Thermal decomposition process of silver behenate

The thermal decomposition processes of silver behenate have been studied by infrared spectroscopy (IR), X-ray diffraction (XRD), combined thermogravimetry-differential thermal analysis-mass spectrometry (TG-DTA-MS), transmission electron microscopy (TEM) and UV-vis spectroscopy. The TG-DTA and the higher temperature IR and XRD measurements indicated that complicated structural changes took place while heating silver behenate, but there were two distinct thermal transitions. During the first transition at 138 °C, the alkyl chains of silver behenate were transformed from an ordered into a disordered state. During the second transition at about 231 °C, a structural change took place for silver behenate, which was the decomposition of silver behenate. The major products of the thermal decomposition of silver behenate were metallic silver and behenic acid. Upon heating up to 500 °C, the final product of the thermal decomposition was metallic silver. The combined TG-MS analysis showed that the gas products of the thermal decomposition of silver behenate were carbon dioxide, water, hydrogen, acetylene and some small molecule alkenes. TEM and UV-vis spectroscopy were used to investigate the process of the formation and growth of metallic silver nanoparticles.     

Crystallization of silver stearate from sodium stearate dispersions

Silver carboxylates, the common silver source used for photothermographic imaging materials, are normally obtained from the reaction between sodium soap (e.g., sodium stearate) and silver nitrate. They form platelet-like crystals with a lamellar structure in water at room temperature. Light microscopy investigations reveal that the formation of silver stearate (AgSt) crystals follows a diffusion-controlled mechanism. The reaction between the sodium soap and silver nitrate preferentially occurs in solution rather than on the soap fiber solid interface. Cryogenic transmission electron microscopy, together with an on-the-grid reaction technique, provides a useful tool to directly image silver stearate microstructures at the initial stages of AgSt precipitation. The AgSt reaction product first forms particles about 5 nm in size, which is similar to the d-spacing of final AgSt crystals. Those particles aggregate to produce larger and loosely packed embryonic crystals, the precursors to the ultimate silver stearate crystals.     

Crystallization of silver carboxylates from sodium carboxylate mixtures

Silver carboxylates can be made by the reaction of silver nitrate and the corresponding sodium carboxylates. The length of the alkyl chain has a significant impact on the product behavior. In this study, 18, 20, and 22 carbon chains (stearate, arachidate, and behenate, respectively) have been selected. All three sodium carboxylates are very insoluble in water at room temperature. Solutions are obtained above the Krafft temperature, which precipitates lamellar crystals if cooled at the proper cooling rate. Depending on the chain length, metastable morphologies, such as vesicles and tiny fibers, can be seen consecutively before hexagonal plates form. The carboxylate with the shorter chain length reaches equilibrium more quickly. All three silver carboxylates also take on a lamellar structure. Small-angle X-ray scattering (SAXS) shows that the d spacing of the crystals increases as the chain length increases. Cryo-TEM illustrates that the crystallites are the result of micelle nucleation and micelle aggregation. In addition, the crystallization process in the presence of silver bromide nanocrystals has been investigated. In the initial stage, an epitaxial interface is formed between the silver carboxylate crystallites and the cubic silver bromide grains. Budlike and strandlike structures grow because of it. The consequent strand enclosure restrains the crystal growth, which reduces the size and changes the morphology of the crystals.     

Formation of silver nanoparticles in the redox reaction of silver(I) nitrate with crystalline macrocyclic nickel(II) compounds

The redox reaction of crystalline macrocyclic nickel(II) carboxylates with silver(I), gold(III), and palladium(II) salts leads to the formation of nanoclusters of the corresponding metals. The reaction with silver nitrate was used to show that the size of the nanoparticles formed depends both on the chemical and crystal structure of the solid matrix and the reaction time. The results open the possibility of forming noble metal nanoparticles with desired dimensions and dispersion.     

Morphologic characteristics of bismuth and silver particles formed upon the reduction of metal stearates with benzyl alcohol

The products of the reduction of individual and mixed bismuth oxohydroxostearate and silver stearate with benzyl alcohol are studied by electron microscopy and X-ray powder diffraction. The reduction of mixed bismuth and silver carboxylates with benzyl alcohol is a promising route to both individual submicronzised bismuth and silver metal powders and to their alloys.     

Polymerization products of p-benzoquinone as thermal stabilizers for rigid poly(vinyl chloride): Part I—Preparation of the stabilizer

The solid phase cationic polymerization of p-benzoquinone using tin (II) chloride as catalyst has been investigated by isolation and identification of the reaction products. The polymerization reaction leads to formation of polymeric chains of hydroquinone nuclei linked together by SnOSn bonds and free from combined chlorine. The tin content of the polymer is increased by increasing the molar ratio of the catalyst and ranges from 4·7 to 55·6% tin. It is probable that the tin atoms are involved in the reaction products as a result of the interaction between polymeric chains having terminal catalyst residues. The resulting polymeric products are characterized by high thermal stability with a decomposition temperature in the region of 400°C. A mechanism which can account for the polymerization products has been developed. In view of the expected high potency of these products, together with their high thermal stability, they will be investigated as radical scavengers in the stabilization of polymeric material against radical degradation processes.     

Constitution and Properties of Nanocomposites Prepared by Thermal Decomposition of Silver Salts Sorbed by Polyacrylate Matrix

Constitution and dispersity of the products of thermal decomposition of silver nitrate ammonia complex sorbed by polyacrylate matrix are studied by the methods of small- and wide-angle X-ray scattering, optical, photoelectron and Auger-electron spectroscopies. It is shown that, at temperatures of 140–150°C, the complete decomposition of the complex occurs with the formation of nanoparticles and charged silver clusters in polymer bulk. No initial or intermediate products were observed. The average size of obtained nanoparticles is equal to 5 nm. The particles with the size less than 5 nm are amorphous according to X-ray data. The stabilization of nanoparticles occurs due to the adsorption of acrylic copolymer (presumably, via oxygen atoms) on their surfaces. Upon long-term storage in air, the self-diffusion of silver particles and clusters takes place from the surface to composite bulk caused by the detachment of oxygen-containing groups occurring at the metal–polymer interface.     

Specific features of polyol synthesis of silver nanoparticles with the use of solid carboxylates as precursors

Electron microscopy, X-ray diffraction, and chromatography-mass spectrometry have been employed to investigate the reduction of solid silver caprylate in ethylene glycol with the formation of silver nanoparticles. The structural characteristics of silver nanoparticles have been studied as depending on the conditions of their synthesis, including temperature, reduction time, and silver salt concentration. It has been found that, in the studied range of parameters under the conditions, when solid silver caprylate is dispersed in ethylene glycol, the characteristics of resulting nanoparticles are almost independent of the synthesis temperature. This peculiarity is related to the fact that the formation and growth of nanoparticles occur on the surface of silver salt crystals and are accompanied by gradual dissolution thereof. In this system, ethylene glycol plays the roles of a reductant and a solvent for liquid reaction products.     

Imidazol(in)ium‐2‐Carboxylates as Efficient Precursors to N‐Heterocyclic Carbene Complexes of Copper and Silver

Copper and silver N‐heterocyclic carbene (NHC) complexes were prepared through a simple, base‐free protocol involving the decomposition of corresponding imidazol(in)ium‐2‐carboxylates under thermolytic conditions and a subsequent reaction of the in situ generated carbenes with copper(I) or silver(I) chloride, respectively. The desired NHC metal complexes were isolated with good yields after simple crystallization.     

The thermal decomposition of calcium,sodium, silver and copper(II) acetates

The thermal decomposition of the acetates of calcium, sodium, silver and copper(II) have been investigated using thermogravimetry and differential thermal analysis, together with analysis of the gaseous products formed during the decomposition process. The results indicate that the major organic product formed is either acetone or acetic acid, depending on whether the final solid product is the oxide or the metal.     

Dynamic in situ characterization of organic monolayer formation via a Novel substrate-mediated mechanism

Ultrahigh vacuum scanning tunneling microscopy data investigating octylsilane (C8H17SiH3) monolayer pattern formation on Au(111) are presented. The irregular monolayer pattern exhibits a 60 A length scale. Formation of the octylsilane monolayer relaxes the Au(111) 23 x square root3 surface reconstruction and ejects surface Au atoms. Au adatom diffusion epitaxially extends the Au(111) crystal lattice via step edge growth and island formation. The chemisorbed monolayer covers the entire Au surface at saturation exposure. Theoretical and experimental data suggest the presence of two octylsilane molecular adsorption phases: an atop site yielding a pentacoordinate Si atom and a surface vacancy site yielding a tetracoordinate Si atom. Theoretical simulations investigating two-phase monolayer self-assembly dynamics on a solid surface suggest pattern formation results from strain-induced spinodal decomposition of the two adsorption phases. Collectively, the theoretical and experimental data indicate octylsilane monolayer pattern formation is a result of interfacial Au-Si interactions and the alkyl chains play a negligible role in the monolayer pattern formation mechanism.     

Gels from mixed ligand silver(I) carboxylates: a promising approach for gel formation utilizing surface modifications

Mixtures of Ag(hexanoate) and Ag(palmitate) give thermoreversible gels at very low concentration in toluene. The framework of the gel is composed of the branched nanosized fibers, contrary to the microsized wire precipitates of silver(I) carboxylates. The randomness of mixed-ligand silver(I) carboxylate polymeric chains hinders the crystallization process, resulting in very thin fibrils. This may be a new approach to design and control the properties of materials, which do not have properties involving gels or nanostructures in a conventional process.     

Catalytic Systems Based on Magnesium and Zinc Compounds in the Oxidation Reactions of Alkylarenes and the Decomposition Reactions of the Corresponding Hydroperoxides

The oxidation of aromatic hydrocarbons in the presence of magnesium and zinc 2-ethylhexanoates and a mixed catalyst based on these compounds is studied. It is shown that magnesium and zinc carboxylates are active catalytic systems which catalyze the decomposition of hydroperoxides representing the primary alkylarene oxidation products alongside with activation of oxygen.     

磷钨杂多酸银盐催化合成缩酮(醛)

利用沉淀法制备了一系列磷钨杂多酸银盐(AgxH3-xPW12O40,0相似文献   

Formation of silver nanoparticles from a complex of Ag(I) with 2-[4,6-di(tert-butyl)-2,3-dihydroxyphenylsulfanyl]acetic acid in organic solvents

Specific features of the formation of silver nanoparticles upon the decomposition of the complex of Ag(I) with 2-[4,6-di(tert-butyl)-2,3-dihydroxyphenylsulfanyl]acetic acid in organic solvents characterized by large donor numbers (27–34) are studied. It is established that the stability of prepared organosols depends to a significant extent on the nature of a dispersion medium and the presence of water and oxygen in this medium. The Ag(I) complex is a solid precursor for the preparation of silver nanoparticles.     

The mass spectra of some silver salts

Fifteen of twenty-four silver(I) carboxylates examined give useful electron impact mass spectra. The compounds vaporize at moderate temperatures, apparently mainly as dimer with traces of higher oligomer in only a few cases. The molecular ion for the dimer is generally weak or absent, with the most abundant silver containing ion being [Ag₂(O₂CR)]⁺ in most cases. Metastable defocusing and deuterium labeling experiments on silver acetate have established some of the fragmentation pathways. The reported loss of carbon dioxide from perfluorocarboxylates to give intense peaks for organosilver ions was not observed in this study. Attempts to obtain spectra on the silver salts of organic materials other than carboxylic acids were successful in several cases. Silver trifluoromethanesulfonate, although much less volatile, gives a spectrum and fragmentation very much like the carboxylates, whereas silver trifluoromethanethiolate gives a complex spectrum which suggests tetramer as a major gas phase species. Of three compounds examined which have silver to nitrogen bonding only silver(II) phthalocyanine is sufficiently volatile to give a spectrum without decomposition. The field desorption spectra of the four compounds examined all show the ions Ag_nX_{n ? 1} for X=acetate (n=1 ? 6), X=p-chlorobenzoate (n=1 ? 4), X=methanesulfonate (n=1 ? 7) and X=p-toluenesulfonate (n=1 ? 5).     

Thermal decomposition study of intumescent additives: Pentaerythritol phosphate and its blend with melamine phosphate

Thermal decomposition of pentaerythritol phosphate (PEPA) and its blend (PEPAMP) with melamine phosphate were studied by TG, DSC, TOF MS, and FTIR of volatile and solid decomposition products. Both PEPA and PEPAMP produce intumescent char on heating, however that of PEPAMP is less stable to thermo-oxidative decomposition. The main decomposition pathway of PEPA is liberation of phosphoric acid followed by formation of a foamed carbonized residue. In the mixture of PEPAMP, reaction between the components occurs, which strongly reduces the heat release peaks of PEPA. In addition, condensates of melamine and their products of hydrolysis are formed. The hydrolysis reaction causes a low-temperature decomposition of the melamine ring, which results in the formation of urea, carbon dioxide and ammonia. The thermal decomposition of PEPA and PEPAMP is discussed.     

Nitrosyl isocyanate (ONNCO): gas-phase generation and a HeI photoelectron spectroscopy study

The nitrosyl isocyanate (ONNCO) has been generated from a heterogeneous reaction of gaseous nitrosyl chloride with silver isocyanate and studied for the first time in the gas phase. This structurally and energetically novel transient specimen is characterized by HeI photoelectron spectroscopy combined with DFT calculations. Both the calculations and the spectroscopic results suggest that the molecule adopts an open-chain trans structure. The observed decomposition products indicate the formation of ONNCO and further confirm the previously reported decomposition pathway.     

The mechanism of solid-state decompositions in a retrospective

This is an overview of the early investigations into the mechanism of solid decompositions since the fundamental studies by Ostwald on catalysis during 1890–1902 and the first experimental study of the autocatalytic decomposition of Ag₂O by Lewis in 1905. In order to explain the formation mechanism of the solid product, Volmer suggested in 1929 that the decomposition of Ag₂O includes two sequential stages: first, a thermal decomposition of the oxide into gaseous silver atoms and oxygen molecules and second, the condensation of the supersaturated silver vapor. This revolutionary idea was immediately used by Schwab to explain the autocatalytic peculiarity of solid-state decomposition reactions. However, this mechanism did not receive the acceptance of the scientific community. On the contrary, as can be seen from the results presented at the conference “Chemical reactions involving solids” in Bristol in 1938, this model was dismissed as unrealistic and, as a result, was since forgotten. Instead, considerable attention at this conference was devoted to the disorder theory proposed earlier by Wagner and Schottky, and to the mechanism of ion transport in the solid crystals. During the subsequent 70 years, decomposition mechanisms have been interpreted, without visible progress, on the latter basis. The mechanism of congruent dissociative vaporization proposed independently in 1990 turned out to be in complete agreement with the Volmer–Schwab model. It has been treated with the same distrust. These historical events, in the author’s opinion, are responsible for the prolonged stagnation in the development of solid-state decomposition theory.     

Thermal Decomposition of Silver Flake Lubricants

There is a thin layer of organic lubricant on commercial silver flake surfaces. This lubricant layer is a fatty acid salt formed between a fatty acid and silver flake surfaces. Thermal decomposition behavior of the silver flake lubricant is investigated in this study. The heat flow and mass loss of a silver flake are studied using differential scanning calorimetry (DSC) and thermogravimetry (TG), respectively. The silver flake is also oven heated to different isothermal temperatures (150,190, 250 and 300°C) for one h. Then chemical nature of the lubricant of the heated silver flake sample are studied using diffuse reflectance infrared Fourier transfer spectroscopy (DRIFTS). Based on the results, a mechanism of thermal decomposition of the silver flake lubricant is proposed. It is found that decomposition of the lubricant - the fatty acid salt -includes the release of the fatty acid, formation of short chain acids by decomposition of hydrocarbon moiety of the fatty acid, and formation of alcohols through decarbonation of the short chain acids. This revised version was published online in July 2006 with corrections to the Cover Date.