The influence of a large build area on the microstructure and mechanical properties of PBF-LB Ti-6Al-4 V alloy.

This study investigated the print homogeneity of Ti-6Al-4 V alloy parts, when printed over a large build area of 250 × 250 × 170 mm3, using a production scale laser powder bed additive manufacturing system. The effect of part location across this large build area was investigated based on printed part porosity, microstructure, hardness, and tensile properties. In addition, a Hot Isostatic Pressing (HIP) treatment was carried out on the as-built parts, to evaluate its impact on the material properties. A small increase in part porosity from 0.01 to 0.09%, was observed with increasing distance from the argon gas flow inlet, which was located on one side of the build plate, during printing. This effect, which was found to be independent of height from the build plate, is likely to be associated with enhanced levels of condensate or spatter residue, being deposited at distances, further from the gas flow. Despite small differences in porosity, no significant differences were obtained for microstructural features such as prior ß grain, α lath thickness, and phase fraction, over the entire build area. Due to this, mechanical performances such as hardness and tensile strengths were also found to be homogenous across the build area. Additionally, it was also observed based on the lattice constants that partial in-situ decomposition of α ' → α + ß phases occurred during printing. Post HIP treatment result showed a decrease of 7 and 6%, in the yield strength (YS) and ultimate tensile strength (UTS), respectively, which was associated with a coarsening of α lath widths. The potential of the laser powder bed system for large area printing was successfully demonstrated based on the homogenous microstructure and mechanical properties of the Ti-6Al-4 V alloy parts.

Fabrication and Performance of Continuous 316 Stainless Steel Fibre-Reinforced 3D-Printed PLA Composites.

This study investigates the feasibility of 3D printing continuous stainless steel fibre-reinforced polymer composites. The printing study was carried out using 316L stainless steel fibre (SSF) bundles with an approximate diameter of 0.15 mm. This bundle was composed of 90 fibres with a 14 µm diameter. This fibre bundle was first coated with polylactic acid (PLA) in order to produce a polymer-coated continuous stainless steel filament, with diameters tailored in the range from 0.5 to 0.9 mm. These filaments were then used to print composite parts using the material extrusion (MEX) technique. The SSF's volume fraction (Vf) was controlled in the printed composite structures in the range from 4 to 30 Vf%. This was facilitated by incorporating a novel polymer pressure vent into the printer nozzle, which allowed the removal of excess polymer. This thus enabled the control of the metal fibre content within the printed composites as the print layer height was varied in the range from 0.22 to 0.48 mm. It was demonstrated that a lower layer height yielded a more homogeneous distribution of steel fibres within the PLA polymer matrix. The PLA-SSF composites were assessed to evaluate their mechanical performance, volume fraction, morphology and porosity. Composite porosities in the range of 2-21% were obtained. Mechanical testing demonstrated that the stainless steel composites exhibited a twofold increase in interlaminar shear strength (ILSS) and a fourfold increase in its tensile strength compared with the PLA-only polymer prints. When comparing the 4 and 30 Vf% composites, the latter exhibited a significant increase in both the tensile strength and modulus. The ILSS values obtained for the steel composites were up to 28.5 MPa, which is significantly higher than the approximately 13.8 MPa reported for glass fibre-reinforced PLA composites.

3D Printing of Fibre-Reinforced Thermoplastic Composites Using Fused Filament Fabrication-A Review.

Three-dimensional (3D) printing has been successfully applied for the fabrication of polymer components ranging from prototypes to final products. An issue, however, is that the resulting 3D printed parts exhibit inferior mechanical performance to parts fabricated using conventional polymer processing technologies, such as compression moulding. The addition of fibres and other materials into the polymer matrix to form a composite can yield a significant enhancement in the structural strength of printed polymer parts. This review focuses on the enhanced mechanical performance obtained through the printing of fibre-reinforced polymer composites, using the fused filament fabrication (FFF) 3D printing technique. The uses of both short and continuous fibre-reinforced polymer composites are reviewed. Finally, examples of some applications of FFF printed polymer composites using robotic processes are highlighted.

Correlating in-situ process monitoring data with the reduction in load bearing capacity of selective laser melted Ti-6Al-4V porous biomaterials.

Selective Laser Melting allows for the creation of intricate porous structures, that possess favourable biological properties. These structures are known as porous biomaterials. The focus of this paper is to evaluate the use of an in-line photodiode based process monitoring system, for the monitoring of the operational behaviour of the laser, and to correlate this with the resultant parts mechanical performance. In this study the production scale Renishaw 500M was used to produce porous structures, using Ti-6Al-4V feedstock powder. During the process, a co-axial process monitoring system was utilised to generate data relating to both the meltpool and the operational behaviour of the laser. An advanced scanning technique was used to produce the structures, whereby the laser parameters determine the strut dimensions. In this study, the laser input energy was reduced by 33%, 66% and 100%, at specific layers within the structures. Computer Tomography and Scanning Electron Microscopy was utilised to characterise the affected struts within the structures, while quasi-static compression testing was used to determine the structure's mechanical properties. It was demonstrated that as the level of input energy decreased and the number of affected layers increased, a corresponding decrease in the load bearing capacity of the structures occurred. With the structures experiencing a significant loss in strength also exhibiting a change in the failure mode during compression testing. Data generated during the processing of such structures was compared to the data generated during the processing of control structures, with the difference between the two been calculated on a layer-by-layer basis. A clear correlation was demonstrated between the total level of deviation between the two signal sets and a reduction in the load bearing capacity of the structures. This indicates that by comparing build data to a benchmark data set, valuable information relating to the structural integrity of the porous structures can be obtained.

Electrochemically Deposited NiO Films as a Blocking Layer in p-Type Dye-Sensitized Solar Cells with an Impressive 45% Fill Factor.

The enhancement of photoelectrochemical conversion efficiency of p-type dye-sensitized solar cells (p-DSSCs) is necessary to build up effective tandem devices in which both anode and cathode are photoactive. The efficiency of a p-type device (2.5%) is roughly one order of magnitude lower than the n-type counterparts (13.1%), thus limiting the overall efficiency of the tandem cell, especially in terms of powered current density. This is mainly due to the recombination reaction that occurs especially at the photocathode (or Indium-doped Tin Oxide (ITO))/electrolyte interface. To minimize this phenomenon, a widely employed strategy is to deposit a compact film of NiO (acting as a blocking electrode) beneath the porous electrode. Here, we propose electrodeposition as a cheap, easy scalable and environmental-friendly approach to deposit nanometric films directly on ITO glass. The results are compared to a blocking layer made by means of sol-gel technique. Cells embodying a blocking layer substantially outperformed the reference device. Among them, BL_1.10V shows the best photoconversion efficiency (0.166%) and one of the highest values of fill factor (approaching 46%) ever reported. This is mainly due to an optimized surface roughness of the blocking layer assuring a good deposition of the porous layer. The effectiveness of the implementation of the blocking layer is further proved by means of Electrochemical Impedance Spectroscopy.

Evaluation of the effectiveness of kINPen Med plasma jet and bioactive agent therapy in a rat model of wound healing.

Chronic nonhealing wounds, particularly those complicated by multidrug resistant infections, represent a major health and economic challenge. Plasma treatment promotes wound repair due to its antimicrobial, angiogenic, and cell modulating properties. This study investigated the efficacy of the kINPen Med system in promoting healing and assessed if efficacy was enhanced by adding collagen or hyaluronic acid (HA). Two 6 mm diameter punch biopsy wounds were created on the lumbar spine of Sprague Dawley rats. Based on the results of a pilot study, operating process conditions involving 30 s plasma/day were selected for the pivotal study. In the pivotal study, six groups of rats (n = 28/group) received either control (1), plasma (2), HA (3), plasma and HA (4), collagen (5), or plasma and collagen (6). Wound measurements were obtained on Days 0, 4, 7, and 14. The mean reduction in wound size was significantly higher in all treatment groups compared to controls on Day 4; group 6 performed best. On Day 7, group 6 still performed significantly better compared to groups 1, 2, 3, and 4. Day 14 results were more comparable between groups. Histology (Day 14) revealed epidermal hyperplasia and serocellular crusts. Neutrophilic infiltrates in group 6 were significantly lower compared to group 2. Mononuclear infiltrates were highest in groups 3 and 5, while Langerhans cells were observed in all groups. These results underpin the clinical benefits of the kINPen Med plasma system, particularly when combined with collagen during early inflammatory phases, and support the conduct of future human clinical trials.

Evaluation of the sensitivity of bacterial and yeast cells to cold atmospheric plasma jet treatments.

The focus of this research was first to determine the influence of the atmospheric plasma drive frequency on the generation of atomic oxygen species and its correlation with the reduction of bacterial load after treatment in vitro. The treatments were carried out using a helium-plasma jet source called PlasmaStream™. The susceptibility of multiple microbial cell lines was investigated in order to compare the response of gram-positive and gram-negative bacteria, as well as a yeast cell line to the atmospheric plasma treatment. It was observed for the source evaluated that at a frequency of 160 kHz, increased levels of oxygen-laden active species (i.e., OH, NO) were generated. At this frequency, the maximum level of bacterial inactivation in vitro was also achieved. Ex vivo studies (using freshly excised porcine skin as a human analog) were also carried out to verify the antibacterial effect of the plasma jet treatment at this optimal operational frequency and to investigate the effect of treatment duration on the reduction of bacterial load. The plasma jet treatment was found to yield a 4 log reduction in bacterial load after 6 min of treatment, with no observable adverse effects on the treatment surface. The gram-negative bacterial cell lines were found to be far more susceptible to the atmospheric plasma treatments than the gram-positive bacteria. Flow cytometric analysis of plasma treated bacterial cells (Escherichia coli) was conducted in order to attain a fundamental understanding of the mode of action of the treatment on bacteria at a cellular level. This study showed that after treatment with the plasma jet, E. coli cells progressed through the following steps of cell death; the inactivation of transport systems, followed by depolarization of the cytoplasmic membrane, and finally permeabilization of the cell wall.

Effect of an active packaging with citrus extract on lipid oxidation and sensory quality of cooked turkey meat.

An antioxidant active packaging was prepared by coating a citrus extract, consisting of a mixture of carboxylic acids and flavanones, on polyethylene terephthalate trays. The effect of the packaging in reducing lipid oxidation in cooked turkey meat and on meat pH, colour characteristics and sensorial parameters was investigated. An untrained sensory panel evaluated the odour, taste, tenderness, juiciness and overall acceptability of the meat, using triangle, paired preference and quantitative response scale tests. A comparison between the antioxidant effects of the different components of the extract was also carried out. The packaging led to a significant reduction in lipid oxidation. After 2 days of refrigerated storage the sensory panel detected differences in odour and, after 4 days, rated the meat stored in the active packaging higher for tenderness and overall acceptability. Citric acid appeared to be the most important component of the extract with regard to its antioxidant potency.

Probing the redox states at the surface of electroactive nanoporous NiO thin films.

Nanoporous NiO thin film electrodes were obtained via plasma-assisted microwave sintering and characterized by means of a combination of electrochemical techniques and X-ray photoelectron spectroscopy (XPS). The aim of this study is the elucidation of the nature of the surface changes introduced by the redox processes of this nanostructured material. NiO undergoes two distinct electrochemical processes of oxidation in aqueous electrolyte with the progress of NiO anodic polarization. These findings are consistent with the sequential formation of oxyhydroxide species at the surface, the chemical nature of which was assessed by XPS. Electronic relaxation effects in the Ni 2p spectra clearly indicated that the superficial oxyhydroxide species resulted to be ß-NiOOH and γ-NiOOH. We also show for the first time spectral evidence of an electrochemically generated Ni(IV) species. This study has direct relevance for those applications in which NiO electrodes are utilized in aqueous electrolyte, namely catalytic water splitting or electrochromism, and may constitute a starting point for the comprehension of electronic phenomena at the NiO/organic electrolyte interface of cathodic dye-sensitized solar cells (p-DSCs).

Overall migration and kinetics of release of antioxidant compounds from citrus extract-based active packaging.

Overall migration (OM) tests were conducted on an antioxidant active packaging prepared by coating plasma pretreated and untreated polyethylene terepthalate (PET) trays with a citrus extract. The release of antioxidant compounds into food simulants was measured to permit their subtraction from OM values in line with active packaging legislation. The results demonstrated the compliance of the packaging with the limit for OM for plastic material in contact with food. The validity of the procedure for OM in aqueous food simulants was questioned, with the loss of volatile compounds during evaporation of the simulant resulting in an underestimation of total compounds released. The study showed a total release of 75% of the citrus extract coating into water and 25% into oil, which decreased to 45 and 12.5%, respectively, following plasma pretreatment of the trays.

Dye sensitised solar cells with nickel oxide photocathodes prepared via scalable microwave sintering.

Photoactive NiO electrodes for cathodic dye-sensitised solar cells (p-DSCs) have been prepared with thicknesses ranging between 0.4 and 3.0 µm by spray-depositing pre-formed NiO nanoparticles on fluorine-doped tin oxide (FTO) coated glass substrates. The larger thicknesses were obtained in sequential sintering steps using a conventional furnace (CS) and a newly developed rapid discharge sintering (RDS) method. The latter procedure is employed for the first time for the preparation of p-DSCs. In particular, RDS represents a scalable procedure that is based on microwave-assisted plasma formation that allows the production in series of mesoporous NiO electrodes with large surface areas for p-type cell photocathodes. RDS possesses the unique feature of transmitting heat from the bulk of the system towards its outer interfaces with controlled confinement of the heating zone. The use of RDS results in a drastic reduction of processing times with respect to other deposition methods that involve heating/calcination steps with associated reduced costs in terms of energy. P1-dye sensitized NiO electrodes obtained via the RDS procedure have been tested in DSC devices and their performances have been analysed and compared with those of cathodic DSCs derived from CS-deposited samples. The largest conversion efficiencies (0.12%) and incident photon-to-current conversion efficiencies, IPCEs (50%), were obtained with sintered NiO electrodes having thicknesses of ~1.5-2.0 µm. In all the devices, the photogenerated holes in NiO live significantly longer (τ(h) ~ 1 s) than have previously been reported for P1-sensitized NiO photocathodes. In addition, P1-sensitised sintered electrodes give rise to relatively high photovoltages (up to 135 mV) when the triiodide-iodide redox couple is used.

Diffusion within ultrathin, dense nanoporous silica films.

In this work the origin of permselectivity in dense silica films which possess a pore structure with pore sizes commensurate with the molecular size of the diffusing gas species is investigated. Much of the recently reported work in this field has involved the development of composite membrane films, and while it is generally assumed that the transport process of the gas species within the selective layer of these films is activated in nature, there are anomalies with this simplified picture. In this paper a new model is developed which, for the first time, explains the permselective behavior of the thin selective coatings ubiquitous to membrane separation processes. The model involves the existence of two primary transport domains within the solid film, one of which rapidly conducts the permeating gas (under non-Fickian conditions), while the second domain involves a slow diffusion mode characterized by normal Fickian transport. To validate the model, molecular dynamics simulations are conducted for diffusion of a number of simple gases (He, N(2), and CO(2)) within silica glasses over a range of solid densities. The silica media employed in these studies are based on a novel approach developed in this work for the construction of three-dimensionally periodic atomistic structures of silica of arbitrary density in which network bond connectivity is ensured. The results obtained from this work are in qualitative agreement with experimental observations and confirm the existence of dual mode transport which is central to the interpretation of the permselectivity in composite membranes systems.

Atomistic simulation of the formation of nanoporous silica films via molecular chemical vapor deposition on nonporous substrates.

To distinguish thin deposited film characteristics clearly from the influence of substrate morphological properties, the growth mechanism and the macroscale and nanoscale properties of nanoporous SiO(2) films deposited on nonporous silica (SiO(2)) substrates from chemical precursors Si(OH)(4) and TEOS (tetraethoxysilane) via low-pressure chemical vapor deposition are the primary targets of this study. This work employs a kinetic Monte Carlo (KMC) simulation method coupled to the Metropolis Monte Carlo method to relax the strained silica structure. The influence of the deposition temperature (473, 673, and 873 K) on the properties of the SiO(x) layers is addressed via analysis of the film growth rates, density profiles of the deposited thin films, pore size distributions, carbon depth profiles (with respect to TEOS), and voidage analysis for layers of different thicknesses (8-18 nm). A comparison of simulation with experimental results is also carried out.

Microwave-assisted rapid discharge sintering of a bioactive glass-ceramic.

Bioactive glass-ceramics have been developed as successful bone graft materials. Although conventional sintering in an electrically-heated furnace is most commonly used, an alternative microwave plasma batch processing technique, known as rapid discharge sintering (RDS), is examined to crystallise the metastable base glass to form one or more ceramic phases. Apatite-mullite glass-ceramics (AMGC) were examined to elucidate the effects of RDS on the crystallization of a bioactive glass-ceramic. By increasing the fluorine content of the glass, the fluorapatite (FAp) and mullite crystallization onset temperatures can be reduced. Samples were sintered in a hydrogen and hydrogen/nitrogen discharge at temperatures of ≈800 and 1000 °C respectively with the higher sintering temperature required to form mullite. Results show that the material can be densified and crystallised using RDS in a considerably shorter time than conventional sintering due to heating and cooling rates of ≈400 °C/min.

Novel, nanoporous silica and titania layers fabricated by magnetron sputtering.

Composite asymmetric membranes are fabricated through the deposition of submicrometer thick (100 nm) silica (SiO(2)) and titania (TiO(2)) films onto flat nanoporous silica and zirconia substrates by magnetron sputtering. The deposition conditions for both coating types were systematically altered to determine their influence on the deposited coating morphology and thickness. Ideal He/N(2) gas selectivity was measured for all of the membranes. The TiO(2) coatings, when deposited onto a ZrO(2) support layer with a pore size of 3 nm, formed a long columnar grain structure with average column diameter of 38 nm. A similar columnar structure was observed for TiO(2) coatings deposited onto a SiO(2) support layer with a pore size of 1 nm. Under the same conditions, SiO(2) coatings, deposited onto the same SiO(2) supports, formed a closely packed spherical grain structure whereas, when deposited onto ZrO(2) supports, the SiO(2) coatings formed an open grain structure. The average SiO(2) grain diameter was 36 nm in both cases. This preliminary investigation was aimed at studying the effect of sputtering parameters on the density and morphology of the deposited coatings. For the depositions carried out, the coating material was found to be very dense. However, the presence of grain boundaries resulted in poor ideal He/N(2) separation efficiencies.

Effect of surface wettability and topography on the adhesion of osteosarcoma cells on plasma-modified polystyrene.

Biomaterials interact with the biological environment at their surface, making accurate biophysical characterization of the surface crucially important for understanding subsequent biological effects. In this study, the surface of polystyrene (PS) was systematically altered in order to determine the effect of plasma treatment and surface roughness on cell adhesion and spreading. Surfaces with water contact angle from hydrophilic (12°) to superhydrophobic (155°) were obtained through a combination of modifying surface roughness (R (a)), the deposition of siloxane coatings and the fluorination of the PS surface. R (a) values in the range of 19-2365 nm were obtained by grinding the PS surface. The nanometer-thick siloxane coatings were deposited using an atmospheric pressure plasma system, while the fluorination of the PS was carried out using a low-pressure radio frequency (RF) plasma. The siloxane coatings were obtained using a liquid poly(dimethylsiloxane) precursor that was nebulized into helium or helium/oxygen plasmas. Water contact angles in the range of 12-122° were obtained with these coatings. Cell adhesion studies were carried out using human MG63 osteosarcoma cells. It was observed that higher polymer surface roughness enhanced cell adhesion, but had a negative effect on cell spreading. Optimum cell adhesion was observed at ∼64° for the siloxane coatings, with a decrease in adhesion observed for the more hydrophilic and hydrophobic coatings. This decrease in cell adhesion with an increase in hydrophobicity was also observed for the fluorinated PS surfaces with water contact angles in the range of 110-155°.

Deposition of hybrid organic-inorganic composite coatings using an atmospheric plasma jet system.

The objective of this study is to investigate the influence of alcohol addition on the incorporation of metal oxide nanoparticles into nm thick siloxane coatings. Titanium oxide (TiO2) nanoparticles with diameters of 30-80 nm were incorporated into an atmospheric plasma deposited tetramethylorthosilicate (TMOS) siloxane coating. The TMOS/TiO2 coating was deposited using the atmospheric plasma jet system known as PlasmaStream. In this system the liquid precursor/nanoparticle mixture is nebulised into the plasma. It was observed that prior to being nebulised the TiO2 particles agglomerated and settled over time in the TMOS/TiO2 mixture. In order to obtain a more stable nanoparticle/TMOS suspension the addition of the alcohols methanol, octanol and pentanol to this mixture was investigated. The addition of each of these alcohols was found to stabilise the nanoparticle suspension. The effect of the alcohol was therefore assessed with respect to the properties of the deposited coatings. It was observed that coatings deposited from TMOS/TiO2, with and without the addition of methanol were broadly similar. In contrast the coatings deposited with octanol and pentanol addition to the TMOS/TiO2 mixture were significantly thicker, for a given set of deposition parameters and were also more homogeneous. This would indicate that the alcohol precursor was incorporated into the plasma polymerised siloxane. The incorporation of the organic functionality from the alcohols was confirmed from FTIR spectra of the coatings. The difference in behaviour with alcohol type is likely to be due to the lower boiling point of methanol (65 degrees C), which is lower than the maximum plasma temperature measured at the jet orifice (77 degrees C). This temperature is significantly lower than the 196 degrees C and 136 degrees C boiling points of octanol and pentanol respectively. The friction of the coatings was determined using the Pin-on-disc technique. The more organic coatings deposited with octanol and pentanol exhibited friction values of 0.2, compared with approx. 0.8 for the coatings deposited from TMOS/TiO2 mixture (with and without methanol). Wear performance comparison between the two types of coating again indicated a significant organic component in the coatings deposited from the higher boiling point alcohols.