State estimation for high-dimensional chemical processes

The application of conventional observer designs for high-dimensional systems may not always be practical due to high computational requirements or the resulting observers being too sensitive to measurement noise. In order to address these issues, this paper presents two observer design techniques for state estimation of high-dimensional chemical processes. One technique is used for systems with inputs, whereas the other one is specifically geared towards systems that are not excited from the outside. Both of these observers are applicable to linear and with a modification to non-linear systems.The main idea behind the presented observer designs is that a reduced-order observer is implemented instead of a conventional state estimator. The motivation is that subspaces, which are close to being unobservable, cannot be correctly reconstructed in a realistic setting due to measurement noise and inaccuracies in the model. The presented approaches make use of this observation and only reconstruct the parts of the system where accurate state estimation is possible. The observer designs are illustrated on a 30-tray distillation column model. Additionally, it has been shown that the location of process measurements has a major effect on the performance of the presented reduced-order observers.     

Acoustic emission behavior of epoxies during tensile loading

The acoustic emission behavior during tensile loading of two common epoxy systems of different ductility was investigated at different loading rates. At low threshold voltage, it was possible to register acoustic emissions before the final failure. Only very few emissions were recorded compared with the amount commonly recorded for metals and composite materials. The acoustic emissions detected were of burst-type, revealing a brittle damage accumulation process. They originated from the initiation and incremental growth of microcracks of stochastic nature. The events occurred before gross yielding and during the final “brittle” failure process. Basically no events were detected between gross yielding and the final failure during which large scale yielding, necking, and stable crack growth took place. The occurrence of events at the different loading rates was strongly influenced by the yielding behavior and fracture toughness, characterized by the yield stress σ_y and the plane-strain fracture toughness K_Ic respectively. K_Ic was inversely dependent on the total number of events up to gross yielding. The event distribution normalized with respect to the conditions at gross yielding was hardly affected by the loading rate.     

An in situ Raman study of the intercalation of supercapacitor-type electrolyte into microcrystalline graphite

An initial Raman study on the effects of intercalation for aprotic electrolyte-based electrochemical double-layer capacitors (EDLCs) is reported. In situ Raman microscopy is employed in the study of the electrochemical intercalation of tetraethylammonium (Et₄N⁺) and tetrafluoroborate (BF₄⁻) into and out of microcrystalline graphite. During cyclic voltammetry experiments, the insertion of Et₄N⁺ into graphite for the negative electrode occurs at an onset potential of +1.0 V versus Li/Li⁺. For the positive electrode, BF₄⁻ was shown to intercalate above +4.3 V versus Li/Li⁺. The characteristic G-band doublet peak (E_2g2(i) (1578 cm⁻¹) and E_2g2(b) (1600 cm⁻¹)) showed that various staged compounds were formed in both cases and the return of the single G-band (1578 cm⁻¹) demonstrates that intercalation was fully reversible. The disappearance of the D-band (1329 cm⁻¹) in intercalated graphite is also noted and when the intercalant is removed a more intense D-band reappears, indicating possible lattice damage. For cation intercalation, such irreversible changes of the graphite structure are confirmed by scanning electron microscopy (SEM).     

Physical gelation of crystallizing metallocene and Ziegler-Natta ethylene-hexene copolymers

The effect of molecular architecture on the evolution of viscoelastic properties during crystallization was investigated using ethylene-hexene copolymers manufactured via metallocene (M-LLDPE) and Ziegler-Natta (ZN-LLDPE) processes. Differences in branching distribution were shown to have a drastic effect on the viscoelastic properties near the gel point. It is shown that the branching distribution rather than branch content is the determining parameter for the evolution of the rheological properties during isothermal and non-isothermal crystallization, and for the width of the solidification interval. We developed a partial melting technique for the preparation of stable critical gels of LLDPE whose viscoelastic properties correspond to the intermediate state between melt and solid. Local molecular conformation and crystallinity in these gels were characterized by Raman spectroscopy, which shows that the transition from melt-like to solid-like rheological behavior (physical gelation) in LLDPE occurs at a very low overall crystallinity of less than 5%.     

Piezo- and pyroelectricity in polymer blends of poly(vinylidene fluoride)/poly(methyl methacrylate)

Compatible polymer blends of poly(vinylidene fluoride) (PVDF) and poly(methyl methacrylate) (PMMA) can be used as suitable model systems for investigating the relationship between the physico-chemical structure of polymers and their piezo- and pyroelectric activity. The structure of PVDF/PMMA blends can be varied over a very wide range which can lead to a strong influence on the piezo- and pyroelectric activity and the corresponding coefficients d₃₁ and g₃. The values of d₃₁ and g₃ were found to vary over nearly five decades whereas the normalized coefficients $\text{d}{}_{31}\text{P}$ and $\text{g}{}_3\text{P}$ remain largely unaffected. This emphasizes the importance of the molecular processes causing the macroscopic polarization P during the poling procedure. For a given polarization P and a given temperature T the properties of the polymer matrix, however, are far less important for the values obtained for d₃₁ and g₃. The experimental results were compared with theoretical predictions based on models which were recently developed by Tashiro et al., Broadhurst et al. and by Mopsik et al.. Considering the appropriate scope of each model a good agreement between theory and experiment is observed and general contradictions have not been found.     

UBET analysis of the closed-pass ring rolling of rings having arbitrarily shaped profiles

A simple but effective upper-bound elemental technique (UBET) for prediction of the torque and the deformation pattern during the ring-rolling of rings having arbitrarily shaped profiles is proposed. In order to describe the three-dimensional material flow of profile ring rolling, a new element with a curvilinear side is introduced and the corresponding kinematically admissible velocity field is derived. Upper-bound analysis is carried out for rolling rings with a circular groove or protrusion having a round corner fillet. Comparing with the experimental results, the roll torque and the profile formation are predicted with reasonable accuracy. The effects of some parameters are investigated also. Despite the simplifying assumptions, some aspects of the deformation mechanics in profile ring rolling are shown to be described successfully by the proposed method.     

Influences of Ta, Nb, or Mo additions in Zr-based bulk metallic glasses on microstructure and thermal properties

The master-alloy ingots for casting bulk metallic glasses are routinely prepared by arc melting a mixture of pure elements. This paper addresses the difficulty in achieving complete and homogeneous melting of refractory component additions in Zr-based BMGs using the above procedure, and its influences on the microstructure and thermal behavior of alloys.