Eco-Design of Multifunctional System Based on a Shape Memory Polymer and ZnO Nanoparticles for Sportswear

Since the beginning of the 20th century, sportswear has a major contribution to the impact of fashion on our lives. Nowadays, the embracing of sportswear fashion/looks is undoubtedly noticeable, as the modern consumer searches for high comfort and linear aesthetics for its clothes. This compromise lead to the arise of the athleisure trend. Athleisure surges as a new style area that combines both wearability and fashion sense, differentiated from the archetypal sportswear, usually associated to “gym clothes”. Additionally, the possibility to functionalize and implement new technologies have shifted and progressively empowers the connection between the concepts of physical activities practice and well-being, allowing clothing to be more interactive and responsive with its surroundings. In this study, a design inspired in retro and urban lifestyle was envisioned, engineering textile structures that can respond to external stimuli. These structures are enhanced to be responsive to heat, water vapor and humidity, integrating shape memory polymers (SMP) to improve the breathability and heat-responsive behavior of the textiles and zinc oxide nanoparticles (ZnO NPs) to heighten the surface hydrophobic properties. The best results for hydrophobic exhibited superhydrophobic behavior with water contact angle (WAC) of more than 150 degrees. For the breathability and heat-response properties, SMP-coated samples showed an increase in water vapour permeability values of about 50% when compared with non SMP-coated samples. These innovative technological approaches were endorsed to design innovative clothing, in line with circular economy and eco-design principles, by assigning a substantial degree of mutability and versatility to the clothing. The development of a coat and shirt, in which different parts can be purchased separately to create multiple products, aims to combine the technicality of both the fabrics used and the making of the garments. This concept translates itself into a real constructive mechanism through the symbiosis of high-tech functionalities and the timeless design that follows the athleisure aesthetics.

Separation of Water/Organic Mixtures Using Micro- and Nanostructured Membranes of Special Type of Wettability

Both hydrophilic-oleophobic and hydrophobic-oleophilic membranes were obtained by coating of the substrate of membranes, presented by stainless steel meshes with various dimensions of their openings, with a composition that forms the special type of their surface wettability via spray-coating method. The surface morphology of resulting membranes was studied using SEM, the type of their wettability was identified by measuring the contact angle between the surface of membrane and a drop of studied liquid (water or organic liquid) and efficiency of continuous separation of water and organic liquid was studied on self-assembled setup.

A Dynamic Mechanical Thermal T-Peel Test Approach to Characterize Interfacial Behavior of Polymeric Textile Composites

Basic understanding of interfacial mechanisms is of importance for the development of polymer composites. For this purpose, we need techniques to analyze the quality of interphases, their chemical and physical interactions and their strength and fracture resistance. In order to investigate the interfacial phenomena in detail, advanced characterization techniques are favorable. Dynamic mechanical thermal analysis (DMTA) using a rheological system is a sensitive tool. T-peel tests were performed with this system, to investigate the temperature-dependent peel behavior of woven textile composites. A model system was made of polyamide (PA) woven fabric laminated with films of polypropylene (PP) or PP modified by grafting with maleic anhydride (PP-g-MAH). Firstly, control measurements were performed with solely PP matrixes. Polymer melt investigations, as well as the extensional stress, extensional viscosity and extensional relaxation modulus at -10°C, 100 °C and 170 °C, demonstrate similar viscoelastic behavior for films made of PP-g-MAH and its non-modified PP-control. Frequency sweeps have shown that PP-g-MAH has a zero phase viscosity of around 1600 Pa·s and PP-control has a similar zero phase viscosity of 1345 Pa·s. Also, the gelation points are similar at 2.42*104 Pa (118 rad/s) and 2.81*104 Pa (161 rad/s) for PP-control and PP-g-MAH, respectively. Secondly, the textile composite was analyzed. The extensional stress of PA66 fabric laminated with either PP-control or PP-g-MAH at -10 °C, 25 °C and 170 °C for strain rates of 0.001 – 1 s-1 was investigated. The laminates containing the modified PP need more stress for T-peeling. However, the strengthening effect due to the modification decreases by increasing temperature and at 170 °C, just above the melting temperature of the matrix, the difference disappears. Independent of the matrix used in the textile composite, there is a decrease of extensional stress by increasing temperature. It appears that the more viscous is the matrix, the weaker the laminar adhesion. Possibly, the measurement is influenced by the fact that the laminate becomes stiffer at lower temperatures. Adhesive lap-shear testing at room temperature supports the findings obtained with the T-peel test. Additional analysis of the textile composite at the microscopic level ensures that the fibers are well embedded in the matrix. Atomic force microscopy (AFM) imaging of a cross section of the composite shows no gaps between the fibers and matrix. Measurements of the water contact angle show that the MAH grafted PP is more polar than the virgin-PP, and that suggests a more favorable chemical interaction of PP-g-MAH with PA, compared to the non-modified PP. In fact, this study indicates that T-peel testing by DMTA is a technique to achieve more insights into polymeric textile composites.

Biodegradable Cellulose-Based Materials for the Use in Food Packaging

Cellulose acetate (CA) is a natural biodegradable polymer. It forms transparent films by the casting technique. CA suffers from high degree of water permeability as well as the low thermal stability at high temperatures. To adjust the CA polymeric films to the manufacture of food packaging, its thermal and mechanical properties should be improved. The modification of CA by grafting it with N-Amino phenyl maleimide (N-APhM) led to the construction of hydrophobic branches throughout the polymeric matrix which reduced its wettability as compared to the parent CA. The branches built onto the polymeric chains had been characterized by UV/Vis, 13C-NMR and ESEM. The improvement of the thermal properties was investigated and compared to the parent CA using thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), differential thermal analysis (DTA), contact angle and mechanical testing measurements. The results revealed that the water-uptake was reduced by increasing the graft percentage. The thermal and mechanical properties were also improved.

Investigating the Effects of Thermal and Surface Energy on the Two-Dimensional Flow Characteristics of Oil in Water Mixture between Two Parallel Plates: A Lattice Boltzmann Method Study

A hybrid quasi-steady thermal lattice Boltzmann model was used to study the combined effects of temperature and contact angle on the movement of slugs and droplets of oil in water (O/W) system flowing between two parallel plates. The model static contact angle due to the deposition of the O/W droplet on a flat surface with simulated hydrophilic characteristic at different fluid temperatures, matched very well the proposed theoretical calculation. Furthermore, the model was used to simulate the dynamic behavior of droplets and slugs deposited on the domain’s upper and lower surfaces, while subjected to parabolic flow conditions. The model accurately simulated the contact angle hysteresis for the dynamic droplets cases. It was also shown that at elevated temperatures the required power to transport the mixture diminished remarkably.

Effect of the Polymer Modification on the Cytocompatibility of Human and Rat Cells

Tissue engineering includes combination of materials and techniques used for the improvement, repair or replacement of the tissue. Scaffolds, permanent or temporally material, are used as support for the creation of the "new cell structures". For this important component (scaffold), a variety of materials can be used. The advantage of some polymeric materials is their cytocompatibility and possibility of biodegradation. Poly(L-lactic acid) (PLLA) is a biodegradable,  semi-crystalline thermoplastic polymer. PLLA can be fully degraded into H2O and CO2. In this experiment, the effect of the surface modification of biodegradable polymer (performed by plasma treatment) on the various cell types was studied. The surface parameters and changes of the physicochemical properties of modified PLLA substrates were studied by different methods. Surface wettability was determined by goniometry, surface morphology and roughness study were performed with atomic force microscopy and chemical composition was determined using photoelectron spectroscopy. The physicochemical properties were studied in relation to cytocompatibility of human osteoblast (MG 63 cells), rat vascular smooth muscle cells (VSMC), and human stem cells (ASC) of the adipose tissue in vitro. A fluorescence microscopy was chosen to study and compare cell-material interaction. Important parameters of the cytocompatibility like adhesion, proliferation, viability, shape, spreading of the cells were evaluated. It was found that the modification leads to the change of the surface wettability depending on the time of modification. Short time of exposition (10-120 s) can reduce the wettability of the aged samples, exposition longer than 150 s causes to increase of contact angle of the aged PLLA. The surface morphology is significantly influenced by duration of modification, too. The plasma treatment involves the formation of the crystallites, whose number increases with increasing time of modification. On the basis of physicochemical properties evaluation, the cells were cultivated on the selected samples. Cell-material interactions are strongly affected by material chemical structure and surface morphology. It was proved that the plasma treatment of PLLA has a positive effect on the adhesion, spreading, homogeneity of distribution and viability of all cultivated cells. This effect was even more apparent for the VSMCs and ASCs which homogeneously covered almost the whole surface of the substrate after 7 days of cultivation. The viability of these cells was high (more than 98% for VSMCs, 89-96% for ASCs). This experiment is one part of the basic research, which aims to easily create scaffolds for tissue engineering with subsequent use of stem cells and their subsequent "reorientation" towards the bone cells or smooth muscle cells.

Submicron Laser-Induced Dot, Ripple and Wrinkle Structures and Their Applications

Polymers exposed to laser or plasma treatment or modified with different wet methods which enable the introduction of nanoparticles or biologically active species, such as amino-acids, may find many applications both as biocompatible or anti-bacterial materials or on the contrary, can be applied for a decrease in the number of cells on the treated surface which opens application in single cell units. For the experiments, two types of materials were chosen, a representative of non-biodegradable polymers, polyethersulphone (PES) and polyhydroxybutyrate (PHB) as biodegradable material. Exposure of solid substrate to laser well below the ablation threshold can lead to formation of various surface structures. The ripples have a period roughly comparable to the wavelength of the incident laser radiation, and their dimensions depend on many factors, such as chemical composition of the polymer substrate, laser wavelength and the angle of incidence. On the contrary, biopolymers may significantly change their surface roughness and thus influence cell compatibility. The focus was on the surface treatment of PES and PHB by pulse excimer KrF laser with wavelength of 248 nm. The changes of physicochemical properties, surface morphology, surface chemistry and ablation of exposed polymers were studied both for PES and PHB. Several analytical methods involving atomic force microscopy, gravimetry, scanning electron microscopy and others were used for the analysis of the treated surface. It was found that the combination of certain input parameters leads not only to the formation of optimal narrow pattern, but to the combination of a ripple and a wrinkle-like structure, which could be an optimal candidate for cell attachment. The interaction of different types of cells and their interactions with the laser exposed surface were studied. It was found that laser treatment contributes as a major factor for wettability/contact angle change. The combination of optimal laser energy and pulse number was used for the construction of a surface with an anti-cellular response. Due to the simple laser treatment, we were able to prepare a biopolymer surface with higher roughness and thus significantly influence the area of growth of different types of cells (U-2 OS cells).

Effect of Acids with Different Chain Lengths Modified by Methane Sulfonic Acid and Temperature on the Properties of Thermoplastic Starch/Glycerin Blends

In this study, acids with various chain lengths (C6, C8, C10 and C12) modified by methane sulfonic acid (MSA) and temperature were used to modify tapioca starch (TPS), then the glycerol (GA) were added into modified starch, to prepare new blends. The mechanical properties, thermal properties and physical properties of blends were studied. This investigation was divided into two parts.  First, the biodegradable materials were used such as starch and glycerol with hexanedioic acid (HA), suberic acid (SBA), sebacic acid (SA), decanedicarboxylic acid (DA) manufacturing with different temperatures (90, 110 and 130 °C). And then, the solution was added into modified starch to prepare the blends by using single-screw extruder. The FT-IR patterns indicated that the characteristic peak of C=O in ester was observed at 1730 cm-1. It is proved that different chain length acids (C6, C8, C10 and C12) reacted with glycerol by esterification and these are used to plasticize blends during extrusion. In addition, the blends would improve the hydrolysis and thermal stability. The water contact angle increased from 43.0° to 64.0°.  Second, the HA (110 °C), SBA (110 °C), SA (110 °C), and DA blends (130 °C) were used in study, because they possessed good mechanical properties, water resistances and thermal stability. On the other hand, the various contents (0, 0.005, 0.010, 0.020 g) of MSA were also used to modify the mechanical properties of blends. We observed that the blends were added to MSA, and then the FT-IR patterns indicated that the C=O ester appeared at 1730 cm-1. For this reason, the hydrophobic blends were produced. The water contact angle of the MSA blends increased from 55.0° to 71.0°. Although break elongation of the MSA blends reduced from the original 220% to 128%, the stress increased from 2.5 MPa to 5.1 MPa. Therefore, the optimal composition of blends was the DA blend (130 °C) with adding of MSA (0.005 g).

Study on Hydrophilicity of Anodic Aluminum Oxide Templates with TiO2-NTs

This paper aims to discuss the hydrophilicity about the anodic aluminum oxide (AAO) template with titania nanotubes (NTs). The AAO templates with pore size diameters of 20-250 nm were generated by anodizing 6061 aluminum alloy substrates in acid solution of sulfuric acid (H2SO4), oxalic acid (COOH)2, and phosphoric acid (H3PO4), respectively. TiO2-NTs were grown on AAO templates by the sol-gel deposition process successfully. The water contact angle on AAO/TiO2-NTs surface was lower compared to the water contact angle on AAO surface. So, the characteristic of hydrophilicity was significantly associated with the AAO pore size and what kinds of materials were immersed variables.

Functionalization of Polypropylene with Chiral Monomer for Improving Hemocompatibility

Polypropylene (PP) is one of the most commonly used plastics because of its low density, outstanding mechanical properties, and low cost. However, its drawbacks such as low surface energy, poor dyeability, lack of chemical functionalities, and poor compatibility with polar polymers and inorganic materials, have restricted the application of PP. To expand its application in biomedical materials, functionalization is considered to be the most effective way. In this study, PP was functionalized with a chiral monomer, (S)-1-acryloylpyrrolidine-2-carboxylic acid ((S)-APCA), by free-radical grafting in the solid phase. The grafting degree of PP-g-APCA was determined by chemical titration method, and the chemical structure of functionalized PP was characterized by FTIR spectroscopy, which confirmed that the chiral monomer (S)-APCA was successfully grafted onto PP. Static water contact angle results suggested that the surface hydrophilicity of PP was significantly improved by solid phase grafting and assistance of surface water treatment. Protein adsorption and platelet adhesion results showed that hemocompatibility of PP was greatly improved by grafting the chiral monomer.

Cold Plasma Surface Modified Electrospun Microtube Array Membrane for Chitosan Immobilization and Their Properties

Electrospun microtube array membranes (MTAMs) made of PLLA (poly-L-lactic acid) have wide potential applications in tissue engineering. However, their surface hydrophobicity and poor biocompatability have limited their further usage. In this study, the surface of PLLA MTAMs were made hydrophilic by introducing extra functional groups, such as peroxide, via an acetic acid plasma (AAP). UV-graft polymerization of acrylic acid (G-AAc) was then used to produce carboxyl group on MTAMs surface, which bonded covalently with chitosan through EDC / NHS crosslinking agents. To evaluate the effects of the surface modification on PLLA MTAMs, water contact angle (WCA) measurement and cell compatibility tests were carried out. We found that AAP treated electrospun PLLA MTAMs grafted with AAc and, finally, with chitosan immobilized via crosslinking agent, exhibited improved hydrophilic and cell compatibility.

Enhancement and Characterization of Titanium Surfaces with Sandblasting and Acid Etching for Dental Implants

Titanium and its alloys have been used extensively over the past 25 years as biomedical materials in orthopedic and dental applications because of their good mechanical properties, corrosion resistance, and biocompatibility. It is known that the surface properties of titanium implants can enhance the cellular response and play an important role in Osseo integration. The rate and quality of Osseo integration in titanium implants are related to their surface properties. The purpose of this investigation was to evaluate the effect of sandblasting and acid etching on surface morphology, roughness, the wettability of titanium. The surface properties will be characterized by scanning electron microscopy and contact angle and roughness measurements. The results show that surface morphology, roughness, and wettability were changed and enhanced by these treatments.

Drop Impact Study on Flexible Superhydrophobic Surface Containing Micro-Nano Hierarchical Structures

Superhydrophobic surfaces are abundant in nature. Several surfaces such as wings of butterfly, legs of water strider, feet of gecko and the lotus leaf show extreme water repellence behaviour. Self-cleaning, stain-free fabrics, spill-resistant protective wears, drag reduction in micro-fluidic devices etc. are few applications of superhydrophobic surfaces. In order to design robust superhydrophobic surface, it is important to understand the interaction of water with superhydrophobic surface textures. In this work, we report a simple coating method for creating large-scale flexible superhydrophobic paper surface. The surface consists of multiple layers of silanized zirconia microparticles decorated with zirconia nanoparticles. Water contact angle as high as 159±10 and contact angle hysteresis less than 80 was observed. Drop impact studies on superhydrophobic paper surface were carried out by impinging water droplet and capturing its dynamics through high speed imaging. During the drop impact, the Weber number was varied from 20 to 80 by altering the impact velocity of the drop and the parameters such as contact time, normalized spread diameter were obtained. In contrast to earlier literature reports, we observed contact time to be dependent on impact velocity on superhydrophobic surface. Total contact time was split into two components as spread time and recoil time. The recoil time was found to be dependent on the impact velocity while the spread time on the surface did not show much variation with the impact velocity. Further, normalized spreading parameter was found to increase with increase in impact velocity.

Learning Materials of Atmospheric Pressure Plasma Process: Turning Hydrophilic Surface to Hydrophobic

This paper investigates the use of atmospheric pressure plasma for improving the surface hydrophobicity of polyurethane synthetic leather with tetramethylsilane (TMS). The atmospheric pressure plasma treatment with TMS is a single-step process to enhance the hydrophobicity of polyurethane synthetic leather. The hydrophobicity of the treated surface was examined by contact angle measurement. The physical and chemical surface changes were evaluated by scanning electron microscopy (SEM) and infrared spectroscopy (FTIR). The purpose of this paper is to provide learning materials for understanding how to use atmospheric pressure plasma in the textile finishing process to transform a hydrophilic surface to hydrophobic.

Experimental Investigation of the Impact of Biosurfactants on Residual-Oil Recovery

The increasing high price of natural gas and oil with attendant increase in energy demand on world markets in recent years has stimulated interest in recovering residual oil saturation across the globe. In order to meet the energy security, efforts have been made in developing new technologies of enhancing the recovery of oil and gas, utilizing techniques like CO2 flooding, water injection, hydraulic fracturing, surfactant flooding etc. Surfactant flooding however optimizes production but poses risk to the environment due to their toxic nature. Amongst proven records that have utilized other type of bacterial in producing biosurfactants for enhancing oil recovery, this research uses a technique to combine biosurfactants that will achieve a scale of EOR through lowering interfacial tension/contact angle. In this study, three biosurfactants were produced from three Bacillus species from freeze dried cultures using sucrose 3 % (w/v) as their carbon source. Two of these produced biosurfactants were screened with the TEMCO Pendant Drop Image Analysis for reduction in IFT and contact angle. Interfacial tension was greatly reduced from 56.95 mN.m-1 to 1.41 mN.m-1 when biosurfactants in cell-free culture (Bacillus licheniformis) were used compared to 4. 83mN.m-1 cell-free culture of Bacillus subtilis. As a result, cell-free culture of (Bacillus licheniformis) changes the wettability of the biosurfactant treatment for contact angle measurement to more water-wet as the angle decreased from 130.75o to 65.17o. The influence of microbial treatment on crushed rock samples was also observed by qualitative wettability experiments. Treated samples with biosurfactants remained in the aqueous phase, indicating a water-wet system. These results could prove that biosurfactants can effectively change the chemistry of the wetting conditions against diverse surfaces, providing a desirable condition for efficient oil transport in this way serving as a mechanism for EOR. The environmental friendly effect of biosurfactants applications for industrial purposes play important advantages over chemically synthesized surfactants, with various possible structures, low toxicity, eco-friendly and biodegradability.

Surface Characteristics of Bacillus megaterium and Its Adsorption Behavior onto Dolomite

Surface characteristics of Bacillus megaterium strain were investigated; zeta potential, FTIR and contact angle were measured. Surface energy components including Lifshitz-van der Waals, Hamaker constant, and acid/base components (Lewis acid/Lewis base) were calculated from the contact angle data. The results showed that the microbial cells were negatively charged over all pH regions with high values at alkaline region. A hydrophilic nature for the strain was confirmed by contact angle and free energy of adhesion between microbial cells. Adsorption affinity of the strain toward dolomite was studied at different pH values. The results showed that the cells had a high affinity to dolomite at acid pH comparing to neutral and alkaline pH. Extended DLVO theory was applied to calculate interaction energy between B. megaterium cells and dolomite particles. The adsorption results were in agreement with the results of Extended DLVO approach. Surface changes occurred on dolomite surface after the bio-treatment were monitored; contact angle decreased from 69° to 38° and the mineral’s floatability decreased from 95% to 25% after the treatment.

Anticorrosive Polyurethane Clear Coat with Self-Cleaning Character

We have aimed to produce a self-cleaning transparent polymer coating with polyurethane (PU) matrix as the latter is highly solvent, chemical and weather resistant having good mechanical properties. Nano-silica modified by 1H, 1H, 2H, 2Hperflurooctyltriethoxysilane was incorporated into the PU matrix for attaining self-cleaning ability through hydrophobicity. The modification was confirmed by particle size analysis and scanning electron microscopy (SEM). Thermo-gravimetric (TGA) studies were carried to ascertain the grafting of silane onto the silica. Several coating formulations were prepared by varying the silica loading content and compared to a commercial equivalent. The effect of dispersion and the morphology of the coated films were assessed by SEM analysis. All coating standardized tests like solvent resistance, adhesion, flexibility, acid, alkali, gloss etc. have been performed as per ASTM standards. Water contact angle studies were conducted to analyze the hydrophobic character of the coating. In addition, the coatings were also subjected to salt spray and accelerated weather testing to analyze the durability of the coating.

Separation of Hazardous Brominated Plastics from Waste Plastics by Froth Flotation after Surface Modification with Mild Heat-Treatment

This study evaluated to facilitate separation of ABS plastics from other waste plastics by froth flotation after surface hydrophilization of ABS with heat treatment. The mild heat treatment at 100oC for 60s could selectively increase the hydrophilicity of the ABS plastics surface (i.e., ABS contact angle decreased from 79o to 65.8o) among other plastics mixture. The SEM and XPS results of plastic samples sufficiently supported the increase in hydrophilic functional groups and decrease contact angle on ABS surface, after heat treatment. As a result of the froth flotation (at mixing speed 150 rpm and airflow rate 0.3 L/min) after heat treatment, about 85% of ABS was selectively separated from other heavy plastics with 100% of purity. The effect of optimum treatment condition and detailed mechanism onto separation efficiency in the froth floatation was also investigated. This research is successful in giving a simple, effective, and inexpensive method for ABS separation from waste plastics.

Separation of Chlorinated Plastics and Immobilization of Heavy Metals in Hazardous Automotive Shredder Residue

In the present study, feasibility of the selective surface hydrophilization of polyvinyl chloride (PVC) by microwave treatment was evaluated to facilitate the separation from automotive shredder residue (ASR), by the froth flotation. The combination of 60 sec microwave treatment with PAC, a sharp and significant decrease about 16.5° contact angle of PVC was observed in ASR plastic compared with other plastics. The microwave treatment with the addition of PAC resulted in a synergetic effect for the froth flotation, which may be a result of the 90% selective separation of PVC from ASR plastics, with 82% purity. While, simple mixing with a nanometallic Ca/CaO/PO4 dispersion mixture immobilized 95-100% of heavy metals in ASR soil/residues. The quantity of heavy metals leached from thermal residues after treatment by nanometallic Ca/CaO/PO4 was lower than the Korean standard regulatory limit for hazardous waste landfills. Microwave treatment can be a simple and effective method for PVC separation from ASR plastics.

Wetting Properties of Silver Based Alloys

The temperature dependence of wettability (wetting angle, Θ (T)) for Ag-based melts on graphite and Al2O3 substrates is compared. Typical alloying effects are found, as the Ag host metal is gradually replaced by various metallic elements. The essence of alloying lies in the change of the electron/atom (e/a) ratio. This ratio is also manifested in the shift of wetting angles on the same substrate. Nevertheless, the effects are partially smeared by other (metallurgical) factors, like the interaction between the oxygenalloying elements and by the graphite substrate-oxygen interaction. In contrast, such effects are not pronounced in the case of Al2O3 substrates. As a consequence, Θ(T) exhibits an opposite trend in the case of two substrates. Crossovers of the Θ(T) curves were often found. The positions of crossovers depend on the chemical character and concentration of solute atoms. Segregation and epitaxial texture formation after solidification were also observed in certain alloy drops, especially in high concentration range. This phenomenon is not yet explained in every detail.