Polymerization of lactams

Summary The following limit (ceiling) temperatures of polymerization were extrapolated from kinetic data for the anionic polymerization of 2-pyrrolidone initiated with potassium salt of 2-pyrrolidone and the initiation systems of optimum compositions: 66°C for the nonactivated polymerization, 68°C and 73°C for the polymerization accelerated with 1-(1-pyr-rolin-2-yl)-2-pyrrolidone and carbon dioxide, respectively, 73°C and 76°C for the polymerization activated with N-benzoyl-2-pyrrolidone and N-acetyl-2-pyrrolidone,respectively.     

Characteristics of Microscale Combustion in a Narrow Heated Channel

The characteristics of microscale combustion were investigated by using a microchannel heated by an external source. The inner diameter of the channel was 2 mm, which was slightly smaller than the quenching distance of the stoichiometric methane–air mixture under normal conditions. The effects of the equivalence ratio and the averaged flow velocity on the characteristics of combustion in the microchannel were examined. At a channelwall temperature of 1000°C, flames could be stabilized at equivalence ratios of 0.05–1.9 and mixture velocities up to 150 cm/sec in a Ushaped quartzglass channel. At moderate equivalence ratios and lower velocity conditions within the flammability region, oscillatory combustion was observed. A simple analytical model predicting flame oscillations on the basis of the linear analysis of steady solutions is proposed.     

Ultradrawing of “springy” polypropylene films

Summary It is demonstrated that in the process of ultradrawing of semicrystalline polypropylene the morphology of the initial material plays major role. Extremely high draw ratios are obtained (_max50) when drawing hard elastic polypropylene films perpendicular to their initial molecular orientation. This behaviour is explained by the molecular processes of plastic deformation.     

Selective catalytic reduction of nitric oxide over vanadia grafted on titania. Influence of vanadia loading on structural and catalytic properties of catalysts

The selective catalytic reduction (SCR) of NO by NH₃ has been studied over vanadia/ titania catalysts prepared by selective immobilization of vanadyl alkoxide species on two structurally different titania supports. The loading of vanadia was varied from 1.8 to 7.5 ,mol V⁵⁺ per m² surface area. Comparative kinetic measurements at 150 °C show that the NO turnover frequencies increase by more than an order of magnitude when the vanadia loading is increased from 1.8 to 3 mol V⁵⁺/m². In the region of lower SCR activity, i.e. at lower coverages ( 2 mol V⁵⁺/m²), small clusters and ribbons of vanadia are detected in the Raman spectra, whereas at loadings where maximum NO turnovers are achieved ( 3 mol V⁵⁺/m²) the prevalent vanadia species are well-developed two-dimensional vanadia layers bound to titania.     

Structure of the Reaction Zone of a Steady Detonation Wave in Dinitrodiazapentane

The massvelocity profiles in 2,4dinitro2,4diazapentane samples of different densities were registered by a laser interferometer and the electromagnetic technique. The reaction time was shown to reach 300 nsec and weakly depend on density, while the pressure in the chemical spike can be twice as high as that at the Chapman–Jouguet point. No special features due to diamond formation were observed in the massvelocity profiles registered in the chemical reaction zone.     

Does Density of Cationic Sites Affect Catalytic Activity of Co Zeolites in Selective Catalytic Reduction of NO with Methane?

Selective catalytic reduction of NO with methane (CH₄-SCR) in an excess of oxygen over Co ions located in ZSM-5 of various Si/Al composition and in ferrierite, mordenite, chabazite and beta zeolite was investigated. From the comparison of the dependence of the TOF values per Co ion for NO conversion to N₂ and Co ions distribution among the cationic sites on total Co ion concentration, the catalytic activity of the individual Co ions was estimated. The -type Co²⁺ ions, located in the main channel of mordenite and ferrierite and coordinated above the rectangle of four framework oxygens of the channel wall exhibit the highest activity in these zeolites. On the other hand, the -type Co²⁺ ions coordinated in the plane of four oxygens of the deformed six-member ring located in the channel intersection of ZSM-5 and in channels of beta zeolite control the activity of these Co zeolites. The sequence of activity of Co²⁺ ions in CH₄-SCR of NO was FER Co>ZSM-5 Co>BEA CoZSM-5 CoFER CoMOR CoCHA CoMOR Co. A correlation between the activity of the individual Co ions in CH₄-SCR of NO and a distance between the cationic sites was observed.     

Partial oxidation of methane over platinum metal gauze

The partial oxidation of methane to synthesis gas has been studied over a platinum gauze catalyst. The experiments were carried out at atmospheric pressure with a single gauze in a quartz reactor heated in an electric furnace. The furnace temperature was varied in the range 200–900°C and the space time in the range 0.00021–0.00042 s. The feed consisted of a mixture of CH₄O₂Ar2110 and carbon oxides and water were the main products. Oxygen was only partly consumed and relatively small amounts of hydrogen were formed.     

On the preparation and properties of CuZSM-5 catalysts for NO decomposition

Equilibrium exchange isotherms were determined for the exchange of Cu²⁺ with NaZSM-5 at varying Cu(Ac)₂ concentrations in solutions of constant volume and zeolite weight. At low Cu²⁺ levels the solid scavenged all the copper ions. When copper could be detected in the equilibrated solutions, overexchange was observed. The extent of overexchange was higher at pH 6 than at pH 4. These results were analyzed in relation to catalytic activity.On leave from the Central Institute for Chemistry, Hungarian Academy of Sciences, H1525 Budapest, Hungary.     

Propagation of the Chain Explosive‐Decomposition Reaction in Silver Azide Crystals

The velocity of the chain explosivedecomposition reaction in silver azide whiskes has been measured (1500 m/sec). The measured velocity is identified as the propagation velocity of the diffusion front of holes generated in the course of explosive decomposition.     

Interaction of Two Diffusion Flames Spreading Along a Metal Substrate Wetted with Different Fuels

The paper reports an experimental and theoretical study of the interaction of two diffusion flames propagating over the surface of two different liquid fuels applied to both sides of a thin metal substrate. It is shown that in this system, there may be formation of a unified complex — a doublesided flame which has the properties of a steadystate flame with a peculiar structures. Some velocity and structural dependences for doublesided flames are determined. A mathematical model for a doublesided flame is proposed that adequately describes experimental relations. A physical model for a doublesided flame with a pulsating flame of the heavier fuel is formulated.     

Characterization of poly(diethoxyphosphazene) by size exclusion chromatography and viscometry

Two samples of poly(diethoxyphosphazene) (PDEP) having very different molecular weights have been studied by viscometry and size exclusion chromatography in THF solution. The results obtained, together with light scattering data of these samples, allow the calculation of the Mark-Houwink constants a=0.65 and K=2.5 10^-4 in THF at 25°C. The method of calculation employed takes into account the great polydispersity of the samples. The characteristic ratio of the unperturbed dimensions was also calculated giving C_n = r²_o/n² 18, a value slightly higher than those previously reported for poly(dihexoxyphosphazene), C_n13 and poly (dichlorophosphazene), C_n13.5.     

Amination of dimethyl ether on zeolite catalysts. 2. Acidic properties of the used T-zeolites and their influence on the catalytic reaction

Freshly prepared and used H/Na, K-T-zeolite catalysts for the conversion of dimethyl ether and ammonia to the three methylamines have been characterized by temperature-programmed desorption of ammonia and IR spectroscopy. Activity and selectivity depend on the nature and number of the acid sites. With time on-stream, deep alterations in the catalyst behaviour have been observed. The activity of the catalyst is decreased by blocking of active sites 5–10 h: furthermore, during an initial period hydrocarbons were formed almost exclusively on strong-acid sites. A second period is characterized by an increased shape selectivity observed in the distribution of the methylamines. The amination will proceed probably on left weak-acid sites and on the outer surface in a third period, however, without shape selectivity due to the progressive blocking of the inner catalyst surface.     

Dependence of the Fluctuation Free Volume of Amorphous Substances on the Cooling Rate

The dependence of the fraction f _g of fluctuation free volume (frozen at the glass transition temperature) on the cooling rate is determined using the Bartenev equation for the dependence of the glass transition temperature on the cooling rate. Both dependences are found to be similar to each other. It is shown that the constancy of the ratio of the empirical coefficients involved in this equation (C ₁/C ₂ const 0.03) stems from the criterion for glass transition (f _g const 0.02–0.03) in the theory of fluctuation free volume.     

Model Detonation of Solid Explosives by the Homogeneous Mechanism

A twophase detonation model of solid porous explosives, which takes into account the compression of solidstate particles and the presence of a solid component in detonation products, is developed. The homogeneous detonation mechanism based on the Arrheniustype reaction is studied. Detonation is initiated by the region of highpressure and hightemperature gases modeling the detonator explosion. A numerical experiment confirms that there exists an initiationpressure limit below which no homogeneous mechanism of detonation is active. The detonation wave has the leading front in which the explosive is precompacted and the gas in the porous volume is compressed up to a pressure of 100 GPa without any significant change in particle density. Then the gas compresses the particles themselves up to the pressure and temperature of the thermal explosion. As a result, the leading front is followed (after a certain delay) by a narrow reaction zone where detonation products are formed with a further increase in pressure.     

Unsteady creep equation in refractory materials during monoaxial compression

Conclusions The creep curves for porous refractories under monoaxial compression can be described by the Andrade equation, the parameters of which depend on the nature of the macroscopic structural changes in the material. With significant densification or embrittlement of the specimens in the testing procedure during deformation the degree factor in the equation = P+q, p 1/2; if the structure of the specimen does not undergo marked changes then the degree factor is close to the classic value (p 1/3).Translated from Ogneupory, No. 1, pp. 22–26, January, 1989.     

Triggering of Detonation upon Flame Interaction with an Expansion Wave

The transition of a deflagration wave into an abruptly expanding part of a plane channel, where a quasisteady supersonic underexpanded jet of an unburned gas is formed, is studied for a propane–oxygen mixture using schlieren pictures. Two explosioninitiation modes (weak and strong) are registered. In the first case, almost instantaneous onset of the detonation wave occurs when the flame front enters the expanding section; the initial velocity of this wave is approximately 1.5 times the Chapman–Jouguet detonation velocity (D_CJ) and then decreases to a value corresponding to selfsustaining detonation. In the second case, the front velocity gradually increases from 0.4D _CJ to 1.0D _CJ. It is established that the starting pulse triggering the transformation of turbulent combustion to explosion and detonation regimes is generated by interaction of the flame front with expansion waves, which are elements of the structure of the initial section of the jet.     

Lean NOx catalysis over alumina‐supported catalysts

aluminasupported catalysts show promise as lean NO_x catalysts. The role of alumina in influencing the structural and chemical properties of the active phase supported on it is discussed using some effective aluminabased lean NO_x catalysts. These include Ag/Al₂O₃, CoO_x/Al₂O₃ and SnO₂/Al₂O₃. Alumina plays an important role in stabilizing Ag in the oxidic phase and cobalt in the 2+ oxidation state. For SnO₂/Al₂O₃, alumina increases the SnO₂ surface area. On both Ag/Al₂O₃ and SnO₂/Al₂O₃, alumina also participates actively in the NO_x reduction reaction. An active organic intermediate is formed on Ag or Sn oxide which reacts with NO_x subsequently on alumina to form N₂.     

Electrodeposition, composition and structure of Zn—Cr alloys

The effect of polyethylene glycol (PEG 1500) as additive and of deposition conditions on Zn—Cr alloy electrodeposition from an acidic sulfate electrolyte at room temperature, without agitation was investigated. PEG polarizes the overall cathodic reaction and inhibits Zn deposition. Cr codeposition with Zn starts at a cathodic potential of about –1,95 V vs Hg/Hg₂SO₄, which is reached at current density of about 20 A dm^–2 in galvanostatic conditions. Zn—Cr alloy coatings containing up to 28 at % Cr were obtained depending on the plating conditions. SEM observations showed an island-like structure, formed by the local growth of crystals, which covered the surface during further deposition. In the first stages of electrodeposition the powder diffraction spectra contain lines of b.c.c. -(Zn,Cr) phase (a 3.02 Å). After 30 s deposition time weak lines of Zn-based phase (a 2.67 Å, c 4.90 Å) appear, and become clearly visible in coatings deposited for 90 s. The average Cr content in the alloy coatings decreases with advancing deposition. The as-plated surface contains C in organic compounds and Zn(OH)₂. After 50 min sputtering, Zn and a mixture of Cr, Cr₂O₃ and Cr₇C₃ were found. The presence of organic C and O, probably from inclusions of PEG, were also detected.     

Heterogeneous asymmetric reactions. 23. Enantioselective hydrogenation of ethyl pyruvate over cinchonine- and α-isocinchonine-modified platinum catalysts

The enantioselective hydrogenation of ethyl pyruvate to (S)-ethyl lactate over cinchonine- and -isocinchonine-modified Pt/Al₂O₃ catalysts was studied as a function of modifier concentration and reaction temperature. The maximum enantioselectivities obtained under the applied mild conditions were 89% ee using cinchonine (0.014 mmoldm^–3, 1 bar H₂, 23°C, 6% AcOH in toluene), and 76% ee in the case of -isocinchonine (0.14 mmoldm^–3, 1 bar H₂, –10°C, 6% AcOH in toluene). Since -isocinchonine of rigid structure exists only in anti-open conformation these data provide additional experimental evidence to support the former suggestion concerning the dominating role of anti-open conformation in these cinchona-modified enantioselective hydrogenations.     

Phase transition in swollen gels

Summary The temperature dependence of the swelling and mechanical behaviour of two poly(N,N-diethylacrylamide) networks has been investigated in aqueous solutions at pH 7.5. While one network was prepared by the copolymerization of N,N-diethylacrylamide with N,N -methyl-enebisacrylamide in the presence of 92 vol 1.% water, 3 mol.% sodium methacrylate was added to the mixture used in the preparation of the second network. In the network without charges on the chain, both the swelling ratio and modulus were found to be continuously dependent on temperature. On the other hand, the ionized network containing sodium methacrylate showed a pronounced phase transition at the temperature T 51 °C connected with a jumpwise change in both the volume and modulus of the network.