Study of free volume parameters of polystyrenes of different molecular architecture by positron annihilation lifetime measurement

Differences of size, content and size distribution of free volumes in linear branched and three-armed polystyrenes, synthesized by radical and anionic processes, were observed by positron annihilation lifetime measurements. The temperature dependence of an average free volume radius was quite similar among polystyrenes of different architectures and molecular weight distributions. The free volume radius increased with temperature, from 0.27 nm (T:60 K) to 0.29 nm (T:260 K) and 0.30 nm (T _g:363 K), then to 0.35 nm (423 K), showing turning at and transition temperature. The free volume content decreased from 60 K to 220 K to 300 K showing peculiar minimum at 220 K to 300 K depending on the molecular shape, increased above 320 K, upto 340 to 360 K. The free volume contents decreased with an increase of molecular weight and by an addition of oligomer or plasticiser, suggesting differences in relaxation time or molecular motion between the edge and middle portions of molecular chain and filling effect of smaller molecules in free volumes, respectively. The apparent free volume fraction showed clear variations atT andT _g. Size distribution of free volumes suggested more complicated behavior of free volume upon the molecular relaxations and filling effect.     

Cyclization ofα- andβ-(arylseleno)alkylcarboxylic acids and their derivatives

The cyclization of- and-(arylseleno)alkylcarboxylic acids in polyphosphoric acid was studied. It was found that-(arylseleno)alkylcarboxylic acids do not cyclize under those conditions in which cyclization of the analogous-(arylseleno)alkylcarboxylic acids does occur. A convenient method for the preparation of 2-methylselenonapthanone by the cyclization of-phenylselenopropionyl chloride is proposed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 333–334, March, 1971.     

Dependence of the glass transition temperature of poly (methyl methacrylates) on their tacticity

The specific isobaric heat capacities of poly (methylmethacrylates) (PMMA) having various tacticities were measured by the DSC method within a broad range of temperatures including the glass transition. Glasses with uniform thermal history were used in the measurements and the data were treated by employing a procedure which provided the thermodynamic T_g independent of the experimental conditions. The semiquantitative validity of Boyer's empirical relationT _g ×c_p=const. was confirmed; also it was found that within the limits of experimental accuracy the c_p,g values at 298 K andC _p,l values at 400 K are independent of the tacticity of the sample.Using the data thus measured and linearized equations representing the dependence ofT _g on the content of iso-, syndio- and heterotriads, the T_g values of pure isotactic PMMA and pure syndiotactic PMMA were found to be respectively 315 K and 397 K.Dedicated to Professor Dr. F. H. Müller.     

Chain entanglement,mechanical properties and drawability of poly(lactide)

The observed brittle fracture behavior of amorphous polylactides seems to be contradicted by the low value ofC =2 determined for poly(L-lactide) by Flory and coworkers. Such very flexible polymer chains deform by shear yielding, and fracture in a ductile manner. In this study,C was estimated in a number of ways, resulting in much higher values ofC =11.7 andC =9.1 for poly(L-lactide) and L- and D-lactide copolymers, respectively. These high values ofC and the low entanglement density account for the brittle fracture behavior of amorphous poly(lactide), as well as for the maximum attainable draw ratios of poly(L-lactide) networks and melt spun fibers. Bulk polymerized poly(L-lactide) networks, where crystallization during polymerization impedes severe entangling, could be hot-drawn most effectively to draw ratios of 8–16, resulting in very strong materials with tensile strengths of 550–805 MPa. By comparison, amorphous, non-crystallizable L/D lactide networks, which do not crystallize during polymerization, could be drawn less, to =7. These materials with strengths up to 460 MPa could, nevertheless, be oriented much more effectively than linear, amorphous L/D lactide copolymers.     

Dynamic shear compliance of polymer melts and networks in dependence on crosslinking density

Mechanical relaxation processes in polymer melts and networks are discussed. This is performed by decomposing master curves of the dynamic shear compliance into i) glass relaxation with its plateau complianceJ _eN ; ii) shearband process with its relaxation strengthJ _B , which is reciprocal to the total crosslink densityp _c ; and iii) flow relaxationJ _F and viscous flow (for uncrosslinked melts only). Plateau complianceJ _eN > is exponentially reduced only by effective crosslinks (p _c ^* p _c /30). This behavior is understood on the level of a meander superstructure, which includes shearbands. The observed saturation inJ _eN at higher dicumylperoxide (DCUP) crosslinking-which doesn't appear with radiation-can be explained by the lack of chemically induced effective crosslinks across the interfaces among meander cubes. This lack may be a consequence of DCUP molecules concentrating at the interfaces and thereby preventing the contact and radical recombination between chains at adjacent meander faces.Crosslink densitiesp _c (per monomer), determined from the reduction of shearband relaxation strength, vary linearly with the crosslinking agent and read: p_c2.4 · 10^–2 Dose/MGy andp _c 0.97 · 10^–2 DCUP/phr for radiation and DCUP crosslinking, respectively. This implies, e.g., that a dose of 0.4 MGy (40 Mrad) is equivalent to 1 part DCUP phr in a crosslinking polyisoprene. From activation-curve analysis it follows that3 r/d stays constant, and _s - _so (free energy of formation of a segment-dislocation) andQ _y -Q _yo (activation energy for segmental jumps) vary with the square ofP _c , as does the glass temperaturT _g -T _go from DSC measurements.     

Ritter reactions. X. Structure of a new multicyclic amide-benzene inclusion compound

5H-Dibenzo[a, d]cyclohepten-5-ol1 can undergo Ritter reaction with acetonitrile and sulfuric acid to afford either the acetamide derivative2 or the multicyclic amide3 depending on the conditions used. The X-ray structure of the inclusion compound of3 with benzene is reported here and analysed in structural terms. This material [(C₁₉H₁₈N₂O)–(C₆H₆),Cc,a=10.694(5),b=22.843(5),c=9.901(4) Å,=124.02(2)°,Z=4,R=0.054] has molecules of3 linked by –N–HO=C intermolecular hydrogen bonds to form parallel chains alongc. Additional inter-host stabilisation is achieved by face-face interactions involving one of the two benzo rings of3. A hydrogen atom of the other host benzo group participates in an edge-face interaction with the benzene guest molecule to produce the inclusion compound. Benzenebenzene inter-guest interactions provide a further, but minor, contribution to the net stability of the structure. Supplementary Data relating to this article are deposited with the British Library as supplementary publication No. SUP 82189 (10 pages).     

Study on the variation of intraionic distance between Fe3+ and F− in methanol-water system based on its stability constant

The stability constants, ₁, of the monofluoride complex of Fe(III) have been determined in mixed methanol + water solvent system with 0.3 mol·dm^–3 HClO₄ using a solvent extraction technique. The values, in less than 0.31 mole fraction of CH₃OH (X _s) in the mixed CH₃OH+H₂O solvent solution, increase asX _s increases. The variation of in ₁ againstX _s was analyzed to elucidate the variation of intraionic distance between Fe³⁺ and F^–. The intraionic distance maintains constant inX _s<0.05 and lengthens with an increase ofX _s in 0.05<X _s<0.31.     

Heat transfer to a particle under plasma conditions with vapor contamination from the particle

Heat transfer to a copper particle immersed into an argon plasma is considered in this paper, including the effects of contamination of the plasma (transport coefficients) by copper vapor from the particle. Except for cases of high plasma temperatures, the vapor content in the plasma is shown to have a considerable influence on heat transfer to a nonevaporating particle, and, to a lesser extent, on heat transfer to an evaporating particle. Evaporation itself reduces heat transfer to a particle substantially as shown in a previous paper [Xi Chen and E. Pfender, Plasma Chem. Plasma Process.,2, 185 (1982)]. Comparisons of the calculated results with those based on a method suggested in the above reference show that the simplified assumptions employed, i.e., that the surface temperature is equal to the boiling point and that plasma properties based on a fixed composition are applicable, can be employed to simplify calculations for many cases. This study reveals that a considerable portion of a particle must be vaporized before a steady concentration distribution is established around the particle.Nomenclature C _p specific heat at constant pressure - D diffusion coefficient of copper in the mixture - D _a diffusion coefficient of copper atoms in the mixture - D _i ambipolar diffusion coefficient of copper ions in the mixture - f mass fraction of copper in the mixture - f _a mass fraction of copper atoms in the mixture - f _i mass fraction of copper ions in the mixture - f mass fraction of copper in the plasma far away from the particle - f _s mass fraction of copper at the particle surface - G total mass flow rate due to evaporation - G _a mass flow rate of copper atoms - G _i mass flow rate of copper ions - H function defined in Eq. (19) - h specific enthalpy - h _s specify enthalpy at the particle surface - h specific enthalpy corresponding toT andf - k thermal conductivity - L latent heat of evaporation - M ₁ molecular weight of argon (M ₁=39.99) - M ₂ molecular weight of copper (M ₂=63.55) - p ₀ pressure of the gas mixture - p _s partial pressure of copper vapor at the particle surface - Q ₀ heat flux to a particle without evaporation - Q ₁ heat flux to a particle with evaporation - R gas constant - r radical coordinate - r _s particle radius - S heat conduction potential defined in Eq. (4) - S _s surface value ofS, corresponding toT _s andf _s - S free-stream value ofS, corresponding toT andf - T temperature - T _b boiling temperature of particle material - T _s particle surface temperature - T plasma temperature - density - T temperature step for numerical integration     

Dependence of the internal energy on the temperature during chemical reactions

Summary Using results obtained earlier it has been shown that the internal energy varies during chemical reactions with the temperature according toU=U ₀+f(T)+DT for the reactants andU=U ₀+f(T)+DT for the products.

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Abhängigkeit der inneren Energie von der Temperatur bei chemischen Reaktionen (Kurze Mitt.)

Zusammenfassung Unter Verwendung früher erhaltener Ergebnisse konnte gezeigt werden, daß die innere Energie bei chemischen Reaktionen nachU=U ₀+f(T)+DT (Reaktanden) bzw.U=U ₀+f(T)+DT (Produkte) von der Temperatur abhängt.

     

Boundary conditions in the theory of the relaxation field

The perturbationf _ji ^' generated by an external field in the distribution function is derived by integration of the Onsager-Fuoss equation of continuity. The solution isf _ji ^' (r)=C(I+Ah₁+Bh₂) whereCI is a particular integral andh ₁ andh ₂ are solutions of the homogeneous equation. The physical significance of the boundary conditions which evaluate the constantsA andB is discussed. It is then shown that the conditionf _ji ^' () 0 requiresB=0 and that the condition lim(f _ji ^' /n²) 0 at zero concentration is satisfied if and only ifA=–1.     

Heat of transformation of chains in amorphous sulphur

The heatQ of transformation of the chains in amorphous sulphur was measured calorimetrically. The mean value ¯Q for samples remelted atT _f=443 K increases from 31.5 to 45.9 J g^–1 in the measurement temperature range from 288 to 303 K.For samples remelted in theT _f range from 443 to 573 K, the ¯Q values are from 30.6 to 24.0 J g^–1.The results are discussed on the basis of the theory of nucleation and growth of nuclei.     

Wide angle X-ray diffraction studies of polytetrafluoroethylene and ethylen-tetrafluoroethylen-bipolymers in the range 9.5 K–270 K

PTFE shows in the whole temperature range investigated a triclinic crystal structure with cell parametersa=0.952 nm,b=0.559 nm,c=1.706 nm,=87.9°, = 90.0° and=91.8°. The temperature dependence ofa andb-axis is linear, thec-axis shows a change in thermal expansion at 150 K. The inherent strain is small. The crystallite sizes are measured, paracrystalline distortions are absent.The bipolymers show only an ordered arrangement in lateral direction under maintenance of the helical structure. The lateral arrangement is very distorted and the range of order is aboutD _L 10 nm.     

The phenomenon of conglomerate crystallization. XIX. Clavic dissymmetry in coordination compounds. XVII

[Co(NH₃)₄(oxalato)]NO₃·H₂O (1) crystallizes as a conglomerate in space groupP2₁2₁2₁ with unit cell constants ofa=7.944(3),b=9.904(11), andc=12.700(2) Å;V=999.15 ų;d(calc.;z=4)=1.968 g cm^–3. [Co(NH₃)₄(oxalato)]¦·H₂O (2) crystallizes in space groupP2₂/n with cell constants ofa=7.285(1),b=9.959(3),c=15.410(5) Å;=102.63(2)° andV=1090.98 ų; d(calc;z=4) = 2.192 g cm^–3. Data were collected over the ranges of 4°270° and 4°255°, respectively for compounds1 and2. This resulted in a total of 2515 and 2823 data for the solution and refinement of the structures of compounds1 and2, respectively. When the refinements converged, the finalR(F) andR _w (F) values were, respectively, 0.073 and 0.080 for1 and 0.0378 and 0.0353 for2.Since neither data set was sufficiently good to give a sensible set of positions for all of the hydrogens, the stereochemistry of the two cations could only be defined by the positions of the heavy atoms. In the absence of reliable amine hydrogen positions, N(amine)-O(nitrate and oxalate) distances were examined. Close N(amine)-O(nitrate and oxalate) contacts indicate the presence of a network of significant hydrogen bonds in1. The N-O distances for compound2 also show the presence of hydrogen bonding between the amines and the oxalate ligand and water; however, the bonds are not of the same magnitude as the interactions involving the nitrate oxygens in1. Despite the similarity between the cations of1 and2, the Co-N distances in the two do not exhibit the same pattern. In1, the Co-N distances for amines trans to one another are shorter than the Co-N distances for amines trans to oxalate oxygens; this effect is reversed in2.     

Some perspectives on the modeling of plasma jets

A mathematical representation is developed describing the temperature and the velocity profiles and mixing in a plasma jet discharging into ambient air. In the model, realistic allowance is made for turbulent behavior, the temperature-dependent property values, and also for the boundary conditions, including entrainment. The more precise definition of the boundary conditions, mixing, and entrainment are thought to be important novel features of this work. The theoretical predictions were found to be in good agreement with measurements reported by Vardelle regarding the behavior of a nitrogen plasma, but the agreement was less satisfactory for an argon plasma jet. Possible reasons for the discrepancy are discussed.Notation C ₁,C ₂,C _D constants inK- turbulence model - h enthalpy - H ₁ length of integration region - H ₂ width of integration region - K turbulent kinetic energy per unit mass - m mass concentration of plasma - Q _f mass flow rate of plasma gas for flat inlet profiles - Q _P mass flow rate of plasma gas for parabolic inlet profiles - P _w torch power - r radial coordinate - R ₀ internal radius of torch exit - S source term for dependent variable - S _R radiation loss per unit volume of plasma - T _a ambient temperature - T _m maximum temperature - T _t torch tip temperature - u velocity inz-direction - u _{C 1} velocity at and in the direction of the symmetry axis of the flow - u _m velocity of plasma atr=0 andz=0 (maximum velocity) - u axial direction velocity difference across the width of the mixing region - v velocity in r direction - Y radial width of the mixing region - z axial coordinate - density - , _e, _t molecular, effective, and turbulent viscosities, respectively - dissipation rate of turbulence energy - thermal efficiency of plasma torch - Prandtl/Schmidt number forh, K, , andm Visiting Fulbright Scholar and Associate Professor of Chemical Engineering, on leave from the Institute of Chemical Engineering and Technology, Punjab University, Lahore-20, Pakistan.     

Comparison of the crystal structures of Co2(X 2O7)·2H2O,X=P and As

Summary Crystals of Co₂(X ₂O₇)·2H₂O,X=P/As were synthesized under hydrothermal conditions. Their crystal structures were determined by single crystal X-ray diffraction:a=6.334(1)/6.531(2),b=13.997(2)/14.206(4),c=7.637(1)/7.615(2)Å, =94.77(2)/94.74(2)°, space group P2₁/n,R=0.032/0.046,R _w=0.028/0.034 for 2423/2042 reflections and 131/119 variables. Within the twoXO₄ tetrahedra connected via a common corner to anX ₂O₇ group the average P-O bond lengths are approximately equal (1.540 and 1.543 Å), but As-O differs significantly (1.685 and 1.696 Å). A comparison with the isotypic Mn and Mg pyrophosphates shows a correlation between the ratio Me-O/X-O and the angle O-X-O.

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Vergleich der Kristallstrukturen von Co₂(X ₂O₇)·2H₂O,X=P und As

Zusammenfassung Kristalle von Co₂(X ₂O₇)·2H₂O,X=P/As wurden unter Hydrothermalbedingungen synthetisiert. Ihre Kristallstrukturen wurden mittels Röntgenbeugung an Einkristallen bestimmt:a=6.334(1)/6.531(2),b=13.997(2)/14.206(4),c=7.637(1)/7.615(2) Å, =94.77(2)/97.74(2)°, Raumgruppe P2₁/n,R=0.032/0.046,R _w=0.028/0.034 für 2423/2042 Reflexe und 131/119 Variable. In den beiden über eine gemeinsame Ecke zuX ₂O₇-Gruppen verknüpftenXO₄-Tetraedern sind die mittleren P-O-Abstände ungefähr gleich (1.540 und 1.543 Å), hingegen differiert As-O signifikant (1.685 und 1.696 Å). Ein Vergleich mit den isotypen Mn- und Mg-Pyrophosphaten zeigt eine Korrelation zwischen dem Quotienten Me-O/X-O und dem WinkelX-O-X.

     

Temperature and velocity fields in a gas stream exiting a plasma torch. A mathematical model and its experimental verification

A mathematical model was developed to predict the velocity and temperature fields in a free plasma jet issuing from a D.C. plasma torch. It was assumed that the temperature and velocity at the torch nozzle were specified and the turbulent Navier-Stokes equations were solved in conjunction with a two-equation model of turbulence and the energy transport equation. The model was formulated in terms of the two-dimensional elliptic equations to facilitate its future extension to nonparabolic problems. The predictions of the model were compared with experimental measurements obtained from laser Doppler and spectroscopic techniques. Good overall agreement was found between the theoretical predictions and the experimental measurements for two sets of initial conditions corresponding to nitrogen/hydrogen and argon/hydrogen plasmas. Radiation was found to have a small effect on the overall heat transfer process, and it is suggested that the assumption of an optically thin radiation loss per unit volume is sufficiently accurate for most engineering applications. The significance of this work lies in the fact that, for the first time, it is possible to test the assumptions of the current model against a reliable set of experimental measurements.Notation C ₁,C ₂,C _D constants inK- turbulence model, Table III - C _P average specific heat of plasma at constant pressure - h ₁ length of integration region - h ₂ width of integration region - K turbulent kinetic energy per unit mass - P pressure - r radial coordinate - R ₀ internal radius of anode - S _K source term forK equation - S _R radiation loss per unit volume - S source term for equation - T ₀ temperature of plasma atz=0 - T temperature of plasma - T _a ambient temperature - u velocity inz direction - u ₀ velocity of plasma atz=0 - v radial velocity of plasma - z axial coordinate - dissipation rate of turbulence energy - , _eff, _t molecular, effective, and turbulent viscosities, respectively - density - _K, _T, Prandtl numbers forK, T, and, respectively     

The biological half-life of137Cs in snails

The biological half-life of¹³⁷Cs in snails Helix pomatia after a single administration of contaminated diet has been investigated. The calculation was based on the retention of¹³⁷Cs in snails in vivo. It was found that loss of cesium from snails can be explained by a two-exponential retention curve leading to biological loss constants _{B 1}=0.27 d^–1 and _{B 2}=0.024 d^–1, which correspond to biological half-lives of T_{B 1}=2.5 d and T_{B 2}=28.5 d respectively. The equation describing the retention of¹³⁷Cs in snails is also presented.     

Lattice modes of polyethylene

Summary The lattice modes of polyethylene with the phase differences ( and along the-axis and theb-axis were calculated at intervals of 30 for the phase differences. They wereT _x, T_y, T_x, T_y, R_z andR _z, and some special conditions of the phase differences separated the six modes. To know the reliability of the intermolecular force constants used in this calculation, the elastic moduli of polyethylene crystal along thea-axis and theb-axis were calculated with the modified potential functions and compared with the observed values.

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Zusammenfassung Die Gitterschwingungen in PolyÄthylen mit den Phasendifferenzen und lÄngs dera- undb-Achsen wurden in Intervallen von 30 der Phasendifferenzen berechnet. Das gibt 6 Hauptschwingungen,T _x, T_y, T_x,T _y, R_z und R_z. Um die ZuverlÄssigkeit der intermolekularen Kraftkonstanten, die bei diesen Berechnungen verwendet wurden, zu prüfen, wurden die elastischen Moduln von PolyÄthylen-Kristallen in Richtung dera- undb-Achse unter bestimmten modifizierten PotentialverlÄufen berechnet und mit den beobachteten Werten verglichen.