Creep testing of carbon containing refractories under reducing conditions

Mechanical testing of carbon containing refractories at high temperatures requires measures to protect the sample from oxidation. Therefore, special setups for tensile and compressive creep testing were developed to prevent the oxidation of carbon in the sample. A MgO-C refractory was selected for a case study. These developments allow the quantification of the tensile and compressive creep behaviour of MgO-C refractories at temperatures up to 1500?°C. The creep parameters are determined by an inverse evaluation method for the obtained experimental data. They enable the consideration of creep in a thermomechanical finite element simulation of refractory linings in service.     

A method to characterize asymmetrical three-stage creep of ordinary refractory ceramics and its application for numerical modelling

During operation, thermomechanical stresses occur in refractory linings. Under elevated stress and temperatures, these ceramics experience primary creep, which can further proceed to the secondary and tertiary creep stages. This necessitates a characterization of their three-stage creep behavior. Hence, two advanced uniaxial tensile and compressive creep testing devices are utilized. The Norton-Bailey creep equations and an inverse identification procedure are applied for the evaluation of the creep curves. To account for the full three-stage creep behavior in thermomechanical modelling activities, a creep-stage transition criterion is identified and subsequently implemented together with the Norton-Bailey creep-strain rate representations in a new developed creep model. The finite element simulation results from different creep testing procedures are in accordance with the corresponding experimental results of a magnesia-chromite refractory ceramic. The study also reveals the temperature-dependent asymmetrical creep behavior of the material in terms of the creep-strain rates and critical creep strains.     

Comprehensive branching analysis of polyethylene by combined fractionation and thermal analysis

Linear low density polyethylene (LLDPE) and low density polyethylene (LDPE) differ significantly in their branching types and branching distributions. For a comprehensive analysis, preparative temperature rising elution fractionation and/or preparative molar mass fractionation are used to fractionate typical LLDPE and LDPE bulk resins into narrowly distributed fractions. The chain structures of the bulk resins and their fractions are further analysed using SEC, crystallization analysis fractionation, DSC and high‐temperature HPLC to provide detailed information on short chain branching in LLDPE and long chain branching in LDPE. For LDPE it is shown that the multiple fractionation approach is a powerful source of sample libraries that may have similar molar masses and different branching structures or alternatively similar branching but different molar masses. The analysis of these library samples by thermal analysis provides a much deeper insight into the molecular heterogeneity of the samples compared to bulk sample analysis. © 2018 Society of Chemical Industry     

Fiber formation and properties of polyester/lignin blends

Thermotropic liquid crystalline polyesters with varied chemical structure are synthesized by melt transesterification polycondensation. They are employed as matrix for blends with lignin materials to obtain melt-spinnable precursors for carbon fibers. The lignin samples are carefully purified by fractionation, enzymatic removal of reducing sugars, and subsequent modification of the terminal OH groups. Effective melt blending is achieved with liquid-crystalline aromatic–aliphatic polyesters having melting ranges that match the softening temperature of the lignin fractions, which is necessary to prevent thermal decomposition of the lignin. Polyester/lignin blends are partially compatibilized, phase-separated materials. The polyester/lignin materials are melt-spun successfully. The fiber properties depend on the lignin purification process. X-ray scattering reveals that orientation in lignin-containing fibers is maintained. First experiments show that the fibers can be converted successfully to carbon fibers by thermal annealing procedures. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48257.     

Targeted Synthesis of Complex Spiro[3H-indole-3,2′-pyrrolidin]-2(1H)-ones by Intramolecular Cyclization of Azomethine Ylides: Highly Potent MDM2–p53 Inhibitors

Mouse double minute 2 (MDM2) is a main and direct inhibitor of the crucial tumor suppressor p53. Reports from initial clinical trials showed that blocking this interaction with a small-molecule inhibitor can have great value in the treatment of cancer for patients with p53 wild-type tumors; however, it also revealed dose-limiting hematological toxicities and drug-induced resistance as main issues. To overcome the former, an inhibitor with superior potency and pharmacokinetic properties to ultimately achieve full efficacy with less-frequent dosing schedules is required. Toward this aim, we optimized our recently reported spiro-oxindole inhibitors by focusing on the crucial interaction with the amino acid side chain of His96_MDM2. The designed molecules required the targeted synthesis of structurally complex spiro[indole-3,2′-pyrrolo[2,3-c]pyrrole]-2,4′-diones for which we developed an unprecedented intramolecular azomethine ylide cycloaddition and investigated the results by computational methods. One of the new compounds showed superior cellular potency over previously reported BI-0252. This finding is a significant step toward an inhibitor suitable to potentially mitigate hematological on-target adverse effects.     

Screening,Molecular Cloning,and Biochemical Characterization of an Alcohol Dehydrogenase from Pichia pastoris Useful for the Kinetic Resolution of a Racemic β‐Hydroxy‐β‐trifluoromethyl Ketone

The stereoselective synthesis of chiral 1,3‐diols with the aid of biocatalysts is an attractive tool in organic chemistry. Besides the reduction of diketones, an alternative approach consists of the stereoselective reduction of β‐hydroxy ketones (aldols). Thus, we screened for an alcohol dehydrogenase (ADH) that would selectively reduce a β‐hydroxy‐β‐trifluoromethyl ketone. One potential starting material for this process is readily available by aldol addition of acetone to 2,2,2‐trifluoroacetophenone. Over 200 strains were screened, and only a few yeast strains showed stereoselective reduction activities. The enzyme responsible for the reduction of the β‐hydroxy‐β‐trifluoromethyl ketone was identified after purification and subsequent MALDI‐TOF mass spectrometric analysis. As a result, a new NADP⁺‐dependent ADH from Pichia pastoris (PPADH) was identified and confirmed to be capable of stereospecific and diastereoselective reduction of the β‐hydroxy‐β‐trifluoromethyl ketone to its corresponding 1,3‐diol. The gene encoding PPADH was cloned and heterologously expressed in Escherichia coli BL21(DE3). To determine the influence of an N‐ or C‐terminal His‐tag fusion, three different recombinant plasmids were constructed. Interestingly, the variant with the N‐terminal His‐tag showed the highest activity; consequently, this variant was purified and characterized. Kinetic parameters and the dependency of activity on pH and temperature were determined. PPADH shows a substrate preference for the reduction of linear and branched aliphatic aldehydes. Surprisingly, the enzyme shows no comparable activity towards ketones other than the β‐hydroxy‐β‐trifluoromethyl ketone.     

Avoiding filter cake cracking: Influence of consolidation on desaturation characteristics

In cake filtration processes with an air-blowing step, cracking is an undesirable phenomenon as it leads to deterioration of the filtration process by highly increasing gas throughput. This leads to higher residual moisture if the pressure difference cannot be maintained and an increase in overall cost. Crack formation can be avoided by compacting the filter cake before desaturation. While this action will make the separation process applicable by highly reducing gas consumption, there are also potential negative effects. Compaction increases filter cake resistance and might therefore slow down desaturation kinetics. Therefore, the authors investigated how the filter cake characteristics governing desaturation change from the nonconsolidated to the consolidated state of the filter cake and compared these findings to the actual dewatering kinetics. The results showed that for the case where cracking could be oppressed, dewatering kinetics of the consolidated cake are actually faster than for the nonconsolidated cake, despite higher resistance of the consolidated cake. Thus, compaction is an appropriate action when dealing with filter cake cracking.     

Influence of textile parameters on the in‐plane permeability characteristics of non‐crimped fabric preforms

Material parameters such as the permeability of dry reinforcing textiles are key variables for modern composite production using liquid composite molding (LCM) technique. Nowadays numerical filling simulations are required for predicting the mold filling behavior. Inaccurate predictions can lead to a high risk of air inclusion and corresponding need for cost‐intense revision of the mold design. Permeability values of the textiles used in the process are basic requirements for a numerical filling simulation, since the permeability is directly linked to the filling behavior. Nevertheless, the permeability values of non‐crimped fabrics (NCF) which are used for aerospace and automotive structures are rare. In this study the influence of textile parameters of NCF on the in‐plane permeability has been investigated using a capacitive in‐plane permeability measurement technology. The results show the influence of the roving filament number as well as the used stitch length on the in‐plane permeability. It is confirmed that the textile grammage is not affecting the in‐plane permeability of NCF reinforcements. The results of this study are valuable for textile selection with specific permeability data as well as for numerical filling simulations. POLYM. COMPOS., 37:1854–1863, 2016. © 2015 Society of Plastics Engineers     

Durability of Brick Lined Steel Ladles from a Mechanical Point of View

The refractory lining in steel ladles is exposed to chemical and mechanical loads during the heats. Mechanical loads develop from the thermal expansion of the refractories which is confined either by the steel construction or by regions of different temperature within the refractory material. The aim of this work was the investigation of factors influencing the mechanical durability of refractory steel ladle linings and the clarification of failure mechanisms. Especially irreversible strains at the hot face of the working lining caused by compressive stresses induce an opening of joints at the hot face. The irreversible strains reduce the compressive stresses in circumferential direction and increase the probability of tensile failure. A further effect of the irreversible strains is a reduced stability of the working lining. Of special interest in this context is a possible controlled expansion of bricks to counterbalance the irreversible compressive strains.     

Efficient polymer solar cell modules

Polymer solar cell modules based on the standard polymer–fullerene system of to-date, P3HT–PCBM, have been prepared and characterized. We have observed a loss of only 20% when up-scaling the active area of the solar cell by a factor somewhat larger than 10. An average solar cell efficiency of 3% and a module efficiency of 1.9% for three serially interconnected solar cells of 5.4 cm² each are reported. The route for further optimization of module performance is discussed based on analyzing the existing loss factors within this design.