Kinetics of electroless silver deposition using cobalt(II)-ammonia complex compounds as reducing agents

The kinetics of electroless silver deposition from solutions containing Co(II)-ammonia complex compounds as reducing agents was studied at 20 and 50 °C. The process rate depends on the solution pH and the concentration of Ag(I), Co(II) and ammonia species. Under optimum operating conditions selected a silver deposition rate up to 1.2 m h^–1 can be obtained at 20 °C with high solution stability. At elevated temperature (50 °C) the rate increases and reaches 3 m h^–1. The silver coatings obtained are of high quality, compact and bright.     

Alkylation of benzene with ethane over platinum-loaded zeolite catalyst

Alkylation of benzene with ethane was carried out using various zeolite catalysts at temperature ranges of 400–550°C. Loading of platinum onto zeolite greatly enhanced the yield of ethylbenzene. Among the zeolites tested, H-ZSM5 and H-MCM22 showed catalytic activities. By contrast, mordenite did not yield ethylbenzene. Moderate acid strength distribution is the key factor of zeolite catalysts. Optimum catalyst and conditions for this reaction are as follows. The platinum-loaded H-ZSM5 catalyst containing 6.8 wt% Pt, at a reaction temperature of 500°C, afforded ethylbenzene and styrene formation rates of 14.2 and 0.8 mmolh^–1g-cat^–1, respectively (benzene-based yields 7.3 and 0.4%). In the alkylation of benzene with ethane over platinum-loaded H-ZSM5, ethene was initially formed from ethane over the metallic platinum. Then the alkylation proceeded over the acid sites of H-ZSM5.     

Interconnection of relaxation transitions with the strength properties of hydrocellulose yarns

Conclusions The nature of relaxation processes in two types of hydrocellulose fibres has been examined, plus their connection with strength properties.In addition to the basic relaxation transition (180–240°C), secondary relaxation transitions are observed, caused by breakage and redistribution of hydrogen bonds of the cellulose hydroxyl group-water type have been observed (at 40 or 60°C), plus a rotation of the pyranose rings (100 or 120°C).Translated from Khimicheskie Volokna, No. 4, pp. 30–31, July–August, 1985.     

Partial oxidation of methane to syngas over Co/MgO catalysts. Is it low temperature?

Co/MgO catalysts with high Co-loading (>28 wt%) are able to initiate the reaction of methane with oxygen at temperatures around 500 °C. High conversions of methane ( 70%) and very high selectivities for hydrogen and carbon monoxide ( 90%) are obtained at very high reactant gas space velocities (10⁵–10⁶ h^–1). The temperature of the catalyst at the conditions of partial oxidation of methane to form syngas was found to be extremely high (1200–1300 °C); it is about 600–850 °C higher than that previously reported by others. At these temperatures, high temperature homogeneous reactions may prevail. It is suggested that combustion of methane to carbon dioxide occurs on the catalyst with major heat release and that methane and water, respectively methane and carbon dioxide are reformed thermally in an endothermic reaction leading to syngas.     

Chemical Transformations in the Course of Solid-Phase Synthesis of Fibrous Alkali-Free Fluoroamphibole

This paper reports on the results of investigations into the possible chemical transformations occurring in the course of the solid-phase synthesis of fibrous alkali-free fluoroamphibole from synthetic magnesium silicate dihydrate (MSDH) MgO · SiO₂ · 2H₂O in the MSDH–MgF₂–NaCl model system in the concentration range of compositions corresponding to Mg-fluorocupfferite (Mg₇Si₈O₂₂F₂) at temperatures ranging from 60 to 1000°C. It is found that the formation of Mg-fluorocupfferite from MSDH under these conditions is a complex multistage chemical process. In the temperature range 60–700°C, dehydration, dehydroxylation of MSDH, and pyrohydrolysis of fluorides (MgF₂, SiF₄, etc.) proceed near the lower temperature boundary of the fluoroamphibole formation region (T 750°C). These processes result in the formation of compounds containing monomeric and simple polymeric silicon–oxygen anions [SiO₄]^4– and [SiO₃]^2– (forsterite, fluoronorbergite, enstatite, etc.). In the temperature range 850–900°C, the transformation of intermediate compounds leads to the formation of the fluoroamphibole structure. The main elements of this structure are silicon–oxygen anions of the [Si₄O₁₁]^6– type.     

Acid‐catalyzed isobutane–isobutylene alkylation in liquid carbon dioxide solution

Liquid carbon dioxide was studied as a solvent for the isobutane–isobutylene alkylation. The acid catalysts in the reaction were anhydrous HF (AHF), pyridinium–poly(hydrogen fluoride) complex (PPHF), concentrated sulfuric acid and trifluoromethanesulfonic acid (TFSA). The effect of the acid–hydrocarbon volume ratio, temperature and residence time on the alkylate quality were studied over the temperature range of 50 T 0 °C. Carbon dioxide as a competing weak base decreases the acidity of the system which parallels the alkylate quality. In the case of HF and TFSA catalysts, solvent CO₂ increased the octane number of the alkylate product (RON 95.6 for HF and 88.0 for TFSAcatalyzed alkylation with CO₂ solvent).     

Microinterferometry of poly-p-phenyleneterephthalamide fibres dried at various temperatures

Conclusions Poly-p-phenyleneterephthalamide fibres which have been subjected to drying at various temperatures have been studied by use of the Biolar polarizing interference microscope.A significant change in the n(r) curves on change in temperature has been detected. Temperature elevation essentially does not show up in the axial orientation of the polymer macromolecules; however, the transverse orientation of the structural elements changes considerably.Translated from Khimicheskie Volokna, No. 3, pp. 40–41, May–June, 1989.     

Synergistic Effect of Ethanol to α-Pinene in Primary Attraction of the Larger Pine Shoot Beetle, Tomicus piniperda

-Pinene and ethanol were released in the approximate proportions 1:0.1, 1:0.9 and 1:9 (at 21°C). Ethanol, released in the range of 3–279 mg/day, generally synergized the attraction of T. piniperda to -pinene (30 mg/day at 21°C), although attraction to the mixtures varied within and between years. The low release rate of ethanol together with -pinene attracted a significantly higher number of beetles than -pinene alone in 1995, April of 1996, and in 1997. Lures with the medium release rate of ethanol were the most attractive only in March of 1996. The high dose of ethanol significantly synergized attraction to -pinene in 1995 and 1997. The variable attraction of T. pinipeda to ethanol and -pinene at various release rates and proportions may be due to the temperature dependent nature of beetle antennal sensitivity. At ambient temperatures of 10–13°C. T. piniperda was most attracted to the lures with -pinene and high release rates of ethanol, at 14–17°C it was most attracted to those with medium release rates of ethanol, and at 18°C and higher it was most attraacted to those with low release rates of ethanol.     

Elucidating the mechanism of carbocationic polymerization of α-methylstyrene

Summary The polymerization of -methylstyrene (MeSt) using the H₂O/SnCl₄ initiating system and ethyl chloride solvent has been investigated over the temperature range from –40° to –122°C in the presence and absence of the proton trap 2,6-di-tert-butylpyridine (DtBP). Arrhenius (In ¯M_n versus 1/T) plots obtained with poly (methylstyrene) (PMeSt) samples prepared in the absence of DtBP reveal the existence of two sharply defined temperature regimes (see Figure 1): at higher temperatures from –40 to –86°C, the slope of the Arrhenius plot yields H_{M n} = –4.90±0.25 kcal/mole whereas at lower temperatures, from –86° to –122°C,H_{M n} = –0.3 kcal/mole. With PMeSt samples prepared in the presence of DtBP the H_{M n} obtained for the higher temperature regime increases to –1.67 ± 0.20 kcal/mole whereas the H_{M n} reflecting the lower temperatures remains the same as that obtained in the absence of DtBP. These observations are readily explained by postulating a change in mechanism at –86°C: Evidently the ¯M_n of PMeSt is determined over the higher temperature regime by chain transfer to monomer which is frozen out at lower temperatures where termination becomes ¯M_n determinant. In the absence of DtBP chain transfer to monomer is operative which leads to the higher Arrhenius slope over the higher temperature regime; however, over the lower temperature regime where chain transfer is absent and termination is ¯M_n controlling, the Arrhenius slope remains unchanged. Evidence obtained from a Mayo plot (negligible intercept in the 1/¯M_n versus 1/[MeSt]_o plot, Figure 2) with samples prepared at –92°C, corroborate this postulate. Molecular weight dispersities (¯M_W/¯M_n) as a function of temperature have been determined in the presence and absence of DtBP (Figure 3). The proton trap affects ¯M_W/¯M_n only over the higher temperature regime which also suggests that chain transfer to monomer is frozen out at –86°C and that the polymerization becomes termination dominated at low temperatures.     

Adsorption Isotherm and Pore Characteristics of Nano Alumina Derived from Sol-Gel Boehmite

This paper deals with a systematic investigation on the synthesis of aluminium oxide starting from mono hydroxy aluminium oxide (boehmite, (AlOOH)) which in turn is synthesized from aluminium nitrate. Boehmite on heating forms , transitional alumina and -alumina phases in the temperature range 400–600, 800–1050 and 1050–1100°C respectively. Calculation from XRD, using Scherer equation shows that -alumina has crystallite size in the range 5–10 nm, while and -alumina are in the range 10–20 nm and -alumina is about 33 nm. The textural features of aqueous sol-gel boehmite samples calcined at various temperatures were analyzed by specific surface area measurements and adsorption isotherm features. Maximum specific surface area of 266 m²/g is observed for the precursor calcined at 400°C and a minimum of 5 m²/g at 1100°C. Total pore volume is maximum for the precursor calcined at 600°C (0.2653 cm³/g). Average pore size ranges from 3 nm (400°C) to 11 nm (1100°C). The adsorption isotherms also show a change from Type IV to Type II with increase in temperature showing difference in surface properties. The information from t-plots, pore size distribution and cumulative pore volume data also indicates differences in porosity features of boehmite on calcination. The adsorption isotherm and pore size distribution analysis show maximum microporosity at 400°C, while maximum mesoporosity is observed at 600°C. At higher temperatures, porosity decreases, even though small fraction of pores in the mesopore range is still retained. At 1100°C, there is structural transformation from transitional to -alumina, with very low specific surface area 5 m²/g and pores in the size range of 11 nm. The various data presented in this study will be useful in the synthesis of alumina with tailor made properties.     

Kinetics of electroless copper deposition using cobalt(II)-ethylenediamine complex compounds as reducing agents

Electroless copper deposition using Co(II)-ethylenediamine (En) complexes as reducing agents was investigated in 0.4–1.2 M En solutions at 50 and 70 °C. There is a complicated dependence of the process rate on pH, En concentration and temperature. A copper deposition rate up to 6 m h^–1 (50–70 °C) in relatively stable solutions (pH 6) can be achieved. The stoichiometry of the Cu(II) reduction at pH 6–7 corresponds to the reaction:

Syntheses of aromatic polyesters from silylated monomers

Summary Aromatic polyesters were synthesized either from silylated bisphenols and diacid chlorides or from trimethyl siloxy benzoyl chlorides by thermal condensation at 200–300°C. Yields and molecular weights were compared with those obtained by other condensation methods. The Silyl Method seems to be most useful for the synthesis of polyesters of aromatic -hydroxy acids.     

Characterization of the conformers in poly(3,3-diethyl oxetane) by vibrational spectroscopy

Summary The monoclinic and orthorhombic conformers of Poly(3,3-Diethyl oxetane) can be obtained depending on crystallization temperature. However, if the crystallization of a given modification is unaccomplished, the other modification can be crystallized from the amorphous phase. The molecular vibrations in the region 700–800 cm^–1, which are associated with the breathing mode, are highly dependent on the conformation of the polymer chain. This band is used to study the influence of the temperatures and times of crystallization on the structural modifications of this polymer.     

On the promotional effect of Sn in Co–Sn/Al2O3 catalyst for NO selective reduction

NO reduction with propylene over Co/Al₂O₃ and Co–Sn/Al₂O₃ catalysts has been investigated. For the Co/Al₂O₃ catalyst, a calcination temperature exceeding 800°C led to a decrease of NO conversion. Calcination of the Co/Al₂O₃ catalyst at 1000°C resulted in the formation of -Al₂O₃ and Co₃O₄. The presence of 20% water vapor showed a significant shift for the maximum NO reduction temperature from 450 to 600°C over Co/Al₂O₃. It has been found that modification of 6 wt% Co/Al₂O₃ with 2 wt% Sn significantly enhanced the catalyst thermal stability and improved the inhibitory effect of water on NO conversion and reaction temperature. The promotional effect of Sn on the catalyst thermal stability was attributed to the suppression of the phase transformation from highly dispersed Co²⁺ species on -Al₂O₃ to -Al₂O₃ and Co₃O₄. The smaller influence of water vapor on NO reduction conversion and temperature over Co–Sn/Al₂O₃, compared to Co/Al₂O₃, was attributed to the dispersion effect of Sn species on Co²⁺ species as well as the involvement of Sn species in NO reduction at a relatively lower temperature. The synergetic effect between the octahedral Co²⁺ species and -alumina plays a significant role in the catalysis of NO selective reduction by C₃H₆.     

Study of the thermal stability of a poremit emulsion

Results are presented from a study of the thermal stability of a poremit emulsion. Safe storage and processing times and temperatures are indicated along with the effect of the emulsion on the thermal stability of other materials. Satisfactory thermal stability is attained with an emulsion of poremit in lubricating oils and fuel oils containing up to 3.5% sulfur and from 10 to 17% water. No heat is released for several days at temperatures of 90–110°C. The emulsion begins to break down at 205–210°C, this process intensifying at 240–250°C. The self-ignition temperature of the emulsion is within the range 310–370°C.State Scientific Research Institute Kristall, 606007, Dzerzhinsk. Translated from Fizika Goreniya i Vzryva, Vol. 30, No. 6, pp. 89–96, November–December, 1994.     

Pulse electrodeposition of titanium on carbon steel in the LiF–NaF–KF eutectic melt

Electrodeposition of titanium was carried out in the K₃TiF₆–LiF–NaF–KF melt using both direct (DC) and unipolar pulse current (PC) techniques. Dense and smooth titanium coatings were obtained by PC plating at 750 °C whereas DC plating led to rough and dendritic deposits. The best results were obtained using a 100C cm^–2 pulse charge and a cathodic current density of 50 and 75mA cm^–2. The cathodic current efficiency was in the range 60–65%. The titanium deposits obtained under such conditions behaved similarly to CP-titanium in NaCl and HNO₃ solutions at room temperature.     

Joule heating induced local electrodeposition for microelectronic circuits

A fundamental study is performed for local electrodeposition of copper utilizing thermal potential induced by Joule heating. The feasibility of the process for microelectronic applications is assessed by both experiment and mathematical modeling. The results of the investigation show that (i) a copper wire is coated under conditions of a.c. 50 Hz Joule heating in electrolyte containing 1.0 M CuSO₄ and 0.5m H₂SO₄ with relatively high deposition rate of about 0.4 µm min^–1, (ii) the Joule heating current should be kept below the boiling point of the solution to realize uniform deposition, and (iii) results of calculations by the present model based on one-dimensional heat conduction agree well with experimental results.Nomenclature D diameter of wire (m) - D ₀ initial diameter of wire (m) - F Faraday constant (96 487 C mol¹ ) - g acceleration due to gravity (9.807 m s²) - Gr Grashof number - H thickness of electrodeposit (m) - I current (A) - i ₀ exchange current density (Am^–2) - i _n current density normal to electode (Am^–2) - J current density (I/S) (Am^–2) - L length of wire (m) - M molar concentration of electrolyte (mol dm^–3 or M) - m atomic weight (kg mol^–1) - n number of electrons participating - n unit normal vector to boundary - Nu Nusselt number - Pr Prandtl number - q heat per unit volume (W m^–3) - R universal gas constant (8.314 3 J mol^–1 K^–1) - (r, z) cylindrical coordinate (m) - S cross section of wire (m²) - T temperature (K) - T ₀ fixed temperature at both ends of wire (K) - T _y temperature of electrolyte (K) - t time (s) - x longitudinal coordinate over wire (m) Greek symbols heat transfer coefficient (W m^–2 K^–1 - _a,c anodic (a) and cathodic (c) transfer coefficient - thermal expansion coefficient of solution (K^–1) - specific heat (J kg^–1K^–1) - potential (V) - _e electrode potential (V) - thermal conductivity (W m^–1 K^–1 ) - _y ionic conductivity of electrolyte (^–1m^–1) - _e electronic conductivity of electrode (^–1 m^–1) - kinematic viscosity (m²s^–1) - surface overpotential ( _e – ) (V) - time constant (s) - density (kg m^–3) This work was presented at The 7th International Microelectronics Conference, Yokohama, Japan (1992).     

Crystallization and melting of <Emphasis Type="Italic">α</Emphasis> and <Emphasis Type="Italic">β</Emphasis> phases in bulk syndiotactic polystyrene as monitored in situ via high-temperature wide-angle X-ray diffraction

Direct and non-intrusive observations of crystallization and melting behavior of and polymorphs in bulk syndiotactic polystyrene were made by means of temperature-programmed x-ray diffraction. Results indicated that the highest sustainable temperature identifiable via wide-angle x-ray diffraction using stepwise annealing at increasingly higher temperatures (T _a) for the perfected (with the initial crystallization temperature T _c = 245 °C, followed by annealing at stepwise increased T _a above 250 °C) phase may be at least 286 °C. In a similar manner, the highest sustainable temperature of the perfected (with T _c = 265 °C, followed by annealing at stepwise increased T _a above 275 °C) phase may be at least 280 °C. These observations suggest complete melting should occur only above the respective sustainable temperatures. It thus follows that equilibrium melting of the and the phases should occur at temperatures higher than 286 and 280 °C, respectively. Perfection of the less ordered form into the better ordered form within the family is observed to occur in the vicinity of 270 °C; no evidence of transformation between and phases is identified.     

Concentration and temperature dependences of the viscosity of liquid-crystalline solutions of cellulose ethers

Conclusions At concentrations greater than 30 and 35% by wt., respectively, solutions of ethyl cellulose and hydroxypropyl cellulose at 20°C go over into the liquid-crystalline state.The flow curves of the liquid-crystalline solutions are characterized by the presence of three sections which correspond (as stress increases) to the following: a yield point and orientation decrease in viscosity; quasi-Newtonian flow of aggregates of a constant size; and flow of the fragmented preparation with presence of turbulent streams.Maxima are clearly discernible on the concentration and temperature dependences of viscosity in the region of the transition into the liquid-crystalline state.Translated from Khimicheskie Volokna, No. 2, pp. 42–44, March–April, 1985.     

Effect of chemical crosslinking on molecular mobility in swollen polystyrenes

Summary Proton relaxation time measurements of chemical crosslinked polystyrenes swollen in protonated and deuterated benzene have been done in order to get informations on the microdynamic behaviour of polystyrene as well as of benzene molecules under the influence of the polymeric network. By means of additional T_1d-measurements further evidences for a slow anisotropic motion could be obtained, which cause a T₂-plateau in the high temperature region. The results are compared with those of MAR-experiments.Presented at the 22nd Microsymposium, Characterization of Structure and Dynamics of Macromolecular Systems by NMR Methods, Praque, CSSR, July 20–23, 1981