Fabrication and characterization of PMMA/ZrO2 nanocomposite 3D printing filaments

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The 3D printing PMMA/ZrO2 filaments with a diameter of 1.75±0.05 mm were fabricated by using a single-screw extruder at temperatures of four heating zones of 190, 200, 210, and 210°C. Testing samples were prepared from the extruded filaments by using a fusion deposition modeling 3D printer and a Haake MiniJet piston injection molding machine. Fourier transform infrared spectroscopy, mechanical properties, field emission scanning electron microscopy (FESEM), differential scanning calorimetry, and thermogravimetric analysis of the filaments were investigated.

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Nội dung Text: Fabrication and characterization of PMMA/ZrO2 nanocomposite 3D printing filaments

Cite this paper: Vietnam J. Chem., 2023, 61(4), 461-469 Research article DOI: 10.1002/vjch.202200185 Fabrication and characterization of PMMA/ZrO2 nanocomposite 3D printing filaments Nguyen Thi Dieu Linh1,2, Khuc Duong Huy1, Nguyen Thi Kim Dung3, Ngo Xuan Luong4, Thai Hoang2, Do Quang Tham1,2* 1 Graduated University of Science and Technology, Vietnam Academy of Science and Technology (VAST), 18 Hoang Quoc Viet, Cau Giay, Hanoi 10072, Viet Nam 2 Insitute for Tropical Technology, Vietnam Academy of Science and Technology (VAST), 18 Hoang Quoc Viet, Cau Giay, Hanoi 10072, Viet Nam 3 National Academy of Education Management, 31 Phan Dinh Giot, Thanh Xuan, Hanoi 10000, Viet Nam 4 Hong Duc University, 565 Quang Trung, Dong Ve, Thanh Hoa 40100, Viet Nam Submitted November 7, 2022; Revised March 20, 2023; Accepted April 24, 2023 Abstract The 3D printing PMMA/ZrO2 filaments with a diameter of 1.75±0.05 mm were fabricated by using a single-screw extruder at temperatures of four heating zones of 190, 200, 210, and 210°C. Testing samples were prepared from the extruded filaments by using a fusion deposition modeling 3D printer and a Haake MiniJet piston injection molding machine. Fourier transform infrared spectroscopy, mechanical properties, field emission scanning electron microscopy (FESEM), differential scanning calorimetry, and thermogravimetric analysis of the filaments were investigated. It was suggested the formation of physical and molecular interactions between surface hydroxyl groups of ZrO2 nanoparticles and C-O-C groups of PMMA in the PMMA/ZrO2 filaments. FESEM images of the filaments indicated the good dispersion of ZrO2 nanoparticles in the PMMA matrix, nevertheless, there was still the formation of clusters of ZrO 2 nanoparticles in the nanocomposite filaments. The incorporation of nano ZrO2 increased the thermal properties, bending, and tensile moduli of PMMA. The mechanical properties of the 3D-printed samples were lower than those of the molded samples. However, the bending strength of the 3D-printed samples was much higher than 50 MPa, bending modulus was much higher than 1800 MPa, as required for acrylic bone cement (in ISO 5833:2002). Keywords. 3D printing filaments, PMMA, ZrO2 nanoparticle, fusion deposition modeling, mechanical properties. 1. INTRODUCTION reports related to the preparation and characterization of PMMA/ZrO2 nanocomposites. M. A. Reyes- Poly (methyl methacrylate) (PMMA) is one kinds of Acosta et al. prepared the different PMMA/ZrO2 thermoplastics, commonly called “organic glass”, polymer nanocomposites via extrusion method and PMMA has many excellent properties such as high investigated the influence of ZrO2 loadings on the transparency, light weight, high hardness, good thermal stability and UV radiation resistance of the weather-resistant, high elastic modulus, low polymer nanocomposites.[9] Fourier transform shrinkage and other good properties. PMMA can be infrared (FTIR) and proton nuclear magnetic also used as a biomedical material, such as an resonance (1HNMR) spectral measurements indicated important component of bone cement, and acrylic the electrostatic interaction between the polymer and denture base because of its biocompatibility with ZrO2 nanoparticles. Therefore, the PMMA/ZrO2 human and animal bodies.[1-4] Zirconia is a well- nanocomposites showed higher thermal stability, UV known biomedical ceramic material that has been absorption, elastic modulus and hardness in used as bone tissue because of its excellent comparison with those of neat PMMA. bioactivity.[5-7] Recently, polymer nanocomposites Q. Y. Hu et al.[10] prepared PMMA/ZrO2 via bulk have been the hot topic in material science because of polymerization from methyl methacrylate some superior properties to conventional polymer (MMA)/ZrO2 dispersions, and 2-hydroxyethyl composites.[8] Up to now, there have been some methacrylate (HEMA) as a coupling agent. The 461 Wiley Online Library © 2023 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH
25728288, 2023, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/vjch.202200185 by Readcube (Labtiva Inc.), Wiley Online Library on [01/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License Vietnam Journal of Chemistry Do Quang Tham et al. results showed that the PMMA/ZrO2 nanocomposites rectangular shape via UV curing 3D-printing method were transparent with ZrO2 content of up to 7.0 wt.%. and then using the same polishing procedure. Their FTIR spectra indicated that hydrogen bonding was study revealed that heat-polymerized acrylic resin formed between PMMA and ZrO2 nanoparticles. showed higher mechanical properties when compared Tensile measurements and dynamic mechanical with those of the unmodified 3D-printed resins, analysis (DMA) of the PMMA/ZrO2 nanocomposites however, the addition of ZrO2 nanoparticles demonstrated the reinforcement ability of ZrO2 improved the mechanical properties of 3D-printed nanoparticles. The thermogravimetric analysis resins. (TGA) results revealed that the thermal stability of In the presence study, we employed the melt PMMA was enhanced with the addition ZrO2 extrusion method for fabricating PMMA/ZrO2 3D nanoparticles. C.G. Alvarado-Beltrán et al.[11] printing filaments. This method is commercially prepared and investigated the properties of PMMA- more attractive because of its simplicity, ZrO2 hybrid films by using sol-gel method, in which environment-friendliness and industrial-scale zirconium propoxide and methyl methacrylate possibility.[18-20] For comparison, testing samples (MMA) were used as the inorganic and organic from the filaments were made by using two sources, and 3-trimetoxy-silyl-propyl-methacrylate techniques, using a piston injection molding machine (TMSPM) was used as the coupling agent. The strong and a fusion deposition modeling (FDM) 3D printing interaction between organic and inorganic phases of machine. The infrared spectra, mechanical properties, the hybrid films was verified by FTIR, TGA, and T morphology, and thermal analysis of the testing and R spectroscopy measurements. Scanning electron samples containing different loadings of ZrO2 microscopy (SEM) and atomic force microscopy nanoparticles have been investigated. (AFM) images of the hybrid films displayed a uniform, smooth, and flat surface with average 2. MATERIALS AND METHODS roughness lower than 1 nm. The TGA measurements also demonstrated that the thermal stability of the 2.1. Materials PMMA phase in the hybrid film was improved in comparison with that of neat PMMA. Alhotan A. et Nano ZrO2 (ZrO2 nanoparticles, 99.9%) in white al.[12] evaluated the bending strength and surface color with density (d = 5.68 g/cm3), particle size of hardness of heat-cured PMMA/ZrO2, PMMA/TiO2 20-80 nm was provided by Aladdin Chemical and PMMA/E-glass fiber nanocomposites. Corporation (Shanghai, China). Acetone (99.7%), Specimens were prepared via curing the PMMA methanol (99.7%), ethanol (99.7%) were provided by powder, nano fillers with MMA monomer Guangzhou Chemical Company, (Guangzhou, (solid/liquid mass ratio of 2:1). The obtain results China). Poly (methyl methacrylate) (PMMA, VH5- showed that the bending strength was remarkably 001) is a product of Mitsubishi (Japan) with melt flow improved in the groups filled with 3 wt.% ZrO2 and 5 index of 5.5 (load 3.8 kg, at 230°C) and density of and 7 wt.% E-glass fiber in comparison with control 1.185 g/cm3 at 25°C. group (without filler). Kumari S. et al.[13] also used heat cure method for the preparation of PMMA/ZrO2 2.2. Sample preparation nanocomposites. They showed that the PMMA/ZrO2 (5 wt.%) nanocomposites exhibited the maximum First, PMMA and nano ZrO2 were dried in a hot air compressive strength (76.6 MPa), Young's modulus oven at 100°C for 2 h. Dried PMMA and nano ZrO2 (590 MPa), and fracture toughness (6.58 MPa-m1/2). with predetermined contents were physically mixed Nowadays, 3D printing technology and 3D together. The mixture was fed into the hoper of the a printing materials have been attracted much attention. single-screw extruder (Haake Rheomix 252p). The PMMA and its composites have been under extruder has 4 heating zones, the L/D ratio of 25:1 (L investigation as 3D printing materials. As a base in = 475 mm, D = 19 mm). The four zones of the dental materials, there are a number of studies related extruder were heated at temperatures of 190; 200; 210 to PMMA composites and polymer blends as printing and 210 °C (figure 1). materials, such as PMMA/hydroxyapatite-zirconia, The PMMA/ZrO2 nanocomposites were extruded PMMA-based denture, PMMA/hydroxyapatite, at a rotor speed of 80 round per min through a 2.5- PMMA/TiO2 based denture, PMMA/silica mm circular die, extruded filaments were cooled with [1,2,14-17] [1] filaments. Alshaikh et al. prepared 3D- air and drawn at a constant speed for diameter of printing denture base (acrylic resin) without and with 1.75±0.05 mm. the addition of 1-5 wt.% of silane-modified ZrO2 Testing samples were prepared by using 2 nanoparticles, the specimens were printed in a techniques from the extruded filaments: © 2023 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH www.vjc.wiley-vch.de 462
25728288, 2023, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/vjch.202200185 by Readcube (Labtiva Inc.), Wiley Online Library on [01/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License Vietnam Journal of Chemistry Fabrication and characterization of PMMA/ZrO2… (2) Fusion deposition modeling (FDM) 3D printing machine (figure 2b), with controlling printer nozzle temperature of 220°C and bed temperature of 100°C. Samples in beam shape have dimensions (width, height, length) of 70×12.8×3.2 mm. 2.3. Characterization The FTIR spectra of the filaments were recorded using a Nicolet iS10 Fourier transform infrared spectrometer (USA) at room temperature, in the wavenumber region from 4000 to 400 cm-1 with a 4 Figure 1: The temperature profile of 190, 200, 210, cm-1 resolution and 32 scans. The films were made 210°C for the extrusion processing of PMMA/ZrO2 from the filaments by using a hot-pressing mold at filaments 220 °C. The tensile properties of the testing samples were (1) Using a Haake MiniJet piston injection molding performed on a universal testing machine (Zwick machine (figure 2a), with controlling the cylinder V.2.5, Germany) with a crosshead speed of temperature of 220°C and mold temperature of 10 mm/min, in accordance with ASTM D638 for 100±1°C and a pressure of 650 bar. Samples in beam plastic. Four-point bending test was performed with a shape have dimensions (width, height, length) of crosshead speed of 5 mm/min, in accordance with 63.4×12.8×3.2 mm. Samples in dumbbell shape were ISO 5833:2002 standard with at least 3 testing prepare with the type IV mold in ASTM D638, the samples for a test. Molding shrinkage was conducted narrow section width of 6 mm. via measuring the length dimension of cooled testing samples compared with that of the mold. Figure 2: (a) Haake MiniJet piston injection molding machine, (b) FDM 3D printer and testing samples Thermal gravimetric analysis (TGA) Germany) with a heating rate of 10°C/min, from 30 measurements of the filaments were carried out by to 250°C, using nitrogen gas with constant flow of 40 using a NETZSCH TG 209F1 Libra instrument mL/min. (Netzsch, Munich, Germany) under nitrogen gas, in Morphology of the samples were analyzed by the temperature range from 30°C to 700°C, a heating using a field emission scanning electron microscopy rate of 10°C/min. Differential scanning calorimetry (FESEM, HITACHI S4800, Japan). The samples (DSC) measurements of the filaments were were coated with platinum prior to FESEM conducted on a DSC 204F1 instrument (NETZSCH, observation. © 2023 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH www.vjc.wiley-vch.de 463
25728288, 2023, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/vjch.202200185 by Readcube (Labtiva Inc.), Wiley Online Library on [01/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License Vietnam Journal of Chemistry Do Quang Tham et al. 3. RESULTS AND DISCUSSION absorption region can be seen at 800-400 cm-1, where the peaks at 745, 580.7, 506.6 are attributed to Zr-O- 3.1. FTIR spectra of PMMA/ZrO2 filaments Zr stretching vibrations (lattice).[21-23] In the FTIR spectra of PMMA/ZrO2 materials containing different FTIR spectra of PMMA, nano ZrO2 and PMMA/ZrO2 ZrO2 contents (Figures 3c, 3d, and 3e), it can be seen filaments are displayed in Figure 3. Figure 3a shows that vibration bands of PMMA/ ZrO2 are similar to the specific absorption bands of PMMA, such as, the those of the neat PMMA. Comparison with the stretching vibrations (ν) of CH3 OCH3 and CH2 spectra of neat ZrO2, the absorption band of ZrO2 in groups at 2995.4, 2950.9 and 2842.5 cm-1, ν(C=O) at spectra of PMMA/ZrO2 indicates some slight shift of 1731.8 cm-1, ν(C=C) at 1737.3 cm-1, bending about 5 cm-1 (from 580.7 to 575.6 cm-1). This can be vibrations (δ) of CH3 at 1484.5 and 1448.8 cm-1, suggested that there are some physical and molecular δ(CH2) at 1386.8 cm-1, ν(C-O) at 1242.3 and 1150.6 interactions between OH surface groups of ZrO2 cm-1, δ(C=O) at 750.3 cm-1.[1,3,9] Figure 3b shows that nanoparticles and the C-O-C groups of PMMA in the the broad and strong infrared absorption properties of PMMA/ZrO2 materials, which arise from the ZrO2 nanoparticles. The peak centered at 3398.7 adsorption polymer molecules onto ZrO2 cm-1 is assigned for ν(OH), the peak at 1631.8 cm-1 is nanoparticles.[9] assigned for δ (OH). Another strong and broad (a): PMMA 3438.5 1637.3 488.1 3554.2 3621.7 2842.6 1064 750.3 1386.8 988.6 .5 2995.4 1484.5 1448.8 2950.9 1242.3 1731.8 1150.6 (b): Nano ZrO2 1631.8 3398.7 745.0 420.4 580.7 (c): PMMA/ZrO2 (1 wt.%) 506.6 Transmittance 2843.4 3440.8 3554.3 1637.6 503.3 3621.3 483 1065 753.1 989.3 1388.5 2994.9 (d): PMMA/ZrO2 (5 wt.%) 2951.2 1482.0 1449.4 1148.4 1733.3 1242.9 3439.7 3553.2 1636.6 3618.8 2843.0 575.6 421 1065 507.2 1387.8 751.8 2994.7 2951.0 988.8 1482.3 1449.0 1732.1 (e): PMMA/ZrO2 (7.5 wt.%) 1147.9 1242.6 1636.8 3555.4 3439.7 2843.0 3622.5 575.6 1065 423.6 509.1 1388 752 2994.6 989 2950.9 1732.3 1483.0 1449 1242 1149 4000 3000 2000 1000 500 Wavenumber (cm-1) Figure 3: FTIR spectra of (a) PMMA, (b) nano ZrO2, (c, d, e) PMMA/ZrO2 with 2.5, 5, and 7.5 wt.% ZrO2, respectively 3.2. Morphology matrix at the nanoscale, and well adhered to the PMMA matrix due to the good interaction between Figure 4 shows the FESEM images of the cross- the PMMA matrix and ZrO2 nanoparticles. However, section of the neat PMMA (0 wt.% ZrO2) at different the higher magnification images (30k or 50k) that magnifications, which clearly indicate the absence of were focused on an example cluster of each filament inorganic particles. Figure 4a or 4b can be used as a show that there are some large clusters, each cluster polymer matrix reference. Figures 5, 6, and 7 is comprised of several tens to hundreds of represent the FESEM images of the cross-section of nanoparticles with a size of about 0.5-2 μm. The size the PMMA/ZrO2 filaments filled with 2.5, 5, and 7.5 of the cluster tends to increase with increasing ZrO2 wt.% of ZrO2 at different magnifications, content in the PMMA/ZrO2 filaments. This respectively. Figures 5a, 6a, and 7a show that most phenomenon can affect the mechanical properties of ZrO2 nanoparticles are well dispersed in the PMMA the filaments as discussed in the next investigation. © 2023 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH www.vjc.wiley-vch.de 464
25728288, 2023, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/vjch.202200185 by Readcube (Labtiva Inc.), Wiley Online Library on [01/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License Vietnam Journal of Chemistry Fabrication and characterization of PMMA/ZrO2… Figure 4: FESEM images of neat PMMA filament (0 wt.% of ZrO2, cross-section) Figure 5: FESEM images of neat PMMA/ZrO2 (2.5 wt.%) filament (cross-section) Figure 6: FESEM images of neat PMMA/ZrO2 (5 wt.%) filament (cross-section) Figure 7: FESEM images of neat PMMA/ZrO2 (7.5 wt.%) filament (cross-section) © 2023 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH www.vjc.wiley-vch.de 465
25728288, 2023, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/vjch.202200185 by Readcube (Labtiva Inc.), Wiley Online Library on [01/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License Vietnam Journal of Chemistry Do Quang Tham et al. 3.3. Mechanical properties of molded samples the testing samples. However, when deformation from the PMMA/ZrO2 filaments becomes higher, the stress concentration at the ZrO2 clusters contributes to a soon failure, lowering in Figure 8 shows the tensile modulus, strength and tensile strain and tensile strength of the strain of the molded PMMA/ZrO2 nanocomposites nanocomposites. Figure 9 displays the bending with different contents of nano ZrO2. It can be clearly modulus, bending strength and molding shrinkage of seen that the tensile modulus of the nanocomposites the molded PMMA/ZrO2 nanocomposites. Figure 9a is higher than that of the neat PMMA and increases shows that the bending modulus of PMMA (2755 from 1610 MPa to about 1600 MPa with increasing MPa) is improved with the incorporation of nano ZrO2 contents from 1 to 7.5 wt.%. Whereas, tensile ZrO2, the bending modulus of PMMA/ZrO2 strength and strain of the PMMA/ZrO2 nanocomposites increases from 2765 to 2932 MPa nanocomposites decrease as increasing ZrO2 content. with increasing ZrO2 content from 1 to 10 wt.%. In However, the tensile strength of the nanocomposites contrast, the bending strain and bending strength of with 7.5 wt.% of ZrO2 is still as high as 60 MPa. The the PMMA/ZrO2 nanocomposites are lower than improvement in tensile modulus can be explained by those of the neat PMMA and strongly reduce as the physical and polar interactions between ZrO2 increasing ZrO2 content (figures 9b and 9c). The nanoparticles and PMMA matrix as mentioned above, reasons for that are similar to the tensile properties of which enhance the stress transfer from ZrO2 the PMMA/ZrO2 nanocomposites as mentioned nanoparticles to PMMA matrix at low deformation of above. 1620 (a) 10 (b) 75 (c) Tensile modulus (M Pa) Tensile strength (M Pa) 8 1600 70 Tensile strain (%) 6 1580 65 4 1560 60 2 1540 0 55 0 2.5 5 7.5 0 2.5 5 7.5 0 2.5 5 7.5 ZrO2 content (wt.%) ZrO2 content (wt.%) ZrO2 content (wt.%) Figure 8: Tensile properties (a) Tensile modulus, (b) Tensile strain, (c) Tensile strength of PMMA/ZrO2 nanocomposites (molded samples) 3000 (a) 120 (b) 1.6 (c) Bending modulus (M Pa) Bending strength (M Pa) 110 Molding shrinkage (%) 2900 100 1.4 90 2800 80 1.2 70 2700 60 1.0 0 2.5 5 7.5 10 0 2.5 5 7.5 10 0 2.5 5 7.5 10 ZrO2 content (wt.%) ZrO2 content (wt.%) ZrO2 content (wt.%) Figure 9: Bending properties (a) Bending modulus, (b) Bending strain and (c) Molding shrinkage of the PMMA/ZrO2 nanocomposites (molded samples) 3.4. Mechanical properties of 3D-printed samples in the range of 2294-2447 MPa. The decrements of from the PMMA/ZrO2 filaments bending strength, bending modulus (ΔBS, ΔBM, respectively) of printed samples and those of molded Table 1 presents the bending properties of 3D-printed samples from the same PMMA/ZrO2 3D filaments are beams from the PMMA/ZrO2 3D printing filaments. negative. It is evident that both the bending strength The test results show that the bending strength of the and bending modulus of the printed samples are lower printed samples is still as high as from 78.7 to 97 than those of the molded samples because of the MPa, the bending modulus of the printed samples is formation of air voids when making a 3D printing job © 2023 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH www.vjc.wiley-vch.de 466
25728288, 2023, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/vjch.202200185 by Readcube (Labtiva Inc.), Wiley Online Library on [01/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License Vietnam Journal of Chemistry Fabrication and characterization of PMMA/ZrO2… from the filaments. thermal degradation rate (Tatmax) and weight losses at Although bone cement is commonly used as a 350, 400 and 600°C (W350, W400, W600). Table 2 bonding agent for anchoring the prosthetic shows that the Ton3% and Tatmax of the PMMA/ZrO2 3D component to the bone, in some cases, bone cement printing filaments are higher than those of the neat can be used for making a prosthetic implant.[24] PMMA. In other words, the thermal stability of Therefore, we employed ISO 5833:2002 standard for PMMA is improved with the incorporation of ZrO2 evaluating the bending properties of 3D-printed nanoparticles. samples. It is worth to note that the required bending strength and modulus of PMMA acrylic bone cements are 50 and 1800 MPa, respectively. Table 1 reveals that the bending strength and bending modulus of the 3D-printed testing samples are much higher than those of the required values in the ISO 5833:2002 standard. This suggests that 3D printing technology can be applied to make acrylic resin implants. Table 1: Bending properties of 3D printed beams from PMMA/ZrO2 filaments ZrO2 Bending Bending ΔBS ΔBM content strength modulus (wt.%) (MPa) (%) (MPa) (%) 0 97.0±6 – 11.8 2294±45 – 16.7 1.0 92.9±4 – 9.7 2346±59 – 15.1 2.5 84.8±5 – 9.5 2410±56 – 13.6 5.0 78.7±8 – 9.4 2447±46 – 13.2 Note: ΔBS or ΔBM are respectively the decrement of bending strengths, bending modulus of printed samples and those of molded samples from the same PMMA/ZrO2 3D filament. BSp – BSm BMp – BMm (ΔBS = ; ΔBM = ) Figure 10: (a) TGA and (b) DSC diagrams of the BSm BMm PMMA/ZrO2 filaments 3.5. TGA and DSC of the PMMA/ZrO2 filaments Table 2: Analysis results from TGA measurements of the PMMA/ZrO2 filaments Figure 10 plots the TGA and DSC diagrams of the PMMA/ZrO2 3D printing filaments. Figure 10a ZrO2 Ton3% Tatmax W350 W400 W600 shows that thermal decomposition of PMMA and content (°C) (°C) (%) (%) (%) PMMA/ZrO2 nanocomposite filaments only occurs (wt.%) mainly in one region from 280-420 °C, this indicates 0 282 362 55.7 2.1 0.00 that the industrial grade PMMA (VH5-001) has less 2.5 325 378 89.5 10.2 1.67 of residual monomers and the less affection of the 5.0 312 373 82.5 8.6 4.90 unsaturated end groups of PMMA (revealed by the 7.5 312 372 82.8 10.6 7.25 ν(C=C) at 1637 cm-1 in figure 3). For some as- synthesized PMMA, the thermal decomposition of Figure 10b shows that glass transition PMMA commonly occurred with 2 stages, a minor temperature (Tg) of PMMA is 107.5°C, whereas, that stage (at below 220°C) and a major stage (above 280 of the PMMA/ZrO2 3D printing filaments is in the °C), this means that residual monomers play a range of 112.5-113.5°C (about 5°C higher than that dominant role rather than the unsaturated end of the PMMA). This indicates the incorporation of groups.[25] In comparison with the TGA curves of the ZrO2 slightly change the Tg of polymer phase in the neat PMMA, the TGA curves of PMMA/ZrO2 3D PMMA/ZrO2 nanocomposites, this may be due to the printing filaments are shifted to higher temperature physical and polar interactions between PMMA and regions. In detail, filaments. Table 2 represents the ZrO2. Although PMMA and the PMMA/ZrO2 TG analysis results including 3% loss onset nanocomposites can be extruded and 3D-printed in temperature (Ton3%), the temperature at maximum the melting stage at 200-210°C, the melting peaks of © 2023 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH www.vjc.wiley-vch.de 467
25728288, 2023, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/vjch.202200185 by Readcube (Labtiva Inc.), Wiley Online Library on [01/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License Vietnam Journal of Chemistry Do Quang Tham et al. these materials are absent (even up to 250°C, data not Dent. Res., 2015, 6(2), 46-151. shown), demonstrating that the polymer phase in the 6. B. Wang, G. L. Wilkes. Novel hybrid inorganic- PMMA/ZrO2 nanocomposites is quite amorphous. organic abrasion-resistant coatings prepared by a sol- gel process, J. Macromol. Sci. A, Part A, 1994, 31(2), 249-260. 4. CONCLUSION 7. K. Soygun, S. Şimşek, E. Yılmaz, G. Bolayır. Investigation of mechanical and structural properties The 3D printing PMMA/ZrO2 nanocomposite of blend lignin-PMMA, Adv. Mater. Sci. Eng., 2013, filaments have been fabricated via melt extrusion 2013, 435260. process. The FTIR spectra, mechanical properties, 8. S. Krishnakumar, T. Senthilvelan. Polymer morphology, TGA and DSC diagrams of the composites in dentistry and orthopedic applications-a PMMA/ZrO2 nanocomposite filaments with different review, Mater. Today: Proc., 2021, 46, 9707-9713. nano ZrO2 contents have been characterized. The 9. M. A. Reyes-Acosta, A. M. Torres-Huerta, M. A. FTIR suggested the formation of physical and Domínguez-Crespo, A. I. Flores-Vela, H. J. Dorantes- molecular interactions between OH surface groups of Rosales, E. Ramírez-Meneses. Influence of ZrO2 nanoparticles and thermal treatment on the properties ZrO2 nanoparticles and the C-O-C groups of PMMA. of PMMA/ZrO2 hybrid coatings, J. Alloys Compd., On the whole, nano ZrO2 dispersed in the PMMA 2015, 643, S150-S158. matrix in the nanoscale despite some micron-size 10. Y. Hu, G. Gu, S. Zhou, L. Wu. Preparation and clusters. 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