Self-bonding in an amorphous polymer below the glass transition: A T-peel test investigation

Films of amorphous polystyrene (PS) with a weight-average molecular weight (M_w) of 225 × 10³ g/mol were bonded in a T-peel test geometry, and the fracture energy (G) of a PS/PS interface was measured at the ambient temperature as a function of the healing time (t_h) and healing temperature (T_h). G was found to develop with (t_h)^1/2 at T_h = T_g-bulk − 33 °C (where T_g-bulk is the glass-transition temperature of the bulk sample), and log G was found to develop with 1/T_h at T_g-bulk − 43 °C ≤ T_h ≤ T_g-bulk − 23 °C. The smallest measured value of G = 1.4 J/m² was at least one order of magnitude larger than the work of adhesion required to reversibly separate the PS surfaces. These three observations indicated that the development of G at the PS/PS interface in the temperature range investigated (<T_g-bulk) was controlled by the diffusion of chain segments feasible above the glass-transition temperature of the interfacial layer, in agreement with our previous findings for fracture stress development at several polymer/polymer interfaces well below T_g-bulk. Close values of G = 8–9 J/m² were measured for the symmetric interfaces of polydisperse PS [M_w = 225 × 10³, weight-average molecular weight/number-average molecular weight (M_w/M_n) = 3] and monodisperse PS (M_w = 200 × 10³, M_w/M_n = 1.04) after healing at T_h = T_g-bulk − 33 °C for 24 h. This implies that the self-bonding of high-molecular-weight PS at such relatively low temperatures is not governed by polydispersity. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1861–1867, 2004     

Rheological and physical properties of aliphatic hyperbranched polyesters

The effects of the size (pseudo‐generation number) and nature of end groups on physical and rheological properties were investigated for a series of hyperbranched polyesters based on an ethoxylated pentaerythritol core and 2,2‐bis‐(hydroxymethyl)propionic acid repeat units. The observed linear dependence of the melt viscosity on the molar mass in the high pseudo‐generation‐number limit indicated that entanglement effects were substantially absent. Moreover, the marked influence of end capping of the end groups on the physical and rheological properties suggested that intermolecular interactions were dominated by contacts between the outer shells of the molecules, in which the end groups were assumed to be concentrated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1218–1225, 2004     

Dependence of impurity incorporation upon substrate misorientation during GaAs growth by metalorganic vapour phase epitaxy

Doping studies of the incorporation behaviour of three different dopants (Zn, In and Si) versus the misorientation of the (100) surface during MOVPE growth of GaAs have been carried out with diethylzinc, trimethylindium and disilane as precursors. The incorporation of the dopants has been studied as function of the input mole fraction dopant, growth temperature, degree and direction of misorientation. In order to explain the results we discuss the BCF theory and the nature of the steps as function of above mentioned parameters. It appears that the BCF theory alone cannot explain the results, a counteracting mechanism has been introduced based on preferential arsenic desorption from the step edges.     

The equivalence problem

The equivalence problem is the problem of deciding whether two metric tensors are related by a coordinate transformation or not. I give a brief historical review of work done on this problem in Stockholm around 1980.     

Anionic polymerization of vinyl chloride

Anionic polymerization of vinyl chloride has been studied. Of the organometallic compounds tested as initiators, only butyllithium was found to initiate polymerization. Polymerization in bulk at 0°C and with tert-butyllithium as initiator gave poly(vinyl chloride) in a yield of 38% with M _n = 55,000. Tacticity of the anionic PVC was similar to that of conventional PVC prepared at similar temperatures. Anionic PVC was found to be less branched and more heat-stable than the conventional polymer.     

Advances in 14 MeV neutron activation analysis by means of a new intense neutron source

A new intense 14 MeV neutron generator with cylindrical acceleration structure has been put in operation at the GKSS Research Center Geesthacht. The sealed neutron tube is combined with a fast pneumatic rabbit system with particular capabilities for neutron activation analysis involving shortlived reaction products. The sample transfer time is less than 140 ms. The maximum neutron flux available for activation is 5.2·10¹⁰ n/cm²s. Theoretical sensitivity predictions made in a previous study have been verified for some important trace elements. As a first application, samples of freeze-dried suspended matter and fishes of the Elbe river were analyzed.     

Determination of stability constants of chelate complexes: Part II. Applications

The proposed simplified method for calculating the stability constants of chelate complexes from pH and pM measurements (Part I) is applied to two systems. On the basis of data reported by Österberg, the stability constants of copper o-phosphorylserylglutamic acid are calculated and good agreement is achieved. In addition, the stability constants of the mononuclear, binuclear and trinuclear silver complexes of TTHA (triethylenetetraminehexaacetic acid) were calculated from potentiometric pAg data. These calculations yielded the following values of the cumulative constants: log β_AgL=8.7, log β_AgHL= 17.6, log β_AgH2L= 23.8, log β_Ag2L= 14.0, log β_Ag2HL = 20.5, log β_Ag2H2L = 25.6, log β_Ag2L =17.0.     

Photometric titrations with indicators

Various types of photometric titration curves are discussed. If a metal M is titrated conipleximetrically using a metal indicator and the absorbance is plotted vs. the titrant consumed, the inflection point appears at a pM value defined by the equation 3 pM_infl = pM_trans + 2 pM_eqThis expression is valid when M combines in a 1 : 1 ratio with the complexing agent and the indicator and when the indicator concentration is small compared to the total metal concentration.The difference between the pM values at the inflection and equivalence points can be calculated from the equation ΔpM = pM_infl — pM_eq = $\text{1}\text{3}$(pM_trans — pM_eq) = $\text{1}\text{6}$log(C_MK²_MI/K_MY)If the inflection point is taken as the equivalence point, the error arising can be calculated from ΔpM, or more simply, read from a diagram.If transmittance, instead of absorbancc, is plotted as a function of the titrant volume, the inflection point depends on the added amount of indicator. However, at high transmittance values, i.e., at low indicator concentrations, the inflection point of a transmittance curve occurs practically at the same volume of added titrant as the inflection point of an absorbance curve. Rules are given for applying an indicator correction for the amount of metal bound to the indicator at the end-point.The derived equations and discussions can also be applied to acid-base titrations.     

Capillary isoelectric focusing of proteins utilizing poly(vinylpyrrolidone)- and plexiglas-coated columns

Fused-silica capillaries chemically derivatized with silane/poly(vinylpyrrolidone) (PVP) or dynamically modified with plexiglas [poly(methyl methacrylate)] were prepared and evaluated with regard to column stability and separation performance for capillary isoelectric focusing of standard proteins. The PVP coating showed the better stability and was good for at least 100 runs while the plexiglas coating started to deteriorate after about 30 runs. The time spent for the plexiglas coating is about 40 minutes while the PVP coating requires two days. The migration time reproducibility was better with the PVP capillary (RSD 0.7-1.6%, n = 5) compared to the plexiglas-coated column (RSD 1.2-2.9%, n = 5) while peak area and height varied over a similar interval (RSD 2-28.1% area; 0.9-22.7% height, n = 5). The two most consistent proteins in this evaluation, viz. myoglobin A and carbonic anhydrase II, showed linear dynamic ranges between 5-150 and 5-50 microg/mL, and limits of detections at 2 and 1 microg/mL, respectively, employing UV detection at 280 nm.     

Complexometric titration of Aluminium

A procedure is given for the complexometric titration of aluminium. A known volume of a standard solution of EDTA is added to the sample solution, and the excess is back-titrated with a zinc sulphate solution, dithizone being used as indicator. The titration is performed at pH = 4.0 — 4.5 and 40 — 50% alcohol is added as solvent for the indicator.The theoretical basis of the method is developed, and the theoretical titration error with various amounts of aluminium and zinc is calculated.The results of some titrations are given.