Alkali activated fuel ash and slag mixes:optimization study from paste to concrete building blocks

Alkali activated binders, based on ash and slag, also known as geopolymers, can play a key role in reducing the carbon footprint of the construction sector by replacing ordinary Portland cement in some concretes. Since 1970s, research effort has been ongoing in many research institutions. In this study, pulverized fuel ash (pfa) from a UK power plant, ground granulated blast furnace slag (ggbs) and combinations of the two have been investigated as geopolymer binders for concrete applications. Activators used were sodium hydroxide and sodium silicate solutions. Mortars with sand/binder ratio of 2.75 with several pfa and ggbs combinations have been mixed and tested. The optimization of alkali dosage (defined as the Na2O/binder mass ratio) and modulus (defined as the Na2O/SiO2 mass ratio) resulted in strengths in excess of 70 MPa for tested mortars. Setting time and workability have been considered for the identification of the best combination of pfa/ggbs and alkali activator dosage for different precast concrete products. Geopolymer concrete building blocks have been replicated in laboratory and a real scale factory trial has been successfully carried out. Ongoing microstructural characterization is aiming to identify reaction products arising from pfa/ggbs combinations.

Ca(2+)-sparks constitute elementary building blocks for global Ca(2+)-signals in myocytes of retinal arterioles.

Spontaneous Ca2+-events were imaged in myocytes within intact retinal arterioles (diameter < 40 mu m) freshly isolated from rat eyes. Ca2+-sparks were often observed to spread across the width of these small cells, and could summate to produce prolonged Ca2+-oscillations and contraction. Application of cyclopiazonic acid (20 mu M) transiently increased spark frequency and oscillation amplitude, but inhibited both sparks and oscillations within 60 s. Both ryanodine (100 mu M) and tetracaine (100 mu M) reduced the frequency of sparks and oscillations, while tetracaine also reduced oscillation amplitude. None of these interventions affected spark amplitude. Nifedipine, which blocks store filling independently of any action on L-type Ca2+-channels in these cells, reduced the frequency and amplitude of both sparks and oscillations. Removal of external [Ca2+] (1 mM EGTA) also reduced the frequency of sparks and oscillations but these reductions were slower in onset than those in the presence of tetracaine or cyclopiazonic acid. Cyclopiazonic acid, nifedipine and low external [Ca2+] all reduced SR loading, as indicated by the amplitude of caffeine evoked Ca2+-transients. This study demonstrates for the first time that spontaneous Ca2+-events in small arterioles of the eye result from activation of ryanodine receptors in the SR and suggests that this activation is not tightly coupled to Ca2+-influx. The data also supports a model in which Ca2+-sparks act as building blocks for more prolonged, global Ca2+-signals. (c) 2006 Elsevier Ltd. All rights reserved.

Lorentz TEM investigation of the switching behavior in artificial spin ice building blocks

Frustration – the inability to simultaneously satisfy all interactions – occurs in a wide range of systems including neural networks, water ice and magnetic systems. An example of the latter is the so called spin-ice in pyrochlore materials [1] which have attracted a lot of interest not least due to the emergence of magnetic monopole defects when the ‘ice rules’ governing the local ordering breaks down [2]. However it is not possible to directly measure the frustrated property – the direction of the magnetic moments – in such spin ice systems with current experimental techniques. This problem can be solved by instead studying artificial spin-ice systems where the molecular magnetic moments are replaced by nanoscale ferromagnetic islands [3-8]. Two different arrangements of the ferromagnetic islands have been shown to exhibit spin ice behaviour: a square lattice maintaining four moments at each vertex [3,8] and the Kagome lattice which has only three moments per vertex but equivalent interactions between them [4-7]. Magnetic monopole defects have been observed in both types of lattices [7-8]. One of the challenges when studying these artificial spin-ice systems is that it is difficult to arrive at the fully demagnetised ground-state [6-8].
Here we present a study of the switching behaviour of building blocks of the Kagome lattice influenced by the termination of the lattice. Ferromagnetic islands of nominal size 1000 nm by 100 nm were fabricated in five island blocks using electron-beam lithography and lift-off techniques of evaporated 18 nm Permalloy (Ni80Fe20) films. Each block consists of a central island with four arms terminated by a different number and placement of ‘injection pads’, see Figure 1. The islands are single domain and magnetised along their long axis. The structures were grown on a 50 nm thick electron transparent silicon nitride membrane to allow TEM observation, which was back-coated with a 5 nm film of Au to prevent charge build-up during the TEM experiments.
To study the switching behaviour the sample was subjected to a magnetic field strong enough to magnetise all the blocks in one direction, see Figure 1. Each block obeys the Kagome lattice ‘ice-rules’ of “2-in, 1-out” or “1-in, 2-out” in this fully magnetised state. Fresnel mode Lorentz TEM images of the sample were then recorded as a magnetic field of increasing magnitude was applied in the opposite direction. While the Fresnel mode is normally used to image magnetic domain structures [9] for these types of samples it is possible to deduce the direction of the magnetisation from the Lorentz contrast [5]. All images were recorded at the same over-focus judged to give good Lorentz contrast.
The magnetisation was found to switch at different magnitudes of the applied field for nominally identical blocks. However, trends could still be identified: all the blocks with any injection pads, regardless of placement and number, switched the direction of the magnetisation of their central island at significantly smaller magnitudes of the applied magnetic field than the blocks without injection pads. It can therefore be concluded that the addition of an injection pad lowers the energy barrier to switching the connected island, acting as a nucleation site for monopole defects. In these five island blocks the defects immediately propagate through to the other side, but in a larger lattice the monopoles could potentially become trapped at a vertex and observed [10].
References

[1] M J Harris et al, Phys Rev Lett 79 (1997) p.2554.
[2] C Castelnovo, R Moessner and S L Sondhi, Nature 451 (2008) p. 42.
[3] R F Wang et al, Nature 439 (2006) 303.
[4] M Tanaka et al, Phys Rev B 73 (2006) 052411.
[5] Y Qi, T Brintlinger and J Cumings, Phys Rev B 77 (2008) 094418.
[6] E Mengotti et al, Phys Rev B 78 (2008) 144402.
[7] S Ladak et al, Nature Phys 6 (2010) 359.
[8] C Phatak et al, Phys Rev B 83 (2011) 174431.
[9] J N Chapman, J Phys D 17 (1984) 623.
[10] The authors gratefully acknowledge funding from the EPSRC under grant number EP/D063329/1.

Dendrons with spermine surface groups as potential building blocks for nonviral vectors in gene therapy

This paper investigates a series of dendrons based on the Newkome dendritic scaffold that displays a naturally occurring polyamine (spermine) on their surface. These dendrons have previously been shown to interact with DNA in a generation dependent manner with the more highly branched dendrons exhibiting a strong multivalency effect for the spermine surface groups. In this paper, we investigate the ability of these dendrons to transfect DNA into cells (human breast carcinoma cells, MDA-MB-231, and murine myoblast cells, C2C12) as determined by the luciferase assay. Although the dendrons are unable to transfect DNA in their own right, they are capable of delivering DNA in vitro when administered with chloroquine, which assists with escape from endocytic vesicles. The cytotoxicity of the dendrons was determined using the XTT assay, and it was shown that the dendrons were nontoxic either alone or in the presence of DNA. However, when administered with DNA and chloroquine, the most highly branched dendron did exhibit some cytotoxicity. This paper elucidates the relationship between in vitro transfection efficiency and toxicity. While transfection efficiencies are modest, the low toxicity of the dendrons, both in their own right, and in the presence of DNA, provides encouragement that this type of building block, which has a relatively high affinity for DNA, will provide a useful starting point for the further synthetic development of more effective gene transfection agents.

Dynamical instability in surface permeability characteristics of building sandstones in response to salt accumulation over time

This paper explores how the surface permeability of sandstone blocks changes over time in response to repeated salt weathering cycles. Surface permeability controls the amount of moisture and dissolved salt that can penetrate in and facilitate decay. Connected pores permit the movement of moisture (and hence soluble salts) into the stone interior, and where areas are more or less permeable soluble salts may migrate along preferred pathways at differential rates. Previous research has shown that salts can accumulate in the near-surface zone and lead to partial pore blocking which influences subsequent moisture ingress and causes rapid salt accumulation in the near-surface zone.

Two parallel salt weathering simulations were carried out on blocks of Peakmoor Sandstone of different volumes. Blocks were removed from simulations after 2, 5, 10, 20 and 60 cycles. Permeability measurements were taken for these blocks at a resolution of 20 mm, providing a grid of 100 permeability values for each surface. The geostatistical technique of ordinary kriging was applied to the data to produce a smoothed interpolation of permeability for these surfaces, and hence improve understanding of the evolution of permeability over time in response to repeated salt weathering cycles.

Results illustrate the different responses of the sandstone blocks of different volumes to repeated salt weathering cycles. In both cases, after an initial subtle decline in the permeability (reflecting pore blocking), the permeability starts to increase — reflected in a rise in mean, maximum and minimum values. However, between 10 and 20 cycles, there is a jump in the mean and range permeability of the group A block surfaces coinciding with the onset of meaningful debris release. After 60 cycles, the range of permeability in the group A block surface had increased markedly, suggesting the development of a secondary permeability. The concept of dynamic instability and divergent behaviour is applied at the scale of a single block surface, with initial small-scale differences across a surface having larger scale consequences as weathering progresses.

After cycle 10, group B blocks show a much smaller increase in mean permeability, and the range stays relatively steady — this may be explained by the capillary conditions set up by the smaller volume of the stone, allowing salts to migrate to the ‘back’ of the blocks and effectively relieving stress at the ‘front’ face.

High-surface thermally stable mesoporous gallium phosphates constituted by nanoparticles as primary building blocks

In constant, search for micro/mesoporous materials, gallium phosphates, have attracted continued interest due to the large pore size reported for some of these solids in comparison with analogous aluminum phosphates. However up to now, the porosity of gallium phosphates collapsed upon template removal or exposure to the ambient moisture. In the present work, we describe high-surface thermally stable mesoporous gallium phosphates synthesized from gallium propoxide and PCl3 and different templating agents such as amines (dipropylamine, piperidine and aminopiperidine) and quaternary ammonium salts (C16H33(CH3)3NBr and C16PyCl). These highly reactive precursors have so far not been used as gallium and phosphate sources for the synthesis of gallophosphates. Conceptually, our present synthetic procedure is based on the fast formation of gallium phosphate nanoparticles via the reaction of gallium propoxide with PCl3 and subsequent construction of the porous material with nanoparticles as building blocks. The organization of the gallophosphate nanoparticles in stable porous structures is effected by the templates. Different experimental procedures varying the molar composition of the sol-gel, pH and the pretreatment of gallium precursor were assayed, most of them leading to satisfactory materials in terms of thermal stability and porosity. In this way, a series of gallium phosphates with surface are above 200 m(2) g(-1), and narrow pore size from 3 to 6 nm and remarkable thermal stability (up to 550 degrees C) have been prepared. In some cases, the structure tends to show some periodicity and regularity as determined by XRD. The remarkable stability has allowed us to test the catalytic activity of gallophosphates for the aerobic oxidation of alkylaromatics with notable good results. Our report reopens the interest for gallophosphates in heterogeneous catalysis. (C) 2010 Elsevier Inc. All rights reserved.

Concrete building blocks made with recycled demolition aggregate

A study undertaken at the University of Liverpool has investigated the potential for using recycled demolition aggregate in the manufacture of precast concrete building blocks. Recycled aggregates derived from construction and demolition waste (C&DW) can be used to replace quarried limestone aggregate, usually used in coarse (6 mm) and fine (4 mm-to-dust) gradings. The manufacturing process used in factories, for large-scale production, involves a “vibro-compaction” casting procedure, using a relatively dry concrete mix with low cement content (˜100 kg/m3). Trials in the laboratory successfully replicated the manufacturing process using a specially modified electric hammer drill to compact the concrete mix into oversize steel moulds to produce blocks of the same physical and mechanical properties as the commercial blocks. This enabled investigations of the effect of partially replacing newly quarried with recycled demolition aggregate on the compressive strength of building blocks to be carried out in the laboratory. Levels of replacement of newly quarried with recycled demolition aggregate have been determined that will not have significant detrimental effect on the mechanical properties. Factory trials showed that there were no practical problems with the use of recycled demolition aggregate in the manufacture of building blocks. The factory strengths obtained confirmed that the replacement levels selected, based on the laboratory work, did not cause any significant strength reduction, i.e. there was no requirement to increase the cement content to maintain the required strength, and therefore there would be no additional cost to the manufacturers if they were to use recycled demolition aggregate for their routine concrete building block production.

An Gaelaras, by O'Donnell and Tuomey:The Building blocks of Language: Review by Rick LeVert and Tarla MacGabhann

The opening of An Gaelaras - the Irish language cultural centre in Derry designed by O'Donnell + Tuomey - is the most significant architectural addition to the symbolic landscape of the Walled City in recent times. It marks nothing less than a physical re-surfacing and a normalisation of the Irish language in this long fragmented city. This alone places An Gaelaras in a delicate historical arc that spans over 1500 years of architectural heritage and links it with the now invisible ruins of St Columba's original 6th century monastery.

Alkali Activated Fuel Ash and Slag Mixes:Optimization Study from Mortars to Concrete Building Blocks

Alkali activated binders, based on ash and slag, also known as geopolymers, can play a key role in reducing the carbon footprint of the construction sector by replacing ordinary Portland cement in some concretes. Since 1970s, research effort has been ongoing in many research institutions. In this study, pulverized fuel ash (PFA) from a UK power plant, ground granulated blast furnace slag (GGBS) and combinations of the two have been investigated as geopolymer binders for concrete applications. Activators used were sodium hydroxide and sodium silicate solutions. Mortars with sand/binder ratio of 2.75 with several PFA and GGBS combinations have been mixed and tested. The optimization of alkali dosage (defined as the Na2O/binder mass ratio) and modulus (defined as the Na2O/SiO2 mass ratio) resulted in strengths in excess of 70 MPa for tested mortars. Setting time and workability have been considered for the identification of the best combination of PFA/GGBS and alkali activator dosage for different precast concrete products. Geopolymer concrete building blocks have been replicated in laboratory and a real scale factory trial has been successfully carried out. Ongoing microstructural characterization is aiming to identify reaction products arising from PFA/GGBS combinations.

Self-assembly using dendritic building blocks - towards controllable nanomaterials

Dendritic molecules have well defined, three-dimensional branched architectures, and constitute a unique nanoscale toolkit. This review focuses on examples in which individual dendritic molecules are assembled into more complex arrays via non-covalent interactions. In particular, it illustrates how the structural information programmed into the dendritic architecture controls the assembly process, and as a consequence, the properties of the supramolecular structures which are generated. Furthermore, the review emphasises how the use of non-covalent (supramolecular) interactions, provides the assembly process with reversibility, and hence a high degree of control. The review also illustrates how self-assembly offers an ideal approach for amplifying the branching of small, synthetically accessible, relatively inexpensive dendritic systems (e.g. dendrons), into highly branched complex nanoscale assemblies.

The review begins by considering the assembly of dendritic molecules to generate discrete, well-defined supramolecular assemblies. The variety of possible assembled structures is illustrated, and the ability of an assembled structure to encapsulate a templating unit is described. The ability of both organic and inorganic building blocks to direct the assembly process is discussed. The review then describes larger discrete assemblies of dendritic molecules, which do not exist as a single well-defined species, but instead exist as statistical distributions. For example, assembly around nanoparticles, the assembly of amphiphilic dendrons and the assembly of dendritic systems in the presence of DNA will all be discussed. Finally, the review examines dendritic molecules, which assemble or order themselves into extended arrays. Such systems extend beyond the nanoscale into the microscale or even the macroscale domain, exhibiting a wide range of different architectures. The ability of these assemblies to act as gel-phase or liquid crystalline materials will be considered.

Taken as a whole, this review emphasises the control and tunability that underpins the assembly of nanomaterials using dendritic building blocks, and furthermore highlights the potential future applications of these assemblies at the interfaces between chemistry, biology and materials science.