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1.
Thermal degradation of blends containing chloroprene rubber (CR) and butadiene rubber (BR) cross-linked with copper(II) oxide (CuO) with the addition of anti-aging substance ((N-(1.3-dimethylbutyl)-N-phenyl-p-phenylenediamine (6PPD), polymerized 2.2.4-trimethyl-1.2-dihydroquinoline (TMQ), or 2-mercaptobenzimidazole (MBI)) under high temperature was investigated using a Fourier Transform Infrared spectroscopy (FTIR) spectroscopy and color measurement. Additionally, changes in mechanical properties (such as tensile strength, elongation at break, hardness, tear resistance) causes by aging factors have also been investigated. The results indicated that the 6PPD and the MBI provided better protection of the CR/BR/CuO vulcanizates against degradation at elevated temperature than the TMQ. As a result of thermo-oxidative aging, in an infrared spectrum, a peak assigned to stretching vibration of carbonyl groups was observed. Differences in protection against thermo-oxidative aging by the anti-aging substance are caused by their different structure, consequently, by the differences in their protection mechanism.  相似文献   

2.
Investigations of the pyrolysis of poly(vinyl chloride) (PVC) in the presence of copper metal (Cu), copper(II) oxide (CuO) and copper(II) chloride (CuCl2) are of potential importance because of the likelihood of the formation of these copper compounds during the thermal degradation of PVC-coated copper wires, a step in the recovery of copper from waste. The presence of Cu, CuO and CuCl2 (i) retards the thermal degradation of PVC in air and in nitrogen and (ii) decreases the percentages of volatile products produced at both stages of the decomposition. These effects are greatest for PVC-CuO. The presence of copper, CuO or CuCl2 in PVC has a major effect on the nature of the gaseous emissions of the thermal decomposition in air and in nitrogen. The concentrations of total chlorine, aliphatic hydrocarbons, aromatic hydrocarbons, chlorinated hydrocarbons and soot particulates are all affected relative to an equivalent amount of PVC. These changes are greatest for the PVC-CuO system for which total chlorine emissions in air and nitrogen are reduced by 40% in air and 20% in nitrogen, benzene emissions are reduced by greater than 90% in air and nitrogen, other aromatic and chloroaromatic emissions are reduced, and soot particulate emissions are reduced by more than 50% as the concentrations of aliphatic compounds are increased. These changes are consistent with the presence of copper or its compounds permitting more efficient combustion of the carbon content of the PVC and particularly in the case of PVC-CuO with the removal of chlorine during pyrolysis in the inorganic phase.  相似文献   

3.
The oxidative degradation of isotactic polypropylene films coated on well-defined Cu(Cu2O), CuO0.67, and CuO films in a temperature range of 90–120°C in a quartz-spoon-gauge-reaction vessel was studied. This catalytic reaction has been compared with the oxidation of polypropylene without copper or oxide films. The reaction vessel contained, if needed, P2O5 and/or KOH as “getters” for H2O and CO2, these substances could be menitored continuously. Cu(Cu2O) films were transformed during oxidation of the polymer to yellow CuO0.67 below 100°C and above this temperature to black CuO in the presence of H2O and CO2, whereas in the absence of these compounds CuO was formed below 100°C and CuO0.67 at 120°C. Characteristic autoxidation curves obtained in the absence of H2O and CO2 showed induction periods that were shorter for copper oxide-polymer interfaces than for glass-polymer interfaces (i.e., for uncatalyzed oxidation). Abnormalities were observed for Cu(Cu2O)-polymer interfaces because of further oxidation of Cu during the reaction. The rates of oxygen consumption were faster for CuO0.67-polymer and CuO-polymer than for the uncatalyzed reaction; the catalytic action of CuO0.67 was somewhat larger than that of CuO. The important observation was made that the mechanism of oxidation is not the same in the absence and presence of reaction products; that is, H2O and CO2. This was confirmed by ion beam scattering experiments, which also revealed that an oxidation-reduction process takes place at Cu and their oxide interfaces. A mechanism for the catalytic oxidation process, based on the ease by which copper ions are released from the metal oxides at the interface, was formulated. These ions diffuse subsequently as actions of carboxylate anions into the bulk of the polymer. Arrhenius equations of oxygen consumption are given for all cases; the energy of activation calculated for the initiation of the uncatalyzed oxidation agrees with its literature value. The energy of activation for the initiation of the catalyzed reaction was a few kilocalories lower than that for the uncatalyzed reaction. Catalytic action is mainly operative for the initiation reaction at the interface and for the decomposition of hydroperoxides by copper ions. Preventing the delivery of copper ions to the polymer would be the most efficient way of inhibiting the catalysis.  相似文献   

4.
The solid-state reactions in the system Cu—Sb—O were investigated by thermogravimetry and X-ray diffraction. Equimolar mixtures of CuO and Sb2O3 form Cu(II)Sb2O6 when slowly heated in air up to 1000°C. The firt step in this reaction is the oxidation of Sb2O3 to Sb2O4 at 380–500°C, followed by further oxidation of Sb2O4 and the formation of CuSb2O6 at 500–1000°C. Thermal decomposition of CuSb2O6 in a flowing nitrogen atmosphere occurs in three stages; the first, with an activation energy of 356 kJ mole?1, results in the formation of a new copper(I) antimony oxide, with a composition of Cu4SbO4.5, as determined by atomic absorption analysis and X-ray fluoresecence. Confirmation of predominantly monovalent copper and pentavalent antimony in the new compound was by ESR and ESCA, respectively. Two forms of Cu4SbO4.5 have been distinguished; one of these (form II) has a structure of lower symmetry, and decomposes when heated in air at 600°C to a mixture of CuO and another new copper antimony oxide, as yet uncharacterized. On further heating to 1100°C in air, Cu4SbO4.5 (form I) gradually reforms. Details of these reactions are summarized and X-ray powder data presented for Cu4SbO4.5.  相似文献   

5.
The conditions of thermal decomposition of copper(II) benzenetricarboxylates in air atmosphere at heating rates of 10 and 5 deg·min–1 were studied. At 10 deg · min–1, the hemimellitate and trimesinate of copper(II) lose crystallization water and then decompose directly to CuO, whereas at 5 deg·min–1 they decompose to CuO through Cu2O. The trimellitate of copper(II) heated at various rates decomposes in the same way: it loses 1 water molecule and then decomposes directly to CuO.  相似文献   

6.
The effect of hydroxyethylidenediphosphonic acid (HEDP) on the kinetics of copper(II) oxide dissolution in aqueous sulfuric acid was studied. The addition of HEDP in acidic media decreases the CuO dissolution rate. The simulation of these processes showed that the inhibiting effect is due to the decrease in the concentration of the intermediate compound (CuOH+), which restricts the dissolution of Cu2+ ions, due to adsorption of the HEDP ions (H4Y?) on the oxide surface.  相似文献   

7.
The formation of copper(II) hydroxide gels from aqueous precursors requires very critical conditions. Gels have been obtained by adding ammonia to aqueous solutions of copper(II) acetate, in the presence of a small amount of sulphate ions. Other salts (chloride, nitrate, sulphate) or bases (NaOH, KOH) lead to precipitation rather than gelation. These gels are actually made of an intimate mixture of acetate-based organic/inorganic polymers and nanometric posjnakite crystals Cu4(OH)6(SO4) · H2O. Acetate ions and ammonia can be partially removed upon washing, which after drying leads to crystalline copper(II) hydroxide needles deposited on a strongly oriented layer of posjnakite crystals. A theoretical model based on the electronegativity equalisation principle is used to describe these experimental results. It provides a better understanding of the role of complexing anions during the formation of condensed phases.  相似文献   

8.
Depth profiling has been performed by using X-ray photoelectron spectrometry (XPS) in combination with Ar-ion sputtering, Rutherford backscattering spectrometry (RBS) and glow discharge optical emission spectrometry (GDOES). The data obtained by XPS have been subjected to factor analysis in order to determine the compositional layering of the copper oxides. This leads to two or three relevant components within the oxide layers consisting of Cu2O or CuO dependent on the sample preparation. GDOES measurements show sputtering profiles which are seriously influenced by a varying sputter rate. To ensure the results obtained so far, RBS measurements of the oxide layers have been carried out in order to discover artefacts of the other methods used and to demonstrate the excellent suitability of RBS for quantitative analysis of these layers. Chemical analysis consisting of (1) carrier-gas fusion analysis (CGFA) and (2) selective dissolution of Cu2O/CuO allows the determination of the total amount of oxygen and copper, respectively, and can serve as a cornerstone of quantitative analysis.  相似文献   

9.
The relative effectiveness of CuO and Cu2O were compared as catalysts for the methylchlorosilane (MCS) reaction. MCS reactions catalyzed by CuO had higher rates (0.15 g/g Si-h) than MCS reactions catalyzed by Cu2O (0.08) AND higher selectivities (4–5 points in % Di higherfor CuO). A synthetic method was found for making 17O-labeledCu2O based on reaction of CuCl with excess NaCl and >2equivalents of Na17OH. The Na17OH was made from17O-enriched water and Na. The % enrichment of theCu2O was determined by reduction of the Cu2O with H2 to form Cu and water and then subsequent reaction of the water product with Me2SiCl2 to make cyclo-octamethyltetrasiloxane (D4). The 17O enrichment of the D4 wasthen determined by mass spectroscopy. Thus Cu2O was made with27% 17O ±5%. The labeled Cu2Owas used as the catalyst in the MCS lab reactor. A 14% enrichmentin 17O in D4 and dichlorotetramethyldisiloxane(MClMCl) was found vs. the controlexperiment with natural abundance oxygen Cu2O. Thus all of the oxygen from the copper oxide catalyst ends up as siloxane; 50% of the oxygen in the product siloxane comes from other sources. Copper oxide catalyst was used in the presence of the phosphorus promoters Cu3P and PEt3. In both phosphorus promoter experiments, the resultant MCS lab beds were subjected toacetonitrile extraction and then NMR analysis of the extracts. Theseextracts showed that phosphorus-containing species were present and thatwhen Cu3P was the promoter, phosphorus products containing17O were present. Thus for Cu3P, some of thephosphorus reacts with the 17O from the Cu2O catalyst.  相似文献   

10.
《Analytical letters》2012,45(19):2183-2196
Abstract

A polarographic procedure was developed which permits the analysis of powdered cupric and cuprous oxides in the presence of metallic copper. To determine CuO, Cu2O and metallic copper content in the sample two weight aliquots were used. The first aliquot was dissolved in medium of 50 % ethanol + 3 M hydrochloric acid + saturated ascorbic acid solution. Insoluable metallic copper was determined polarographically after its' separation and additional dissolving in concentrated nitric acid.

The second sample aliquot was dissolved in 6 M hydrochloric acid and the ratio of Cu(I) / Cu(II) in the solution was determined from the polarographic curves. To calculate CuO, Cu2O and Cu content in a sample the proposed procedure was applied. The developed method provides the accurate results of the determination of CuO, Cu2O and Cu content in a powdered mixture. The reproducibility expressed as the relative standard deviation is from 1 % to 5 %.  相似文献   

11.
The thermal decomposition of copper(II) acetate monohydrate (CuAc2·H2O) under 500 °C in air was studied by TG/DTG, DTA, in situ FTIR and XRD experiments. The experimental results showed that the thermal decomposition of CuAc2·H2O under 500 °C in air included three main steps. CuAc2·H2O was dehydrated under 168 °C; CuAc2 decomposed to initial solid products and volatile products at 168–302 °C; the initial solid products Cu and Cu2O were oxidized to CuO in air at 302–500 °C. The copper acetate peroxides were found to form between 100 and 150 °C, and the dehydration of these peroxides resulted in the presence of CuAc2·H2O above 168 °C. The initial solid products were found to be the admixture of Cu, Cu2O, and CuO, not simply the single Cu2O as reported before. Detailed reactions involved in these three steps were proposed to describe the complete mechanism and course of the thermal decomposition of CuAc2·H2O in air.  相似文献   

12.
Oxidized copper surfaces have attracted significant attention in recent years due to their unique catalytic properties, including their enhanced hydrocarbon selectivity during the electrochemical reduction of CO2. Although oxygen plasma has been used to create highly active copper oxide electrodes for CO2RR, how such treatment alters the copper surface is still poorly understood. Here, we study the oxidation of Cu(100) and Cu(111) surfaces by sequential exposure to a low-pressure oxygen plasma at room temperature. We used scanning tunnelling microscopy (STM), low energy electron microscopy (LEEM), X-ray photoelectron spectroscopy (XPS), near edge X-ray absorption fine structure spectroscopy (NEXAFS) and low energy electron diffraction (LEED) for the comprehensive characterization of the resulting oxide films. O2-plasma exposure initially induces the growth of 3-dimensional oxide islands surrounded by an O-covered Cu surface. With ongoing plasma exposure, the islands coalesce and form a closed oxide film. Utilizing spectroscopy, we traced the evolution of metallic Cu, Cu2O and CuO species upon oxygen plasma exposure and found a dependence of the surface structure and chemical state on the substrate''s orientation. On Cu(100) the oxide islands grow with a lower rate than on the (111) surface. Furthermore, while on Cu(100) only Cu2O is formed during the initial growth phase, both Cu2O and CuO species are simultaneously generated on Cu(111). Finally, prolonged oxygen plasma exposure results in a sandwiched film structure with CuO at the surface and Cu2O at the interface to the metallic support. A stable CuO(111) surface orientation is identified in both cases, aligned to the Cu(111) support, but with two coexisting rotational domains on Cu(100). These findings illustrate the possibility of tailoring the oxidation state, structure and morphology of metallic surfaces for a wide range of applications through oxygen plasma treatments.

A low-pressure oxygen plasma oxidized Cu(100) and Cu(111) surfaces at room temperature. The time-dependent evolution of surface structure and chemical composition is reported in detail for a range of exposure times up to 30 min.  相似文献   

13.
Isotherms of copper cation sorption by H-ZSM-5 zeolite from aqueous and aqueous ammonia solutions of copper acetate, chloride, nitrate, and sulfate are considered in terms of Langmuir’s monomolecular adsorption model. Using UV-Vis diffuse reflectance spectroscopy, IR spectroscopy, and temperatureprogrammed reduction with hydrogen and carbon monoxide, it has been demonstrated that the electronic state of the copper ions is determined by the ion exchange and heat treatment conditions. The state of the copper ions has an effect on the redox properties and reactivity of the Cu-ZSM-5 catalysts in the selective catalytic reduction (SCR) of NO with propane and in N2O decomposition. The amount of Cu2+ that is sorbed by zeolite H-ZSM-5 from aqueous solution and is stabilized as isolated Cu2+ cations in cationexchange sites of the zeolite depends largely on the copper salt anion. The quantity of Cu(II) cations sorbed from aqueous solutions of copper salts of strong acids is smaller than the quantity of the same cations sorbed from the copper acetate solution. When copper chloride or sulfate is used, the zeolite is modified by the chloride or sulfate anion. Because of the presence of these anions, the redox properties and nitrogen oxides removal (DeNO x ) efficiency of the Cu-ZSM-5 catalysts prepared using the copper salts of strong acids are worse than the same characteristics of the sample prepared using the copper acetate solution. The addition of ammonia to the aqueous solutions of copper salts diminishes the copper salt anion effect on the amount of Cu(II) sorbed from these solutions and hampers the nonspecific sorption of anions on the zeolite surface. As a consequence, the redox and DeNO x properties of Cu-ZSM-5 depend considerably on the NH4OH/Cu2+ ratio in the solution used in ion exchange. The aqueous ammonia solutions of the copper salts with NH4OH/Cu2+ = 6–10 stabilize, in the Cu-ZSM-5 structure, Cu2+ ions bonded with extraframework oxygen, which are more active in DeNO x than isolated Cu2+ ions (which form at NH4OH/Cu2+ = 30) or nanosized CuO particles (which form at NH4OH/Cu2+ = 3).  相似文献   

14.
Cuprous oxide (Cu2O) was synthesized via reactions between cupric oxide (CuO) and copper metal (Cu) at a low temperature of 300 °C. This progress is green, environmentally friendly and energy efficient. Cu2O crystals with truncated octahedra morphology were grown under high pressure using sodium hydroxide (NaOH) and potassium hydroxide (KOH) with a molar ratio of 1:1 as a flux. The growth mechanism of Cu2O polyhedral microcrystals are proposed and discussed.  相似文献   

15.
A spectroscopic investigation of the products formed in the reaction of emeraldine base (EB-PANI) with copper(II) ions in dimethylacetamide (DMA) is presented. It is well known that metal cations can dope emeraldine base polyaniline (EB-PANI) through a pseudo-protonation reaction. Resonance Raman, UV–vis-NIR, and EPR data, obtained for Cu2+/EB-PANI solutions prepared using CuCl2·2 H2O, Cu(NO3)2· 3 H2O or Cu(CH3COO)2·H2O as Cu2+ sources, showed that the species formed in reactions of EB-PANI and Cu2+ ions are dependent on the anions of the copper salt employed. EPR spectra pointed out that the environments of Cu2+ ions with acetate, chloride or nitrate as anions in DMA solution are distinct. Resonance Raman and UV–vis-NIR data demonstrated that the main reactions are the oxidation of EB-PANI to pernigraniline base (PB-PANI) and doping of EB-PANI to ES-PANI (emeraldine salt) when a direct coordination of Cu2+ ions to PANI exists. With nitrate as very weak coordinating anion, ES-PANI is formed preferentially. When copper chloride is used, both oxidation and doping of EB-PANI are verified. Conversely with acetate, the dimeric cage structure of this copper salt is preserved in solution, and oxidation of EB-PANI to PB-PANI is the only observed reaction. These results demonstrate the possibility of modulating the products of reaction between Cu2+ ions and EB-PANI in DMA solution by changing the counter ion of the Cu2+ source.  相似文献   

16.
The electrochemical behaviour of the copper-substituted Keggin-type and sandwich-type polyoxotungstate anions of the compounds α-[(C4H9)4N]4H[PW11CuIIO39] and α-B-[(C4H9)4N]7H3[CuII4(H2O)2(PW9O34)2] was studied by cyclic voltammetry in acetonitrile. In both cases two copper 1-electron reduction waves were detected in the cathodic scan. The first one was due to the reduction of one CuII to CuI in the polyoxoanion and the second one to the consecutive reduction of the preformed CuI to Cu0, with the consequent deposition/adsorption of the ejected metal atom at the glassy carbon electrode surface. In the anodic scan, Cu0 was re-oxidised with regeneration of the initial copper(II) complexes, via a CuI intermediate. The observed two-step reduction of copper(II) to copper(0) and the formation of intermediate species containing copper(I) is here reported for the first time for copper substituted polyoxotungstates. The co-ordination of the acetonitrile molecules to the copper ions must play a role in the formation of the copper(I) species, which are not detected in aqueous solution.  相似文献   

17.
Polymeric complexes of [Cu2Cl2L2] copper(I) chloride (1) (L = N1,N2-bis(5-methylpyridin-2-yl)-oxalamide)) and {[Cu2(C2O4)Cl2L](L)·2H2O} copper(II) chloride (2) are obtained. The complexes are studied by powder and single crystal XRD. It is found that during the reaction of L with copper(II) chloride in the formation of complex 1 copper(II) is reduced to copper(I), while the formation of complex 2 is accompanied by the hydrolysis of the ligand.  相似文献   

18.
Experimental data on the synthesis of crystalline Cu, Cu2O, and CuO nanoparticles obtained earlier by the vapor-phase decomposition of copper(II) acetylacetonate (Cu(acac)2) were systematized and generalized. Studies were performed using a laminar flow reactor at atmospheric pressure within the ranges of precursor partial vapor pressure P prec = 0.06–44 Pa and reactor temperature from 432 to 1216°C. The decomposition of Cu(acac)2 was studied in an inert nitrogen atmosphere and in the presence of various reagents (water vapors, H2, O2, and CO). The composition of synthesized particles varied from pure copper to its oxides (Cu2O and CuO) depending on experimental conditions and used reagents. A semi-empirical kinetic model was proposed for describing the product dynamics. The hypothesis on the predominant role of copper dimers in a particles growth was stated. It was established that the composition of products is determined by the surface reactions on growing particles and is dependent on the ratio between the concentrations of the gaseous reagents. Calculated phase diagrams of the products of Cu(acac)2 decomposition in the presence of various reagents were in good agreement with experimental data. The proposed method of construction of the phase diagram of decomposition products can be employed for other systems. It was established that, upon the Cu(acac)2 decomposition in the presence of CO, carbon nano-onions were formed in addition to copper nanoparticles.Translated from Kolloidnyi Zhurnal, Vol. 67, No. 1, 2005, pp. 5–25.Original Russian Text Copyright © 2005 by Nasibulin, Shurygina, Kauppinen.  相似文献   

19.
Copper oxide impregnated activated carbon was prepared by three methods and studied as a respirator carbon. Using techniques such as dynamic flow testing, X-ray diffraction (XRD), thermal analysis, scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX), copper oxide impregnants, derived from different sources such as basic copper carbonate (Cu2CO3(OH)2), copper nitrate (Cu(NO3)2) and copper chloride (CuCl2) reacted with sodium hydroxide (NaOH), have been studied. Dynamic flow tests performed using sulfur dioxide (SO2), ammonia (NH3) and hydrogen cyanide (HCN) challenge gases allow the determination of the stoichiometric ratio of reaction (SRR) between challenge gas and impregnant. Thermal gravimetric analysis experiments showed that an inert heating environment was required when thermally decomposing the Cu(NO3)2 impregnant to CuO to avoid damaging the activated carbon substrate. SEM has been used to investigate dispersal and particle size of the impregnant on the activated carbon. XRD permits the identification of crystalline and amorphous phases as well as the grain size of the impregnant. XRD analysis of samples before and after exposure to SO2 has allowed the active impregnant in SO2 adsorption to be identified. The relationship between SRR, impregnant loading and grain size is discussed. Methods to improve impregnant distribution are presented and their impact discussed.  相似文献   

20.
One novel important application of sinter-based additive manufacturing involving binder jetting is copper-based products. Three different variants of nominally pure copper powder having particle size distributions with D90 < 16, 22, or 31 μm were investigated in this study. The packing behavior and the flow properties using dynamic test and shear cell, as well as specific surface area were evaluated. The analyses employed illustrate the multidimensional complexity. Because different measurements capture different aspect of the powder, it is imperative to apply a characterization approach involving different methods. Surface chemical analysis by means of X-ray photoelectron spectroscopy (XPS) showed that all powder variants were covered by Cu2O, CuO, and Cu (OH)2, with Cu2O being dominant in all cases. The finest powder with D90 < 16 μm tended to have higher relative amount of copper in divalent state. The average apparent oxide thickness estimated by XPS depth profiling showed that the two coarser variants had similar overall average oxide thickness, whereas the finest one possessed smaller oxide thickness. The surface chemistry of the powder grades is found to be related to their rheological behavior in dynamic condition. Considering the specific surface areas in combination with the average oxide thicknesses, the amount of surface bound oxygen was estimated to be about ~220 ppm for all three variants. Specific concerns need to be taken during the sintering of powder to keep oxygen level below that of electrolytic pitch copper (400 ppm).  相似文献   

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