Predicting stereolithography injection mould tool behaviour using models to predict ejection force and tool strength

The work reported involved Finite Element Analysis (FEA) modelling of heat transfer in a stereolithography (SL) tool and then performing a series of experiments to measure true heat transfer in the tool. The results from the practical measurement of heat transfer were used to validate and modify the FEA model. The results from the modified FEA model were then used to predict the tensile strength of the tool at various stages after injection of the thermoplastic melt. Previously developed equations to predict ejection forces were used to estimate the ejection forces required to push the moulding from the SL core. During the practical experiments the true ejection forces were measured. The combination of predicted tool strength and ejection forces were intended to be used a basis for to determine whether certain SL tool designs will fail under tension during part ejection. This would help designers and manufacturers to decide whether SL tooling is suitable for a specific application. The initial FEA heat transfer model required some modifications and the measured ejection forces were higher than the predicted values, possible reasons for these discrepancies are given. For any given processing conditions there was an inherent variance in the ejection forces required however longer cooling periods prior to ejection resulted in higher ejection forces. The paper concludes that, due to the variations in required ejection forces, a reliable tool to predict tensile failure will be difficult to produce however improved performance may be gained by adopting processing conditions contrary to those recommended in the current process guidelines.     

Innovation in Creative Cities: Evidence from British Small Firms

Creative cities are seen as important sites for the generation of new ideas, products and processes. Yet, beyond case studies of a few high-profile cities, there is little empirical evidence on the link between local creative industries concentration and innovation. This paper addresses this gap with an analysis of around 1,300 UK small- and medium-sized enterprises. The results suggest that firms in local economies with high shares of creative industries employment are significantly more likely to introduce entirely new products and processes than firms elsewhere, but not innovations which are simply new to the firm. This effect is not exclusive to creative industries firms and seems to be largely due to firms in medium-sized, rather than large, cities. The results imply that creative cities may have functional specialisations in new content creation and so firms are more innovative in them.     

Synthesis, Characterization, and Reactions of Isolable (β-Diketiminato)Nb(III) Imido Complexes

We have investigated both the chemical reduction of (BDI)Nb(V) imido complexes (BDI = HC[C(Me)NAr](2); Ar = 2,6-(i)Pr(2)-C(6)H(3)) to the formal Nb(III) oxidation state and the ability of these Nb(III) complexes to behave as two-electron reductants. The reduction of the Nb(V) species was found to depend heavily on the nature of available supporting ligands, but the chemistry of the reduced compounds proceeded cleanly with a number of unsaturated organic reagents. Accordingly, the novel Nb(V) bis(imido) complexes supported by the monoazabutadiene (mad) ligand (mad)Nb(N(t)Bu)(NAr)(L') (L' = py, thf) were formed by either KC(8) reduction of (BDI)Nb(N(t)Bu)Cl(2)(py) in the absence of strong π-acids or by H(2) reduction of the Nb(V) dimethyl complex (BDI)Nb(N(t)Bu)Me(2) in THF. These products are likely formed though an intramolecular, 2 e(-) reductive C-N bond cleavage, as has been observed previously for related Group 4 systems, suggesting that transient Nb(III) intermediates were present in both cases. In the presence of 1,2-bis(dimethylphosphino)ethane (dmpe), KC(8) reduction of (BDI)Nb(N(t)Bu)Cl(2)(py) was arrested at the Nb(IV) oxidation state to give (BDI)Nb(N(t)Bu)Cl(dmpe), which was characterized by solution-state EPR spectroscopy as a Nb-centered paramagnet with strong coupling to the two equivalent phosphorus nuclei (A(iso){(93)Nb} = 120.5×10(-4) cm(-1), A(iso){(31)P} = 31.0×10(-4) cm(-1), g(iso) = 1.9815). When strong π-acids were used to intercept the thermally unstable Nb(III) complex (BDI)Nb(N(t)Bu)(py) prior to reductive cleavage of the ligand C-N bond, the thermally stable Nb(III) species (BDI)Nb(N(t)Bu)(CX)(2)(L″) (X = O, L″ = py; X = NXyl, L″ = CNXyl; Xyl = 2,6-Me(2)-C(6)H(3)) were obtained in good yields. The Nb(III) complexes (BDI)Nb(N(t)Bu)py, (BDI)Nb(N(t)Bu)(CO)(2)(py) and (BDI)Nb(N(t)Bu)(CO)(2) were subsequently investigated for their ability to serve as two-electron reducing reagents for both metal-ligand multiple bond formation and for the reduction of organic π-systems. The reduction of mesityl azide by (BDI)Nb(N(t)Bu)(py) and diphenylsulfoxide by (BDI)Nb(N(t)Bu)(CO)(2) led to the monomeric bis(imido) and dimeric oxo complexes (BDI)Nb(N(t)Bu)(NMes)(py) and [(BDI)Nb(N(t)Bu)](2)(μ2-O)(2), respectively. MeLi addition to (BDI)Nb(N(t)Bu)(CO)(2)(py) resulted in the formation of a Nb-acylate via methide addition to one of the carbonyl carbons. The acylate product was revealed to have a short Nb-C(acylate) bond distance (2.059(4) ?), consistent with multiple Nb-C bond character resulting from Nb(III) back-bonding into the acylate carbon. The interaction of (BDI)Nb(N(t)Bu)(CO)(2) with two equivalents of 4,4'-dichlorobenzophenone resulted in the clean, quantitative formation of the corresponding pinacol coupling product, but introduction of the ketone in 1: 1 molar ratios resulted in mixtures of the pinacol product and the starting material, suggesting that ketone coordination to the Nb(III) complex may be reversible. Relatedly, addition of 1-phenyl-1-propyne to (BDI)Nb(N(t)Bu)(CO)(2) formed a thermally unstable 1: 1 Nb/alkyne complex, as characterized by NMR and IR spectroscopies; reaction of this species with HCl/MeOH yielded a 2: 1 mixture of 1-phenyl-1-propene and the free alkyne, suggesting a high degree of covalency in the Nb-C bonds.     

A facile procedure to shorten multiwalled carbon nanotubes

Multi-walled carbon nanotubes (MWCNTs) with > 95% purity were synthesized over a Fe-Co/CaCO3 catalyst using chemical vapour deposition (CVD). Both the CNT yield and the outer diameters increased with time on line in the presence of acetylene. More significantly, the tubes were reduced in length and became stub-like with time. TEM analysis revealed that the CNTs commenced shortening after 2 h of reaction time. Reagent residues (e.g., Ca, CaO, OH/COOH groups and Fe-Co oxides) were found not to influence the CNT bond breaking reaction. CNT growth over Fe-Co supported on silica or CaCO3-Ca3(PO4)2 gave similar results. Further, MWCNTs produced by a floating catalyst method, carbon helices produced from Fe-Co-In/A2O3, and N doped CNTs also revealed tube shortening as a function of reaction time under a flow of acetylene. It is thus apparent that MWCNTs can readily be shortened by the facile procedure of depositing carbon from excess C2H2 on the outer walls of CNTs.     

Directed assembly of functional light harvesting antenna complexes onto chemically patterned surfaces

We report the directed assembly of the photosynthetic membrane proteins LH1 and LH2 isolated from the purple bacterium Rhodobacter sphaeroides onto chemically patterned substrates. Nanoimprint lithography was used to pattern discrete regions of amino-?and fluoro-terminated or poly(ethylene glycol) self-assembled monolayers onto a glass substrate. Densely packed layers of assembled protein complexes were observed with atomic force microscopy. The protein complexes attached selectively to the amino-terminated regions by electrostatic interactions. Spectral images generated with a hybrid scanning probe and fluorescence microscope confirmed that the patterned proteins retained their native optical signatures.     

Seat belt misuse among children transported in belt-positioning booster seats

Objective

Observe and report seat belt use among children transported in belt-positioning booster seats.

Design

We conducted a cross-sectional, observational survey of children transported in motor vehicles between 2006 and 2007. While drivers completed a survey reporting the child's age, weight and gender, and the driver's age, gender, race, income, education, and relationship to the child; a child passenger safety technician recorded vehicle seating location, restraint type, and use of the car safety seat harness or seat belt as appropriate for the child.

Setting

Twenty-five fast food restaurants and discount department stores throughout Indiana.

Participants

A convenience sample of drivers transporting children younger than 16 years.

Main exposure

Seat belt use among children transported in belt-positioning booster seats.

Outcome measure

Seat belt misuse.

Results

Overall, 1446 drivers participated, 2287 children were observed with 564 children in belt-positioning booster seats. At least one seat belt misuse was observed for 64.8% of the children transported. Common misuses were the shoulder belt being placed over the booster seat armrest (35.8%); shoulder belt not at mid-shoulder position (28.5%), seat belt was too loose (24.5%), and the shoulder belt was either behind the child's back (9.1%) or under their arm (10.0%).

Conclusion

There is a high frequency of seat belt misuses among children transported in booster seats. Advice to parents on appropriate car seat selection, and encouragement to parents to supervise seat belt use may decrease misuse.     

Analysis and Compression Testing of Laminates Optimised for Damage Tolerance

Barely Visible Impact Damage (BVID) can occur when laminated composite material is subject to out-of-plane impact loads and can result in a significant reduction in compressive strength. This paper reports on three compression tests of laminates optimised to maximise damage tolerance. Results from these tests were analysed using a semi-analytical, fracture mechanics based method that predicts the strain below which laminated coupons containing BVID subject to axial compression will not fail. A further experiment was conducted on an artificially delaminated coupon in order to validate the modelling methodology. Results from one of the two optimised stacking sequences considered show an increase of over 40% in Compression After Impact (CAI) strength compared with a baseline configuration. Analysis of results has indicated that CAI strength is dependent to a great extent on damage morphology and stability of damage growth, both of which are functions of laminate stacking sequence.     

Hybrid inorganic-organic adsorbents Part 1: Synthesis and characterization of mesoporous zirconium titanate frameworks containing coordinating organic functionalities

A series of functional hybrid inorganic-organic adsorbent materials have been prepared through postsynthetic grafting of mesoporous zirconium titanate xerogel powders using a range of synthesized and commercial mono-, bis-, and tris-phosphonic acids, many of which have never before been investigated for the preparation of hybrid phases. The hybrid materials have been characterized using thermogravimetric analysis, diffuse reflectance infrared (DRIFT) and 31P MAS NMR spectroscopic techniques and their adsorption properties studied using a 153Gd radiotracer. The highest level of surface functionalization (molecules/nm2) was observed for methylphosphonic acid (～3 molecules/nm2). The level of functionalization decreased with an increase in the number of potential surface coordinating groups of the phosphonic acids. Spectral decomposition of the DRIFT and 31P MAS NMR spectra showed that each of the phosphonic acid molecules coordinated strongly to the metal oxide surface but that for the 1,1-bis-phosphonic acids and tris-phosphonic acids the coordination was highly variable resulting in a proportion of free or loosely coordinated phosphonic acid groups. Functionalization of a porous mixed metal oxide framework with the tris-methylenephosphonic acid (ATMP-ZrTi-0.33) resulted in a hybrid with the highest affinity for 153Gd3+ in nitric acid solutions across a wide range of acid concentrations. The ATMP-ZrTi-0.33 hybrid material extracted 153Gd3+ with a Kd value of 1×10(4) in 0.01 M HNO3 far exceeding that of the other hybrid phases. The unfunctionalized mesoporous mixed metal oxide had negligible affinity for Gd3+ (Kd<100) under identical experimental conditions. It has been shown that the presence of free or loosely coordinated phosphonic acid groups does not necessarily translate to affinity for 153Gd3+. The theoretical cation exchange capacity of the ATMP-ZrTi-0.33 hybrid phase for Gd3+ has been determined to be about 0.005 mmol/g in 0.01 M HNO3. This behavior and that of the other hybrid phases suggests that the surface-bound ATMP ligand functions as a chelating ligand toward 153Gd3+ under these acidic conditions.     

Top-down approaches for measuring expression ratios of intact yeast proteins using Fourier transform mass spectrometry

The extension of quantitation methods for small peptides to ions above 5 kDa, and eventually to global quantitative proteomics of intact proteins, will require extensive refinement of current analytical approaches. Here we evaluate postgrowth Cys-labeling and 14N/15N metabolic labeling strategies for determination of relative protein expression levels and their posttranslational modifications using top-down mass spectrometry (MS). We show that intact proteins that are differentially alkylated with acrylamide (+71 Da) versus iodoacetamide (+57 Da) have substantial chromatographic shifts during reversed-phase liquid chromatography separation (particularly in peak tails), indicating a requirement for stable isotopes in alkylation tags for top-down MS. In the 14N/15N metabolic labeling strategy, we achieve 98% 15N incorporation in yeast grown 10 generations under aerobic conditions and determine 50 expression ratios using Fourier transform ion cyclotron resonance MS in comparing these cells to anaerobically grown control (14N) cells. We devise quantitative methods for top-down analyses, including a correction factor for accurate protein ratio determination based upon the signal-to-noise ratio. Using a database of 200 yeast protein forms identified previously by top-down MS, we verify the intact mass tag concept for protein identification without tandem MS. Overall, we find that top-down MS promises work flows capable of large-scale proteome profiling using stable isotope labeling and the determination of >5 protein ratios per spectrum.