C, the temperature of the third zone is 170°C, the temperature of the fourth zone is 140°C, the inner diameter of the extrusion die is 2.0mm, the screw speed is 30rpm / min; the temperature of the controllable constant temperature cooling water tank is 25°C; the traction speed of the crawler traction device is 3m / min.

[0042] Figure 1 This is the SEM image of the bamboo biochar prepared in this example. Figure 1 It can be seen that the size of bamboo chip biochar is small and uniform. Figure 2 This is the XRD pattern of the bamboo biochar prepared in this example. Figure 2 It can be seen that biochar was successfully prepared from bamboo chips by nitrogen pyrolysis.

[0043] Figure 3 This is a SEM image of the 3D printing consumables prepared in Example 1 of the present invention. Figure 3 It can be seen that the bamboo biochar is evenly inserted in the TPU, so it can be considered that the bamboo biochar is evenly dispersed in the TPU and is tightly compounded with the TPU, which shows that the present invention utilizes vacuum melt blending to ensure the uniform dispersion of the bamboo biochar in the TPU.

[0044] Example 2

[0045] The preparation method of bamboo biochar and 3D printing consumables in Example 2 is the same as that in Example 1, except that the amount of TPU particles and bamboo biochar in step (2) is adjusted to 99 parts of TPU particles and 1 part of bamboo biochar.

[0046] Example 3

[0047] The preparation method of bamboo biochar and 3D printing consumables in Example 3 is the same as that in Example 1, except that the amount of TPU particles and bamboo biochar in step (2) is adjusted to 98 parts of TPU particles and 2 parts of bamboo biochar.

[0048] Example 4

[0049] The preparation method of bamboo biochar and 3D printing consumables in Example 4 is the same as that in Example 1, except that the amount of TPU particles and bamboo biochar in step (2) is adjusted to 97 parts of TPU particles and 3 parts of bamboo biochar.

[0050] Comparative Example 1

[0051] The preparation method of the 3D printing consumables in Comparative Example 1 is the same as that in Example 1, except that only TPU particles are used to prepare the 3D printing consumables, that is, bamboo chip biochar is not used.

[0052] Comparative Example 2

[0053] The preparation method of the 3D printing consumables in Comparative Example 1 is the same as that in Example 1, except that the amounts of TPU particles and bamboo biochar in step (2) are adjusted to 95 parts of TPU particles and 5 parts of bamboo biochar.

[0054] Figure 4 This is a particle size distribution diagram of the bamboo charcoal biochar prepared in Example 1 of the present invention. Figure 4 It can be seen that the bamboo biochar is an irregular block with different lengths and widths. Therefore, when performing FDM type 3D printing, the present invention prints samples in two directions of 0° and 90°.

[0055] The 3D printing consumables prepared in the above embodiments and comparative examples were used for FDM type 3D printing. A cubic sample with a size of 8 mm × 8 mm × 1 mm was printed in the 0° direction. The surface quality of the sample was observed, and the thermal diffusivity, specific heat and density of the sample were tested. The test results are shown in Table 1.

[0056] Table 1

[0057]

[0058] The 3D printing consumables prepared in the above embodiments and comparative examples were used for FDM type 3D printing. A cubic sample with a size of 8 mm × 8 mm × 1 mm was printed at 90°. The surface quality of the sample was observed, and the thermal diffusivity, specific heat and density of the sample were tested. The test results are shown in Table 2.

[0059] Table 2

[0060]

[0061] It can be seen from Tables 1 and 2 that the thermal conductivity of the samples printed in the two directions gradually increases with the increase of the bamboo biochar content, and the thermal conductivity in the 90° direction is better than that in the 0° direction, indicating that the bamboo biochar prepared by the present invention is arranged in the 90° direction in the sample during printing and exhibits excellent thermal conductivity in this direction.

[0062] The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention. It should be understood by those skilled in the art that the present invention is not limited to the above embodiments. The above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which fall within the scope of the present invention to be protected. The scope of protection of the present invention is defined by the attached claims and their equivalents.

Claims

1. A biomass waste composite material, characterized in that: The biomass legacy composite material comprises the following components in parts by weight: 97 to 99.5 parts of thermoplastic polymer and 0.5 to 3 parts of biomass charcoal.

2. The biomass waste composite material according to claim 1, characterized in that: The raw materials for preparing the biomass charcoal are one or more of bamboo chips, rice husks, straw, wood chips and sawdust.

3. The biomass waste composite material according to claim 1, characterized in that: The particle size of the biomass charcoal is 10 to 50 μm.

4. The biomass waste composite material according to claim 1, characterized in that: The thermoplastic polymer is one or more of TPU, polyester, polyamide, polyethylene, polypropylene, and polystyrene; preferably, the thermoplastic polymer is TPU; more preferably, the hardness of the TPU is 85-98A.

5. The method for preparing the biomass waste composite material according to any one of claims 1 to 4, characterized in that: The following steps are involved: (1) melt-blending the biochar and the thermoplastic polymer, cooling and shearing the mixture into masterbatch by a pelletizer; (2) The masterbatch is melt-extruded through an extruder to obtain a biomass-based composite material.

6. The preparation method according to claim 5, characterized in that: The biochar and the thermoplastic polymer are dried separately before use.

7. The preparation method according to claim 5, characterized in that: The melt blending is carried out under a vacuum environment; preferably, the melt blending temperature is 180-185° C. and the time is 5-10 min.

8. The preparation method according to claim 5, characterized in that: The extruder is a single-screw extruder, and the extrusion temperature is set as follows: zone 1 temperature 25-35°C, zone 2 temperature 175-185°C, zone 3 temperature 165-175°C, zone 4 temperature 135-145°C; the inner diameter of the extrusion die is 1.8-2.1 mm, and the screw speed is 25-40 rpm / min.

9. Use of the biomass legacy composite material according to any one of claims 1 to 4 or the biomass legacy composite material prepared by the preparation method according to any one of claims 5 to 8 as a 3D printing consumable.

10. The use according to claim 9, characterized in that: The 3D printing is FDM type 3D printing.

Images