C-H bond activation over metal oxides: A new insight into the dissociation kinetics from density functional theory

The C-H activation on metal oxides is a fundamental process in chemistry. In this paper, we report a density functional theory study on the process of the C-H activation of CH4 on Pd(111), Pt(111), Ru(0001), Tc(0001), Cu(111), PdO(001), PdO(110), and PdO(100). A linear relationship between the C-H activation barrier and the chemisorption in the dissociation final state on the metal surfaces is obtained, which is consistent with the work in the literature. However, the relationship is poor on the metal oxide surfaces. Instead, a strong linear correlation between the barrier and the lattice O-H bond strength is found on the oxides. The new linear relationship is analyzed and the physical origin is identified. (c) 2008 American Institute of Physics.

Effect of corrosion of reinforcement on the mechanical behaviour of highly corroded RC beams

This paper describes an experimental investigation of the behaviour of corroded reinforced concrete beams. These have been stored in a chloride environment for a period of 26 years under service loading so as to be representative of real structural and environmental conditions. The configuration and the widths of the cracks in the two seriously corroded short-span beams were depicted carefully, and then the beams were tested until failure by a three-point loading system. Another two beams of the same age but without corrosion were also tested as control specimens. A short span arrangement was chosen to investigate any effect of a reduction in the area and bond strength of the reinforcement on shear capacity. The relationship of load and deflection was recorded so as to better understand the mechanical behaviour of the corroded beams, together with the slip of the tensile bars. The corrosion maps and the loss of area of the tensile bars were also described after having extracted the corroded bars from the concrete beams. Tensile tests of the main longitudinal bars were also carried out. The residual mechanical behaviour of the beams is discussed in terms of the experimental results and the cracking maps. The results show that the corrosion of the reinforcement in the beams induced by chloride has a very important effect on the mechanical behaviour of the short-span beams, as loss of cross-sectional area and bond strength have a very significant effect on the bending capacity.

Bond and Interfacial Properties of Reinforcement in Self-Compacting Concrete

This paper reports a study carried out to assess the impact of the use of self-compacting concrete (SCC) on bond and interfacial properties around steel reinforcement in practical concrete element. The pull-out tests were carried out to determine bond strength between reinforcing steel bar and concrete, and the depth-sensing nano-indentation technique was used to evaluate the elastic modulus and micro-strength of the interracial transition zone (ITZ) around steel reinforcement. The bond and interracial properties around deformed steel bars in different SCC mixes with strength grades of 35 MPa and 60 MPa (C35, C60) were examined together with those in conventional vibrated reference concrete with the same strength grades. The results showed that the maximum bond strength decreased when the diameter of the steel bar increased from 12 to 20 mm. The normalised bond strengths of the SCC mixes were found to be about 10-40% higher than those of the reference mixes for both bar diameters (12 and 20 mm). The study of the interfacial properties revealed that the elastic modulus and the micro-strength of the ITZ were lower on the bottom side of a horizontal steel bar than on the top side, particularly for the vibrated reference concrete. The difference of ITZ properties between top and bottom side of the horizontal steel bar appeared to be less pronounced for the SCC mixes than for the corresponding reference mixes.

抗剪加固FRP与混凝土界面粘结性能的试验研究

In this study, 21 small beam specimens with a pre-set through-crack were tested with FRP strips bonded to the sides to study the bond behavior between shear-strengthening FRP and concrete (referred to as "the interface" for simplicity hereafter). The test parameters included the bond length, width, thickness of FRP strip and the angle between fiber orientation and crack opening direction (referred to as "fiber tensile angle" θ hereafter) on the bond behavior of the interface. Test results showed that: 1) the small beam test setup with a pre-set crack is suitable for studying the bond behavior between FRP and concrete; 2) the bond length, width, and thickness of the FRP as well as the fiber angle have significant effects on the bond strength; 3) the distribution of FRP strains along the direction perpendicular to the fiber orientation (FRP width direction) is non-uniform; this is mainly attributed to the progressive debonding of the FRP strips in the width direction, with the FRP at the location of larger crack width debonding earlier.

Bond behavior of NSM FRP strips between two adjacent cracks in concrete beams: A numerical study

Strengthening RC structures with near-surface mounted (NSM) fibre reinforced polymer (FRP) composites has a number of advantages compared with that with externally bonded (EB) FRP sheets/plates. As with EB FRP, the performance of the bond between NSM FRP and concrete is one of the key factors affecting the behaviour of the strengthened structure. This paper presents a numerical investigation into the behaviour of NSM FRP loaded at its both ends to simulate the NSM FRP-toconcrete bond between two adjacent cracks in RC members. The main objective of this study is to quantitatively clarify the effect of the bondline damage during slip reversal on the ultimate load (bond strength). The results show that the bondline damage has a significant effect on the load-carrying capacity of the NSM FRP-to-concrete bonded interface and should be considered in FE modeling of the interface.

Basalt Fibre Reinforced Polymer Strengthening of Normal Strength Reinforced Concrete Floor Slabs Subject to Arching Effects

With ever increasing demands to strengthen existing reinforced concrete structures to facilitate higher loading due to change of use and to extend service lifetime, the use of fibre reinforced polymers (FRPs) in structural retrofitting offers an opportunity to achieve these aims. To date, most research in this area has focussed on the use of glass fibre reinforced polymer (GFRP) and carbon fibre reinforced polymer (CFRP), with relatively little on the use of basalt fibre reinforced polymer (BFRP) as a suitable strengthening material. In addition, most previous research has been carried out using simply supported elements, which have not considered the beneficial influence of in-plane lateral restraint, as experienced within a framed building structure. Furthermore, by installing FRPs using the near surface mounted (NSM) technique, disturbance to the existing structure can be minimised.
This paper outlines BFRP NSM strengthening of one third scale laterally restrained floor slabs which reflect the inherent insitu compressive membrane action (CMA) in such slabs. The span-to-depth ratios of the test slabs were 20 and 15 and all were constructed with normal strength concrete (~40N/mm2) and 0.15% steel reinforcement. 0.10% BFRP was used in the retrofitted samples, which were compared with unretrofitted control samples. In addition, the bond strength of BFRP bars bonded into concrete was investigated over a range of bond lengths with two different adhesive thicknesses. This involved using an articulated beam arrangement in order to establish optimum bond characteristics for use in strengthening slab samples.

Use of recycled demolition aggregate in precast products, phase II: Concrete paving blocks

A study undertaken at the University of Liverpool has investigated the potential for using construction and demolition waste (C&DW) as aggregate in the manufacture of a range of precast concrete products, i.e. building and paving blocks and pavement flags. Phase II, which is reported here, investigated concrete paving blocks. Recycled demolition aggregate can be used to replace newly quarried limestone aggregate, usually used in coarse (6 mm) and fine (4 mm-to-dust) gradings. The first objective, as was the case with concrete building blocks, was to replicate the process used by industry in fabricating concrete paving blocks in the laboratory. The compaction technique used involved vibration and pressure at the same time, i.e. a vibro-compaction technique. An electric hammer used previously for building blocks was not sufficient for adequate compaction of paving blocks. Adequate compaction could only be achieved by using the electric hammer while the specimens were on a vibrating table. The experimental work involved two main series of tests, i.e. paving blocks made with concrete- and masonry-derived aggregate. Variables that were investigated were level of replacement of (a) coarse aggregate only, (b) fine aggregate only, and (c) both coarse and fine aggregate. Investigation of mechanical properties, i.e. compressive and tensile splitting strength, of paving blocks made with recycled demolition aggregate determined levels of replacement which produced similar mechanical properties to paving blocks made with newly quarried aggregates. This had to be achieved without an increase in the cement content. The results from this research programme indicate that recycled demolition aggregate can be used for this new higher value market and therefore may encourage demolition contractors to develop crushing and screening facilities for this. (C) 2011 Published by Elsevier Ltd.

The use of recycled demolition aggregate in precast concrete products – Phase III: Concrete pavement flags

A study undertaken at the University of Liverpool has investigated the potential for using construction and demolition waste (C&DW) derived aggregate in the manufacture of a range of precast concrete products, i.e. building and paving blocks and pavement flags. Phase III, which is reported here, investigated
concrete pavement flags. This was subsequent to studies on building and paving blocks. Recycled demolition aggregate can be used to replace newly quarried limestone aggregate, usually used in coarse (6 mm) and fine (4 mm-to-dust) gradings. The first objective was, as was the case with concrete building
and paving blocks, to replicate the process used by industry in fabricating concrete pavement flags in the laboratory. The ‘‘wet’’ casting technique used by industry for making concrete flags requires a very workable mix so that the concrete flows into the mould before it is compressed. Compression squeezes out water from the top as well as the bottom of the mould. This industrial casting procedure was successfully replicated in the laboratory by using an appropriately modified cube crushing machine and a special mould typical of what is used by industry. The mould could be filled outside of the cube crushing machine and then rolled onto a steel frame and into the machine for it to be compressed. The texture and mechanical properties of the laboratory concrete flags were found to be similar to the factory ones. The experimental work involved two main series of tests, i.e. concrete flags made with concrete- and
masonry-derived aggregate. Investigation of flexural strength was required for concrete paving flags. This is different from building blocks and paving blocks which required compressive and tensile splitting strength respectively. Upper levels of replacement with recycled demolition aggregate were determined
that produced similar flexural strength to paving flags made with newly quarried aggregates, without requiring an increase in the cement content. With up to 60% of the coarse or 40% of the fine fractions replaced with concrete-derived aggregates, the target mean flexural strength of 5.0 N/mm2 was still
achieved at the age of 28 days. There was similar detrimental effect by incorporating the fine masonry-derived aggregate. A replacement level of 70% for coarse was found to be satisfactory and also conservative. However, the fine fraction replacement could only be up to 30% and even reduced to 15% when used for mixes where 60% of the coarse fraction was also masonry-derived aggregate.

The importance of hydrogen's potential-energy surface and the strength of the forming R-H bond in surface hydrogenation reactions

An understanding of surface hydrogenation reactivity is a prevailing issue in chemistry and vital to the rational design of future catalysts. In this density-functional theory study, we address hydrogenation reactivity by examining the reaction pathways for N+H -> NH and NH+H -> NH2 over the close-packed surfaces of the 4d transition metals from Zr-Pd. It is found that the minimum-energy reaction pathway is dictated by the ease with which H can relocate between hollow-site and top-site adsorption geometries. A transition state where H is close to a top site reduces the instability associated with bond sharing of metal atoms by H and N (NH) (bonding competition). However, if the energy difference between hollow-site and top-site adsorption energies (Delta E-H) is large this type of transition state is unfavorable. Thus we have determined that hydrogenation reactivity is primarily controlled by the potential-energy surface of H on the metal, which is approximated by Delta E-H, and that the strength of N (NH) chemisorption energy is of less importance. Delta E-H has also enabled us to make predictions regarding the structure sensitivity of these reactions. Furthermore, we have found that the degree of bonding competition at the transition state is responsible for the trend in reaction barriers (E-a) across the transition series. When this effect is quantified a very good linear correlation is found with E-a. In addition, we find that when considering a particular type of reaction pathway, a good linear correlation is found between the destabilizing effects of bonding competition at the transition state and the strength of the forming N-H (HN-H) bond. (c) 2006 American Institute of Physics.

Interfacial shear strength and tensile properties of injection-molded, short- and long-glass fiber-reinforced polyamide 6,6 composites

Injection-molded short- and long-glass fiber/polyamide 6,6 composites were subjected to tensile tests. To measure the effectiveness of the fibers in reinforcing the composites, a computational approach was employed to compute the fiber– matrix ISS, orientation factor, reinforcement efficiency, tensile-, and fiber length-related properties. Although the LFCs showed great improvement in fiber characteristics compared to the SFCs, enhancement in tensile properties was small, which is believed to be due to the larger fiber diameter. Kelly–Tyson model provides good approximation for the computation of ISS and tensile-related properties.

Zinc Phosphate Cement: Variations in proportioning affects dimetral tensile strength

Objectives: To quantify variability in hand proportioning of zinc phosphate cement among a cohort of dental undergraduates and to determine the effect of any such variability on the diametral tensile strength (DTS) of the set cement. The null hypothesis was that such variability has no effect on DTS. 
Methods: Thirty-four operators dispensed a zinc phosphate cement [Fleck's® Cement] according to the manufacturers' instructions. The mass of powder and liquid dispensed was recorded. Cylindrical specimens (n = 2 x 34) of dimensions 6mm x 3mm were prepared using a stainless steel split mould. The maximum mass of powder and the minimum volume of liquid were used as one extreme ratio and the minimum mass of powder and the maximum volume of liquid used on the other extreme. The manufacturers' recommended ratio was also tested (n=34).The samples were left to set for one hour before being transferred into distilled water for 48 hours. Compression across a diameter was carried out using a universal testing machine, H10KS [Tinius Olsen], at a constant crosshead speed of 0.75 ±0.25 mm/min. Statistical analyses (α = 0.05) were by Student's t-test for the powder/liquid ratio and one-way ANOVA and Tukey HSD for for pair-wise comparisons of mean DTS. Tests were carried out for normality and constant variability. 
Results: The mean (range) amount of powder dispensed was 0.863g (0.531-1.216)g. The mean (range) amount of liquid dispensed was 0.341ml (0.265-0.394)ml. The manufacturer's recommended amounts were 0.8g of powder and 0.3ml of liquid. The mean powder/liquid ratio was not significantly different from the manufacturer's recommended value (p=0.64). Mean (SD) DTS were (MPa) max: 7.19(1.50), min: 2.65(1.01), manufacturer: 6.01(1.30). All pair-wise comparisons were significantly different (p<0.001). 
Conclusions: Variability exists in the hand proportioning powder and liquid components of zinc phosphate cement. This variability can affect the DTS of zinc phosphate cement.