Laser-induced changes in the electron density distribution of crystals: Ca3Cr2Si3O12

Difference of electron density distribution between a crystal being He–Ne laser-irradiated and non-irradiated has been investigated by in situ X-ray diffraction methods. Difference Fourier analysis between these data revealed electron density decrease of 2.1 eÅ^–3 at the trivalent site occupied 64% by Cr³⁺, the absorbant; while the calcium, silicon, and oxygen sites remained practically unchanged. Crystal data: [Natural uvarovite from Outokumpu, Finland; Ca₃(Cr_1.284Al_0.692Fe_0.024)Si₃O₁₂ (EPMA analysis); Cubic garnet structure; ;Z=8;a ₀=11.936(1) Å;V=1700.5 ų D _x =3.775 Mgm^–3; (MoK)=0.71069 Å; =4025 m^–1;F(000)=1900;T=293 K].     

Domain-wall energy in sintered Nd15Fe77B8 permanent magnet

From measurements of the magnetic domain widthsD versus grain thicknessL, we have determined the domain wall energy in the demagnetized state for a sintered Nd₁₅Fe₇₇B₈ magnet: = 56 erg/cm². Using this wall energy and the published magnetocry-stalline constantK ₁=4.9×10⁷ erg/cm³, we have calculated the exchange constantA=4.0×10^–6 erg/cm, domain wall thickness _B=89 Å, and the critical diameter for single domain particlesD _c=0.67 m.     

High Ni2+-mobility in the Chevrel phase Ni2Mo6S8: a quasielastic neutron scattering study

A quasielastic neutron scattering study of Ni₂Mo₆S₈ has established relatively fast long-range motion of the intercalated Ni²⁺ ions, with a diffusion constantD=3×10^–9 cm² s^–1. A model with a jump distance of about 2.1 Å and an activation energy of 24 kJ/mol is favoured. A critical consideration of the information contained in fixed window measurements is given.     

Chemical structure and internal diffusion within polymer chains in the melt

The single chain dynamics of polydimethylsiloxane in the melt is studied by means of quasielastic neutron scattering. For this polymer the wave vector range 0.03 Å^–1q0.30 Å^–1 covers the regime of universal modes as well as local diffusive processes. A model is described which incorporates the specific chemical structure of the macromolecule and allows to interpret our data in the full wave vector regime. The only parameter which enters the model, the monomer diffusion constantD _m, is found to be (1.2±0.2)·10^–5 cm²s^–1.     

Implantation doping of germanium with Sb,As, and P

The ions of Sb, As, and P have been implanted into germanium at energies ranging from 200 keV to 700 keV. Annealing was performed at 400°C, 550°C, and 650°C. The doping profile was determined by differentialCV-measurements. Strong outdiffusion (80%) and diffusion into the bulk material was observed after annealing. The remaining doping concentration and the diffusion constants were determined by a computer fit at 650°C. We foundD _Sb=1.8×10⁻¹³ cm²/s,D _As=9×10⁻¹⁴ cm²/s andD _P=4×10⁻¹⁴ cm²/s. Lower values of the diffusion constant were determined when the samples were covered with a SiO₂ layer.     

Au diffusion in α-Ti

The solubility and diffusion of Au in -Ti have been studied in a 823–1023 K temperature range using the Rutherford backscattering technique. For this purpose we have implanted Au into -Ti samples. Our results show that the solubility of Au varies between 0.2 and 0.35 at.%. In addition, we found that the diffusion coefficients follow a normal Arrhenius behavior with Q=260 kJ/mol and D _o=1.9×10^–5 m²/s¹. These values are typical for a substitutional diffusion mechanism.     

Volume and grain boundary diffusion of implanted 113Sn in aluminium

Volume and grain boundary diffusion of ¹¹³Sn in aluminium was investigated with the radiotracer method. The implantation technique was used for tracer deposition to avoid problems of tracer hold-up caused by the oxide layer always present on aluminium. The diffusion penetration was chosen large enough to permit serial sectioning of samples with the aid of a microtome.The temperature dependence of the volume diffusivity was determined as D(T)=4.54×10^–5×exp[–(114.5±1.2)kJmol^–1/RT] m ² s ^–1. This confirms previous measurements from our group which already showed that Sn is the fastest foreign metal diffusor so far investigated in aluminium.Grain boundary diffusion of ¹¹³Sn in Al polycrystals was measured in the type-B kinetic regime. The grain boundary diffusion product P=sD _gb (s=segregation factor, =grain boundary width, D _gb=grain boundary diffusivity) was found to be strongly affected by the impurity content of aluminium. For Al polycrystals of 99.9992% nominal purity we obtained P _5N(T)=1.08×10^–8exp [–(96.9±7.5) kJ mol^–1/RT] m³ s^–1 and for less pure Al polycrystals of 99.99% nominal purity P _4N(T)=3.0×10^–10 exp [–(90.1±4.2) kJ mol^–1/RT] m³ s^–1 was determined. The grain boundary diffusion product in the purer material is more than one order of magnitude higher than in the less pure material. Very likely this is an effect of co-segregation of non-diffusant impurities into the grain boundaries.     

Correlation between the Soret coefficient and the static structure factor in a polymer blend

Mutual mass diffusion and thermal diffusion has been investigated in poly(dimethylsiloxane)/ poly(ethylmethylsiloxane) (PDMS/PEMS) polymer blends of equal weight fractions. Molar masses ranged from below 1 to over 20 kg/mol. Both the mutual mass (D) and the thermal diffusion (D_T) coefficient contain a thermally activated factor with an activation temperature of 1415 K. The molar mass dependence of D_T is due to an end-group effect of the local friction coefficient. The thermal diffusion coefficient in the limit of long chains and infinite temperature is D_T^0, = - 1.69×10^-7cm²(sK)^-1. The Soret coefficient S_T of blends far enough away from a critical point is proportional to the static structure factor S(q = 0).     

The Ground StateXΣof NaK Revisited

Laser-induced fluorescence (LIF) optical spectra of theD¹Π–X¹Σ⁺system of the NaK molecule have been reinvestigated. In this new analysis, quantum numbers have been assigned to 3000 selected fluorescence lines for a wide range of vibrational and rotational levels (J≤ 149,v′ ≤ 23,v″ ≤ 47). A new set of constants of theX¹Σ state (Dunham-type coefficients) and term values of theD¹Π state have been determined by a weighted least-squares fit of the LIF optical lines of theD–Xsystem, some lines of theC–Xsystem, and microwave spectral data reported recently. Constants forX¹Σ (in cm⁻¹) are as follows: ω_e= 123.993, ω_ex_e= 0.3045,B_e= 0.095229, and α_e= 4.48 × 10⁻⁴. The equilibrium internuclear distance isr_e= 3.49903 Å, very little changed from the microwave value.     

Measurement of the average polarization of12B in the polarized-muon capture reaction12C(μ −,v μ)12B (g.s.)

The average polarization P_av of the recoil nucleus¹²B (ground state) produced by the polarized-muon capture reaction¹²C(^–,v )¹²B was measured by a new approach which involved the muon spin resonance, and the adoption of Grafoil as a carbon target where the polarization of¹² B can be preserved completely under 3 kG holding field. Our observed resultP _av=0.473±0.053 yields g_p/g_A=9.6 _–2.7 ^2.4 which seems to be consistent with the canonical PCAC prediction within the error.The authors would like to express their sincere thanks to the members of the Meson Science Laboratory and of the Van de Graaff Accerelator at Osaka University. They also acknowledge helpful discussions and suggestions given by Professors M. Morita, H. Ohtsubo and K. Kubodera. This work is supported by the Grant-in-Aid of the Ministry of Education, Science and Culture.     

Spectra of europium-doped yttrium oxide and yttrium vanadate phosphors

The spectral distributions of the visible absorption and fluorescence emission under electron beam excitation of Eu³⁺-doped (Y₂O₃) and (YVO₄) powders have been detected and analyzed. (Y₂O₃: Eu³⁺) has a cubicC crystal structure with a unit cell dimension a=10·61 Å. Its observed transitions from⁷ F ₀ to many upper states have been recognized; the observed number of Stark components is in agreement with that based on theC ₂ site symmetry of the Eu³⁺ ion in Y₂O₃. Eu³⁺-doped yttrium vanadate has a typical zircon tetragonal crystal structure with unit cell dimensions ofc=6·29 Å anda=7·11 Å. The observed transitions in (Eu³⁺: YVO₄) have been identified and assigned in accordance with theD _2d site symmetry of the Eu³⁺ ion in this lattice.The authors would like to express their deep gratitude to Professor G. F. J.Garlick, University of Hull, England, for offering experimental facilities in his Physics Department.     

X-ray superstructure determination of ordered oxygen and Cu-displacements in a single domain of YBa2Cu3O6.35

The superstructure of ordered oxygen atoms in a single domain of YBa₂Cu₃O_6.35 has been determined by X-ray diffraction. The 45^o rotated superstructure cell is orthorhombic—spacegroup Pbam, lattice constants , witha=3.8652(3) Å,c=11.815(2)Å the dimensions of the fundamental tetragonal cell. The arrangement of the oxygen atoms in the basal plane minimizes their electrostatic repulsion by avoiding near and next-near neighbors. There are displacements of copper atoms of 0.13 Å in the Cu(1) plane and 0.06 Å in the Cu(2) plane. Only 12% of the oxygen atoms in the basal plane contribute to the superstructure.     

Superconductivity,crystallization, and structural relaxation of the new metallic glass system La1−x Si x (0.15≤x≤0.27)

New metallic glass alloys have been prepared by melt spinning of La–Si samples in a pumped system. The superconducting transition temperature,T _c , increases linearly with the La concentration, from 3.00 K at 73 at. % La to 3.80 K at 85 at. %. Three new metastable phases: -, -, and -La₃Si, were formed by annealing and crystallizing amorphous La₃Si. Their crystal structures are orthorhombic (a=6.32 Å,b=8.06 Å,c=9.96 Å), hcp (a=10.55 Å,c=5.05 Å), and tetragonal (a=6.92 Å,c=5.05 Å) resp.T _c increased to 3.75 K, 6.00 K and 6.80 K, resp. During low temperature anneals of an amorphous La₃Si alloy,T _c changed logarithmically with time.On leave from Institute of Physics, Academica Sinica, Beijing, China     

Self-diffusion in liquid metals

A survey is made of all published data on self-diffusion in liquid metals and an examination is carried out on the temperature-dependence of D for studies covering a wide range of temperatures. Log D versus 1/T and D versus T represent the best data equally well, while D versus T ^1/2 and D versus T ² do not. The proper functional form is taken to be D=CT experimentally, and a simple free diffusion theory is developed from the standpoint of vibrational atom motion. An equation having no adjustable parameters results (D=k ² ? _D T/hk), in which κ is the vibrational force constant. Values calculated for D at the melting point are in good agreement with experimental values for potassium, sodium, copper and silver, but are below the measured values for lead, indium, zinc and tin.     

Heterodiffusion of Cr in molten Fe in the temperature range 1800 to 1970 K

Heterodiffusion of Cr has been studied using the method of thin layer and the radionuclide⁵¹Cr. The diffusion characteristics determined from the experimental results in the temperature range 1800 KT1970 K areD _o=1·59×10^–2 cm²/s andE=22·3±1·6 kcal/mol. The experimental method is discussed in detail and the results are compared with those of other authors.     

The sub-millimeter and Fourier transform microwave spectrum of HZnCl (X Σ)

The pure rotational spectrum of HZnCl (X ¹Σ⁺) has been recorded using sub-millimeter direct-absorption methods in the range of 439-540 GHz and Fourier transform microwave (FTMW) techniques from 9 to 39 GHz. This species was produced by the reaction of zinc vapor and chlorine gas with H₂ or D₂ in a d.c. glow discharge for the sub-millimeter studies. In the FTMW measurements, HZnCl was created in a discharge nozzle from Cl₂ and (CH₃)₂Zn. Between 5 and 10 rotational transitions were measured in the sub-millimeter regime for four zinc and two chlorine isotopologues; four transitions were recorded with the FTMW machine for the main isotopologue, each consisting of several chlorine hyperfine components. The data are consistent with a linear molecule and a ¹Σ⁺ ground electronic state. Rotational and chlorine quadrupole constants were established from the spectra, as well as an r_m⁽²⁾ structure. The Zn-Cl and Zn-H bond lengths were determined to be 2.0829 and 1.5050 Å, respectively; in contrast, the Zn-Cl bond distance in ZnCl is 2.1300 Å, longer by ∼0.050 Å. The zinc-chlorine bond distance therefore shortens with the addition of the H atom. The ³⁵Cl electric quadrupole coupling constant of eQq = −27.429 MHz found for HZnCl suggests that this molecule is primarily an ionic species with some covalent character for the Zn-Cl bond.     

Grain Boundary Diffusion and Segregation in Interstitial Solid Solutions Based on BCC Transition Metals: Carbon in Niobium

Bulk and grain boundary (GB) diffusion of ¹⁴C in Nb has been studied by the radiotracer serial sectioning technique. B and C kinetic regimes were realized for GB diffusion in the temperature range from 800 to 1173 K. The values of P = sD _gb, D _gb and s follow the Arrhenius dependencies: P = 5.15 × 10^–15 exp[–(83.1 kJ/mol)/RT] m³/s (973–1173 K), D _gb = 2.3 × 10^–6 exp[–(133.0 kJ/mol)/RT] m²/s (800–950 K), and s = 4.7 exp[(49.9 kJ/mol)/RT].The increase in the GB diffusion compared with self-diffusion is very large despite the probable retardation effect due to the strong segregation.The results for GB diffusion of C in Nb as well as for other interstitial solutes (P, S) in bcc transition metals (- Fe, Mo) are discussed in the framework of the transition state theory. It is assumed that GB segregation decreases the energy of the ground state whereas the change in the diffusion mechanism (e.g. from vacancy to interstitial) leads to a strong decrease of the transition state energy. This change in the diffusion mechanism results in a fast GB diffusion of interstitial solutes in spite of their large tendency to segregate to GBs.     

Crystal structure and thermal behavior of two new organic monosulfates NH3(CH2)5NH3SO4 1.5H2O and NH3(CH2)9NH3SO4 H2O

The chemical preparation, the calorimetric studies and the crystal structure are given for two new organic sulfates NH₃(CH₂)₅NH₃SO₄ 1.5H₂O (DAP-S) and NH₃(CH₂)₉NH₃SO₄·H₂O (DAN-S). DAP-S is monoclinic P2₁/n with unit cell dimensions: a=11.9330(2) Å; b=10.9290(2) Å; c=17.5260(2) Å; β=101.873(1)°; V=2236.77(6) Å³; and Z=8. Its atomic arrangement is described as inorganic layers of units and water molecules separated by organic chains. DAN-S is monoclinic P2₁/c with unit cell parameters: a=5.768(2) Å; b=25.890(10) Å; c=11.177(5) Å; β=115.70(4)°; V=1504.0(11) Å³ and Z=4. Its structure exhibits infinite chains, parallel to the [100] direction where the organic cations are interconnected. In both structures a network of strong and weak hydrogen bonds connects the different components in the building of the crystal.     

Diffusion of Au in amorphous Zr x Ni100−x alloys studied by Rutherford Backscattering Spectrometry

The diffusion coefficients (D) of Au in three binary amorphous Zr _x Ni_100–x (x=61, 65, and 67) alloys were measured in the temperature range 549–623 K using the technique of the Rutherford Backscattering Spectrometry (RBS). The D values were found to lie in the range 1.0×10^–21–9.0×10^–20 m²s^–1 for different alloys. The activation energy (Q) was calculated in each case on the basis of an observed Arrhenius temperature dependence of D. The activation energy was found to scale with the crystallization temperature (T _x) of the alloy. Other published measurements for Au diffusion in amorphous Zr-Ni alloys also appear to follow the scaling relation between Q and T _x.