The influence of fatty acid methyl ester profiles on inter-cycle variability in a heavy duty compression ignition engine

With the advent of alternative fuels, such as biodiesels and related blends, it is important to develop an understanding of their effects on inter-cycle variability which, in turn, influences engine performance as well as its emission. Using four methanol trans-esterified biomass fuels of differing carbon chain length and degree of unsaturation, this paper provides insight into the effect that alternative fuels have on inter-cycle variability. The experiments were conducted with a heavy-duty Cummins, turbo-charged, common-rail compression ignition engine. Combustion performance is reported in terms of the following key in-cylinder parameters: indicated mean effective pressure (IMEP), net heat release rate (NHRR), standard deviation of variability (StDev), coefficient of variation (CoV), peak pressure, peak pressure timing and maximum rate of pressure rise. A link is also established between the cyclic variability and oxygen ratio, which is a good indicator of stoichiometry. The results show that the fatty acid structures did not have a significant effect on injection timing, injection duration, injection pressure, StDev of IMEP, or the timing of peak motoring and combustion pressures. However, a significant effect was noted on the premixed and diffusion combustion proportions, combustion peak pressure and maximum rate of pressure rise. Additionally, the boost pressure, IMEP and combustion peak pressure were found to be directly correlated to the oxygen ratio. The emission of particles positively correlates with oxygen content in the fuel as well as in the air-fuel mixture resulting in a higher total number of particles per unit of mass.

A novel bioreactor for ligament tissue engineering

Bioreactors are defined as devices in which biological and/or biochemical processes develop under closely monitored and tightly controlled environmental and operating conditions (e.g. pH, temperature, mechanical conditions, nutrient supply and waste removal). In functional tissue engineering of musculoskeletal tissues, a bioreactor capable of controlling dynamic loading plays a determinant role. It has been shown that mechanical stretching promotes the expression of type I and III collagens, fibronectin, tenascin-C in cultured ligament fibroblasts (J.C.-H. Goh et al., Tissue Eng. 9 (2003), S31) and that human bone marrow mesenchymal stem cells (hBMMSC) – even in the absence of biochemical regulators – could be induced to differentiate into ligament-like fibroblast by the application of physiologically relevant cyclic strains (G. Vunjak-Novakovic et al., Ann. Rev. Biomed. Eng. 6 (2004), 131; H.A. Awad et al., Tissue Eng. 5 (1999), 267; R.G. Young et al., J. Orthop. Res. 16 (1998), 406). Different bioreactors are commercially available but they are too generic to be used for a given tissue, each tissue showing specific mechanical loading properties. In the case of ligament tissue engineering, the design of a bioreactor is still an open question. Our group proposes a bioreactor allowing cyclic traction–torsion on a scaffold seeded with stem cells.

Electrospinning and crosslinking of low-molecular-weight poly(trimethylene carbonate-co-L-lactide) as an elastomeric scaffold for vascular engineering

The growth of suitable tissue to replace natural blood vessels requires a degradable scaffold material that is processable into porous structures with appropriate mechanical and cell growth properties. This study investigates the fabrication of degradable, crosslinkable prepolymers of l-lactide-co-trimethylene carbonate into porous scaffolds by electrospinning. After crosslinking by γ-radiation, dimensionally stable scaffolds were obtained with up to 56% trimethylene carbonate incorporation. The fibrous mats showed Young’s moduli closely matching human arteries (0.4–0.8 MPa). Repeated cyclic extension yielded negligible change in mechanical properties, demonstrating the potential for use under dynamic physiological conditions. The scaffolds remained elastic and resilient at 30% strain after 84 days of degradation in phosphate buffer, while the modulus and ultimate stress and strain progressively decreased. The electrospun mats are mechanically superior to solid films of the same materials. In vitro, human mesenchymal stem cells adhered to and readily proliferated on the three-dimensional fiber network, demonstrating that these polymers may find use in growing artificial blood vessels in vivo.

Fatigue behaviour of corrugated roofing under cycling wind loading

Low cycle fatigue cracking of light gauge metal roofing was investigated by testing a number of two-span corrugated roofing assemblies with different spans and fastening systems under cyclic uplift wind loading. Fatigue results correlated quite well with the corresponding static results reported earlier, and revealed the dependence of fatigue behaviour on the fastening system used. A comparison was made of one fastening system with the other regarding fatigue performance .

Generation of active surface states of gold and the role of such states in electrocatalysis

The cyclic voltammetry behaviour of gold in aqueous media is often regarded in very simple terms as a combination of two distinct processes, double layer charging/discharging and monolayer oxide formation/removal. This view is questioned here on the basis of both the present results and earlier independent data by other authors. It was demonstrated in the present case that both severe cathodization or thermal pretreatment of polycrystalline gold in acid solution resulted in the appearance of substantial Faradaic responses in the double layer region. Such anamolous behaviour, as outlined recently also for other metals, is rationalized in terms of the presence of active metal atoms (which undergo premonolayer oxidation) at the electrode surface. Such behaviour, which is also assumed to correspond to that of active sites on conventional gold surfaces, is assumed to be of vital importance in electrocatalysis; in many instances the latter process is also quite marked in the double layer region.

Morphology changes and mechanistic aspects of the electrochemically-induced reversible solid-solid transformation of microcrystalline TCNQ into Co TCNQ 2-based materials (TCNQ= 7, 7, 8, 8-Tetracyanoquinodimethane)

The chemically reversible solid−solid phase transformation of a TCNQ-modified glassy carbon, indium tin oxide, or metal electrode into Co\[TCNQ]2(H2O)2 material in the presence of Co2+(aq) containing electrolytes has been induced and monitored electrochemically. Voltammetric data reveal that the TCNQ/Co\[TCNQ]2(H2O)2 interconversion process is independent of electrode material and identity of cobalt electrolyte anion. However, a marked dependence on electrolyte concentration, scan rate, and method of electrode modification (drop casting or mechanical attachment) is found. Cyclic voltammetric and double potential step chronoamperometric measurements confirm that formation of Co\[TCNQ]2(H2O)2 occurs through a rate-determining nucleation and growth process that initially involves incorporation of Co2+(aq) ions into the reduced TCNQ crystal lattice at the TCNQ|electrode|electrolyte interface. Similarly, the reverse (oxidation) process, which involves transformation of solid Co\[TCNQ]2(H2O)2 back to parent TCNQ crystals, also is controlled by nucleation−growth kinetics. The overall chemically reversible process that represents this transformation is described by the reaction:  2TCNQ0(s) + 2e- + Co2+(aq) + 2H2O \[Co(TCNQ)2(H2O)2](s). Ex situ SEM images illustrated that this reversible TCNQ/Co\[TCNQ]2(H2O)2 conversion process is accompanied by drastic size and morphology changes in the parent solid TCNQ. In addition, different sizes of needle-shaped nanorod/nanowire crystals of Co\[TCNQ]2(H2O)2 are formed depending on the method of surface immobilization.

Shape dependent electrocatalytic behaviour of silver nanoparticles

The electrochemical and electrocatalytic behaviour of silver nanoprisms, nanospheres and nanocubes of comparable size in an alkaline medium have been investigated to ascertain the shape dependent behaviour of silver nanoparticles, which are an extensively studied nanomaterial. The nanomaterials were synthesised using chemical methods and characterised with UV-visible spectroscopy, transmission electron microscopy and X-ray diffraction. The nanomaterials were immobilised on a substrate glassy carbon electrode and characterised by cyclic voltammetry for their surface oxide electrochemistry. The electrocatalytic oxidation of hydrazine and formaldehyde and the reduction of hydrogen peroxide were studied by performing cyclic voltammetric and chronoamperometric experiments for both the nanomaterials and a smooth polycrystalline macrosized silver electrode. In all cases the nanomaterials showed enhanced electrocatalytic activity over the macro-silver electrode. Significantly, the silver nanoprisms that are rich in hcp lamellar defects showed greater activity than nanospheres and nanocubes for all reactions studied.

The role of defects, or active states, in surface electrochemistry with particular reference to gold in neutral solution

Metastable, active, or nonequilibrium states due to the presence of abnormal structures and various types of defects are well known in metallurgy. The role of such states at gold surfaces in neutral aqueous media (an important electrode system in the microsensor area) was explored using cyclic voltammetry. It was demonstrated that, as postulated in earlier work from this laboratory, there is a close relationship between premonolayer oxidation, multilayer hydrous oxide reduction and electrocatalytic behaviour in the case of this and other metal electrode systems. Some of the most active, and therefore most important, entities at surfaces (e.g., metal adatoms) are not readily imageable or detectable by high resolution surface microscopy techniques. Cyclic voltammetry, however, provides significant, though not highly specific, information about such species. The main conclusion is that further practical and theoretical work on active states of metal surfaces is highly desirable as their behaviour is not simple and is of major importance in many electrocatalytic processes.

AFM study of morphological changes associated with electrochemical solid--solid transformation of three-dimensional crystals of TCNQ to metal derivatives (metal= Cu, Co, Ni; TCNQ= tetracyanoquinodimethane)

In situ atomic force microscopy (AFM) allows images from the upper face and sides of TCNQ crystals to be monitored during the course of the electrochemical solid–solid state conversion of 50 × 50 μm2 three-dimensional drop cast crystals of TCNQ to CuTCNQ or M[TCNQ]2(H2O)2 (M = Co, Ni). Ex situ images obtained by scanning electron microscopy (SEM) also allow the bottom face of the TCNQ crystals, in contact with the indium tin oxide or gold electrode surface and aqueous metal electrolyte solution, to be examined. Results show that by carefully controlling the reaction conditions, nearly mono-dispersed, rod-like phase I CuTCNQ or M[TCNQ]2(H2O)2 can be achieved on all faces. However, CuTCNQ has two different phases, and the transformation of rod-like phase 1 to rhombic-like phase 2 achieved under conditions of cyclic voltammetry was monitored in situ by AFM. The similarity of in situ AFM results with ex situ SEM studies accomplished previously implies that the morphology of the samples remains unchanged when the solvent environment is removed. In the process of crystal transformation, the triple phase solid∣electrode∣electrolyte junction is confirmed to be the initial nucleation site. Raman spectra and AFM images suggest that 100% interconversion is not always achieved, even after extended electrolysis of large 50 × 50 μm2 TCNQ crystals.

An investigation of silver electrodeposition from ionic liquids : influence of atmospheric water uptake on the silver electrodeposition mechanism and film morphology

The electrodeposition of silver from two ionic liquids, 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF4]) and N-butyl-N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide ([C4mPyr][TFSI]), and an aqueous KNO3 solution on a glassy carbon electrode was undertaken. It was found by cyclic voltammetry that the electrodeposition of silver proceeds through nucleation–growth kinetics. Analysis of chronoamperometric data indicated that the nucleation–growth mechanism is instantaneous at all potentials in the case of [BMIm][BF4] and [C4mPyr][TFSI], and instantaneous at low overpotentials tending to progressive at high overpotentials for KNO3. Significantly, under ambient conditions, the silver electrodeposition mechanism changes to progressive nucleation and growth in [C4mPyr][TFSI], which is attributed to the uptake of atmospheric water in the IL. It was found that these differences in the growth mechanism impact significantly on the morphology of the resultant electrodeposit which is characterised ex situ by scanning electron microscopy and X-ray diffraction.

The active site behaviour of electrochemically synthesised gold nanomaterials

Even though gold is the noblest of metals, a weak chemisorber and is regarded as being quite inert, it demonstrates significant electrocatalytic activity in its nanostructured form. It is demonstrated here that nanostructured and even evaporated thin films of gold are covered with active sites which are responsible for such activity. The identification of these sites is demonstrated with conventional electrochemical techniques such as cyclic voltammetry as well as a large amplitude Fourier transformed alternating current (FT-ac) method under acidic and alkaline conditions. The latter technique is beneficial in determining if an electrode process is either Faradaic or capacitive in nature. The observed behaviour is analogous to that observed for activated gold electrodes whose surfaces have been severely disrupted by cathodic polarisation in the hydrogen evolution region. It is shown that significant electrochemical oxidation responses occur at discrete potential values well below that for the formation of the compact monolayer oxide of bulk gold and are attributed to the facile oxidation of surface active sites. Several electrocatalytic reactions are explored in which the onset potential is determined by the presence of such sites on the surface. Significantly, the facile oxidation of active sites is used to drive the electroless deposition of metals such as platinum, palladium and silver from their aqueous salts on the surface of gold nanostructures. The resultant surface decoration of gold with secondary metal nanoparticles not only indicates regions on the surface which are rich in active sites but also provides a method to form interesting bimetallic surfaces.

Large amplitude Fourier transformed AC voltammetric investigation of the active state electrochemistry of a copper/aqueous base interface and implications for electrocatalysis

The higher harmonic components available from large-amplitude Fourier-transformed alternating current (FT-ac) voltammetry enable the surface active state of a copper electrode in basic media to be probed in much more detail than possible with previously used dc methods. In particular, the absence of capacitance background current allows low-level Faradaic current contributions of fast electron-transfer processes to be detected; these are usually completely undetectable under conditions of dc cyclic voltammetry. Under high harmonic FT-ac voltammetric conditions, copper electrodes exhibit well-defined and reversible premonolayer oxidation responses at potentials within the double layer region in basic 1.0 M NaOH media. This process is attributed to oxidation of copper adatoms (Cu*) of low bulk metal lattice coordination numbers to surface-bonded, reactive hydrated oxide species. Of further interest is the observation that cathodic polarization in 1.0 M NaOH significantly enhances the current detected in each of the fundamental to sixth FT-ac harmonic components in the Cu*/Cu hydrous oxide electron-transfer process which enables the underlying electron transfer processes in the higher harmonics to be studied under conditions where the dc capacitance response is suppressed; the results support the incipient hydrous oxide adatom mediator (IHOAM) model of electrocatalysis. The underlying quasi-reversible interfacial Cu*/Cu hydrous oxide process present under these conditions is shown to mediate the reduction of nitrate at a copper electrode, while the mediator for the hydrazine oxidation reaction appears to involve a different mediator or active state redox couple. Use of FT-ac voltammetry offers prospects for new insights into the nature of active sites and electrocatalysis at the electrode/solution interface of Group 11 metals in aqueous media.

Reduction of Au3+ ions by activated surface atoms of platinum

In this work it is demonstrated that Pt electrodes can be activated by cathodic polarisation in the hydrogen evolution region which makes it prone to oxidation at potentials below that of bulk oxide formation. When an activated Pt electrode is placed in an aqueous HAuCl4 solution the electroless deposition of Au onto the surface of the electrode is observed and confirmed by cyclic voltammetry and XPS measurements. It is demonstrated that the oxidation of active Pt surface atoms provides the driving force for the spontaneous reduction of Au3+ ions into metallic Au to generate a Pt/Au surface which is highly active for the electro-oxidation of ethanol.

The facile formation of silver dendritic structures in the absence of surfactants and their electrochemical and SERS properties

In this work a simple approach to the creation of highly dispersed electrocatalytically active silver microstructured dendrites on indium tin oxide in the absence of any surface modification or surfactant is presented. It is found that the addition of low concentrations of supporting electrolyte to the AgNO3 solution dramatically influences the morphology of electrodeposited silver which is independent of both the anion and the cation employed. The silver dendrites are characterized by SEM, XRD, XPS as well as by cyclic voltammetry under alkaline conditions. It is found that the surface oxide formation and removal processes are significantly influenced by the microstructured morphology of the silver electrodeposits compared to a smooth macrosized silver electrode. The facile formation of dendritic silver microstructures is also shown to be beneficial for the electrocatalytic oxidation of both formaldehyde and hydrazine and oxygen reduction. The formation of a continuous film of dendritic silver is also investigated for its SERS activity where the connectivity between the individual dendrites is found to be particularly important.

Electrodeposited α- and β-phase MoO3 films and investigation of their gasochromic properties

α- and β-Phase MoO3 are synthesized using an electrodeposition method on fluorine-doped tin oxide (FTO) glass substrates from sodium-molybdate (Na2MoO4) solutions. We show that it is possible to obtain both α- and β-MoO3 by manipulating the cyclic voltammetry (CV) parameters during electrodeposition. Raman spectroscopy, X-ray diffraction, and scanning electron microscopy indicate that the applied potential range and sweep rate are strongly influential on the phase obtained and the surface morphology of the electrodeposited thin films. Gasochromic measurements were carried out on the annealed samples by exposing them to H2 gas. It was revealed that α-MoO3 thin films provided better response to H2 interaction than β-MoO3 films did. Additionally, porous films provided significantly larger responses than smooth films.