Graphene-containing polyurethane composite material with light-heat-electricity-heat conversion and hydrophobic surface structure as well as preparation method and application of graphene-containing polyurethane composite material

Abstract

The invention discloses a graphene-containing polyurethane composite material with a light-heat-electricity-heat conversion and hydrophobic surface structure as well as a preparation method and application of the graphene-containing polyurethane composite material. The composite material sequentially comprises a pure polyurethane layer, a graphene-polyurethane composite material layer and a hydrophobic surface with a rough micro-nano structure from bottom to top. The bottom of the composite material is a pure polyurethane layer, so that efficient heat collection, temperature rise and heat slow release can be realized. According to the preparation method disclosed by the invention, the graphene is directionally arranged in the process of printing the molten graphene-polyurethane composite material layer by utilizing an FDM 3D printing process, so that the obtained composite material layer has a high anisotropic heat conductivity ratio. According to the method, the surface of the composite material is subjected to laser induction treatment by using high-energy beam irradiation, so that hydrophobic chemical components and chemical bonds on the surface of the material are increased, and a rough micro-nano porous structure generated on the surface of the material under the action of laser is combined, so that the composite material has a hydrophobic characteristic and has extremely high application potential in the field of all-weather deicing / anti-icing application.

Description

Technical Field

[0001] The present invention belongs to the technical field of additive manufacturing, and specifically relates to a polyurethane composite material containing graphene with photothermal and electrothermal conversion and a hydrophobic surface structure, and a preparation method and application thereof. Background Art

[0002] Solar energy, as a clean, sustainable and widely available resource, is gaining increasing attention as a means of anti-icing and de-icing, especially in the context of global carbon neutrality and energy transition goals. Solar thermal conversion technology, by directly converting solar energy into thermal energy, has shown potential in improving conversion efficiency, especially by extending the solar spectral response range from ultraviolet (UV) to visible and infrared (IR) ranges.

[0003] Graphene, with its unique electronic band structure, can efficiently absorb a wide spectrum of light, including visible light, infrared light, and microwaves, and convert these wavelengths of light into heat energy. Its unique electronic structure not only arranges carbon atoms into a honeycomb structure, but also gives graphene excellent thermal and electrical conductivity properties. These unique light absorption and thermal properties make graphene a promising material for solar thermal conversion and photothermal deicing applications. In addition, the in-plane thermal conductivity of graphene sheets is extremely high, ranging from 1000 to 3000 W / (m·K), while its out-of-plane thermal conductivity is about 5 W / (m·K). In order to effectively utilize the anisotropic thermal properties of graphene, it is crucial to orient it during the manufacturing process.

[0004] In addition to photothermal conversion, hydrophobicity also plays a vital role in anti-icing and de-icing applications. An effective hydrophobic surface can minimize the retention of water droplets, thereby reducing the possibility of ice formation and facilitating the shedding of ice.

[0005] How to make full use of the properties of graphene to prepare a product with excellent photothermal and electrothermal conversion performance and apply it in the field of anti-icing and de-icing has great research value. Summary of the invention

[0006] The purpose of the present invention is to fill the gap in the prior art field and provide a polyurethane composite material containing graphene with photothermal and electrothermal conversion and a hydrophobic surface structure, as well as a preparation method and application thereof.

[0007] To achieve the above object, the technical solution adopted by the present invention is:

[0008] A method for preparing a polyurethane composite material containing graphene having photothermal and electrothermal conversion and a hydrophobic surface structure, comprising the following steps:

[0009] The polyurethane and graphene sheets are dried and mixed uniformly to prepare a blend; preferably, the polyurethane is a thermal polyurethane TPU particle with a hardness of 95A; the graphene sheet is a two-dimensional single-layer graphene, a multi-layer graphene, a single-crystal graphene, a polycrystalline graphene or a combination thereof, with an average in-plane size of about 30 μm to 50 μm; the mass ratio of polyurethane to graphene sheets in the blend is 7:3; the preparation of the blend is completed using a double-cone mixer, and the method is: using a double-cone mixer to melt-mix the polyurethane and graphene sheets under a vacuum environment, the melt-mixing temperature is 180 to 185°C, and the mixing time is 6 to 10 minutes. More preferably, the melt-mixing temperature is 185°C and the mixing time is 10 minutes.

[0010] The blend is sheared into a mixture masterbatch, and the mixture masterbatch is melt-mixed and extruded through a multi-stage 3D printing consumables extrusion device to prepare a graphene-polyurethane 3D printing consumables; the multi-stage 3D printing consumables extrusion device adopts the existing technology, which includes a twin-screw mixer, a screw extruder, a temperature-controllable cooling water tank, a crawler traction device and a micro-wire collection and discharge device; the screw extruder is a single screw extruder; preferably, the extrusion temperature of the single screw extruder is set to: the temperature of the first zone is 25 to 35°C, the temperature of the second zone is 175 to 185°C, the temperature of the third zone is 165 to 175°C, and the temperature of the fourth zone is 135 to 145 ℃, the inner diameter of the extrusion die of the single screw extruder is 1.5 to 2.5 mm, and the screw speed is 30 to 100 rpm / min; further preferably, the temperature of zone 1 is 35℃, the temperature of zone 2 is 185℃, the temperature of zone 3 is 175℃, the temperature of zone 4 is 145℃, the inner diameter of the extrusion die of the single screw extruder is 2 mm, and the screw speed is 30rpm / min; the traction speed of the crawler traction device is 1 to 5m / min; the temperature of the controllable constant temperature cooling water tank is 20 to 30℃; preferably, the traction speed of the crawler traction device is 3m / min; the temperature of the controllable constant temperature cooling water tank is 30℃.

[0011] The polyurethane is sheared into polyurethane masterbatches by a pelletizer, and the polyurethane masterbatches are melt-mixed and extruded through a multi-stage 3D printing consumables extrusion device to prepare pure polyurethane 3D printing consumables;

[0012] The graphene-polyurethane 3D printing consumables and the pure polyurethane 3D printing consumables are printed by a 3D printer into an intermediate product with a bottom layer of pure polyurethane and an upper layer of a graphene-polyurethane composite material layer; the 3D printer is an extrusion-based 3D printer with a nozzle diameter of 0.2 to 0.8 mm, a layer height of 0.1 mm to 0.5 mm per layer, a printing speed of 10 mm / s to 100 mm / s, a hot end nozzle temperature of 200°C to 250°C during printing, and a printer hot bed temperature of 50°C to 80°C; preferably, the 3D printer selects a fused deposition modeling (FDM) 3D printer with a nozzle diameter of 0.4 mm, a layer height of 0.1 mm per layer, a printing speed of 10 mm / s, a hot end nozzle temperature of 230°C during printing, and a hot bed temperature of 70°C during printing.

[0013] The upper surface of the intermediate product is laser-induced treated by irradiating with a high-energy beam in an air atmosphere to obtain the final product. Preferably, the high-energy beam is a laser or an electron beam. The light source of the laser is a combination of one or more of a solid-state laser, a semiconductor laser, a fiber laser, and a gas laser; preferably, the laser wavelength is 1 μm to 20 μm, the power is 1 W to 80 W, the pulse frequency is 1 kHz to 100 kHz, and the scanning speed is 0 mm / s to 500 mm / s; preferably, the laser is selected as CO 2 Infrared laser, wavelength 10.6μm, power 6W, pulse frequency 20kHz, scanning speed 200mm / s. The electron beam line spacing is 0mm to 10mm, the focal length is 10cm to 100cm, the power is 1W to 100W, and the scanning speed is 0mm / s to 500mm / s; preferably, the electron beam line spacing is 0.1mm, the focal length is 50cm, the power is 48W, and the scanning speed is 200mm / s.

[0014] A polyurethane composite material containing graphene with photothermal and electrothermal conversion and a hydrophobic surface structure is prepared according to the preparation method described above. The polyurethane composite material containing graphene is composed of a pure polyurethane layer, a graphene-polyurethane composite material layer and a hydrophobic surface with a rough micro-nano structure from bottom to top. The polyurethane composite material has an electrical conductivity of 0.1S / m to 0.5S / m and a surface roughness of 6 to 8μm, and can be used for anti-icing and de-icing.

[0015] The present invention has the following beneficial effects:

[0016] (1) The present invention utilizes the FDM 3D printing process to orient the graphene during the FDM 3D printing of the fused graphene-polyurethane composite material layer, thereby making the obtained graphene-polyurethane composite material layer have a high anisotropic thermal conductivity ratio.

[0017] (2) The bottom of the composite material prepared by the present invention is a pure polyurethane layer, which can achieve efficient heat collection and temperature increase and slow heat release.

[0018] (3) The present invention uses high-energy beam irradiation to perform laser-induced treatment on the surface of the composite material, thereby degrading the polyurethane and generating a rough micro-nano porous hydrophobic structure on the surface of the loaded hydrophobic graphene sheet material. As a result, the hydrophobic components on the surface of the material are increased, making it hydrophobic, and having extremely high application potential in the field of all-weather deicing / anti-icing applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a SEM image of the upper surface of the product prepared in Example 1.

[0020] Figure 2 This is a diagram of the hydrophobic angle of the upper surface of the product prepared in Example 1.

[0021] Figure 3 This is a photothermal cycle temperature rise and fall curve of the product prepared in Example 1.

[0022] Figure 4 This is the electric heating cycle temperature rise and fall curve of the product prepared in Example 1. DETAILED DESCRIPTION

[0023] In order to make the purpose, technical solutions and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with the accompanying drawings and Examples. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. It should be noted that the reagents and raw materials used in the following examples are all commercially available products and are commercially available.

[0024] The models and suppliers of the reagents used in this example are as follows:

[0025] Thermoplastic polyurethane particles, hardness 95A, supplier is Dingyu New Materials Co., Ltd.; graphene nanosheets, 20-50μm, supplier is Xiamen Kaina Graphene Technology Co., Ltd.

[0026] The above reagents are only for illustrating the sources and components of the reagents used in the experiments of the present invention so as to fully disclose the information, and do not mean that the present invention cannot be realized by using other similar reagents or reagents provided by other suppliers.

[0027] Example 1

[0028] A method for preparing a polyurethane composite material containing graphene having photothermal and electrothermal conversion and a hydrophobic surface structure, comprising the following steps:

[0029] (1) Thermoplastic polyurethane particles and two-dimensional multilayer graphene sheets were dried in a vacuum oven at 80° C. for 4 h; the dried materials were weighed according to the mass percentage formula, namely 70 parts of thermoplastic polyurethane particles and 30 parts of two-dimensional graphene sheets, and added into a double cone mixer, and melt-mixed for 10 min in a vacuum environment at 185° C. to prepare a blend.

[0030] (2) The blend is sheared into a mixture masterbatch by a pelletizer, and the mixture masterbatch is extruded through a multi-stage 3D printing consumables extrusion device to obtain graphene-polyurethane 3D printing consumables with a diameter of 1.75mm±0.05mm and rolled into bundles. The screw extruder in the multi-stage 3D printing consumables extrusion device is a single screw extruder, and the extrusion temperature of the single screw extruder is set as follows: the temperature of the first zone is 35℃, the temperature of the second zone is 185℃, the temperature of the third zone is 175℃, and the temperature of the fourth zone is 145℃. The inner diameter of the extrusion die of the single screw extruder is 2.0mm, and the screw speed is 30rpm / min. The traction speed of the crawler traction device is 3m / min, and the temperature of the controllable constant temperature cooling water tank is 30℃.

[0031] (3) Shearing the polyurethane into polyurethane masterbatches, melt-mixing and extruding the polyurethane masterbatches through a multi-stage 3D printing consumables extrusion device to prepare pure polyurethane 3D printing consumables; the process parameter setting of the multi-stage 3D printing consumables extrusion device is the same as that in step (2).

[0032] (4) Printing graphene-polyurethane 3D printing consumables and pure polyurethane 3D printing consumables through a fused deposition modeling (FDM) 3D printer to produce an intermediate product with a bottom layer of pure polyurethane and an upper layer of graphene-polyurethane composite material; the printer parameters are set as follows: the printer nozzle diameter is 0.4 mm, the layer height of each layer during printing is 0.1 mm, the printing speed is 10 mm / s, the hot end nozzle temperature is 230° C., and the printer hot bed temperature is 70° C.

[0033] (5) placing the intermediate product obtained in step (4) in an air environment using CO 2 Infrared laser surface treatment, CO 2 The infrared laser wavelength is 10.6 μm, the power is 6 W, the pulse frequency is 20 kHz, and the scanning speed is 200 mm / s to obtain the final product.

[0034] Figure 1 This is the SEM image of the upper surface of the product prepared in Example 1. It can be seen that after the laser treatment, the surface graphene sheets of the material are exposed and the direct contact is closer, thus forming a tighter thermal and electrical conductive network.

[0035] Figure 2This is a diagram of the upper surface hydrophobic angle of the product prepared in Example 1. The surface hydrophobic angle of the material is greater than 120°, and the surface has good hydrophobicity.

[0036] Figure 3 This is a photothermal cycle heating and cooling curve of the product prepared in Example 1. From the results of multiple heating and cooling, it can be seen that the prepared composite material has small temperature fluctuation, fast heating speed, and good photothermal cycle thermal stability.

[0037] Figure 4 This is an electric heating cycle heating and cooling curve of the product prepared in Example 1. From the results of multiple heating and cooling at a safe voltage of 20V, it can be seen that the prepared composite material has a fast electric heating response, a high final temperature, and good electric heating cycle thermal stability.

[0038] It should be noted that, for the process parameters in Example 1, for example:

[0039] The parameters that can be adjusted in step (2) include, but are not limited to: the extrusion temperature of the screw extruder, the traction speed of the crawler traction device, the temperature of the controllable constant temperature cooling water tank, one or more thereof, and their combinations.

[0040] In step (4), the parameters that can be adjusted include, but are not limited to: printer nozzle diameter, layer height during printing, printing speed, hot end nozzle temperature, printer hot bed temperature, etc., or one or more thereof, and their combinations.

[0041] In step (5), the parameters that can be adjusted include but are not limited to: CO 2 Infrared laser power, frequency, spot size, focal length, scanning speed, etc., or a combination thereof.

[0042] Those skilled in the art can make appropriate selections of the above process parameters according to actual needs, and all of them can achieve the purpose of the present invention.

[0043] Obviously, the described embodiments are only some embodiments of the present invention, but not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

Claims

1. A method for preparing a polyurethane composite material containing graphene with photothermal and electrothermal conversion and a hydrophobic surface structure, characterized in that: The following steps are involved: The polyurethane and the graphene sheets are dried and uniformly mixed to prepare a blend; The blend is sheared into a mixture masterbatch, and the mixture masterbatch is melt-mixed and extruded through a multi-stage 3D printing consumables extrusion device to prepare a graphene-polyurethane 3D printing consumables; The polyurethane is sheared into polyurethane masterbatches, and the polyurethane masterbatches are melt-mixed and extruded through a multi-stage 3D printing consumables extrusion device to prepare pure polyurethane 3D printing consumables; Printing the graphene-polyurethane 3D printing consumables and the pure polyurethane 3D printing consumables by a 3D printer into an intermediate product having a bottom layer of pure polyurethane and an upper layer of a graphene-polyurethane composite material layer; The upper surface of the intermediate product is laser-induced treated by high-energy beam irradiation in an air atmosphere to obtain a final product.

2. The preparation method according to claim 1, characterized in that: The polyurethane is thermoplastic polyurethane particles with a hardness of 95A.

3. The preparation method according to claim 1, characterized in that: The graphene sheet is at least one of two-dimensional single-layer graphene, multi-layer graphene, single-crystal graphene, and polycrystalline graphene.

4. The preparation method according to claim 1, characterized in that: The mass ratio of polyurethane to graphene sheets in the blend is 7:

3.

5. The preparation method according to claim 1, characterized in that: The preparation of the blend is completed by using a double cone mixer, and the method is: using a double cone mixer to melt mix the polyurethane and graphene sheets under a vacuum environment, the melt mixing temperature is 180 to 185° C., and the mixing time is 6 to 10 minutes.

6. The preparation method according to claim 1, characterized in that: The multi-stage 3D printing consumables extrusion device includes a twin-screw mixer, a screw extruder, a temperature-controllable cooling water tank, a crawler-type traction device and a micro-wire collection and discharge device; the screw extruder is a single-screw extruder.

7. The preparation method according to claim 1, characterized in that: The 3D printer is a dual-nozzle fused deposition modeling 3D printer.

8. The preparation method according to claim 1, characterized in that: The high energy beam is one of a laser beam and an electron beam.

9. A polyurethane composite material containing graphene with photothermal and electrothermal conversion and a hydrophobic surface structure, characterized in that: The invention relates to a novel nanostructured carbon foam prepared according to the preparation method according to any one of claims 1 to 8.

10. The polyurethane composite material according to claim 9 is used for anti-icing and de-icing.

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