Cationic Alkylaluminum-Complexed Zirconocene Hydrides as Participants in Olefin Polymerization Catalysis

The alkylaluminum-complexed zirconocene trihydride cation [(SBI)Zr(μ-H)_3(AliBu_2)_2]^+, which is obtained by reaction of (SBI)ZrCl_2 with [Ph_3C][B(C_6F_5)_4] and excess HAl^iBu_2 in toluene solution, catalyzes the formation of isotactic polypropene when exposed to propene at -30 °C. This cation remains the sole observable species in catalyst systems free of AlMe compounds. In the presence of AlMe_3, however, exposure to propene causes the trihydride cation to be completely converted, under concurrent consumption of all hydride species by propene hydroalumination, to the doubly Me-bridged cation [(SBI)Zr(μ-Me)_2AlMe_2]^+. The latter then becomes the resting state for further propene polymerization, which produces, by chain transfer to Al, mainly AlMe_2-capped isotactic polypropene

Alkylaluminum-complexed zirconocene hydrides: identification of hydride-bridged species by NMR spectroscopy

Reactions of unbridged zirconocene dichlorides, (R_nC_5H_5−n)_2ZrCl_2 (n = 0, 1, or 2), with diisobutylaluminum hydride (HAl^iBu_2) result in the formation of tetranuclear trihydride clusters of the type (R_nC_5H_5−n)_2Zr(μ-H)_3(Al^iBu_2)_3(μ-Cl)_2, which contain three [Al^iBu_2] units. Ring-bridged ansa-zirconocene dichlorides, Me_2E(R_nC_5H_4−n)_2ZrCl_2 with E = C or Si, on the other hand, are found to form binuclear dihydride complexes of the type Me_2E(R_nC_5H_4−n)_2Zr(Cl)(μ-H)_2Al^iBu_2 with only one [Al^iBu_2] unit. The dichotomy between unbridged and bridged zirconocene derivatives with regard to tetranuclear versus binuclear product formation is proposed to be connected to different degrees of rotational freedom of their C_5-ring ligands. Alkylaluminum-complexed zirconocene dihydrides, previously observed in zirconocene-based precatalyst systems activated by methylalumoxane (MAO) upon addition of HAl^iBu_2 or Al^iBu_3, are proposed to be species of the type Me_2Si(ind)_2Zr(Me)(μ-H)_2Al^iBu_2, stabilized by interaction of their terminal Me group with a Lewis acidic site of MAO

Cationic Alkylaluminum-Complexed Zirconocene Hydrides: NMR-Spectroscopic Identification, Crystallographic Structure Determination, and Interconversion with Other Zirconocene Cations

The ansa-zirconocene complex rac-Me_2Si(1-indenyl)_2ZrCl_2 ((SBI)ZrCl_2) reacts with diisobutylaluminum hydride and trityl tetrakis(perfluorophenyl)borate in hydrocarbon solutions to give the cation [(SBI)Zr(μ-H)_3(Al^iBu_2)_2]^+, the identity of which is derived from NMR data and supported by a crystallographic structure determination. Analogous reactions proceed with many other zirconocene dichloride complexes. [(SBI)Zr(μ-H)_3(Al^iBu2)_2]^+ reacts reversibly with ClAl^iBu_2 to give the dichloro-bridged cation [(SBI)Zr(μ-Cl)_2Al^iBu_2]^+. Reaction with AlMe_3 first leads to mixed-alkyl species [(SBI)Zr(μ-H)_3(AlMe_x^iBu_(2−x))_2^]+ by exchange of alkyl groups between aluminum centers. At higher AlMe_3/Zr ratios, [(SBI)Zr(μ-Me)_2AlMe_2]^+, a constituent of methylalumoxane-activated catalyst systems, is formed in an equilibrium, in which the hydride cation [(SBI)Zr(μ-H)_3(AlR_2)_2]^+ strongly predominates at comparable HAl^iBu_2 and AlMe_3 concentrations, thus implicating the presence of this hydride cation in olefin polymerization catalyst systems

A review of modular strategies and architecture within manufacturing operations

This paper reviews existing modularity and modularization literature within manufacturing operations. Its purpose is to examine the tools, techniques, and concepts relating to modular production, to draw together key issues currently dominating the literature, to assess managerial implications associated with the emerging modular paradigm, and to present an agenda for future research directions. The review is based on journal papers included in the ABI/Inform electronic database and other noteworthy research published as part of significant research programmes. The research methodology concerns reviewing existing literature to identify key modular concepts, to determine modular developments, and to present a review of significant contributions to the field. The findings indicate that the modular paradigm is being adopted in a number of manufacturing organizations. As a result a range of conceptual tools, techniques, and frameworks has emerged and the field of modular enquiry is in the process of codifying the modular lexicon and developing appropriate modular strategies commensurate with the needs of manufacturers. Modular strategies and modular architecture were identified as two key issues currently dominating the modular landscape. Based on this review, the present authors suggest that future research areas need to focus on the development and subsequent standardization of interface protocols, cross-brand module use, supply chain power, transparency, and trust. This is the first review of the modular landscape and as such provides insights into, first, the development of modularization and, second, issues relating to designing modular products and modular supply chains

Self-Consistent Response of a Galactic Disk to an Elliptical Perturbation Halo Potential

We calculate the self-consistent response of an axisymmetric galactic disk perturbed by an elliptical halo potential of harmonic number m = 2, and obtain the net disk ellipticity. Such a potential is commonly expected to arise due to a galactic tidal encounter and also during the galaxy formation process. The self-gravitational potential corresponding to the self-consistent, non-axisymmetric density response of the disk is obtained by inversion of Poisson equation for a thin disk. This response potential is shown to oppose the perturbation potential, because physically the disk self-gravity resists the imposed potential. This results in a reduction in the net ellipticity of the perturbation halo potential in the disk plane. The reduction factor denoting this decrease is independent of the strength of the perturbation potential, and has a typical minimum value of 0.75 - 0.9 for a wide range of galaxy parameters. The reduction is negligible at all radii for higher harmonics (m > or = 3) of the halo potential. (abridged).Comment: 26 pages (LaTex- aastex style), 3 .eps figures. To appear in the Astrophysical Journal, Vol. 542, Oct. 20, 200

Abundances of s-process elements in planetary nebulae: Br, Kr & Xe

We identify emission lines of post-iron peak elements in very high signal-to-noise spectra of a sample of planetary nebulae. Analysis of lines from ions of Kr and Xe reveals enhancements in most of the PNe, in agreement with the theories of s-process in AGB star. Surprisingly, we did not detect lines from Br even though s-process calculations indicate that it should be produced with Kr at detectable levels.Comment: 2 pages, 1 figure, to be published in the Proceedings of the IAU Symposium 234: Planetary Nebulae in Our Galaxy and Beyond, eds. M.J. Barlow, R.H. Mende

Thermal Behavior in the Lens Process

Direct laser metal deposition processing is a promising manufacturing technology which could significantly impact the length oftime between initial concept and finished part. For adoption ofthis technology in the manufacturing environment, further understanding is required to ensure robust components with appropriate properties are routinelyfabricated. This requires a complete understanding ofthe thermal history.during part fabrication and control ofthis behavior. This paper will describe our research to understand the thermal behavior for the Laser Engineered Net Shaping (LENS) process!, where a component is fabricated by focusing a laser beam onto a substrate to create a molten pool in which powder particles are simultaneously injected to build each layer. The substrate is moved beneath the l~ser beam to deposit a thin cross section, thereby creating the desired geometry for each layer. After deposition of each layer, the powder delivery nozzle and focusing lens assembly is incremented in the positive Z-direction, thereby building a three dimensional component layer additively. It is important to control the thermal behavior to reproducibly fabricate parts. The ultimate intent is to monitor the thermal signatures and to incorporate sensors and feedback algorithms to control part fabrication. With appropriate control, the geometric properties (accuracy, surface finish, low warpage) as well as the materials' properties (e.g. strength, ductility) of a component can be dialed into the part through the fabrication parameters. Thermal monitoring techniques will be described, and their particular benefits highlighted. Preliminary details in correlating thermal behavior with processing results will be discussed.Mechanical Engineerin