993 resultados para Cu-Al system


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Structural relations between quasicrystalline and related crystalline rational approximant phases have been of interest for some time now. Such relations are now being used to understand interface structures. Interfaces between structural motif - wise related, but dissimilarly periodic phases are expected to show a degree of lattice match in certain directions. Our earlier studies in the Al-Cu-Fe system using the HREM technique has shown this to be true. The structural difference leads to well defined structural ledges in the interface between the icosahedral Al-Cu-Fe phase and the monoclinic Al13Fe4 type phase. In the present paper we report our results on the HREM study of interfaces in Al-Cu-Fe and Al-Pd-Mn systems. The emphasis will be on heterophase interfaces between quasiperiodic and periodic phases, where the two are structurally related. An attempt will be made to correlate the results with calculated lattice projections of the two structures on the grain boundary plane.

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Structural relations between quasicrystalline and related crystalline rational approximant phases have been of interest for some time now. Such relations are now being used to understand interface structures. Interfaces between structural motif - wise related, but dissimilarly periodic phases are expected to show a degree of lattice match in certain directions. Our earlier studies in the Al-Cu-Fe system using the HREM technique has shown this to be true. The structural difference leads to well defined structural ledges in the interface between the icosahedral Al-Cu-Fe phase and the monoclinic Al13Fe4 type phase. In the present paper we report our results on the HREM study of interfaces in Al-Cu-Fe and Al-Pd-Mn systems. The emphasis will be on heterophase interfaces between quasiperiodic and periodic phases, where the two are structurally related. An attempt will be made to correlate the results with calculated lattice projections of the two structures on the grain boundary plane.

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Thin foils of Cu, Au and Cu + Au alloys embedded in indium sesquioxide were equilibrated with controlled streams of CO-CO2 mixtures. The equilibrium concentrations of indium in the foils were determined by neutron activation analysis. The corresponding chemical potentials of indium were calculated from the standard free energies of formation of carbon monoxide, carbon dioxide, and indium oxide. It was found that the size difference between the solute and the solvent does not make significant contributions to the solute—solute interaction energy in the α-phase. The chemical potential of indium at one at.% concentration is 8.6 Kcals more negative in gold than in copper at 900°K. The variation of this chemical potential with alloy composition in Cu + Au system was in good agreement with Alcock and Richardson's quasichemical equation. The agreement is strengthened by the accurate knowledge of the co-ordination number in these substitutional solid solutions from X-ray diffraction studies.

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A detailed diffusion study was carried out on Cu(Ga) and Cu(Si) solid solutions in order to assess the role of different factors in the behaviour of the diffusing components. The faster diffusing species in the two systems, interdiffusion, intrinsic and impurity diffusion coefficients, are determined to facilitate the discussion. It was found that Cu was more mobile in the Cu-Si system, whereas Ga was the faster diffusing species in the Cu-Ga system. In both systems, the interdiffusion coefficients increased with increasing amount of solute (e.g. Si or Ga) in the matrix (Cu). Impurity diffusion coefficients for Si and Ga in Cu, found out by extrapolating interdiffusion coefficient data to zero composition of the solute, were both higher than the Cu tracer diffusion coefficient. These observed trends in diffusion behaviour could be rationalized by considering: (i) formation energies and concentration of vacancies, (ii) elastic moduli (indicating bond strengths) of the elements and (iii) the interaction parameters and the related thermodynamic factors. In summary, we have shown here that all the factors introduced in this paper should be considered simultaneously to understand interdiffusion in solid solutions. Otherwise, some of the aspects may look unusual or even impossible to explain.

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The amorphous phases of the Pd-Cu-P system has been obtained using the technique of rapidly quenching from the liquid state. Broad maxima in the diffraction pattern were obtained in the X-ray diffraction studies which are indicative of a glass-like structure. The composition range over which the amorphous solid phase is retained for the Pd-Cu-P system is (Pd100-xCux)80P20 with 10 ≤ x ≤ 50 and (Pd65Cu35)100-yPy with 15 ≤ y ≤ 24 and (Pd60Cu40)100-yPy with 15 ≤ y ≤ 24.

The electrical resistivity for the Pd-Cu-P alloys decreases with temperature as T2 at low temperatures and as T at high temperatures up to the crystallization temperature. The structural scattering model of the resistivity proposed by Sinha and the spin-fluctuation resistivity model proposed by Hasegawa are re-examined in the light of the similarity of this result to the Pt-Ni-P and Pd-Ni-P systems. Objections are raised to these interpretations of the resistivity results and an alternate model is proposed consistent with the new results on Pd-Cu-P and the observation of similar effects in crystalline transition metal alloys. The observed negative temperature coefficients of resistivity in these amorphous alloys are thus interpreted as being due to the modification of the density of states with temperature through the electron-phonon interaction. The weak Pauli paramagnetism of the Pd-Cu-P, Pt-Ni-P and Pd-Ni-P alloys is interpreted as being modifications of the transition d-states as a result of the formation of strong transition metal-metalloid bonds rather than a large transfer of electrons from the glass former atoms (P in this case) to the d-band of the transition metal in a rigid band picture.

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Dentre os óxidos de nitrogênio, o N2O é um gás do efeito estufa altamente nocivo. Devido ao potencial contaminante que este possui, torna-se importante a implementação de processos capazes de reduzir a sua emissão, bem como a dos NOx. Tradicionalmente, têm-se empregado catalisadores baseados em metais nobres, porém estes apresentam como principal desvantagem o elevado custo. Desse modo, sempre houve o interesse pelo uso de outros tipos de catalisadores e metais neste sistema de reação. Nesse contexto, na presente dissertação procurou-se sintetizar precursores de catalisadores tipo hidrotalcita Cu-AlCO3 e avaliar o seu desempenho na reação de redução do NO pelo CO, visando melhorar a atividade e a seletividade a N2. Foram estudados diversos parâmetros de síntese e diferentes composições. Os parâmetros mais influentes na síntese foram a relação molar H2O/(Al+Cu) e a temperatura de secagem do sólido, cujos melhores valores foram 434 e 25C, respectivamente. Testaram-se dois sólidos, o primeiro composto pela fase hidrotalcita quase pura e o segundo com uma clara mistura entre fases hidrotalcita e malaquita. As análises térmica e química revelaram presença da fase malaquita em ambos os materiais com porcentagens de 14 e 40%, respectivamente. Os resultados de difração de raios X indicaram a presença da fase CuO para os catalisadores provenientes da calcinação dos materiais tipo hidrotalcita, porém a espectroscopia Raman evidenciou a presença de Cu2O no catalisador proveniente do material com maior mistura de fases. Os ciclos redox mostraram uma melhora na redutibilidade dos catalisadores após um ciclo de oxidação-redução. Além disso, foi estudado o impacto do envelhecimento térmico a 900C por 12 h no desempenho dos catalisadores. Pelos resultados de teste catalítico os melhores desempenhos foram alcançados pelos catalisadores envelhecidos, contudo o catalisador proveniente do precursor mais puro apresentou-se melhor tanto novo como envelhecido em termos de menor rendimento de N2O. Uma comparação com catalisadores à base de metal nobre mostrou um bom desempenho dos catalisadores à base de cobre, com a vantagem destes apresentarem menor emissão de N2O em temperaturas menores

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、I钠原子激光增强电离光谱(LEIS)方法的研究-以石墨杯为原子化器在LEIS方法中,最常见的原子化器是火焰。但由于火焰背景噪声严重且难以克服,在火焰原子化过程中,雾化和热离解不充分,仅有10~(-2)%的分析溶液参与吸收以及火焰气体使测定元素受到高度稀释等不利因素的影响,火焰原子化限制了LEIS方法灵敏度的进一步提高。考虑到石墨炉原子化器较火焰具有取样量少,绝对灵敏度高;样品(包括固态、液态)可直接引入石墨炉内;不会发生如同火焰中所存在的干扰效应;蒸发效率和原子化效率较高,几乎全部样品都能参与吸收等优点,本工作在已建立火焰LEIS方法的实验基础上,将原子化器改换为石墨杯进行了钠原子LEIS方法的研究。到目前为止,国内外仅有的几篇有关石黑炉LEIS的研究报告中,都报导了该方法对钠原子的检出限估计可达到10~(-14)-10~(-15)克,由于此项研究尚处于探索性研究阶段,故有关方法性的系统研究几乎还未见报导。本工作在未使用任何放大器的情况下(实验条件限制)对影响钠原子LEIS信号强度的诸因互进行了实验观察。主要包括:钠原子化条件;激光束位置、阳极电压、激光输出能量、电极位置以及激光脉冲重复率对LEIS信号强度的影响等。并绘制了校准曲线,统计方法的相对标准偏差分别为11%(高浓度)18.2%(低浓度),在现有仪器条件下,还不能测出检出限,测定下限为3*10~(-9)克。对固体粉末直接进行了尝试,检测下限为5*10~(-8)克,进样是为5毫克。在进一步的研究工作中,如有条件使用低噪声的放大器及Bxear积分器,选择门检时间窗,或采用分步激发等手段,估计本方法定会达到预想的高灵敏度,检敏度至少提高了个数量级。对石墨炉原子化LEIS法来说,似比较详细的研究报告,截至实验停止时还未见报导。II原子吸收光谱法对发样中Zn、Cu、Mn、Al的测定发中微量元素ZN、Cu、Mn均属人体必需元素,与人体的生长发育和多种生理功能,临床医学等方面有着极为密切的关系,而Al则被认为是异致某种疾病的元素之一。本工作报告了用火焰法测定Zn、Cu;石墨炉法测定Al、Mn的结果,其中,对Al的测定,为摆脱基体干扰,加入改进剂Mg(NO_3)_2,并采用平台石墨炉进行试验,得到了线性较好的工作曲线,但在实际测定时,由于实验条件的限制,只能采用一般石墨管加基体改进剂对少娄样品中Al含量进行测定。Zn、Cu、Al三种元素由标准曲线法测定;而Mn由于Fe的干扰无法消除而采用标准加入法测定,并因此限制了测定样品数。Cu、ZN、Mn三种元素的回收率分别为102.8%, 99.7%, 102.5%,变异系数为9.6%, 11.3%, 9.7%,对本地居民发中(30个发样)Zn、Cu含量进行测定,Zn、Cu的含量范围为148-318ppm,7.2-15ppm,并计算了Zn/Cu比。本方法对发样中四种元素的测定结果与ICP法进行对照。两种方法测定结果吻合得较好。

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Al-Li合金是近年发展起来的新型航空材料,具有低密度、高强度的特点。目前世界上正就如何进一步提高其断裂韧性,使Al-Li合金尽早走出实验室,获得实际用进行广泛,深入的研究。熔盐电解法就是在这种情况下发展起来的。虽然此法现在尚处于研究的初级阶段,但已以其能够在较简单的设备上制备低Na高纯Al-Li合金的特点受到广泛的重视,是一种很有前途的发展方向。针对我国的技术、设备现状,在参考国外研究结果的基础上,采用熔盐电解法制备Al-Li母合金 → 应用合金的制备方法是可以尽快赶上世界发步伐的有效途径。因此,本文作为整个熔盐电解制备Al-Li合金系统研究的一部分,针对目前在此领域中很多应用基础问题,诸如:作为新的电解体系正在探索中的LiCl-KCl-LiF三元相图,Li在液体Al阴极中的扩散系数,利用熔盐电解法制备低Na高纯Al-Li合金的热力学基础及如何克服LiCl强烈的吸水性给电解工艺带来的种种不便等均未得到系统研究的现状,设计完成了一系列有关熔盐电化学和热力学实验,填补了本领域的一些研究空白,并为进一步系统研究工艺条件提供了重要的参考数据。1.用NH_4Cl氯化Li_2CO_3的研究 根据热力学从理论上论证了在200 ℃左右下述氯化反应:Li_2CO_3 + 2NN_4Cl = 2LiCl + 2NH_3~↑ + H_2O~↑ + CO_2~↑可以进行完全。利用DSC方法测定反应产物LiCl的纯度,并用离子色谱法分析反应产物中CO_3~=的含量,结果均证明:在Li_2CO_3:NH_4Cl = 1:4 (mol)时,Li_2CO_3可以定量转化为LiCl,剩余的NH_4Cl完全分解。根据热重分析结果推测NH_4Cl氯化Li_2CO_3的反应历程为:Li_2CO_3 + 2NH_4Cl = 2LiCl + 2NH_3~↑ + H_2O~↑ + CO_2~↑ NH_4Cl = HCl~↑ + NH_3~↑ 而并非是想像中的:NH_4Cl = HCl~↑ + NH_3~↑ 2HCl + Li_2CO_3 = 2LiCl + H2O~↑ + CO_2~↑利用X-射线衍射方法分析产物,结果亦说明氯化可以成功。将1:4(mol)= Li_2CO_3:NH_4Cl混合样品在差热分析反应炉中直接加热测定反应产物LiCl的溶点,并与纯LiCl样品熔点的测定结果相比较,二者完全一致。以上结果说明:不仅可用此氯化反应产物代替LiCl应用于熔盐电解制备Al-Li合金中,而且还可将其应用于LiCl体系的相图测定中。因Li_2CO_3,NH_4Cl均不吸水,极易处理,因此以上研究结果无论对于Al-Li合金的工艺研究还是其他有关LiCl体系的基础研究都是很有价值的。2.直接氯化法制备LiCl-KCl-LiF三元相图的研究。LiCl-KCl-LiF三元相图是研究此体系电解机制的重要基础。为将以上直接氯化法应用于差热分析中制作此三元体系相图,首先用直接氯化法测定了三个已知二元LiCl体系相图:LiCl-KCl;LiCl-LiF;LiCl-NaCl。与文献结果吻合很好。说明将此法应用于差热分析中制作LiCl体系相图结果是可靠的。在LiCl-KCl-LiF三元相图的测定中共做出七个垂直截面,在各截面上读出等温条件下的相界点投影到浓度三角形中,得到等温投影图。结果说明LiCl-KCl-LiF是固态完全不互溶的三元共晶体系,共有三个液-固两相区;三个液-固-固三相区;一个液-固-固-固四相区,(三元共晶平面)和一个固-固-固三相区。四相点温度为348 ℃,其组成在三相平衡线的交点处,在实验上测出近似等于:41.4KCl + 57.3LiCl + 1.3LiF (mol)。3.氯化物体系中Li~+, Na~+析出电位的比较及其去极化作用的研究。在正常电化序中,Li~+应先于Na~+析出。但在以Al作阴极电解LiCl体系时,则由于Li~+在Al上有较强的去极化作用而提前析出。这是熔盐电解法可以制备低Na,高纯Al-Li合金的基础。本文在理论上对此问题进行了较深入的研究。具体内容包括(1)。测定Li~+, Na~+在二元氯化物体系中的析出电位。通过在Al阴极,Mo阴极上二离子析出电位的比较,确认了Li~+在Al阴极上产生很强的去极化作用是能利用电解法制备低Na高纯Al-Li合金的根本原因。并为在工艺研究中选择合适的电流密度提供了参考依据。(2).根据热力学理论推导出合金化反应产生的自由焓变化与去极化作用的关系:ΔG_x + ΔG_m = -nFΔE。揭示了产生去极化作用的原因。并根据ΔG_x(偏摩尔过剩自由焓)与合金结构的关系提出可以利用二元合金相图推测极化类型及极化大小。并根据动力学原理对温度对极化的影响提出了自己的看法。(3).求出合金化反应的热效应,认为在一定条件下亦可利用此值作为判断去极化作用大小的标准。(4).测定Li~+, Na~+在Al-Cu, -Al-RE合金上的析出电位。结果表明Cu,RE的存在均可加强Li~+在阴极上的去极化作用,进一步加大了Li~+, Na~+析出电位之间的差别,有利于制备更纯的Al-Li 使金。为直接生产Al-Cu-Li, Al-RE-Li三元母合金奠定了基础。(5)测定Li~+在不同组成配比的LiCl-KCl熔体中,在Al阴极上的析出电位,并求出LiCl的离子平均活度系数γ=0.71 (T = 740 ℃), 熔体对理想状态产生负偏离。4.利用阳极计时电位法测定T=720 ℃时Li在液体Al中的扩散系数D_(Li/Al) = 4.94 * 10~(-5)cm~2·s~(-1),与利用Stocks-Einstan公式计算出的理论值D_(Li/Al) = 4.85 * 10~(-5)cm~2·s~(-1)吻合较好。5.在上述理论研究的基础之上进行了工艺初探,所得初步结论有:(1).加入LiF可以提高电效。(2).采用电流密度为1 A/cm~2时,不加搅拌亦可制备出成份均匀,含Li量为10%(w.f)的Al-Li合金。(3).根据实验结果提出 Li在熔体中的熔解可能是影响电流效果的主要原因。

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Methyl radicals are generated by pyrolysis of azomethane, and the condition for achieving neat adsorption on Cu(110) is described for studying their chemisorption and reaction characteristics. The radical-surface system is examined by X-ray photoemission spectroscopy, ultraviolet photoemission spectroscopy, temperature-programmed desorption, low-energy electron diffraction (LEED), and high-resolution electron energy loss spectroscopy under ultrahigh vacuum conditions. It is observed that a small fraction of impinging CH3 radicals decompose into methylene possibly on surface defect sites. This type of CH2 radical has no apparent effect on CH3(ads) surface chemistry initiated by dehydrogenation to form active CH2(ads) followed by chain reactions to yield high-mass alkyl products. All thermal desorption products, such as H-2, CH4, C2H4, C2H6, and C3H6, are detected with a single desorption peak near 475 K. The product yields increase with surface coverage until saturation corresponding to 0.50 monolayer of CH3(ads). The mass distribution is, however, invariant with initial CH3(ads) coverage, and all desorbed species exhibit first-order reaction kinetics. LEED measurement reveals a c(2 x 2) adsorbate structure independent of the amount of gaseous exposure. This strongly suggests that the radicals aggregate into close-packed two-dimensional islands at any exposure. The islanding behavior can be correlated with the reaction kinetics and is deemed to be essential for the chain propagation reactions. Some relevant aspects of the CH3/Cu(111) system are also presented. The new results are compared with those of prior studies employing methyl halides as radical sources. Major differences are found in the product distribution and desorption kinetics, and these are attributed to the influence of surface halogen atoms present in those earlier investigations.

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Copper-Aluminium Hydrotalcite-like compounds are synthesized by coprecipitation and characterized with XRD and IR. Catalysis of the above mentioned HTLcs are investigated in the phenol hydroxylation, good results are obtained. Meanwhile, the effects of the ratio of Cu/Al, reaction temperature, reaction medium and pH of reaction system are discussed, The reaction mechanism is also proposed.

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近年来对一些稀土和重金属离子在碱土金属硫化物的热释发光有过研究,,如CaS: Ce~(3+)和CaS:Bi~(3+)体系。N.Singh et al.(3)研究了CaS:Cu,Al以及CaS:Cu,Cl在UV辐照下热释发光峰值温度分别为80℃和75℃。我们用二甲亚砜硝酸钙为原料合成的CaS :Cu~+磷光体,在UV(366nm)辐照下,热释发光峰值温度大于100℃,峰值温度随铜离子浓度变化。

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The growth behavior of intermetallic layer with or without adding 0.3 wt% Ni into the Sn-0.7Cu solder was studied during the wetting reaction on Cu-substrate and thereafter in solid-state aging condition. The Cu-solder reaction couple was prepared at 255, 275 and 295 °C for 10 s. The samples reacted at 255 °C were then isothermally aged for 2-14 days at 150 °C. The reaction species formed for the Sn-0.7Cu/Cu and Sn-0.7Cu-0.3Ni/Cu soldering systems were Cu6Sn5 and (CuNi)6Sn5, respectively. The thickness of the intermetallic compounds formed at the solder/Cu interfaces and also in the bulk of both solders increased with the increase of reaction temperature. It was found that Ni-containing Sn-0.7Cu solder exhibited lower growth of intermetallic layer during wetting and in the early stage of aging and eventually exceeded the intermetallic layer thickness of Sn-0.7Cu/Cu soldering system after 6 days of aging. As the aging time proceeds, a non-uniform intermetallic layer growth tendency was observed for the case of Sn-0.7Cu-0.3Ni solder. The growth behavior of intermetallic layer during aging for both solders followed the diffusion-controlled mechanism. The intermetallic layer growth rate constants for Sn-0.7Cu and Sn-0.7Cu-0.3Ni solders were calculated as 1.41 × 10-17 and 1.89 × 10-17 m2/s, respectively which indicated that adding 0.3 wt% Ni with Sn-0.7Cu solder contributed to the higher growth of intermetallic layer during aging. © 2006 Elsevier B.V. All rights reserved.

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For the theoretical investigation of local phenomena (adsorption at surfaces, defects or impurities within a crystal, etc.) one can assume that the effects caused by the local disturbance are only limited to the neighbouring particles. With this model, that is well-known as cluster-approximation, an infinite system can be simulated by a much smaller segment of the surface (Cluster). The size of this segment varies strongly for different systems. Calculations to the convergence of bond distance and binding energy of an adsorbed aluminum atom on an Al(100)-surface showed that more than 100 atoms are necessary to get a sufficient description of surface properties. However with a full-quantummechanical approach these system sizes cannot be calculated because of the effort in computer memory and processor speed. Therefore we developed an embedding procedure for the simulation of surfaces and solids, where the whole system is partitioned in several parts which itsself are treated differently: the internal part (cluster), which is located near the place of the adsorbate, is calculated completely self-consistently and is embedded into an environment, whereas the influence of the environment on the cluster enters as an additional, external potential to the relativistic Kohn-Sham-equations. The basis of the procedure represents the density functional theory. However this means that the choice of the electronic density of the environment constitutes the quality of the embedding procedure. The environment density was modelled in three different ways: atomic densities; of a large prepended calculation without embedding transferred densities; bulk-densities (copied). The embedding procedure was tested on the atomic adsorptions of 'Al on Al(100) and Cu on Cu(100). The result was that if the environment is choices appropriately for the Al-system one needs only 9 embedded atoms to reproduce the results of exact slab-calculations. For the Cu-system first calculations without embedding procedures were accomplished, with the result that already 60 atoms are sufficient as a surface-cluster. Using the embedding procedure the same values with only 25 atoms were obtained. This means a substantial improvement if one takes into consideration that the calculation time increased cubically with the number of atoms. With the embedding method Infinite systems can be treated by molecular methods. Additionally the program code was extended by the possibility to make molecular-dynamic simulations. Now it is possible apart from the past calculations of fixed cores to investigate also structures of small clusters and surfaces. A first application we made with the adsorption of Cu on Cu(100). We calculated the relaxed positions of the atoms that were located close to the adsorption site and afterwards made the full-quantummechanical calculation of this system. We did that procedure for different distances to the surface. Thus a realistic adsorption process could be examined for the first time. It should be remarked that when doing the Cu reference-calculations (without embedding) we begun to parallelize the entire program code. Only because of this aspect the investigations for the 100 atomic Cu surface-clusters were possible. Due to the good efficiency of both the parallelization and the developed embedding procedure we will be able to apply the combination in future. This will help to work on more these areas it will be possible to bring in results of full-relativistic molecular calculations, what will be very interesting especially for the regime of heavy systems.

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A new series of high temperature copper based shape memory alloys has recently been patented. These alloys contain 8-20 wt% Al, 1-20 wt% Ag, 0-2 wt% of a minor element (preferably Co), balance copper. The martensitic start transformation temperatures of these alloys are above 200 degrees C and, in some cases, they have good high temperature stability and may be useful in commercial applications where higher operating temperatures than those obtained from Cu-Zn-Al and Cu-Al-Ni shape memory alloys are required.

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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)