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Reinforcement of High Impact Polystyrene by Aramid Nanoparticle Fillers Prepared via an In situ Bottom-up Approach
RESEARCH ARTICLE | Updated：2024-08-06
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    • Reinforcement of High Impact Polystyrene by Aramid Nanoparticle Fillers Prepared via an In situ Bottom-up Approach

    • Gong Xiang-Jun

      ,  

      Zhao Zhi-Ping

      ,  

      Sun Chang-Mei

      ,  

      Zhang Ying

      ,  

      Qu Rong-Jun

      ,  

      Wang Ying

      ,  
    • Chinese Journal of Polymer Science   Vol. 42, Issue 8, Pages: 1167-1176(2024)

    • DOI：10.1007/s10118-024-3124-6    

      CLC：

    • 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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  • Xiang-Jun Gong, Zhi-Ping Zhao, Chang-Mei Sun, et al. Reinforcement of High Impact Polystyrene by Aramid Nanoparticle Fillers Prepared via an In situ Bottom-up Approach. [J]. Chinese Journal of Polymer Science 42(8):1167-1176(2024) DOI： 10.1007/s10118-024-3124-6.

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    Abstract

    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.

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    Keywords

    High impact polystyrene; PPTA nanoparticle; Reinforce; Mechanical property

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    INTRODUCTION

    High impact polystyrene (HIPS) is a type of modified polystyrene (PS) material by polybutadiene (PB).[

    1] Ease of processing, low cost, and non-toxicity of HIPS[2] render its wide uses in the electronics and medical industries and as a key military and construction material.[3] Although HIPS is a modified product of PS, the flame retardancy, toughness and strength of HIPS are still poor.[4]
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    Modification of the HIPS material to improve its properties has been the focus of many recent studies.[

    5] Modification efforts mainly fall into two categories—chemically functionalizing HIPS [6]and adding various composite fillers. Amongst the fillers, nanomaterials, such as SiO2 nanoparticles,[7] CaCO3 nanoparticles[8] and carbon nanotubes,[9] showed great promise in improving its flame retardancy and mechanical properties. For example, Chatterjee et al.[8] studied the rheology, thermal, mechanical and morphological properties of CaCO3/HIPS nanocomposites. The experimental results showed that the rheology, thermal, mechanical and morphological properties of hybrid nano-CaCO3/PS particles were enhanced in HIPS matrix. This filler approach, however, often encounters the issues of poor dispersion and ease of filler agglomeration, which would lead to abnormal growth of particles, formation of stress concentration points or defect points, and fast deterioration of polymer properties.[10,11]
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    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.[

    12] However, the aromatic rings in the polymer backbone of PPTA macrofibers and the interchain hydrogen bonding between the ―NH2 and ―C＝O functional groups result in rigidity and therefore smooth surface when used as a filler, which leads to poor distribution in the matrix and low interfacial bonding strength with the polymer.
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    Aramid nanofibers (ANFs), which was successfully prepared using a "top-down" method by Yang et al. in 2011,[

    13] compensate for some of the disadvantages of macro aramid fiber.[14] The large number of functional groups on the surface of ANFs enhances their interaction with the polymer matrix, compensating for the disadvantage of macroscopic fibers that have smooth surfaces and are difficult to bind other substances. ANFs combine some desirable characteristics of PPTA and nano materials, including good mechanical properties, high aspect ratio and surface area, which can improve reactivity and interfacial bonding strength with polymer.[15] For example, ANFs composited with poly(vinyl alcohol) (PVA) well,[16] and the resulting composites showed high toughness, tensile strength, and unexpected modified thermal stability. The interfacial adhesion of carbon fibers was found to be improved with the addition of ANFs.[17] At the same time, the addition of ANFs realized the toughening of the original masterbatch. Despite the interfacial compatibility issue addressed by ANFs, more problems remain such as ease of agglomeration, difficulty in dispersion, and long preparation time.[18]
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    Recently, our group successfully synthesized nano aramid in a PVC-containing solution via a "bottom-up" method.[

    19] Interestingly, the obtained nano aramid was observed to be spherical in shape, which made us realize that nano aramid can present in various forms besides the typical ANF line shape. The spherical nano aramid was named aramid nanoparticle (ANP) by us. It was subsequently discovered that the shapes of nano aramids varied with the polymer structures in the reaction solution. In a polystyrene-containing solution, nano aramids were obtained as nanorods and nanobundles.[20] All nano aramids with various shapes distributed uniformly and compatibly within the polymer matrices without undesirable agglomeration. Material performance including thermal stability and mechanical properties was greatly enhanced by the nano aramid fillers. In addition, the "bottom-up" approach takes only a few hours, whereas the "top-down" approach usually takes at least a week.
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    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.

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    EXPERIMENTAL

    Materials and Instruments

    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.

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    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.

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    Synthesis of ANP/HIPS Composite Filler

    Table 1 shows the synthesis recipes of HIPS and ANP/HIPS with varied PPD and TPC contents. The ANP/HIPS composites are denoted as ANP/HIPS-X, where X is the level of PPD and TPC with 1 being the lowest and 3 having triple the amount of PPD and TPC in 1.

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    Table 1  Preparation recipes of ANP/HIPS composites.
    SamplesDMF (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
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    The preparation of ANP/HIPS can be found in the literature,[

    20] where the specific preparation process is shown below.
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    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 Table 1). The TPC portion was added dropwise to the PPD portion in an ice bath, and then the polymerization reaction was carried out for 3 h at room temperature under dry nitrogen. Finally, the product solution (ANP/HIPS-X) was washed repeatedly with deionized water to pH neutrality to produce white pellets. The white pellets are dried at 50 °C to make the ANP/HIPS composite filler.

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    Preparation of ANP/HIPS Composite Sheet

    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.

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    Fig 1  Flowchart of the experimental preparation of ANP/HIPS composite sheet.

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    RESULTS AND DISCUSSION

    FTIR Analysis of ANP/HIPS Composite Filler

    The FTIR spectra of neat HIPS and ANP/HIPS-1 to ANP/HIPS-5 nanocomposites are shown in Fig. 2. The characteristic bands of PPTA at 3328, 1540 and 1317 cm−1 are present in the composite samples, indicating the formation of PPTA. Their band heights also increase with the starting PPD and TPC monomer contents as expected.[

    21]
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    Fig 2  FTIR spectra of neat HIPS and ANP/HIPS-X samples

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    XPS Analysis of ANP/HIPS Composite Filler

    Fig. 3(a) compares the XPS spectra of neat HIPS and ANP/HIPS-X composites. An additional N 1s peak is present in the composites. The N 1s peak of ANP/HIPS-5 was fitted to the split peaks using CasaXPS, as shown in Fig. 3(c). The characteristic peak of the amide bond (N―C＝O) in ANP appears at 399.7 eV. As shown in Fig. 3(b), the C 1s peak of the same sample was also fitted to the split peaks at 284.2, 284.6 and 286.2 eV, corresponding to the presence of O＝C―N, C―C, C＝C and C―N bonds, respectively.[

    22] The expected chemical bonds of PPTA were therefore confirmed by XPS.
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    Fig 3  (a) Overlaid XPS spectra of samples; (b) C 1s spectra of ANP/HIPS-5; (c) N 1s spectra of ANP/HIPS-5.

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    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.

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    Micromorphological Analysis of ANP/HIPS Composite Filler

    As shown in the TEM images of the ANP/HIPS-X nanocomposites in Fig. 4, the ANPs in the composites are spherical and well distributed with no significant particle aggregation. This may be due to the steric hindrance of long chains of HIPS matrix to the chain growth of the PPTA from the monomers PPD and TPC. As a result, only short chains of PPTA intertwine in the solvent DMF to form spheres. The well dispersed ANPs lead to improved mechanical properties of HIPS. Another interesting observation is that the average particle size increases with the ANP content. This may be due to the increase in solution viscosity with the monomer content, and longer PPTA molecular tend to be formed. As a result, larger ANPs can be obtained. The formation of spheres may be attributed to high solution viscosity, slow movement of matrix and entanglement of PPTA chains.[

    23,24]
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    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.

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    Fig. 5 shows polarized light microscopy images of ANP synthesized in situ in HIPS systems with different monomer PPD/TPC contents. Figs. 5(a)−5(c) show the samples with lower monomer contents, the ANP crystals (black dots) exist almost entirely as well-dispersed mono-spherical crystals. At higher monomer contents as shown in Figs. 5(d)−5(e), crystal aggregation occurs at 30 °C due to an increase in the number of crystals per unit volume.[

    20]
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    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.

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    XRD Analysis of ANP/HIPS Composite Sheet

    XRD patterns of ANP/HIPS-1 to ANP/HIPS-5 samples in Fig. 6 show peaks at similar positions to those of the Kevlar (PPTA) characteristic peaks at 2θ angles of 18°, 25° and 29°, which correspond to reflections at positions (110), (200) and (004), respectively. Based on the three lattice planes corresponding to the above three diffraction peaks, the crystallinity (Xc) can be calculated by Eq. (1) and the results are listed in Table 2.

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    Fig 6  XRD patterns of neat HIPS and ANP/HIPS samples at 25°C

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    Table 2  Crystallinity of neat HIPS and ANP/HIPS-X.
    SamplesAsAgXc (%)
    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
    icon Download:  CSV

    Xc=As/Ag×100%math 1

    where As is area from integration of the strongest diffraction peaks, Ag is area from standard substance integration.

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    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.[

    16,25] Similarly, the peak intensities also increase with the starting PPD and TPC monomer contents. However, the ANP/HIPS-6 sample had a change in the amount of ANP produced due to excessive monomer additions, an increase in the viscosity of the solution, and a slow movement of the monomers. This could be due to the combined effect of covalent bonding between the amide bond and the benzene ring as well as the π-π conjugation effect, inducing the growth of the crystals in the direction of the a-axis, which results in the intensity enhancement of the diffraction peaks.[26]
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    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.

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    SEM-EDS Analysis of ANP/HIPS Composite Sheet

    SEM images of upper surfaces of neat HIPS and ANP/HIPS-X nanocomposite samples are shown in Fig. 7. Neat HIPS has a flat surface (Fig. 7a), while the surface roughness of the composite increases with the monomer content (Figs. 7b−7f). The EDS images of ANP/HIPS-5 are shown in Fig. 8. The N (in green) and O (in yellow), both unique to PPTA, are well dispersed in the images without forming large aggregates. This indicates that PPTA is well dispersed in the HIPS matrix and can be well compatible with HIPS.[

    27,28]
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    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.

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    Fig 8  EDS images of ANP/HIPS-5.

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    AFM Analysis of ANP/HIPS Composite Sheet

    Fig. 9 shows the AFM results of HIPS and ANP/HIPS-X composite films and the roughness values are listed in Table 3. The average roughness (Ra) is 1.06 nm for neat HIPS (1.06 nm) and ranges from 1.58 nm to 4.72 nm for ANP/HIPS-X composites. A positive correlation can be observed between Ra of nanocomposites and the ANP content. This phenomenon may occur as the monomer PPD/TPC content increases, the dense layer formed during the process of blending and vulcanization with HIPS becomes thinner, resulting in increased roughness. Moreover, the compatibility between the solvent DMF and water is poor, which leads to increased surface roughness of ANP/HIPS-X. A third contributing factor may be temperature, which leads to thermodynamic instability and the tendency of ANP nanoparticles to copolymerize during the process of blending and vulcanization with the masterbatch, increasing roughness.[

    29]
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    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.

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    Table 3  Roughness values of samples.
    SamplesRoughness
    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
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    Thermal Stability Analysis of ANP/HIPS Composite Sheet

    The DSC curves labelled with the glass transition temperature (Tg) of the samples are shown in Fig. 10. All samples only exhibit one phase transition step (one peak), suggesting that the ANPs are well dispersed. For materials having multiple phases, multiple phase transitions may occur.

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    Fig 10  DSC curves of neat HIPS and ANP/HIPS-1 to ANP/HIPS-5.

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    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.[

    30]
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    The TGA curves of composites are shown in Fig. 11. The weight loss between 300−350 °C is attributed to the thermal decomposition of the HIPS matrix material and the formation of its volatile degradation products. A second weight loss in the 500−600 °C region is due to the thermal decomposition of the ANPs. As shown in the literature,[

    31] more monomer content in the HIPS matrix has no great influence on the thermal stability performance of PPTA.[32]
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    Fig 11  TGA curves of neat HIPS and ANP/HIPS-X.

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    Analysis of Mechanical Properties of ANP/HIPS Sample Sheet

    The mechanical stress-strain curves for neat HIPS and ANP/HIPS-X nanocomposites are shown in Fig. 12. The values of tensile strength, toughness, and Young’s modulus obtained from a universal material testing machine are listed in Table 4 with the percentage increase over the neat HIPS in parentheses. The ANP/HIPS-X nanocomposites significantly improved mechanical properties against neat HIPS as shown by stress-strain curves. The degrees of improvement are also positively correlated with the ANP content. ANP/HIPS-5 has the most significant improvement, showing a 721% increase in the Young's modulus, an 869% increase in tensile strength, and above all a 1125% increase in toughness from 0.32 N/mm2 to 3.92 N/mm2. The toughness of the composite material, as imparted by the ANP fillers, may derive from the macroscopic PPTA. As shown previously that the molecular weight of ANP increases with the monomer content, the strengthening effect of HIPS is more significant, potentially enabling practical industrial production of HIPS materials.[

    33,34]
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    Fig 12  Stress-strain diagrams of neat HIPS and ANP/HIPS-X.

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    Table 4  Mechanical properties of samples.
    SampleYoung'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%)
    icon Download:  CSV

    Table 5 shows the comparison of tensile stresses of HIPS composites in other studies and it can be clearly seen that the tensile stresses of ANP/HIPS composites in the present study have improved very significantly. This indicates that the mechanical properties of HIPS can be effectively improved by the ANP prepared by the "bottom-up" in situ polymerization method. Moreover, this method is simple, safe and efficient.

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    Table 5  Comparison of tensile stress of ANP/HIPS composites with other modifiers.
    ModifiersTensile stress (MPa)References
    Multiwalled carbon nanotubes (MWNT) 25.5 [35]
    Aluminum nitride 15.2 [36]
    Coconut fiber 24.51 [37]
    Rubber toughened glass fibre 13 [2]
    Recycled polypropylene (R-PP) 22.91 [38]
    ANP 29.76 This study
    icon Download:  CSV

    The SEM photos of the fracture surfaces of composites after stretching are presented in Fig. 13. The fracture surface of HIPS (Fig. 12a) is clearly flatter and smoother, confirming the observation in the AFM image. With the introduction of ANPs, the fracture starts to appear rough to different degrees, showing a "drawn" form. With the increase of ANP content, the composites show a gradual trend from brittle fracture to ductile fracture, suggesting improved toughness of the composite materials. ANPs, as a rigid rod-like molecule, are thermodynamically incompatible with HIPS, prompting their uniform dispersion in the ANP/HIPS system. The composites have limited compatibility at high temperatures during mixing with the masterbatch. They do not segregate in the matrix to form suspensions, but exist in a form similar to uniformly dispersed microspheres with good stability.[

    39]
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    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.

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    CONCLUSIONS

    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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