Mellum Island (southern North Sea): dynamic processes and sedimentary structures. I. Southern tidal flat, transition zone and high-surface.[p.72 (Blasensand) only][Translation from: Senckenbergiana Maritima 11, 59-113, 1979]

This partial translation of a longer article describes the phenomenon of ”Blasensand”. Blasensand is formed when sedimentation of dried out sand is suddenly flooded from above. A more detailed explanation of Blasensand is given in this translated part of the paper.

Absolute oscillator strengths for iron, copper, cadmium and gold measured by the atomic beam method

Absolute f-values for 7 transitions in the first spectra of 4 elements have been measured using the atomic beam absorption technique. The equivalent widths of the absorption lines are measured with a photoelectric scanner and the atomic beam density is determined by continuously weighing a part of it with a sensitive automatic microbalance. The complete theory is presented and corrections are calculated to cope with gas absorption by the deposit on the microbalance pan and atoms which do not stick to the pan. An additional correction for the failure of the assumption of effusive flow in the formation of the atomic beam at large densities has been measured experimentally.

The following f-values were measured:

Fe: f_λ3720 = 0.0430 ± 8%

Cu: f_λ3247 = 0.427 ± 4.5%, f_λ3274 = 0.206 ± 4.7%, f_λ2492 = 0.0037 ± 9%

Cd: f_λ3261 = 0.00190 ± 7%, f_λ2288 = 1.38 ± 12%

Au: f_λ2428 = 0.283 ± 5.3%

Comparison with other accurately measured f-values, where they exist, shows agreement within experimental errors.

Stationary absolute distributions for chains of infinite order

Let {Ƶ_n}^∞_{n = -∞} be a stochastic process with state space S₁ = {0, 1, …, D – 1}. Such a process is called a chain of infinite order. The transitions of the chain are described by the functions

Q_i(i⁽⁰⁾) = Ƥ(Ƶ_n = i | Ƶ_{n - 1} = i ⁽⁰⁾₁, Ƶ_{n - 2} = i ⁽⁰⁾₂, …) (i ɛ S₁), where i⁽⁰⁾ = (i⁽⁰⁾₁, i⁽⁰⁾₂, …) ranges over infinite sequences from S₁. If i⁽ⁿ⁾ = (i⁽ⁿ⁾₁, i⁽ⁿ⁾₂, …) for n = 1, 2,…, then i⁽ⁿ⁾ → i⁽⁰⁾ means that for each k, i⁽ⁿ⁾_k = i⁽⁰⁾_k for all n sufficiently large.

Given functions Q_i(i⁽⁰⁾) such that

(i) 0 ≤ Q_i(i⁽⁰) ≤ ξ ˂ 1

(ii)D – 1/Ʃ/i = 0 Q_i(i⁽⁰⁾) Ξ 1

(iii) Q_i(i⁽ⁿ⁾) → Q_i(i⁽⁰⁾) whenever i⁽ⁿ⁾ → i⁽⁰⁾,

we prove the existence of a stationary chain of infinite order {Ƶ_n} whose transitions are given by

Ƥ (Ƶ_n = i | Ƶ_{n - 1}, Ƶ_{n - 2}, …) = Q_i(Ƶ_{n - 1}, Ƶ_{n - 2}, …)

With probability 1. The method also yields stationary chains {Ƶ_n} for which (iii) does not hold but whose transition probabilities are, in a sense, “locally Markovian.” These and similar results extend a paper by T.E. Harris [Pac. J. Math., 5 (1955), 707-724].

Included is a new proof of the existence and uniqueness of a stationary absolute distribution for an Nth order Markov chain in which all transitions are possible. This proof allows us to achieve our main results without the use of limit theorem techniques.

Nature of the radical intermediates in a substituted cyclopropylcarbiny-allylcarbinyl system

We have sought to determine the nature of the free-radical precursors to ring-opened hydrocarbon 5 and ring-closed hydrocarbon 6. Reasonable alternative formulations involve the postulation of hydrogen abstraction (a) by a pair of rapidly equilibrating classical radicals (the ring-opened allylcarbinyl-type radical 3 and the ring-closed cyclopropylcarbinyl-type 4), or (b) by a nonclassical radical such as homoallylic radical 7.

[Figure not reproduced.]

Entry to the radical system is gained via degassed thermal decomposition of peresters having the ring-opened and the ring-closed structures. The ratio of 6:5 is essentially independent of the hydrogen donor concentration for decomposition of the former at 125° in the presence of triethyltin hydrdride. A deuterium labeling study showed that the α and β methylene groups in 3 (or the equivalent) are rapidly interchanged under these conditions.

Existence of two (or more) product-forming intermediates is indicated (a) by dependence of the ratio 6:5 on the tin hydride concentration for decomposition of the ring-closed perester at 10 and 35°, and (b) by formation of cage products having largely or wholly the structure (ring-opened or ring-closed) of the starting perester.

Relative rates of hydrogen abstraction by 3 could be inferred by comparison of ratios of rate constants for hydrogen abstraction and ortho-ring cyclization:

[Figure not reproduced.]

At 100° values of k_a/k_r are 0.14 for hydrogen abstraction from 1,4-cyclohexadiene and 7 for abstraction from triethyltin hydride. The ratio 6:5 at the same temperature is ~0.0035 for hydrogen abstraction from 1,4-cyclohexadiene, ~0.078 for abstraction from the tin hydride, and ≥ 5 for abstraction from cyclohexadienyl radicals. These data indicate that abstraction of hydrogen from triethyltin hydride is more rapid than from 1,4-cyclohexadiene by a factor of ~1000 for 4, but only ~50 for 3.

Measurements of product ratios at several temperatures allowed the construction of an approximate energy-level scheme. A major inference is that isomerization of 3 to 4 is exothermic by 8 ± 3 kcal/mole, in good agreement with expectations based on bond dissociation energies. Absolute rate-constant estimates are also given.

The results are nicely compatible with a classical-radical mechanism, but attempted interpretation in terms of a nonclassical radical precursor of product ratios formed even from equilibrated radical intermediates leads, it is argued, to serious difficulties.

The roles played by hydrogen abstraction from 1,4,-cyclohexadiene and from the derived cyclohexadienyl radicals were probed by fitting observed ratios of 6:5 and 5:10 in the sense of least-squares to expressions derived for a complex mechanistic scheme. Some 30 to 40 measurements on each product ratio, obtained under a variety of experimental conditions, could be fit with an average deviation of ~6%. Significant systematic deviations were found, but these could largely be redressed by assuming (a) that the rate constant for reaction of 4 with cyclohexadienyl radical is inversely proportional to the viscosity of the medium (i.e., is diffusion-controlled), and (b) that k_a/k_r for hydrogen abstraction from 1,4-cyclohexadiene depends slightly on the composition of the medium. An average deviation of 4.4% was thereby attained.

Degassed thermal decomposition of the ring-opened perester in the presence of the triethyltin hydride occurs primarily by attack on perester of triethyltin radicals, presumably at the –O-O- bond, even at 0.01 M tin hydride at 100 and 125°. Tin ester and tin ether are apparently formed in closely similar amounts under these conditions, but the tin ester predominates at room temperature in the companion air-induced decomposition, indicating that attack on perester to give the tin ether requires an activation energy approximately 5 kcal/mole in excess of that for the formation of tin ester.

Normal structures and automorphism groups of t-designs

Combinatorial configurations known as t-designs are studied. These are pairs ˂B, ∏˃, where each element of B is a k-subset of ∏, and each t-design occurs in exactly λ elements of B, for some fixed integers k and λ. A theory of internal structure of t-designs is developed, and it is shown that any t-design can be decomposed in a natural fashion into a sequence of “simple” subdesigns. The theory is quite similar to the analysis of a group with respect to its normal subgroups, quotient groups, and homomorphisms. The analogous concepts of normal subdesigns, quotient designs, and design homomorphisms are all defined and used.

This structure theory is then applied to the class of t-designs whose automorphism groups are transitive on sets of t points. It is shown that if G is a permutation group transitive on sets of t letters and ф is any set of letters, then images of ф under G form a t-design whose parameters may be calculated from the group G. Such groups are discussed, especially for the case t = 2, and the normal structure of such designs is considered. Theorem 2.2.12 gives necessary and sufficient conditions for a t-design to be simple, purely in terms of the automorphism group of the design. Some constructions are given.

Finally, 2-designs with k = 3 and λ = 2 are considered in detail. These designs are first considered in general, with examples illustrating some of the configurations which can arise. Then an attempt is made to classify all such designs with an automorphism group transitive on pairs of points. Many cases are eliminated of reduced to combinations of Steiner triple systems. In the remaining cases, the simple designs are determined to consist of one infinite class and one exceptional case.

New measurements on the absolute cosmic ray ionization from sea level to 1540 kilometers altitude

An air filled ionization chamber has been constructed with a volume of 552 liters and a wall consisting of 12.7 mg/cm² of plastic wrapped over a rigid, lightweight aluminum frame. A calibration in absolute units, independent of previous Caltech ion chamber calibrations, was applied to a sealed Neher electrometer for use in this chamber. The new chamber was flown along with an older, argon filled, balloon type chamber in a C-135 aircraft from 1,000 to 40,000 feet altitude, and other measurements of sea level cosmic ray ionization were made, resulting in the value of 2.60 ± .03 ion pairs/cm³ sec atm) at sea level. The calibrations of the two instruments were found to agree within 1 percent, and the airplane data were consistent with previous balloon measurements in the upper atmosphere. Ionization due to radon gas in the atmosphere was investigated. Absolute ionization data in the lower atmosphere have been compared with results of other observers, and discrepancies have been discussed.

Data from a polar orbiting ion chamber on the OGO-II, IV spacecraft have been analyzed. The problem of radioactivity produced on the spacecraft during passes through high fluxes of trapped protons has been investigated, and some corrections determined. Quiet time ionization averages over the polar regions have been plotted as function of altitude, and an analytical fit is made to the data that gives a value of 10.4 ± 2.3 percent for the fractional part of the ionization at the top of the atmosphere due to splash albedo particles, although this result is shown to depend on an assumed angular distribution for the albedo particles. Comparisons with other albedo measurements are made. The data are shown to be consistent with balloon and interplanetary ionization measurements. The position of the cosmic ray knee is found to exhibit an altitude dependence, a North-South effect, and a small local time variation.

Topology optimization of silicon anode structures for lithium-ion battery applications

This thesis presents a topology optimization methodology for the systematic design of optimal multifunctional silicon anode structures in lithium-ion batteries. In order to develop next generation high performance lithium-ion batteries, key design challenges relating to the silicon anode structure must be addressed, namely the lithiation-induced mechanical degradation and the low intrinsic electrical conductivity of silicon. As such, this work considers two design objectives of minimum compliance under design dependent volume expansion, and maximum electrical conduction through the structure, both of which are subject to a constraint on material volume. Density-based topology optimization methods are employed in conjunction with regularization techniques, a continuation scheme, and mathematical programming methods. The objectives are first considered individually, during which the iteration history, mesh independence, and influence of prescribed volume fraction and minimum length scale are investigated. The methodology is subsequently extended to a bi-objective formulation to simultaneously address both the compliance and conduction design criteria. A weighting method is used to derive the Pareto fronts, which demonstrate a clear trade-off between the competing design objectives. Furthermore, a systematic parameter study is undertaken to determine the influence of the prescribed volume fraction and minimum length scale on the optimal combined topologies. The developments presented in this work provide a foundation for the informed design and development of silicon anode structures for high performance lithium-ion batteries.