Effect of Density and Processing Conditions on Oxide Transformations and Mechanical Properties in Cr–Mo-Alloyed PM steels

To improve the mechanical properties and performances of water-atomized powder metallurgy steels, it is necessary to enhance the density. Consolidating water-atomized steel powders via conventional pressing and sintering to a relative density level > 95 pct involves processing challenges. Consolidation of gas-atomized powders to full density by hot isostatic pressing (HIP) is an established process route but utilizing water-atomized powders in HIP involves challenges that result in the formation of prior particle boundaries due to higher oxygen content. In this study, the effect of density and processing conditions on the oxide transformations and mechanical properties from conventional press and sintering, and HIP are evaluated. Hence, water-atomized Cr–Mo-alloyed powder is used and consolidated into different density levels between 6.8 and 7.3 g cm⁻³ by conventional die pressing and sintering. Fully dense material produced through HIP is evaluated not only of mechanical properties but also for microstructural and fractographic analysis. An empirical model based on power law is fitted to the sintered material properties to estimate and predict the properties up to full density at different sintering conditions. A model describing the mechanism of oxide transformation during sintering and HIP is proposed. The challenges when it comes to the HIP of water-atomized powder are addressed and the requirements for successful HIP processing are discussed.

     

Evaluation and characterization of ammoniumpolyphosphate–pentaerythritol‐based systems for intumescent coatings

Intumescent coatings are increasingly used as a method of passive fire protection on steel constructions. By forming a carbon network and releasing a blowing agent, the thin intumescent film swells 100‐fold at elevated temperatures. The highly insulating foam effectively prevents the load bearing steel from reaching its critical temperature at which it looses its mechanical properties and collapses. The role of the carbon donor in intumescent coatings has been studied. Comparison in temperature development, foaming ratios, and rheological behavior has been performed between formulations containing pentaerythritol (penta), di–penta, and tri–penta. A simulated fire test, in which the temperature development during intumescence was studied, showed that the formulations containing penta were considerably more efficient in keeping a low temperature throughout the process. A more rapid temperature development was displayed when using di–penta and tri–penta as the carbon donor. Rheometer tests indicate that penta formulations enter the intumescent process at a lower temperature and stays in it for a longer time than di–penta and tri–penta formulations. Furthermore, the crossover temperature and maximum phase angle are shifted towards higher temperatures by replacing penta with di–penta and with tri–penta in the formulations, respectively. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 748–753, 2007     

Sorption and diffusion of ionic dyes in anionic cellophane membranes

Experimental steady-state permeability studies have been made with non-ionic, anionic and cationic dyes using carboxy cellulose membranes as anionic substrates. The experimental results show that with increasing bulk ionic strength the diffusion velocities of anionic and cationic compounds increase and decrease, respectively. The diffusion behavior of non-ionic compounds is independent of the ionic strength. Empirical relationships have been deduced which fit the permeation data of the anionic compounds. A new concept is introduced which postulates that the diffusion behavior of colons within an anionic membrane is dependent on the basicity of the fixed ionic groups. In substrates with matrix-bound anionic groups of high basicity, such as carboxy cellulose, the permeability behavior is described in terms of a new diffusion mechanism referred to as the “fluctuating” charge mechanism. This concept can provide a semi-quantitative understanding of the different electrostatic obstruction effects which matrix-bound carboxylate and sulfonate groups have on the permeability of colons. The measured permeability of the counter ions is in qualitative agreement with the proposed diffusion model.     

Mining non-derivable hypercliques

A hyperclique (Xiong et al. in Proceedings of the IEEE international conference on data mining, pp 387–394, 2003) is an itemset containing items that are strongly correlated with each other, based on a user-specified threshold. Hypercliques (HCs) have been successfully used in a number of applications, for example, clustering (Xiong et al. in Proceedings of the 4th SIAM international conference on data mining, pp 279–290, 2004) and noise removal (Xiong et al. in IEEE Trans Knowl Data Eng 18(3):304–319, 2006). Even though HC has been shown to respond well to datasets with skewed support distribution and low support threshold, it may still grow very large for dense datasets and lower h-confidence threshold. In this paper, we propose a new pruning method based on combining HCs and non-derivable itemsets (NDIs) (Calders and Goethals in Proceedings of the PKDD international conference on principles of data mining and knowledge discovery, pp 74–85, 2002) in order to substantially reduce the amount of generated HCs. Specifically, we propose a new collection of HCs, called non-derivable hypercliques (NDHCs). The NDHC collection is a lossless representation of HCs, that is, given the itemsets in NDHCs, we can generate the complete HC collection and their support, without additional scanning of the dataset. We present an efficient algorithm to mine all NDHC sets, NDHCMiner, and an algorithm to derive all HC sets and their support from NDHCs, NDHCDeriveAll. We experimentally compare our collection, NDHC with HC, with respect to runtime performance as well as total number of generated sets, using real and artificial data. We also show comparisons with another condensed representation of HCs, maximal hyperclique patterns (MHPs). Our experiments show that the NDHC collection offers substantial advantages over HCs, and even MHPs, especially for dense datasets and lower h-confidence values.     

Anonymity preserving sequential pattern mining

The increasing availability of personal data of a sequential nature, such as time-stamped transaction or location data, enables increasingly sophisticated sequential pattern mining techniques. However, privacy is at risk if it is possible to reconstruct the identity of individuals from sequential data. Therefore, it is important to develop privacy-preserving techniques that support publishing of really anonymous data, without altering the analysis results significantly. In this paper we propose to apply the Privacy-by-design paradigm for designing a technological framework to counter the threats of undesirable, unlawful effects of privacy violation on sequence data, without obstructing the knowledge discovery opportunities of data mining technologies. First, we introduce a k-anonymity framework for sequence data, by defining the sequence linking attack model and its associated countermeasure, a k-anonymity notion for sequence datasets, which provides a formal protection against the attack. Second, we instantiate this framework and provide a specific method for constructing the k-anonymous version of a sequence dataset, which preserves the results of sequential pattern mining, together with several basic statistics and other analytical properties of the original data, including the clustering structure. A comprehensive experimental study on realistic datasets of process-logs, web-logs and GPS tracks is carried out, which empirically shows how, in our proposed method, the protection of privacy meets analytical utility.     

New N,O-containing ligands for the biomimetic copper-catalyzed polymerization of 2,6-dimethylphenol

Poly(2,6-dimethyl-1,4-phenylene ether) (PPE), which is widely used in high-performance engineering plastics, is obtained by the copper-catalyzed oxidative coupling of 2,6-dimethylphenol. The oxidative polymerizations have been carried out in acetonitrile with structurally related [copper-(N,O-containing ligand)] complexes as the catalyst precursor compounds, which appeared to be of great interest for a better understanding of the factors influencing the catalytic activities. Steric effects (influence of a methyl group close to the metal center; ligands 4–7) or electronic effects (imino versus amino group; ligands 4, 5, 8 and 6, 7, 9, respectively) on the polymerization rates have been demonstrated. The use of mono- or dinucleating ligands has strengthened the proposed mechanism of the reaction involving dinuclear active species.     

Generating hydrogen-rich fuel-cell feeds from dimethyl ether (DME) using physical mixtures of a commercial Cu/Zn/Al2O3 catalyst and several solid–acid catalysts

Homogeneous physical mixtures containing a commercial Cu/ZnO/Al₂O₃ catalyst and a solid–acid catalyst were used to examine the acidity effects on dimethyl ether hydrolysis and their subsequent effects on dimethyl ether steam reforming (DME-SR). The acid catalysts used were zeolites Y [Si/Al = 2.5 and 15: denoted Y(Si/Al)], ZSM-5 [Si/Al = 15, 25, 40, and 140: denoted Z(Si/Al)] and other conventional catalyst supports (ZrO₂, and γ-Al₂O₃). The homogeneous physical mixtures contained equal amounts, by volume, of the solid–acid catalyst and the commercial Cu/ZnO/Al₂O₃ catalyst (BASF K3-110, denoted as K3). The steam reforming of dimethyl ether was carried out in an isothermal packed-bed reactor at ambient pressure.

The most promising physical mixtures for the low-temperature production of hydrogen from DME contained ZSM-5 as the solid–acid catalyst, with hydrogen yields exceeding 90% (T = 275 °C, S/C = 1.5, τ = 1.0 s and P = 0.78 atm) and hydrogen selectivities exceeding 94%, comparable to those observed for methanol steam reforming (MeOH-SR) over BASF K3-110, with values equaling 95% and 99%, respectively (T = 225 °C, S/C = 1.0, τ = 1.0 s and P = 0.78 atm). Large production rates of hydrogen were directly related to the type of acid catalyst used. The hydrogen production activity trend as a function of physical mixture was

     

The content and composition of sterols and sterol esters in low erucic acid rapeseed (Brassica napus)

The low temperature crystallization technique for the enrichment of “minor” components, such as sterols and sterol esters, from vegetable oils was applied to low erucic acid rapeseed oils. The recovery of free sterols and sterol esters was estimated by use of¹⁴C-cholesterol and¹⁴C-cholesterol oleate. 80% of the free sterols and 45% of the sterol esters were recovered in the liquid fraction, while in two studies total recoveries were 95% and 99%, respectively. This technique showed some selectivity toward the sterol bound fatty acids when compared to direct preparative thin layer chromatography (TLC) of the crude oil. Gas liquid chromatography (GLC) analysis of the free and esterified sterols as TMS-derivatives showed very little selectivity in the enrichment procedure. The fatty acid patterns of the sterol esters demonstrated, however, a preference in the liquid fraction for those sterol esters which have a high linoleic and linolenic acid content. The content of free sterols was 0.3–0.4% and that of sterol esters 0.7–1.2% of the rapeseed oils in both winter and summer types of low erucic acid rapeseed (Brassica napus) when the lipid classes were isolated by direct preparative TLC of the oils. The free sterols in the seven cultivars or breeding lines analyzed were composed of 44–55% sitosterol, 27–36% campesterol, 17–21% brassicasterol, and a trace of cholesterol. The esterified sterols were 47–57% sitosterol, 36–44% campesterol, 6–9% brassicasterol, and traces of cholesterol and Δ5-avenasterol. The fatty acid patterns of these esters were characterized by ca. 30% oleic acid and ca. 50% linoleic acid, whereas these acids constitute 60% and 20%, respectively, of the total fatty acids in the oil. Little or no variation in sterol and sterol ester patterns with locality within Sweden was observed for the one cultivar of summer rapeseed investigated by the low temperature crystallization technique.     

Surface properties of block and graft polystyrene–polydimethylsiloxane copolymers

The surface compositions of a series of polystyrene‐b‐polydimethylsiloxane (PS‐b‐PDMS) and polystyrene‐g‐polydimethylsiloxane (PS‐g‐PDMS) copolymers were investigated using ATR‐FTIR and XPS technique. The results showed that enrichment of PDMS soft segments occurred on the surface of the block copolymers as well as on that of graft copolymers. And the magnitude order of the enrichment was as follows: PS‐b‐PDMS > PS‐g‐PDMS, which was attributed to the facilitating of the movement of the PDMS segments in PS‐b‐PDMS copolymer. Meanwhile, the solvent type and the contact medium had influence on the accumulation of PDMS on the surfaces. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

In Situ EXAFS Study on the Chemical State of Arsenic Deposited on a NiMoP/Al2O3 Hydrotreating Catalyst

The chemical state of arsenic deposited on a NiMoP/Al₂O₃ hydrotreating catalyst exposed to ppb levels of arsenic over several years in a refinery reactor has been studied by in situ EXAFS. In the as-received As-NiMoP catalyst, arsenic is exclusively coordinated to oxygen atoms. Upon sulfiding the sample in 2%H₂S/2%H₂/96%He, the As atoms become surrounded by approximately two sulfur atoms. No evidence was found for Ni–As bond formation. A possible model for the As local environment is suggested on the basis of combined EXAFS results, STM data and FEFF8.0 simulations (program for ab initio calculations on multiple scattering XAFS and XANES). The FEFF8.0 simulations of the proposed model are in accord with the experimental data measured at the As K edge. In this model, an As atom is located at the edge of a hexagonally truncated Ni-MoS₂ slab and is blocking the active NiMoS site.