Synthesis and characterization of soluble (porphyrinato)iron(II) polymers

The use of (tetrakis(4-hexylphenyl)porphyrinato)Fe(II) in polymerization reactions with bidentate ligands such as 9,10-diisocyanoanthracene and 1,4-diisocyanobenzene led to well-defined stacked polymers1 and2 which are still soluble in common organic solvents such as chloroform, dichloromethane, and tetrahydrofurane. They have been completely characterized by¹H-NMR and UV/vis spectropscopy in solution, even allowing end-group analysis for determination of the average degree of polymerization, yieldingn=10 andn=5 for1 and2, respectively. Mößbauer and IR spectroscopy further established the strong Fe-CN bonding reflected by very small isomer shifts and quadrupole splittings (E _Q0.2 mm s^–1) and a large decrease in the IR stretching frequency (v _CN60 cm^–1). The axially stacked polymers exhibit semiconducting properties only upon doping.Presented at the 5th International Symposium on Macromolecule-Metal Complexes (MMV), Summer 1993 in Bremen, Germany.     

Rheology of poly(n‐butyl methacrylate) and its composites with calcium carbonate

Poly(n‐butyl methacrylate) (PBMA) composites with calcium carbonate (CaCO₃) were prepared by in situ radical copolymerization of butyl methacrylate (BMA) and methacrylic acid (MA) with precipitated calcium carbonate. To compare the different rheological behaviors of the monomer mixtures with CaCO₃ and the composites, the steady and dynamic viscosities of BMA/MA/CaCO₃ and poly(BMA/MA/CaCO₃) were measured by means of steady and oscillatory shear flows. The viscosity of the mixture BMA/MA/CaCO₃ was found to increase evidently with the increasing of CaCO₃%. The influence of MA% on viscosity of BMA/MA/CaCO₃ was slight. During the in situ polymerization, the viscosity of the reacting system was measured to be enhanced by a factor of about 10⁴ from the monomer/CaCO₃ mixture to composites. The dependency of zero‐shear viscosity on molar mass of PBMA was also investigated. The relation between the zero‐shear viscosity and molar mass is η₀ = 10^?15 M_w^3.5. The evolution of the viscosity with the temperature for both PBMA and its composites was obtained and time–temperature superposition was used to build master curves for the dynamic moduli. The flow activation energies were found to be 115.0, 148.6, and 178.7 kJ/mol for PBMA, composite PBMA/CaCO₃ (90/10), and PBMA/MA/CaCO₃ (89/1/10), respectively. The viscosity of the composites containing less than 10% CaCO₃ was lower than that of pure PBMA with the same molar mass. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1376–1383, 2003     

Engineering microfluidic papers: effect of fiber source and paper sheet properties on capillary-driven fluid flow

In the present study, we introduce a novel approach to control and modulate fluid transport inside microfluidic papers using lab-engineered paper sheets. Lab-sheets consisting of different fiber sources (eucalyptus sulfate and cotton linters pulp) and varying porosities were designed and further modified with small millimeter-scaled channels using hydrophobic barriers consisting of fiber-attached, hydrophobic polymers. The capillary-driven transport of an aqueous solution was monitored visually, and the influence of parameters such as fiber source, paper grammage, and channel width on the flow rates through the channel was investigated. The experimental results were compared with those obtained with commercially available filter papers. Our findings suggest that accurate control of fluid transport processes with standard filter papers is complex. Additionally, if the channel width is smaller than the mean fiber length, flow rates become dependent on the geometric parameters of the channel because of the formation of dead-end pores at the hydrophobic barriers. Finally, control of the paper sheets porosity, by varying the fiber density of the lab-made paper, affords the fabrication of chemically identical sheets whereby capillary flow is largely influenced and can be modulated accordingly by simple papermaking processes.     

Improved methods for evaluating the molar mass distributions of cellulose in kraft pulp

Multi‐angle laser light scattering (MALLS) was used to characterize birch kraft pulps with respect to their absolute molecular mass distributions (MMDs). The pulps were dissolved in lithium chloride/N,N‐dimethylacetamide and separated by size exclusion chromatography (SEC). The weight‐average and number‐average molecular masses of the cellulose fractions of the pulps obtained from the absolute MALLS measurements were compared with the molar masses obtained by direct‐standard‐calibration relative pullulan standards. Discrepancies between the two detection methods were found, and two ways of correlating the relative pullulan molar masses to the absolute molar masses were examined. In the first method, the correlation was made over a large range of molecular masses. The second method correlated the molecular masses of the standards to the molecular masses of samples by the calculation of fictitious, cellulose‐equivalent molar masses of the standards. With the preferred second method, a more correct MMD of kraft pulp samples could, therefore, be obtained from an SEC system calibrated with narrow standards. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1170–1179, 2003     

Detailed Molecular Structure Modeling – A Path Forward to Designing Application Properties of ldPE

Summary: This paper describes a step on the ambitious aim to “design” application properties of ldPE by first simulating the detailed molecular structure of a high‐pressure tubular reactor product. The reactor of a certain configuration produces under well‐defined operating conditions. The next step is to correlate the structure with the application properties. Finally, the sequence will be reversed in order to deduce the operating conditions, which lead to the desired product quality. Two‐dimensional distributions, in molecular weight and branching frequency, as well a two compartment models with a core and a shell stream were simulated and compared with experimental results. Therefore, CFD simulations were carried out to discretize the reaction medium. Samples were taken from both pilot and commercial plants. The TREF‐SEC analytical method was successfully applied in order to measure the microscopic structure of the material. The tremendous numerical problems were solved with the help of the software PREDICI .

Detailed MWD for a pilot scale reactor product.     

Application of the percolation model to gelation of an epoxy resin

The percolation model has been applied to the study of gelation of the TGDDM-DDS system (tetraglycidyldiaminodiphenylmethane–diaminodiphenylsulfone) at a mass concentration of 100–30. For each temperature the experimental viscosity curves are satisfactorily described by a percolation law. Using the degree of chemical reactions, X, as a variable, a very clear change in the reaction mechanism with temperature can be shown. Then a rate of advancement of effective reactions, Y, is defined. This value only takes intermolecular-type reactions into account, and is probably the only variable on which viscosity depends in a percolation law: η = B(1 ? Y/Y_c)^?p. We obtain Y_c= 0.45 and p= 2.0. Comparing X_c and Y_c at the gel point, we obtain information on the proportion of intramolecular reactions with temperature. It is also demonstrated that the critical percolation threshold agrees closely with the gel point determined experimentally on log G″= f(t) curves.     

Well-defined polymer precursors synthesized by RAFT polymerization of N,N-dimethylacrylamide/N-acryloxysuccinimide: random and block copolymers

N,N-dimethylacrylamide (DMA) and N-acryloxysuccinimide (NAS) were copolymerized by the reversible addition–fragmentation chain transfer (RAFT) polymerization technique, to obtain random and block copolymer precursors onto which different side-groups may be statistically grafted via the reactive NAS units. These reactive copolymers have interesting applications in various fields such as coatings and paints, water purification and biology. Random poly(DMA-co-NAS) copolymer chains were synthesized with a 75/25 molar ratio, high conversion, an excellent molecular weight (MW) control from 5000 to 130 000 g mol⁻¹, and low polydispersity index (M_w/M_n<1.1). Poly(DMA-b-NAS) block copolymers were synthesized by a two step method, in which a poly(DMA) homopolymer was prepared first and then used as macro-chain transfer agent to polymerize NAS. For example, a poly(DMA-b-NAS) sample was obtained with an average molecular weight of 44 300/7400 g mol⁻¹ corresponding to 447 DMA and 44 NAS units. Such block copolymers had not yet been synthesized by any controlled polymerization technique. They can be used to prepare polymers with exactly the same backbone and an increasing number of different side groups (e.g. hydrophobic, ionic or fluorescent).     

Effect of Step Size in Incremental Loading Tests

Using the crack-growth model, the deviation of real fracture stress from the stressing level measured by stepwise incremental loading with three starting modes is calculated. For both static and dynamic fatigue, the relative error depends only on the relative increment size and the crack-growth parameter, n. The usefulness of stepwise incremental loading for strength testing can be confirmed.     

Automated bank cheque verification using image processing and deep learning methods

Multimedia Tools and Applications - Automated bank cheque verification using image processing is an attempt to complement the present cheque truncation system, as well as to provide an alternate...