Titanium nitride / thermoplastic polyurethane composite 3D printing consumable and preparation method thereof

Abstract

The invention discloses a titanium nitride / thermoplastic polyurethane composite 3D printing consumable and a preparation method thereof.The preparation method comprises the following steps that thermoplastic polyurethane particles and titanium nitride nanoparticles are mixed after being dried, and a blended material is obtained; cooling the co-mixture, and shearing the co-mixture into master batches; and extruding the master batch through a multi-stage 3D printing consumable extrusion device to obtain the titanium nitride / thermoplastic polyurethane composite 3D printing consumable. The prepared titanium nitride / thermoplastic polyurethane composite 3D printing consumable has excellent heat-conducting property and good mechanical property, meanwhile, the viscosity is low after melting, the melt fluidity is good, a nozzle of a printer is not prone to being blocked, the preparation method is easy to operate, raw materials are easy to obtain, popularization is convenient, and the application prospect is wide. 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 particularly to a titanium nitride / thermoplastic polyurethane composite 3D printing consumable and a preparation method thereof. Background Art

[0002] 3D printing technology is a technology for manufacturing three-dimensional objects by layer-by-layer stacking of materials, also known as additive manufacturing. With its flexibility, high efficiency and innovation, 3D printing technology is widely used in future manufacturing, medical field, aerospace, construction industry and education field, etc. These advantages make 3D printing an important technology in these fields, promoting the transformation and innovation of production methods.

[0003] According to the working principle, 3D printing technology can be divided into fused deposition modeling (FDM), stereolithography apparatus (SLA) and digital light processing (DLP), etc. Among them, FDM is widely used because of its low cost, simple operation, diverse materials and large-size printing and other advantages. At the same time, the synthesis and application of printing consumables are one of the core technologies of FDM-type 3D printing technology. Currently, the 3D printing materials widely used on the market all have problems such as excessive brittleness, poor durability, easy deformation after printing, and generation of toxic gases during printing, which limit their popularization and application. With the continuous development of technology, the performance requirements for materials are also constantly increasing, and it is increasingly difficult for single polymer materials to meet the requirements. Therefore, it is urgent to find composite printing consumables with better performance. Summary of the Invention

[0004] Based on this, aiming at the problems existing in the current prior art, the purpose of the present invention is to provide a titanium nitride / thermoplastic polyurethane composite 3D printing consumable and a preparation method thereof. The prepared titanium nitride / thermoplastic polyurethane composite 3D printing consumable has excellent thermal conductivity and good mechanical properties. At the same time, the preparation method of the present invention is simple, the materials are easy to obtain, and the viscosity after melting is low, the melt fluidity is good, and it will not cause blockage of the printer nozzle, which is convenient for popularization. Therefore, it has a wide application prospect in the field of additive manufacturing based on photothermal conversion applications.

[0005] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0006] A preparation method of a titanium nitride / thermoplastic polyurethane composite 3D printing consumable, comprising the following steps:

[0007] (1) Put the thermoplastic polyurethane (TPU) particles and titanium nitride nanoparticles into a vacuum drying oven respectively, and dry them at a temperature of 60 - 80°C for 6 - 8 hours; after weighing the thermoplastic polyurethane particles and titanium nitride nanoparticles according to the mass ratio of (95 - 99.5):(0.5 - 5), add them into a double-cone mixer, and melt and mix them at 180 - 185°C for 6 - 10 minutes under a vacuum environment to obtain a blend. After cooling the blend, cut it into masterbatch by a pelletizer.

[0008] (2) Extrude the masterbatch through a multi-stage 3D printing consumable extrusion device to obtain a titanium nitride / thermoplastic polyurethane composite 3D printing consumable. The multi-stage 3D printing consumable extrusion device adopts the existing technology and includes a twin-screw mixer, a single-screw extruder, a temperature-controlled cooling water tank, a crawler traction device, and a micro wire winding and discharging device; the single-screw extruder has an extrusion temperature set as follows: the temperature of the first zone is 25 - 35°C, the temperature of the second zone is 175 - 185°C, the temperature of the third zone is 165 - 175°C, and the temperature of the fourth zone is 135 - 145°C; the inner diameter of the extrusion die orifice of the single-screw extruder is 2.0 mm, and the screw rotation speed is 30 rpm / min. The temperature of the temperature-controlled constant-temperature cooling water tank 200 is 20 - 30°C; the traction speed of the crawler traction device 300 is 3 m / min.

[0009] Compared with the prior art, the present invention has the following beneficial effects:

[0010] 1. The present invention uses thermoplastic polyurethane particles with good processability and excellent comprehensive properties as the matrix material, and prepares a high thermal conductivity polyurethane-based 3D printing consumable by combining thermoplastic polyurethane particles with titanium nitride nanoparticles with excellent thermal conductivity: on the one hand, as a nanomaterial with excellent thermal conductivity, with the increase of the content of titanium nitride nanoparticles, the 3D printing consumable shows better thermal conductivity; on the other hand, thermoplastic polyurethane particles have good mechanical and mechanical properties, and are wear-resistant and oil-resistant. Combining with the excellent mechanical and mechanical properties of TPU, with the increase of the content of titanium nitride nanoparticles, the 3D printing consumable can still maintain good processability and printing smoothness.

[0011] 2. The present invention uses a double-cone mixer for vacuum mixing and melt blending, which ensures good and uniform dispersion of titanium nitride nanoparticles in the polyurethane matrix, effectively improves the thermal conductivity effect of the consumable, and is not easy to block the printing nozzle at the same time. The preparation method is simple in operation and control, suitable for large-scale industrial production, and has broad application prospects.

[0012] 3. The printing consumables prepared by the present invention have excellent thermal conductivity and good mechanical properties. At the same time, they have a low viscosity after melting, good melt fluidity, and are not easily blocked by the printer nozzle. Moreover, the preparation method of the present invention is simple in operation and the raw materials are easily available, which is convenient for popularization. Therefore, it has a wide application prospect in the field of additive manufacturing based on thermal management applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 It is a transmission electron microscope (TEM) image of the titanium nitride nanoparticles used as raw materials in the present invention.

[0014] Figure 2 It is a thermogravimetric graph of the titanium nitride / thermoplastic polyurethane composite 3D printing consumables prepared in Example 1 of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0015] In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention. It should be noted that the reagents and raw materials used in the following embodiments are all commercially available products and can be obtained through commercial purchase.

[0016] The models and suppliers of the reagents used in this embodiment are as follows:

[0017] TPU particles, hardness 95A, supplied by Dingyu New Materials Co., Ltd.

[0018] The above reagents are only used to illustrate the sources and components of the reagents used in the experiments of the present invention for full disclosure, and do not mean that the present invention cannot be realized by using other similar reagents or reagents provided by other suppliers.

[0019] Example 1

[0020] A preparation method of a titanium nitride / thermoplastic polyurethane composite 3D printing consumable, comprising the following steps:

[0021] (1) After drying the TPU particles and titanium nitride nanoparticles in a vacuum oven at 60°C for 6 hours, 99.5 parts of the dried TPU particles and 0.5 part of the titanium nitride nanoparticles are weighed by mass and added to a double-cone mixer, and melted and mixed in a vacuum environment at 183°C for 6 minutes to obtain a blend. After cooling the obtained blend, it is pelletized by a pelletizer to obtain masterbatch.

[0022] (2) The masterbatch is extruded through a multi-stage 3D printing consumable extrusion device to obtain a titanium nitride / thermoplastic polyurethane composite 3D printing consumable (T-TPU) with a diameter of 1.75 mm ± 0.05 mm, and it is wound into bundles. Among them: the parameters of the single-screw extruder in the multi-stage 3D printing consumable 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 orifice of the single-screw extruder is 2.0 mm, and the screw rotation speed is 30 rpm / min; the temperature of the controllable constant-temperature cooling water tank is 25 °C; the traction speed of the caterpillar traction device is 3 m / min.

[0023] Figure 1 This is the transmission electron microscope (TEM) image of the titanium nitride nanoparticles used in the present invention. From Figure 1 it can be seen that the titanium nitride nanoparticles have regular and uniform morphologies, and the average particle size is mainly distributed in the range of 10 - 20 nm. Figure 2 This is the thermogravimetric graph of the titanium nitride / thermoplastic polyurethane composite 3D printing consumable prepared in Example 1 of the present invention. It is the thermogravimetric graph obtained from five randomly intercepted segments of materials (T-TPU-1 to T-TPU-5) during the preparation process. From the graph, it can be seen that the titanium nitride content of each segment is the same. Therefore, it can be considered that the titanium nitride nanoparticles are evenly dispersed in the polyurethane matrix and are closely combined with the polyurethane, indicating that the use of double-cone vacuum mixing and melt blending ensures the good and uniform dispersion of the titanium nitride nanoparticles in the polyurethane matrix.

[0024] Example 2

[0025] A preparation method of a titanium nitride / thermoplastic polyurethane composite 3D printing consumable, comprising the following steps:

[0026] (1) After drying the TPU particles and titanium nitride nanoparticles in a 60 °C vacuum oven for 6 h, 99 parts by mass of the dried TPU particles and 1 part by mass of the titanium nitride nanoparticles are weighed and added to a double-cone mixer, and melt mixing is carried out in a vacuum environment at 183 °C for 6 min to obtain a blend. After the obtained blend is cooled, it is pelletized by a pelletizer to obtain a masterbatch.

[0027] (2) The masterbatch is extruded through a multi-stage 3D printing consumable extrusion device to obtain a titanium nitride / thermoplastic polyurethane composite 3D printing consumable with a diameter of 1.75 mm ± 0.05 mm, and it is wound into bundles. Among them: the parameters of the single-screw extruder in the multi-stage 3D printing consumable 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 orifice of the single-screw extruder is 2.0 mm, and the screw rotation speed is 30 rpm / min; the temperature of the controllable constant-temperature cooling water tank is 25 °C; the traction speed of the caterpillar traction device is 3 m / min.

[0028] Example 3

[0029] A preparation method of a titanium nitride / thermoplastic polyurethane composite 3D printing consumable, comprising the following steps:

[0030] (1) After drying TPU particles and titanium nitride nanoparticles in a vacuum oven at 60 °C for 6 h, 98 parts by mass of the dried TPU particles and 2 parts by mass of the titanium nitride nanoparticles are weighed and added to a double-cone mixer, and melt-mixed in a vacuum environment at 183 °C for 6 min to obtain a blend. After cooling the obtained blend, it is pelletized by a pelletizer to obtain masterbatch.

[0031] (2) The masterbatch is extruded through a multi-stage 3D printing consumable extrusion device to obtain a titanium nitride / thermoplastic polyurethane composite 3D printing consumable with a diameter of 1.75 mm ± 0.05 mm, and it is wound into a bundle. Among them: the parameters of the single-screw extruder in the multi-stage 3D printing consumable 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 orifice of the single-screw extruder is 2.0 mm, and the screw speed is 30 rpm / min; the temperature of the controllable constant-temperature cooling water tank is 25 °C; the traction speed of the crawler-type traction device is 3 m / min.

[0032] Example 4

[0033] A preparation method of a titanium nitride / thermoplastic polyurethane composite 3D printing consumable, comprising the following steps:

[0034] (1) After drying TPU particles and titanium nitride nanoparticles in a vacuum oven at 60 °C for 6 h, 95 parts by mass of the dried TPU particles and 5 parts by mass of the titanium nitride nanoparticles are weighed and added to a double-cone mixer, and melt-mixed in a vacuum environment at 183 °C for 6 min to obtain a blend. After cooling the obtained blend, it is pelletized by a pelletizer to obtain masterbatch.

[0035] (2) The masterbatch is extruded through a multi-stage 3D printing consumable extrusion device to obtain a titanium nitride / thermoplastic polyurethane composite 3D printing consumable with a diameter of 1.75 mm ± 0.05 mm, and it is wound into a bundle. Among them: the parameters of the single-screw extruder in the multi-stage 3D printing consumable 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 orifice of the single-screw extruder is 2.0 mm, and the screw speed is 30 rpm / min; the temperature of the controllable constant-temperature cooling water tank is 25 °C; the traction speed of the crawler-type traction device is 3 m / min.

[0036] Comparative Example

[0037] This comparative example provides a polyurethane-based 3D printing consumable, and its preparation method comprises the following steps:

[0038] (1) After drying the TPU particles in a vacuum oven at 60 °C for 6 h, 100 parts by mass of the dried TPU particles were weighed and added to a double-cone mixer, and melted in a vacuum environment at 183 °C for 6 min to obtain a blend. After cooling the obtained blend, it was pelletized by a pelletizer to obtain masterbatch.

[0039] (2) The masterbatch was extruded through a multi-stage 3D printing consumable extrusion device to obtain a titanium nitride / thermoplastic polyurethane composite 3D printing consumable with a diameter of 1.75 mm ± 0.05 mm, and it was wound into bundles. Among them: the parameters of the single-screw extruder in the multi-stage 3D printing consumable extrusion device were: the temperature of the first zone was 25 °C, the temperature of the second zone was 185 °C, the temperature of the third zone was 170 °C, the temperature of the fourth zone was 140 °C, the inner diameter of the extrusion die orifice of the single-screw extruder was 2.0 mm, and the screw speed was 30 rpm / min; the temperature of the controllable constant-temperature cooling water tank was 25 °C; the traction speed of the crawler-type traction device was 3 m / min.

[0040] Performance Test

[0041] The 3D printing consumables prepared in Examples 1-4 and the comparative example were printed into cube samples with a length of 8 mm, a width of 8 mm, and a height of 1 mm at 230 °C using a 3D printing device, and the thermal diffusivity, specific heat, and density of the cube samples were tested. The test results are shown in Table 1.

[0042] Table 1 Test Results of Sample Performance

[0043]

[0044] It can be seen from the results in Table 1 that as the content of titanium nitride nanoparticles increases, the thermal diffusivity of the sample gradually increases, indicating that the titanium nitride / thermoplastic polyurethane composite 3D printing consumable prepared by the present invention exhibits excellent thermal conductivity.

[0045] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as the scope described in this specification.

[0046] The above-described embodiments only represent several implementation manners of the present invention, and their descriptions are relatively specific and detailed, but they should not be construed as limiting the scope of the invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the present invention patent should be subject to the appended claims.

Claims

1. A method for preparing titanium nitride / thermoplastic polyurethane composite 3D printing consumables, characterized in that: The following steps are involved: Thermoplastic polyurethane particles and titanium nitride nanoparticles are dried and then mixed to obtain a blend; the blend is cooled and then sheared into master batches; The masterbatch is extruded through a multi-stage 3D printing consumables extrusion device to obtain titanium nitride / thermoplastic polyurethane composite 3D printing consumables.

2. The preparation method according to claim 1, characterized in that: The mass ratio of the thermoplastic polyurethane particles to the titanium nitride nanoparticles is (95-99.5): (0.5-5).

3. The preparation method according to claim 1, characterized in that: The size of the titanium nitride nanoparticles is 10-20 nm.

4. The preparation method according to claim 1, characterized in that: The hardness of the thermoplastic polyurethane particles is 85-95A.

5. The preparation method according to claim 1, characterized in that: The drying is completed in a vacuum drying oven, the drying temperature is 60-80° C., and the drying time is 6-8 hours.

6. The preparation method according to claim 1, characterized in that: The mixing method is: adding thermoplastic polyurethane particles and titanium nitride nanoparticles into a double cone mixer, and melting and mixing them under a vacuum environment.

7. The preparation method according to claim 6, characterized in that: The temperature of the melt mixing is 180-185° C. and the time is 6-10 minutes.

8. 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 traction device and a micro-wire collection and discharge device; the screw extruder is a single-screw extruder, and the extrusion temperature of the single-screw extruder is set to: 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 of the single-screw extruder is 2.0 mm, and the screw speed is 30 rpm / min.

9. The preparation method according to claim 1, characterized in that: The cooling is cooling to 20-30°C.

10. A titanium nitride / thermoplastic polyurethane composite 3D printing consumable, characterized in that: The invention discloses a novel novel nanostructured carbon foam prepared by the preparation method described in any one of claims 1 to 9.

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