Synthesis,characterisation and catalytic activity of cadmium cobaltite nanoparticles: part 87

In this paper, we report the synthesis of cadmium cobaltite nanoparticles (CCNs) and their characterisation by X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM) and transmission electron microscope (TEM). The particles are spherical in shape and the average particle size is of the order of 20–30 nm. Its catalytic activity was investigated through the thermal decomposition of ammonium perchlorate (AP), composite solid propellants (CSPs), 5-nitro-2,4-dihydro-3H-1,2,4-triazole-3-one (NTO) and 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) using thermogravimetry (TG), TG coupled with differential scanning calorimetry (TG-DSC) and ignition delay measurements. The kinetics of thermal decomposition of AP + CCNs has also been investigated using isoconversional and model-fitting approaches, which have been applied to data for isothermal TG decomposition. The burning rate of CSPs was considerably enhanced by these nanoparticles. The ignition delays and activation energies are found to decrease when CCNs were incorporated in the system. The addition of CCNs to AP led to a shifting of the high-temperature decomposition peak towards lower temperature. All these studies show enhancement in the rate of decomposition of AP, NTO, HMX and CSPs.     

Synthesis and characterization of KNd2Ti3O9.5 nanocrystal and its catalytic effect on decomposition of ammonium perchlorate

A novel kind of perovskite type oxide KNd₂Ti₃O_9.5 nanocrystals with an average size of 12 nm were successfully fabricated by a stearic acid sol–gel method (SAM) using Ti(OBu)₄, KOH, Nd₂O₃ and stearic acid as the raw materials. X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to characterize the products. The catalytic effect of the KNd₂Ti₃O_9.5 nanoparticles on thermal decomposition of ammonium perchlorate (AP) was investigated by differential thermal analysis (DTA) and thermal gravimetry (TG) experiments. Results indicated that the obtained KNd₂Ti₃O_9.5 nanocrystals took on cubic structure and presented both good dispersibility and uniform crystallite size. Also, they have an intense catalytic effect on the thermal decomposition of AP. Adding 2% of KNd₂Ti₃O_9.5 nanoparticles to AP can obviously decrease the thermal decomposition temperature of AP by 50 °C, increase the heat of decomposition from 590 J g⁻¹ to 1659 J g⁻¹ and obviously quicken the decomposition reaction rate.     

Barium hydroxyapatite nanoparticles synthesized by citric acid sol-gel combustion method

Barium hydroxyapatite (BaHAP) nanoparticles have been synthesized by citric acid sol-gel combustion method using citric acid as a reductant/fuel and nitrate as an oxidant at a relatively low temperature of 600 °C. The thermal decomposition of nitrate-citrate xerogel was investigated by thermogravimetric/differential thermal analysis (TG/DTA) technique. The yielding powders calcined at 600 °C have been characterized by Fourier transform infrared (FT-IR), X-ray diffraction (XRD), and transmission electron microscope (TEM). The possible combustion process was presented.     

膨化高氯酸铵的制备及其性能研究

使用膨化剂在减压条件下制备出膨化高氯酸铵（AP）。利用扫描电镜、粒度分析仪、傅里叶红外光谱仪、比表面积仪、差示扫描量热仪、热失重分析仪及感度仪分别对膨化AP进行形貌分析和性能测试。结果表明:膨化AP颗粒表面具有沟壑,内部具有孔洞结构,粒径D₅₀=22.559 μm;与未膨化的原料AP相比,膨化AP低温分解温度提高16.0 ℃,高温分解温度提高6.7 ℃,分解热提高322.3 J/g;比表面积增大92.2%,吸湿性增大;极限撞击能为10 J,撞击感度提高。制备AP/HTPB(端羟基聚丁二烯)和膨化AP/HTPB复合推进剂并测定其燃速,膨化AP/HTPB复合推进剂燃速提高4.1%。     

Cu/Fe hydrotalcite derived mixed oxides as new catalyst for thermal decomposition of ammonium perchlorate

Cu/Fe mixed oxides (Cu/Fe-MOs) were prepared by calcination of Cu/Fe hydrotalcite (Cu/Fe-HT) precursors. They were used as new catalyst for thermal decomposition of ammonium perchlorate (AP) and their catalytic activity was studied by thermal gravimetric and differential thermal analysis. With the addition of 4 wt.% Cu/Fe-MOs, thermal decomposition of AP was accelerated by 104 °C. Higher catalyst addition favors further decomposition of AP. The catalytic activity order is: Cu/Fe-MOs-500 > Cu/Fe-MOs-800 > CuO·Fe₂O₃. The proposed catalytic mechanism is the presence of O₂⁻ on the surface of Cu/Fe-MOs which can simplify thermal decomposition of AP.     

纳米Cu对HTPB-AP推进剂性能的影响

为研究纳米铜Cu对丁羟推进剂性能的影响,制备了含纳米Cu的推进剂,作为比较,同时制备了含有纳米CuO的推进剂和空白推进剂试样。采用SEM和TG-DSC表征推进剂的形貌和热性能,采用靶线法测试推进剂的燃速,并拍摄推进剂的燃烧火焰。TG-DSC结果表明,纳米Cu和纳米CuO主要影响AP的高温热分解阶段,但是纳米CuO比纳米Cu对推进剂的热分解具有更好的催化作用。纳米Cu可使AP的终止热分解温度降低67.0 ℃,使推进剂的终止热分解温度降低24.7 ℃。燃速测试结果表明,纳米Cu和纳米CuO均可提高推进剂的燃速,但是纳米Cu对推进剂燃速的改善效果更显著。加入纳米Cu和纳米CuO后,推进剂在燃烧过程中均出现蓝色火焰。     

HTPB/PTMEG/DADMT聚氨酯弹性体的动态性能

以端羟基聚丁二烯(HTPB)、聚四氢呋喃醚二醇(PTMEG)和2,4-甲苯二异氰酸酯(TDI-100)为原料,二甲硫基甲苯二胺(DADMT)为扩链剂,制得聚氨酯弹性体(PUE)。采用力学性能测试、差示扫描量热(DSC)、动态力学分析(DMA)及热重分析(TG)研究了HTPB/PTMEG比值、HTPB相对分子质量对PUE性能的影响。结果表明,HTPB(羟值0.836mmol/g)/PTMEG质量比为1∶4时,PUE力学性能最佳,拉伸强度30.3MPa,撕裂强度99.8kN/m;PU0(0.8)的tanδ峰位于-56.2℃,0℃以后,tanδ值低于0.08,说明丁羟型PUE比PTMEG型具有更好的动态性能,且HTPB分子量高,动态性能好;丁羟型PUE具有更高的热稳定性。     

Plasma oxidation of electron beam evaporated cadmium thin films

Thin films of pure cadmium have been deposited using electron beam evaporation technique. Effect of radio frequency (RF) plasma oxidation on structural, optical and electrical properties of cadmium thin films has been investigated. It was found that the RF plasma treatment affects on the physical properties of the oxidized cadmium films. Transmittance values of 87% in the visible region and 90% in the near infrared region have been obtained for cadmium oxide (CdO) film oxidized at a plasma-processing power of 600 W. The optical energy gap, E_g, was found to increase as the RF plasma-processing power increases. The resistivity values of 3 × 10^− 3 and 5 × 10^− 3 (Ω cm) have been obtained for CdO films oxidized at RF plasma-processing powers of 550 and 600 W respectively.     

Bio-template route for facile fabrication of Cd(OH)2@yeast hybrid microspheres and their subsequent conversion to mesoporous CdO hollow microspheres

Cadmium oxide (CdO) microspheres with a porous hollow microstructure were prepared by a facile yeast mediated bio-template route. The yeast provides a solid scaffold for the deposition of cadmium hydroxide (Cd(OH)₂) from cadmium acetate and sodium hydroxide solutions to form the hybrid Cd(OH)₂@yeast precursor. Thermal conversions of this at above 500 °C in air have produced hollow CdO microspheres. The products were characterized by scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), X-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FT-IR), thermal gravimetric and differential thermal analysis (TGA-DTA), and Brunauer-Emmett-Teller (BET) surface analysis respectively. The obtained CdO microspheres have uniform size (length = 2.6 ± 0.4 μm; width = 2.0 ± 0.2 μm) and a well defined, continuous, mesoporous hollow microstructure. The shell is about 250-280 nm in thickness. The mechanism of formation of Cd(OH)₂@yeast precursor and its conversion to CdO hollow microspheres is discussed. In comparison with traditional template-directed method, the present strategy represents a general, economical and environmentally benign route for the formation of metal oxide hollow microspheres. These materials have potential applications in different fields such as encapsulation, drug delivery, efficient catalysis, battery materials and photonic crystals. The method presented can be extended to the synthesis of other inorganic hollow microstructures of different sizes and shapes by pre-selecting suitable bio-templates.     

Effect of cadmium oxide incorporation on the microstructural and optical properties of pulsed laser deposited nanostructured zinc oxide thin films

CdO doped (doping concentration 0, 1, 3 and 16 wt%) ZnO nanostructured thin films are grown on quartz substrate by pulsed laser deposition and the films are annealed at temperature 500 °C. The structural, morphological and optical properties of the annealed films are systematically studied using grazing incidence X-ray diffraction (GIXRD), energy dispersive X-ray analysis (EDX), scanning electron microscopy (SEM), atomic force microscopy (AFM), Micro-Raman spectra, UV–vis spectroscopy, photoluminescence spectra and open aperture z-scan. 1 wt% CdO doped ZnO films are annealed at different temperatures viz., 300, 400, 500, 600, 700 and 800 °C and the structural and optical properties of these films are also investigated. The XRD patterns suggest a hexagonal wurtzite structure for the films. The crystallite size, lattice constants, stress and lattice strain in the films are calculated. The presence of high-frequency E₂ mode and the longitudinal optical A₁ (LO) modes in the Raman spectra confirms the hexagonal wurtzite structure for the films. The presence of CdO in the doped films is confirmed from the EDX spectrum. SEM and AFM micrographs show that the films are uniform and the crystallites are in the nano-dimension. AFM picture suggests a porous network structure for 3% CdO doped film. The porosity and refractive indices of the films are calculated from the transmittance and reflectance spectra. Optical band gap energy is found to decrease in the CdO doped films as the CdO doping concentration increases. The PL spectra show emissions corresponding to the near band edge (NBE) ultra violet emission and deep level emission in the visible region. The 16CdZnO film shows an intense deep green PL emission. Non-linear optical measurements using the z-scan technique indicate that the saturable absorption (SA) behavior exhibited by undoped ZnO under green light excitation (532 nm) can be changed to reverse saturable absorption (RSA) with CdO doping. From numerical simulations the saturation intensity (I_s) and the effective two-photon absorption coefficient (β) are calculated for the undoped and CdO doped ZnO films.     

Preparation,characterization and catalytic behavior of copper oxide nanoparticles on thermal decomposition of ammonium perchlorate particles

In this study, copper oxide nanoparticles (CuO NPs) with mean particle size of 43–32?nm were prepared by wet grinding of commercial micronized CuO powders in a high-energy wet ball-milling apparatus during 20 and 30?h, respectively. X-ray diffraction (XRD) and field emission scanning electron microscope (FE-SEM) analyses were used to characterize the structure, mean particle size and morphology of the resulting CuO NPs. The results confirmed that the CuO NPs obtained at different milling times consist of nanostructures with nearly spherical morphology and by increasing the milling time, smaller particle size was obtained. The catalytic activities of the synthesized CuO NPs on the thermal decomposition of ammonium perchlorate (AP) particles were examined through differential scanning calorimetry and thermogravimetry (DSC/TG) analyses. Evaluation of the experimental results illustrated that the surfaces of CuO NPs were effectively coated with AP particles and by adding 5%CuO NPs with 32?nm, the thermal decomposition temperature of the treated particles reduced by 83.0°C and the heat of decomposition reached 1553.7?Jg^?1. Moreover, the kinetic and thermodynamic parameters of the thermal decomposition of pure and AP?+?5%CW30 nanocomposites have been investigated by using the Kissinger, Boswell and Ozawa methods.     

Electrochemical deposition and characterization of elongated CdO nanostructures

CdO nanostructures were synthesized by electrodeposition on the indium doped tin oxide conducting glass substrate at low temperatures (70, 80 and 90 °C) from aqueous solution. Scanning electron microscopy (SEM), X-ray diffraction (XRD), UV-vis spectroscopy and X-ray photoelectron spectroscopy (XPS) were employed to characterize the CdO nanostructures. The results demonstrated that the CdO nanostructures synthesized by electrodeposition grew preferably along the [1 1 1] and have face-centered cubic CdO structures and possessed good crystallinity. XPS measurements showed that the nanostructures had Cd and O elements present in the oxide state and no traces of metallic Cd were observed. The nanostructures were highly transparent in the visible region of spectrum and their energy gap was about 2.45 eV.     

Low resistivity transparent conducting CdO thin films deposited by DC reactive magnetron sputtering at room temperature

Transparent conducting cadmium oxide (CdO) films were deposited on PET (polyethylene terephthalate) substrate by DC reactive magnetron sputtering at room temperature. All the films deposited at room temperature were polycrystalline in rock-salt structure. Dependences of the physical properties of the CdO films on the oxygen partial pressure were systematically studied. The films deposited at low oxygen flow rate were (200) oriented, while the films deposited at an oxygen flow rate greater than 20 sccm were (111) oriented. The average grain size of the CdO films decreased as the oxygen flow rate increases as determined by XRD and SEM. The Hall effect measurement showed that CdO films have high concentration, low resistivity, and high mobility. Both the mobility and the concentration of the carrier decreased with the increase of the oxygen flow rate. A minimum sheet resistance of 36.1 Ω/□, or a lowest resistivity of 5.44 × 10^− 4 Ω cm (6.21 × 10²⁰/cm³, μ = 19.2 cm²/Vs) was obtained for films deposited at an oxygen flow rate of 10 sccm.     

Growth and characterization of an organic nonlinear optical material: l-alanine alaninium nitrate

l-alanine alaninium nitrate (LAAN), an organic nonlinear optical material was grown by slow evaporation technique at room temperature from its aqueous solution at pH value of 2.5. As grown single crystals were characterized for its spectral, thermal, linear and second order nonlinear optical properties. LAAN crystallizes in monoclinic system with space group P₂₁ and cell parameters a = 7.846 Å, b = 5.431 Å, c = 12.806 Å and β = 94.65°. The mode of vibrations of different molecular groups present in LAAN were identified by FTIR studies. The thermal behaviour of the crystals has been investigated using thermogravimetry (TG) and differential thermal analysis (DTA), which indicates that the material does not decompose before melting. Transmittance spectrum reveals that the crystal has a low UV cut-off of 320 nm and has a good transmittance in the entire visible region. NLO property of the crystal was confirmed by Kurtz SHG powder technique.     

Structural and gas sensing behavior of nanocrystalline BaTiO3 based liquid petroleum gas sensors

In this paper nanosized BaTiO₃ thick films based gas sensor has been fabricated for liquid petroleum gas (LPG). Doping with different concentrations of metal oxides influenced the sensitivity of BaTiO₃ thick films for LPG sensor. We present the characterization of both their structural properties by means of X-ray powder diffraction (XRD) and the electrical characteristics by using gas-sensing properties. X-ray powder diffraction analyses revealed the persistence of cubic phase with grain growth 65 nm. The LPG-sensing properties of BaTiO₃ thick films doped with CuO and CdO are investigated. It was found that 10 wt.% CuO: 10 wt.% CdO doped BaTiO₃ based LPG sensor shows better sensitivity and selectivity at an operating temperature 250 °C which is an important commercial range for LPG alarm development. Incorporation of 0.3 wt.% Pd doped CuO:CdO:BaTiO₃ element shows maximum sensitivity with high cross selectivity to the other gases including CO, H₂ and H₂S at an operating temperature 225 °C for low concentrations of LPG sensor.     

Large-scale synthesis of highly pure Cd metal hexagonal nanosheets

Highly pure and large-scale single crystalline cadmium (Cd) metal hexagonal nanosheets with 10-12 nm thickness were obtained by catalyst-free thermal decomposition of cadmium oxide (CdO) powder under nitrogen gas at 1000 °C. The as-prepared product was characterized by X-ray diffraction, energy dispersive X-ray spectroscopy, scanning electron microscopy, transmission electron microscopy and selected area electron diffraction. Room temperature photoluminescence (PL) spectrum for Cd nanosheets exhibited three very distinct emission bands at 360 nm, 402 nm and 426 nm. UV emission band at 360 nm is attributed to radiative recombination of electrons in the s, p conduction band near the Fermi surface and the holes in the d bands generated by xenon light excitation whereas visible emission bands at 402 nm and 426 nm may be due to surface oxidation effects or induced defects in the nanosheets. The growth mechanism for the formation of Cd metal hexagonal nanosheets is also proposed and discussed briefly.     

Physicochemical properties and theoretical explanation of ZnCd(SCN)4 crystal

The crystal density and Mohs hardness of zinc cadmium thiocyanate (ZCTC), ZnCd(SCN)₄ have been measured at room temperature. The specific heat of the crystal is 699.5 J mol⁻¹ K⁻¹ at 300 K. The thermal expansion coefficient (TEC) along the a and c axes, respectively, is interpreted on the basis of crystal structure. The thermal decomposition process is characterized by thermogravimetry analysis and differential scanning calorimetry (TGA/DSC). The intermediates and final products of the thermal decomposition were identified by X-ray powder diffraction at room temperature. The high-temperature effect in air on the optical transmission of the crystal was also studied.     

Fabrication of metallic Cd multifarious prismatic microcrystals (CMPMCs) under NH3 gas ambient

We report here highly dense and pure metallic cadmium (Cd) multifarious prismatic microcrystals (CMPMCs) fabricated by thermal decomposition of cadmium oxide (CdO) powder at 700 °C for 60 min under NH₃ gas ambient inside horizontal tube furnace. CMPMCs were observed to be 1-1.5 μm in size with interesting morphologies of various cross sections such as triangular, trapezoidal, pentagonal and hexagonal etc. having solid, hollow/semi-hollow appearances. The as-synthesized CMPMCS were characterized by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) and selected area electron diffraction (SAED). Room temperature photoluminescence (PL) spectrum for Cd metal microcrystals exhibited a prominent emission band at 365 along with a shoulder peak at 404 nm. The UV main emission band is ascribed to radiative recombination of the electrons in the s, p conduction band near the Fermi surface and holes in the d bands generated under xenon light excitation whereas shoulder peak may be owing to surface oxidation effects or induced defects. This study shows the potential of CMPMCs for applications in optical devices. Based on vapour-solid (VS) process, growth mechanism for the formation of CMPMCs is also proposed and discussed briefly.     

Annealing studies on the structural and optical properties of electrodeposited CdO thin films

Cadmium oxide (CdO) thin films were electrodeposited on indium doped tin oxide glass substrates from aqueous solution and subsequently annealed at higher temperatures up to 600 °C in air, oxygen and inert gas ambients, respectively. The effect of annealing on the morphology, crystalline quality and optical properties of CdO films was investigated. The CdO films were polycrystalline in nature and the grain size strongly depended on the annealing temperature as well as annealing ambient. CdO films were highly transparent in the visible region of the spectrum. The transmittance of the films decreased with increasing annealing temperatures in all the three ambients. Optical bandgap of the nanocrystalline CdO films varied in the range of 2.20–2.54 eV.     

纳米HMX的制备及热性能分析和感度研究

采用机械球磨法批量制备了纳米奥克托今(HMX),用激光粒度仪分析其粒度分布,并用扫描电子显微镜(SEM)观察其大小和形貌;使用热重分析仪(TG)和差示扫描量热仪(DSC)分析其热分解特性和热安定性;同时对纳米HMX的5 s爆发点和感度进行了测试。结果表明,制备的HMX颗粒大部分在100 nm以下;与原料HMX相比,纳米HMX的最大热失重温度降低了3.66℃,表观活化能E a降低了11.19 kJ/mol,自发火温度降低了2.11K;5s爆发点降低了4.9℃,纳米HMX的静电感度和火焰感度与原料HMX相当,纳米HMX的摩擦感度、撞击感度和冲击波感度分别降低了32.5%、20.2%和56.4%。