text:
\section*{Introduction}
Carbon nanotubes (CNTs) are extraordinary building blocks due to their exceptional combination of mechanical, electrical and thermal properties along the tube axis. They can be produced in large quantities as a highly graphitic material with a well defined structure, in some cases with molecular composition control in terms of number of layers, diameter of nanotubes and chiral angle. Their assembly into fibers and further arrays (yarns, tows, fabrics) has unlocked numerous applications in diverse fields, including electrodes for energy storage \cite{senokos2016}, neural stimulation \cite{Neural} and water desalination \cite{Cleis}, composite reinforcement elements \cite{Gonzalez2017}, sensors  \cite{Toribio2016}, and multiple wearable devices \cite{ReviewQingwen}.

This has been possible through the development of fiber spinning processes that can reproducibly produce uniform highly controlled materials. An example is the direct spinning method, whereby an aerogel of CNTs is produced by floating catalyst chemical vapor deposition (FC-CVD) and directly drawn out of a reactor and wound continuously as a macroscopic fiber \cite{Windle2004}. It is of particular interest because it combines independent control of CNT alignment,\cite{Aleman2015} composition in terms of number of layers \cite{Reguero2014} and CNT morphology, \cite{Selenio2016} with large scale production in laboratory setting ($>10$ km/day) and at industrial scaled-up facilities. CNT fibers are stronger than carbon fibers \cite{Science}, with higher thermal conductivity than copper \cite{copper12017,Science2013} and higher mass-normalized electrical conductivity than most metals \cite{Science2013,Lewaka2014} have been produced using this method.

There have been substantial efforts to understand the key parameters during synthesis and spinning that control CNT fiber structure and resulting properties. The process shares some features of conventional substrate-based CVD growth of CNT, both being based on catalytic decomposition of a carbon source and extrusion as a CNT from a transition metal catalyst particle, typically in a reducing (H\textsubscript{2}) atmosphere.

In the case of traditional substrate growth of CNTs by CVD, control over CNT type, quality and yield depend strongly  on  the presence and choice of a MO\textsubscript{x} support layer. The MO\textsubscript{x} acts as a barrier for catalyst diffusion but has also influence on the catalyst particle size/shape and catalytic activity \cite{Cantoro,Bronikowski2007}. The activity of supported catalyst vary depending on reducibility of the metal oxide and formation of silicides \cite{Wagner2007}. In the context of CNT growth from pre-deposied Fe catalyst particles on Si wafers with either SiO\textsubscript{2} or Al\textsubscript{2}O\textsubscript{3} thin coatings, for example, \textit{in-situ} studies have shown that CNT morphology and areal density strongly depend on  strength (i.e. charge transfer at) of the molten Fe nanoparticle/MOx interface \cite{Hofmann1,Hofman2}. In general, the use of a thin (100-400 nm) layer of SiO\textsubscript{2} has been an effective route to achieve reproducible synthesis of highly graphitic aligned, long CNTs on substrates ranging from Si wafers to carbon fibers \cite{Vilatela2015,Hermite2012}.

On the other hand, FC-CVD is conducted at higher temperature ($>1000$ ºC) under conditions leading to the formation of catalyst nanoparticles "floating" in the gas phase, and which are assumed to entirely produce the decomposition of the carbon source and formation of carbon nanotubes\cite{moisala2003,moisala2005,moisala2006}. In the case of the direct spinning process, the presence of sulfur or another promoter enables the formation of an aerogel that can be continuously drawn out of the reactor during CNT growth to form a continuous macroscopic fiber. The promoter reduces carbon solubility in the catalyst, while also assists stabilization of the nascent CNT nucleus through the minimization of the interfacial energy between the CNT edge and the catalyst particle. CNT number of layers and yield are hence dependent on sulfur/carbon ratio (S/C) in the reaction, \cite{Reguero2014} thus indirectly also on the choice of sulfur precursor \cite{Sundaram2011}. These roles are similar to the effect of S and other group 16 elements as a "surfactant" in cast iron and graphitic poison in methanation reactions. In contrast, the concentration of Fe catalyst particles in the direct spinning process has a minor effect on CNT morphology or yield, provided there are sufficient to carry out the reaction, with only $< 0.01\%$ being active.

A prevalent assumption in CNT growth by FC-CVD is that the ceramic reactor tube, typically alumina, mullite or silica, plays no active role in the reaction and simply act as reaction vessels. However, here we show that the ceramic tube that hosts the FC-CVD plays an unsuspected active role in the FC-CVD reaction through carbon precursor decomposition. While it does not change CNT morphology, which remains controlled by the S/C ratio, it can double reaction yield when mullite (Al\textsubscript{4+2x}Si\textsubscript{2-2x}O\textsubscript{10-x}(x $\approx 0.4)$) is used instead of alumina (Al\textsubscript{2}O\textsubscript{3}), for example. Analysis of Si-based impurities, occasionally found in CNT fiber samples and presumed to detach from the reactor tube, helps understand general aspects of the reaction mechanism.

\section*{Results}
\subsection*{Synthesis in different reactor tubes}
We have produced continuous CNT fibers in reactor tubes with different contents of SiO$_{2}$. In our typical set-up mullite (62.6$\%$ Al$_{2}$O$_{3}$, 35.2$\%$ SiO$_{2}$, 2.2$\%$ others) is used as a reactor tube, leading to the formation of a dark aerogel of CNTs that can be continuously spun for hours (Figure \ref{fig1}a). Interestingly, the use of an alumina reactor under otherwise identical synthesis (with ferrocence as catalyst source, thiophene as S promoter source and a liquid carbon source) conditions, while still leading to stable and continuous fiber spinning, produces a clear reduction in reaction conversion and changes in aerogel morphology.

\begin{figure}[ht]
\centering
\includegraphics[width=0.9\linewidth]{Fig1v2.jpg}
\caption{Effects of reactor tube composition for the spinning CNT fibers directly from the gas phase during FC-CVD. a) Schematic of the reactor set-up. b) Carbon efficiency for mullite and allumina under different synthesis conditions including low (high) S/C ratio to produce SWNTs (MWNTs) or when using different carbon sources (butanol and toluene). Ferrocene used as Fe catalyst source}
\label{fig1}
\end{figure}

This behaviour is observed under a wide range of synthesis conditions, for example when varying the S/C ratio so as to control CNT number of layers, or when using different carbon sources. Figure \ref{fig1}b shows consistently higher carbon efficiency in terms of conversion of injected carbon to graphitic carbon for mullite, under synthesis conditions to produce: predominantly single-walled carbon nanotubes (SWCNT), multi-walled carbon nanotubes (MWCNTs), and when using butanol or toluene as carbon sources.

To investigate intermediate SiO$_{2}$ compositions we performed an additional experiment in which a mullite inner tube was gradually introduced from the top of the reactor into the alumina reactor tube, until the bottom of the inner mullite tube was in the region of $1250 ^{\circ}C$, as schematically shown in Figure \ref{fig2}a. The resulting CNT fiber had an intermediate linear density between those produced in alumina or mullite (Figure \ref{fig2}(a)).  At a spinning rate of 5 $m/min$, the linear mass density of the fiber produced in mullite is around $0.60 g/km$, higher than the fiber produced in alumina, which is $0.35 g/km$, whereas the fiber produced in alumina after insertion of a mullite tube had a linear density of $0.43 g/km$ (Figure \ref{fig2}(a)). These differences in linear density correlated well with the perceived darkness of the CNT aerogel observed from the bottom of the reactor, as shown in the photographs in Figure \ref{fig2}(b). No other major differences in the position or shape of the aerogel that could suggest growth of the CNTs on the ceramic surface, were observed.

\begin{figure}[ht]
\centering
\includegraphics[width=0.8\linewidth]{Fig1}
\caption{Effects of reactor tube material on CNT aerogel properties. (a) Relationship between linear density (g/km) and the type of reactor tube. (b) Optical images showing increasing perceived thickness of the CNT aerogel when comparing reactions in alumina, alumina + mullite or mullite.}
\label{fig2}
\end{figure}

\begin{figure}[ht]
\centering
\includegraphics[width=0.5\linewidth]{Fig3_chrom.jpg}
\caption{Chromatographs of gases present at the outlet of the reactor. Four gases have been sampled in four different scenarios: when using either alumina or mullite tubes, and with or without catalyst. Chromatographs have been tiled vertically for clarity.}
\label{fig3_chrom}
\end{figure}

In order to shed light into the effect of the reactor tube on the reaction conditions, we studied the chemical composition of gases at the reactor outlet by performing chromatography measurements on gas samples extracted from the reactor when using mullite or alumina tubes. Reference measurements also included gas samples produced in the absence of Fe catalyst but with the same injection of the remaining precursors. At present, the experimental protocol used (see experimental section) only enables gas extraction from the lower part of the reactor, which can contain substantial nitrogen gas purposely introduced to replace hydrogen at the reactor exit for safety reasons, but which does not take part in the reaction. As a consequence, only relative concentrations of different species can be analyzed based on the chromatography data (Figure \ref{fig3_chrom}).

\begin{figure}[ht]
\centering
\includegraphics[width=0.8\linewidth]{Fig2}
\caption{Characterization of samples produced in different reactor tubes showing changes in reaction yield but not in CNT morphology. (a) Typical Raman spectra showing nearly identical peak positions and ratio I\textsubscript{D}/I\textsubscript{G}. (b) Thermo-gravimetric curves indicating similar composition of graphitic material and confirming higher yield for samples produced in mullite  (through a lower fraction of residual catalyst).}
\label{fig4}
\end{figure}

Interestingly, the analysis of the gases at the outlet of both reactor tubes reveals extensive thermal decomposition of the carbon source (1-butanol) irrespective of the presence of catalyst. CO$_{2}$ and C$_{1}$-C$_{3}$ hydrocarbons (methane, ethane, ethylene, acetylene) are found in all conditions studied, together with minor amounts of carbonyl sulphide. Benzene, propene and propyne are also observed in small quantities. These results are in agreement with thermal decomposition studies of n-butanol reported in the literature \cite{Harper2011}. The presence or absence of the main products does not appear to depend on the addition of catalyst or the type of reactor tube used. This result reveals that the catalyst does not play an active role in the decomposition of the carbon source, contrary to what is generally assumed. Having established that the reactor tube plays a central role in the decomposition of the C source, it is not surprising that its composition affects the concentration of different C species in the reactor. As observed in the comparison in Figure \ref{fig3_chrom}, the fraction of methane, ethylene and carbon dioxide, amongst other species, is clearly sensitive to the composition of the rector tube. Determining the precise thermodynamic pathway for the cracking of the hydrocarbons during FC-CVD synthesis of CNT fibers requires dedicated, advanced in-situ sampling methods that can operate at reaction temperatures above 1000$^{\circ}$ \cite{boies2016}, and is beyond the scope of this work.

In spite of the substantial change in reaction conversion the type and morphology of the constituent CNTs are not significantly affected by the choice of reactor tube. The Raman spectra for samples produced in the different reactor tubes, but with the same precursor composition, presented in Figure  \ref{fig4}(a), show that in all three cases the CNTs consist of highly graphitic few-layer multi-wall nanotubes (MWNTs). The spectra reveal no appreciable change in peak positions, for instance in the G band (1583 $cm^{-1}$, 1584 $cm^{-1}$, 1583 $cm^{-1}$ for alumina, alumina with concentric mullite tube and mullite tube, respectively). Similarly, the ratio of intensities of $I\textsubscript{D}/I\textsubscript{G}$ for the three fiber types ($0.3$ for alumina, $0.4$ for alumina with mullite and $0.3$ for mullite) are within typical variation between samples and suggest no substantial differences in CNT morphology or degree of graphitization.

Thermo-gravimetric analysis (TGA) (Figure \ref{fig4}(b)) also indicates that the use of different reactor tubes has no effect on the quality and morphology of the graphitic materials, only on yield. A comparison of thermograms shows the three samples to have similar thermal decomposition curves, with nearly identical onset for CNT oxidation at 530 ºC. The content of poorly graphitized impurities, evolving at temperatures below 400 ºC, is very similar too. On the other hand, the relative content of residual catalyst also follows the trend observed in Figure \ref{fig2}a ($8.5 \%, 7.4 \% and 4.0 \%$ for mullite, mullite plus alumina and alumina, respectively), reflecting mainly an increase in graphitic material and nearly constant Fe content.

\begin{figure}[ht]
\centering
\includegraphics[width=0.8\linewidth]{Fig3}
\caption{Electron micrographs of CNT fibers produced in an alumina (a) and mullite (b) reactor tubes, showing no changes in composition or CNT type.}
\label{fig5}
\end{figure}

Electron microscopic analysis of samples produced in mullite and alumina tubes, respectively, while only being qualitative, also confirms the observations discussed above. Scanning electron micrographs (Figure \ref{fig5}(a)) gave no indication of the formation of more particulate impurities or changes in bundle morphology. Similarly, transmission electron microscopy (TEM) analysis (Figure \ref{fig5}(b)) confirmed that the CNTs produced in both reactor tubes have a high degree of graphitization (i.e. high sp$^{2}$ conjugation) and have predominantly 3-5 walls, with some of them being collapsed due to their relatively large diameter.

\subsection*{Analysis of Si-containing impurities}
The preceding discussion leaves no doubt that the reactor tube plays an active role in the synthesis of CNTs in the direct fiber process. As a result of reactions at the reactor tube wall and of the SiO$_{2}$ in the tube itself (\textit{vide infra}), Si-containing impurities are occasionally found in CNT fibers. They are scarce, mostly found on samples collected for long times ($> 30$ min) produced in heavily used reactor tubes and when inspecting the samples with methods that probe large sample volumes and/or are sensitive to Si-containing compounds, hence why they had been undetected so far. In fact, their presence in our CNT fiber samples has been elucidated after analysis of combined data obtained using different characterization techniques over several years. Some degree of analysis of these particles is instructive in trying to understand the role of the mullite reactor tube in the CNT growth process.

\begin{figure}[ht]
\centering
\includegraphics[width=0.8\linewidth]{Fig4_nueva.jpg}
\caption{Evidence of Si-containing impurities occasionally found in CNT fibers. (a) EDS spectrum showing a strong Si signal obtained from a thick CNT fiber sample observed under SEM. (b) Si 2p peak in the XPS spectrum of a CNT fiber, corresponding to SiO\textsubscript{2}.}
\label{fig6}
\end{figure}

Figure \ref{fig6}(a) presents an example of an energy dispersive X-ray spectroscopy (EDS) spectrum obtained from a location on a relatively thick CNT fiber sample, which gave a particularly high signal from the Si K${\alpha}$-shell emission line at 1.74 KeV. EDS intensities are strongly dependent on atomic ratio and probe a large sample volume, thus this result only confirms that Si is present in the sample.
Generally X-ray photo-electron spectroscopy (XPS) analysis of CNT fibers shows no indication of the presence Si \cite{Reguero2014,Aleman2016,BelenXPS}, however, in our extensive use of this technique we have occasionally found contributions from Si. The example in Figure \ref{fig6}(b) shows the Si 2p XPS peak, fitted by Gaussian/Lorentzian peak shapes and after Shirley background profile subtraction. The peaks at $102.6$ and $103.8$ eV are assigned to SiO\textsubscript{2},\cite{Sivakumar2011}. This observation indicates that some of the Si-containing impurities are in the form of SiO\textsubscript{2}, but without ruling out other forms of Si (e.g. SiC), particularly considering the limited ($<5$nm) probing depth of XPS.
\begin{figure}[ht]
\centering
\includegraphics[width=0.8\linewidth]{Fig5}
\caption{Observation of Si-containing impurities in CNT fibers observed by synchrotron radiation WAXS in transmission mode. a) 2D WAXS pattern showing the standard reflections from CNTs and residual catalyst and the presence of sharp powder rings from impurities. b) Radial profile after integration with assignation showing reflections from SiO\textsubscript{2} and SiC. The latter implies that SiO\textsubscript{2} in the reactor tube reacts with carbon precursors.}
\label{fig7}
\end{figure}

Another evidence of Si-containing impurities in CNT fibers is found in X-ray diffraction patterns from fibers grown in mullite, our standard reactor tube. Yet, the associated features can only occasionally be resolved and only when using synchrotron radiation in transmission mode, which probes a large sample volume with a high intensity beam. An example is presented in Figure \ref{fig7}, chosen because of the particularly strong intensity of impurity reflections in this part of the sample, which favors their analysis. The same impurity features have been occasionally observed in fibers of single-wall nanotubes (SWNTs) produced with a lower S/C ratio or in samples made using different carbon precursors.

The 2D wide-angle X-ray scattering (WAXS) pattern (Figure \ref{fig7}a) shows that in addition to the standard features of CNT fibers, namely the (002) reflection from CNTs on the equator and broad powder rings associated with the catalyst overlapped with the {100} reflection from CNTs \cite{davies2009}, there are abnormal sharp powder rings. These extraneous peaks are clearly visible in the radial profile obtained after azimuthal integration (Figure \ref{fig7}b).  Interestingly, in addition to a strong reflection at q = 2.06 $\mbox{\AA}^{-1}$ attributed to SiO\textsubscript{2} (96 – 500 – 0036) there are strong reflections at 2.50 $\mbox{\AA}^{-1}$ and 2.74 $\mbox{\AA}^{-1}$, which we assign to SiC (96 – 231 – 0936). These results do not fully determine the structure of these impurities, but they clearly show the presence of SiC, which is a key observation as it implies a reaction of carbon precursors with SiO\textsubscript{2} in the reactor tube.

Note that the Si-containing particles discussed above give rise to sharp X-ray diffraction (XRD) peaks and thus large crystal sizes ($>$ 120 nm). We take this observation as indicative that these impurities correspond to fragments of the reactor tube that detach during fiber spinning, particularly during stringing, and attach to the porous CNT fiber structure at its exit of the reactor. These fragments originate from the inside wall of the reactor tube and thus correspond to the materials that is exposed to the reaction and the highly reducing atmosphere, hence its composition is different from that of mullite.

Further analysis of these impurities is problematic because of the difficulty in locating them, since they are not associated to the catalyst or the CNTs. Conventional analysis of samples by either SEM or TEM has not revealed the presence of Si-based nanoparticles after years of studying these CNT fibers, which explains why, to our knowledge, there are no previous reports suggesting the presence of Si-based impurities after CNT growth by CVD in mullite or quartz. SiO\textsubscript{2} particles on graphene grown by CVD on Cu in hydrogen in a quartz tube have indeed been observed \cite{Benji}, but this in fact supports the view that the reactor tube degrades under nanocarbon growth conditions typically used in CVD, irrespective of the presence of a transition metal catalyst.

In order to gain more insight into the structure of Si-containing impurities in the fibers we subjected a CNT fiber sample to ultrasonication in acetone, a known procedure to selectively remove extraneous materials from CNT fibers while preserving their CNT network structure \cite{Sundaram2017}. The resultant dispersion was deposited on a holey carbon grid to perform TEM analysis.

\begin{figure}[ht]
\centering
\includegraphics[width=0.8\linewidth]{Fig6}
\caption{TEM and EDS analysis of impurities obtained after dispersion. (a) TEM micrograph showing irregular particles of different sizes. (b) EDS elemental maps confirm the presence of Si, mostly associated with O but not spatially correlated with either Fe or C.}
\label{fig8}
\end{figure}

Extensive analysis of impurities showed mainly C- or Fe-based particles, as expected, but some evidence of Si-based particles was also present. Figure \ref{fig8}(a) shows an example of extracted impurities consisting of agglomerated particles of irregular morphology and size ranging from a few to hundreds of nanometers. TEM-EDS mappings performed on these agglomerated  particles clearly show that many of them are Silicon-based \ref{fig8}b. Yet, very importantly, there is no spatial correlation between the Si and Fe signals. This confirms that while playing an active role in the CNT growth process, the SiO\textsubscript{2} in the reactor tube does not directly act on the catalyst particles, nor associates with them, for example as a silicide (FeSi\textsubscript{2}).

\section*{Discussion}
The results presented above demonstrate that SiO$_{2}$ in the reactor tubes plays an active role in CVD reaction, increasing yield of CNTs but without affecting composition. They also show that some SiO$_{2}$ reacts with carbon, leading to the formation of SiC, but very importantly, there is no evidence that Si associates with the Fe-based catalyst or is even present near the catalyst in CNT fibers. While these results might be surprising in the context of CNT growth, they are fully consistent with observations in hydrocarbon heterogeneous catalysis, where SiO$_{2}$ and aluminosilicates are known to catalyze multiple reactions, including cracking of hydrocarbons. Referred to as examples of inorganic solid acids, aluminosilicates are amongst the most studied catalysts in hydrocarbon reactions, most notably, because of their widespread use in oil refining-related reactions. Extensive reviews can be found elsewhere \cite{Corma1995}, but we note some related examples that help clarify the results presented above for the high-temperature catalytic decomposition of n-butanol.

The decomposition of hydrocarbons on the surface of aluminosilicates can lead to multiple path ways that produce both carbon-carbon bond rupture and formation. Early studies showed, for example, that in low-temperature (320 to 550 ºC) decomposition of a wide range of hydrocarbons (alkanes, aliphatic alcohols, etc) in the presence of an aluminosilicate with 85.6 wt.$\%$ SiO$_{2}$ and 12.9 wt. \% Al$_{2}$O$_{3}$, the rate of thermal cracking is negligible compared to the rate of catalytic cracking \cite{Earlycat}. Similarly, a monolayer of SiO$_{2}$ on Al$_{2}$O$_{3}$ has been shown to act as an electron acceptor for 2-butanol dehydration and alkane cracking, amongst other reactions \cite{Herman1966,KNOZINGER1970}. It is most likely that the SiO$_{2}$-catalyzed reaction in the direct spinning corresponds to this type, whereby n-butanol decomposes at the surface of the reactor tube and forms smaller chemical species, including carbocations, that ultimately react with the Fe-based catalyst particle and supply C for the nascent CNT, as shown in the simplified schematic in Figure \ref{fig9}.

\begin{figure}[ht]
\centering
\includegraphics[width=0.5\linewidth]{Fig7}
\caption{Scheme of carbon nanotube growth in FC-CVD used for direct spinning. Carbon source (n-butanol) decomposition takes place at the reactor tube and forms smaller carbocations that finally react with the S-coated Fe catalyst particle and supply C for the nascent CNTs}
\label{fig9}
\end{figure}

We note that mullite also assists CNT fiber growth when using CH$_{4}$ as a C precursor \cite{Tortech}, a common choice in scaled-up facilities. The catalytic degradation of CH$_{4}$, which is more stable than butanol, could involve the formation of its carbenium ion ($\mbox{CH$_{3}$}^{+}$), a chemical species also found in various aluminosilicate-catalyzed hydrocarbon reactions \cite{Corma1995}. In fact, examples of the effect of Si-based reactor tubes on the synthesis of graphitic materials by CVD date back to as early as 1948.\cite{Si1948}.

But to gain more insight into the extent to which the reactor tube can take part in the catalytic decomposition of C-precursors, we have calculated the approximate total surface of Fe catalyst nanoparticles relative to that of the reactor tube. Under the assumption that the residence time in the reactor is dictated by the carrier gas velocity and that the carried gas behaves as an ideal gas, we find that the ratio of surfaces can be expressed as (see SOM)

\begin{equation}
\label{Sratio}
\frac{S_{Fe}}{S_{reactor}} = \frac{3}{2} \frac{\dot{m}_{Fe} r_{reactor}}{r_{Fe}\rho_{Fe} f_{H_{2}}}
\end{equation}

Where $\dot{m}_{Fe}$ is the mass flow rate of Fe injected in the reactor, $r_{reactor}$ is the radius of the reactor tube ($3.5 cm$), $r_{Fe}$ the average Fe catalyst particle radius ($4.5 nm$), $\rho_{Fe}$ the density of Fe and $f_{H_{2}}$ the flow rate of the $H_{2}$ carrier gas. For typical CNT fiber spinning parameters used in laboratory settings the rate comes out as $0.05$. This be initially surprising considering that the radius of the particles is much smaller than that of the reactor tube, but note that the mass flow rate is very low (less than $3 \mu g /s$) and hence the concentration of Fe particles is extremely small, which makes the two surfaces of similar order of magnitude. Very importantly, we have observed gradual roughening of the surface of the reactor tube after its regular use over months. Such roughening occurs through repetitive use in a highly reducing atmosphere (containing H$_{2}$ and CH$_{4}$), causing partial reduction and re-oxidation (on cooling) of mullite \cite{Iso1982,Nasa1996} and its consequent amorphization (see SOM). Together with catalyst plating near the injection point at the cold end of the reactor, this could lead to even higher values of $\frac{S_{Fe}}{S_{reactor}}$ and variations in reaction yield through a higher contribution of hydrocarbon decomposition at the reactor tube.

\section*{Conclusions}
This work shows that the ceramic reactor tube used in FC-CVD synthesis of CNT fibers plays an active role in the reaction by assisting in the decomposition of the n-butanol carbon source. Using a mullite reactor leads to higher reaction yields, i.e. a higher fiber mass linear density, compared to alumina. This is consistent with their established catalytic activity for the decomposition of hydrocarbons. In spite of the key contribution of the reactor tube to the synthesis of CNT fibers, the morphology of the CNTs in terms of degree of graphitization and number of layers remains unaffected by the choice of reactor tube and is instead controlled by the ratio of promoter to carbon source.
Si-based impurities are occasionaly observed in CNT fibers using different techniques. Their structure suggests that they correspond to reactor tube fragments that detach from the main tube and end up trapped in the porous CNT fibers. All evidence suggests that Si does not associate with the Fe catalyst nor take direct part in the extrusion of graphitic carbon at the catalyst particle surface.
A main corollary of these results is the possibility to decouple hydrocarbon decomposition from catalytic growth, which could greatly help increase reaction yield and bring new opportunities for molecular control.This requires, amongst other advances, determining more precisely the catalytic decomposition route of different C sources and separating contributions from the Fe catalyst particles and the reactor tube to this process.

\section*{Methods}

\subsection*{Materials}
Thiophene (extra purity $\geq$ 99 $\%$) from Sigma Aldrich, ferrocene (purity $=$ 98$\%$) obtained from Acros Organics, 1-butanol and toluene (purity $>$ 99$\%$) from Sigma Aldrich were used for the synthesis of CNT fibers. Ferrocene was purified by a sublimation/recrystallization process.

\subsection*{Synthesis of CNT fibers}

Carbon nanotubes fibers were synthesized by direct spinning method. The assembly of CNTs into a fiber in this method occurs in the gas phase during growth by floating catalyst chemical vapor deposition, where the very long CNTs (1mm) entangle and form an aerogel, which is then drawn through and out of the reactor tube and continuously deposited onto a winder, \cite{Windle2004}. The reaction was carried out at 1250 ºC under hydrogen atmosphere and three kind of CNT fibers was produced in three different vertical tubular furnace reactors of alumina, alumina with mullite and mullite.
Synthesis conditions were adjusted so as to produce predominantly few-layer multiwalled CNTs (MWCNT) by using ferrocene as iron catalyst source, thiophene as sulfur catalyst promoter and butanol and toluene as carbon sources, with different relative contents ranging from (0.8 : 1.5 : 97.7) to (0.8 : 0.2 : 99.0).\cite{Reguero2014}

\subsection*{Characterization of CNT fibers}

Raman spectroscopy was performed mainly using a Raman micro-spectroscopy system Renishaw with 532 nm laser line (2.33 eV), taking three accumulations at $\approx 1.68$ mW. In order to maximize the Raman signal, the polarization of the excitation signal was kept parallel to the CNT fiber axis.

SEM micrographs and EDS spectra were taken with a FIB-FEGSEM dual-beam microscope (Helios NanoLab 600i, FEI).
TEM samples were prepared by dispersing a small amount of CNT fiber sample in 99$\%$ pure acetone and sonicated in an ultrasonic power bath to debundle the CNTs and isolate the extraneous materials or impurities. This resulted in the formation of dark dispersion and sedimentation of material. Impurities were collected by depositing a drop of the dark dispersion on a holey carbon TEM grid.
TEM images and EDS elemental maps were taken using a FEG S/TEM microscope (Talos F200X, FEI) equipped with a chemical analysis system via EDS mode.

Thermo-gravimetric analysis were recorded under air atmosphere in a TGA Q50 (TA Instruments). The analyses were performed under air from 25ºC to 800ºC using a 10ºC/min ramp.

XPS data were collected with synchrotron radiation X-Ray source using a Phoibos 100 hemispherical energy analyzer (SPECS GmbH) in ESCAmicroscopy beamline (ELECTRA synchrotron in Trieste, Italy), using a photon energy of 650 eV. Si 2p core level spectrum was fitted by Gaussian/Lorentzian peak shapes and Shirley background profile.

2D WAXS patterns were collected at NCD BL11 ALBA Light Source using a wavelength of 1 Å. The data shown are after sample-detector distance calibration and azimuthal integration. Powder XRD measurements of the reactor tube were performed with a Bruker-AXS SMART 1000 single-crystal diffractometer using Mo KR radiation and a CCD detector. The sample detector distance was determined sing a silicon single-crystal standard.

\subsection*{Gases sampling method}
The gas near the outlet of the reactor tube was sampled by extracting a volume of gas from inside the lower part of the reactor tube into Tedlar bags using a manual pump. The gas samples were then analyzed with a gas chromatograph (Agilent 7820 GC) coupled to a mass spectrometer (Agilent 5977B MSD). The gas was injected through an automatic valve into a CarbonPLOT column (30 m x 0.32 mm) using He as carrier gas with a split ratio of 1:20. The mass spectra were obtained by electronic impact with a single quadruple analyzer and an extractor ion source. The identification of the peaks was performed using the NIST Mass Spectral Search Program.

redpajama_set_name: RedPajamaArXiv


How do I know if it is the Lord speaking? This is the biggest question when it comes to learning to listen to the Lord in prayer. When we look in Scripture, everyone seems to know when it is God who is speaking, but, but the prophets and priests who heard from God had to learn how to recognize God's voice.
When the Lord called Samuel in the middle of the night he did not recognize who was calling to him. He thought it was Eli. Eli did not realize it was the Lord at first. But the Lord was patient and persistent and eventually Eli clued into what was happening and instructed Samuel to respond and say "Speak, Lord, for your servant is listening" (1 Samuel 3:10).
Samuel began to learn to listen to the Lord and the Lord continued to reveal himself to Samuel through his Word (1 Samuel 3:21). Samuel learned to recognize the Lord's voice by studying his Word. So as we spend more time in God's Word we will grow in discerning whether what we we hear is from the Lord or not. God is not going to give us direction to do something which is contrary to his Word in scripture. So as we read, study and immerse ourselves in Scripture we will grow in being able to say "that sounds like the Lord." We always need to examine what we hear to determine if its God or not.
Is what we are hearing something which will exalt Jesus in the present and future?
Is what we are hearing consistent with Scripture's revelation of God's will and character?
Do other people affirm what we are hearing?
Is their fruit? Is there confirmation, through other people or through what happens?
Samuel and Eli talked about what had happened after the Lord had spoken to Samuel. It helped to confirm that it was the Lord speaking and it was further confirmed when what Samuel had heard actually happened. There was fruit.
Praying together in corporate prayer should be an important part of our prayer lives. As God's Word shows, when we pray in agreement our prayers become powerful.
But how do we pray in agreement? Is it simply saying, "Yes, I agree!" when someone else prays? To some extent, it is as simple as that, as we join together in prayer simply saying I agree is the easiest way of agreeing. But joining together in a prayer of agreement can be far richer.
Often when we pray someone begins with one issue and then the next person prays for something else and so the prayer time continues. We join together in agreement for one another but at the end of the prayer time everyone has really just been praying their own prayers. Now, if we imagine that each prayer offered is like a piece of a jigsaw puzzle, then at the end of the prayer time there would just be a bunch of random pieces on the table.
A better way forward is to let our prayers build on each other's prayers. One person starts and the next person picks up the theme and continues the prayer. To use the jigsaw illustration, the first person puts their puzzle piece down and then the next person puts a connecting piece down. To do that well it requires everyone paying attention to what is being prayed and everyone needs to be listening to the Holy Spirit, who guides and directs where the next prayer piece needs to go. So at the end of the prayer time there is a picture, which has formed.
For example, if one person begins to pray for the leaders in the church the next person could pray specifically for the elders and then some one else could pray for a particular issue the elders may be dealing with and someone else may then pray for a family who is affected by the issue the elders are working on and so the prayer continues to build. If one theme comes to an end then someone can pick up another theme and pray. For example, they could pray for the work of the deacons.
Praying in agreement by building on each other's prayers is a powerful way of effectively covering issues with prayer. It allows the different gifts of individuals to be used together, it enhances fellowship as the Holy Spirit directs, and brings the jigsaw puzzle picture together.
When we look at the life and ministry of Jesus we see that he was continually doing what the Father instructed him to do. We could say that Jesus was continually on the father's agenda. Because of that Jesus did not always react the way we might expect him to react. He waited two days before leaving to visit Lazarus, because he was on his father's agenda and not his own. Jesus wanted to do the work His father had for him to do, even when that ultimately meant that he had to go through the agony of rejection, crucifixion and death. Jesus listened to the direction of his father and was obedient, obedient to death – even death on a cross (Philippians 2:8).
How did Jesus stay on the Father's agenda? As we look at the gospels we see that when Jesus chose the 12 disciples he did so after spending time in prayer. When Peter confessed that Jesus was the Christ and Jesus explained the necessity of his suffering, death and resurrection. The interaction is done out of a context of prayer (Luke 9:18) Jesus was able to stay upon the Father's agenda because he spent daily time in prayer with the Father. As he did this he was in continual relationship and was available to receive the directions he required.
"So what do you have for me today, Lord?" has become a frequent line in my prayer journal, its written and prayed in a sense of anticipation and excitement. Quite often there is a glimpse or a hint at what it to come, sometimes just the affirmation "wait and see!" It changes the perspective of the day because there is now an anticipation of what God is going to do. It maybe small but it can at times be big.
On my recent trip to Israel, I had prayed in the morning for God's direction for the day and the response "I have something for you, wait and see" came back it was a dull and rainy day and as we arrived at a point in Jerusalem overlooking the temple mount abd the Western wall there was this amazing double rainbow arching over the temple mount and mount of Olives. The most vivid of rainbows I have ever seen. God did indeed have something for us and in a big way. He was giving us a sense of affirmation for the ministry we were doing but also just demonstrating his amazing grace to us. An expression of his love..
The Lord wants us to enjoy abundant prayer times with him everyday, where by he is showing us what he is doing and inviting us to join Him in His agenda.
Throughout the Scriptures we find passages, which confirm that prayer makes a difference. When Joshua and the Israelites were fighting the Amalekites (Exodus 17) it was the prayers of Moses, on top of the hill, which made the difference in the battle. When Elijah was on the top of mount Carmel it was prayer that caused the end of the drought. Seven times Elijah bent down to the ground in prayer before the rain came (1 Kings 18:41-45). "The prayer of a righteous man is powerful and effective," writes James (James 5:16).
Pray was a strategic tool for building the early church. In Acts 1:14, we see that the disciples "all joined together constantly in prayer." Prayer was effective in initiating the release of Peter from prison through the intervention of an angel (Acts 12:1-19). Paul instructed the believers in Colossi to "devote themselves to prayer" (Colossians 4:2). He also included prayer as a vital piece of the armour of God instructing the Ephesians to "pray in the Spirit on all occasions with all kinds of prayers and requests" (Ephesians 6:18).
James Houston describes prayer as "rather like joining an underground resistance movement in an enemy-occupied country. We fight back in prayer to overthrow the kingdom of darkness with the light of the gospel." We sometimes forget the true power that prayer has. Prayer can quickly get absorbed into the everyday part of our lives, the quick prayer before a meal or before climbing into bed at night and that is important for us to do. But it can also lend itself to us taking prayer for granted and to miss the potential power that is present in prayer.
When Paul tells the church in Corinth, "The weapons we fight with are not the weapons of the world. On the contrary, they have divine power to demolish strongholds" (2 Corinthians 10:4), one of the weapons he was talking about is prayer! If you have ever watched a building being demolished by a controlled explosion, you know that the explosive charged are strategically placed and only after sufficient warning is given does the person hit the button or press down the plunger causing the explosion and the demolition of the building. We do not hear sirens blasting and a warning announcement saying "clear the area and watch out, we are about to pray!" But perhaps we should!
It can be helpful to think of prayer like a stick of dynamite. It's not something that should be treated lightly because of the powerful explosion it can produce. We get the word dynamite from the Greek word dunamis, which means "the power to do something." Prayer is the power to do something. Prayer has the power to change hearts, transform lives, demolish strongholds and push back the kingdom of darkness.
After the believers prayed together in Acts 4 we read that "the place where they were meeting was shaken. And they were all filled with the Holy Spirit and spoke the word of God boldly" (Acts 4:31).
Acts 1:14 shows the believers were constantly in prayer. It was out of that time of continual prayer that the Holy Spirit came at Pentecost.
It was the work of prayer which caused the collapse of the Berlin wall. It was the prayer of the nation during World War II which led to the miracles of Dunkirk and the Battle of Britain.
It is important to remember that our prayers are powerful weapons. It is why after Paul had instructed the believers in Ephesus to put on the full armour he instructs them to pray in the Spirit on all occasions with all kinds of prayers and requests (Ephesians 6:18).
The work of the kingdom must be bathed in prayer. Scripture gives us numerous examples of this: Moses who stood in intercession on the hillside during the battle at Rephidim (Exodus 17) or Daniel, who stood in the gap for the nation of Israel while they were in exile (Daniel 9). The prophet Ezekiel reminds us that God is looking "for a man among them who would build up the wall and stand before me in the gap on behalf of the land (Ezekiel 22:30). But what do these watchmen on the wall do? How are those who stand on the wall and in the gap pray?
In two words the role of the intercessor is to pray "in" and to pray "out." They pray "in" what God is doing, the advancement of the kingdom of God. Then they pray "out" the plans and the schemes of the enemy. The watchman stands in the gap between the kingdom of darkness and the kingdom of light.
An intercessor listens to the Holy Spirit to discern what it is God want to do in a particular situation and then they begin to pray as they have been directed into the things, which the Lord wants to do. The job of the intercessor is to join in the work of praying into existence the things of the Lord, "Thy kingdom come, on earth as it is in heaven." So the intercessor is praying for hearts to be changed or for people to be drawn deeper into a relationship with the Lord. They are praying for God's kingdom to be advanced.
At the same time an intercessor is also discerning through the Holy Spirit what the strongholds and schemes the enemy is using to prevent the advancement of the gospel. Then they are praying for the removal of those strongholds and barriers. Prayer is the weapon, which can demolish strongholds "The weapons we fight with are not the weapons of the world. On the contrary they have divine power to demolish strongholds (2 Corinthians 10:4). Through prayer the hindrances to the advancement of the gospel can be removed.


Classic soft and chewy gingerbread cookies, perfect for gifting and decorating. A must make holiday treat!
Gingerbread cookies have always been one of my absolute favorite holiday treats to make, and eat! They're a classic must make cookie, perfect for enjoying as is or decorating! No cookie platter is complete without a batch of soft and chewy gingerbread cookies. Prefer them crispy? Bake a little longer! This recipe is super easy to adjust to your personal preferences. Grab your favorite holiday cookie cutters and get baking!
Below is the original post from November 2010. The pictures were in dire need of updating. What I find funny about this post is that I made mini cookies, by hand – no cutters involved. That isn't something I would ever consider doing now. Cookie cutters make life so much easier. I've linked to two different cookie cutter sets below that are perfect for making mini cookies – whether you want them plain or with stamped decorations, as you see in the updated images.
Gingerbread cookies are like the Christmas season sugar cookie to me. The special cookie that gets a lot of focus this time of year. They're dipped, decorated, used in crafts of all kinds and of course eaten. Who doesn't love gingerbread cookies? They're light while still having wonderful flavor. I've yet to make a gingerbread house or use gingerbread cookies in a craft but I do have plans to, even if it isn't this year.
Last week when I made gingerbread cupcakes I decided I wanted to top them off with mini gingerbread man cookies. I knew it'd be cute if the cookies turned out. The first task was to find an image of a gingerbread man and size it how I wanted, then print and cut out. Easier said than done. I did this because I don't own any mini Christmas cookie cutters. After the fact, I did come across a Wilton kid that included a mini gingerbread man. It figures right? So if you want to recreate those cupcakes or just make mini gingerbread man cookies in general, do pick up that box of mini cookie cutters. It'll save you so much time and hassle. I made two sizes of gingerbread man cookies, both of which are smaller than a key. Picture proof to show just how crazy I was, cutting each out by hand. Thankfully I only did a few of each size.
In a large bowl or stand mixer, cream together butter and sugar. Mix in egg and molasses, followed by spices, salt and baking powder. Scrap bowl as needed. Add flour in small batches, mixing and increasing speed as needed until dough comes together and no streaks remain.
Divide dough in half. Shape into discs and wrap well in plastic. Chill for several hours or overnight.
Generously flour a silicone counter mat or work station. Place one disc on flour, dust well with flour and roll to 1/4-inch thickness. Cut with desired cookie cutters. *Add different sized cookies to separate trays for proper baking; mini cookies to one tray and larger to another.
Freeze tray with cookies for 10-15 minutes.
Bake mini cookies for 7-8 minutes, larger cookies for 12-14 minutes. Allow cookies to rest for 1-2 minutes before transferring to a wire rack to cool completely.
Decorate cookies as desired. Store in an airtight container for up to a week.
*The amount of cookies made from this dough will vary greatly depending on the size of the cookie cutters used.
**Omit baking powder if you don't want the dough to spread or puff up at all.
I cannot believe you did this by hand, super impressive! They are so cute and your cupcakes looked great too. I'm ready to bring on the gingerbread!
Your little gingerbread are so cute and so tiny! Great job, especially cutting them by hand.
Do you have to use molasses?
Yes, molasses is essential to this recipe.
How many mini gingerbread men did this recipe yield?
It will vary greatly depending on the cookie cutter size and shapes used.
Haha! Only for that one session, not for the new images you see. Looking back, that was definitely crazy but it was still a lot of fun. :) Good luck with your cookies!
These look so cute. I never have made gingerbread cookie men before!
These are the cutest gingerbread cookies that I have ever seen! Love that they are soft too!
If we omit baking powder, will it still be soft and chewy? Has anyone tried without baking powder?
The baking powder will primarily give lift. Typically you would want to remove the baking powder only if you're planning on decorating them and don't want the cookies to spread at all. If you bake for the minimum amount, they should still be soft. Also, even with the baking powder, this particular recipe doesn't spread significantly. Be sure to freeze the dough well before baking.
Thanks for the prompt reply ! Merry Xmas to you !
Hi. What did you use to shape the mouth ave to get the indention that goes around the cookie. These are so beautiful!!
There is a link to where you can purchase the cookie cutters at the bottom of the post.
Will the baking time change if the cookies are a different size/shape? I'd prefer to make them round with a 2-3″ diameter. Thanks!
Yes, the recipe notes that mini cookies are 7-8 minutes and larger cookies are roughly 12-14 minutes. Keep your eye on them, as the timing can vary depending on your oven and the cookie size you make. Good luck!
Hi Rachel, I just love these adorable cookies!!!! I wish that I had seen this post before Christmas, but I will definitely be making these for next Christmas though! I know you said in your post that you have the link for the cutters, but that link is for mini cutters of just the shape. Do you have the link for the embellished shape cutters? Just by looking on Amazon, I think I found it, but not sure. Thank you so much!!!!! Love looking through all of your wonderful recipes…thank you for sharing them with us!


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Transparency Directive Amending Directive (TDAD) and its Impact on UK DTR 5
Transparency Directive Amending Directive (TDAD)…
On 17th October 2013, the EU Council adopted the Transparency Directive Amending Directive (TDAD). On the 6thNovember 2013, the TDAD was published in the Official Journal and came into force on 26thNovember 2013. The final regulatory technical standards (RTS) were published on 13thMay 2015. Each Member State was required to implement this within 24 months of that date. Therefore, Member States had until 26th November 2015 to implement the changes.
The UK provisions are set out in DTR5. The UK super-equivalent obligations require disclosure of major shareholdings at 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% and each 1% threshold thereafter up to 100%. The thresholds apply to UK companies listed on UK regulated markets and UK prescribed markets. The Transparency Directive limits apply to Non-UK companies on UK regulated markets.
The UK additional thresholds will remain. Beyond that, the TDAD amendments brought the EU rules broadly in line with UK DTR 5 which has, since June 2009, required the disclosure of financial instruments which give a long position in an issuer's shares. The UK Rules were super-equivalent and already included contracts for difference positions, and holdings of other financial instruments which have a similar economic effect to (but are not) qualifying financial instruments (i.e. they do not have a legal right to acquire shares, but have a similar effect in practice).
However, there will still be some impact in respect of UK disclosures as summarised below:
Disclosures relating to non-UK incorporated issuers with the UK as their Home Member State will also be subject to the requirement to disclose related financial instruments;
Going forward, the rules will only relate to instruments relating to shares in issue, the previous DTR provisions captured interests in shares that had not yet been issued;
Investment Managers exemption – All investment managers, irrespective of their jurisdiction will now be exempt from the disclosure obligations other than those of EU minimum, i.e. 5%, 10% and higher thresholds. The DTR has been amended which will allow all investment managers (including those in the UK) to disclose at the EU minimum standard. Previously, only EEA and US investment managers could avail of the exemption and all other investment managers were subject to the super-equivalent thresholds
Client Serving Intermediary –Unlike the existing UK regime, the TDAD does not provide a standalone, uncapped exemption from the vote holder notification rules for entities operating in a client-serving capacity. Instead, a client-serving intermediary will have to rely on the existing trading book exemption, which is capped at 5%. Therefore, the UK has removed the standalone client-serving intermediary exemption. Financial instruments with similar economic effect held in a client-serving capacity will need to be aggregated with the holder's position in other financial instruments of the same issuer. If the aggregated holding reaches or crosses the 5% trading book exemption threshold, the holder will have to disclose that holding.
Stock Lending and Borrowing:under previous rules, stock lenders could conclude that, on entering a loan agreement, both parties disposed of (lend) and acquired (right of recall) matching interests in the same shares, thereby netting off their interests and releasing them fromthe obligation to notify a change in position. Following the TDAD and ESMA RTS, the previous exemptions for stock borrow and lending have been removed. Initially the FCA had proposed requiring disclosure from the EU thresholds –so beginning at 5%, however following feedback it was decided that no separate provisions on reporting were required and stock lending transactions will need to be treated in the same way as all other holdings and should be notified at the appropriate thresholds set out in the DTRs
There have also been changes as regards calculation of delta and the treatment of depository receipts which are identical to the requirements of the TDAD.
The FCA has also removed much of the specific guidance contained in DTR 5 and replaced with references to ESMA's RTS.
Note that the FCA updated its form for notifying major shareholdings which came into force on 30th June 2017. Member States have discretion to make changes to the ESMA standard notification form as they see appropriate. In the UK, the FCA have decided to make some amendments to the content of the form as follows:
Include a new box to identify non-UK issuers
Include a box to indicate the date on which issuer was notified (to reflect the current TR-1 form requirement)
Include an email address to which the form and annex should be sent to the FCA (majorshareholdings@fca.org.uk)
Request our full briefing paper on the Transparency Directive Amending Directive and its impact on UK DTR 5.
Category: Blog 4th December 2018
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Fire works are fun, but this is an awesome experiment you can try at home to make your own homemade sparkler using just steel wool. Since the metal is shredded into such small piece, it easily burns when lit on fire.
The Crazy Russian Hacker took a large piece of steel wool and by attaching to to a rope was able to spin it around in his backyard to make a giant spraying sparkler. Of course, it you do try this at home, please be very careful!


But the reality is, of the roughly 310,000 financial advisers in the U.S., less than 10% are legally obligated to put your interests first at all times on all of your accounts. These are called "registered investment advisers" or RIAs for short. RIAs don't accept sales commissions. Instead, they typically charge a flat fee or a percentage of your total assets for unbiased financial advice. It's a cleaner model that removes awkward conflicts of interest and hidden agendas.
As for the other 90%, they're simply brokers in disguise. Many of them work for enormous Wall Street banks, brokerage houses, and insurance companies — the kind that splash their names on sports arenas.
Why does this matter? Because brokers have a vested interest in hawking expensive products, which might include actively managed mutual funds, whole-life insurance policies, variable annuities, and "wrap" accounts.
Don't get me wrong, this is not an indictment on the good people that work in the industry. I have lots of friends and clients in the financial industry, so I'm speaking with firsthand knowledge when I tell you that they — and the vast majority of their colleagues — are people of real integrity. They have good hearts and good intentions. The trouble is, they work in a system that's beyond their control — a system that has tremendously powerful financial incentives to focus on maximizing profits above all else.
This is a system that richly rewards employees who put their employer's interests first, their own interests second, and their clients' interests a distant third. Even the best-intentioned financial advisers are often working within the confines of this system. They're under intense pressure to grow profits, and they're rewarded for doing so. If you — the client — happen to do well, too, that's great. But don't kid yourself. You're not the priority.
1. Are you a registered investment adviser?
If the answer is no, this adviser is a broker. Smile sweetly and say good-bye. If the answer is yes, he or she is required by law to be a fiduciary. But you still need to figure out if this fiduciary is wearing one hat or two. That's because Its not enough that your financial adviser is an independent RIA. You need to be careful that the RIA is not also a broker.
You heard that right. In a strangely allowable arrangement, an RIA can be both a broker and a fiduciary in a process called "dual registration." When someone is "dually registered," at one moment they play the part of an unbiased adviser, reassuring you that they abide by the fiduciary standard and can provide you with conflict-free advice for a fee. But they can switch hats and act as a broker, earning commissions or kickbacks by selling you specific products. When they're playing this broker role, they no longer have to abide by the fiduciary standard. In other words, they're sometimes obliged to serve your best interests and sometimes not. How warped is that? These arrangements are perhaps the most dangerous for consumers as it creates immense confusion.
2. Are you or your firm affiliated with a broker-dealer?
If the answer is yes, you're dealing with someone who can act as a broker and usually has an incentive to steer you to specific investments. One easy way to figure this out is to glance at the bottom of the adviser's website or business card and see if there's a sentence like this: "Securities offered through [adviser's company name], member FINRA and SIPC." This refers to the Financial Industry Regulatory Authority and the Securities Investor Protection Corporation, respectively. If you see these words, it means he or she can act as a broker. If so, run. Run for your life!
3. Does your firm offer proprietary mutual funds or separately managed accounts?
You want the answer to be an emphatic "no." If the answer is yes, then watch your wallet. It probably means they're looking to generate additional revenues by steering you into these products that are highly profitable for them (but probably not for you).
4. Do you or your firm receive any third-party compensation for recommending particular investments?
This is the ultimate question you want answered. Why? Because you need to know that your adviser has no incentive to recommend products that will shower him or her with commissions, kickbacks, consulting fees, trips, or other goodies.
5. What's your philosophy when it comes to investing?
This will help you to understand whether or not the adviser believes that he or she can beat the market by picking individual stocks or actively managed funds.
6. What financial planning services do you offer beyond investment strategy and portfolio management?
Investment help may be all you need, depending on your stage of life. But as you grow older and/or you become more wealthy with various holdings to manage, things often become more complex financially. For example, you may need to deal with saving for a child's college education, retirement planning, handling your vested stock options, or estate planning. Most advisers have limited capabilities once they venture beyond investing. In fact, most aren't legally allowed to offer tax advice due to their broker status. Ideally you want an adviser who can bring tools for tax efficiency in all aspects of your planning — from investment planning to business planning to estate planning.
7. Where will my money be held?
A fiduciary adviser should always use a third-party custodian to hold your funds. For example, Fidelity, Schwab, and TD Ameritrade all have custodial arms that will keep your money in a secure environment. You then sign a limited power of attorney that gives the adviser the right to manage the money but never to make withdrawals. The good news about this arrangement is that if you ever want to fire your adviser, you don't have to move your accounts. You can simply hire a new adviser who can take over managing your accounts without missing a beat. This custodial system also protects you from the danger of getting fleeced by a con man like Bernie Madoff.
Tony Robbins is a life- and business strategist and author. His books include Money: Master the Game and Unshakeable: Your Financial Freedom Playbook (Simon & Schuster). This article is adapted from Robbins's monthly "Power Report,"which provides advice and tips about money, investing, and personal finance.


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News / Turkish-Canadian Groups Celebrate Armenian Genocide
Turkish-Canadian Groups Celebrate Armenian Genocide
Category: News, Press Releases
VIEW VIDEO HERE: http://www.youtube.com/watch?v=PdNHw6zRZfw
OTTAWA – The annual Armenian Genocide Memorial Day protest in front of the Turkish embassy was met with 50 Turkish-Canadian counter-protesters denying the well-established actuality of the Armenian Genocide. The group quickly turned to singing and jubilant chanting at the face of the Armenians.
Further to this shameful act, the group was clearly attempting to incite a confrontation with their Armenian counterparts to undermine the annual gathering. Repeated name calling and general insults towards the Armenians could be heard from across the barrier.The Armenian group chose to ignore this immature and reprehensible behavior and kept their focus on the Turkish embassy demanding an end to the Turkish government's denial campaign around the world and acknowledge the dark chapter from its past.
The Armenian Genocide is the first modern genocide of the 20th century, during which an estimated 1.5 million Armenians were killed by the Ottoman Empire leadership in an attempt to rid it's Christian minority. Countless international organizations, scholars (such as the International Association of Genocide Scholars) and 22 countries have formally recognized these massacres during World War One as Genocide. The Canadian parliament passed a motion in 2004 acknowledging the Armenian Genocide and condemned these crimes against humanity.
Police officers present were questioned about the Turkish group's permit to gather and answered that the Turkish group had applied for a barbeque party permit in the park.
Afterwards, the Turkish group was invited into the Turkish embassy by Ambassador Tuncay Babali. In an attempt to undermine Canada's domestic policies, the ambassador recently held an interview with the Canadian Press indicating that Turkey will limit economic developments with Canada unless the government reverses its position on the Armenian Genocide.


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Home » Veterans in Need
Communities for Veterans in Need (by state)
Note: If you're interested in supporting this effort, please see the Mayors Challenge to End Veteran Homelessness for helpful resources.
Alabama: The men of Phi Kappa Psi at the University of Alabama in Huntsville have started Foundations for Tomorrow to create a tiny home village for homeless veterans.
California: Residence for Patriots has a vision of utilizing the tiny home movement to solve homelessness and bring back community in the San Diego area.
Colorado: Heroes Home Colorado is raising funds for a community.
Florida: In St. Pete, Celebrate Outreach is planning a tiny house community for veterans.
Georgia: The Chatham-Savannah Homeless Authority is creating a community of 12 tiny homes for veterans along with a possible additional 60 tiny houses for other homeless folks. A three-acre plot of land was recently purchased for the community whose name is expected to be The Cove at Dundee.
Illinois: The Vets4Vets Village in rural Williamson County, Illinois, is exclusively for veterans, families of deployed troops, and families of those who lost their lives.
Kentucky: Steve O'Bryan is working toward a tiny house community for veterans in Louisville, KY.
Massachusetts: Carolyn Love Scalise is working on a tiny house community for veterans in Natick, MA.
Missouri: Veterans Community Project, founded by veterans Chris Stout, Kevin Jamison, and Mark Solomon, has built its first tiny house at Veterans Village, a community intended to grow to 52 tiny houses and a day outreach center on four acres of land on 89th and Troost in Kansas City. They plan to teach living skills, provide case management and PTSD treatment to veterans that do not qualify for VA services or consistently fail in other programs.
New Hampshire: Veteran Peter Macdondald is building the Veterans Resort Chapel and Tiny House Community in Lee, NH.
New Jersey: Amazing Grace Ministries in Franklinville is nearly done with the first four tiny homes in their Operation Safe Haven community for veterans.
Wisconsin: A tiny house community is under construction in Racine, sponsored by the Veterans Outreach of Wisconsin. One tiny house is completed and 14 more planned, as part of the James A. Peterson Veterans Village.


You may find the announcement of the 45th Andernach FairyChessFriendsMeeting (may 30 -- June 02, 2019) at http://www.feenschach.de/downloads/Andernach_2019_d_e.pdf.
Hope to see you at Andernach this year!
I think there is ample time to change either.
The Andernach meeting takes place on the Ascension weekend.
"Andernach Thursday" is a public holiday in Germany and many surrounding countries, which allows many participants to attend.


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Wood picket fences can be built in a wide variety of styles, with various distances between the pickets to allow for a breeze and relatively clear sightlines through the fence.
Overview. Pressure-treated pine is often used for residential wood fences because the wood is chemically treated to help prevent insect damage, decay, and rot as it ages to a silvery gray.
Veranda 5 in. x 5 in. White Vinyl Gothic Fence Post Cap.
Superior Fence & Rail – Florida Fence Products. SUPERIOR FENCE & RAIL OFFERS A COMPLETE RANGE of fence products, with the highest quality material available. From pool fencing and screen enclosures, to ornamental and decorative styles of fencing for dog fence, field fencing, security fence, and all different types of privacy fencing.


This afternoon I have been enjoying sewing some Happy Blocks.These are such fun to make. It's hard to stop!
This is a great block for a group quilt. Practically no seams to match up. very forgiving too if they need a wee trim. Hmmmm, not sure about the one second from the left. Think I'll undo that one and put a different border on. Not enough contrast there.If you would like to learn how to make Happy Blocks Mary has an excellent tutorial on her site.
This year the members of our in house quilting group Sweet Peas are participating in a Row by Row Round Robin. As well as sewing Happy Blocks I have been preparing my bag of goodies ready to go on its way. We have our first handover on Wednesday.
Hope your Sunday has been relaxed and fun.
what a good name for the blocks, they certainly made me smile and no seam matching, perfect!
I love the bright colors off the Happy Blocks.
Still on the slow boat…..
…this quilt is not the Orient Express…..


This article is a part of Summer Lovin' Week 2017.
Ashley Robin Franklin is an artist & comic creator living in Austin, Texas. She's a lover of all things spooky, comics, animation, dogs, and watercolors. You can follow her on Instagram and Tumblr, both under Arfranklinstein, to see more works by her.


To add a product here, simply click the icon. This design ethos allows Lavish Alice to consistently deliver unique and detailed pieces, exclusively in-house. Add to Bag Quick View. Per Page.
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Registered in England - Co No. From illustration to construction, each garment in every collection is individually designed, meticulously hand cut and beautifully crafted with astute attention to detail. Cut from different cloth: Lavish Alice. Milan Fashion Week: Drapers Footwear Awards 19 will recognise and celebrate the footwear's very best from across the UK and Ireland.
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This is significant for traditional networks, but we've seen wireless companies switch to all IP in the past. what is significant, and perhaps unprecedented, is that all telcos that are doing this are probably still going to charge customers the same (or more) money and continue to split these services from data offerings as a marketing practice. As customers walk away from land lines, they're walking into a telco that has already placed it's voice infrastructure on IP networks.
In other words, the infrastructure to support voice calls will be completely paid off for the telco and, after this switch, start becoming pure profit for them. Clever companies will include voice calls in already crazy data usage charges. The fact that the Internet (and IP networks) are largely unregulated should help telcos reap huge profits.


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text:
Q: Create Folder in List Definition with Elements.xml I am creating list definitions.Now what I want to create some folder when We create Elements.xml for list definition.
Thanks in advance

A: Add the following code in Elements.xml to create folder in list.
<Data>
           <Rows>
        <Row>
          <Field Name="ContentTypeId">0x0120004F994A3C0FF76546A528DA0D4B515898</Field>
          <Field Name="FileLeafRef">MyTestFolder</Field>
          <Field Name="Title">MyTestFolder</Field>
          <Field Name="FSObjType">1</Field>
        </Row>
      </Rows>
    </Data>

Refer to following articles for more information
http://msdn.microsoft.com/en-IN/library/ms478860(v=office.14).aspx
http://johnlearnt.blogspot.in/2012/09/provision-folder-inside-document-library.html
Also, you can do it from an event receiver when the list is created:
Create an event receiver (ListAdded) for the library definition (Dev Center).
Add code to create the folder structure.
SPList list = web.Lists.TryGetList("ListTitle");
SPFolderCollection folderColl = list.RootFolder.SubFolders;
SPFolder newFolder = folderColl.Add(FolderUrl);

redpajama_set_name: RedPajamaStackExchange


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Turn back the clock on this traditional, move-in ready,home in the heart of the Arbor District. Quality built in 1943, it is easy walking or biking distance to S.I.U. or shopping! Gleaming hardwood floors flow from the living/dining rooms into the bedrooms. The windows & doors are framed by natural woodwork & the home is freshly painted. The living room offers a fireplace with brick surround. Two bedrooms are on the main level & upstairs is a 35'x12' en-suite bedroom, with amazing closet space. All appliances stay in the stepsaver kitchen. The basement has been waterproofed so that one can store those special items with peace of mind. The back yard is full of surprises with a butterfly garden, asparagus patch & many perennials. A two car garage has a storage shed. New HVAC 2015.


Geographic coordinates are the approximate centre of the area covered by HP2 7SW, and are not necessarily those of any specific postal address within it.
HP2 7SW is a residential postcode in Hemel Hempstead, Hertfordshire. It was first introduced in October 1985.
The most common council tax bands are F and E. Estimated residential property values, based on historical transactions and adjusted for inflation, range from £371,998 to £612,288 with an average of £477,185. Housing types are typically detached. None of the houses sold since 1995 have been new builds.
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HP2 7SW is in the Luton travel to work area. NHS services are provided by the Hertfordshire Primary Care Trust.
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Ofcom publishes annual statistics for Broadband availability. This is the most recent data for HP2 7SW.
The most recent Ofsted rankings for schools near HP2 7SW.


Today there where less of us in the Ceramics studio. We worked together to finish our abstract sculpture space, but because other team members where not there it was a chance for us to think about their creativity together with ours. We used the scoring technique to put the objects individually created into the collective space.
Whilst we made decisions with finalising our space, the topic of our conversation was psychology: How to read people? Why people exaggerate their difficulties? Why people lie? How far we have come, focussing on the positives.
After we finished our space and left it to dry, we decided to glaze our sculptor coil pots made on the first day.
We where all looking forward to glazing.
Glazes can be thought of as a glass coating, the texture can be rough, matt, glossy and so on. The colours and textures are made by mixing a formulated powder with water. We where shown a range of glazes we could use and mix together, the glaze will only work properly with 3 or more coats!
The beauty of glazing is that when spreading the mixture onto the dry clay, the colour is not what it will come out like when put through the kiln. For instance; if you want a red, the colour will look pink before firing and orange would look white. Also putting more that one colour onto the same surface is a chemical gamble, it could come out with the colour expected or be the total opposite of what was intended. We really enjoyed not knowing!
"It was a really relaxed day, I liked the glazing because you don't know what is going to happen"
"I really enjoyed doing something different, glazing is really exciting"
"Not having an exact way you want it to look, but enjoying the colours given, it becomes your own artistic science experiment!"
We also glazed the other artists work that couldn't make it to the session, again this gave us an opportunity to think about what we know about them and what they would appreciate us giving to their work.
We are looking forward to the final product!


text:
Q: Why we cannot have overloaded function signatures with optional parameters in Typescript? According to official documentation (and corresponding example) it's not possible. But I still cannot understand why 3rd function declaration doesn't match 3rd makedate call. Please, tell me what I don't understand? Thanks.
// @errors: 2575
function makeDate(timestamp: number): Date;
function makeDate(m: number, d: number, y: number): Date;
function makeDate(mOrTimestamp: number, d?: number, y?: number): Date {
  if (d !== undefined && y !== undefined) {
    return new Date(y, mOrTimestamp, d);
  } else {
    return new Date(mOrTimestamp);
  }
}
const d1 = makeDate(12345678);
const d2 = makeDate(5, 5, 5);
const d3 = makeDate(1, 3); //No overload expects 2 arguments, but overloads do exist that expect either 1 or 3 arguments.

A: Here's a slightly artificial example, which destroys the confusion. Let's assume makeDate with two parameters accepts month and year and still makes a new Date.
// @errors: 2575
function makeDate(timestamp: number): Date;
function makeDate(m: number, d: number, y: number): Date;
function makeDate(m: number, y: number): Date;
function makeDate(mOrTimestamp: number, d?:number, y?:number) {
  if (d !== undefined && y !== undefined) {
    return new Date(y, mOrTimestamp, d);
  } else if (d !== undefined && y === undefined) {
    return new Date(mOrTimestamp, d);
  } else {
    return new Date(mOrTimestamp);
  }
}
const d1 = makeDate(12345678);
const d2 = makeDate(5, 5, 5);
const d3 = makeDate(1, 3);

The same example on the playground. The key for me was distinguishing that
the call signature and the implementation signature are different entities.


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Dusty Houses and Type 1 Diabetes – microBEnet: the microbiology of the Built Environment network.
microBEnet: the microbiology of the Built Environment network.
Among the cleanest and wealthiest countries in the world, Finland has the highest rate of Type 1 diabetes, while other messier and poorer countries have much lower rates. A recent article in the Washington Post discusses ongoing research to explore how exposure to dust and bacteria in houses might contribute to the onset of Type 1 Diabetes in children.
Maybe this is also the secret to the mystery of why elephants dust bathe?
Holly Ganz is a project scientist at UC Davis working with Jonathan Eisen on the microbiomes of built environments where animals live.
Jonathan Eisen on Antimicrobial chemicals and antibiotic resistance in dust – now open access!


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