Polystyrene Samples Research Articles

Thermal Stability and Flammability Studies of MXene-Organic Hybrid Polystyrene Nanocomposites.

Polystyrene (PS) is widely used in the plastics industry, but the application range of PS is limited due to its inherently high flammability. A variety of two-dimensional (2D) nanomaterials have been reported to impart excellent flame retardancy to polymeric materials. In this study, a 2D nanomaterial MXene–organic hybrid (O-Ti3C2) was applied to PS as a nanofiller. Firstly, the MXene nanosheets were prepared by acid etching, intercalation, and delamination of bulk MAX (Ti3AlC2) material. These exfoliated MXene nanosheets were then functionalized using a cationic surfactant to improve the dispersibility in DMF. Even with a small loading of functionalized O-Ti3C2 (e.g., 2 wt%), the resulting PS nanocomposite (PS/O-Ti3C2) showed good thermal stability and lower flammability evidenced by thermogravimetric analysis (TGA) and pyrolysis-combustion flow calorimetry (PCFC). The peak heat release rate (pHRR) was significantly reduced by 32% compared to the neat PS sample. In addition, we observed that the temperature at pHRR (TpHRR) shifted to a higher temperature by 22 °C. By comparing the TGA and PCFC results between the PS/MAX and different weight ratios of PS/O-Ti3C2 nanocomposites, the thermal stability and 2D thermal- and mass-transfer barrier effect of MXene–organic hybrid nanosheets were revealed to play essential roles in delaying the polymer degradation.

Development of a gamma-ray scintillation detector based on blue-emitting oligomers and ZnO nanoparticles

We report the design of flexible, inexpensive, enduring, and efficient composite scintillation based on polystyrene (PS)/blue-emitting conjugated oligomer (CO)/ZnO nanoparticles. The oligomer utilized was 1,4-bis(9-ethyl-3-carbazo-vinylene)-9,9-dihexyl-fluorene (ADS086BE or BECV-DHF). Polystyrene was used as a matrix, and ZnO NPs were used as γ-ray stoppers. The formation of blends was analyzed using X-ray diffraction (XRD) and EDS. Field emission scanning electron microscopy (FE-SEM) images showed micron-sized bun (nearly square)-shaped domains, noodle-like structures, and submicron-sized domains with square-shaped nanosized domains for PS, PS/BECV-DHF, and PS/BECV-DHF/ZnO scintillator samples. The optical properties show that PS/BECV-DHF and PS/BECV-DHF/ZnO had absorption peaks at 350 and 375 nm and fluorescence peaks at 455 nm and 475 nm, respectively. The fabricated scintillators were coupled to the R6094 Hamamatsu Photomultiplier and gamma data acquisition system based on a multichannel analyzer (MCA). Gamma spectra were measured via three gamma-ray sources, Am-241, Cs-137 and Co-60. The results show better scintillation counting in the fabricated PS/BECV-DHF/ZnO than PS/BECV-DHF and the PS sample reference samples.

Ecotoxic emissions generated by illegal burning of household waste

The practice of burning household waste including different types of plastic is illegal in Hungary, still an existing problem. As environmental consequences are hardly known, this study attempts to give an initial estimation of the ecotoxicity generated during controlled combustion of different waste types. These samples included polystyrene (PS), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyurethane (PU), oriented strand board (OSB) and rag (RAG). Ecotoxicological profiling was completed using the following test battery: Vibrio fischeri bioluminescence inhibition assay, Daphnia magna immobility test and the seedling emergence assay. Also, genotoxicity of plastic waste samples was assessed using the SOS Chromotest. Concerning main pollutants in the samples, the samples could be distinguished as ‘PAH-type’ and ‘heavy metal-type’ samples. PVC, PU and PS samples showed the highest toxicity in the Vibrio and Daphnia assays. The PVC sample was characterized by an extremely high cadmium concentration (22.4 μg/L), PS, PP and PU samples on the contrary had high total PAH content. While Vibrio and Daphnia showed comparable sensitivity, the phytotoxicity assay had no response for any of the samples tested. Samples originating from the controlled burning of different plastic types such as PU, PVC, PS and PP were classified as genotoxic, PS sample showed extremely high genotoxicity. Genotoxicity expressed as SOSIF showed strong correlation with most of the PAHs detected.

Introduction of 3‐Hydroxypropionate Moieties to Polystyrene by “Graft Through” Strategy

Abstract3‐hydroxypropionate moieties grafted polystyrene [poly(S‐g‐3HP)] was prepared by sequentially applying the hydrogen‐transfer polymerization (HTP) and the free‐radical polymerization (FRP) via “grafting through” strategy. For this purpose, oligomeric poly(3‐hydroxypropionate) with vinyl end‐group (P3HP) was prepared via HTP of acrylic acid in the presence of tNaBuO as an alkaline catalyst. Then, the oligomeric P3HP was used as a comonomer in the FRP of styrene yielding the poly(S‐g‐3HP) copolymer, namely chemically modified polystyrene. 1H‐NMR, FTIR, DSC, TGA, GPC, and MALDI MS techniques were applied to confirm the structures of both the oligomer and modified polystyrene. Glass transition temperatures of the modified polystyrene samples were found to be decreased from 103 to 84 °C depending upon the amount of 3‐hydroxypropionate (3HP) moieties. Solution‐cast films were prepared by the polystyrene homopolymer and modified polystyrenes. The contact angle values were determined to decrease gradually from 87.5 to 53.7° with increasing the amount of the 3HP moiety grafted polystyrene.

Quantifying nanoscale forces using machine learning in dynamic atomic force microscopy.

Dynamic atomic force microscopy (AFM) is a key platform that enables topological and nanomechanical characterization of novel materials. This is achieved by linking the nanoscale forces that exist between the AFM tip and the sample to specific mathematical functions through modeling. However, the main challenge in dynamic AFM is to quantify these nanoscale forces without the use of complex models that are routinely used to explain the physics of tip–sample interaction. Here, we make use of machine learning and data science to characterize tip–sample forces purely from experimental data with sub-microsecond resolution. Our machine learning approach is first trained on standard AFM models and then showcased experimentally on a polymer blend of polystyrene (PS) and low density polyethylene (LDPE) sample. Using this algorithm we probe the complex physics of tip–sample contact in polymers, estimate elasticity, and provide insight into energy dissipation during contact. Our study opens a new route in dynamic AFM characterization where machine learning can be combined with experimental methodologies to probe transient processes involved in phase transformation as well as complex chemical and biological phenomena in real-time.

Сверхизлучение и синтез наночастиц металла в полистирольном композите с многоспиновыми комплексами Eu при быстром одноосном сдавливании

Composites of heterospin molecular magnet [EuIII(SQ)3bipy] in a polystyrene (PS) matrix have been synthesized. This complex [EuIII(SQ)3bipy] contains four paramagnetic centers - the Eu3+ ion and three SQ ligands (SQ—3,6-di-tert-butyl benzoquinone radical anion); bipy (bipyridyl) is diamagnetic. It has been established that intensive mechanical activation of [EuIII(SQ)3bipy]/PS samples leads to an reological explosion, as a result of which radio frequency superradiance, the appearance of free electrons and the formation of Eu metal nanoparticles are observed. The duration of this process is 10 ns.

Thermal Pyrolysis of Polystyrene Aided by a Nitroxide End-Functionality Improved Process and Modeling of the Full Molecular Weight Distribution.

A significantly improved thermal pyrolysis process for polystyrene (PS) is reported and mathematically modeled, including the description of the time evolution of the full molecular weight distribution of the polymer during its degradation by direct integration of the balance equations without simplifications. The process improves the styrene yield from 28–39%, reached in our previous report, to 58–75% by optimizing the heating ramp during the initial stage of the pyrolysis process. The process was tested at 390 and 420 °C on samples of conventional PS synthesized via free-radical polymerization (FRP) and PS with a nitroxide end-functionality synthesized via nitroxide mediated polymerization (NMP) with three levels of the nitroxide to initiator (N/I) molar ratio: 0.9, 1.1 and 1.3. The NMP-PS produced with N/I = 1.3 generates the highest styrene yield (75.2 ± 6.7%) with respect to the best FRP-PS yield (64.9 ± 1.2%), confirming the trends observed in our previous study. The mathematical model corrects some problems of a previous model that was based on assumptions that led to significant errors in the predictions; this is achieved by solving the full molecular weight distribution (MWD) without assumptions. The model provides further insight into the initial stages of the pyrolysis process which seem to be crucial to determine the chemical paths of the process and the styrene yield, as well as the influences of the initial heating ramp used and the presence of a nitroxide end-functionality in the polymer.

COMPLEX GEOMETRIC EVALUATION OF POLYMER MATERIALS QUALITY

A computational technique of comparative evaluation of polymer material quality in a homogeneous set of samples according to a complex geometric criterion is proposed. Samples of physical and mechanical parameters of samples of industrial impact-resistant polystyrene are used for calculation. The most averaged complex of physical and mechanical properties is used as the calculation base.

Sintering graded foamed beads: Compressive properties

AbstractDesigning the foam structures in terms of density and morphology gives the chance to tune their mechanical and functional properties to the specific application. Nowadays, this design has been leveled up by the introduction of graded foams which are characterized by spatially nonuniform densities and/or morphologies. Graded foams have proved superior compared to uniform one in numerous examples and loading conditions but in pure compressive loading, where properties such as the Young's modulus of graded foams are always inferior to uniform ones. When using sintered beads foams, macroscopic pure compression may induce local bending on the single bead, which can be exploited to induce stiffening. This thesis was investigated on both polystyrene and thermoplastic polyurethane samples made by foamed beads sintered in a cylindrical mold. The response to compressive tests of graded foams made by sintering beads having nonuniform cells structures was compared to the uniform counterparts. The results evidenced that, at same average density, foams had up to a 30% ca. of increase of the Young's modulus when the beads are characterized by a denser outer layer.

Development of an asymmetrical flow field-flow fractionation system for the size characterization of starch granules

淀粉颗粒粒径与分子尺寸分别在1~100 μm和20~250 nm之间,是影响淀粉功能特性的重要因素之一。非对称场流分离(AF4)是一种基于样品与外力场相互作用机制的分离技术,已应用于表征淀粉分子尺寸分布。商品化的AF4系统的粒径检测范围为1 nm~10 μm,对于淀粉颗粒粒径表征具有一定的局限性。该文研制了AF4分离系统;考察了其在微米尺度下对红薯、莲子和大米淀粉颗粒粒径表征的性能;采用微米尺寸的聚苯乙烯乳化球(PS)标准样品验证了构建的AF4系统的分离性能。实验结果显示,构建的AF4系统对PS混合样品(粒径2、6、12、20 μm)实现了基线分离,同商品化AF4相比提高了检测上线,具有分离表征淀粉颗粒的潜力。此外,该文研究了载液组成对淀粉颗粒分离表征的影响;通过光学显微镜验证了构建的AF4系统在微米尺度上对淀粉颗粒粒径分布的表征能力。最后,采用商品化的AF4系统串联多角度激光光散射检测器和示差折光检测器对3种淀粉分子进行了分离表征,考察了淀粉的溶解温度对其表征结果的影响。在摩尔质量10 6~108 g/mol范围内,红薯和莲子淀粉的回转半径和水合半径的比值(Rg/Rh)在0.9~1.1之间,大米淀粉的Rg/Rh在1.2~1.4之间。实验结果证明构建的AF4系统是一种快速、准确的淀粉颗粒粒径表征方法,与商品化的AF4系统结合可为研究淀粉尺寸分布与其功能性质之间的关系提供技术支持。

Pressure stress modeling on expanded polystyrene materials using genetic programming

In the production of expanded polystyrene, the standards are very high in terms of thermal, fire, dimensional, and mechanical characteristics, because each of the characteristics is a condition for achieving quality that allows competitiveness in the market. To ensure high-quality products, it is necessary to achieve optimal performance and product quality through carefully adjusted input parameters of production. Since the production of expanded polystyrene is specific in several ways, an experimental study was conducted in which the basic parameters affecting product quality were detected and through which a series of experiments were performed to prove product quality. Experimental research for this work was conducted on three types of expanded polystyrene samples whose purpose is to insulate floors exposed to pressure. The samples were made of the same material of different densities and aging times for which the pressure stress at a deformation of 10% was tested. After the experimental phase, the modeling of the output parameters was performed. Modeling involved the development of a model that describes a given problem and the obtained modeled values were analyzed and compared with the experimental one. The modeling method used genetic programming using the GPdotNET software package. The goal of modeling with the GpdotNET tool is to obtain a realistic model that would give the value of the compression stress at a deformation of 10% as an output variable in materials made of expanded polystyrene.

Occurrence, potential release and health risks of heavy metals in popular take-out food containers from China

Global consumption of take-out food increased rapidly and the chemicals in their containers become a potential source of human exposure. However, available information on heavy metals in the containers is extremely limited and the associated health risks remain poorly understood. We investigated Cd, Cr, Pb, Sb, Mn, Ni and Co in the popular take-out food containers from China and found the concentrations of these metals were moderate in comparison to the concentrations reported in other food contact materials. The metal concentrations in sampled containers by material type differed significantly, and higher concentrations of Cd, Pb, Sb, Mn and Co were observed in expanded polystyrene samples. The metals in the containers likely originated from intentional addition and/or contamination of materials. The potential release of the metals from containers was simulated and found the median leaching rates of Cd, Pb, Sb, Ni and Co in the range of 0.36–4.80% under typical conditions, which depended largely on the material types. Based on the observed leaching rates, we estimated that the summed carcinogenic risks of Cd, Pb, Ni and Co were unacceptable under specific exposure frequency, although the total non-carcinogenic risks from metal intake were low.

A Dual-Phase Approach to Reveal the Presence and the Impact of the TLL Transition in Polymers Melts. Part I: Predicting the Existence of Boyer’s TLL Transition from the Vogel–Fulcher Equation

R.F. Boyer recognized the manifestations of a T > Tg transition-relaxation as early as 1963 and named it TLL, the liquid-liquid transition. He suggested that it was due to the melting of “local order”, a controversial issue conflicting with the dominant theories at the time, led by P. Flory, which asserted a structure-less liquid state for melts. At the same time as this controversy unrolled, de Gennes published his reptation model of polymer physics which, after some modifications and ramifications, quickly became the new paradigm to describe the dynamic properties of polymer flow. The new model of reptation has no theoretical arguments to account for a T > Tg transition occurring in the melt; hence, the current consensus about the existence of TLL is still what it was already in 1979, that it is probably an artifact only existing in the imagination of Boyer. In part I of this paper on the TLL transition we mathematically derive the existence and the characteristics of TLL from a dual-phase description of the free volume using a modification of the Vogel-Fulcher equation (VF), a well-known formulation of the temperature dependence of the viscosity of polymer melts. This new expression of the VF formula, that we call the TVF equation, permits to determine that TLL is in an iso-free volume and iso-enthalpic state when M, the molecular weight, varies. The data analyzed by the TVF equation are the dynamic rheological results for a series of monodispersed, un-entangled polystyrene samples taken from the work of Majesté. The new analysis also permits to put in evidence the existence of a new transition, which we call Mmc, approximately located at Mmc ≈ Mc/10, where Mc is the molecular weight for entanglement. A Dual-Phase interpretation of Mmc is proposed.

Third-Order Elastic Moduli of Polystyrene Samples Fabricated by Different Technologies

Third-Order Elastic Moduli of Polystyrene Samples Fabricated by Different Technologies

Influence of Polymer Molecular Weight on Chain Conformation at the Polystyrene/Silver Interface.

The dependence between the conformation of polystyrene (PS) and its molecular weight (Mw) in the vicinity of a metal interface was investigated by sum frequency generation (SFG) spectroscopy. Tilt angles θ ≥ 50° (the angle between the C2 axis of the pendant phenyl ring and the surface normal) were observed for all samples because of the interaction between the aromatic rings and the metal surface. Furthermore, it was found that θ decreases with increasing Mw for PS samples ranging from 20 × 103 g/mol to 400 × 103 g/mol. The intensity of the backbone SFG signal was higher for high Mw PS, compared to low Mw PS, indicating a greater number of backbone interactions with the silver substrate surface for the high Mw sample. These structural differences are driven by different entropic and enthalpic contributions to the free energy of adsorption for different polymer molecular weights. Differences in the polymer free volume and in the relative amount of chain ends with higher mobility may also influence the chain conformation. These results suggest that important interfacial properties of polymeric thin films, such as adhesion and wettability, could be tailored by modifying the polymer Mw to achieve the desired interfacial conformation.

Effect of molecular weight and architecture on nanoscale viscoelastic heterogeneity at the surface of polymer films

Dissipated energy mapping in amplitude-modulation atomic force microscopy was employed to characterize the nanoscale heterogeneous behavior of the viscoelastic response at the surface of polystyrene (PS) films of different molecular weight and architecture. By using an ultra-sharp probe with tip radius of ~1 nm, we were able to visualize the viscoelastic heterogeneities at the free surface of all PS samples. While the length scale of these heterogeneities at the surface of linear PS films was measured to be ~2.2 nm nearly independent of the molecular weight, it was significantly increased to ~3.1 nm at the surface of four-arm star-shaped PS films. We also demonstrated that similar nanoscale heterogeneous features were not observed when using a common probe with tip radius of ~10 nm, thereby confirming the intrinsic nature of the observed viscoelastic heterogeneities with sizes on the order of a few nanometers at the surface of PS films. This result provides important insights into the fundamental role of the molecular architecture in controlling the heterogeneous dynamics and many associated physical properties of amorphous polymer surfaces.

Plasma Oxygen Interaction with Organic Polymer Films: A Mechanistic Study

In this presentation, first principles calculations combined with advanced surface diagnostics are used to unravel the mechanisms of plasma oxygen interaction with organic films, of interest for advanced patterning in semiconductor device manufacturing. Results from a combination of X-ray photoelectron spectroscopy (XPS) diagnosed oxygen plasma-exposed polystyrene films and first principles modeling of organic films (polystyrene, polyethylene and derivatives) provide insights into how organic films are oxidized by oxygen atoms. XPS measurements show the rapid formation of C-O structures and their saturation after oxygen exposure on both pristine and argon bombarded polystyrene samples. Quantum mechanics calculations confirm that C-OH formation can be immediate without recourse to previously formed dangling bonds. Multiple oxygen impacts are required for scission of pristine ethylene carbon strands. Therefore, ethylene films can be converted to polyols that are stable, whereas more likely strands are broken before polyol formation through the formation of water and C=O. On the contrary, intermediate compounds with adjacent C=O bonds are not likely to form stable structures. The combination of XPS measurements and modeling imply that the oxidation of polystyrene and polyethylene is self-limiting on both hydrogen saturated and de-hydrogenated (after argon ion plasma bombardment) surfaces.

Biodegradation of polystyrene by bacteria from the soil in common environments

Polystyrene (PS), a major plastic waste, is difficult to biodegrade due to its unique chemical structure that comprises phenyl moieties attached to long linear alkanes. In this study, we investigated the biodegradation of PS by mesophilic bacterial cultures obtained from various soils in common environments. Two new strains, Pseudomonas lini JNU01 and Acinetobacter johnsonii JNU01, were specifically enriched in non-carbonaceous nutrient medium, with PS as the only source of carbon. Their growth after culturing in basal media increased more than 3-fold in the presence of PS. Fourier transform infrared spectroscopy analysis, used to confirm the formation of hydroxyl groups and potentially additional chemical bond groups, showed an increase in the amount of oxidized PS samples. Moreover, field emission scanning electron microcopy analysis confirmed PS biodegradation by biofilms of the screened microbes. Water contact angle measurement additionally offered insights into the increased hydrophilic characteristics of PS films. Bioinformatics and transcriptional analysis of A. johnsonii JNU01 revealed alkane-1-monooxygenase (AlkB) to be involved in PS biodegradation, which was confirmed by the hydroxylation of PS using recombinant AlkB. These results provide significant insights into the discovery of novel functions of Pseudomonas sp. and Acinetobacter sp., as well as their potential as PS decomposers.

Influence of Polymer Insulating Barriers on The AC Breakdown Behaviour of Small Oil Gaps.(Dept.E)

The paper reports the influence of some different, currently used, polymer Insulating barriers on the AC withstand voltage of small oil gaps. The experiments have been conducted using barrier Samples of bakelite (Ba), polystyrene (PS) and polyvinyl chloride (PVC). The insulating barriers have been inserted in small oil gaps subjected to AC high voltage stress of weakly as well as, of very highly divergent fields. The improvement of the dielectric strength of all gaps through the insertion of polymer barriers has been found to be dependent on the kind of barrier material, barrier placement in the gap, barrier dimensions as well as, on the degree of the field homogeniousity of the gap. plantations of the different parameter effects are attempted by considering the different possible space charge distributions as well as, the special features of the used dielectric polymers. The achieved results are, not only important for barrier effect considerations, but also can be helpful as a guide for the design of oil - solid composite dielectrics.

Uncertainty Quantification Guided Parameter Selection in a Fully Coupled Molecular Dynamics-Finite Element Model of the Mechanical Behavior of Polymers.

The objective of investigating macroscopic polymer properties with a low computing cost and a high resolution has led to the development of efficient hybrid simulation tools. Systems generated from such simulation tools can fail in service if the effect of uncertainty of model inputs on its outputs is not accounted for. This work focuses on quantifying the effect of parametric uncertainty in our coarse-grained molecular dynamics-finite element coupling approach using uncertainty quantification. We consider uniaxial deformation simulations of a polystyrene sample at T = 100 K in our study. Parametric uncertainty is assumed to originate from parameters in the molecular dynamics model with a nonperiodic boundary (the force constant between polymer beads and anchor points, the number of anchor points, and the size of the surrounding dissipative particle dynamics domain) and a parameter to blend the energies of particles and continuum (weighting factor). Key issues that arise in uncertainty quantification are discussed on the basis of the quantities of interest including mass density, end-to-end distance, and radial distribution function. This work reveals the influence of key input parameters on the properties of polymer structure and facilitates the determination of those parameters in the application of this hybrid molecular dynamics-finite element approach.