Staff

Abstract:
This article presents the influence of severe plastic deformation by hydrostatic extrusion (HE) on the thermal and structural properties of polyamide 6 (PA6). During the hydrostatic extrusion process, a fibrous structure oriented along the extrusion direction is formed, which was visualized during microscopic observations. The degree of crystallinity was analyzed by differential scanning calorimetry (DSC). Wide-angle X-ray scattering diffraction (WAXS) analysis was used to partially characterize the PA6 structure after the HE process. The contents of various forms of the crystalline phase in PA6 samples before and after the HE process were analyzed in fragments of spectroscopy in infrared (FTIR). The favorable properties of PA6 after the HE process were obtained after deformation under conditions generating an adiabatic temperature higher than the glass transition temperature and lower than the temperature of the onset of melting of the crystalline phase. Thermal analysis using DSC allowed us to conclude that in the PA6 after the HE process generating deformations in the range of 0.68–1.56, the proportion of the crystalline phase α increases in PA6. As the deformation increases in the HE process, the crystalline phase proportion increases by 12% compared to the initial material (before HE). The glass transition temperature of PA6 is ca. 50.6 °C, reduced for the sample after the HE process at a small deformation of 0.68 (PA6_0.68) to ca. 44.2 °C. For other samples, Tg is ca. 53.2–53.5 °C. As a result of the analysis of WAXS diffractograms of PA6 samples after various deformations in the HE process, the presence of typical peaks of phases α1 and α2 and γ was observed. The results of the FTIR spectroscopic analysis confirm these observations that as the deformation increases, the proportion of the crystalline phase α increases.

Keywords:
hydrostatic extrusion, polyamide 6, structure, thermal properties

Abstract:
We present the deposition and characterization of tungsten-tantalum diboride (W,Ta)B2 coatings prepared by the high-power impulse magnetron sputtering technique. We evaluated the influence of pulse duration and substrate bias on the properties of (W,Ta)B2 films. A high hardness of up to 35 GPa measured by nanoindentation was simultaneously obtained with good elastic properties. Changing the pulse duration greatly affected the B/(W+Ta) atomic ratio, which influenced the properties of the coatings. The deposited films are thermally stable at up to 1000 ◦C in vacuum and are able to withstand oxidation at 500 ◦C.

Keywords:
tungsten diboride, high power impulse magnetron sputtering (HiPIMS), hardness, thermal stability, oxidation resistance

Abstract:
Skin wound healing is one of the most challenging processes for skin reconstruction, especially after severe injuries. In our study, nanofiber membranes were prepared for wound healing using an electrospinning process, where the prepared nanofibers were made of different weight ratios of polycaprolactone and bioactive glass that can induce the growth of new tissue. The membranes showed smooth and uniform nanofibers with an average diameter of 118 nm. FTIR and XRD results indicated no chemical interactions of polycaprolactone and bioactive glass and an increase in polycaprolactone crystallinity by the incorporation of bioactive glass nanoparticles. Nanofibers containing 5% w/w of bioactive glass were selected to be loaded with atorvastatin, considering their best mechanical properties compared to the other prepared nanofibers (3, 10, and 20% w/w bioactive glass). Atorvastatin can speed up the tissue healing process, and it was loaded into the selected nanofibers using a dip-coating technique with ethyl cellulose as a coating polymer. The study of the in vitro drug release found that atorvastatin-loaded nanofibers with a 10% coating polymer revealed gradual drug release compared to the non-coated nanofibers and nanofibers coated with 5% ethyl cellulose. Integration of atorvastatin and bioactive glass with polycaprolactone nanofibers showed superior wound closure results in the human skin fibroblast cell line. The results from this study highlight the ability of polycaprolactone-bioactive glass-based fibers loaded with atorvastatin to stimulate skin wound healing.

Keywords:
nanofibers, polycaprolactone, bioactive glass, coating, wound healing

Abstract:
The use of injectable biomaterials for cell delivery is a rapidly expanding field which may revolutionize the medical treatments by making them less invasive. However, creating desirable cell carriers poses significant challenges to the clinical implementation of cell-based therapeutics. At the same time, no method has been developed to produce injectable microscaffolds (MSs) from electrospun materials. Here the fabrication of injectable electrospun nanofibers is reported on, which retain their fibrous structure to mimic the extracellular matrix. The laser-assisted micro-scaffold fabrication has produced tens of thousands of MSs in a short time. An efficient attachment of cells to the surface and their proliferation is observed, creating cell-populated MSs. The cytocompatibility assays proved their biocompatibility, safety, and potential as cell carriers. Ex vivo results with the use of bone and cartilage tissues proved that NaOH hydrolyzed and chitosan functionalized MSs are compatible with living tissues and readily populated with cells. Injectability studies of MSs showed a high injectability rate, while at the same time, the force needed to eject the load is no higher than 25 N. In the future, the produced MSs may be studied more in-depth as cell carriers in minimally invasive cell therapies and 3D bioprinting applications.

Abstract:
Magnetron sputtered WB2 coatings doped with 8, 11 and 16 at.% zirconium were analysed using energy dispersive spectroscopy, X-ray diffraction and nanoindentation under the load of 4, 7 and 10 mN. It has been observed that these coatings crystallize in the α-AlB2 and ω-W2B5 prototype structure. Phenomenon responsible for this is an increase of the zirconium content which causes an increase in the ω-W2B5 phase. All the deposited coatings have a hardness of about 45 GPa while Young's modulus drops down from 497 to 480 GPa with increasing zirconium content. Coatings without doping and doped with 16 at.% zirconium were annealed at 650 °C and subjected to cyclic thermal loads using a maximum temperature 600 °C and cooling with a compressed air. It has been observed that addition of zirconium improved coatings phase stability.

Keywords:
superhard coatings, tungsten diboride, zirconia doping, magnetron sputtering, cycling thermal loads, annealing

Abstract:
In the present work, we report the synthesis of surface modified activated carbon (AC). The surface of the activated carbon have been modified by using silver nanoparticles. The synthesis process is simple, cost effective and environment friendly. The modified-AC powders have been characterized by using X-ray diffraction, scanning electron microscopy and surface area and pore size measurements. The electrochemical performance of the prepared materials have been tested by fabricating symmetric configuration of EDLC by using magnesium-ion based polymer electrolytes. The cells have been tested by using cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge-discharge technique. AC with 3 wt% of silver presents best results with specific capacitance of the order of 398 F g−1 energy density and power density of 55 Wh kg−1 and 2.4 kW kg−1 making it an interesting material for supercapacitor application.

Keywords:
supercapacitor, activated carbon-silver composite, gel polymer electrolyte, electrochemical studies

Abstract:
Prediction of carbonation progress in concrete exposed to ionizing radiation is important for the durability assessment of nuclear power plants, eventually needed for operational license extension. The objective of this work is to reveal the influence of gamma irradiation on the carbonation development and resulting microstructural features of cement mortar. The composition of mortar was varied by using mineral additions. Canned specimens at elevated CO2 concentration environment were exposed to gamma irradiation up to the absorbed dose of 1.6 MGy in the vicinity of spent nuclear fuel rods in pool of research reactor. Micromechanical properties of carbonation reaction products were determined using nanoindentation tests. The carbonation depth was found to increase with increasing absorbed γ dose. The size of calcite crystals was about three times greater in irradiated specimens. Gamma irradiation improved the micromechanical properties of carbonation products. Effects of mineral additives on the characteristics of irradiated mortar are discussed.

Keywords:
calcite, carbonation, cement mortar, gamma irradiation, microstructure, mineral additions, nanoindentation

Abstract:
In this work, novel W-Zr-B coatings were developed by a hybrid process combining pulsed laser deposited ZrB2 and radio frequency magnetron sputtered W2B5. The influence of the laser power density on the structure and mechanical properties of the deposited films was studied. Addition of zirconium causes a change in the structure of the deposited films from columnar to mainly amorphous. The nanoindentation tests and compression of nanopillars showed that doped W-Zr-B layers are still super-hard and incompressible in comparison to WB2 films without doping, but they change their behaviour from brittle to ductile. Films obtained with a fluence of 1.06 J/cm2 are superhard (H = 40 ± 4 GPa) and incompressible (12 ± 1 GPa), but possess a relatively low Young’s modulus (E = 330 ± 32 GPa) and a high elastic recovery (We = 0.9). Further increase in the fluence causes films to consist of deeply embedded fragments of laser ablated ZrB2 target in the deposited layer. Taking into account that the particles are made of ZrB2 which possess extraordinary thermal properties, and the matrix is made of W-Zr-B, a super-hard material, such a composite can also be interesting for industrial applications.

Keywords:
superhard tungsten borides, hybrid magnetron sputtering – pulsed laser deposition, nanopillar compression

Abstract:
Three series of tests performed on fibre-reinforced gypsum composites are described herein. Sheep wool fibres and hemp fibres were used as reinforcement. The aim was to evaluate the capability of these biomaterials to enhance the fracture toughness of the gypsum matrix. The mechanical properties were measured by means of flexural tests on small specimens, whereas scanning electron microscopy with energy dispersive spectroscopy and X-ray diffraction were used to analyse the microstructure and composition of the fibres and of the gypsum composites. As a result, wool fibres were shown to improve the mechanical performance of the gypsum matrix, better than hemp fibres. This is due to the high adhesion at the interface of the fibre and gypsum matrix, because the latter tends to roughen the surface of the wool and, consequently to increase the bond strength. This preliminary research carried out shows that this type of biofiber—a waste material—can be considered a promising building material in sustainable and environmentally friendly engineering.

Keywords:
organic waste material, fibre-reinforced gypsum, mechanical properties, microstructure

Abstract:
An improved method for the production of luminescent carbon nanoparticles is proposed in this work. The new method overcomes the disadvantages of commonly used approaches. It involves two-stage laser ablation in water and in aqueous solutions, where the first stage is the laser ablation of a graphite target and the second is the shredding of particles produced in the first step. The two-stage method offers the optimization of the laser pulse fluence for the performance of each process. It was found that the two-stage process of laser ablation allows producing photoluminescent carbon structures in pure water. The additional reagent may be added either in the first or second stage. The first stage performed in pure water allows avoiding the contamination of the target. Moreover, it simplifies the identification of the origin of photoluminescence. Two synthesis routes for the preparation of carbon nanoparticles by the proposed method using pure water as well as urea aqueous solution are investigated. It was found that the use of urea as a reagent results in luminescence properties similar to those obtained with other more hazardous amine-based reagents. The influence of the synthesis approach and process parameters on the structural and luminescent properties of nanoparticles is also explored in this work.

Keywords:
pulsed laser ablation in liquid, carbon nanoparticles, photoluminescent particles

Abstract:
Tungsten borides (WBx; x = 2.5 or 4.5) with an increasing substitution of tungsten by zirconium from 0 to 24 at.% were synthesized by spark plasma sintering (SPS) for the first time. The influence of the holding time (2.5–30 min) on the densification behavior, microstructure evolution and development of the properties of W–Zr–B compounds were studied. The samples were characterized using scanning electron microscopy (SEM) for microstructure analysis, X-ray diffraction (XRD) for phase identification, Vickers micro-indentation for microhardness measurements, tribological tests to determine the coefficient of friction and specific wear rate, as well as measurements of electrical conductivity. The XRD results confirm the presence of the WB4 phase in the microstructure, despite the high sintering temperature (1800 °C) and small overstoichiometric excess of boron (4.5) addition in the sintered samples. This is caused by the high heating rate (400 °C/min), short holding time (2.5 min) and addition of zirconium. The Vickers hardness (HV) values measured at 1 N are 24.8 ± 2.0 and 26.6 ± 1.8 GPa for 24 at.% zirconium in WB2.5 and for 0 at.% zirconium in WB4.5, respectively. In addition, the hardest sample (W0.76Zr0.24B2.5) showed electrical conductivity up to 3.961·10^6 S/m, which is similar to WC–Co cemented carbides. The friction and wear test results reveal the formation of a boron-based film which seems to play the role of a solid lubricant.

Abstract:
In 2002, Robert Langer proposed that new polyester for tissue engineering should have good mechanical properties followed by: covalent bonding (as crosslinking) and hydrogen-bonding interactions; and should be elastic like rubber materials due to three-dimensional network structure. Considering these hypotheses, a polyester made of glycerol and citric acid was designed in this work. Poly(glycerol citrate) should be attractive for tissue engineering because both glycerol and citric acid, taking part in natural human metabolic pathways; and due to the reactant's functionality, 3D networks should be produced easily. Moreover, the reagents are cheap, available, and often used in the food and pharmaceutical industries. In this work, poly(glycerol citrate) was synthesized and then used with PLA for creating porous nonwovens by electrospinning. Produced materials were tested for possible application in the field of tissue engineering. The obtained materials have properties similar to collagen fibers, but still, require refinement for medical applications.

Keywords:
electrospinning, poly(glycerol citrate), polylactide, tissue engineering

Abstract:
This paper explores an anomalous size effect in thermal residual stresses occurring in the alumina matrix of Al2O3/Cr sintered composite upon varying the particle size of the chromium reinforcement. When a coarse chromium powder (45 µm mean particle size) is used the average residual stress in the alumina phase after cooling is compressive in accordance with the classical Eshelby solution. However, in the case of a fine chromium (5 µm mean particle size) it switches to tension. This effect, detected by photoluminescence piezospectroscopy, is also confirmed by X-ray and neutron diffraction experiments. As the classical micromechanics models are incapable to capture it, a finite element model is developed with the actual composite microstructure being reconstructed from the microtomography images. It is shown by numerical simulations that the anomalous size effect is associated with the complex microstructure of the composite fabricated with the fine chromium powder. It is also pointed out that the temperature dependence of the coefficients of thermal expansion of the matrix and the reinforcement affects the residual stress levels.

Keywords:
thermal residual stress, metal-ceramic composites, size effect, microcomputed tomography, finite element analysis

Abstract:
The coatings of tungsten borides (WBx) and tungsten borides doped with titanium (WyTi1−yBx) were deposited by using combined magnetron sputtering - pulsed laser deposition technique. In the case of WBx coatings, pure tungsten target was evaporated by a laser pulse at 1064 nm wavelength and pure boron target was sputtered by a magnetron. In the case of WyTi1−yBx coatings, the W2B5 target was sputtered by the magnetron and titanium target was evaporated by the laser pulse at 1064 nm wavelength. The content of titanium dopant changed from 1.1 to 5.5 at.%. The microstructure, chemical and phase composition of deposited coatings were investigated by means of Scanning Electron Microscopy, Energy Dispersive X-Ray Spectroscopy, X-Ray Photoelectron Spectroscopy and X-Ray Diffractometry, respectively. The Vickers hardness and Young's modulus were determined by using the nanoindentation test. Nanocrystalline WB coatings with dominant WB2 phase were obtained at a substrate temperature of 520 °C. The coatings were superhard with a hardness of 47–50 GPa and the mean value of surface roughness was <6 nm. The WBx coatings doped with 5.5 at.% Ti had hardness similar to the coatings sputtered by magnetron from W2B5 target.

Keywords:
The superhard WyBx thin films was deposited with hybrid laser-magnetron technology, The MS-PLD method allows for the deposition of ternary borides such as WyTi1−yBx, The MS-PLD method enables to control the chemical and phase composition of films, The deposited films are smooth with hardness above 50 GPa, Crystalline films were deposited only on a substrate kept an elevated temperature

Abstract:
Two types of poly(glycerol sebacate) (PGS) prepolymers were synthesized and electrospun with poly(l-lactic acid) (PLA), resulting in bicomponent nonwovens. The obtained materials were pre-heated in a vacuum, at different times, to crosslink PGS and investigate morphological and structural dependencies in that polymeric, electrospun system. As both PGS and PLA are sensitive to pre-heating (crosslinking) conditions, research concerns both components. More interest is focused on the properties of PGS, considering further research for mechanical properties and subsequent experiments with PGS synthesis. Electrospinning of PGS blended with PLA does not bring difficulties, but obtaining elastomeric properties of nonwovens is problematic. Even though PGS has many potential advantages over other polyesters when soft tissue engineering is considered, its full utilization via the electrospinning process is much harder in practice. Further investigations are ongoing, especially with the promising PGS prepolymer with a higher esterification degree and its variations.

Keywords:
electrospinning, degradable polymers, synthesis, structure, crosslinking

Abstract:
In this paper, the mechanical properties of composites consisting of electroplated Ni and co-electrodeposited SiC particles, coated with a thin protective layer of Ni, were studied. The protective layer was on the SiC particles prior to adding them to the electrolyte bath. It was demonstrated that due to the application of the protective layer it was possible to decrease sliding friction force, and improve the wear resistance, of the composite coatings in comparison with standard electroplated composite coatings made of Ni and co-electrodeposited pure SiC particles. Coating SiC particles with Ni was achieved by means of a PVD process. The main advantage of this step is avoiding oxidation of the surface of the particles during the contact with an electrolyte. Particles protected from oxidation lead to stronger interfacial bonding between the matrix and the reinforcement. Furthermore, better bonding protects the SiC particles from being extracted from the matrix by a counter-probe during friction and wear tests. The influence of the particle's concentration is studied. A smaller friction force and constant wear rate was observed.

Keywords:
wear, friction, interfacial bonding strength, metal matrix composites, silicon carbide, electrodeposited nickel

Abstract:
A surface of polymeric nonwovens may be coated with various types of nanoparticles for medical applications, filtration, and so forth. However, quite often methods used for surface modification are difficult to scale up or are not applicable for polymers. In this article, we present one-step process enabling nonwovens functionalization. Poly(l-lactide-co-glicolide) (PLGA) nonwovens were prepared by electrospinning process and coated with hydroxyapatite nanoparticles (HAp) using ultrasonic processing. The effect of the process was evaluated with various techniques. HAp layer was successfully attached without loss of structural properties of HAp or PLGA nonwovens. The analysis confirmed the decrease of hydrophobicity of coated nonwoven, as well as its biocompatibility, making this material valuable from the perspective of medical applications. The sonochemical functionalization of polymeric nonwovens may be considered as an effective and economic method, enhancing surface properties of electrospun nonwovens for various applications.

Keywords:
lectrospinning, fibrous composites, nanoparticles, surface modification, ultrasonic treatment

Abstract:
Closed-form analytical formulas describing kinetics of oriented crystallization under constant or variable amorphous orientation and isothermal or non-isothermal conditions are derived, valid in the whole range of orientation. Master relation for the deformation free energy vs. orientation factor, or tensile stress, is derived accounting for non-linear effects of finite chain extensibility. The Avrami-Evans model is expanded to account for the effects of orientation in thermodynamic driving force of nucleation and crystal growth. Involvement of predetermined and spontaneous nucleation varies strongly with the orientation and leads to domination of spontaneous nucleation at high orientations. Crystallization half-time involving separated or coexisting predetermined and spontaneous nucleation is discussed. A formula predicting equal contribution of both nucleation modes vs. orientation factor and temperature is derived and ranges of domination of the modes are discussed. Example computations illustrate the model predictions for an example polymer (PLLA) and are in good agreement with the experimental results.

Keywords:
amorphous orientation, oriented crystallization kinetics, nucleation rate

Abstract:
The current work studies the electrospun poly (vinyl alcohol) (PVA) nanofibers and its nanocomposites including nanohydroxy apatite (nHAp) and nHAp/cellulose nanofibers (CNFs), emphasizing the impact of nanofillers on the toughness of nanofibers. PVA nanofibers were incorporated with 10 wt% of nHAp and then various amounts of CNF were added to subsequent PVA/nHAp fibrous nanocomposites. The morphology of nonwoven mats was studied by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). While neat PVA nanofibers were smooth and uniform in thickness, the nanofiller loading resulted in thinner fibers with less uniformity. Furthermore, the thermal properties of the nonwoven network of fibers were characterized employing thermogravimetric analysis (TGA). Although the maximum loss mass temperature of PVA was partially reduced upon addition of nanofillers, the onset of decomposition was not altered. The mechanical characterizations were performed using static tensile and dynamic mechanical analysis (DMA). Compared to neat PVA mats, the tensile test of nanocomposites mats demonstrated the significant increase in Young's modulus; however, strain at break was dramatically reduced. In addition, the fracture work was assessed from the area under the stress-strain curve, which showed brittleness of fibrous nanocomposites due to the nanofiller incorporation. Field emission SEM (FE-SEM) was employed to scan the fracture surface of stretched fibers. The increase in modulus of electrospun mats was also shown by DMA in frequency mode. In parallel, both tensile test and DMA confirmed the change in fracture of PVA fibers from a tough to brittle mode, due to the nanofiller addition.

Keywords:
electrospun nanocomposites, nanofillers, toughness, mechanical properties

Abstract:
Tungsten and boron compounds belong to the group of superhard materials since their hardness could exceed 40 GPa. In this study, the properties of the tungsten boride WBx coatings deposited by radio frequency magnetron sputtering were investigated. The sputtering was performed from specially prepared targets that were composed of boron and tungsten mixed in a molar ratio of 2.5 and sintered in Spark Plasma Sintering (SPS) process. WB films were deposited on silicon (100) and stainless steel 304 substrates at temperatures of 23 ÷ 770 °C. Microstructure, chemical and phase composition were investigated by using Scanning Electron Microscope (SEM), X-Ray Photoelectron Spectroscopy (XPS) and X-Ray Diffraction (XRD), respectively. The mechanical properties like Vickers hardness and Young's modulus were obtained by using nanoindentation test at a load of 5 ÷ 100 mN. The friction coefficient and wear resistance of αWB coatings were investigated in scratch test and reciprocal sliding wear instrumentation. Moreover, in order to investigate thermal properties, the αWB films were annealed at 1000 °C in argon/air for 1 h and at 250 °C for 2 h in air atmosphere. Results of our research confirm that αWB coatings can be considered as an alternative to superhard materials in the production of wear resistant, long-lasting tools.

Keywords:
Hard coatings, Hard materials, Magnetron sputtering, Mechanical properties, Thermal properties, Tungsten boride

Abstract:
Bicomponent polycaprolactone/gelatin and polycaprolactone/collagen fibres were formed by electrospinning using two kinds of solvents: a representative of commonly used solvents with this polymer composition, highly toxic hexafluoroisopropanol (HFIP) and alternative, less harmful one, the mixture of acetic (AA) and formic (FA) acids. Both material types were subjected to investigations of structure and in-vitro cellular activity. Viscosity and Fourier transform infrared spectroscopy (FTIR) measurements shown that the type of solvent used influences the structure of solution and conformation of polymer molecules. In-vitro quantitative tests as well as cell culture morphology observations proved that materials electrospun with the use of 'green' solvents can yield similar results to those obtained by made with toxic ones. Slightly better cellular response to materials electrospun from HFIP can be explained by relatively well dispersed components within the fibre and more expanded conformation of molecules, resulting in better exposition of RGD (Arg-Gly-Asp) binding sites to cells' integrin receptors.

Keywords:
Cellular tests, Electrospinning, Biopolymers, Viscosity, Solvents

Abstract:
Tungsten borides belong to the group of potentially superhard materials which hardness could be compared to cubic boron nitride and diamond. However, difficulty in fabrication of single phase material using conventional methods is the main drawback of this group of ceramics. In order to overcome this problem material can be deposited as a thin layer e.g. in the pulsed laser deposition process. In this paper, the effect of laser wavelength and energy density of nanosecond Nd:YAG laser on the WBx-type layers were analyzed using wavelengths 355 and 1064 nm with the energy density of laser beam from 1.7 to 5 J/cm2 and from 1.7 to 9.3 J/cm2, respectively. The WB2.5 and WB4.5 targets synthesized in Spark Plasma Sintering process were used and the layers were deposited onto Si (100) substrate heated to a temperature of 570 °C. Layers' microstructure were analyzed using X-ray Diffraction and scanning electron microscope equipped with energy dispersive X-ray spectrometer. Change of laser wavelength and energy density resulted in variations of the chemical composition and morphology of deposited layers. Finally, W2B-βWB, αWB-WB-WB3 and WB3, and boron layers were deposited wherein WB3 structure is formed in a wide range of laser fluences and at both investigated wavelength. Next, WB3 layers were investigated in the indentation test at a load of 5–30 mN and its hardness was up to 50 ± 10 GPa

Keywords:
Pulsed laser deposition, Super-hard materials, Tungsten borides, Tungsten triboride

Abstract:
Bicomponent polycaprolactone/gelatin and polycaprolactone/collagen nanofibers formed by electrospinning using various solvents were subjected to biodegradation and compared. Hexafluoroisopropanol (HFIP) was used as a reference solvent, while the second, alternative solvent system was the mixture of acetic acid (AA) with formic acid (FA). Biodegradation of investigated materials was manifested mainly by the gelatin leaching, including collagen which is indeed denaturated to gelatin during electrospinning, leading to nanofibers erosion. There was no molecular degradation of PCL during 90 days of biodegradation procedure as deduced from no change in the elongation stress at break. The rate of biopolymer leaching was very fast from all materials during the first 24 h of biodegradation, being related to surface leaching, followed by a slower rate leaching from deeper material layers. Mass measurements showed much faster biopolymer leaching from nanofibers electrospun from AA/FA than from HFIP because of strongly emulsive nature of the solution in the former case. Irrespective of the solvent used, the leaching rate increased with initial content of gelatin. The analysis of Young modulus during biodegradation indicated complex mechanism of changes, including biopolymer mass loss, increase of PCL crystallinity and partial gelatin renaturation.

Keywords:
Bicomponent nanofibers, Biodegradation, Biopolymer

Abstract:
Rhenium diboride (ReB2) thin films have been deposited by a nanosecond pulsed laser deposition method on Si (100) substrate heated to 570°C. The coatings were formed in the ablation process of SPS sintered ReB2 target. The effect of laser wavelength, energy density and postannealing on the films' properties was studied. Investigated wavelengths were 355 and 1064 nm of Nd:YAG nanosecond laser. Laser beam energy density varied from 2.1 to 6.1 J cm− 2 and from 4.1 to 9.4 J cm− 2 at 355 and 1064 nm, respectively. Layer thickness was of the order of several hundred nanometres. Deposition efficiency increases with an energy density in quasi linear way and strongly grows for shorter wavelength. The layers consist of two characteristic microstructures: a smooth basis and stick debris (typical diameters of several hundred nanometres). Lower energy density of laser beam and longer wavelength favour dominance of smooth basis and minimization of debris. The XRD analysis of all samples indicate the crystalline ReB2 with preferred (002) orientation and fine grain size of about 20 nm. Shorter wavelength and higher energy density foster stronger (002) orientation. Moreover, an annealing right after the deposition (25 min in 350°C) causes minimization of degree of orientation and decrease of hardness. The Vickers hardness of ReB2 films is at about 60 GPa and is reduced to about 40 GPa after the annealing process. Deposition efficiency and physical and chemical structures of layers produced under variety of conditions were studied and compared.

Keywords:
Ceramics ablation, Pulsed laser deposition, Rhenium diboride, ReB2 optical properties, Super-hard films, Wavelength influence

Abstract:
Bicomponent polycaprolactone/gelatin (PCL/Gt) nanofibers were successfully formed for the first time by electrospinning using a novel polymer–solvent system with solvents being alternative to the commonly used toxic solvents like fluorinated alcohols. The mixture of acetic acid (AA) with formic acid (FA; 90:10) was applied. Stable electrospinning was possible despite the fact the mixture of PCL and gelatin in AA/FA solvent showed emulsive structure. From the practical perspective, there is no doubt that it is possible to obtain PCL/Gt fibers using AA/FA mixture with morphology similar to that for fibers spun from hexafluoroisopropanol (HFIP) solutions.

Keywords:
Alternative solvents, electrospinning, gelatin, nanofibers, polycaprolactone, structure

Abstract:
Novel polyurethanes based on synthetic, atactic poly[(R, S)-3-hydroxybutyrate] (a-PHB) and polycaprolactone (PCL) or polyoxytetramethylene (PTMG) diols were synthesized. It was shown that the presence of a-PHB within soft segments reduces crystallinity of PUR. Because of the low melting temperature for polyurethanes with PCL in soft segments, at this stage of work, electrospinning was limited to polyurethanes containing PTMG and a-PHB. Polyurethane containing 80% of PTMG and 20% of a-PHB was electrospun at various parameters from hexafluoro-2-propanole solution, resulting in formation of fibers with the average diameter ca. 2 μm. The fiber diameter decreased with decreasing polymer concentration in a solution and was practically insensitive to the needle-collector distance in the applied range of distances.

Keywords:
polyurethane, polyhydroxybutyrate, electrospinning, scaffolds

Abstract:
Concretes for the shields against ionizing radiation should be executed with particular care to satisfy all requirements, not only effective attenuation of different radiation but also sufficient durability. In the paper fundamental problems are presented that are related with designing of such protective concretes in order to avoid alkali-aggregate reaction. The results of preliminary investigations are presented that indicate how to select barite aggregate and to define composition of concrete mix. Present knowledge in that area of materials engineering should be completed before initiation of construction of nuclear power stations at industrial scale in Poland.

Keywords:
Alkali Aggregate Reaction (AAR), heavy aggregate, ionizing radiation

Abstract:
Synthetic and natural polymers blends represent a new brand of materials with application in wound healing, scaffolds or drug delivery systems. Polycaprolactone/gelatin (PCL/Gt) blends were analyzed in terms of their miscibility. The PCL structure was investigated as a function of Gt content. Changes in the PCL spherulitic structure with Gt content were investigated by a polarizing-interference microscope. The analysis of the glass transition temperature (Tg) of both components as a function of PCL/Gt ratio by differential scanning calorimetry indicates that the system of polycaprolactone/gelatin belongs to a type of s.c. compatible system, being intermediate between miscible and immiscible systems. There is possibility of very limited miscibility of both components. Supplementary wide angle X-ray scattering results are presented.

Keywords:
lends, compatibility, miscibility, polycaprolactone, gelatin

Abstract:
In the present study the potential of alkali-silica reaction (ASR) in fine fraction of aggregate was analyzed. The investigation was focused on mineral composition of siliceous sand and its influence on ASR. Three siliceous sands from different origin and localization in Poland were tested. Petrographic analysis on thin sections was conducted. The automatic image analysis was used to estimate the content of reactive minerals (micro- and crypto-crystalline quartz). The XRD measurements were performed. Alkali-silica reactivity of fine aggregate was tested by mortar-bar test according to ASTM C1260 Standard. Petrographic analysis showed that all tested siliceous sands contained reactive form of quartz, micro- and cryptocrystalline. Mortar-bar tests according to ASTM C1260 indicated that one from the selected sands exceeded expansion over the limit and was considered as reactive. The content of reactive minerals in sands estimated by automatic image analysis corresponded to ASTM C1260 results. The higher content of reactive form of quartz in siliceous sand, the larger expansion of mortar-bar test.

Keywords:
Siliceous sand, Alkali-Silica Reaction (ASR), digital image analysis, micro- and cryptocrystalline quartz, expansion

Abstract:
In the present study the potential appearance of the alkali-silica reaction (ASR) in heavy aggregates was studied. ASTM C1260 Standard Test Method for Potential Alkali Reactivity of Aggregates (Mortar-Bar Method) was applied. In order to investigate the effect of the content of alkalies in cement on the expansions due to ASR, three levels of total and soluble alkali content of cement were studied. Three portland cements Type I with different alkali content were selected. Two ordinary portland cements, which are commonly available in the market and one special cement were tested. That cement was specially made for the purpose of the nuclear shielding concrete CEM I NA-SR-LH of low-alkali, increased sulphate resistance and low heat of hydration. For the tests according to ASTM C 1260 the high-density aggregates, known as absorbing gamma radiation were selected: barite, magnetite and hematite. The expansion test revealed that hematite was highly reactive, regardless of the type of cement. Already after four days of storage in 1 N NaOH and 80°C the mortar bar expansion exceeded the limit of 0.1%, and after next four days was more than 0.2%., which qualifies it extremely reactive aggregate. Other aggregates after 14 days of testing did not exceed 0.1% elongation limit, but the influence of the type of cement was noticed. There was a noticeable tendency for increasing the total expansion with increasing the alkali content of cement.

Keywords:
Alkali-Silica Reaction (ASR), high density aggregate, cement composition

Abstract:
The results of microscopic analysis on thin sections of aggregates intended for nuclear shielding concrete are presented. The petrographic analysis was performed on different barite, magnetite and hematite aggregates used as the high-density aggregate to absorb gamma radiation. Both optical microscopy and accelerated expansion tests were used to recognise the potential for alkali-reactivity of the aggregates. The mineral composition of the tested aggregates was analysed on thin sections in transmitted cross-polarized light and XRD tests were additionally performed. Expansion tests of mortar bars exposed to 1 N NaOH solution at the temperature of 80°C were also performed following ASTM C1260. The high-density aggregates contained ore deposits - metallic opaque phases providing the required shielding properties. These aggregates also contained various amounts of non-metallic phases, with both innocuous non-ore minerals and deleterious, potentially reactive materials. Barite aggregates contained siderite, fluorite and hawleyite in varying amounts, apart from the barium sulphate being the principal component. Moreover, particularly reactive cristobalite and muscovite were identified in barite aggregates from certain quarries. Tests according to ASTM C1260 performed on mortars showed the expansion above the accepted criterion for non-reactive aggregate and confirmed the threat due to the presence of cristobalite in barite aggregates.

Keywords:
high-density aggregate, heavy concrete, alkali-silica reaction, thin section, XRD

Abstract:
In the paper the barite aggregate has been analyzed as a potential source of ASR in heavy concrete. Special attention was paid to BaSO4 and minor mineral components in aggregates and their influence on ASR development in tested mortars

Keywords:
heavy aggregate, Alkali Silica Reaction (ASR), ionizing radiation

Keywords:
RF magnetron sputtering, hard materials, PLD, tungsten boride

Abstract:
Electrospun nonwovens from PCL/gelatin and PCL/collagen structurally mimic native extracellular matrix and provide cells with chemical cues affecting them. Electrospinning of bicomponent nanofibres requires the use of a solvent which dissolves both of the polymers.
We have optimized the process of electrospinning of PCL/gelatin and PCL/collagen nanofibers based on the use of non-toxic, alternative solvents: acetic acid and formic acid (AA/FA) as previously described [1].
Bicomponent PCL/gelatin and PCL/collagen nanofibers were formed by electrospinning using the mixture of acetic acid and formic acid (9:1 w/w ratio), while hexafluoroisopropanol (HFIP) was used as a reference solvent. Nonwoven materials were subjected to cellular in vitro and biodegradation tests and compared.
All in vitro tests were performed using L929 mouse fibroblast cells. Cytotoxicity test was carried out on extracts and showed that all type of materials are not cytotoxic. Materials with 10% biopolymer content as well as made from PCL only underwent experiment in direct contact. Cells were cultured on materials for 3, 5 and 7 days and afterwards taken for SEM as well as fluorescent dying of nuclei and cytoskeleton. Obtained results proved that the addition of Arg-Gly-Asp (RGD) amino acid sequences from biopolymer, in comparison to pure PCL materials, facilitates cell adhesion and spreading on the surface of nonwovens regardless of solvent used in electrospinning.
PCL/gelatin and PCL/collagen nonwovens underwent biodegradation in PBS solution at 37°C. After different times, ranging from 1 to 90 days samples were subjected for comparative analysis via various methods.
Despite the fact that bicomponent nanofibers electrospun from alternative solvents have similar morphology to those electrospun from perfluorinated alcohols, they differ in the internal structure which seriously affects biodegradation process. Biodegradation of investigated materials is manifested mainly by the gelatin leaching, which leads to nanofibers erosion, particularly large for nanofibers spun from AA/FA.

Keywords:
electrospinning, bicomponent nanofibers, biodegradation, cellular studies

Keywords:
molecular orientation, scaffolds, fibres, tissue engineering

Abstract:
Tungsten boride compounds are very promising new hard and super - hard materials. This kind of materials could be used in production of high-speed tools, durable bearings and nonabrasive surfaces. The hardness of tungsten borides strongly depends on boron content as well as material microstructure. For example hardness of W2B is about 12.4 GPa, WB hardness is 18 – 36 GPa, WB2 hardness is 28.5–39.7 GPa and WB3 hardness is 28.6 – 36.9 GPa. Moreover production of tungsten borides in the form of layers or nano -grained structured increase its hardness even above 40 GPa. Although the properties of tungsten boride structures are known from theoretical calculations, the data concerning structures produced experimentally are scare. Therefore, the properties of tungsten boride layers deposited by pulsed laser deposition (PLD) process are investigated in this paper. Layers were deposited using two types of targets: with boron to tungsten ratio of 2.5:1 and 4.5:1 and with the use of two laser wavelengths: 355 and 1064 nm.

Keywords:
pulsed laser deposition, tungsten borides

Abstract:
Cells sense subtract stiffness, elasticity and transduce that information into morphological changes and lineage specification. Polymer molecular order and mechanical properties, specially stiffness and elasticity indicate influence on cellular response during in- vitro study [e.g. Bershadskye et al 2013]. The aim of proposed presentation is to evaluate the effect of tailored crystallinity and mechanical properties of one- and bicomponent polymer films in terms of cells morphology and proliferation without changing other parameters. Polycaprolactone (PCL) and Gelatin (Ge) were used. As a solvents: Hexafluoroisopropanole (H), Acetic Acid (AA) were chosen. Two methods of foil preparation were analysed: forming from melt (onecomponent), forming from solution (one- and bicomponent).In both methods, the degree of crystallinity was modified mainly by the different type of PCL molecular weight, solvent type and/or annealing. Films were analysed using polarizinginterference microscopy allowing characterization of spherulities morphology. Degree of crystallinity was analysed by differential scanning calorimetry. Foils topography was analysed by atomic force microscopy, selected mechanical properties and hydrophilicity (contact angle) as the significant from the viewpoint of cellular activity were determined as well. L929 cells adhesion and morphology ware analysed by immunohistochemical staining for actin and nuclei. Cell activity and proliferation were analysed also. It is evident that conditions of PCL films preparation affect the morphology of spherulites. All samples were birefringent, indicating in general crystallinity, being different for particular samples. Maltese cross was observed in few samples. Crystallinity of PCL films determined from DSC measurements was in range 0,45-0,70 depending on solvent and polymer molecular weight used. Young Modulus strongly depends on Mw of PCL and Ge additive. L929 cells interact with subtract; morphology and proliferation degree change with crystallinity and elasticity of one- and bicomponet films.

Keywords:
crystallinity, PCL, mechanical properties, casted films

Keywords:
pulsed laser deposition, rhenium borides

Abstract:
Bicomponent polycaprolactone/gelatin nanofibers were formed by electrospinning as previously described [1] using a novel polymer – solvent system with solvents being alternative to the commonly used toxic solvents like fluorinated alcohols. PCL/Gelatin nanofibres were electrospun from the mixture of acetic acid (AA) with formic acid (FA) (90:10) and from hexafluoroisopropanol (HFIP), that was used as reference solvent. PCL/Gelatin nanofibres with polymers w/w ratios 9:1, 8:2 and 7:3, underwent biodegradation in PBS solution at 37°C. After different times, ranging from 1 to 90 days, they were rinsed in demineralized water and dried. Weight loss and FTIR tests were performed to assess the kinetics of gelatin leaching, while SEM imaging and hydrophobicity tests to show its depletion from the surface. DSC measurements were carried out to examine changes in fibres’ internal structure and uniaxial tensile testing to compare their mechanical properties. Morphology of PCL/Gt fibers obtained from AA/FA is similar to that obtained from HFIP. Despite similar morphology, the internal structure of nanofibers formed from alternative solvents is different, reflecting the emulsive nature of PCL/gelati n mixture in AA/FA solvents contrary to clear, transparent solutions in HFIP. This apparent difference affects strongly the kinetics of leaching of gelatin from bicomponent fibres and thus how their mechanical and bioactive properties are changing in time after placing in living organism. There is substantial difference in kinetics of gelatin leaching depending on solvent used. Mass measurements show much faster gelatin degradation in nanofibres electrospun from AA/FA than from HFIP. For instance, for PCL/Gt 7:3 samples, gelatin content loss is 85% for AA/FA and 68% for HFIP after 90 days. Moreover, irrespective of the solvent used, the degradation rate increases with initial content of gelatin and is the highest in the first 24 hours: 27% for AA/FA 9:1 and 67% for 7:3 and 13% and 32% for HFIP respectively. The observed changes can be explained by nonuniform distribution of gelatin within fibres spun form AA/FA due to emulsive character of solution. Comparison of SEM images reveals linear groove-like sites remaining after gelatin leaching on a surface of fibres spun from AA/FA solvent. Contrary to this, fibres spun from HFIP remain smooth which can be attributed to molecular dispersion of both components.

Keywords:
nanofibers, biodegradation, polycaprolactone, gelatin

Abstract:
Influence of the crystallinity of the substrate on cell proliferation during in-vitro study was highlighted in few articles. Methods of forming 3-D scaffolds usually do not take into account crystallinity optimisation. The aim of proposed presentation is to investigate an influence of polycaprolactone (PCL) crystallinity on cells spreading, their activity and proliferation. PCL Mn 45k and Mn 80k g/mol were used. As a solvents: HFIP (H) and Acetic Acid (AA) were used. Two methods of foil preparation were analysed: -forming from melt (PCL45, PCL80) -forming from 10%wt solution (e.g. PH45, PAA45) Samples were analyzed using interfered-polarization microscopy (MIP) which allows to describe the morphology of spherolites (crystalline and amorphous phase). Degree of crystallinity was analysed by differential scanning calorimetry (DSC) and wide angle X-ray scattering (WAXS). Selected samples surfaces were O2 plasma treated to decrease hydrophobic properties of PCL. L929 cells adhesion and morphology were analyzed by immunohistochemical staining for actin and nuc lei. Cell activity and proliferation were analyzed. Morphology of spherolites was analyses using interfered-polarization microscopy (MIP). Analyses indicate changes in spherolites shape, size and also crystalline/ amorphous phase amount. Differences of crystallinity for PCL using different molecular weight were analysed by DSC and WAXS measurements. Decrease of contact angle was observed for O2 plasma treated samples. All PCL films were found as nontoxic for L929 cells. Differences in cells spreading, activity and proliferation degree were found. Modification of Mn, solvent and concentration of PCL enable film formation in wide range of crystallinity. L929 during in-vitro study interact with the PCL film. Crystallinity as part of the supermolecular structure influence on cells morphology.

Keywords:
crystallinity, PCL, cellular responce, structure

Abstract:
Introduction In the case of semicrystalline polymers, crystallinity is the parameter determining their physical properties. Some research groups indicate influence of crystallinity on cells response during in- vitro study. Commonly used methods of three-dimensional scaffolds formation do not take into account crystallinity optimisation. The aim of proposed presentation is to evaluate the effect of molecular weight and solvent on crystallinity and crystal size in case of polycaprolactone (PCL) films. Methodology Material: PCL with Mn:10, 45 and 80k g/mol (Sigma Aldrich) was used. As a solvents: Hexafluoroisopropanole, HFIP (Iris Biotech GmbH.), Acetic Acid, AA and Dichloromethane, DCM (Avantor and Chempol respectively) were used. Methods: Films were prepared from the PCL with different molecular weight using various solvents differing in evaporation rate. Characterization: Films were analysed using polarizing-interference microscopy (MPI) allowing characterization ofspherulities morphology. Degree of crystallinity was analysed by differential scanning calorimetry (DSC) and comparatively bywide angle X-ray scattering (WAXS). Results and Discussion It is evident from MPI observations that conditions of PCL films preparation affect the morphology of spherulites. All samples were birefringent, indicating in general crystallinity, being different for particular samples. Sphorulities size depends on Mw and solvent type; sharp Maltese cross was observed on few samples. Crystallinity of PCL films determined from DSC measurements was in the range 0,45-0,68 depending on solvent and polymer Mn used. Generally crystallinity of films formed from DCM is lower than from AA as a result of lower boiling point of DCM. Additional annealing enables increase in crystallinity to 0,8. WAXS crystallinity correlates with values determined by DSC. Changes of full width of half maximum(FWHM) of crystal peaks indicate variations of crystal size and/or defects depending on molecular weight and solvent what correlates with MPI observations also. Conclusions spherulites shape and crystallinity are strongly dependent on Mn and solvent type. Structural parameters of films decide on Young modulus and elasticity in terms of applications

Keywords:
crystallinity, PCL, solvents WAXS, molecular structure

Abstract:
In this study bicomponent polycaprolactone/gelatin nanofibers were successfully formed by electrospinning using for the first time a novel polymer – solvent system consisting of acetic acid and formic acid. Such solvent system is alternative to the commonly used toxic solvents like fluorinated alcohols, mainly hexafluoroisopropanol. The effect of electrospinning conditions on morphology and structure of nanofibers were investigated.

Keywords:
nanofibers, electrospinning, polycaprolactone, gelatin, alternative solvents, structure

Abstract:
Few research groups have highlighted the unexpected degree of cell proliferation depending on the degree of crystallinity of the substrate. Commonly used methods of forming three-dimensional scaffolds do not take into account crystallinity optimisation.
The aim of proposed presentation is to investigate polycaprolactone (PCL) substrate supermolecular structure effect, mainly crystallinity, on cells spreading, activity and proliferation.

Keywords:
crystalllinity, PCL, solvent, molecular structure, L929