1. Introduction
Additive manufacturing (AM) is a process in which 3D objects are built layer by layer from a 3D digital model [
1]; it is commonly known as 3D printing. The manufacturing process begins with the creation of the 3D model usually using computer-aided design (CAD) software [
2,
3,
4] or by scanning the existing object using 3D scanners [
5]. While the scanners limit the 3D model to the external appearance of the existing object, the CAD software offers a much wider range of possibilities, such as relatively easy modification of the model and adaptation of both the external and internal shape and structure of the object to the application and manufacturing requirements [
5]. With the rapid progress of additive manufacturing [
6,
7], the accompanying software is also evolving, developing and becoming more user-friendly and easier to use. Thus, it is possible to choose any from the wide range of CAD software (e.g., FreeCAD, AutoCAD, Catia, Solidworks, Blender, and Autodesk Fusion 360). This manufacturing method offers the possibility of creating highly complex geometries [
8,
9] with high quality and accuracy at an affordable price [
10]. This is not possible with conventional methods.
One of the most well-known and widely used additive manufacturing technologies is fused filament fabrication (FFF) [
5]. This technology is also often termed as fused deposition modelling (FDM) [
11]. The 3D printer’s main parts are an extruder and a heated bed. FFF uses thermoplastic polymer materials in the form of a 1.75mm- or 3mm-diameter filament. The material is extruded through the nozzle onto the heated bed layer by layer [
5,
12].
Before the actual 3D printing, the model created in the CAD software must be translated into code that the 3D printer can process. This is conducted in the so-called slicer software. In the slicer software, print settings are defined, such as the nozzle temperature, the bed temperature, the print speed, the cooling fan speed, the infill shape and density, and many more. In addition, the support structures required for successful prints are defined and created for the overhanging parts of the model [
12].
Polymer matrices offer a cost-effective option for materials that have a wide range of capabilities regarding physico-chemical properties and configuration options. It is also relatively easy to modify the properties of polymer materials by making composites, i.e., by the addition of the fillers, which gives them a much broader range of applications. Fillers can be added to the polymer matrix in various forms and contents. Due to their effects on the properties of the composite material, it is important to achieve good mixing and homogeneity [
13,
14,
15,
16,
17]. The addition of fillers, especially more than 10 wt%, poses a number of problems for this technology when 3D printing the composite material. Surface roughness, low detail quality, and nozzle clogging are some of the most common [
18]. For this reason, other 3D-printing technologies such as SLA (stereolithography) and DLP (digital light processing) are often used for composites containing higher filler content (>10 wt%) [
19,
20]. One of the well-known fillers is titanium dioxide (TiO
2).
Carbon nanotubes (CNTs) are an allotropic modification of carbon that have a cylindrical nanostructure. They possess a variety of advantageous properties such as low mass, high electrical and thermal conductivity, excellent mechanical properties, etc. [
21], but have no photocatalytic properties. CNTs have been shown to enhance the photocatalytic activity of TiO
2 due to a drastic synergistic effect as described in the work of Ahmmad et al. [
22]. The photocatalytic effect, which can be enhanced by using the CNTs as electron transfer channels, induces the formation of the highly reactive radical ions from adsorbed oxygen [
23].
During the preparation of composite materials, it is necessary to monitor the changes in mechanical and thermal properties in order to determine the 3D printability and end-use applicability of the material. Mechanical properties describe the behavior of materials under the influence of stress or deformation under an applied force. Material structure and composition affect mechanical properties, as do temperature, load duration, and force direction [
24]. The thermal properties of the polymer are defined by three major thermal transitions: glass transition, melting, and crystallization. These transitions can give an indication of the compatibility of the phases within the composite and the thermal stability of the material [
25].
The aim of this work is to prepare functional PET-G/TiO
2 and PET-G/TiO
2/CNT filaments with different filler contents and to evaluate the possibility of 3D printing static mixers with the produced composites. The composites will be studied in order to determine the influence of the filler addition on the thermo-mechanical properties of the material. The photocatalytic properties of these composites will be tested in systems for the purification of polluted water using sunlight as a radiation source in subsequent research. These composites offer a novelty in the field of polluted-water purification in comparison with previous works of 3D printing monoliths containing TiO
2 by paste extrusion technology [
26] or by creating TiO
2 films on the polymer surface [
27,
28,
29]. Additionally, 3D printing of the photocatalytic composite material allows the fabrication of new static mixers with complex geometries.
2. Experimental Section
2.1. Materials
In this work, glycol-modified polyethylene terephthalate (PET-G) was used as the polymer matrix (Devil Design, Mikolow, Poland). Nano-titanium dioxide, trade name AEROXIDE TiO2 P25 (Evonik industries, Essen, Germany), and multi-walled carbon nanotubes (MWCNT) (Sigma Aldrich, Burlington, MA, USA) were used as fillers for the production of functional composite filaments. The manufacturer of the PET-G recommends using the temperature range of 220 °C to 250 °C for the nozzle and the range of 70 °C to 80 °C for the platform during the 3D printing. The manufacturer data for TiO2 indicate the mass ratio of anatase:rutile = 80:20, bulk density of nanoparticles equal to 130 g/L, a specific surface area of 50 m2/g and the particle size range of 10 to 50 nm. The CNTs are specified as multi-walled (MWCNT), with 50 to 90 nm diameter and >95% carbon basis.
2.2. Sample Preparation
The purchased PET-G filament was in the shape of filament with a 1.75 mm diameter and was first cut into granules on a Rondol granulator. These pure PET-G granules were then dry blended for 2 min with varying TiO
2 and CNT filler contents (
Table 1).
The obtained mixtures were then melted and blended in a Rondol 21 mm LAB TWIN twin-screw extruder with the temperature zones indicated in (
Table 2) at a speed of 50 rpm. The samples with higher filler content were extruded at higher temperature due to their higher viscosity. The extruded composite filaments were cooled in a distilled water bath and, after cooling, were again cut into granules on the granulator. No particular challenges were encountered in the fabrication process, such as polymer burnout or nozzle clogging due to filler agglomeration.
The composite granules were fed into a Noztek Pro single-screw extruder for the production of the filament. The diameter of the extruded filament was 1.75 mm ±5%, which is required for the 3D printer. All filaments were extruded at 186 °C and air-cooled with the built-in ventilator. This extruder has a single rotation speed. The extruded functional filaments were later used in a 3D printer to produce functional static mixers.
The samples for the tensile test were prepared on the Fontijne hydraulic press. The composite granules were placed in a steel mold with dimensions 100 mm × 10 mm × 1 mm and covered with Teflon sheets to prevent sticking. The molds containing the composites were first preheated at 190 °C for 4 min, then pressed at 15 MPa for 4 min and finally cooled for 4 min before the mold was removed. The pressed plates were cut into the desired shape using a tensile test sample punch. The punch used was manufactured according to the standard DIN EN ISO 8256, specimen type 3 [
30]. The samples for the tensile test were molded instead of 3D printed in order to determine the mechanical properties of the material itself without the influence of 3D-printing parameters.
2.3. Characterization
The functional composites were characterized using the Davenport melt flow rate (MFR) tester. The viscosity of the composite is inversely proportional to the melt flow rate. An amount of 6–8 g of composite granules was placed in the machine at a working temperature of 190 °C, and the press weight used was 5 kg. The results were obtained as the mass of sample that flowed out of the machine within 10 min, in grams. The MFR value was calculated according to the equation:
where
t is the flow time of the sample in seconds and
m is the mass of the sample which flowed through the tester in grams, weighted on the analytical scale.
Differential scanning calorimetry (DSC) was used to determine the glass transition temperature shift upon addition of filler content using a Mettler Toledo 823e measuring module. The analysis was conducted in two heating cycles with a nitrogen flow of 50 mL/min as inert atmosphere.
First cycle:
Heating 0–260 °C at 10 °C/min.
Isothermal 260 °C for 2 min.
Cooling 260–0 °C at −10 °C/min.
Isothermal 0 °C for 2 min.
Second cycle:
Heating 0–260 °C at 10 °C/min.
Cooling 260–25 °C at −30 °C/min.
Thermogravimetric analysis (TGA) was performed on a TA Instruments Q500 instrument to determine the thermal stability of the materials. The onset of weight loss was monitored as the initial decomposition temperature. The tests were performed in the temperature range of 25–500 °C at 10 °C/min in a nitrogen flow of 50 mL/min as an inert atmosphere.
The mechanical properties of the prepared samples were determined with a tensile test on a Zwick Röell AG UTM 1445 universal testing machine. The crosshead speed used was 10 mm/min and the initial gauge length was 30 mm.
The surface of the composites was examined using a scanning electron microscope (SEM) Tescan Vega 3 SEM. Samples for the microscope were first sputter coated with conductive platinum/palladium and then examined in SEM with a secondary electron (SE) detector.
2.4. 3D Printing
In this work, a Zortrax M200 3D printer was used. The printer uses fused filament fabrication (FFF) additive manufacturing technology. As aforementioned, the filament for this printer is required to have a diameter of 1.75 mm ±5%. The first step of the process is to design a 3D model of the static mixer [
31] using Autodesk Fusion 360 CAD (Computer-Aided Design) software (
Figure 1 and
Figure 2). The designed model is later exported in the .stl format. This format is used in the slicer program Z-suite, where the print settings are defined and the model is transferred to the 3D printer (
Figure 3).
4. Conclusions
Functional filament composites of a PET-G polymer matrix with TiO2 and CNT fillers were successfully prepared using a Noztek Pro extruder. The diameter of the prepared filaments was within 5% deviation from 1.75 mm, as required for a 3D printer. All of the prepared composites were used for successful 3D printing using the Zortrax M200 3D printer, allowing all the planned static mixers to be successfully manufactured.
The thermal and mechanical properties of the composite materials were analyzed and compared to pure PET-G. MFR analysis indicated a decrease in viscosity of the composites compared to PET-G, reaching a plateau after 2 wt% fillers were added. Changes in the viscosity are not directly related to the addition of the fillers but to the degradation of the polymer matrix during processing. The glass transition temperature was determined using DSC analysis and no shift in the values was found, indicating that the addition of fillers cancels the influence of the previously mentioned polymer degradation on this property of the PET-G polymer. Additionally, the SEM micrographs confirmed good filler–matrix distribution and adhesion. Thermal decomposition temperature was determined using TGA analysis and it was determined that the addition of fillers will not influence the working range of the material at elevated temperatures. A significant influence of the fillers on the mechanical properties was found. The addition of the fillers impacted the overall strength and elongation of the material. Strength was significantly increased with the initial addition of the filler, but it began to decrease with the further increase in the filler content. Elongation at break values were inversely proportional to those of strength. All results were within the required values for the 3D printing of the static mixers and the final application in the tubular reactors for polluted-water purification.