Thermal decomposition and pore structure of pure and doped stannic oxide gel

The surface properties of a stannic oxide gel and its thermal dehydration products obtained both in vacuo and in the presence of air in the temperature range 100–600°C have been examined by N₂ adsorption. Phase and structural changes have been followed by differential thermal analysis and X-ray diffractometry. Complete pore structure analysis showed that samples dehydrated at or below 250°C were microporous. Above 250°C the pores were found to widen with increase of temperature, the widening occurring concurrently with the crystallisation process. Doping with cations of lower valency (Li⁺ and Al³⁺) than the host cation (Sn⁴⁺) had little effect on the pore structure and specific surface area for the low temperature samples (≤250°), whereas at higher temperatures, e.g. 600°C, it increased the specific area remarkably. The dope ions produce oxygen vacancies and hinder or retard sintering in SnO₂.     

Morphology and microstructure of autoclaved clinker and slag-lime pastes in presence and in absence of silica sand

Development of microstructure in four hydrothermal reactions has been undertaken using scanning electron microscopy. These are clinker, clinker-sand, slag-lime and slag-lime-sand hydrothermal reactions. The microstructure of clinker hydration products displayed crumpled foils and tabular masses of calcium silicate hydrates; few cubic crystals of hydrogarnet appeared only during the initial stage of the reaction. In clinker-sand mixture the C-S-H phase was the only product identified. In slag-lime hydration the microstructure displayed both of the hydrogarnet crystals and the C-S-H phase. The hydration of slag-lime-sand mixture (an optimum composition) was associated with the formation of ill-crystallized tobermorite and crystalline 11A tobermorite as the main products.     

Dimensions of the average pore,the number of pores,and the surface area of hardened Portland cement paste

In the course of their small angle x-ray scattering work, Winslow and Diamond also calculated the radius of gyration of the pores. Using its value for a paste, Diamond adopted two models for the average pore: a sphere and a cylinder of equal height and diameter. This model leads to absurd values for the surface area of the paste. Using a cylindrical model, and the radius of gyration plus the hydraulic radius, the present authors calculated for a similar paste the dimensions of the average pore and obtained the values: $\text{diameter}\text{= 47.2}\text{A}\text{?}\text{,}\text{length}\text{= 466}\text{A}\text{?}$. The number of pores per gram of paste was 2.26 × 10¹⁷. The paper also discusses the surface area of hardened paste, and points out the extremely important contributions of Winslow and Diamond to the subject.     

Physical gelation of crystallizing metallocene and Ziegler-Natta ethylene-hexene copolymers

The effect of molecular architecture on the evolution of viscoelastic properties during crystallization was investigated using ethylene-hexene copolymers manufactured via metallocene (M-LLDPE) and Ziegler-Natta (ZN-LLDPE) processes. Differences in branching distribution were shown to have a drastic effect on the viscoelastic properties near the gel point. It is shown that the branching distribution rather than branch content is the determining parameter for the evolution of the rheological properties during isothermal and non-isothermal crystallization, and for the width of the solidification interval. We developed a partial melting technique for the preparation of stable critical gels of LLDPE whose viscoelastic properties correspond to the intermediate state between melt and solid. Local molecular conformation and crystallinity in these gels were characterized by Raman spectroscopy, which shows that the transition from melt-like to solid-like rheological behavior (physical gelation) in LLDPE occurs at a very low overall crystallinity of less than 5%.     

Engineering of functional supramacromolecular complexes of proteins (enzymes) using reversed micelles as matrix microreactors

The size of the inner water cavity of reversed micelles formedin a triple system ‘water-surfactant-organic solvent’can be widely varied by changing the degree of surfactant hydration.This gives grounds to use reversed micelles as matrix microreactorsfor the design of supramolecular complexes of proteins. Usingultracentrifugation analysis, it has been demonstrated thatthe oligomeric composition of various enzymes (ketoglutaratedehydrogenase, alkaline phosphatase, lactic dehydrogenase, glyceraldehyde-3-phosphatedehydrogenase) solubilized in reversed micelles of Aerosol OT[sodium bis(2-ethylehexyl)sulfosuccinate] in octane changesupon variation of the degree of hydration. An oligomeric complexforms under conditions when the radius of the micelle innercavity is big enough to incorporate this complex as a whole.At lower degrees of hydration the micelles ‘uncouple’such complexes to their components. The catalytic propertiesof various oligomeric complexes have been studied. Possibilitiesof using reversed micelles for the separation of subunits ofoligomeric enzymes under non-denaturating conditions have beendemonstrated. In particular, the isolated subunits of alkalinephosphatase, lactic dehydrogenase and glyceralde-hyde-3-phosphatedehydrogenase have been found to be active in Aerosol OT reversedmicelles. The dependences of the catalytic activity of oligomericenzymes represent saw-like curves. The maxima of the catalyticactivity observed at these curves relate to the functioningof various oligomeric forms of an enzyme. The radii of the micelleinner cavity under conditions when these maxima are observedcorrelate with the linear dimensions of the enzyme oligomericforms. Correlation of the position of a maximum with the shapeof an oligomeric complex is discussed.     

Function Approximation Technique Based Adaptive Control for Chaos Synchronization between Different Systems with Unknown Dynamics

This paper presents a function approximation technique based immersion and invariance adaptive controller for chaos synchronization between nonidentical systems with unknown dynamics. In the proposed control scheme, the control system is reconstructed as the combination of a controllable linear system and a variation term from the original system. The variation term is treated as time-varying uncertainty and approximated by a group of weighted chosen basis functions. The immersion and invariance methodology is employed to design the adaptive control law such that both the synchronization error and uncertainty estimation error converge to zero. Two typical chaos synchronization problems are used in numerical simulations to verify the effectiveness and superiority of the proposed controller.

     

Hydrogen effect on the molecular weight distribution of polymers obtained by polymerization of ethylene and α-olefins over supported titanium-magnesium catalysts

Comparative data on the molecular weight distribution of polymers obtained by polymerization of ethylene, propylene and 1-hexene, and copolymerization of ethylene with α-olefins over the titanium-magnesium catalysts (TMC) in the absence and presence of hydrogen are presented. In contrast to the ethylene polymerization, in the cases of propylene and 1-hexene polymerization and copolymerization of ethylene with α-olefins, the hydrogen addition is characterized by noticeable narrowing of the molecular weight distribution (MWD) due to lower contribution of the MWD component with high molecular weight. This result is an evidence of the increased reactivity of TMC active sites producing high molecular weight poly-α-olefins and copolymers of ethylene with α-olefins in the chain transfer reaction with hydrogen. It is suggested that the increased reactivity of these sites in the transfer reaction with hydrogen appears after the 2,1-addition of α-olefin to the growing polymer chain.     

Construction and verification of PLC-programs by LTL-specification

An approach to construction and verification of PLC-programs for discrete problems is proposed. For the specification of program behavior we use the linear-time temporal logic LTL. Programming is carried out in the ST-language according to an LTL-specification. The correctness analysis of an LTL-specification is carried out by the symbolic model checking tool Cadence SMV. A new approach to programming and verification of PLC-programs is shown by an example. For a discrete problem we give a ST-program, its LTL-specification and an SMV-model. The purpose of the article is to describe an approach to programming PLC, which would provide the possibility of PLC-program correctness analysis by the model checking method. Under the proposed approach the change of the value of each program variable is described by a pair of LTL-formulas. The first LTL-formula describes situations that increase the value of the corresponding variable, the second LTL-formula specifies conditions leading to a decrease of the variable value. The LTL-formulas (used for specification of the corresponding variable behavior) are constructive in the sense that they construct the PLC-program, which satisfies temporal properties expressed by these formulas. Thus, the programming of PLC is reduced to the construction of LTL-specification of the behavior of each program variable. In addition, an SMV-model of a PLC-program is constructed according to LTL-specification. Then, the SMV-model is analysed by the symbolic model checking tool Cadence SMV.     

A tree-covering problem arising in integrity of tree-structured data

We introduce and solve a problem motivated by integrity verification in third-party data distribution: Given an undirected tree, find a minimum-cardinality set of simple paths that cover all the tree edges and, secondarily, have smallest total path lengths. We give a linear time algorithm for this problem.