Syarifa Nur'ainia,
Akmal Zulfi*b,
Bagas Haqi Arrosyida,
Ande Fudja Rafryantoa,
Alfian Noviyanto*ac,
Dian Ahmad Hapidind,
Dafit Feriyantoc,
Kurniawan Eko Saputroa,
Khairurrijal Khairurrijald and
Nurul Taufiqu Rochmane
aNano Center Indonesia, Jalan Raya PUSPIPTEK, South Tangerang, Banten 15314, Indonesia. E-mail: a.noviyanto@nano.or.id
bResearch Center for Environmental and Clean Technology, National Research and Innovation Agency, Bandung Advanced Science and Creative Engineering Space (BASICS), Jl. Cisitu, Bandung 40135, Indonesia. E-mail: akmal.zulfi.m@brin.go.id
cDepartment of Mechanical Engineering, Mercu Buana University, Jl. Meruya Selatan, Kebun Jeruk, Jakarta 11650, Indonesia. E-mail: alfian.noviyanto@mercubuana.ac.id
dDepartment of Physics, Institut Teknologi Bandung, Jalan Ganesa 10, Bandung 40132, Indonesia
eResearch Center for Metallurgy and Materials, National Research and Innovation Agency, South Tangerang, Banten 15314, Indonesia
First published on 24th November 2022
Acrylonitrile butadiene styrene (ABS) is one of the most common fused-filament feedstocks for 3D printing. The rapid growth of the 3D printing industry has resulted in huge demand for ABS filaments; however, it generates a large amount of waste. This study developed a novel method using waste ABS to fabricate electrospun nanofiber membranes (ENMs) for water filtration. Polyvinylpyrrolidone (PVP) was employed to modify the properties of waste ABS, and the effect of PVP addition in the range of 0–5 wt% was investigated. The results showed that adding PVP increased the viscosity and surface tension but decreased the conductivity of the precursor solution. After electrospinning, PVP could reduce the number of beads, increase the porosity and fiber diameter, and improve the wettability of the fabricated fibers. Moreover, the bilayer of ABS ENMs achieved a high flux value between 2951 and 48041 L m−2 h−1 and a high rejection rate of 99%. Our study demonstrates a sustainable strategy to convert waste plastics to inexpensive materials for wastewater treatment membranes.
Several studies have attempted to utilize ABS waste in higher-value products such as additive bitumen binders,18 green catalysts for oil and metal recovery,19 recycled filaments for reuse in 3D printing,20 and epoxy materials.4 Recently, ABS waste has been recycled into nanofiber membranes for air filtration.21,22 Nanofiber membranes made from recycled ABS waste exhibited filtration efficiencies of approximately 95% for PM 2.5 because the interconnected pore structures and the large surface area were suitable for particle capture during gas filtration. Nanofiber membranes also have a unique pore structure, narrow pore size, and high selectivity,23 which are ideal for water treatment and filtration.24–28 Excellent performance has been achieved with an efficiency of 99.99% and a flux of 5000–35000 L m−2 h−1.29–32 However, to the best of the authors knowledge, there are no reports on recycling ABS waste into water filtration membranes.
Electrospinning is a well-known technique for fabricating nanofiber membranes from various polymers. This technique is versatile and has the ability to control nanofiber morphology by adjusting the solution and process parameters.33 ABS nanofiber membranes have hydrophobic surfaces,21,34 which are unfavorable for water filtration because they can increase energy consumption.35 Therefore, water-soluble materials are often added to enhance the membrane flux. Polyvinylpyrrolidone (PVP) and polydopamine (PDA) increased the surface hydrophilicity and flux rate of the membranes.36 Another study by Park et al. reported that the modification of a hydrophobic membrane with polyvinyl alcohol (PVA) could enhance membrane performance.37
The present work aimed to recycle ABS to electrospun nanofiber membranes (ENMs) for microfiltration in a 2500 ppm antacid solution. This study also investigated the surface modification of ENMs by blending waste ABS with PVP. Adding PVP is expected to improve the hydrophilicity of ENMs and enhance the permeate flux as well as filtration efficiency. The ENMs prepared with waste ABS in this study have comparable filtration performance to the membranes prepared using expensive polymers. In addition, recycling ABS waste has a positive impact on the environment.
Parameter/code | ABSP0 | ABSP1 | ABSP3 | ABSP5 |
---|---|---|---|---|
ABS (wt%) | 28 | 27 | 25 | 23 |
PVP (wt%) | 0 | 1 | 3 | 5 |
Viscosity (cP) | 153.91 | 384.82 | 858.12 | 1259.81 |
Conductivity (μS) | 9.07 | 4.05 | 3.71 | 2.87 |
Surface tension (dyne cm−1) | 62.72 | 64.95 | 65.37 | 66.43 |
The precursor solution was loaded into a commercial syringe-fitted stainless-steel needle with an inner diameter of 0.7 mm. The filled syringe was controlled by a syringe pump at a constant rate of 0.3 mL hour−1. The tip of the needle was connected to a high-voltage source operated at 12 kV. The distance between the needle tip and the drum collector was 12–15 cm. The drum collector was grounded and rotated to deposit the spun fibers. To compile the nanofibers easily, the drum collector was also wrapped with nonwovens. The apparatus was set up in a horizontal-spinning configuration at room temperature (25 ± 5 °C) under a relative humidity of 60%. ENMs were continuously synthesized for 7 h to obtain nanofibers on an electrospinning apparatus (ILMI-N101, Integrated Laboratory of Materials and Instrumentation, ITB, Indonesia).
Because the ENMs are projected for water filtration, the water contact angle (WCA) is an important parameter to ensure hydrophilicity. Therefore, WCA was investigated using a contact angle apparatus (Nachriebe 320, Nachriebe). Water (5 μL) was used to create a droplet and the shape of the droplet on the membrane surface was captured using a camera, and the image was digitally processed using Image J software to obtain the WCA.
(1) |
The feed and permeate concentrations were measured using a UV/Vis spectrophotometer (Labtron LUS-B13). The concentration was determined based on a calibration curve.45 The concentrations used for calibration were 2500, 1875, 1250, 625, 317, and 0 ppm. The permeate concentration was derived from the calibration curve. The retention ratio (%) was calculated using eqn (2):46,47
(2) |
Fig. 4 shows the FTIR spectra of the ENMs. ABS was formed by polymerizing three monomers, i.e., acrylonitrile, polybutadiene, and styrene. The spectra of ABS waste were similar to the previous report.54,55 The peak at 3000–3100 cm−1 was the absorption of asymmetric C–H aromatic bonds in styrene compounds, while the peak at 2800–3000 cm−1 corresponded to the aliphatic C–H bond, and that at 2237 cm−1 was the deformation of nitrile CN bonds. The CC aromatic double bond stretching vibration was found at 1602 cm−1. The peaks between 1495 and 1452 cm−1 corresponded to the stretching of C–C in the aromatic ring, and the stretching of unsaturated CC in polybutadiene. The bending C–H in-plane and (mono)-substituted out-of-plane vibrations were at 1074 and 1024 cm−1 and 758 and 699 cm−1, respectively. In our ABS waste, a carbonyl (CO) stretching peak was observed at 1736 cm−1 because of the oxidation during its usage and application.4 The spectral peak of the pure PVP was in line with previous studies. The peak at 3464 cm−1 was related to the stretching of a hydroxyl group (hydrogen bonding). The peaks at 2913 cm−1, 1644 cm−1, 1425 cm−1, and 1279 cm−1 were assigned to the asymmetric CH2 stretching, carbonyl group CO, bending of C–H bond, C–N bond stretching, respectively. The peaks at 1019 cm−1, 930 cm−1, and 844 cm−1 were attributed to the C–C bending. In the spectra of ABSPs, sharp peaks at 3455 cm−1 and 1644 cm−1 were observed due to the stretching of the hydrogen bonding (O–H) and carbonyl group (CO), respectively. The reaction might occur between the CO groups in the pyrrolidone ring and the hydrocarbons from polybutadiene or benzene compound36 to form O–H and CO bonds. DMF as a solution was not detected in the spectra of all samples, confirming that the solvent was completely evaporated.56
The SEM morphology of the ENMs (Fig. 5) shows the formation of bead nanofibers. A similar bead nanofiber was reported by Jiang et al. when 15 wt% of ABS in DMSO and CHCl3 was used for electrospinning. The same method generated bead-free nanofiber when the ABS content was increased to 20–25 wt%.34 Bead-free ABS nanofibers were obtained by mixing the solvent (DMF and THF) at a ratio of 9:1, as reported by Moradi et al.57 Zulfi et al. prepared bead-free nanofibers from 30 wt% of ABS waste.21 Therefore, the formation of bead nanofibers in this study was more likely due to the low concentration of ABS waste. Moreover, the source of ABS, solvent, and other additives might influence the formation of bead nanofiber.
Interestingly, the total number of beads was closely related to the weight percentage of PVP. For instance, the total number of beads for ABSP0, ABSP1, ABSP3, and ABSP5 were ∼643, ∼550, ∼454, and ∼262, respectively. PVP increased the viscosity of the precursor solution and improved jet stability, resulting in a decrease in bead formation. Moreover, the average bead diameter reduced with increasing PVP content. The average bead diameters of the ABSP0, ABSP1, ABSP3, and ABSP5 ENMs were 5.832, 5.382, 3.485, and 3.137 μm, respectively (Fig. 6). In addition to decreasing the number and size of the beads, PVP changed the beads from spherical to elongated shapes.58 In this study, the shape change was not evident, and the coefficient of variance (CV) of the size was >0.3, suggesting the uniformity of beads or fibers.59 The small number of beads in ABSP5 indicated that the size of the beads changed from large to small, eventually forming bead-free fibers. As shown in Table 1, a higher PVP content in the solution increased the viscosity and surface tension, and reduced the conductivity. This result is in agreement with published reports that showed bead-free fibers with higher PVP content.60–62 However, the dependence of surface tension on the formation of beads was inconsistent in the literature. Almetwally et al. found that higher surface tension produced more beads on fiber.63 However, Liu et al. reported that a high surface tension could yield a bead-free fiber.64
Fig. 6 Distribution of beads diameter based on the SEM images in Fig. 5. |
Fig. 7 shows the distribution of fiber diameters when different contents of PVP were added. The mean fiber diameters of the ABSP0, ABSP1, ABSP3, and ABSP5 ENMs were 108.46, 136.39, 173.71, and 216.64 nm, respectively. The fiber diameter increased with PVP, as reported previously.65 The fiber diameters of ABSP3 and ABSP5 were considered a homogeneous distribution, characterized by CV < 0.3. In contrast, the CV values of ABSP0 and ABSP1 were 0.37 and 0.4, respectively, implying an inhomogeneous fiber size. As shown in Table 1, the conductivity of the solution decreased with PVP; therefore, the thin fiber of ABSP0 was due to the high conductivity of the solution, consistent with a previous report that high conductivity generated thin fibers.27
Fig. 7 Distribution of fiber diameter based on the SEM images in Fig. 5. |
The morphology of the ENMs also influenced the surface porosity. A high PVP concentration was reported to increase the porosity, which agreed with the present study that the porosities of ABSP1, ABSP3, and ABSP5 increased from 64.18, 70.33, to 71.78%, respectively. Porosity was more likely to be affected by the size of the fiber rather than the size of the bead. ABSP5 had a small bead diameter; however, the fiber diameter increased by a factor of two or more, resulting in its high porosity (71.78%). Comparatively, despite the large bead diameter of ABSP0, its porosity was only 65.23% owing to the small fiber diameter.
Fig. 8 shows the WCA of the ENMs that represent the hydrophilicity of membrane.66 The two mechanisms of water passing through the membrane are (1) water penetrates the porous membranes and (2) water seeps into the membranes. As mentioned above, PVP is a water-soluble material;67,68 thus, a high PVP content will increase the permeability of the membrane. Therefore, it was evident that the lowest WCA was found in ABSP5. Moreover, ABSP5 had more pores than the others, making it easier for water to pass through.48 The average WCAs of ABSP0, ABSP1, ABSP3, and ABSP5 were 131.97°, 129.09°, 85.48°, and 53.40°, respectively, as shown in Fig. 8. It should be noted that ABSP0 was hydrophobic, consistent with previous studies.21,34 Although PVP was water-soluble, adding 1 wt% PVP into ABS did not change the WCA. The WCA of ABS was reduced by adding at least 3 wt% of PVP. The ABSP3 had a WCA of 85.48° and could be categorized as hydrophilic, as well as ABSP5 which had WCA of 53.40°. Hydrophilic behavior is characterized by WCA < 90°.69
(3) |
Fig. 9 Performance evaluation of ENMs (a) permeation flux at a fixed pressure (0.025 bar), and (b) permeation flux as a function of pressures. |
This study used microfiltration because the particle model size was between 900 and 2600 nm. Therefore, besides the suspended solid larger than 0.1 μm, the other contaminants, such as oil emulsion, bacteria, cells, and colloidal haze, will be suspended in the membrane.74 Fig. 10(a) shows the permeability of the ENMs using the particle model of antacids (Fig. 2). The rejection rates of ABSP1, ABSP3, and ABSP5 were 99%. Hence, the permeate solutions of ABSP1, ABSP3, and ABSP5 were clear, as shown in Fig. 10(b). In contrast, the permeate solution of ABSP0 was turbid in Fig. 10(b), corresponding to a rejection rate of 83%. These results indicated the importance of adding PVP to enhance the permeability of ABS ENMs. To the best of our knowledge, adding PVP to ABS waste has rarely been reported, particularly for water filtration applications. Moreover, this study successfully modified the surface characteristics of ABS waste, changing it from hydrophobicity suitable for air filtration21 to hydrophilicity with the addition of PVP. Although the porosity of ABSP0 was smaller than that of the other ENMs, the filtration ability was not solely dependent on porosity. For instance, ABSP0 had a porosity of 65.23% and a rejection rate of 83%. Meanwhile, the rejection rate of ABSP1 was 99%, despite its similar porosity to ABSP0 (64.18%). Therefore, it can be concluded that PVP enhances the applicability of ABS waste for water filtration.
Fig. 10 (a) Permeation flux while filtration at 0.05 bar; (b) photographs of feed and permeate solutions after the filtration process. |
Three mechanisms are involved in the filtration process, i.e., sieving, adsorption, and cake formation. Sieving occurs first as larger particles are retained on the surface of the membranes. Smaller particles flow through the inner membrane and are adsorbed on the fiber surface. Lastly, the particles in the membrane pores are retained on the surface and form a cake layer.75 In this study, the cake layer was formed in two-hour filtration with 2500 ppm feed solution and remove manually. From the SEM images of ABSP1 after the filtration process (Fig. 11), depth filtration was confirmed in ABSP1. This membrane first accumulated particles on the surface, then small particles remained in the inner layer, resulting in a clear permeate. It seemed the cake formation mainly occurred on the surface for ABSP1. A previous study reported that depth filtration in bead fibers would extend the lifetime of the membrane, whereas filtration onto the membranes had a short lifetime and high-pressure drop.76 Recently, clean-up processes for depth clogging have been developed to enhance the reusability of the membranes. Latest studies to achieve surface filtration, remove a cake layer, and improve the mechanical and morphological properties are important contributions to minimizing the disadvantages.77
Fig. 11 SEM images of the first layer of ABSP1 ENMs after the filtration process and heating at 40 °C (a) filtered particles from surface view, and (b) cross-section view. |
Based on this significant result, nanofiber membranes can be used in more advanced applications. However, challenges remain to make the membranes sufficiently strong, antifouling, and applicable to all types of waste treatment. The cake layer of pollutants in the nanofiber membranes is easy to remove and expected to render the membranes reusability. To restrict the pollutant on the surface, the nanofiber membranes should have a sufficiently strong surface to separate the pollutant. Fig. 12 depicts six types of surface modification methods in recent studies: (a) normal nanofiber synthesis, (b) heat treatment with annealing or direct warming at a specific temperature, (c) blending polymers with different properties or chemical crosslinking, (d) incorporating functional materials to obtain specific properties, (e) layering the nanofiber, and (f) combining two types of modified nanofiber.83 The heat-annealed ENMs shown in Fig. 12(b) have several advantages, such as small pore size and excellent mechanical strength.31,77 Blending with other copolymers makes the fiber more hydrophilic, and crosslinking with other materials can enhance the mechanical strength,36,84 as shown in Fig. 12(c). Incorporating various functional material can achieve antibacterial, hydrophobic, and antifouling properties,85–87 as shown in Fig. 12(d). The coating layer in Fig. 12(e) is usually made from water-soluble materials, enhancing the water flux and retaining the pollutant on the surface.37 Furthermore, Fig. 12(f) is usually applied in membrane distillation applications, wherein two types of different polymers with modifications in each layer are incorporated; each layer can be heated to decrease the surface, crosslinked with other materials, or developed with a support layer.88
Table 2 compares the precursors, electrospinning parameters, ENMs characteristics, and efficiencies reported in the literature. Indeed, most of the published reports in Table 2 used non waste precursors to fabricate effective and high-performance nanofiber membranes. This study employed ABS waste to reduce the cost of the precursor and alleviate the environmental burden. As shown in Table 2, the fiber diameter in this study was comparable to that in other published reports. Moreover, compared with polylactic acid (PLA), polyether sulfones (PES), cellulose acetate (CA), polyimides (PI), and polysulfone (PSU) precursors with fiber diameters of 500–1700 nm, our study showed a reduced fiber diameter (108.46–216.64 nm). The rejection rate in this study was comparable to other ENMs, as shown in Table 2. Based on the comparison, nanofibers prepared by ABS waste with a simple PVP modification are suitable for the microfiltration process. This study provides a new strategy to reduce the amounts of WEEE in the environment, enhance the added value of recycled products and help to manage water resources. This result provides a promising way to utilize waste for more advanced membranes in the future.
Precursor solution (polymer/solvent) | Electrospinning parameters concentration (wt%), voltage (kV), flow rate (mL h−1), diameter needle tip (mm), collector distance (cm), humidity (%) | ENMs characteristics diameter (nm), porosity (%), water flux | Efficiency (%) |
---|---|---|---|
a PAN, polyacrylonitrile; PLA, polylactic acid; PES, polyether sulfones; PVA, polyvinyl alcohol; CA, cellulose acetate; PI, polyimides; PSU, polysulfone; NMP, N-methyl-2-pyrrolidone, THF tetrahydrofuran. | |||
PAN/DMF78 | 7–12, 18, 0.5, 0.4, NA, NA | 150–250, 34 to 86, 500–10000 L m−2 h−1 | 99.3 |
PLA/acetone77 | 11–13, 20, 0.5, 0.4, 10, 30 | 500–1200, 5–70, 52000–65000 L m−2 h−1 | 10–85 |
PAN-PET/DMF32 | 4–18, 35, NA, 0.6, 7–19, 40 | 100–500, 61–74, 12500–35000 L m−2 h−1 | 93–99 |
PES/NMP31 | 25–40 w/v%, 10–15, 0.5, 1, 10–20, 50–60 | 550–1300, NA, 16006 L m−2 h−1 bar−1 | 100 |
PVA/distilled water79 | 10, 32, 0.6, 1, 10, 50–60 | 100–182, NA, ∼5417 L m−2 h−1 bar−1 | ∼95 |
CA/acetic acid–acetone80 | 10, 10, 10 mL h−1, 0.4, 15, NA | 500–1700, NA, 27900 L m−2 h−1 bar−1 | 87.7 |
PAN/DMF29 | 8–12, 20, 1.5–3, NA, 15, NA | 151–535, NA, 5000–7000 L m−2 h−1 | 81.4–99 |
PI/NMP–xylene (4:1)81 | 12, 16, 0.4, 0.4, NA, NA | <1000, NA, 514–17607 L m−2 h−1 | 96.7 |
PVA/citric acid–water (1:8)30 | 10, 22, 2 μL min−1, NA, 12/5, NA | 510–535, NA, 7500–13500 L m−2 h−1 | 99 |
PSU/DMF–THF (4:1)82 | 20, 16, 2.5, 1.825, 10, 38–41 | 690–830, NA, NA | 75.3 |
R-ABS-PVP/DMF (this study) | 28, 12, 0.3, 0.7, 12–15, 60 | 108.46–216.64, 64.18–71.78, 2951–48041 L m−2 h−1 | 83–99 |
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