Neue thermische Abbauprodukte von Ln2CeMO6Cl3 (M = Nb,Ta; Ln = La–Sm) – Darstellung von strukturverwandtem (La, Tb)3,5TaO6Cl4–x

Contributions on the Investigation of Inorganic Nonstoichiometric Compounds. XLV. New Thermal Decomposition Products of Ln₂CeMO₆Cl₃ – Preparation of Structure‐related (La, Tb)_3.5TaO₆Cl_4–x The thermal decomposition (T £ 900–1050°C) of Ln₂CeMO₆Cl₃ (M = Nb, Ta; Ln = La, Ce, Pr, Nd, Sm) leads to the formation of two mixed‐valenced phases (Ln, Ce)_3.25MO₆Cl_3.5–x (phase ‘‘AB”︁”︁) and (Ln, Ce)_3.5MO₆Cl_4–x (phase ‘‘BB”︁”︁) and to the formation of chlorine according to redox‐reactions between Ce⁴⁺ and Cl^–. Single crystals of both phases (Ln, Ce)_3.25MO₆Cl_3.5–x (‘‘AB”︁”︁) and (Ln, Ce)_3.5MO₆Cl_4–x (‘‘BB”︁”︁) were obtained by chemical transport reactions using both powder of Ln₂CeMO₆Cl₃ (phase ‘‘A”︁”︁) and powder of (Ln, Ce)_3.25MO₆Cl_3.5–x (phase ‘‘AB”︁”︁) as starting materials and chlorine (p{Cl₂; 298 K} = 1 atm) or HCl (p{HCl; 298 K} = 1 atm) as transport agent. A crystal of (La, Ce)_3.25NbO₆Cl_3.5–x (”︁AB”︁”︁) (space group: C2/m, a = 35.288(1) Å, b = 5.418(5) Å, c = 9.522(1) Å, β = 98.95(7)°, Z = 4) was investigated by x‐ray diffraction methods, a crystal of (Pr, Ce)_3.5NbO₆Cl_4–x (”︁BB”︁”︁) was investigated by synchrotron radiation (λ = 0.56 Å) diffraction methods. The lattice constants are a = 18.863(6) Å, b = 5.454(5) Å, c = 9.527(6) Å, β = 102.44(3)° and Z = 4. Structure determination in the space group C2/m (No. 12) let to R1 = 0.0313. Main building units are NbO₆‐polyhedra with slightly distorted trigonally prismatic environment for Nb and chains of face‐sharing Cl₆‐octahedra along [010]. The rare earth ions are coordinated by chlorine and oxygen atoms. These main structure features confirmed the expected relation to the starting material Ln₂CeMO₆Cl₃ (phase ”︁A”︁”︁) and to (Ln, Ce)_3.25MO₆Cl_3.5–x (phase ”︁AB”︁”︁).     

Compressive stress relaxation of metallocene‐based polyolefin foams: Effect of gamma‐ray‐induced crosslinking

Metallocene‐based polyolefin (MPO) foams possess a closed‐cell structure which is in contrast to the open‐celled structure of polyurethane (PU) foams. In this study, we investigate the effects of gamma‐irradiation on the mechanical behavior of MPO foams using PU foam behavior as a basis. Compressive step‐strain experiments reveal a two‐step relaxation process in MPO foams, dominated by polymer chain relaxation at short times and gas diffusion from the closed cells at longer times. On the other hand, the relaxation in PU foams is similar to fully crosslinked polymers with the relaxation modulus reaching an equilibrium value after an initial decay. The closed‐celled structure of MPO foams lends to rapid stress relaxation and low structural recoverability upon application of compressive loads. Exposure to gamma radiation induces crosslinking in MPO foams and improves their resilience and recoverability. Stress relaxation tests reveal that nonradiated MPO foams show complete relaxation and structural loss at high temperatures. In contrast, radiated MPO foams show a significant retardation in relaxation kinetics and structural stability attributed to radiation‐induced crosslinking. Dynamic rheology and solvent‐extraction studies also support the results obtained from stress‐relaxation experiments. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1045–1056, 1999     

Structure and dynamics of MG rubber studied by dynamic mechanical analysis and solid‐state NMR

Methyl‐methacrylate‐grafted natural rubber was prepared by free radical polymerization of methyl methacrylate in natural rubber latex, and their structure and dynamics were investigated by dynamic mechanical analysis and solid‐state nuclear magnetic resonance (NMR). Samples were prepared by chemical initiation and high‐energy radiation. The changes of glass transition temperature and tan δ max with different total poly(methyl methacrylate (PMMA) content are reported. The effect of the change in composition in copolymers on tan δ peak width, tan δ max, and area under the tan δ curve are used to understand the miscibility and damping properties. Solid‐state ¹³C‐NMR measurements were carried out to determine several relaxation time parameters, such as rotating frame and laboratory frame proton and carbon relaxation times. Cross polarization times and carbon relaxation times were interpreted based on the changes in the molecular motion. Proton relaxation times were interpreted based on the heterogeneity of the matrix. Results confirmed phase separation and a presence of an interfacial region. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1141–1153, 1999     

Fast Experiments for Charge-Density Determination: Topological Analysis and Electrostatic Potential of the Amino Acids L-Asn,dl-Glu,dl-Ser,and L-Thr

Synchrotron radiation and CCD detection give the possibility for fast diffraction experiments, which were employed to deduce the exact charge-density distributions of some amino acids. Their topological analysis (the figure shows the negative Laplacian function of dl -serine in the plane of the carboxylate group) yields not only comparable information about intramolecular but also about weak intermolecular interactions.     

Horizon problem in a closed universe dominated by fluid with negative pressure

We discuss the horizon problem in a universe dominated by fluid with negative pressure. We show that for generally accepted value of nonrelativistic matter energy density parameter Ω_m0 < 1, the horizon problem can be solved only if the fluid influencing negative pressure (the so-called “X” component) violates the point-wise strong energy condition and if its energy density is sufficiently large (Ω_X0 > 1). The calculated value of the Ω_X0 parameter allowing for the solution of the horizon problem is confronted with some recent observational data. Assuming that p_X/ρ_X < —0.6 we find that the required amount of the “X” component is not ruled out by the supernova limits. Since the value of energy density parameter Ω_v0 for cosmological constant larger than 1 is excluded by gravitational lensing observations the value of the ratio p_X/ρ_X should lie between the values —1 and —0.6 if the model has to be free of the horizon problem beeing at the same time consistent with observations. The value of Ω_X0 + Ω_m0 in the model is consistent with the constraints 0.2 < Ω_tot < 1.5 following from cosmic microwave background observations provided that Ω_m0 is low (<0.2).     

人造金刚石晶体缺陷的同步辐射X射线衍射形貌像浅析

利用同步辐射X射线对人造金刚石晶体缺陷进行了形貌学研究,实验采用了透射(劳埃)形貌术和反射形貌术两种方法.所得的X射线透射劳埃图上大部分斑点分别分布在四条主晶带上,经分析发现,该金刚石晶体主要的晶体缺陷为位错,并推导出晶体内部存在Frank不全位错.该晶体的反射形貌像中位错呈网状分布,说明其表层缺陷多于内部缺陷.此外,由形貌像分析发现该人造金刚石晶体的晶体缺陷明显少于天然金刚石.     

Nd:LuVO4晶体缺陷的研究

采用提拉法生长的Nd:LuVO4晶体是一种适合二极管泵浦的新型激光晶体,运用化学腐蚀结合光学显微术和同步辐射白光X射线形貌术对Nd:LuVO4晶体缺陷进行观察,结果表明:晶体的主要缺陷为位错和小角晶界.利用高分辨X射线衍射仪进一步验证了这一结果.并初步讨论了缺陷形成的原因.     

光学渡越辐射测量中能量分辨精度分析

 基于光学渡越辐射原理的用于高能强流电子束束流参数在线测量及诊断系统,具有时间响应快、分辨率高等特点,可以测量电子束的束剖面、发散角、能量等多个参数。分析了测量系统的结构参数（包括了透镜的焦距、成像面位置、CCD像元尺寸）对电子束能量测量精度的影响,并在理论上模拟了电子束的发散角的影响。还根据系统数据的特点,阐述了数据噪声对能量测量结果精度的影响,指出了光学渡越辐射测量中电子束能量分辨精度受到多种因素的影响,需要在数据处理时考虑修正。