A MODEL FOR THE COMBINED EFFECTS OF STRESS RATIO AND GRAIN SIZE ON THE LEFM FATIGUE THRESHOLD CONDITION

A long-crack, fatigue-threshold model which explains and predicts the commonly observed effects of stress ratio, R, and grain size, d, on δK₀, is proposed. The inclusion of a grain-size-effect is an extension of a recently proposed model that examined the effect of the R ratio. The extended model is based on the hypothesis that near-threshold, crack growth involves two micro-mechanical processes of fracture; K_max-controlled submicroscopic cleavage, which predominates when the defect concentration is small, and δK-controlled reversed shear which predominates when the defect concentration is large, both processes occurring in a critically stressed volume, V_c, ahead of the crack tip. Defect concentration in V_c is reduced by a low value of R and a coarse grain size and is increased by a high value of R and a fine grain size. Good agreement is shown to exist between predicted and experimental curves of δK₀ versus R and δK₀ versus grain size for several steels and aluminium alloys. In particular, δK₀ is shown to have an upper and a lower bound value for a material. The model may be used as an alternative procedure for obtaining quick, approximate but conservative estimates of δK₀ for practical design applications.     

Determination of uranium in fertilisers using fission track method

Trace contents of uranium in various commercial fertilizers e.g. ureas, superphosphates, diammonium phosphates have been determined using fission track etch technique. The uranium content in ureas varies from .05 to 1.3 mg kg^–1 whereas in superphosphates it varies linearly with phosphate content.     

Effect of alkali on filaments of poly(ethylene terephthalate) and its copolyesters. II. Presence of quaternary ammonium salt in the alkali-bath

Influence of alkyl (C₁₂–C₁₄)-dimethyl-benzyl ammonium chloride in the solution of sodium hydroxide on the hydrolysis of poly(ethylene terephthalate) (PET), anionically modified poly(ethylene terephthalate) copolyster (CDP), and block polymer of poly(ethylene terephthalate)-poly(ethylene glycol) (EDP), has been studied under a variety of proportions, concentrations, time and temperature of reaction, M : L ratio, etc. Mechanical properties of treated polymeric materials are evaluated. Hydrolysis of two polymers in the same bath is compared with that in separate baths.     

Mechanism of Ruthenium (III) Catalysis of Periodate Oxidation of Aldoses in Aqueous Alkaline Medium

The NO/H₂ reaction has been studied over a Ni loaded carbon film catalysts using in situ FTIR spectroscopy at the temperature range 25–350°C. On these catalysts, the differences in activity and selectivity were found depending on the nature of the surface functional groups. These differences were correlated with transient infrared spectral features which appeared during the reaction. It has been proved experimentally that the chemical character of the support is of vital importance during the process. The rise in NO conversion and N₂ selectivity was observed when the surface of the catalysts was changed by the NH₃ chemisorption. Amide and/or imide species formed due to the reduction of ammonium salts of carboxylic acids can play a significant role as active centers during the NO reduction.     

Surface modification of polyacrylonitrile staple fibers via alkaline hydrolysis for superabsorbent applications

The alkaline hydrolysis of polyacrylonitrile staple fibers was investigated for evaluation as superabsorbent materials. Studies were performed to analyze the hydrolysis of fibers and the quantification of the developed functional groups, such as carboxyl and amide groups as well as changes in the nitrile content by means of Micro‐ATR. Dyeing of the samples with methylene blue was carried out to monitor the carboxyl groups formed during the hydrolysis. A gradual decrease in the nitrile groups and built up of the carboxyl and the amide groups was observed during the hydrolysis. Microscopic investigation carried out to investigate the surface structure of hydrolyzed fibers. Hydrolysis led to surface nonhomogeneity and erosion that was dependent on the hydrolysis conditions. The fibers showed good water retention behavior, making them superabsorbent materials. The dyeing showed more intense coloration in the surface region of the modified fibers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3127–3133, 2004     

Elastic-plastic stress-strain calculation in notched bodies subjected to non-proportional loading

An analytical method for calculating notch tip stresses and strains in elastic-plastic isotropic bodies subjected to non-proportional loading sequences is presented. The key elements of the two proposed models are generalized relationships between elastic and elastic-plastic strain energy densities, and the material constitutive relations. These two models form the lower and the upper limits of the actual energy densities at the notch tip. Each method consists of a set of seven linear algebraic relations that can easily be solved for elastic-plastic strain and stress increments, knowing the hypothetical notch tip elastic stress history and the material stress-strain curve. Results of the validation show that the proposed methods compare well with finite element data and each solution set forms the limits of a band within which actual notch tip strains fall.     

Freestanding 3D Graphene–Nickel Encapsulated Nitrogen‐Rich Aligned Bamboo Like Carbon Nanotubes for High‐Performance Supercapacitors with Robust Cycle Stability

3D hierarchical structures are reported based on graphene–nickel encapsulated nitrogen‐rich aligned bamboo like carbon nanotubes, which show not only high‐performance supercapacitance behavior but also a great robust cyclic stability. A facile synthesis route is developed of 2D nickel oxide decorated functionalized graphene nanosheets (2D‐NiO‐f:GNSs) hybrids and 3D nitrogen doped bamboo‐shaped carbon nanotubes (NCNTs) vertically standing on the functionalized graphene nanosheets (3D‐NCNT@f:GNSs) by using a thermal decomposition method. The chemical reduction and morphology‐dependent electrochemical response are investigated. The enhanced specific capacitance of 3D‐NCNT@f:GNSs as compared to that of 2D‐NiO‐f:GNSs suggests the synergistic effects and indicates the importance of energy storage and superior long‐term cycling performance that are achieved. This 3D‐NCNT@f:GNSs hybrid shows a remarkable cycling stability with a maximum power density of 12.32 kW kg⁻¹ and maximum energy density of 109.13 Wh kg⁻¹ due to the good connection of NCNT and f:GNSs. This unique 3D nano network architecture enables the availability of large surface areas of NCNT, thus endowing the nanohybrids with high specific capacitance and excellent reusability.     

Hydroisomerization of n-hexadecane over Brønsted acid site tailored Pt/ZSM-12

Hydroisomerization of n-hexadecane is performed over ZSM-12 framework having tailored Brønsted acidity to investigate the effect in terms of product selectivity and yield. For this purpose, pure phase of ZSM-12 (bulk molar ratio Si/Al ~ 60) has been synthesized using TEABr as a structure directing agent. The framework Brønsted acidity is tailored with group II elements (M) viz. Ca, Ba and Mg, by means of ion-exchange method. The samples so prepared have been characterized for phase purity, textural parameters, morphology by employing powder X-ray diffraction, nitrogen adsorption–desorption isotherm measurement at 77 K, and scanning electron microscopy technique, respectively. Similarly, % metal exchange is estimated using inductively coupled plasma technique. The quantification of Brønsted acidity for H⁺–M⁺⁺–ZSM-12 samples has been estimated by means of ammonia temperature programmed desorption (NH₃-TPD) and Fourier transform infrared spectroscopy of ammonia (NH₃-FTIR). The well characterized H⁺–M⁺⁺–ZSM-12 samples were loaded with Platinum (Pt, 0.5 wt%) and subjected to hydroisomerization of n-hexadecane using an up-flow fixed bed reactor to verify the effect of process parameters like temperature and WHSV. Pt/H⁺–Ba²⁺–ZSM-12 with tailored Brønsted acidity in the range of about 25 % demonstrated the optimum performance among all the catalysts with an increased isomer selectivity and yield (89.2 and 80.3 %, respectively) by about 4 wt% at a conversion level of about 90 % compared to Pt/H⁺–ZSM-12 framework at 568 K. Such enhancement in isomer selectivity and yield is found to be significant from commercial application point of view. Based on the obtained trend, the potential benefits of implementation of Pt/H⁺–Ba²⁺–ZSM-12 (bulk molar ratio Si/Al ~ 60) framework for cold flow property improvement of ‘bio-ATF’ have been envisaged.     

Synthesis,Structure and Luminescence Property of a 3D Diamondoid Interpenetrated Zn(II)-Organic Framework

A new metal–organic framework of Zn(II) ion, [Zn(muco)(bipy)·2H₂O] (where, muco = trans, trans-muconate dianion, bipy = 4,4′-bipyridine) has been synthesized by solvothermal reaction of Zn(II) ion, muco ligand and bipy spacer. X-ray structure determination reveals that compound 1 has a 3D diamondoid (dia) framework with novel fivefold interpenetrating nets. Topological analysis shows the presence of 4-connected Zn(II) nodes with {6⁶} topology. Thermal analysis reveals that the compound is stable up to 340 °C. Photoluminescence study shows the emission of 1 owing to the presence of muco ligand and the intensity of luminescence emission is higher than that of free muco ligand.     

Nanoscale Investigation of Grain Growth in RF-Sputtered Indium Tin Oxide Thin Films by Scanning Probe Microscopy

This work studied the electronic characteristics of the grains and grain boundaries of indium tin oxide (ITO) thin films using electrostatic and Kelvin probe force microscopy. Two types of ITO films were compared, deposited using radiofrequency magnetron sputtering in pure argon or 99% argon + 1% oxygen, respectively. The average grain size and surface roughness increased with substrate temperature for the films deposited in pure argon. With the addition of 1% oxygen, the increase in the grain size was inhibited above 150°C, which was suggested to be due to passivation of the grains by the excess oxygen. Electrostatic force microscopy and Kelvin probe force microscopy (KPFM) images confirmed that the grain growth was defect mediated and occurred at defective interfaces at high temperatures. Films deposited at room temperature with 1% oxygen showed crystalline nature, while films deposited with pure argon at room temperature were amorphous as observed from KPFM images. The potential drop across the grain and grain boundary was determined by taking surface potential line profiles to evaluate the electronic properties.