Fig 1 Flowchart of the experimental preparation of ANP/HIPS composite sheet.
Published:01 August 2024,
Published Online:25 April 2024,
Received:09 January 2024,
Revised:05 March 2024,
Accepted:11 March 2024
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In this work, aramid nanoparticles (ANPs) were prepared in dimethyl formamide (DMF) solution containing high impact polystyrene (HIPS) via a bottom-up approach. Transmission electron microscopy (TEM) images showed that the obtained ANPs were evenly distributed in the HIPS matrix without any agglomeration. Chemical composition of the ANPs, i.e., poly(p-phenyl-p-phenylenediamine) (PPTA), was confirmed by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and X-ray diffractometer (XRD). The ANP/HIPS composites, obtained after ethanol precipitation, were added to neat HIPS as fillers to fabricate ANP/HIPS composite sheets. The surface roughness and the glass transition temperature (Tg) of the sheets were characterized by atomic force microscope (AFM) and differential scanning calorimetry (DSC), respectively. Compared with neat HIPS, the mechanical properties of the composite sheet were significantly improved, and the Young's modulus increased from 246.55 MPa to 2025.12 MPa, the tensile strength increased from 3.07 MPa to 29.76 MPa, and the toughness increased from 0.32 N/mm2 to 3.92 N/mm2, with an increase rate of 721%, 869% and 1125%, respectively. Moreover, the thermal stability of the composites improved with the increase in ANP content.
High impact polystyrene;
PPTA nanoparticle;
Reinforce;
Mechanical property
High impact polystyrene (HIPS) is a type of modified polystyrene (PS) material by polybutadiene (PB).[
Modification of the HIPS material to improve its properties has been the focus of many recent studies.[
Aramid fiber, also known as poly(para-phenylene terephthalamide) (PPTA), is a promising additive used to reinforce polymer matrices because of its excellent properties, such as high strength and modulus, non-flammability, etc.[
Aramid nanofibers (ANFs), which was successfully prepared using a "top-down" method by Yang et al. in 2011,[
Recently, our group successfully synthesized nano aramid in a PVC-containing solution via a "bottom-up" method.[
In this work, the synthesis of ANPs in HIPS systems using a "bottom-up" approach was reported. This simple and efficient synthesis method resulted in HIPS composites with good ANP dispersion. The maximum growth rates of Young's modulus, toughness and tensile strength of ANP/HIPS composite sheets reached 721%, 1125% and 869%, respectively, compared to neat HIPS. More interestingly, other properties of ANP/HIPS composites were also improved.
Materials
HIPS, p-phenylenediamine (PPD) and terephthaloyl chloride (TPC) were purchased from Shanghai Aladdin Biochemical Technology Co. Absolute ethanol was purchased from Sinopharm Chemical Reagent Company. The purity of these reagents ranged between 90% and 99%. Water used in this study was deionized (DI) water.
Instruments
Fourier transform infrared (FTIR) spectra were acquired by Thermo Nicolet iS50 FTIR spectrometer for 0.5×0.5 cm ANP/HIPS composite filler with a scanning wavenumber range of 400−4000 cm−1 and 64 scans with a resolution of 2 cm−1. X-ray photoelectron spectroscopy (XPS) were acquired on a Thermo ESCALAB Xi XPS microprobe equipped with a K-AlKα X-ray source. Transmission electron microscopy (TEM) was carried out using a JEOL JEM-1230 microscope at 100 kV. The ANP/HIPS mixture solution diluted with solvent was dripped onto the copper grid and dried to prepare 2×2 mm sheets of ANP/HIPS composite filler for TEM sampling. Field emission scanning electron microscopy (FE-SEM) was carried out on the surface of ANP/HIPS composite sheets using a Hitachi SU8010 microscope. The morphology of the samples was observed by SEM at 2 kV, and then continued to observe the elemental composition of the surface of the same samples using energy dispersive X-ray spectroscopy (EDS). Atomic force microscopy (AFM) images were acquired by a Bruker ICON AFM with a SCANASYST-AIR tip. Composite fillers prepared from dried ANP/HIPS blend solutions were cut and pasted onto circular patches. Subsequently, the roughness of the upper surface of the composite filler was characterized in scanning mode. A Netzsch STA 409 PC/PG instrument was used to perform thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). For thermogravimetric analysis, the ANP/HIPS composite sheets were heated directly under nitrogen from 25 °C to 800 °C at a heating rate of 10 °C·min−1. For DSC, 10×10 mm ANP/HIPS composite sheets were used to be heated in nitrogen at temperature intervals ranging from 25 °C to 100 °C at a heating rate of 20 °C·min−1. The mechanical properties of the composite sheets were tested on an apparatus manufactured by Ingström (USA). The composite films were dried and cut into rectangles 50 mm long and 10 mm wide. The mechanical properties of each test sample were tested at a speed of 10 mm·min−1.
Samples | DMF (mL) | HIPS (g) | PPD (g) | TPC (g) |
---|---|---|---|---|
HIPS | 70 | 7 | – | – |
ANP/HIPS-1 | 70 | 7 | 0.1081 | 0.2030 |
ANP/HIPS-2 | 70 | 7 | 0.2162 | 0.4060 |
ANP/HIPS-3 | 70 | 7 | 0.3243 | 0.6090 |
ANP/HIPS-4 | 70 | 7 | 0.4324 | 0.8120 |
ANP/HIPS-5 | 70 | 7 | 0.5405 | 1.0150 |
The preparation of ANP/HIPS can be found in the literature,[
First, 7 g of HIPS was added to 70 mL of DMF and stirred at 60 °C for 3 h to obtain a clear colorless solution as matrix solution. In the second step, the matrix solution was divided into two parts, one for dissolving PPD and the other for dissolving TPC (as shown in
ANP/HIPS composite fillers (4 g) and HIPS masterbatch (28 g) were mixed together and thoroughly blended at 150 °C in a two-roll mixer. The well-mixed samples were cut into small pieces and put into a plate vulcanizer for hot pressing at 165 °C for 20 min and cold pressing at room temperature for 10 min, both at a pressure of 10 MPa, in a 6 cm × 8 cm × 1 cm mold. The final product of ANP/HIPS composite films were thus obtained. The specific synthesis process can be seen in
Fig 1 Flowchart of the experimental preparation of ANP/HIPS composite sheet.
The FTIR spectra of neat HIPS and ANP/HIPS-1 to ANP/HIPS-5 nanocomposites are shown in
Fig 2 FTIR spectra of neat HIPS and ANP/HIPS-X samples
Fig 3 (a) Overlaid XPS spectra of samples; (b) C 1s spectra of ANP/HIPS-5; (c) N 1s spectra of ANP/HIPS-5.
FTIR and XPS results show the formation of PPTA in the HIPS matrix. The ANP composed of PPTA molecules can act as a nanofiller for HIPS and interact with the polymer matrix through the abundant functional groups on its surface, through which the binding ability with the polymer matrix can be enhanced and the mechanical properties of HIPS can be strengthened.
As shown in the TEM images of the ANP/HIPS-X nanocomposites in
Fig 4 TEM images of ANP/HIPS nanocomposites: (a) ANP/HIPS-1, (b) ANP/HIPS-2, (c) ANP/HIPS-3, (d) ANP/HIPS-4, (e) ANP/HIPS-5.
Fig 5 Polarizing microscope images of (a) ANP/HIPS-1, (b) ANP/HIPS-2, (c) ANP/HIPS-3, (d) ANP/HIPS-4 and (e) ANP/HIPS-5.
XRD patterns of ANP/HIPS-1 to ANP/HIPS-5 samples in
Fig 6 XRD patterns of neat HIPS and ANP/HIPS samples at 25°C
Samples | As | Ag | Xc (%) |
---|---|---|---|
ANP/HIPS-1 | 571.82 | 152.66 | 26.65 |
ANP/HIPS-2 | 239.94 | 899.86 | 26.66 |
ANP/HIPS-3 | 356.68 | 1131.57 | 31.52 |
ANP/HIPS-4 | 607.36 | 1373.80 | 44.21 |
ANP/HIPS-5 | 850.00 | 1550.95 | 54.81 |
ANP/HIPS-6 | 273.09 | 989.17 | 27.61 |
1
where As is area from integration of the strongest diffraction peaks, Ag is area from standard substance integration.
The diffraction peak positions of the ANP/HIPS composite filler are similar to those of the peaks of the neat PPTA, which confirms the formation of PPTA in the HIPS matrix.[
The formation of PPTA material in the ANP/HIPS-X composites via direct "in situ polymerization" of PPD and TPC monomers was therefore confirmed by FTIR, XRD analysis and XPS.
SEM images of upper surfaces of neat HIPS and ANP/HIPS-X nanocomposite samples are shown in
Fig 7 SEM images of top surfaces of (a) HIPS and (b−f) ANP/HIPS-X: (b) ANP/HIPS-1, (c) ANP/HIPS-2, (d) ANP/HIPS-3, (e) ANP/HIPS-4, (f) ANP/HIPS-5.
Fig 8 EDS images of ANP/HIPS-5.
Fig 9 AFM results of (a) HIPS and (b−f) ANP/HIPS-X: (b) ANP/HIPS-1, (c) ANP/HIPS-2, (d) ANP/HIPS-3, (e) ANP/HIPS-4, (f) ANP/HIPS-5.
Samples | Roughness | ||
---|---|---|---|
Ra (nm) | Rq (nm) | Rmax (nm) | |
Neat HIPS | 1.06 | 1.53 | 23.7 |
ANP/HIPS-1 | 1.77 | 2.57 | 41.7 |
ANP/HIPS-2 | 1.58 | 2.32 | 22.4 |
ANP/HIPS-3 | 1.74 | 2.59 | 31.4 |
ANP/HIPS-4 | 4.72 | 6.11 | 109 |
ANP/HIPS-5 | 4.15 | 5.52 | 67.9 |
The DSC curves labelled with the glass transition temperature (Tg) of the samples are shown in
Fig 10 DSC curves of neat HIPS and ANP/HIPS-1 to ANP/HIPS-5.
This confirms the observations in the microscopic images discussed previously. The ANP/HIPS-X nanocomposites see a positive correlation between Tg and the ANP content, that is, the value of Tg increased from 64.76 °C to 101.04 °C with increasing ANP content. As ANPs can effectively impede the movement of the polymer chain segments of HIPS, higher temperature is required during phase transition to free up those chain segments for composites containing higher content of ANPs. The higher Tg values of the composites versus pure HIPS also indicate improved thermal stability of the composites.[
The TGA curves of composites are shown in
Fig 11 TGA curves of neat HIPS and ANP/HIPS-X.
The mechanical stress-strain curves for neat HIPS and ANP/HIPS-X nanocomposites are shown in
Fig 12 Stress-strain diagrams of neat HIPS and ANP/HIPS-X.
Sample | Young's modulus (MPa) | Toughness(N/mm2) | Tensile stress (MPa) |
---|---|---|---|
HIPS | 246.55 | 0.32 | 3.07 |
ANP/HIPS-1 | 682.64 (176%) | 0.59 (84%) | 14.01 (356%) |
ANP/HIPS-2 | 771.74 (212%) | 1.51 (371%) | 19.86 (546%) |
ANP/HIPS-3 | 1908.17 (673%) | 1.87 (484%) | 22.63 (637%) |
ANP/HIPS-4 | 900.72 (265%) | 2.36 (637%) | 25.41 (727%) |
ANP/HIPS-5 | 2025.12 (721%) | 3.92 (1125%) | 29.76 (869%) |
Modifiers | Tensile stress (MPa) | References |
---|---|---|
Multiwalled carbon nanotubes (MWNT) | 25.5 |
[ |
Aluminum nitride | 15.2 |
[ |
Coconut fiber | 24.51 |
[ |
Rubber toughened glass fibre | 13 |
[ |
Recycled polypropylene (R-PP) | 22.91 |
[ |
ANP | 29.76 | This study |
The SEM photos of the fracture surfaces of composites after stretching are presented in
Fig 13 SEM images of cross sections of (a) HIPS, (b) ANP/HIPS-1, (c) ANP/HIPS-2, (d) ANP/HIPS-3, (e) ANP/HIPS-4 and (f) ANP/HIPS-5.
In this work, ANP was successfully synthesized in a HIPS-containing solution by in situ "bottom-up" polymerization, producing an ANP/HIPS composite filler. A composite sheet was fabricated by blending the ANP/HIPS filler with neat HIPS. As confirmed by a series of characterization methods, the filler-enhanced composite sheets showed a striking improvement in toughness and other mechanical properties as well. The toughness increase rate of ANP/HIPS composites can reach up to 1125% and the increase rate of Young's modulus is 721%. ANP is a new nanofiller material especially suited for toughening HIPS. This finding also provides a promising new direction for the subsequent industrial production of HIPS.
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