The ternary system CsCl−NaCl−LaCl3

The ternary system CsCl?NaCl?LaCl₃ was investigated by means of differential thermal analysis and X-ray powder diffraction analysis. There exists one congruently melting compound, Cs₂NaLaCl₆, crystallizing with the cubic elpasolite structure. No quasi-binary section exists for the whole system, however three binaries range from the ternary compound Cs₂NaLaCl₆ to NaCl, CsLa₂Cl₇ and Cs₃LaCl₆ resp., dividing the system in three areas of composition: one triangle, Cs₃LaCl₆?Cs₂NaLaCl₆?CsLa₂Cl₇, containing additionally a compound Cs₂LaCl₅ below 510°C, and the two areas CsCl?NaCl?Cs₂NaLaCl₆?Cs₃LaCl₆ and Cs₂NaLaCl₆?NaCl?LaCl₃?CsLa₂Cl₇, containing a mixed crystal range between LaCl₃ and Na₃La₅Cl₁₈. These areas could be further divided in five triangles, so that the whole system contains six Alkemade triangles.     

Limited stability of the pH reference material sodium tetraborate decahydrate (“borax”)

Thermogravimetric and X-ray powder diffraction analyses revealed that the pH reference material sodium tetraborate decahydrate (“borax”) is not a stable substance but, loosing some of its water of crystallization, transforms slowly into the pentahydrate. The connected pH changes of the solutions are opposite to and larger than, those expected according to the dilution value of the decahydrate as shown by differential potentiometric measurements. The transformation rate depends on the storing time in the closed original container, the time of and after the first exposure of the material to the atmosphere, the frequency of and the relative humidity during subsequent exposures, and the temperature. The transformation reaction is not understood in detail. However, the experiments showed that sodium tetraborate decahydrate is a reliable pH reference material, whose pH is constant within ΔpH=±0.005 within at least two years after preparation, even if occasionally exposed to the atmosphere. Further work will show whether this time limit can be somewhat extended.     

Elevation of the glass transition temperature in flexible‐chain semicrystalline polymers

In the idealized two‐phase model of a semicrystalline polymer, the amorphous intercrystalline layers are considered to have the same properties as the fully‐amorphous polymer. In reality, these thin intercrystalline layers can be substantially influenced by the presence of the crystals, as individual polymer molecules traverse both crystalline and amorphous phases. In polymers with rigid backbone units, such as poly(etheretherketone), PEEK, previous work has shown this coupling to be particularly severe; the glass transition temperature (T_g) can be elevated by tens of degrees celsius, with the magnitude of the elevation correlating directly with the thinness of the amorphous layer. However, this connection has not been explored for flexible‐chain polymers, such as those formed from vinyl‐type monomers. Here, we examine T_g in both isotactic polystyrene (iPS) and syndiotactic polystyrene (sPS), crystallized under conditions that produce a range of amorphous layer thicknesses. T_g is indeed shown to be elevated relative to fully‐amorphous iPS and sPS, by an amount that correlates with the thinness of the amorphous layer; the magnitude of the effect is severalfold less than that in PEEK, consistent with the minimum lengths of polymer chain required to make a fold in the different cases. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1198–1204, 2007     

A solution to Schrödinger's problem of non-linear integral equations

A solution of Schrödinger's system of non-linear integral equations determines the rate function of a large deviation principle for kernels with prescribed marginal distributions. This kind of large deviation principle has some meaning in quantum mechanics.Diffusion equations associated with Schrödinger equations have typically transition functions with singular creation and killing. Hence they provide measurable non-negative generally unbounded kernels which may vanish on sets with positive measure and which can possess infinite mass.For Schrödinger systems with such kernels, a solution is proved to exist uniquely in terms of a product measure. It is obtained from a variational principle for the local adjoint of a product measure endomorphism. The generally unbounded factors of the solution are characterized by integrability properties.     

Miscibility of polyester/nitrocellulose blends: A DSC and FTIR study

The miscibility of polyester/nitrocellulose blends was investigated by differential scanning calorimetry and Fourier-transform infrared (FTIR) spectroscopy. Two nitrocelluloses (NC) derived from wood and having different nitrogen contents (12.62 and 13.42%) were used. On the basis of the glass transition temperature criterion, poly(?-caprolactone) (PCL), poly(valerolactone), poly(ethylene adipate), and poly(butylene adipate) are miscible with nitrocellulose, whereas poly(α-methyl α-propyl β-propiolactone) and poly(α-methyl β-proiolactone) are immiscible. The T_g versus composition curves of PCL/NC blends do not follow a monotone function but exhibit a singular point at a critical PCL volume fraction of 0.51 for NC-1342 and 0.45 for NC-1262 in agreement with Kovacs' theory. A shift of 17 cm^-1 of the carbonyl stretching band was observed with PCL/NC blends and is taken as evidence for hydrogen bonding interaction between the PCL carbonyl group and NC hydroxyl group. The frequency difference between the free hydroxyl absorbance and the absorbances of the hydrogen-bonded species was found to be 85 cm^-1 in pure NC and 125 cm^-1 in PCL/NC blends; it indicates that the average strength of this interaction is stronger than the corresponding self-associated hydrogen bonding in pure NC. The presence of a dipole-dipole interaction between the nitrate-ester groups of NC and the carbonyl groups of the polyesters is reported. The relative strength of the hydrogen bonding and dipole-dipole interactions is discussed and correlated with polymer miscibility.