Polymers

Every year, the world is producing around 100 metric tons of waste glass (WG), the majority of them are going to landfills that create massive environmental problems. One approach to solve this problem is to transform waste glass into construction materials. Glass is recyclable; however, the melting temperature of the glass is highly dependent on its colour that requires sorting before recycling. To overcome this challenge, many researchers and end-users are using broken glass in concrete either as a binder or aggregates. While significant investigations have done in this area, however, the outcomes of these studies are scattered, and difficult to reach a firm conclusion about the effectiveness of WG in concrete. In this study, the roles of WG and its impact on microstructural and durability properties for both cement and geopolymer concrete are critically reviewed. This review reveals that the amorphous silica in WG effectively participate to the hydration and geopolymerization process and improve concrete microstructural properties. This behaviour of WG help to produce durable concrete against shrinkage, chemical attack, freeze-thaw action, electrical and thermal insulation properties. The optimum replacement volume of binders or natural aggregates and particle size of WG need to be selected carefully to minimise the possible alkali-silica reaction. This review discusses a wide range of parameters for durability properties and challenges associated with WG concrete, which provides necessary guidelines for best practice with future research directions. Full article

Chronic kidney disease (CKD) is a systemic disorder that combines complex bone and mineral abnormalities. The high level of parathyroid hormone (PTH) in the blood causes irreversible renal dysfunction and cardiovascular disease. Therefore, it is necessary to reduce level of PTH in the blood of patients with uremic state. In this study, chitosan and heparin were chosen to form polysaccharide-based multilayer films based on their antibacterial ability, good biocompatibility and hemocompatibility. In addition, a previous study has revealed that PTH is a heparin/polyanion binding protein because of the similarity of heparin to the cell surface proteoglycans. Subsequently, the surface properties including thickness, surface hydrophobicity and surface charge of a series of multilayer films were analyzed. The PTH adsorption rate of a series of multilayer films was also assessed. The results revealed that the optimizing condition is (CHI/HEP)_2.5 and 60 min in both PBS only and PBS with the addition of bovine serum albumin, which demonstrated the specific adsorption of PTH on the materials. Furthermore, the hemolysis test also revealed that (CHI/HEP)_2.5 shows good blood compatibility. It is considered that polysaccharide-based multilayer films may provide an alternative for the surface modification of hemodialysis membranes and equipment. Full article

Nanopattern replication of complex structures by plastic injection is a challenge that requires simulations to define the right processing parameters. Previous work managed to simulate replication for single cavities in 2D and 3D, showing high performance requirements of CPU to simulate periodic trenches in 2D. This paper presents two ways to approach the simulation of replication of complex 3D hydrophobic surfaces. The first approach is based on previous CFD Ansys Fluent and compared to FE based CFD Polyflow software for the analysis of laminar flows typical in polymer processing and glass forming as well as other applications. The results showed that Polyflow was able to reduce computing time from 72 h to only 5 min as desired in the project. Furthermore, simulations carried out with Polyflow showed that higher injection and mold temperature lead to better replication of hydrophobicity in agreement with the experiments. Polyflow simulations are proved to be a good tool to define process parameters such as temperature and cycle times for nanopattern replication. Full article

There is need for developing novel conductive polymers for Digital Light Processing (DLP) 3D printing. In this work, photorheology, in combination with Jacobs working curves, efficaciously predict the printability of polyaniline (PANI)/acrylate formulations with different contents of PANI and photoinitiator. The adjustment of the layer thickness according to cure depth values (C_d) allows printing of most formulations, except those with the highest gel point times determined by photorheology. In the working conditions, the maximum amount of PANI embedded within the resin was ≃3 wt% with a conductivity of 10⁻⁵ S cm⁻¹, three orders of magnitude higher than the pure resin. Higher PANI loadings hinder printing quality without improving electrical conductivity. The optimal photoinitiator concentration was found between 6 and 7 wt%. The mechanical properties of the acrylic matrix are maintained in the composites, confirming the viability of these simple, low-cost, conductive composites for applications in flexible electronic devices. Full article

Optically transparent wood is a type of composite material, combining wood as a renewable resource with the optical and mechanical properties of synthetic polymers. During this study, the effect of monochromatic UV-C (λ—250 nm) radiation on transparent wood was evaluated. Samples of basswood were treated using a lignin modification method, to preserve most of the lignin, and subsequently impregnated with refractive-index-matched types of acrylic polymers (methyl methacrylate, 2-hydroxyethyl methacrylate). Optical (transmittance, colour) and mechanical (shore D hardness) properties were measured to describe the degradation process over 35 days. The transmittance of the samples was significantly decreased during the first seven days (12% EMA, 15% MMA). The average lightness of both materials decreased by 10% (EMA) and 17% (MMA), and the colour shifted towards a red and yellow area of CIE L*a*b* space coordinates. The influence of UV-C radiation on the hardness of the samples was statistically insignificant (W+MMA 84.98 ± 2.05; W+EMA 84.89 ± 2.46), therefore the hardness mainly depends on the hardness of used acrylic polymer. The obtained results can be used to assess the effect of disinfection of transparent wood surfaces with UV-C radiation (e.g., due to inactivation of SARS-CoV-2 virus) on the change of its aesthetic and mechanical properties. Full article

Heavy metals in water are a serious environmental problem due to their accumulation and toxicity; there are several processes we can use to address this issue, but adsorption is the most popular due to its simplicity and efficiency. Polysaccharides such as cellulose have received attention as adsorbents for heavy metals, and cotton–chitosan composites (CCs) were developed here with nontoxic reagents such as carboxylic acids as crosslinkers and NaH₂PO₄ as a catalyst to achieve chitosan covalent crosslinkage into oxidized cotton textiles with H₂O₂. The composites were characterized by fourier-transform infrared spectroscopy (FTIR), elemental analysis (EA), X-ray photoelectron spectroscopy (XPS), atomic-force and scanning electron microscopy (AFM and SEM), and tensile strength; the adsorption of lead ions (Pb) was evaluated with cotton–chitosan composites and quantified by microwave plasma atomic emission spectroscopy (MP-AES). The composites showed a maximum incorporation of chitosan of 27.62 mg per gram of cotton textile. A tensile strength analysis of the composite showed a Young’s modulus approximately 1 MPa higher than that of cotton textile. The adsorption of lead ions with composites in an aqueous solution at pH 5 and 25 °C was circa 74% after 6 h of contact, as determined by MP-AES. This work is an approach to demonstrate the potential of these polysaccharides, modified by “green” procedures to remove pollutants from water. Full article

The literature has shown that there is no consensus regarding the best resin composite photoactivation protocol. This study evaluated the efficiency of the conventional, soft-start, pulse-delay and exponential protocols for photoactivation of resin composites in reducing the shrinkage stress and temperature variation during the photopolymerisation. The photoactivation processes were performed using a photocuring unit and a smartphone app developed to control the irradiance according each photoactivation protocol. These photoactivation methods were evaluated applying photoactivation energies recommended by the resins manufactures. Three brands of resin composites were analysed: Z-250, Charisma and Ultrafill. The cure effectiveness was evaluated through depth of cure experiments. All results were statistically evaluated using one-way and multi-factor analysis of variance (ANOVA). The use of exponential and pulse-delay methods resulted in a significant reduction of the shrinkage stress for all evaluated resins; however, the pulse-delay method required too long a photoactivation time. The increases on the temperature were lower when the exponential photoactivation was applied; however, the temperature variation for all photoactivation protocols was not enough to cause damage in the restoration area. The evaluation of the depth of cure showed that all photoactivation protocols resulted in cured resins with equivalent hardness, indicating that the choice of an alternative photoactivation protocol did not harm the polymerisation. In this way, the results showed the exponential protocol as the best photoactivation technique for practical applications. Full article

Flexible dielectric polymer composites have been of great interest as embedded capacitor materials in the electronic industry. However, a polymer composite has a low relative dielectric permittivity (ε′ < 100), while its dielectric loss tangent is generally large (tanδ > 0.1). In this study, we fabricate a novel, high-permittivity polymer nanocomposite system with a low tanδ. The nanocomposite system comprises poly(vinylidene fluoride) (PVDF) co-filled with Au nanoparticles and semiconducting TiO₂ nanorods (TNRs) that contain Ti³⁺ ions. To homogeneously disperse the conductive Au phase, the TNR surface was decorated with Au-NPs ~10–20 nm in size (Au-TNRs) using a modified Turkevich method. The polar β-PVDF phase was enhanced by the incorporation of the Au nanoparticles, partially contributing to the enhanced ε′ value. The introduction of the Au-TNRs in the PVDF matrix provided three-phase Au-TNR/PVDF nanocomposites with excellent dielectric properties (i.e., high ε′ ≈ 157 and low tanδ ≈ 0.05 at 1.8 vol% of Au and 47.4 vol% of TNRs). The ε′ of the three-phase Au-TNR/PVDF composite is ~2.4-times higher than that of the two-phase TNR/PVDF composite, clearly highlighting the primary contribution of the Au nanoparticles at similar filler loadings. The volume fraction dependence of ε′ is in close agreement with the effective medium percolation theory model. The significant enhancement in ε′ was primarily caused by interfacial polarization at the PVDF–conducting Au nanoparticle and PVDF–semiconducting TNR interfaces, as well as by the induced β-PVDF phase. A low tanδ was achieved due to the inhibited conducting pathway formed by direct Au nanoparticle contact. Full article

Multiblock copolymers containing linear polydimethylsiloxane or polymethyltrifluoropropylsiloxane and ladder-like polyphenylsiloxane were synthesized in a one-step pathway. The functional homopolymer blocks and final multiblock copolymers were characterized using solution and solid-state multinuclear ¹H, ¹³C, ¹⁹F, and ²⁹Si NMR spectroscopy. It was shown that the ladder-like block contains silanol units, which influence the adhesion properties of multiblock copolymers and morphology of their casted films. The adhesion to metals and mechanical properties of multiblock copolymers were tested. The SEM study of casted films of multiblock copolymers shows the variety of formed morphologies, including long-strip-like or globular. Full article

Potentiometric biosensors based on flexible arrayed silver paste electrode and copper-doped zinc oxide sensing film modified by iron-platinum nanoparticles (FePt NPs) are designed and manufactured to detect lactate in human. The sensing film is made of copper-doped zinc oxide (CZO) by a radio frequency (RF) sputtering system, and then modified by iron-platinum nanoparticles (FePt NPs). The surface morphology of copper-doped zinc oxide (CZO) is analyzed by scanning electron microscope (SEM). FePt NPs are analyzed by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). The average sensitivity, response time, and interference effect of the lactate biosensors are analyzed by voltage-time (V-T) measurement system. The electrochemical impedance is analyzed by electrochemical impedance spectroscopy (EIS). The average sensitivity and linearity over the concentration range 0.2 mM–5 mM are 25.32 mV/mM and 0.977 mV/mM, respectively. The response time of the lactate biosensor is 16 s, with excellent selectivity. Full article

In the present study, poly(ethylene-co-vinyl alcohol) with 44 mol % ethylene content (EVOH₄₄) was managed to be processed, for the first time, by electrospinning assisted by the coaxial technology of solvent jacket. In addition to this, different suspensions of cellulose nanocrystals (CNCs), with contents ranging from 0.1 to 1.0 wt %, were also electrospun to obtain hybrid bio-/non-bio nanocomposites. The resultant fiber mats were thereafter optimally annealed to promote interfiber coalescence at 145 °C, below the EVOH₄₄ melting point, leading to continuous transparent fiber-based films. The morphological analysis revealed the successful distribution of CNCs into EVOH₄₄ up to contents of 0.5 wt %. The incorporation of CNCs into the ethylene-vinyl alcohol copolymer caused a decrease in the crystallization and melting temperatures (T_C and T_m) of about 12 and 7 °C, respectively, and also crystallinity. However, the incorporation of CNCs led to enhanced thermal stability of the copolymer matrix for a nanofiller content of 1.0 wt %. Furthermore, the incorporation of 0.1 and 0.5 wt % CNCs produced increases in the tensile modulus (E) of ca. 38% and 28%, respectively, but also yielded a reduction in the elongation at break and toughness. The oxygen barrier of the hybrid nanocomposite fiber-based films decreased with increasing the CNCs content, but they were seen to remain high barrier, especially in the low relative humidity (RH) regime, i.e., at 20% RH, showing permeability values lower than 0.6 × 10⁻²⁰ m³·m·m⁻²·Pa⁻¹·s⁻¹. In general terms, an optimal balance in physical properties was found for the hybrid copolymer composite with a CNC loading of 0.1 wt %. On the overall, the present study demonstrates the potential of annealed electrospun fiber-based high-barrier polymers, with or without CNCs, to develop novel barrier interlayers to be used as food packaging constituents. Full article

In this study, we evaluated the morphological behavior of polyurethane elastomers (PUEs) by modifying the soft segment chain length. This was achieved by increasing the soft segment molecular weight (Mn = 400–4000 gmol⁻¹). In this regard, polycaprolactone diol (PCL) was selected as the soft segment, and 4,4′-cyclohexamethylene diisocyanate (H₁₂MDI) and 1,6-hexanediol (HDO) were chosen as the hard segments. The films were prepared by curing polymer on Teflon surfaces. Fourier transform infrared spectroscopy (FTIR) was utilized for functional group identification in the prepared elastomers. FTIR peaks indicated the disappearance of −NCO and −OH groups and the formation of urethane (NHCOO) groups. The morphological behavior of the synthesized polymer samples was also elucidated using scanning electron microscopy (SEM) and atomic force microscopy (AFM) techniques. The AFM and SEM results indicated that the extent of microphase separation was enhanced by an increase in the molecular weight of PCL. The phase separation and degree of crystallinity of the soft and hard segments were described using X-ray diffraction (XRD). It was observed that the degree of crystallinity of the synthesized polymers increased with an increase in the soft segment’s chain length. To evaluate hydrophilicity/hydrophobicity, the contact angle was measured. A gradual increase in the contact angle with distilled water and diiodomethane (38.6°–54.9°) test liquids was observed. Moreover, the decrease in surface energy (46.95–24.45 mN/m) was also found to be inconsistent by increasing the molecular weight of polyols. Full article

The paper deals with the assessment of the age of oak wood (0, 10, 40, 80 and 120 years) on its fire resistance. Chemical composition of wood (extractives, cellulose, holocellulose, lignin) was determined by wet chemistry methods and elementary analysis was performed according to ISO standards. From the fire-technical properties, the flame ignition and the spontaneous ignition temperature (including calculated activation energy) and mass burning rate were evaluated. The lignin content does not change, the content of extractives and cellulose is higher and the content of holocellulose decreases with the higher age of wood. The elementary analysis shows the lowest proportion content of nitrogen, sulfur, phosphor and the highest content of carbon in the oldest wood. Values of flame ignition and spontaneous ignition temperature for individual samples were very similar. The activation energy ranged from 42.4 kJ·mol⁻¹ (120-year-old) to 50.7 kJ·mol⁻¹ (40-year-old), and the burning rate varied from 0.2992%·s⁻¹ (80-year-old) to 0.4965%·s⁻¹ (10-year-old). The difference among the values of spontaneous ignition activation energy is clear evidence of higher resistance to initiation of older wood (40- and 80-year-old) in comparison with the younger oak wood (0- and 10-year-old). The oldest sample is the least thermally resistant due to the different chemical composition compared to the younger wood. Full article

We synthesized a series of polystyrene derivatives modified with precursors of liquid crystal (LC) molecules via polymer modification reactions. Thereafter, the orientation of the LC molecules on the polymer films, which possess part of the corresponding LC molecular structure, was investigated systematically. The precursors and the corresponding derivatives used in this study include ethyl-p-hydroxybenzoate (homopolymer P2BO and copolymer P2BO#, where # indicates the molar fraction of ethylbenzoate-p-oxymethyl in the side chain (# = 20, 40, 60, and 80)), n-butyl-p-hydroxybenzoate (P4BO), n-hexyl-p-hydroxybenzoate (P6BO), and n-octyl-p-hydroxybenzoate (P8BO). A stable and uniform vertical orientation of LC molecules was observed in LC cells fabricated with P2BO#, with 40 mol% or more ethylbenzoate-p-oxymethyl side groups. In addition, the LC molecules were oriented vertically in LC cells fabricated with homopolymers of P2BO, P4BO, P6BO, and P8BO. The water contact angle on the polymer films can be associated with the vertical orientation of the LC molecules in the LC cells fabricated with the polymer films. For example, vertical LC orientation was observed when the water contact angle of the polymer films was greater than ~86°. Good orientation stability was observed at 150 °C and with 20 J/cm² of UV irradiation for LC cells fabricated with the P2BO film. Full article

The thermal stability of PVC with 1 wt % of spherical porous nanosilica, prepared by roll milling at processing time varied from 1 to 20 min, was investigated by means of visual color changes, Congo red, and thermogravimetric tests (TGA and DTG), as a function of rolling time and composition of PVC matrix. The melt flow rate (MFR) measurements were realized to identify the degradation-induced changes of processing properties. A high level of gelation of the PVC matrix for all samples was verified by DSC (differential scanning calorimetry). It was found that the addition of porous nanosilica to absorb a certain volume of HCl, produced by dehydrochlorination reaction, leads to an improvement of thermal stability, an effect observed in a form of minor color changes of the samples, lower evolution of gas hydrogen chloride, and slight changes of the MFR value. It was demonstrated that the TGA measurements are not sufficiently sensible to detect the degradation of PVC at the processing conditions, i.e., at the temperature equal to 220 °C and below this temperature. Full article

The objective of current work is to analyse the influence of different welding techniques and welding parameters on the morphology and mechanical strength of friction stir welds (FSW) in polymers, based on data collected in the literature. In the current work, only articles that provide data on the joint efficiency, or sufficient information to estimate it are considered. The process using conventional tool is presented and compared with new procedures developed for FSW of polymers, such as those using tools with heated stationary shoulder, preheating of the polymer or double-side passage of the tool. The influence of tool rotational speed (w), welding speed (v), tilt angle and geometry of the pin are discussed. This work focuses on the polymers most studied in the literature, polyethylene (PE) and polypropylene (PP). The use of external heating and tools with stationary shoulder proved to be of great importance in improving the surface finish, reducing defects, and increasing the mechanical strength of the welds. The increase in the w/v ratio increased the joint efficiency, especially when using conventional tools on PE. A trend was obtained for conventional FSW, but it was difficult to establish mathematical relationships, because of the variability of welding conditions. Full article

Wood polymer composites or WPCs are increasingly used as substitutes for natural wood in outdoor applications due to their better environmental sustainability and the consequent reduction in carbon footprint. In this paper, the presence of an elastomer used as a toughening agent (Santoprene by Exxon Mobil) in a polypropylene-based WPC containing 50 wt % wood flour was investigated in terms of its tribological behavior by dry sliding wear tests. These were performed after two environmental pre-conditioning treatments, i.e., drying and water soaking. The ball-on-disk configuration under a constant load was chosen along two sliding distances. Dynamic mechanical thermal analyses were used to reveal the effect of the toughening agent on the storage modulus and damping factor of the composites. Results in terms of weight loss measurement and coefficient of friction were obtained, together with surface morphology analysis of the worn surfaces at the scanning electron microscope and 3D profilometer. An abrasive wear mechanism was identified, and it was shown that the toughening agent improved wear resistance after both pre-treatments. This beneficial effect can be explained by the increase in strain at break of the WPC containing the elastomer. On the other hand, the water soaking pre-treatment produced severe damage, and the loss of material cannot be completely compensated by the presence of the toughening agent. Full article

This study aimed to investigate the influence of ultrasonic heat before photo-polymerization on the structural and physical properties of dental composites. Commercially available bulk-fill, nano-hybrid, micro-hybrid, and flowable composites were used. The samples were divided into three groups i.e., (i) without ultrasonic activation, (ii) ultrasonic activation at 15 Hz for 30 s, and (iii) ultrasonic activation at 15 Hz for 60 s. The degree of conversion percentage (DC%) and structural changes were evaluated with Fourier transform infrared spectroscopy. The presence of voids in restored tooth cavities were investigated with micro-computed tomography. The statistical analysis was performed using a one-way analysis of variance (ANOVA) post hoc Tukey’s test. The DC% was significantly increased with ultrasonic application in all groups except for flowable composites, whereby flowable composite showed a significant increase with 30 s ultrasonic activation only. The highest DC% was observed in 60 s ultrasonically activated nano-hybrid and micro-hybrid composites. The voids were reduced linearly with ultrasonic application in flowable and bulk-fill composites; however, non-linear behavior was observed with micro-hybrid and nano-hybrid composites, whereby the difference was significant within the groups. The frequency and time of the ultrasonic application is an important factor to consider and can be used to preheat composites before clinical application. Full article

An increased demand for energy in recent decades has caused an increase in the emissions of combustion products, among which carbon-dioxide is the most harmful. As carbon-dioxide induces negative environmental effects, like global warming and the greenhouse effect, a decrease of the carbon-dioxide emission has emerged as one of the most urgent tasks in engineering. In this work, the possibility for the application of the polymer-based, dense, mixed matrix membranes for flue gas treatment was tested. The task was to test a potential decrease in the permeability and selectivity of a mixed-matrix membrane in the presence of moisture and at elevated temperature. Membranes are based on two different poly(ethylene oxide)-based polymers filled with two different zeolite powders (ITR and IWS). An additive of detergent type was added to improve the contact properties between the zeolite and polymer matrix. The measurements were performed at three different temperatures (30, 60, and 90 °C) under wet conditions, with partial pressure of the water equal to the vapor pressure of the water at the given temperature. The permeability of carbon-dioxide, hydrogen, nitrogen, and oxygen was measured, and the selectivity of the carbon-dioxide versus other gases was determined. Obtained results have shown that an increase of temperature and partial pressure of the vapor slightly increase both the selectivity and permeability of the synthesized membranes. It was also shown that the addition of the zeolite powder increases the permeability of carbon-dioxide while maintaining the selectivity, compared to hydrogen, oxygen, and nitrogen. Full article