Tribological properties of an antifriction polymer modified by severe plastic deformation

The possibility of applying severe plastic deformation technologies to improving the tribological characteristics of semicrystalline antifriction polymers was studied. By the example of Nylon 6 subjected to equal-channel multiple angular extrusion, it was shown that severe plastic deformation favors a significant (more than three orders of magnitude) increase in the wear resistance of polymer and a 15–20% decrease in its friction coefficient. There are also increases in the maximum allowable contact pressure and temperature in the friction zone, at which the wear and the friction coefficients are stable.     

Nominal and effective strains in severe plastic deformation processes

Severe plastic deformation (SPD) processes may be used for obtaining materials with a nanocrystalline structure and enhanced properties. Recent work on such methods is briefly reviewed, with special emphasis on processes resulting in only minor shape changes, i.e. multi-step forging (MSF), high-pressure torsion (HPT) and equal-channel angular extrusion (ECAE). The nominal strain levels achieved by these processes are discussed, taking into account various possible conditions of deformation (at constant or variable thickness for HPT, according to the exact shape of the die for ECAE). In actual operation, strain values may deviate from the calculated ones, particularly due to strain inhomogeneities (along the sample radius or through the thickness for HPT, longitudinal or transverse inhomogeneities in ECAE). The domains of application for these methods are considered.     

Corrosion and biological behavior of nanostructured 316L stainless steel processed by severe plastic deformation

Nanostructured metals have different mechanical, chemical, and physical behaviors in comparison with the microstructured ones. Numerous research studies demonstrated that the biological behavior of nanostructured metallic implants was improved significantly. Concerning the nanostructured metals, decreasing the corrosion rate and the releasing of hazardous ions from metallic implants, and thus increasing the biocompatibility of implants are due to improving the native oxide layer. In the present study, nanostructured 316L stainless steel (biomedical grade) was manufactured via equal channel angular pressing (ECAP) method. To do so, the 316L stainless steel (SS) was exposed to the ECAP operation for eight passes. The impact of the ECAP process on corrosion behavior of SS samples was evaluated through performing the electrochemical polarization corrosion tests in Ringer's solution. Scanning electron microscopy was employed to study the surface morphology of common SS and ECAPed SS sample after the electrochemical polarization tests. Moreover, the biological behavior of the samples was evaluated via cell culture using fibroblast cells. The corrosion test results revealed a substantial decrease of corrosion rate from 3.12 (coarse‐grained sample) to 0.42 μA cm^?2 (for nanostructured). Furthermore, the cell proliferation in the interface of nanostructured sample and cell culture medium enhanced dramatically compared with the coarse‐grained one. The much better biological behavior of nanostructured SS sample in comparison with the coarse‐grained one is mostly due to the significant decrease of corrosion rate on the surface of SS samples, and the presence of much more chrome oxide on the surface of SS sample. Copyright © 2015 John Wiley & Sons, Ltd.     

A microcalorimetric study of crystallizable polymers subjected to severe plastic deformation

Differential scanning calorimetry has been used to investigate the evolution of the structural and thermophysical parameters of a number of semicrystalline polymers (high-density polyethylene, polyamide-6, polyoxymethylene) that is initiated by severe plastic deformation imposed through equal-channel multiple-angle extrusion. Thermograms of the deformed polymers have been found to exhibit an additional high-temperature melting peak. It has been shown that the onset, maximum, and end temperatures for both melting peaks increase with the strain buildup. The degrees of crystallinity and the thicknesses of crystallites increase as well. The magnitude of the effects is determined by the deformation route selected. It has been revealed that conformational transitions due to the formation of “double-triple” folds in macromolecular chains can occur during the course of equal-channel multiple-angle extrusion.     

Effects of severe plastic deformation on the corrosion behavior of aluminum alloys

Effects of severe plastic deformation on the corrosion behaviors of Al alloys containing precipitates have been investigated. Al and its alloys were severely deformed by equal-channel angular pressing (ECAP) processes and the corrosion behaviors of the Al alloys were evaluated by means of potentiodynamic polarization in a neutral buffer solution containing 0.002 M chloride ion. Introduction of huge plastic deformation to both of Al-5.4 wt% Ni and Al-5 wt% Cu alloys increased pitting potential. In contrast, ECAP treatment of 4N pure Al resulted in a decrease in open circuit potential, slight increase of passive current and shift of pitting potential to the negative direction. The influence of the change in microstructures caused by severe plastic deformation was investigated. Contribution to the Fall Meeting of the European Materials Research Society, Symposium D: 9th International Symposium on Electrochemical/Chemical Reactivity of Metastable Materials, Warsaw, 17th-21st September, 2007     

Electron-irradiated isotropic polyethylene: Structure and mechanical properties of oriented monofilaments produced by drawing

The structure and properties of oriented (draw ratio 12:1) polyethylene filaments, produced by drawing electron-irradiated isotropic monofilament, have been studied by rubber elasticity measurements, x-ray diffraction, differential scanning calorimetry, and tensile creep behavior. The apparent molecular weight M?_c between network junctions, has been calculated from the Flory and Mooney–Rivlin theories, as a function of dose, and extrapolation back to zero dose gives a value of about 16,000 g mol^?1, which is related to the molecular weight between entanglements in the linear polymer (M?_n 28,000). The WAXS and SAXS patterns of the unirradiated and 6.0 Mrad samples were identical, indicating an equivalent extent of crystallite orientation and a constant long period of about 170Å. Up to a gel dose of 2.4 Mrad, the degree of crystallinity (DC) of the drawn filaments remains constant, but the melting temperature T_m decreases slightly owing to network junctions at the fold surfaces. Above the gel dose, DC drops significantly and T_m falls more sharply, as a result of crystallite distortion. Irradiation dramatically affects the creep behavior, decreasing the equilibrium creep rate by up to four orders of magnitude. For all samples, the constant-flow behavior can be described by a combination of two activated processes in parallel: one associated with the amorphous network and the other with the crystalline regions. Irradiation increases the activation volume of the process occurring in the crystal and is ascribed to an increase in crystallite imperfections.     

Features of structure and phase transformations in shape memory TiNi-based alloys after severe plastic deformation

Amorphous and nanostructured TiNi-based alloys (Ti₅₀Ni₅₀, Ti_49.5 Ni_50.5, Ti₅₀Ni₄₉Fe₁, in at.%) were first produced using two techniques of severe plastic deformation (SPD), namely high pressure torsion (HPT) and equal channel angular pressing (ECAP). X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to examine the structural states and phase compositions of initial and SPD specimens, their thermostability on annealing and cooling, including in situ experiments. The nanocrystallization temperatures of the amorphous alloys and critical points of martensitic transformations in the crystalline alloys were also determined by means of measurements of the temperature dependence of electrical resistance. It was shown that martensitic transformations in the sequence B2↔R↔B19′ occur in nanostructured TiNi-based alloys or, on the contrary, only a single B2↔R transition can occur in the amorphous-nanocrystalline alloys. In nanostructured SPD-alloys cooled to below the M_s′ or M_s temperatures, nucleation and growth of R- and B19′-martensites occur by a “B2-austenite single nanocrystal — martensite single crystal” mechanism without microtwinning. Only in submicrocrystalline SPD-alloys with coarser B2-grains (larger than 100 – 200 nm) the R and B19′ martensites had a twinned packet morphology.     

Mechano-ions produced by mechanical fracture of solid polymers

It is said that the free radical caused by C-C-bond scission, homogeneous scission, is produced by mechanical degradation. In addition to free radicals, ionic species are produced due to the mechanical destruction of the polymers. Studies in our group concerning this problem are summarized. When the polymers were ground with tetracyanoethylene (TCNE) powder in a vibration glass ball mill in vacuum in the dark at 77 K, the TCNE anion radical (TCNE$ \bar . $) was detected by electron spin resonance (ESR) method. The TCNE$ \bar . $ is formed by the abstraction of electrons by TCNE from the anion produced by a heterogeneous bond scission of carboncarbon bonds in the polymer main chain. The identification of TCNE$ \bar . $ was carried out by the spectral simulation on the basis of an anisotropic hyperfine tensor including a forbidden transition term. Several polymers were examined; polyethylene, polypropylene, poly(tetrafluoroethylene) and poly(vinylidene fluoride). The ratio of ionic species and free radicals is discussed.     

The effect of processing conditions on the mechanical properties of polyethylene produced by selective laser sintering

A study was performed to explore the feasibility of processing a polyethylene by selective laser sintering. The polyethylene powder was characterised by scanning electron microscopy, particle size analysis and differential scanning calorimetry. The laser sintering processing conditions, especially powder bed temperature, laser power and laser scan counts, were studied. Well defined tensile testing specimens of the polyethylene were produced successfully by double laser scanning. The effect of the thermal history during the laser sintering process on the mechanical properties of the laser sintered parts is discussed for the first time.     

Changes to the physicochemical characteristics of wheat straw by mechanical ultrafine grinding

To investigate changes on the physicochemical characteristics of wheat straw by mechanical ultrafine grinding, wheat straw powders of four different particle sizes and distributions were produced using a sieve-based Retsch ZM100 grind mill and CJM-SY-B ultrafine vibration grind mill. Changes on the microstructure and physicochemical characteristics of the different powders were assessed by scanning electron microscopy, X-ray diffractometry, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis and relevant standard laboratory analysis methods. Ultrafine grinding reduced the crystallite size and crystallinity of the wheat straw. New surfaces were exposed on the ultrafine powder with high levels of cellulose/hemicelluloses components but there was no apparent change in chemical structure. Wheat straw powders were smaller in size but had a higher bulk density (from 0.19 to 0.54 g/mL) and angle of repose (from 46.02° to 55.61°) and slide (from 37.26° to 41.00°). The hydration properties (water-holding capacity and swelling capacity) decreased with reduction in particle size of the wheat straw. Both the sieve-based and ultrafine powder exhibited a good ability to remove Pb²⁺ and Cd²⁺ and there was marginal improvement when using the ultrafine powder. The thermal stability of the ultrafine powder measured by thermogravimetric analysis decreased significantly because of the low cellulose crystallinity.     

Some structural and mechanical properties of bacterially produced poly-β-hydroxybutyrate-co-β-hydroxyvalerate

Some structural and mechanical properties of PHB homopolymer and copolymers containing 17 and 25–30% PHV have been investigated. X-ray scattering, optical microscopy, density measurements and differential scanning calorimetry were used to interpret the results of load-elongation curves and thermomechanical softening measurements.     

Dielectric and mechanical properties of anodic films in the Ta–Ti system

Anodic oxidation at high efficiency of sputtering‐deposited Ta–Ti alloys containing 0.6–40 at.% Ti is shown to result in amorphous films comprising a relatively thin outer layer of TiO₂‐based material and an inner layer consisting of units of TiO₂ and Ta₂O₅. The two layers develop due to the faster migration of Ti⁴⁺ ions in the inner layer relative to that of Ta⁵⁺ ions. The formation ratios for the various films are in the approximate range 1.6–1.9 nm V^?1. The dielectric constants of the films are ～28, which is a similar value to that of anodic tantala. Nanoindentation revealed that the elastic modulus and hardness of the films are essentially independent of film composition, with average values of 134 and 5.3 GPa, respectively. Copyright © 2003 John Wiley & Sons, Ltd.     

Plastic deformation of polyethylene II. Change of mechanical properties during drawing

The crystallinity, elastic modulus, and tensile strength of samples of various draw ratios together with the true stress—strain curves of high-density polyethylene were determined to establish correlations with morphological changes occurring during deformation. Changes of crystallinity at draw ratios below 5, i.e., constancy during drawing of quenched film and a decrease during drawing of annealed film, are explained by the formation of microfibrils with crystallinity independent of the thermal history of the film. The microfibrils slide past each other at higher draw ratios, generating an increasing number of interfibrillar tie molecules, which is reflected in the increasing number of interfibrillar tie molecules, which is reflected in the increase of crystallinity, elastic modulus, and tensile strength. From the true stress—strain curves, the differential work density for the deformation of the volume element was calculated as a function of the draw ratio. It contains two components which reflect two different mechanisms of deformation. The first component, decreasing with increasing draw ratio, can be associated with the destruction of the original microspherulitic structure; the second one, increasing with increasing draw ratio, can be associated with the deformation of the new fiber structure, i.e., with the sliding motion of the microfibrils formed during the first deformation step.     

Physicochemical properties of ultrafine copper-containing powders synthesized by cathode reduction

Copper-containing ultrafine (nanosized) powders were synthesized from solutions of copper dichloride in the water-isopropanol binary solvent by electrochemical reduction. Particles were analyzed using a transmission electron microscope. A combination of thermal analysis with mass spectrometry made it possible to determine the composition of the cathode deposit obtained.     

The deformation behaviour of polyethylene shish-kebabs produced by stirring-induced crystallization

Polyethylene mats of shish-kebab fibrils were prepared from solution by stirring-induced crystallization, and subjected to deformation. A morphological study by scanning electron microscopy showed that the elementary shish-kebabs are elongated during drawing. For low draw ratios, the average distance between the lamellae on the fibrils increases proportionally to the draw ratio. The invariance of the fibril diameter upon drawing indicates a transformation of lamellar into fibrillar material. The molecular topology which underlies this deformation mode is discussed and related to the crystallization process.     

Bonding structure and mechanical properties of carbon nitride bilayer films with Ti and TiN interlayer

Carbon nitride (CN_x) bilayer films with Ti and TiN interlayer were synthesized by cathode arc technique at various nitrogen pressures (P_N2). The dependences of microstructure and bonding composition of the films on the P_N2 and interlayer were analyzed by Raman spectroscopy and X‐ray photoelectron spectroscopy. Microstructure evolution consisting of the ordering and size of Csp² clusters, the faction of N–sp³/N–sp² bonds and graphite‐like/pyridine‐like configurations was dominated by P_N2, interlayer and annealing. The results showed that Ti and TiN interlayer decrease the atomic ratio of N/C and increase clustering Csp². High P_N2 induces the formation of C ≡ N and C ? N bonds, the increase of sp²‐bonding content and the growth of Csp² clusters. A large part of nitrogen atoms are coordinated with sp²‐hybridized carbon (minimum 71% for annealed CN_x monolayer). TiN/CN_x bilayer had a higher content of pyridine‐like configuration. Morphological characteristics of CN_x monolayer and bilayer mainly depend on the surface character (roughness and surface energy) of the sublayer. The internal stress in the as‐deposited Ti/CN_x bilayer is smaller, but it after annealing is higher than that of CN_x monolayer and TiN/CN_x bilayer. These results may be of interest for studying the CN_x films with controlled bonding composition and expected engineering properties. Copyright © 2014 John Wiley & Sons, Ltd.     

Development of a rapid isolation procedure for coccolith ultrafine particles produced by coccolithophorid algae

Applied Biochemistry and Biotechnology - A rapid procedure for effective purification of large quantities of coccolith ultrafine particles from marine algae is reported. Coccoliths are detached...     

Structural and spectroscopic properties of pure and doped Ba6Ti2Nb8O30 tungsten bronze

Pure and doped Ba(6)Ti(2)Nb(8)O(30) (BTN), obtained by substituting M = Cr, Mn, or Fe on the Ti site (Ba(6)Ti(2-x) M(x)Nb(8)O(30), x = 0.06 and 0.18) and Y and Fe on the Ba and Ti sites, respectively (Ba(6-x)Y(x)Ti(2-x)Fe(x)Nb(8)O(30), x= 0.18), are synthesized. The influence of cation doping on the local structure, the cation oxidation state, and the possible defect formation able to maintain the charge neutrality are investigated by spectroscopic (electron paramagnetic resonance (EPR) and micro-Raman), structural (X-ray powder diffraction) and transport (impedance spectroscopy, thermoelectric power) measurements, in the temperature range of 300-1200 K in air and N(2) flow. Starting from the valence state of the doping ions (Fe(3+), Cr(3+), and Mn(2+)), determined by EPR, and from thermoelectric power measurements, evidencing a negative charge transport, different charge-compensating defect equilibria, based on the creation of positive electron holes or oxygen vacancies and electrons, are discussed to interpret the conductivity results.     

Investigation of bulk and in situ mechanical properties of coupling agents treated wood plastic composites

This paper presents the interfacial optimisation and characterisation of WPC by the use of maleated and silane coupling agents (MAPE, Si69 and VTMS), and its effect on the bulk and in situ mechanical properties. The results showed the treated WPC possessed better interface by showing improved compatibility between the constituents, wettability of wood flour, and resin penetration in the SEM images. The enhanced interface led to the increase in the tensile strength and stiffness of the treated WPC, which was confirmed by their superior load bearing capacity, namely the higher storage moduli measured by DMA. The observed shift of the relaxation peak of the treated WPC indicated the constraints on the segmental mobility of the polymeric molecules resulted from the treatments. Nanoindentation investigation revealed that the in situ mechanical properties were subject to a number of phenomena including fibre weakening or softening impact, crystalline structure transformation and cell wall deformation, concluding that the bulk mechanical properties of WPC might not be governed by the local property of materials within the interface.