Electrochemical sensors were developed using track-etched polyethyleneterephthalate (PET TeMs) membranes modified by UV-initiated graft copolymerization to produce PET TeMs-g-p(NHMA-co-HEMA). The modification process, structural features and physicochemical properties of the resulting membranes were comprehensively characterized using scanning electron microscopy (SEM), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), Energy-Dispersive X-ray spectroscopy (EDX), UV-visible spectrophotometry (colorimetric method), gas permeability measurements and contact angle analysis. Optimal grafting conditions were achieved at a monomer concentration of 10% (NHMA : HEMA = 70 : 30), UV irradiation time of 60 min and UV lamp distance of 10 cm at a temperature of 38-40 °C. The modified membranes were subsequently used in an electrode system to determine Eu3+, Gd3+, La3+, Ni2+ and Pb2+ ions using square-wave anodic stripping voltammetry (SW-ASV). The sensors were evaluated over this concentration range of 1 × 10-7-1 × 10-4 for Ni2+, 0.5 × 10-7-1 × 10-5 M for Pb2+, 0.5 × 10-6-5 × 10-5 M for Eu3+, 0.5 × 10-6-0.5 × 10-4 M for Gd3+, and 1 × 10-6-1 × 10-4 M for La3+, with detection limits of 8.5 × 10-7 M for Eu3+ (R 2 = 0.96), 6.3 × 10-6 M for Gd3+ (R 2 = 0.975), 2.51 × 10-6 M for La3+ (R 2 = 0.96), 8.7 × 10-7 M for Pb2+ (R 2 = 0.98), and 7.4 × 10-6 M for Ni2+ (R 2 = 0.98). The results indicate a significant improvement in electrochemical performance due to the grafted PET TeMs-g-p(NHMA-co-HEMA) structure and the developed sensor demonstrates high applicability and stable performance for the detection of rare earth and heavy metal ions in tap water as well.
Electrochemical sensors have been developed based on polyethylene terephthalate track-etched membranes (PET TeMs) modified by photograft copolymerization of N-vinylformamide (N-VFA) and trimethylolpropane trimethacrylate (TMPTMA). The modification, structure and properties of the modified PET TeMs were thoroughly characterized using scanning electron microscopy (SEM) and atomic force microscopy (AFM), thermogravimetric analysis (TGA), Fourier-transform infrared (FTIR) spectroscopy, gas permeability measurements and contact angle analysis. Optimal membrane modification was achieved using C = 10% (N-VFA), 60 min of UV irradiation and a UV lamp distance of 10 cm. Furthermore, the modified membranes were implemented in a two-electrode configuration for the determination of Eu3+, Gd3+, La3+ and Ce3+ ions via square-wave anodic stripping voltammetry (SW-ASV). The sensors exhibited a linear detection range from 10−7 M to 10−3 M, with limits of detection of 1.0 × 10−6 M (Eu3+), 6.0 × 10−6 M (Gd3+), 2.0 × 10−4 M (La3+) and 2.5 × 10−5 M (Ce3+). The results demonstrated a significant enhancement in electrochemical response due to the grafted PET TeMs-g-N-PVFA-TMPTMA structure, and the sensor showed practical applicability and consistent performance in detecting rare earth ions in tap water.
Utilizing reactive DC magnetron sputtering method, TiN coatings were deposited on the silicon substrates at different nitrogen flows and powers. A study of the X-ray phase composition of the coatings was carried out. The stoichiometric composition of the coatings was determined using energy dispersive x-ray spectroscopy. The structure of the surface, cross-section, and thickness of the coatings were determined using scanning electron (SEM) and atomic force microscopy (AFM). A significant change in the surface structure of TiN coatings was established with changes in deposition power and nitrogen flow. SEM images of cross-sections of all coated samples showed that the formation of coatings occurs in the form of a columnar structure with a perpendicular orientation relative to the silicon substrate. The mechanical properties (elastic modulus E and microhardness H) of TiN coatings of the first group demonstrate a maximum at a nitrogen flow of 3 sccm and are 184 ± 11 GPa and 15.7 ± 1.3 GPa, respectively. In the second group, the values of E and H increase due to a decrease in the size of the structural elements of the coating (grains and crystallites). In the third group, E and H decrease. Microtribological tests were carried out in 4 stages: at a constant load, multi-cycle for 10 and 100 cycles, and with increasing load. The coefficient of friction (CoF) and specific volumetric wear ω depend on the roughness, topology, and mechanical properties of the resulting coatings. Fracture toughness was determined using nanoscratch and depends on the mechanical properties of TiN coatings. Within each group, coatings with the best mechanical and microtribological properties were described: in the first group—TiN coating at 3 sccm (with (29.6 ± 0.1) at.% N), in the second group—TiN coating at 2 sccm (with (40.8 ± 0.2) at.% N), and in the third group—TiN coating at 1 sccm (c (37.3 ± 0.2) at.% N).
As a result of anthropogenic activities, the environment is polluted by heavy metals. The most important task is to find methods to control their content in water. Track-etched membranes (TeMs) can be relatively easily modified by nanometer layers of functional materials with using the Langmuir‒Blodgett technique, which makes it possible to specifically change the structural, selective properties of the membrane surface and obtain new materials with desired properties. The aim of the work was to develop flexible sensors for the analysis of lead ions in water based on poly(ethylene terephthalate) (PET) TeMs with perfluorodecanoic acid (PFDA) nanolayers. Techniques for modifying TeMs based on PET with a monolayer coating based on PFDA by the Langmuir‒Blodgett method, and with two-layer coatings, formed by soaking PET TeMs/PFDA in xylenol orange solutions have been developed. The microstructure and local mechanical properties of the sensor surface were studied by atomic force microscopy, and the wettability and values of the specific surface energy of PET TeMs before and after modification were evaluated using the ''sessile'' drop method. Based on the measurement of electrochemical characteristics, it was found that PET TeMs/PFDA have a higher response of electrochemical characteristics compared to PET TeMs and PET TeMs/PFDA/XO. The limit of detection for lead ions in aqueous solutions at pH = 12 was of 0.652 µg/l within 5 measurements.
Nickel films of 40 nm thickness were obtained by means of magnetron sputtering on a single-crystalline silicon substrate. The films were subjected to rapid thermal treatment (RTT) for 7 s until the temperature increased from 200 to 550 °C. By means of the X-ray diffraction method, the structural-phase composition of nickel films before and after RTT was explored. The atomic force microscopy method due to direct contact with the surface under study, made it possible to accurately define the microstructure, roughness, specific surface energy and grain size of the nickel films before and after RTT, as well as to establish the relationship of these parameters with the phase composition and electrical properties of the films. Surface specific resistance was measured using the four-probe method. Based on XRD results, formation of Ni2Si and NiSi phases in the film was ascertained after RTT at 300 °C. At RTT 350–550 °C, only the NiSi phase was formed in the film. The microstructure and grain size significantly depend on the phase composition of the films. A correlation has been established between specific surface energy and resistivity with the average grain size after RTT at 350–550 °C, which is associated with the formation and constant restructuring of the crystal structure of the NiSi phase.
The prospects of development of technological equipment complexes have been considered. It is proposed to start designing mechatronic systems of machine tool complexes by analyzing information connections in hybrid manufacturing, which includes traditional and additive technologies. It is recommended to use sequences of transfer criteria to analyze the processes of forming material structures and surface layers of products during thermomechanical and electrophysical processing. The organization of feedback in managing technological equipment using additional energy flow effects is demonstrated. It is suggested to choose numerical control and design machine tools as mechatronic complexes, taking into account direct and feedback connections in the technological system. The complex of hybrid technological equipment and its modules and units is recommended to be designed as computer peripheral devices, built on the architecture of computers.
Reaction-bonded silicon carbide (RB-SiC) ceramics have been produced using advanced technology for the production of space mirrors. Changing the volume content of SiC (from 78 to 93 %) in the ceramic's composition allows for improved the mechanical properties, which is achieved by a combination of the SiC and Si phases properties. In this work, a thorough study of the structure and micromechanical properties of individual SiC and Si phases for RB-SiC ceramics (with a SiC content of 78-93 vol%) was carried out at the micro- and nanolevel using atomic force microscopy and nanoindentation. The studies have shown the crack resistance limit each phase (an important factor for RB-SiC space mirrors) under mechanical loads, after which microcracks appear (sources of further degradation and destruction). The surface morphology, deformation area and crack propagation in each phase after exposure to mechanical load during indentation were studied using atomic force microscopy. Nanomechanical mapping of elastic modulus and microhardness on the surface, analysis of boundaries between phases (SiC and Si), assessment of mutual influence of phases and determination of micromechanical properties were carried out using the nanoindentation method. The fracture toughness KIC was determined using an improved indentation method with visualization of the deformation areas using atomic force microscopy. The highest values of microhardness H, elastic modulus E and fracture toughness KIC on the SiC and Si phases were obtained on a ceramic sample with 93 vol % SiC: for the SiC phase - E=486 GPa, H=35.6 GPa, KIC=5.03 MPa m1/2, for the Si phase - E=205 GPa, H=12.2 GPa, KIC=2.73 MPa m1/2. This study demonstrated the efficiency and possibility of using the atomic force microscopy and nanoindentation to determine the micromechanical properties of ceramics at the micro- and nanolevel.
Using atomic force microscopy the morphology of 1 and 2% sodium hyaluronate solutions matrix with low molecular weight (LM) and high molecular weight (HM) hyaluronic acid (HA) fabricated by bioenzymatic synthesis was evaluated. The presence of a proteoglycan aggregate with processes of the core protein in the absence of sulfated glycosaminoglycans was established. The effect of irradiation with a light flux on the ordering of the HA matrix was observed. Intermolecular consolidation of high molecular HA was established. The elastic modulus of the matrix with LM and HM HA has also been determined.
The results of a study of the structure and physical and mechanical properties of diamond-like coatings (DLC) on sublayers of different hardness are presented. The coatings have high hardness, but at the same time they are prone to delamination and destruction due to high residual internal stresses. The fracture toughness was determined by the nanoindentation method and the energy calculation method using approach-retraction curves. Atomic force microscopy was used to study the surface structure and deformation region after nanoindentation. A change in the surface structure and roughness of DLC was established depending on the sublayer. Low roughness is characteristic of DLC on a copper sublayer. Applying а titanium sublayer leads to an increase in the elastic modulus of the DLC. The microhardness of both coatings is practically the same. AFM studies have shown two different types of DLC deformation after nanoindentation with a Berkovich pyramid. A crack on coatings with a copper sublayer propagates around the indentation print, and on an DLC with a titanium sublayer, it propagates along the edges of the indentation. It was found that the fracture toughness of DLC on a Ti sublayer is 33 % lower compared to DLC on a Cu sublayer due to a decrease in stress relaxation inside the coating. The considered coatings can be used in microelectronics for protection against mechanical damage on contacting and rubbing surfaces.
The results of using poly(methyl methacrylate) coatings for the development of the capacitive sensors for analyzing the content of heavy metals in water (using Ni2+ ions as example) are presented. Structural and morphological characteristics of the formed conductive nickel layer and nanostructured poly(methyl methacrylate) films were studied by atomic force microscopy. Based on the analysis of the dependence of the capacitive characteristics of the original sensor on the frequency at different concentrations of Ni2+ ions, the following operating characteristics of the sensor were established: response time – 5 min; operating range of Ni2+ ion concentrations: 1 ‧ 10–3–50 mM; lower detection limit ≈ 0,06 mg/l. It is shown that the formation of a poly(methyl methacrylate) coating on a conductive nickel layer by the spin coating method increases the service life of the sensor to eight cycles while maintaining the level of sensor sensitivity.
The work presents the results of mathematical simulation of dynamic atomic force microscopy (AFM). Influences of spring constant, the quality factor of AFM-probe on its vibration amplitude and phase shifts are studied for semi-contact interaction of tip probe and sample surface. The deformation depths of sample by probe are calculated. Also the influence of oscillation amplitude of piezogenerator, which forces probe vibration, on the characteristics of probe oscillation is shown.
Stimuli-responsive membranes play an important role in the fields of biomedicine, food and chemical industries, and environmental applications, including separation of water-oil emulsions. In this study, we present a method to fabricate pH-sensitive membranes using UV-initiated RAFT graft copolymerization of styrene (ST) and acrylic acid (AA) on poly(ethylene terephthalate) (PET) track-etched membranes (TeMs). The optimization of polymerization conditions led to successful grafting of polystyrene (PS) and poly(acrylic acid) (PAA) onto PET TeMs, resulting in membranes with stable hydrophobicity and pH change responsiveness. The membranes show a contact angle of 65° in basic environments (pH 9) and 97° in acidic environments (pH 2). The membranes were characterized by atomic force microscopy (AFM), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX), thermogravimetric analyses (TGA), Fourier transform infrared spectroscopy (FTIR), contact angle (CA) methods. The PET TeMs-g-PS-g-PAA exhibited good performance in separating water-oil emulsions with a high efficiency of more than 90% and flux for direct chloroform-water 2500 L m-2 h-1 and reverse emulsions of benzene-water 1700 L m-2 h-1. This method of preparing stimuli-responsive membranes with controlled wettability and responsiveness to environmental pH provides versatility in their use in separating two types of emulsions: direct and reverse.
Crack resistance of two types of glass was studied – cover glass (0.17 mm thick) and slide glass (2 mm thick) using an improved technique through the use of the probe methods, which makes it possible to increase the accuracy of determining the crack resistance of glass. Colorless silicate glass was used. Crack resistance was determined by the Vickers pyramid indentation method. Microstructure of glasses surface and deformation region after indentation were studied using an atomic force microscope. Mechanical properties of glasses were determined by nanoindentation. Surface relief of a glass slide is rougher than that one of a cover glass. Roughness Rz for a cover glass is less than for a slide glass. Specific surface energy value of 0.26 N/m is higher for the slide glass compared to the coverslip. One elastic modulus value E of the cover glass is 48 GPa, and that one of the slide glass is 58 GPa. The microhardness value H is almost the same for by the glasses and amounts to 6.7 GPa for a slide glass and 6.4 GPa for a cover glass. Atomic force microscope images of deformation region after indentation with a Vickers pyramid show that the first cracks appear at a load of 1 N on the slide glass, and at 2 N on the cover glass. At a load of 3 N, the cover glass is destroyed. Based on the results of crack resistance calculations it was found that critical stress intensity coefficient KIC values are 1.42 MPa∙m1/2 for a glass slide, and 1.10 MPa∙m1/2 for a cover glass.
In this work, we have developed a method for the preparation of pH-responsive track-etched membranes (TeMs) based on poly(ethylene terephthalate) (PET) with pore diameters of 2.0 ± 0.1 μm of cylindrical shape by RAFT block copolymerization of styrene (ST) and 4-vinylpyridine (4-VP) to be used in the separation of water–oil emulsions. The influence of the monomer concentration (1–4 vol%), the molar ratio of RAFT agent: initiator (1:2–1:100) and the grafting time (30–120 min) on the contact angle (CA) was studied. The optimal conditions for ST and 4-VP grafting were found. The obtained membranes showed pH-responsive properties: at pH 7–9, the membrane was hydrophobic with a CA of 95°; at pH 2, the CA decreased to 52°, which was due to the protonated grafted layer of poly-4-vinylpyridine (P4VP), which had an isoelectric point of pI = 3.2. The obtained membranes with controlled hydrophobic-hydrophilic properties were tested by separating the direct and reverse “oil–water” emulsions. The stability of the hydrophobic membrane was studied for 8 cycles. The degree of purification was in the range of 95–100%.
The influence of temperature in the range from 20 to 100 °C on the specific surface energy and fracture toughness of standard silicon wafers of three orientations (100), (110) and (111) was studied. Silicon wafers were heated on a special thermal platform with an autonomous heating controller, which was installed under the samples. At each temperature, the samples were kept for 10 min. The specific surface energy γ after exposure to temperature was determined by atomic force microscopy (AFM). Fracture toughness during and after exposure to temperature was determined by indentation followed by visualization of the deformation region using AFM. It has been established that the specific surface energy γ of Si wafers with orientation (100) and (111) increases with increasing temperature from 20 to 100 °C, and for orientation (110) it increases at temperatures from 20 to 80 °C, and then decreases. The diagonal length d of indentation marks, performed both during the heating process and after heating, decreases by increasing the temperature from 20 to 100 °C. The crack length c decreases on silicon wafers during indentation during heating from 20 to 100 °C, and after exposure to temperature, the length increases. When the plates are exposed to temperature, the fracture toughness K IC increases with increasing temperature: for orientation (100) – up to 1.61 ± 0.08 MPa·m 1/2 , for (110) – up to 1.60 ± 0.08 MPa·m 1/2 and for (111) – up to 1.66 ± 0.04 MPa·m 1/2 . A direct correlation was established between K IC , measured during exposure to temperature, and an inverse correlation between K IC measured after exposure to temperature and specific surface energy for the (100) and (111) orientations. An inverse correlation was obtained by K IC at the (110) orientation when exposed to temperatures of 20–40 and 80–100 °C, and after exposure, a direct correlation was obtained. At 60 °C there is no correlation. The results obtained can be used to improve the mechanical properties of silicon wafers used in solar cells and microelectromechanical systems (operating at temperatures up to 100 °C).
DLC-Si coatings obtained by cathodic arc evaporation on the (CrAlSi)N sublayer were investigated. The effect of Si addition to DLC on the ID/IG ratio, surface morphology, elastic modulus of surface layers, distribution of elastic modulus and microhardness (over the surface and depth of the coating), specific surface energy, coefficient of friction, wear, and thickness of nanoscale layers formed during friction was studied. The nanoscale thickness of the secondary structures has been evaluated by atomic force microscopy for the first time. It has been established that secondary structures are assembled into nanosized layers and chains, which is explained by sp2 bonds between nanosized clusters. The most hardened layer after friction is formed on the DLC + 0.8 % Si coating. The maps of the elasticity modulus and microhardness distributions are presented. The significant contact pressure is the driving force causing the transformation of the DLC phases during friction. According to the results of microtribotests in wear tracks after macrotests, the average values of the coefficient of friction from microtests correlate with the thickness of the secondary structures on the silicon content of the coatings and with the specific volumetric wear of the coating (for the DLC + 5 % Si coating have the highest values).
The technique of poly(ethylene terephthalate) track-etched membranes (PETF TMs) modification to increase of water-in-oil emulsions separations is developed. The water-in-oil emulsions separations by using PETF TMs with regular pore geometry and pore sizes 200 and 350 nm is described in the article. PETF TMs were modified with octadecyltrichlorosilane by spin-coating method to increase their hydrophobic properties. The results of changes in the pore diameters and the contact angle after PETF TMs modification are presented. The obtained samples were characterized by AFM, SEM and gas permeability test. Chloroform–water and n-hexadecane–water emulsions have been used as a test liquid for water-in-oil emulsions separations. At an operating vacuum of 700 mbar, the specific filtration performance of chloroform: water emulsions were 51.5 and 932.0 l/(m2 ⋅ h), hexadecane: water were 46.1 and 203.4 l/(m2 ⋅ h) for PETF-200 / OTS and PETF-350 / OTS, respectively. The degree of purification of emulsions by modified membranes according to the refractive index is of 100 %. Obtained membranes can be used to separate oil-water emulsions in order to prevent the corrosion of pipelines and changes of crude oil viscosity, as well as the treatment of water purification from oil industry waste.
The nanocomposite polymer – inorganic materials formation, the study of their morphology and mechanical properties at the nanolevel is acute in the development of new materials for various functional purposes, including medical ones. As a result of the research the technique for producing singleand multilayer films of polyvinyl alcohol and composite polymer coatings with aluminum oxide nanoparticles by the spin coating method has been developed. It is shown that the optimal mass content of aluminum oxide nanoparticles in suspension for the formation of uniform composite coatings is 0.625 %. Based on experimental data on the structuralmorphological and mechanical properties of the formed coatings obtained by atomic force microscopy, it has been found that an increase in the number of layers of composite coatings leads to an increase in the number of conglomerates which, in turn, increases the surface roughness of the films. The modulus of elasticity of single-layer films of polyvinyl alcohol is (509.5 ± 10 %) MPa. In the case of composite coatings with aluminum oxide nanoparticles, changes in the elastic modulus have been established for multilayer coatings: an increase to 559.0 MPa (5 layers) and a decrease to 415.2 MPa (10 layers). The modulus of elasticity of the investigated single-layer coatings is significantly reduced in the range of 20−40 ºС. The smallest values after exposure to temperatures have been determined for films with nanoparticles (236.2 ± 10 %) MPa. Nanocomposites demonstrate an increase in the contact angle with an increase in the number of layers of composite coatings up to 20. A subsequent increase in the thickness of the coatings (the number of layers) leads to an increase in the hydrophilicity of the nanocomposites. The developed compositions of nanocomposite films are promising as sorption coatings.
Diamond-Like Carbon (DLC) coatings have high wear resistance, hardness, biocompatibility and chemical inertness. Secondary structures, which formed at the track in dry friction conditions, provide friction reduction. Doping DLC with both metallic and non-metallic elements leads to a rearrangement of the structure of graphite clusters, a change in their properties, and facilitates the formation of secondary structures. In the present, the silicon atoms were used to create the compositional structure of DLC surface layers at the level of the crystal lattice. DLC-Si coatings with the thickness of 2 mu m were deposited on a (Cr, Al, Si)N layer with the thickness of 3 mu m formed on a steel substrate. DLC-Si layer was deposited by plasma-enhanced chemical vapor deposition using acetylene and tetramethylsilane. Nanoindentation in the wear mode was used to study the nanomechanical properties of the surface. Atomic force microscopy was used to visualize the surface morphology and wear traces. In this study, secondary structures were created in a microfriction process using a NanoScratch mode. The surface structures after microfriction was observed by atomic force microscopy, and the specific surface energy was measured. The specific volumetric wear rate of the coatings after microfriction was estimated. During microtribological testing with double squares the specific volumetric wear rate of DLC coatings was 5.39.10-14 m3/N.m for 0.8 % Si and 12.39.10-14 m3/N.m for 10 % Si. When tested in the form of scratches, the specific volumetric wear rate for the coating was for the DLC-0.8 % Si (1.22 - 10.71).10-14 m3/N.m and for the DLC-10 % (6.17 - 49.55) .10-14 m3/N.m.
In this work, the nanoindentations on bilayer composite nanofilms composed of metal Ag and polymer PMMA were simulated using molecular dynamics. The effects of the thickness of Ag and PMMA on the elastic moduli of the composite films were analyzed from Hertz contact theory, dislocation evolution and atomic migration. The results show that the maximum penetration depth that the Hertz model could well describe is about 6 Å, and this limiting value is almost independent on the film thickness. The deformation mode of the Ag films gradually changes from bending mode to indentation mode with an increase in Ag thickness, which improves the elastic modulus of the composite films. The rule of mixtures could give a theoretical prediction about the elastic modulus of the composite film close to the nanoindentation, and Hertz theory could also be used as long as the thickness of Ag films exceeded a certain value. The introduction of a PMMA layer impedes the development of dislocation in the Ag layer and improves the elastic limit of the composite films. This work provides an important basis for experimentally measuring the overall elastic modulus of metal/polymer composite film based on nanoindentation or extracting the elastic modulus of metal film from the overall indentation response of the composite film.