The behavior of small fatigue cracks at notches in corrosive environments

The behavior of small cracks growing out of the roots of blunt notches in compact type specimens of an austenitic steel was characterized under fatigue loading in wet H ₂ plus air environment. The growth rates of cracks in the size range of 0.125 mm to 0.75 mm were up to two orders of magnitude higher than the rates expected for conventional cracks at equal stress intensity range, K. It was also observed that the small cracks grew at these fast rates only in corrosive environments when the loading frequency was 0.02 Hz or less. At a frequency of 10 Hz, the behavior was in agreement with the trend predicted for conventional size cracks.The above observations are rationalized in terms of the breakdown of the concept of a single parameter representation of the crack tip stress and strain field by K or in terms of differences in crack tip environments between small and long cracks for the same bulk environment. A simple engineering model is proposed which adequately represents the observed small crack growth behavior.

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Résumé On a procédé à la caractérisation, sous charges de fatigue en atmosphère humide de H ₂ et d'air, de petites fissures se développant à partir des racines d'entailles arrondies dans des éprouvettes compactes.Les vitesses de croissance des fissures d'une taille allant de 0,125 à 0,750 mm se sont révélé être de deux ordres de grandeur plus grandes que les vitesses prévues dans le cas de fissures conventionnelle, soumises aux mêmes variations de l'intensité de contrainte K. On a également observé que de petites fissures croissaient à ces grandes vitesses seulement dans des atmosphères corrosives, lorsque la fréquence de sollicitation était de 0,02 Hz ou moins. A la fréquence de 10 Hz, le comportement observé s'est trouvé en accord avec les tendances prévues pour des fissures de taille conventionnelle.Les observations ci-dessus sont rationnalisées en un élargissement du concept de représentation monoparamétrique par le facteur K du champ de contraintes et de dilatation à l'extrémité de la fissure, ou en termes des différences rencontrées dans l'environnement local de l'extrémité d'une fissure, selon que celle-ci est longue ou courte, et ce dans un même environnement global.On propose un modèle simple utilisable en pratique, pour représenter de manière adéquate le comportement à la croissance observé pour des petites fissures.

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Metallurgy Department     

Preparation and properties of (BATB–ODPA) polyimide–clay nanocomposite materials

A series of polymer–clay nanocomposite (PCN) materials consisting of 1,4‐bis(4‐aminophenoxy)‐2‐tert‐butylbenzene–4,4′‐oxydiphthalic anhydride (BATB–ODPA) polyimide (PI) and layered montmorillonite (MMT) clay were successfully prepared by an in situ polymerization reaction through thermal imidization up to 300°C. The synthesized PCN materials were subsequently characterized by Fourier‐Transform infrared (FTIR) spectroscopy, wide‐angle powder X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The effects of material composition on thermal stability, mechanical strength, molecular permeability and optical clarity of bulk PI and PCN materials in the form of membranes were studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), molecular permeability analysis (GPA) and ultraviolet‐visible (UV/VIS) transmission spectra, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1072–1079, 2004     

The Influence of Diphenyl Siloxane on Morphology and Physical Properties in the Poly(Imide Siloxane)(PIS) Copolymer

Various numbers of diphenyl-siloxane groups were incorporated in α,ω-bis(aminopropyl)polydimethylsiloxane (APPS) to prepare α,ω-bis(aminopropyl)-polydimethyldiphenylsiloxane (APPPS) oligomers of three different number-average molecular weights(Mn = 547,772,1210 g mol⁻¹).These APPPS oligomers were than used, together with 3,3′,4,4′-bezonphenone tetracarboxylic dianhydride (BTDA) and 2-2′-bis[4-(3-aminophenoxy)phenyl] sulfone (m-BAPS), to synthesize a series of APPPS containing poly(imide siloxane) (PIS) copolymers. Microstructural studies showed that at certain APPPS content, a critical microphase separation point existed, beyond which, microphase separation began to develop. This critical point of microphase separation was found to be affected by the Mn of the APPPS oligomers (8.0, 4.3 and 2.1 mol% for Mn of 547, 772 and 1,210 g mol⁻¹, respectively). Diphenyl-siloxane significantly improved compatibility between polyimide and polysiloxane segments. Physical studies showed that the introduction of diphenyl siloxane changed the thermal stabilities and mechanical properties of the PIS copolymers. These findings have potential applications for design purposes in engineering polymers.     

Fischer–Tropsch synthesis. Compositional changes in an iron catalyst during activation and use

The equilibrium phase compositions of iron have been calculated for gas compositions that could be encountered during the Fischer–Tropsch synthesis. The gas compositions measured experimentally for CO conversion levels in the 30–90% range show that iron should be present as the carbide phase. However, experimental characterization of iron catalysts show that a significant fraction of the iron is present as Fe₃O₄ following synthesis for several days. A model that can account for the experimental catalyst phase composition and the gases present in the reactor would have a core of Fe₃O₄ and an outer layer of iron carbides.     

Novel fluorescent polynorbornenes with multi-functional armed structure by using highly stable block macroinitiators via a combination of living ring-opening metathesis polymerization and atom transfer radical polymerization

Novel organosoluble fluorescent polynorbornenes with multi-functional armed structure were designed and prepared by using highly stable block macroinitiators via a combination of living ring-opening metathesis polymerization (ROMP) and atom transfer radical polymerization (ATRP). A bromo-containing functional norbornene (NBMBr) was prepared from the Diels-Alder reaction of cyclopentadiene and allyl bromide. The diblock copolymer of 5-(N-carbazolyl methyl)bicycle[2.2.1]hept-2-ene (CbzNB) and NBMBr was successfully prepared using living ROMP and used as a novel macroinitiator [poly(CbzNB-b-NBMBr)] for ATRP. Carbazoyl-containing multi-functional armed copolymer with poly(methyl methacrylate) (PMMA) was prepared by using poly(CbzNB-b-NBMBr) as a macroinitiator for ATRP. Strong fluorescence emissions (370-450 nm) were observed in the low excimer-forming multi-functional armed fluorescent polynorbornenes. The fact is that low excimer-forming carbazole-containing polymeric compound would apparently be favorable in photoconductive materials. The multi-functional armed structure make this compound an attractive candidate for applications as multi-modified hole transport materials in molecular electronic devices. Multi-modification could be further considered to be carried out by using such a functional bromo group at the end of multi-arms.     

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.     

Discovery of the ammonium substrate site on glutamine synthetase, a third cation binding site

Glutamine synthetase (GS) catalyzes the ATP-dependent condensation of ammonia and glutamate to yield glutamine, ADP, and inorganic phosphate in the presence of divalent cations. Bacterial GS is an enzyme of 12 identical subunits, arranged in two rings of 6, with the active site between each pair of subunits in a ring. In earlier work, we have reported the locations within the funnel-shaped active site of the substrates glutamate and ATP and of the two divalent cations, but the site for ammonia (or ammonium) has remained elusive. Here we report the discovery by X-ray crystallography of a binding site on GS for monovalent cations, Tl+ and Cs+, which is probably the binding site for the substrate ammonium ion. Fourier difference maps show the following. (1) Tl+ and Cs+ bind at essentially the same site, with ligands being Glu 212, Tyr 179, Asp 50', Ser 53' of the adjacent subunit, and the substrate glutamate. From its position adjacent to the substrate glutamate and the cofactor ADP, we propose that this monovalent cation site is the substrate ammonium ion binding site. This proposal is supported by enzyme kinetics. Our kinetic measurements show that Tl+, Cs+, and NH4+ are competitive inhibitors to NH2OH in the gamma-glutamyl transfer reaction. (2) GS is a trimetallic enzyme containing two divalent cation sites (n1, n2) and one monovalent cation site per subunit. These three closely spaced ions are all at the active site: the distance between n1 and n2 is 6 A, between n1 and Tl+ is 4 A, and between n2 and Tl+ is 7 A. Glu 212 and the substrate glutamate are bridging ligands for the n1 ion and Tl+. (3) The presence of a monovalent cation in this site may enhance the structural stability of GS, because of its effect of balancing the negative charges of the substrate glutamate and its ligands and because of strengthening the "side-to-side" intersubunit interaction through the cation-protein bonding. (4) The presence of the cofactor ADP increases the Tl+ binding to GS because ADP binding induces movement of Asp 50' toward this monovalent cation site, essentially forming the site. This observation supports a two-step mechanism with ordered substrate binding: ATP first binds to GS, then Glu binds and attacks ATP to form gamma-glutamyl phosphate and ADP, which complete the ammonium binding site. The third substrate, an ammonium ion, then binds to GS, and then loses a proton to form the more active species ammonia, which attacks the gamma-glutamyl phosphate to yield Gln. (5) Because the products (Glu or Gln) of the reactions catalyzed by GS are determined by the molecule (water or ammonium) attacking the intermediate gamma-glutamyl phosphate, this negatively charged ammonium binding pocket has been designed naturally for high affinity of ammonium to GS, permitting glutamine synthesis to proceed in aqueous solution.     

Physics-Informed Multistage Machine Learning Strategy for the Nanomachining-Induced Plastic Deformation Behavior

The evolution of the dislocation density induced by the nanomachining process dominates the plastic deformation behaviors of materials, thus affecting the mechanical properties significantly. However, a challenging topic related to how to establish an accurate model for predicting the dislocation density based on the limited simulations and experiments arises due to the complicated thermal–mechanical coupling mechanism during the machining process. Herein, a multistage method integrating machine learning, physics, and high-throughput atomic simulation is proposed to investigate the effect of cutting speed on the dislocation behavior in polycrystal copper. Compared with the traditional one-step machine learning method, the constraint of physical features effectively improves the accuracy and generalization ability of the model. The results indicate that the dislocation behaviors depend on the competition between the cutting force and temperature. In the low-cutting speed, the predominated role of the cutting temperature leads to a rapid decline of the dislocation density. In contrast, the dislocation density tends to be stable under a high-speed cutting process due to the dynamic balance between the effects of the cutting force and temperature. Notably, the proposed strategy provides a new and universal framework to design the machining parameters to obtain high-quality products.     

Investigating acceptance toward mobile learning to assist individual knowledge management: Based on activity theory approach

Mobile devices could facilitate human interaction and access to knowledge resources anytime and anywhere. With respect to wide application possibilities of mobile learning, investigating learners’ acceptance towards it is an essential issue. Based on activity theory approach, this research explores positive factors for the acceptance of m-learning systems. In the research, we developed an m-learning system for learners’ knowledge management and invited 152 participants who knew how to use the m-learning system then report on their experience. The results show that enhancing learners’ satisfaction, encouraging learners’ autonomy, empowering system functions, and enriching interaction and communication activities have a significant positive influence on the acceptance of m-learning systems.