Three-Dimensional Printed Polyamide 12 (PA12) and Polylactic Acid (PLA) Alumina (Al2O3) Nanocomposites with Significantly Enhanced Tensile, Flexural, and Impact Properties.

The effect of aluminum oxide (Al2O3) nanoparticles (NPs) as a reinforcing agent of Polyamide 12 (PA12) and Polylactic acid (PLA) in fused filament fabrication (FFF) three-dimensional printing (3DP) is reported herein for the first time. Alumina NPs are incorporated via a melt-mixing compounding process, at four different filler loadings. Neat as well as nanocomposite 3DP filaments are prepared as feedstock for the 3DP manufacturing of specimens which are thoroughly investigated for their mechanical properties. Thermogravimetric analyses (TGA) and Raman spectroscopy (RS) proved the nature of the materials. Their morphological characteristics were thoroughly investigated with scanning electron and atomic force microscopy. Al2O3 NPs exhibited a positive reinforcement mechanism at all filler loadings, while the mechanical percolation threshold with the maximum increase of performance was found between 1.0-2.0 wt.% filler loading (1.0 wt.% for PA12, 41.1%, and 56.4% increase in strength and modulus, respectively; 2.0 wt.% for PLA, 40.2%, and 27.1% increase in strength and modulus, respectively). The combination of 3DP and polymer engineering using nanocomposite PA12 and PLA filaments with low-cost filler additives, e.g., Al2O3 NPs, could open new avenues towards a series of potential applications using thermoplastic engineering polymers in FFF 3DP manufacturing.

Printed Single-Wall Carbon Nanotube-Based Joule Heating Devices Integrated as Functional Laminae in Advanced Composites.

This work reports the design and fabrication of novel printed single-wall carbon nanotube (SWCNT) electrothermal Joule heating devices. The devices are directly deposited on unidirectional (UD) glass fiber (GF) fabrics. The GF-SWCNT Joule heaters were integrated during manufacturing as "system" plies in carbon fiber reinforced polymer (CFRP) composite laminates. Specific secondary functions were imparted on the composite laminate endowing thus a multifunctional character. The efficient out-of-oven curing (OOC) of a CFRP laminate was demonstrated using a sandwich configuration comprising top/bottom GF-SWCNT system plies. A total power consumption of ca. 10.5 kWh for the efficient polymerization of the thermoset matrix was required. Infrared thermography (IR-T) monitoring showed a uniform and stable temperature field before and after impregnation with epoxy resin. Quasi-static three-point bending and dynamic mechanical analysis (DMA) revealed a minor knock-down effect of the OOC-CFRP laminates properties compared to oven cured CFRPs, whereas the glass transition temperature (Tg) was almost identical. The OOC-CFRP laminates were efficient in providing additional functions such as deicing and self-sensing that are highly sought in the energy and transport sectors, i.e., wind turbine blades or aircraft wings. The novel modular design provides unique opportunities for large-area applications via multiple interconnected arrays of printed devices.

On the Mechanical Response of Silicon Dioxide Nanofiller Concentration on Fused Filament Fabrication 3D Printed Isotactic Polypropylene Nanocomposites.

Utilization of advanced engineering thermoplastic materials in fused filament fabrication (FFF) 3D printing process is critical in expanding additive manufacturing (AM) applications. Polypropylene (PP) is a widely used thermoplastic material, while silicon dioxide (SiO2) nanoparticles (NPs), which can be found in many living organisms, are commonly employed as fillers in polymers to improve their mechanical properties and processability. In this work, PP/SiO2 nanocomposite filaments at various concentrations were developed following a melt mixing extrusion process, and used for FFF 3D printing of specimens' characterization according to international standards. Tensile, flexural, impact, microhardness, and dynamic mechanical analysis (DMA) tests were conducted to determine the effect of the nanofiller loading on the mechanical and viscoelastic properties of the polymer matrix. Scanning electron microscopy (SEM), Raman spectroscopy and atomic force microscopy (AFM) were performed for microstructural analysis, and finally melt flow index (MFI) tests were conducted to assess the melt rheological properties. An improvement in the mechanical performance was observed for silica loading up to 2.0 wt.%, while 4.0 wt.% was a potential threshold revealing processability challenges. Overall, PP/SiO2 nanocomposites could be ideal candidates for advanced 3D printing engineering applications towards structural plastic components with enhanced mechanical performance.

Optimization of the Filler Concentration on Fused Filament Fabrication 3D Printed Polypropylene with Titanium Dioxide Nanocomposites.

Polypropylene (PP) is an engineered thermoplastic polymer widely used in various applications. This work aims to enhance the properties of PP with the introduction of titanium dioxide (TiO2) nanoparticles (NPs) as nanofillers. Novel nanocomposite filaments were produced at 0.5, 1, 2, and 4 wt.% filler concentrations, following a melt mixing extrusion process. These filaments were then fed to a commercially available fused filament fabrication (FFF) 3D printer for the preparation of specimens, to be assessed for their mechanical, viscoelastic, physicochemical, and fractographic properties, according to international standards. Tensile, flexural, impact, and microhardness tests, as well as dynamic mechanical analysis (DMA), Raman, scanning electron microscopy (SEM), melt flow volume index (MVR), and atomic force microscopy (AFM), were conducted, to fully characterize the filler concentration effect on the 3D printed nanocomposite material properties. The results revealed an improvement in the nanocomposites properties, with the increase of the filler amount, while the microstructural effect and processability of the material was not significantly affected, which is important for the possible industrialization of the reported protocol. This work showed that PP/TiO2 can be a novel nanocomposite system in AM applications that the polymer industry can benefit from.

Advanced Glass Fiber Polymer Composite Laminate Operating as a Thermoelectric Generator: A Structural Device for Micropower Generation and Potential Large-Scale Thermal Energy Harvesting.

This study demonstrates for the first time a structural glass fiber-reinforced polymer (GFRP) composite laminate with efficient thermal energy harvesting properties as a thermoelectric generator (TEG). This TEG laminate was fabricated by stacking unidirectional glass fiber (GF) laminae coated with p- and n-type single-wall carbon nanotube (SWCNT) inks via a blade coating technique. According to their thermoelectric (TE) response, the p- and n-type GF-SWCNT fabrics exhibited Seebeck coefficients of +23 and -29 µV/K with 60 and 118 µW/m·K2 power factor values, respectively. The in-series p-n interconnection of the TE-enabled GF-SWCNT fabrics and their subsequent impregnation with epoxy resin effectively generated an electrical power output of 2.2 µW directly from a 16-ply GFRP TEG laminate exposed to a temperature difference (ΔT) of 100 K. Both experimental and modeling work validated the TE performance. The structural integrity of the multifunctional GFRP was tested by three-point bending coupled with online monitoring of the steady-state TE current (Isc) at a ΔΤ of 80 K. Isc was found to closely follow all transitions and discontinuities related to structural damage in the stress/strain curve, thus showing its potential to serve the functions of power generation and damage monitoring.

Sustainable Additive Manufacturing: Mechanical Response of Polyethylene Terephthalate Glycol over Multiple Recycling Processes.

The continuous demand for thermoplastic polymers in a great variety of applications, combined with an urgent need to minimize the quantity of waste for a balanced energy-from-waste strategy, has led to increasing scientific interest in developing new recycling processes for plastic products. Glycol-modified polyethylene terephthalate (PETG) is known to have some enhanced properties as compared to polyethylene terephthalate (PET) homopolymer; this has recently attracted the interest from the fused filament fabrication (FFF) three-dimensional (3D) printing community. PET has shown a reduced ability for repeated recycling through traditional processes. Herein, we demonstrate the potential for using recycled PETG in consecutive 3D printing manufacturing processes. Distributed recycling additive manufacturing (DRAM)-oriented equipment was chosen in order to test the mechanical and thermal response of PETG material in continuous recycling processes. Tensile, flexure, impact strength, and Vickers micro-hardness tests were carried out for six (6) cycles of recycling. Finally, Raman spectroscopy as well as thermal and morphological analyses via scanning electron microscopy (SEM) fractography were carried out. In general, the results revealed a minor knockdown effect on the mechanical properties as well as the thermal properties of PETG following the process proposed herein, even after six rounds of recycling.

Enhanced Mechanical, Thermal and Antimicrobial Properties of Additively Manufactured Polylactic Acid with Optimized Nano Silica Content.

The scope of this work was to create, with melt mixing compounding process, novel nanocomposite filaments with enhanced properties that industry can benefit from, using commercially available materials, to enhance the performance of three-dimensional (3D) printed structures fabricated via fused filament fabrication (FFF) process. Silicon Dioxide (SiO2) nanoparticles (NPs) were selected as fillers for a polylactic acid (PLA) thermoplastic matrix at various weight % (wt.%) concentrations, namely, 0.5, 1.0, 2.0 and 4.0 wt.%. Tensile, flexural and impact test specimens were 3D printed and tested according to international standards and their Vickers microhardness was also examined. It was proven that SiO2 filler enhanced the overall strength at concentrations up to 1 wt.%, compared to pure PLA. Atomic force microscopy (AFM) was employed to investigate the produced nanocomposite extruded filaments roughness. Raman spectroscopy was performed for the 3D printed nanocomposites to verify the polymer nanocomposite structure, while thermogravimetric analysis (TGA) revealed the 3D printed samples' thermal stability. Scanning electron microscopy (SEM) was carried out for the interlayer fusion and fractography morphological characterization of the specimens. Finally, the antibacterial properties of the produced nanocomposites were investigated with a screening process, to evaluate their performance against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus).

Thermoelectric Energy Harvesting from Single-Walled Carbon Nanotube Alkali-Activated Nanocomposites Produced from Industrial Waste Materials.

A waste-originated one-part alkali-activated nanocomposite is introduced herein as a novel thermoelectric material. For this purpose, single-walled carbon nanotubes (SWCNTs) were utilized as nanoinclusions to create an electrically conductive network within the investigated alkali-activated construction material. Thermoelectric and microstructure characteristics of SWCNT-alkali-activated nanocomposites were assessed after 28 days. Nanocomposites with 1.0 wt.% SWCNTs exhibited a multifunctional behavior, a combination of structural load-bearing, electrical conductivity, and thermoelectric response. These nanocomposites (1.0 wt.%) achieved the highest thermoelectric performance in terms of power factor (PF), compared to the lower SWCNTs' incorporations, namely 0.1 and 0.5 wt.%. The measured electrical conductivity (σ) and Seebeck coefficient (S) were 1660 S·m-1 and 15.8 µV·K-1, respectively, which led to a power factor of 0.414 µW·m-1·K-2. Consequently, they have been utilized as the building block of a thermoelectric generator (TEG) device, which demonstrated a maximum power output (Pout) of 0.695 µW, with a power density (PD) of 372 nW·m-2, upon exposure to a temperature gradient of 60 K. The presented SWCNT-alkali-activated nanocomposites could establish the pathway towards waste thermal energy harvesting and future sustainable civil engineering structures.

An Approach toward the Realization of a Through-Thickness Glass Fiber/Epoxy Thermoelectric Generator.

The present study demonstrates, for the first time, the ability of a 10-ply glass fiber-reinforced polymer composite laminate to operate as a structural through-thickness thermoelectric generator. For this purpose, inorganic tellurium nanowires were mixed with single-wall carbon nanotubes in a wet chemical approach, capable of resulting in a flexible p-type thermoelectric material with a power factor value of 58.88 µW/m·K2. This material was used to prepare an aqueous thermoelectric ink, which was then deposited onto a glass fiber substrate via a simple dip-coating process. The coated glass fiber ply was laminated as top lamina with uncoated glass fiber plies underneath to manufacture a thermoelectric composite capable of generating 54.22 nW power output at a through-thickness temperature difference οf 100 K. The mechanical properties of the proposed through-thickness thermoelectric laminate were tested and compared with those of the plain laminates. A minor reduction of approximately 11.5% was displayed in both the flexural modulus and strength after the integration of the thermoelectric ply. Spectroscopic and morphological analyses were also employed to characterize the obtained thermoelectric nanomaterials and the respective coated glass fiber ply.

High-Power All-Carbon Fully Printed and Wearable SWCNT-Based Organic Thermoelectric Generator.

In this study, we introduce the fabrication process of a highly efficient fully printed all-carbon organic thermoelectric generator (OTEG) free of metallic junctions with outstanding flexibility and exceptional power output, which can be conveniently and rapidly prepared through ink dispensing/printing processes of aqueous and low-cost CNT inks with a mask-assisted specified circuit architecture. The optimal p-type and n-type films produced exhibit ultrahigh power factors (PFs) of 308 and 258 µW/mK2, respectively, at ΔΤ = 150 K (THOT = 175 °C) and outstanding stability in air without encapsulation, providing the OTEG device the ability to operate at high temperatures up to 200 °C at ambient conditions (1 atm, relative humidity: 50 ± 5% RH). We have successfully designed and fabricated the flexible thermoelectric (TE) modules with superior TE properties of p-type and n-type SWCNT films resulting in exceptionally high performance. The novel design OTEG exhibits outstanding flexibility and stability with attained TE values among the highest ever reported in the field of organic thermoelectrics, that is, open-circuit voltage VOC = 1.05 V and short-circuit current ISC = 1.30 mA at ΔT = 150 K (THOT = 175 °C) with an internal resistance of RTEG = 806 Ω, generating a 342 µW power output. It is also worth noting the remarkable PFs of 145 and 127 µW/mK2 for the p-type and n-type films, respectively, at room temperature. The fabricated device is highly scalable, providing opportunities for printable large-scale manufacturing/industrial production of highly efficient flexible OTEGs.

Sustainable Additive Manufacturing: Mechanical Response of Polyamide 12 over Multiple Recycling Processes.

Plastic waste reduction and recycling through circular use has been critical nowadays, since there is an increasing demand for the production of plastic components based on different polymeric matrices in various applications. The most commonly used recycling procedure, especially for thermoplastic materials, is based on thermomechanical process protocols that could significantly alter the polymers' macromolecular structure and physicochemical properties. The study at hand focuses on recycling of polyamide 12 (PA12) filament, through extrusion melting over multiple recycling courses, giving insight for its effect on the mechanical and thermal properties of Fused Filament Fabrication (FFF) manufactured specimens throughout the recycling courses. Three-dimensional (3D) FFF printed specimens were produced from virgin as well as recycled PA12 filament, while they have been experimentally tested further for their tensile, flexural, impact and micro-hardness mechanical properties. A thorough thermal and morphological analysis was also performed on all the 3D printed samples. The results of this study demonstrate that PA12 can be successfully recycled for a certain number of courses and could be utilized in 3D printing, while exhibiting improved mechanical properties when compared to virgin material for a certain number of recycling repetitions. From this work, it can be deduced that PA12 can be a viable option for circular use and 3D printing, offering an overall positive impact on recycling, while realizing 3D printed components using recycled filaments with enhanced mechanical and thermal stability.

On the Strain Rate Sensitivity of Fused Filament Fabrication (FFF) Processed PLA, ABS, PETG, PA6, and PP Thermoplastic Polymers.

In this study, the strain rate sensitivity of five different thermoplastic polymers processed via Fused Filament Fabrication (FFF) Additive Manufacturing (AM) is reported. Namely, Polylactic Acid (PLA), Acrylonitrile-Butadiene-Styrene (ABS), Polyethylene Terephthalate Glycol (PETG), Polyamide 6 (PA6), and Polypropylene (PP) were thoroughly investigated under static tensile loading conditions at different strain rates. Strain rates have been selected representing the most common applications of polymeric materials manufactured by Three-Dimensional (3D) Printing. Each polymer was exposed to five different strain rates in order to elucidate the dependency and sensitivity of the tensile properties, i.e., stiffness, strength, and toughness on the applied strain rate. Scanning Electron Microscopy (SEM) was employed to investigate the 3D printed samples' fractured surfaces, as a means to derive important information regarding the fracture process, the type of fracture (brittle or ductile), as well as correlate the fractured surface characteristics with the mechanical response under certain strain rate conditions. An Expectation-Maximization (EM) analysis was carried out. Finally, a comparison is presented calculating the strain rate sensitivity index "m" and toughness of all materials at the different applied strain rates.

Decoration of SiO2 and Fe3O4 Nanoparticles onto the Surface of MWCNT-Grafted Glass Fibers: A Simple Approach for the Creation of Binary Nanoparticle Hierarchical and Multifunctional Composite Interphases.

We report on a versatile method for chemically grafting multiwalled carbon nanotubes (MWCNTs) onto the surface of conventional glass fibers (GFs), as well as depositing further silica (SiO2) or superparamagnetic (SPM) magnetite (Fe3O4) nanoparticles (NPs) creating novel hierarchical reinforcements. The CNT-grafted GFs (GF-CNT) were utilized further as the support to decorate nano-sized SiO2 or Fe3O4 via electrostatic interactions, resulting finally into double hierarchy reinforcements. SiO2 NPs were first used as model nano-particulate objects to investigate the interfacial adhesion properties of binary coated GFs (denoted as GF-CNT/SiO2) in epoxy matrix via single fiber pull-out (SFPO) tests. The results indicated that the apparent interfacial shear strength (IFSS or τapp) was significantly increased compared to the GF-CNT. Fe3O4 NPs were assembled also onto CNT-grafted GFs resulting into GF-CNT/Fe3O4. The fibers exhibited a magnetic response upon being exposed to an external magnet. Scanning electron microscopy (SEM) revealed the surface morphologies of the different hierarchical fibers fabricated in this work. The interphase microstructure of GF-CNT and GF-CNT/SiO2 embedded in epoxy was investigated by transmission electron microscopy (TEM). The hybrid and hierarchical GFs are promising multifunctional reinforcements with appr. 85% increase of the IFSS as compared to typical amino-silane modified GFs. It could be envisaged that, among other purposes, GF-CNT/Fe3O4 could be potentially recyclable reinforcements, especially when embedded in thermoplastic polymer matrices.

Three-Dimensional Printed Antimicrobial Objects of Polylactic Acid (PLA)-Silver Nanoparticle Nanocomposite Filaments Produced by an In-Situ Reduction Reactive Melt Mixing Process.

In this study, an industrially scalable method is reported for the fabrication of polylactic acid (PLA)/silver nanoparticle (AgNP) nanocomposite filaments by an in-situ reduction reactive melt mixing method. The PLA/AgNP nanocomposite filaments have been produced initially reducing silver ions (Ag+) arising from silver nitrate (AgNO3) precursor mixed in the polymer melt to elemental silver (Ag0) nanoparticles, utilizing polyethylene glycol (PEG) or polyvinyl pyrrolidone (PVP), respectively, as macromolecular blend compound reducing agents. PEG and PVP were added at various concentrations, to the PLA matrix. The PLA/AgNP filaments have been used to manufacture 3D printed antimicrobial (AM) parts by Fused Filament Fabrication (FFF). The 3D printed PLA/AgNP parts exhibited significant AM properties examined by the reduction in Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) bacteria viability (%) experiments at 30, 60, and 120 min duration of contact (p < 0.05; p-value (p): probability). It could be envisaged that the 3D printed parts manufactured and tested herein mimic nature's mechanism against bacteria and in terms of antimicrobial properties, contact angle for their anti-adhesive behavior and mechanical properties could create new avenues for the next generation of low-cost and on-demand additive manufacturing produced personal protective equipment (PPE) as well as healthcare and nosocomial antimicrobial equipment.

3D Printed Thermoelectric Polyurethane/Multiwalled Carbon Nanotube Nanocomposites: A Novel Approach towards the Fabrication of Flexible and Stretchable Organic Thermoelectrics.

Three-dimensional (3D) printing of thermoelectric polymer nanocomposites is reported for the first time employing flexible, stretchable and electrically conductive 3D printable thermoplastic polyurethane (TPU)/multiwalled carbon nanotube (MWCNT) filaments. TPU/MWCNT conductive polymer composites (CPC) have been initially developed employing melt-mixing and extrusion processes. TPU pellets and two different types of MWCNTs, namely the NC-7000 MWCNTs (NC-MWCNT) and Long MWCNTs (L-MWCNT) were used to manufacture TPU/MWCNT nanocomposite filaments with 1.0, 2.5 and 5.0 wt.%. 3D printed thermoelectric TPU/MWCNT nanocomposites were fabricated through a fused deposition modelling (FDM) process. Raman and scanning electron microscopy (SEM) revealed the graphitic nature and morphological characteristics of CNTs. SEM and transmission electron microscopy (TEM) exhibited an excellent CNT nanodispersion in the TPU matrix. Tensile tests showed no significant deterioration of the moduli and strengths for the 3D printed samples compared to the nanocomposites prepared by compression moulding, indicating an excellent interlayer adhesion and mechanical performance of the 3D printed nanocomposites. Electrical and thermoelectric investigations showed that L-MWCNT exhibits 19.8 ± 0.2 µV/K Seebeck coefficient (S) and 8.4 × 103 S/m electrical conductivity (σ), while TPU/L-MWCNT CPCs at 5.0 wt.% exhibited the highest thermoelectric performance (σ = 133.1 S/m, S = 19.8 ± 0.2 µV/K and PF = 0.04 µW/mK2) among TPU/CNT CPCs in the literature. All 3D printed samples exhibited an anisotropic electrical conductivity and the same Seebeck coefficient in the through- and cross-layer printing directions. TPU/MWCNT could act as excellent organic thermoelectric material towards 3D printed thermoelectric generators (TEGs) for potential large-scale energy harvesting applications.

Mechanical Properties of 3D-Printed Acrylonitrile-Butadiene-Styrene TiO2 and ATO Nanocomposites.

In order to enhance the mechanical performance of three-dimensional (3D) printed structures fabricated via commercially available fused filament fabrication (FFF) 3D printers, novel nanocomposite filaments were produced herein following a melt mixing process, and further 3D printed and characterized. Titanium Dioxide (TiO2) and Antimony (Sb) doped Tin Oxide (SnO2) nanoparticles (NPs), hereafter denoted as ATO, were selected as fillers for a polymeric acrylonitrile butadiene styrene (ABS) thermoplastic matrix at various weight % (wt%) concentrations. Tensile and flexural test specimens were 3D printed, according to international standards. It was proven that TiO2 filler enhanced the overall tensile strength by 7%, the flexure strength by 12%, and the micro-hardness by 6%, while for the ATO filler, the corresponding values were 9%, 13%, and 6% respectively, compared to unfilled ABS. Atomic force microscopy (AFM) revealed the size of TiO2 (40 ± 10 nm) and ATO (52 ± 11 nm) NPs. Raman spectroscopy was performed for the TiO2 and ATO NPs as well as for the 3D printed nanocomposites to verify the polymer structure and the incorporated TiO2 and ATO nanocrystallites in the polymer matrix. The scope of this work was to fabricate novel nanocomposite filaments using commercially available materials with enhanced overall mechanical properties that industry can benefit from.

Three-Dimensional (3D) Conductive Network of CNT-Modified Short Jute Fiber-Reinforced Natural Rubber: Hierarchical CNT-Enabled Thermoelectric and Electrically Conductive Composite Interfaces.

Jute fibers (JFs) coated with multiwall carbon nanotubes (MWCNTs) have been introduced in a natural rubber (NR) matrix creating a three-dimensional (3D) electrically conductive percolated network. The JF-CNT endowed electrical conductivity and thermoelectric properties to the final composites. CNT networks fully covered the fiber surfaces as shown by the corresponding scanning electron microscopy (SEM) analysis. NR/JF-CNT composites, at 10, 20 and 30 phr (parts per hundred gram of rubber) have been manufactured using a two-roll mixing process. The highest value of electrical conductivity (σ) was 81 S/m for the 30 phr composite. Thermoelectric measurements revealed slight differences in the Seebeck coefficient (S), while the highest power factor (PF) was 1.80 × 10-2 µW/m K-2 for the 30 phr loading. The micromechanical properties and electrical response of the composite's conductive interface have been studied in peak force tapping quantitative nanomechanical (PFT QNM) and conductive atomic force microscopy (c-AFM) mode. The JF-CNT create an electrically percolated network at all fiber loadings endowing electrical and thermoelectric properties to the NR matrix, considered thus as promising thermoelectric stretchable materials.

Three-Dimensional Printed Polylactic Acid (PLA) Surgical Retractors with Sonochemically Immobilized Silver Nanoparticles: The Next Generation of Low-Cost Antimicrobial Surgery Equipment.

A versatile method is reported for the manufacturing of antimicrobial (AM) surgery equipment utilising fused deposition modelling (FDM), three-dimensional (3D) printing and sonochemistry thin-film deposition technology. A surgical retractor was replicated from a commercial polylactic acid (PLA) thermoplastic filament, while a thin layer of silver (Ag) nanoparticles (NPs) was developed via a simple and scalable sonochemical deposition method. The PLA retractor covered with Ag NPs (PLA@Ag) exhibited vigorous AM properties examined by a reduction in Staphylococcus aureus (S. aureus), Pseudomonas aeruginosa (P. aeruginosa) and Escherichia coli (E. coli) bacteria viability (%) experiments at 30, 60 and 120 min duration of contact (p < 0.05). Scanning electron microscopy (SEM) showed the surface morphology of bare PLA and PLA@Ag retractor, revealing a homogeneous and full surface coverage of Ag NPs. X-Ray diffraction (XRD) analysis indicated the crystallinity of Ag nanocoating. Ultraviolent-visible (UV-vis) spectroscopy and transmission electron microscopy (TEM) highlighted the AgNP plasmonic optical responses and average particle size of 31.08 ± 6.68 nm. TEM images of the PLA@Ag crossection demonstrated the thickness of the deposited Ag nanolayer, as well as an observed tendency of AgNPs to penetrate though the outer surface of PLA. The combination of 3D printing and sonochemistry technology could open new avenues in the manufacturing of low-cost and on-demand antimicrobial surgery equipment.

Effect of Various Surface Treatments on the Performance of Jute Fibers Filled Natural Rubber (NR) Composites.

In the present study, the suitability of various chemical treatments to improve the performance of jute fibers (JFs) filled natural rubber (NR) composites was explored. The surface of JFs was modified by three different surface treatments, namely, alkali treatment, combined alkali/stearic acid treatment and combined alkali/silane treatment. Surface modified JFs were characterized by X-ray diffraction (XRD) pattern, Fourier transform infrared (FTIR) spectroscopy and field emission scanning electron microscopy (FESEM). The reinforcing effect of untreated and surface treated JFs in NR composites was comparatively evaluated in terms of cure, mechanical, morphological and thermal properties. Combined alkali/silane treated JFs filled NR composite showed considerably higher torque difference, tensile modulus, hardness and tensile strength as compared to either untreated or other surface treated JFs filled NR systems. A crosslink density measurement suggested effective rubber-fibers interaction in combined alkali/silane treated JFs filled NR composite. Morphological analysis confirmed the improvement in the interfacial bonding between NR matrix and JFs due to combined alkali/silane treatment allowing an efficient "stress-transfer" mechanism. As a whole, combined alkali/silane treatment was found to be most efficient surface treatment method to develop strong interfacial adhesion between NR matrix and JFs.

Temperature-Controlled Catalysis by Core-Shell-Satellite AuAg@pNIPAM@Ag Hybrid Microgels: A Highly Efficient Catalytic Thermoresponsive Nanoreactor.

A novel wet-chemical protocol is reported for the synthesis of "temperature-programmable" catalytic colloids consisting of bimetallic core@shell AuAg nanoparticles encapsulated into poly(N-isopropylacrylamide) (pNIPAM) microgels with silver satellites (AgSTs) incorporated within the microgel structure. Spherical AuNPs of 50 nm in diameter are initially synthesized and used for growing a pNIPAM microgel shell with temperature stimulus response. A silver shell is subsequently grown on the Au core by diffusing Ag salt through the hydrophilic pNIPAM microgel (AuAg@pNIPAM microgel). The use of allylamine as a co-monomer during pNIPAM polymerization facilitates the coordination of Ag+ with the NH2 nitrogen lone pair of electrons, which are reduced to Ag seeds (∼14 nm) using a strong reducing agent, obtaining thus AuAg@pNIPAM@Ag hybrid microgels. The two systems are tested as catalysts toward the reduction of 4-nitrophenol (4-Nip) to 4-aminophenol (4-Amp) by NaBH4. Both exhibit extremely sensitive temperature-dependent reaction rate constants, with the highest K1 value of the order of 0.6 L/m2 s, which is one of the highest values ever reported. The presence of plasmonic entities is confirmed by UV-vis spectroscopy. Dynamic light scattering proves the temperature responsiveness in all cases. Transmission electron microscopy and energy-dispersive X-ray (EDX) elemental mapping highlight the monodispersity of the synthesized hybrid nanostructured microgels, as well as their size and metallic composition. The amount of gold and silver in both systems is obtained by thermogravimetric analysis and the EDX spectrum. The reduction reaction kinetics is monitored by UV-vis spectroscopy at different temperatures for both catalytic systems, with the AuAg@pNIPAM@Ag microgels showing superior catalytic performance at all temperatures because of the synergistic effect of the AuAg core and the AgSTs. The principal novelty of this study lies in the "hierarchical" design of the metal-polymer-metal core@shell@satellite nanostructured colloids exhibiting synergistic capabilities of the plasmonic NPs for, among others, temperature-controlled catalytic applications.