text:
# Shear-banding in a lyotropic lamellar phase Part 1: Time-averaged velocity profiles

## I Introduction

A wide class of materials, referred to as complex fluids, exhibit a common feature: when submitted to a shear stress $`\sigma `$, their flow cannot be described easily as in the case of simple fluids Larson (1999). Indeed, the flow of simple liquids is entirely determined by the knowledge of the viscosity $`\eta `$: when submitted to a shear stress $`\sigma `$ far from any hydrodynamic instability and after a very short transient, the velocity profile is linear and characterized by a shear rate $`\dot{\gamma }`$, given by the linear relation $`\dot{\gamma }=\sigma /\eta `$ Guyon et al. (1994). In the case of complex fluids, such a linear relation between $`\sigma `$ and $`\dot{\gamma }`$ does not hold any more. In polymeric fluids for instance, the flow tends to decrease the effective viscosity $`\eta \widehat{=}\sigma /\dot{\gamma }`$, whereas disordered media like emulsions or foams can resist elastically to a small applied stress but flow plastically under large $`\sigma `$ Larson (1999). Such behaviors are due to the presence of a supramolecular architecture that leads to a coupling between the structure of the fluid and the flow Cates and Evans (2000). The shear-thinning effect in polymeric fluids for instance, is due to the alignment of the polymer chains along the flow direction, whereas the crossover between pasty and fluid states in glassy materials is attributed to microscopic rearrangements of the structure Hébraud et al. (1997).

In some cases, because of a strong flow–structure coupling, the flow can induce new organizations. In wormlike micellar systems for instance, a shear flow can induce a nematic phase Berret et al. (1994); Schmitt et al. (1994). In lamellar phases, shear may induce structures that do no exist at rest, like e.g. the onion texture Diat et al. (1993); Roux et al. (1993). Such Shear-Induced Structures (SIS) have been observed in a lot of complex fluids, especially in lyotropic systems Hu et al. (1998); Eiser et al. (2000); Ramos et al. (2000). These behaviors are generally associated with a spatial structuration of the fluid: the SIS nucleates at a critical stress or a critical shear rate and expands in the flow as $`\sigma `$ (or $`\dot{\gamma }`$) is increased. Since the viscosity of the SIS differs from that of the original structure, the flow field is assumed to be composed of two macroscopic bands of different shear rates. This behavior, generically called shear-banding, seems to be a universal feature of complex fluids. Its microscopic origin is not yet clearly understood: the shear-banding behavior may arise from elastic instabilities Spenley et al. (1993), from frozen disorder and local plastic events Kabla and Debrégeas (2003) or from a coupling between shear flow and a phase transition Olmsted and Goldbart (1992). Numerous phenomenological descriptions of shear-banding have emerged during the last decade (see Refs. Lu et al. (2000); Goveas and Olmsted (2001); Yuan (1999); Ajdari (1998); Picard et al. (2002) and references therein). Those theoretical approaches have undoubtedly helped to understand the experiments, while not always providing a microscopic description of the phenomenon.

Most of experimental works relie on rheological data and structural measurements. In those experiments, shear-banding is attributed to the presence of a stress plateau on the flow curve associated with a structural change, observed for instance using x-ray diffraction techniques Berret et al. (1994); Schmitt et al. (1994); Eiser et al. (2000) or direct visualizations of birefringence bands in the flow field Cappelaere et al. (1997); Lerouge et al. (1998). Recently, a few experiments using Nuclear Magnetic Resonance velocimetry have evidenced the fact that velocity profiles in such systems may display bands of different shear rates Mair and Callaghan (1996); Britton and Callaghan (1999). However, some of these experiments have reported a contradictory picture for the shear-banding instability: it seems that the observed structural bands do not always correspond to bands of different shear rates, at least in a specific wormlike micellar system Fischer and Callaghan (2001). More recently, experiments based on dynamic light scattering velocimetry performed in our group have revealed a classical shear-banding phenomenology in another wormlike micellar system Salmon et al. (2003a). Therefore, more experimental data are needed to fully understand the spatial structuration of the flow field in the general SIS and shear-banding phenomenon.

The aim of this paper is to perform an extensive study of shear-banding in a specific complex fluid, a lyotropic lamellar phase. This system is known to exhibit a shear-induced transition, called the layering transition, between two different textures of the phase Diat et al. (1995); Sierro and Roux (1997). In the present article, we present time-averaged velocimetry measurements performed simultaneously to structural measurements using respectively dynamic and static light scattering techniques.

This paper is organized as follows. In Sec. II, we briefly describe the system under study and the experimental setup allowing us to measure both the structure of the fluid and its rheological behavior. In Sec. III, we present the experimental setup for measuring velocity profiles in a Couette flow Salmon et al. (2003b). Sec. IV describes the experiments performed at a given temperature ($`T=30^{}`$C) and under controlled shear rate. These experiments support the classical picture of the shear-banding in this particular system and our data also reveals the presence of wall slip, which is consistent with the observed shear-banding scenario. A detailed mechanical analysis based on wall slip measurements and rheological data is presented in Sec. V and helps us demonstrate that the classical mechanical assumption of shear-banding, in which the interface between the bands is only stable at a given stress, holds in our experiments. We then briefly summarize our results in Sec. VI, and emphasize on the puzzling presence of temporal fluctuations of the flow field near the shear-induced transition. The study of these temporal fluctuations are presented in a related paper where the link with rheochaos is emphasized Salmon et al. (2003c).

## II Global rheology of the onion texture near the layering transition

### II.1 Rheology of lyotropic lamellar phases:
the onion texture

Lyotropic systems are composed of surfactant molecules in a solvent. Because of the chemical duality of the surfactant molecules (polar head and long hydrophobic chain), self-assembled structures at the nanometer scale are commonly observed Larson (1999). Depending on the range of concentrations, one can observe different structures: for instance, long cylinders of some microns long (wormlike micelles) or infinite surfactant bilayers (membranes). In the latter case, because of the interactions, the membranes can form periodic stacks, referred to as lamellar phases and noted $`L_\alpha `$, or randomly connected continuous structures, called sponge phases and noted $`L_3`$ Porte et al. (1991); Roux et al. (1992). In a lamellar phase, the smectic period $`d`$, i.e. the distance between the bilayers, ranges from a few nanometers up to 1 $`\mu `$m whereas the thickness $`\delta `$ of the membranes is 2–4 nm. These liquid crystalline phase are locally organized as a monocrystal of smectic phase. If no specific treatment is applied, lyotropic lamellar phases contain at larger length scales ($`10\mu `$m) a lot of characteristic defects: the organization of these defects is called the texture of the phase.

Since the work of Roux and coworkers, great experimental effort has been devoted to the understanding of the effect of a shear flow on lamellar phases Diat et al. (1993); Roux et al. (1993). A robust experimental fact has emerged: the shear flow controls the texture of the phase. For most systems, the experimental behavior usually observed is as follows. (i) At very low shear rates ($`\dot{\gamma }1`$ s-1), the membranes tend to align with the direction of the flow but textural defects still persist. (ii) Above a critical shear rate of about $`\dot{\gamma }1`$ s-1, the membranes are wrapped into monodisperse multilamellar vesicles called onions and organized as a disordered close-compact texture. The characteristic size $`R`$ of this shear-induced structure (the onion size) is of the order of a few microns. (iii) At higher shear rates ($`10^3`$ s-1), perfectly ordered lamellar phases are recovered Diat et al. (1993). For some specific systems and at intermediate shear rates, spatial organizations of onions are sometimes encountered Diat et al. (1995); Sierro and Roux (1997).

The complex fluid investigated here corresponds to this last behavior. It is made of Sodium Dodecyl Sulfate (SDS) and Octanol (surfactant molecules) in Brine (solvent). At the concentrations considered here (6.5% wt. SDS, 7.8% wt. Octanol, and 85.7% wt. Brine at 20 g.L-1), a lamellar phase is observed Hervé et al. (1993). The smectic period $`d`$ is 15 nm and the bilayers thickness $`\delta `$ is about 2 nm. For the given range of concentrations, the lamellar phase is stabilized by undulating interactions Helfrich (1978). This system is very sensitive to temperature: for $`TT_{L_\alpha \text{}L_3}35^{}`$C, a sponge–lamellar phase mixture appears.

To study the effect of shear flow on this phase, we used the experimental device sketched in Fig. 1. A rheometer (TA Instruments AR1000N) and a Couette cell made of Plexiglas (gap $`e=1`$ mm, inner radius $`R_1=24`$ mm and height $`H=30`$ mm) allow us to perform rheological measurements. The rheometer imposes a constant torque $`\mathrm{\Gamma }`$ on the axis of the Couette cell which induces a constant stress $`\sigma `$ in the fluid. The rotation speed $`\mathrm{\Omega }`$ of the Couette cell is continuously recorded, from which the shear rate $`\dot{\gamma }`$ can be deduced. A computer-controlled feedback loop on the applied torque $`\mathrm{\Gamma }`$, can also be used to apply a constant shear rate without any significant temporal fluctuations ($`\delta \dot{\gamma }/\dot{\gamma }0.01\%`$). The relations between ($`\sigma `$,$`\dot{\gamma }`$) given by the rheometer and ($`\mathrm{\Gamma }`$,$`\mathrm{\Omega }`$) read:

$`\sigma `$ $`=`$ $`{\displaystyle \frac{R_1^2+R_2^2}{4\pi HR_1^2R_2^2}}\mathrm{\Gamma },`$ (1)
$`\dot{\gamma }`$ $`=`$ $`{\displaystyle \frac{R_1^2+R_2^2}{R_2^2R_1^2}}\mathrm{\Omega }.`$ (2)
Such definitions ensure that ($`\sigma `$,$`\dot{\gamma }`$) correspond to the average values of the local stress and shear rate in the case of a Newtonian fluid. Temperature is controlled within $`\pm `$0.1C using a water circulation around the cell. A polarized laser beam (He–Ne, $`\lambda =632.8`$ nm) is directed through the transparent Couette cell to investigate the effect of a shear flow on the structure of the fluid. Since the characteristic sizes of the texture are about 1 $`\mu `$m, well-defined diffraction patterns are obtained and recorded on a Charge-Coupled Device camera (CCD, Cohu). As shown in Fig. 1, the laser beam crosses the sample twice, so that two diffraction patterns are recorded; the first one has an elliptical shape due to the optical refractions induced by the Couette geometry.

### II.2 The layering transition: stationary state and rheological chaos

Figure 2(a) shows a typical flow curve obtained on our lamellar phase at

imposed stress or imposed shear rate for $`T<T_c27^{}`$C. After a transient phase (at least 10–30 min), a stationary state is obtained, i.e. $`\sigma `$ ($`\dot{\gamma }`$ resp.) does not vary significantly in time when $`\dot{\gamma }`$ ($`\sigma `$ resp.) is imposed. At low stress, the diffraction patterns are uniform rings indicating the presence of a disordered texture of onions. When $`\sigma `$ reaches $`\sigma _c`$ ($`15`$ Pa), six peaks appear on the ring indicating that the onions get a long range hexagonal order on layers sliding onto each other (see Fig. 2) Diat et al. (1995); Sierro and Roux (1997). Those layers lie in the ($`𝐯,𝐳`$) plane normally to the shear gradient direction $`v`$. When $`\sigma `$ is increased further, peaks become more contrasted. Note that the peaks with wave-vectors along the rheometer axis ($`𝐪_z`$) are less intense than the others. This is due to the zig-zag motion of the planes of onions when sliding onto each other Sierro and Roux (1997). This shear-induced ordering transition, called the layering transition, has been observed in many monodisperse colloidal systems since the pioneering work of Ackerson and Pusey Ackerson and Pusey (1988). This ordering transition is associated to a shear-thinning of the fluid, i.e. the ordering of the colloids causes the decrease of the viscosity.

More recently, complex dynamical behaviors have been observed in the vicinity of the layering transition for temperatures $`T>T_c27^{}`$C (see Fig. 2) and under controlled stress: the shear rate does not reach a stationary value, but sometimes oscillates indefinitely in time Wunenburger et al. (2001); Salmon et al. (2002). However, when the shear rate is imposed, no oscillations are observed and the responses of the shear stress seem almost stationary. In the stress imposed case, the shear rate oscillations are characterized by a large period of about 10 min. Moreover, the dynamics of the shear rate is correlated to a dynamical structural change: the fluid oscillates between the disordered and the layered states. The origin of such surprising dynamics is not yet understood, but it is now quite clear that it does not correspond to a simple hydrodynamic or elastic instability. Such a new kind of temporal instability was coined rheochaos Grosso et al. (2001); Cates et al. (2002). In a previous work Salmon et al. (2002), a detailed study of such dynamics was performed: depending on the applied stress, several dynamical regimes have been found. Using dynamical system theory, a careful analysis has revealed that the dynamics do not simply correspond to a low-dimensional chaotic system, probably because some spatial degrees of freedom are involved. Moreover, rheological experiments performed with different gap widths $`e`$ support the assumption of a spatial organization of the flow in the gap Salmon et al. (2002). Our idea was that spatial structures such as bands, that lie in the $`v`$ direction and oscillates in time, could lead to the observed dynamics. Therefore, it was essential to measure the local velocity rather than the global rotation speed $`\mathrm{\Omega }`$ of the Couette cell.

In the next section, we present the experimental setup allowing us to perform velocimetry measurements. We then focus on experiments performed on rheological stationary states at $`T=30^{}`$C and under controlled shear rate.

## III Experimental setup: local velocimetry using Dynamic Light Scattering (DLS)

In order to evidence the possibility of a spatial organization of the fluid flow near the layering transition, we have used the experimental setup sketched in Fig. 3 and described in more details in Ref. Salmon et al. (2003b). It consists of a classical heterodyne Dynamic Light Scattering experiment (DLS) mounted around a rheometer. Local velocity measurements using heterodyne DLS rely on the detection of the Doppler frequency shift associated with the motion of the scatterers inside a small scattering volume $`𝒱`$ Berne and Pecora (1995); Ackerson and Clark (1981); Fuller et al. (1980); Maloy et al. (1992); Gollub and Freilich (1974). In classical heterodyne setups, light scattered by the sample under study is collected along a direction $`\theta _i`$ and is made to interfere with a reference beam. Light resulting from the interference is sent to a photomultiplier tube (PMT) and the auto-correlation function $`C(\tau )`$ of the intensity is computed using an electronic correlator.

When the scattering volume $`𝒱`$ is submitted to a shear flow, it can be shown that the correlation function $`C(\tau )`$ is an oscillating function of the time lag $`\tau `$ modulated by a slowly decreasing envelope. The frequency of the oscillations in $`C(\tau )`$ is exactly the Doppler shift $`𝐪𝐯`$, where $`𝐪`$ is the scattering wavevector and $`𝐯`$ is the local velocity averaged over the size of the scattering volume $`𝒱`$. In the experiments presented here, the imposed angle $`\theta _i=62.5^{}`$ has been chosen in such a way that the size of $`𝒱`$ is about about 50 $`\mu `$m Salmon et al. (2003b). Figure 4(a) shows a typical correlation function measured on a sheared latex suspension.

The frequency shift $`𝐪𝐯`$ is recovered by interpolating a portion of $`C(\tau )`$ and looking for the zero crossings. Errorbars on such measurements are obtained through the fitting procedure: typical uncertainties are less than 5 %.

The rheometer sits on a mechanical table whose displacements are controlled by a computer. Three mechanical actuators allow us to move the rheometer in the $`x`$, $`y`$, and $`z`$ directions with a precision of $`1\mu `$m. Once $`y`$ is set so that the incident beam is normal to the cell surface, velocity profiles are measured by moving the mechanical table in the $`x`$ direction by steps of 30 $`\mu `$m.

As discussed in Ref. Salmon et al. (2003b), going from $`𝐪𝐯`$ as a function of the table position to the velocity profile $`v(x)`$ requires a careful calibration procedure to take into account the refraction effects due to the Couette cell. Figure 4(b) presents velocity profiles measured at various known shear rates during the calibration using a Newtonian suspension of latex spheres in a water–glycerol mixture. This simple liquid has the same optical index ($`n=1.35`$) as the lamellar phase under study. Finally, we accumulate the correlation functions over 3–5 s so that a full velocity profile with a resolution of 30 $`\mu `$m takes about 3 min to complete.

## IV Local rheology of the onion texture near the layering transition

### IV.1 Global rheology and local velocimetry

To understand the coupling between spatial degrees of freedom, global rheology and the structural transition, we first present measurements obtained at $`T=30^{}`$C in the shear rate imposed mode. Well-defined rheological stationary states are obtained with such a method (see Sec. II.2). We record global rheological data simultaneously to the velocity profile measurements. In order to obtain reproducible experiments, careful rheological protocols must be used as discussed in Ref. Salmon et al. (2002). At the temperature under study ($`T=30^{}`$C), we apply a first step at $`\dot{\gamma }=5`$ s-1 during 7200 s. This step of applied shear rate allows us to begin the experiment with a well-defined stationary state of disordered onions. We then apply increasing shear rates for 5400 s per step. The increment between two steps is $`\delta \dot{\gamma }=2.5`$–5 s-1. The smaller value of $`\delta \dot{\gamma }`$ is chosen when a fine resolution is needed in the vicinity of the transition. As shown in Fig. 5(b), the temporal responses of the shear stress are almost stationary: small temporal fluctuations ($`\delta \sigma /\sigma 1`$–3%) can be detected. Note that, in the shear rate imposed mode the temporal fluctuations of $`\dot{\gamma }`$ are completely negligible ($`\delta \dot{\gamma }/\dot{\gamma }0.01\%`$, \[see Fig. 5(a)\]).

Global rheological measurements are displayed in Fig. 6 and the corresponding diffraction patterns at various applied

shear rates are shown in Figs. 6(a)–(f). For shear rates below $`\dot{\gamma }_c15`$ s-1, diffraction patterns are uniform rings indicating that the structure of the onions is disordered \[Figs. 6(a)-(b)\]. Above $`\dot{\gamma }_c`$, six fuzzy peaks appear on the diffraction ring, indicating the onset of the layering transition \[Fig. 6(c)\]. When the shear rate is further increased, peaks become more and more contrasted as can be seen in Figs. 6(d)–(f). The flow curve does not display any significant discontinuity at the layering transition: it is rather difficult to locate the various regions of different structures from the rheological data alone and without the information inferred from the diffraction patterns. Significant shear-thinning is observed: $`\eta 2.6`$ Pa.s at $`\dot{\gamma }=5`$ s-1 and $`\eta 0.3`$ Pa.s at $`\dot{\gamma }=60`$ s-1.

Far below or far above the layering transition, well-defined profiles are easily measured. But very surprisingly, near the layering transition, the local velocity is not stationary but displays large temporal fluctuations while $`\sigma `$ only fluctuates within a few percents (see Ref. Salmon et al. (2003c) for a complete study). The characteristic times of these fluctuations range from 100 to 1000 s and are of the order of the time needed to obtain a full velocity profile (2–3 min). Such dynamics prevent us to record well-defined profiles. To obtain valuable data, we chose to measure time-averaged velocity profiles: several profiles were recorded at a given applied shear rate, and later averaged. The typical number of profiles needed to obtain good statistical estimates of the flow field ranges between 10 and 20. The standard deviations of those estimates yield the amplitudes of the temporal fluctuations. Figure 7 displays velocity profiles measured simultaneously to the flow curve of Fig. 6. Each profile corresponds to an average over up to 20 measurements. Errorbars represent the standard deviations of the local velocities.

The main features of these profiles are as follows. (i) Below the layering transition i.e. for $`\dot{\gamma }\dot{\gamma }_115`$ s-1, velocity profiles are perfectly stationary. The flow is homogeneous since the profiles are nearly linear. However, significant wall slip can be detected: the velocity at the stator does not vanish at $`x=e`$, and the fluid velocity does not reach the rotor velocity at $`x=0`$. (ii) At $`\dot{\gamma }\dot{\gamma }_1`$, a highly sheared band nucleates at the rotor. The shear rate in this band is about $`\dot{\gamma }_B23`$ s-1 and the other band is sheared at $`\dot{\gamma }_A7.1`$ s-1 \[see Fig. 7(b)\]. Significant temporal fluctuations are present Salmon et al. (2003c), and important wall slip can still be measured. (iii) When the shear rate is further increased up to $`\dot{\gamma }=\dot{\gamma }_237`$ s-1, the highly sheared band covers the whole gap. The value $`\dot{\gamma }_A7.1`$ s-1 of the weakly sheared band remains almost constant over the coexistence domain (15–37 s-1). (iv) For $`\dot{\gamma }\dot{\gamma }_2`$, the flow becomes homogeneous again. Temporal fluctuations of the velocity also disappear but the fluid still slips at the two walls.

Those results show without any ambiguity that the layering transition can be described by the classical phenomenology of shear-banding. At $`\dot{\gamma }\dot{\gamma }_1`$, the flow is homogeneous and corresponds to a disordered state of onions, as can be checked from the diffraction patterns. At $`\dot{\gamma }\dot{\gamma }_1`$, velocity profiles display two bands corresponding to two given shear rates $`\dot{\gamma }_A`$ and $`\dot{\gamma }_B`$. At $`\dot{\gamma }\dot{\gamma }_1`$, peaks also appear on the ring. When the shear rate is further increased up to $`\dot{\gamma }_2`$, the width of the highly sheared band grows as well as the constrast of the peaks on the diffraction ring. At $`\dot{\gamma }\dot{\gamma }_2`$, the flow is homogeneous again and the contrast of the peaks on the ring is maximal.

Let us recall that the diffraction patterns correspond to a measure of the structure of the fluid integrated along the velocity gradient direction $`v`$ (see Fig. 1). Therefore, the contrast of the peaks on the ring provides an estimate of the relative proportion of layered vs. disordered onions in the gap. Thus, the above results clearly point to a picture of the flow where the highly (weakly resp.) sheared band corresponds to the layered (disordered resp.) onions. To our knowledge, this data set brings the first experimental evidence for both structural shear-banding and banded flows.

In the next paragraph, we present a detailed analysis of the slip velocities. We also demonstrate that the correction due to wall slip allows us to use a mechanical model to fit the velocity profiles consistently with the classical picture of shear-banding.

### IV.2 Wall slip, effective flow curve and lubricating layers

#### IV.2.1 Effective flow curve

Using the measured velocity profiles, it is easy to define an effective shear rate in the bulk onion texture by $`\dot{\gamma }_{\text{eff}}=(v_1v_2)/e`$, where $`v_1`$ ($`v_2`$ resp.) corresponds to the velocity of the fluid at $`x=0`$ ($`x=e`$ resp.) estimated from the measured velocity profiles. Moreover, in order to take into account the stress inhomogeneity in the Couette cell and thus get a quantitative comparison between this effective shear rate and the global shear rate $`\dot{\gamma }`$ indicated by the rheometer, we define $`\dot{\gamma }_{\text{eff}}`$ consistently with Eq. (2) by:

$$\dot{\gamma }_{\text{eff}}=\frac{R_1^2+R_2^2}{R_1(R_1+R_2)}\frac{v_1v_2}{e}.$$
(3)
Figure 6 presents the effective flow curve $`\sigma `$($`\dot{\gamma }_{\text{eff}}`$) ($``$) and the flow curve computed from the values indicated by the rheometer $`\sigma `$($`\dot{\gamma }`$) ($``$). The effective shear rate allows us to remove the contribution due to wall slip. When compared to the global flow curve $`\sigma `$ vs. $`\dot{\gamma }`$, the effective flow curve seems to reveal a stress plateau at a value of about $`16`$ Pa. This plateau extends from $`\dot{\gamma }_A7`$ s-1 to $`\dot{\gamma }_B25`$ s-1. Note that this stress plateau is not perfectly flat but presents a small slope. We will show in Sec. V that such a slope is due to the curvature of the Couette geometry as expected from theoretical models Radulescu and Olmsted (2000).

#### IV.2.2 Lubricating layers

To explain the presence of wall slip in complex fluid flows, one usually considers that thin lubricating layers are present at the walls of the Couette cell. In emulsions for instance, it is well established that wall slip is due to the presence of highly sheared thin films composed of the continuous phase only Barnes (1995). These films play the role of lubricating layers: the bulk material is weakly sheared, whereas the films absorb a part of the viscous stress. In our case, we can reasonably assume that wall slip is due to very thin layers composed of water or of a few membranes lying normally to the velocity gradient direction $`v`$. The resolution of our setup ($`50\mu `$m) does not allow us to measure directly the thicknesses of those layers.

However, in this simple picture, there is no discontinuity of the shear stress inside the gap of the Couette cell. Because the thicknesses of the lubricating layers are very small ($`100`$ nm), one can assume that the flow inside the films is laminar. Under this assumption, we may access the thicknesses of the lubricating layers. Indeed, let us define the slip velocity at the rotor $`v_{s_1}=v_0v_1`$ as the difference between the rotor velocity $`v_0`$ and the velocity $`v_1`$ at the rotor, and the slip velocity $`v_{s_2}=v_2`$ at the stator as the velocity $`v_2`$ measured at the stator. $`v_{si}/h_i`$ then corresponds to the mean shear rate inside the film of thickness $`h_i`$ ($`i=1`$ for the rotor and $`i=2`$ for the stator). By assuming that the stress is continuous inside the gap of the Couette cell, the thicknesses of the layers are then given by:

$$h_i=\frac{\eta _fv_{s_i}}{\sigma _i},$$
(4)
where $`\sigma _i`$ is the shear stress near wall number $`i`$ and $`\eta _f`$ is the viscosity of the lubricating layers. Note that in the Couette geometry the local stress is given by $`\sigma (r)=\sigma _1R_1^2/r^2`$, where $`\sigma _1`$ is the stress at the rotor. The values $`\sigma _i`$ at the walls are linked to $`\sigma `$ according to:

$$\sigma _i=\frac{2R_j^2}{R_1^2+R_2^2}\sigma ,$$
(5)
where $`j=2`$ (resp. $`j=1`$) when $`i=1`$ (resp. $`i=2`$) and $`\sigma `$ is the global value indicated by the rheometer \[see Eq. (1)\].

#### IV.2.3 Wall slip and shear-banding

Figure 8(a) presents the slip velocities $`v_{si}`$

vs. the global stress $`\sigma `$, both at the stator ($`\mathrm{}`$,$``$) and at the rotor ($`\mathrm{}`$,$``$). The homogeneous profiles are indicated by squares ($`\mathrm{}`$,$`\mathrm{}`$) and banded flows by circles ($``$,$``$). Figure 8(a) reveals the three regimes previously observed on both velocity profiles and diffraction patterns: (i) when $`\sigma <\sigma _A15.9`$ Pa, the velocity profiles are nearly linear and the flow is only composed of disordered onions. In this region, the slip velocities $`v_{si}`$ slightly increase under increasing stress $`\sigma `$. (ii) When $`\sigma _A\sigma \sigma _B17.2`$ Pa, the nucleation and growth of the highly sheared band corresponding to the layered state is associated to a decrease of $`v_{si}`$ with $`\sigma `$. (iii) When $`\sigma >\sigma _B`$, the flow is homogeneous again and the slip velocities $`v_{si}`$ slightly increase with $`\sigma `$. Note that the exact values of $`\sigma _A`$ and $`\sigma _B`$ indicating the coexistence domain will be calculated using Eqs. (15) and (16) in Sec. V.

Figure 8(b) presents the same slip velocities but plotted against the local stress $`\sigma _i`$ inferred from Eq. (5). It reveals two important results. (i) When the flow is homogeneous, the slip velocities at the rotor $`v_{s1}`$ and at the stator $`v_{s2}`$ collapse on the same curve when plotted against the local stresses $`\sigma _1`$ and $`\sigma _2`$. In other words, $`v_{si}`$ seem to be a unique function of the local stress in the homogeneous domains, i.e. $`v_{si}=f(\sigma _i)`$. This feature is also observed in concentrated colloidal systems where inertial effects are totally supressed by the osmotic pressure needed to concentrate the colloids Salmon et al. (2003d); Barnes (1995). (ii) In the coexistence domain, i.e. for $`\sigma _A\sigma \sigma _B`$, there is a large difference between slip velocities at the rotor and at the stator, even when $`v_{si}`$ are plotted against the local stress $`\sigma _i`$. This result confirms the observed structuration: wall slip is very different at the two walls because there are two different fluids inside the gap (the layered state of onions lies near the rotor whereas the disordered onions lie near the stator). In the coexistence domain, the fact that the slip velocity $`v_{si}`$ is a unique function of the local stress $`\sigma _i`$ does not hold anymore. Moreover, our data clearly indicate that wall slip is larger at the rotor than at the stator in this domain.

#### IV.2.4 Thicknesses of the lubricating layers

Figure 9 presents the thicknesses $`h_i`$ of the lubricating layers calculated from Eq. (4) and

assuming that the viscosity of the lubricating films is $`\eta _f=10^3`$ Pa.s, the viscosity of water. The thicknesses $`h_i`$ are of the order of 100–200 nm. Such a value is in good agreement with other measurements performed in concentrated colloidal systems Barnes (1995); Salmon et al. (2003d). Let us recall that in the case of our lamellar phase, the smectic period $`d`$ is 15 nm, so that it is reasonable to assume that the lubricating layers are composed of only water or a few membranes ($`10`$), perfectly aligned along the walls. In any case, the viscosity of the film is probably of the order of $`10^3`$ Pa.s.

#### IV.2.5 A possible explanation for the origin of lubricating layers and their variations with $`\sigma `$

In the onion texture, flow can compress the onions by changing the smectic period $`d`$. Such a compression expells some water from inside the onions and helps to lubricate the flow. This effect has been shown in a lot of lyotropic lamellar phases using neutron and x-ray diffraction Diat et al. (1995); Welch et al. (2002). In our system, as measured with neutron scattering, the smectic period changes sligthly over the range of $`\dot{\gamma }`$ under study Diat et al. (1995). If we assume that the expelled water can also migrate from the bulk material to the walls in order to lubricate the flow, the quantity $`h_1+h_2`$ is then proportional to the volume of water in the lubricating layers. Figure 10 presents $`h_1+h_2`$

vs. $`\sigma `$. Again, the three regions of the shear-banding phenomenology can be clearly identified from Fig. 10. At low applied stress, the quantity of water at the walls increases under increasing stress. This confirms the assumption that the viscous stress compresses the onions and expells some water. At intermediate stress, in the coexistence domain, the volume of water decreases while the width of the highly sheared band grows in the gap of the Couette cell.

Such a result may be simply explained if one considers that some water is needed to lubricate the flow between the layers of ordered onions. Indeed, as suggested in Ref. Diat et al. (1995), the layering of onions is probably associated with the expulsion of some water from the onions to lubricate the flow between the layers. The decrease of $`h_1+h_2`$ could be the signature of a migration of the water from the walls to the bulk of the highly sheared band. At higher stress, when the layered band has invaded the gap, $`h_1+h_2`$ increases again with the shear stress $`\sigma `$. This is consistent with the fact that the viscous stress tends to compress the onions in the homogeneous layered state. Such a picture, suggested by our experiments and by previous works Diat et al. (1995), is obviously highly hypothetical. Resolved x-ray or neutron scattering techniques performed in the gap of the Couette cell are needed to confirm such assumptions.

## V A simple mechanical approach of the shear-banding instability

### V.1 Local constitutive flow curve

The aim of this section is to determine whether the classical mechanical picture of the shear-banding instability holds in our experiments. In such a picture, the flow curve is the one sketched in Fig. 11.

Two branches, corresponding to the two different organizations of onions, are separated by a coexistence domain. The rheological behaviors of the two branches are given by $`\sigma =f_i(\dot{\gamma })`$, where $`i=1`$ ($`i=2`$ resp.) stands for the disordered (layered resp.) state of onions. In the simple picture of shear-banding, one generally assumes that the flow field can separate between bands of different structures, whose local rheological behaviors are given by $`\sigma =f_i(\dot{\gamma })`$. One also assumes that the interfaces between the bands are only stable at a critical stress $`\sigma ^{}`$. When the shear rate is imposed in a geometry where stress is homogeneous (e.g. a cone-and-plate geometry), such an assumption leads to a stress plateau on the flow curve at $`\sigma ^{}`$ Radulescu and Olmsted (2000). On the plateau, velocity profiles display bands of shear rates $`\dot{\gamma }_A`$ and $`\dot{\gamma }_B`$. The following equation relates the imposed global shear rate to the proportion of bands locally sheared at $`\dot{\gamma }_A`$ and $`\dot{\gamma }_B`$:

$$\dot{\gamma }=\alpha \dot{\gamma }_A+(1\alpha )\dot{\gamma }_B,$$
(6)
where $`\alpha `$ is the volume fraction of bands sheared at $`\dot{\gamma }_A`$. In stress-controlled experiments, the plateau cannot be seen anymore and one observes a discontinuous jump between $`\dot{\gamma }_A`$ and $`\dot{\gamma }_B`$ when the stress is sligthly increased above $`\sigma ^{}`$. In the next paragraph, we adresss the validity of the assumption that interfaces lie at a critical stress $`\sigma ^{}`$.

### V.2 Width of the highly sheared band in the Couette geometry

In the Couette geometry, the stress is not homogeneous inside the gap of the cell and the simple analysis presented above does not hold anymore. Indeed, the local stress $`\sigma (r)`$, where $`r`$ is the radial position in the flow, is given by:

$$\sigma (r)=\frac{\mathrm{\Gamma }}{2\pi Hr^2}=\sigma _1\frac{R_1^2}{r^2},$$
(7)
where $`\mathrm{\Gamma }`$ is the imposed torque and $`\sigma _1=\mathrm{\Gamma }/(2\pi HR_1^2)`$ is the stress at the rotor. The shear-banding scenario then leads to a picture with only two bands: one sheared at $`\dot{\gamma }_A`$ and one sheared at $`\dot{\gamma }_B`$. If one considers that the interface between bands is only stable at a given stress $`\sigma ^{}`$, one easily calculates the width $`\delta `$ of the highly sheared band:

$$\delta =R_1\left(\sqrt{\frac{\sigma _1}{\sigma ^{}}}1\right).$$
(8)
Such a relation shows that the stress should increase slightly along the coexistence domain. Indeed, when entering the coexistence region, i.e. when $`\delta =0`$, one finds $`\sigma _1=\sigma ^{}`$, and when the highly sheared band has invaded the gap, $`\delta =e`$ and $`\sigma _1=(R_2/R_1)^2\sigma ^{}`$. This means that, in the Couette geometry, the plateau is not perfectly flat and presents a slope $`(R_2/R_1)^212e/R_1`$ due to the stress inhomogeneity Radulescu and Olmsted (2000).

Our velocimetry measurements easily yield the width $`\delta `$ of the highly sheared band. Figure 12 displays the measured $`\delta `$ vs. the measured stationary stress at the rotor $`\sigma _1`$.

We have also added on this figure the theoretical relation of Eq. (8) with $`\sigma ^{}=16.5`$ Pa, which yields a satisfactory agreement with the experimental data. This seems to indicate that the stability criterion for the interface holds in our experiments with $`\sigma ^{}=16.5`$ Pa. However, our data presents relatively large errorbars on the measured $`\delta `$. To proceed further in the analysis and to confirm the mechanical picture of the shear-banding instability, one should now try to fit all the measured velocity profiles from the knowledge of the flow curve.

### V.3 Procedure for fitting the velocity profiles

Our fitting procedure relies on the following relations:

$`\sigma (r)`$ $`={\displaystyle \frac{\mathrm{\Gamma }}{2\pi Hr^2}},`$ (9)
$`\dot{\gamma }(r)`$ $`=r{\displaystyle \frac{}{r}}\left({\displaystyle \frac{v}{r}}\right).`$ (10)
In order to compute velocity profiles from Eqs. (9) and (10), we first have to determine the rheological laws linking the local stress $`\sigma (r)`$ and the local shear rate $`\dot{\gamma }(r)`$.

#### V.3.1 Rheological behaviors of the homogeneous branches

Figure 13 presents the effective flow curve $`\sigma `$($`\dot{\gamma }_{\text{eff}}`$) measured in our experiment at $`T=30^{}`$C and under controlled shear rate. We have fitted the two branches corresponding to the two homogeneous states: (i) for $`\dot{\gamma }6`$ s-1 (disordered onions) by a shear-thinning behavior $`\sigma =f_1(\dot{\gamma })=A\dot{\gamma }^n`$ with $`A=11.49`$ and $`n=0.17`$; (ii) and for $`\dot{\gamma }30`$ s-1 (layered state) by a Bingham fluid $`\sigma =f_2(\dot{\gamma })=\sigma _0+\eta \dot{\gamma }`$ with $`\sigma _0=15.19`$ Pa and $`\eta =0.06`$ Pa.s. The resulting fits are presented in Fig. 13. Since the flow field is homogeneous on these branches, such behaviors fitted from the effective flow curve, i.e. after contributions due to wall slip are removed, represent the local rheological behavior $`\sigma `$ vs. $`\dot{\gamma }`$.

#### V.3.2 Equations for the theoretical flow curve and the velocity profiles

Let us now assume that the interface between the bands lies at a unique stress $`\sigma ^{}`$ and let us consider a given torque $`\mathrm{\Gamma }`$. From $`\mathrm{\Gamma }`$ and Eq. (9), we get the local stress $`\sigma (r)`$. If $`\sigma (r)<\sigma ^{}`$ everywhere in the gap of the Couette cell, the flow is homogeneous and composed of the disordered onions, whereas if $`\sigma (r)>\sigma ^{}`$ everywhere, the flow is also homogeneous but composed of the layered state of onions. Moreover, the local shear rate $`\dot{\gamma }(r)`$ is given by Eq. (10), so that in both cases, the velocity profiles are given by the following integration of the rheological behaviors:

$$\frac{v(r)}{r}=\frac{v_2}{R_2}+_{R_2}^r\frac{\dot{\gamma }(u)}{u}\text{d}u,$$
(11)
where $`\dot{\gamma }(r)`$ is found by solving:

$`\sigma (r)={\displaystyle \frac{\mathrm{\Gamma }}{2\pi Hr^2}}=f_i\left(\dot{\gamma }(r)\right),`$ (12)
and $`i`$ denotes the considered branch.

When there exists one particular position in the gap where $`\sigma (r)=\sigma ^{}`$, the flow is inhomogeneous and composed of two different bands. To calculate the resulting velocity profile, one should separate the previous integration according to:

$`{\displaystyle \frac{v(r)}{r}}`$ $`={\displaystyle \frac{v_2}{R_2}}+{\displaystyle _{R_2}^r}{\displaystyle \frac{\dot{\gamma }(u)}{u}}\text{d}u\text{for }r>R_1+\delta \text{ and}`$
$`{\displaystyle \frac{v(r)}{r}}`$ $`={\displaystyle \frac{v(R_1+\delta )}{R_1+\delta }}+{\displaystyle _{R_1+\delta }^r}{\displaystyle \frac{\dot{\gamma }(u)}{u}}\text{d}u\text{for }r<R_1+\delta ,`$ (13)
where $`\delta `$ is given by Eq. (8), and $`\dot{\gamma }(r)`$ by:

$`\sigma (r)`$ $`=f_1\left(\dot{\gamma }(r)\right)\text{for }r>R_1+\delta \text{,}`$
$`\sigma (r)`$ $`=f_2\left(\dot{\gamma }(r)\right)\text{for }r<R_1+\delta .`$ (14)
The Appendix presents the detailed integration of Eqs. (11)–(14) for the specific behaviors $`\sigma =f_1(\dot{\gamma })`$ and $`\sigma =f_2(\dot{\gamma })`$ obtained previously. Note that Eqs. (11)–(14) require the knowledge of $`v_{s2}=v_2`$ for the arbitrary torque $`\mathrm{\Gamma }`$. Thus, to compute $`v_{s2}`$ at any value of $`\mathrm{\Gamma }`$, we first interpolate the data $`v_{si}`$ vs. $`\sigma `$ displayed in Fig. 8(a).

For each value of $`\mathrm{\Gamma }`$, i.e. for each value of $`\sigma `$ indicated by the rheometer \[see Eq. (1)\], one can calculate a theoretical velocity profile $`v(x)`$ using the fitting procedure detailed above. One can then calculate the corresponding effective shear rate $`\dot{\gamma }_{\text{eff}}`$ using Eq. (3). Such a procedure allows us to compute a theoretical flow curve $`\sigma `$ vs. $`\dot{\gamma }_{\text{eff}}`$. This theoretical flow curve is displayed in Fig. 13 for comparison with the measured rheological data. The coexistence domain is well reproduced by this theoretical effective flow curve, namely the slope of the stress plateau. This good agreement confirms the assumption that the interface between the bands lies at a given value of the stress $`\sigma ^{}`$. Note that the value $`\sigma ^{}=16.5`$ Pa is the only free parameter of the fitting procedure. The value of $`\sigma ^{}`$ also yields the value of the stress $`\sigma _A`$ ($`\sigma _B`$ resp.) at the entrance (at the end resp.) of the coexistence domain:

$`\sigma _A`$ $`={\displaystyle \frac{R_1^2+R_2^2}{2R_2^2}}\sigma ^{}15.9\text{Pa},`$ (15)
$`\sigma _B`$ $`={\displaystyle \frac{R_1^2+R_2^2}{2R_1^2}}\sigma ^{}17.2\text{Pa}.`$ (16)
The above values of $`\sigma _A`$ and $`\sigma _B`$ are those displayed in Fig. 8, 9 and 10 to visualize the coexistence domain.

For each value of $`\mathrm{\Gamma }`$ and thus for each theoretical velocity profile, one can also calculate the shear rate $`\dot{\gamma }`$ indicated by the rheometer. Indeed, it is easy to determine the rotor velocity from $`v(x)`$ and from the values of $`v_{s1}`$ displayed in Fig. 8(b): $`v_0=v(x=0)+v_{s1}`$. $`\dot{\gamma }`$ is then given by Eq. (2). From the calculated velocity profiles, we extracted those corresponding to the shear rates applied in our experiments. Figure 14 shows these theoretical fits $`v(x)`$ and the corresponding experimental velocity profiles. Again, the good agreement indicates that the stability criterion for the interface holds in our experiments. Such an agreement also confirms the observed shear-banding phenomenology and more precisely, the fact that near the layering transition, the flow is composed of two different bands characterized by two different rheological behaviors.

### V.4 Discussion on the validity of the mechanical approach

In the previous mechanical approach, it is important to note that to each value of torque $`\mathrm{\Gamma }`$ and thus to each value of stress $`\sigma `$, we can associate a unique velocity profile $`v(x)`$, and thus a unique shear rate $`\dot{\gamma }`$. This is a direct consequence of the slope of the stress plateau of the flow curve in the Couette geometry. The uniqueness of $`\dot{\gamma }`$ for a given $`\sigma `$ means that the shear-banding phenomenology is also expected when the stress is controlled in a Couette geometry. However, as mentionned in Sec. II.2 (see Fig. 2), the responses of the shear rate under controlled stress for temperatures $`TT_c=27^{}`$C, are no longer stationary and present large oscillations in the vicinity of the layering transition. It is thus obvious that some ingredients are missing in the mechanical approach detailed previously to model such dynamics. For temperatures $`T<T_c`$, the responses of the shear rate under controlled stress are almost stationary and only display relatively small fluctuations at the layering transition. Our mechanical approach may thus be fully validated only at $`T<T_c`$. This led us to repeat our experiments at $`T=26^{}`$C both under controlled stress and under controlled shear rate.

Using careful protocols similar to that of Sec. IV.1, we measure the two stationary flow curves displayed in Fig. 15, as well as the corresponding diffraction patterns.

Figure 16 presents the time-averaged velocity profiles measured simultaneously to the flow curves displayed in Fig. 15.

These experiments clearly demonstrate that the phenomenology of shear-banding, previously observed at $`T=30^{}`$C under controlled $`\dot{\gamma }`$, is also recovered at $`T=26^{}`$C both at imposed $`\dot{\gamma }`$ and imposed $`\sigma `$. As expected from the mechanical approach, there is no difference between controlling the stress or the shear rate in the Couette geometry, as long as the rheological responses are stationary.

## VI Conclusions

In this paper, we have presented an extensive study of a shear-induced transition in a lyotropic system: the layering transition of the onion texture. Using velocimetry, structural measurements and rheological data, we have shown that the classical picture of shear-banding holds for the layering transition. In this picture, velocity profiles display bands in the vicinity of the transition and the nucleation and growth of the highly sheared band is associated to the nucleation and growth of the SIS, i.e. of the layered state of onions. Using the classical mechanical approach Spenley et al. (1993); Lu et al. (2000), in which the interface between the bands lies at a given value of the stress, we were able to fit the velocity profiles and the coexistence domain on the flow curve.

Moreover, our data reveal the presence of strong wall slip. We have shown that the variations of wall slip with stress are in good agreement with the shear-banding behavior: when the flow is homogeneous, the slip velocity is a universal function of $`\sigma `$ since inertial effects are negligible, and when the flow displays bands, wall slip presents a very large dissymmetry at the rotor and at the stator, probably because the two different textures have different behaviors at the walls of the Couette cell.

One of the most puzzling features of our results is the presence of large temporal fluctuations of the flow field in the coexistence domain. Indeed, velocity profiles display localized temporal fluctuations reaching up to 20% at the interface between the two bands. Moreover, the characteristic times of such fluctuations are very long (100–1000 s), and do not correspond to external mechanical vibrations of the Couette cell. In the next part of the paper Salmon et al. (2003c), we analyze these temporal fluctuations and show that they are probably the signature of rheochaos.

## Appendix A

In the particular case of the rheogical behaviors obtained in Sec. V.3.1, i.e. the disordered texture $`\sigma =f_1(\dot{\gamma })`$ has a shear-thinning behavior $`\sigma =A\dot{\gamma }^n`$ and the layered state $`\sigma =f_2(\dot{\gamma })`$ is a Bingham fluid $`\sigma =\sigma _0+\eta \dot{\gamma }`$, Eqs. (11)–(14) read:
(i) if $`\sigma (r)<\sigma ^{}`$, the velocity profile is given by:

$`v(x)=v_{s2}{\displaystyle \frac{r}{R_2}}+r{\displaystyle \frac{n}{2}}\left[{\displaystyle \frac{\mathrm{\Gamma }}{2\pi HR_2^2A}}\right]^{1/n}\left[\left({\displaystyle \frac{R_2}{r}}\right)^{2/n}1\right];`$
(ii) if $`\sigma (r)>\sigma ^{}`$, the flow is also homogeneous and the velocity profile reads:

$`v(x)=v_{s2}{\displaystyle \frac{r}{R_2}}+r{\displaystyle \frac{\mathrm{\Gamma }}{4\pi HR_2^2\eta }}\left[\left({\displaystyle \frac{R_2}{r}}\right)^21\right]+`$
$`r{\displaystyle \frac{\sigma _0}{\eta }}\mathrm{ln}\left({\displaystyle \frac{r}{R_2}}\right);`$
(iii) if there exists $`r`$ for which $`\sigma (r)=\sigma ^{}`$, the flow displays two bands, and for $`R_1+\delta <r<R_2`$:

$`v(x)`$ $`=v_{s2}{\displaystyle \frac{r}{R_2}}+r{\displaystyle \frac{n}{2}}\left[{\displaystyle \frac{\mathrm{\Gamma }}{2\pi HR_2^2A}}\right]^{1/n}\left[\left({\displaystyle \frac{R_2}{r}}\right)^{2/n}1\right],`$
whereas for $`R_1<r<R_1+\delta `$:

$`v(x)=r{\displaystyle \frac{\mathrm{\Gamma }}{4\pi H(R_1+\delta )^2\eta }}\left[\left({\displaystyle \frac{R_1+\delta }{r}}\right)^21\right]+`$
$`r{\displaystyle \frac{\sigma _0}{\eta }}\mathrm{ln}\left({\displaystyle \frac{r}{R_1+\delta }}\right)+`$
$`v_{s2}{\displaystyle \frac{r}{R_2}}+r{\displaystyle \frac{n}{2}}\left[{\displaystyle \frac{\mathrm{\Gamma }}{2\pi HR_2^2A}}\right]^{1/n}\left[\left({\displaystyle \frac{R_2}{R_1+\delta }}\right)^{2/n}1\right].`$
###### Acknowledgements.

The authors are deeply grateful to D. Roux, L. Bécu, and C. Gay for many fruitful discussions and comments on this work. We also thank Pr. F. Nadus for helping us with the figures of this paper. The authors would like to thank the Cellule Instrumentation at CRPP for the realization of the heterodyne DLS setup.


format: text

text:
# Magnetic study of an amorphous conducting polyaniline

## Abstract

We show that newly found BF3-doped polyaniline, though highly conducting, remains amorphous. Magnetic studies reveal many unusual properties, while suggesting that the intrinsic conductivity of this system is significantly larger than all other known forms of conducting polyaniline, establishing it as an interesting class of highly conducting amorphous polymer.

Over a number of years, proton-doped polyaniline (PANI) has become one of the most extensively studied conducting polymers owing to its high electrical conductivity and consequent possibilities of technological applications. Undoped polyaniline is amorphous. However, proton doping induces the formation of highly conducting, crystalline domains separated by amorphous, insulating barriers. hclSM87  It is reported that the doped charge carriers in the protonated PANI are predominantly localized in the amorphous regions, giving rise to local moments, while a relatively small fraction of the doped carriers has three-dimensionally extended wave-functions in the crystalline parts of the sample. epsteinprl  Since, in the doped polyaniline the charge and the spins are associated with the same carrier, mizo  magnetic susceptiblity and ESR measurements can provide detailed understanding about the microscopic nature of these carriers. We report here a detailed study of the nature of charge carriers in a recently reported conducting PANI, sarma  doped with BF3, which has so far been characterized only by spectroscopic methods. Magnetic susceptiblity and temperature dependence of ESR linewidth in conjunction with x-ray diffraction results suggest interesting distinctive features of this compound, including an order of magnitude increase in the intrinsic conductivity compared to all other known conducting PANI systems.

The sample was prepared sarma  by doping BF3 into the emeraldine base, synthesized by chemical oxidation of aniline using (NH4)2S2O8 at 0-5C. smv18  Magnetic susceptiblity measurement was carried out with powdered sample. Since adsorbed molecular oxygen induces ESR line broadening, the powder sample was sealed in a quartz tube under He for those experiments.

In Fig. 1, we show the x-ray diffraction (XRD) patterns from undoped PANI and PANI doped with BF3 in comparison to that from HCl doped PANI, adapted from Ref. 6. The XRD of PANI clearly suggests that the system is amorphous, in agreement with the previous result. jozefowicz  The appearance of a large number of sharp diffraction peaks upon doping with HCl, suggests significant crystallization of PANI on protonation. In contrast, BF3-doped PANI exhibits an almost identical XRD as the undoped, amorphous PANI, except for the emergence of a weak intensity peak at $`2\theta `$ 24.8. We find that the position of this peak matches with the most intense peak in the XRD of HCl-PANI. More significantly, we find that the intensity of this peak grows rapidly with progressive time of exposure of the sample to atmosphere during the recording of XRD, as shown in the inset to Fig. 1 in the form of repeated XRD scans of the relevant region. In view of the extreme sensitivity of BF3 to moisture, forming HF upon hydrolysis, this extraneous peak in XRD of BF3-doped PANI is easily understood in terms of hydrolyzed BF3 reacting with PANI and giving rise to small crystalline domains of protonated PANI. By minimizing the time of exposure during the measurement, the intensity of this peak could be kept at a low level, though it could never be eliminated completely. It is important to note that the conductivity of the sample was found to decrease with increasing exposure to the atmospheric conditions, concomitant with the increase in the intensity of the spurious peak at 24.8. These observations clearly suggest that in sharp contrast to proton-doped PANI, BF3-doped samples remain amorphous as the undoped PANI. Considering that the intrinsic conductivities of BF3-doped samples are orders of magnitude higher than that of the protonated samples, as discussed later, this observation puts the present system in a unique class of amorphous and yet highly conducting polymers.

We show the susceptibility as a function of temperature in Fig. 2. The experimentally obtained susceptibility value has been normalized to a two ring repeat unit and finally corrected for the diamagnetic contributions of the atomic cores ($`\chi _{core}`$) using Pascal constants. pascal  The calculated $`\chi _{core}`$ value for BF3 is 193.6$`\times 10^6`$ emu mol-1. The susceptibility of doped polyaniline has been described epstein87  by $`\chi =\chi _P+C/T`$, where, $`\chi _P`$ is the temperature independent Pauli paramagnetic contribution from the delocalized charge carriers and $`C`$ is the Curie constant arising from the trapped or localized spins in the polymer. $`\chi _P`$ can in turn be expressed in terms of the average density of states at the Fermi level, $`N(E_F)`$, by the relation $`\chi _P=\mu _B^2N(E_F)`$, where $`\mu _B`$ is the Bohr magneton. Thus, $`\chi _P`$ can provide a good estimate of the intrinsic metallic conductivity of the sample, which the bulk resistivity measurement often fails to project, since it depends strongly on the intergrain connectivity in the sample. For instance, the $`N(E_F)`$ value for CSA-PANI csachi , calculated from the $`\chi _P`$ value is 0.7 states eV-1 (2 rings)-1, while that for the HCl-doped sample is 1.6 states eV-1 (2 rings)-1PRBv49  This is consistent with the fact that the room temperature conductivity of CSA doped PANI in the pressed pellet form is 0.047 S cm-1csamacro  which is lower than that of powdered HCl-PANI, though PANI doped with CSA has the highest bulk conductivity among the family of doped polyanilines, in thin film form. csaprb

Fig. 2a shows the susceptibility as a function of temperature ($`\chi `$ vs. $`T`$ plot), indicating a nearly temperature independent Pauli-like susceptiblity in the high temperature region. The rapid increase of susceptibility with decreasing $`T`$ follows a typical Curie behavior, as demonstrated by the $`\chi `$ vs. $`1/T`$ plot in the same figure. This plot shows the expected linear behavior in the low temperature regime. The values of $`C`$, $`\chi _P`$ and $`N(E_F)`$ estimated from the best fit of the susceptibility data are $`3.7\times 10^3`$ emu K mol-1, $`380\times 10^6`$ emu mol-1 and 11.8 states eV-1 (2 rings)-1, respectively. Thus, the calculated density of states at the Fermi level is considerably higher than that for any other conducting polyaniline system known, typical values reported epsteinprl  so far for various protonated samples being in the range of 1.6 states eV-1 (2 rings)-1. Such a higher concentration of delocalized charge carriers in BF3 doped PANI suggests a very high intrinsic conductivity in this system. Also, a high $`\chi _P`$ value in predominantly amorphous BF3-doped PANI is in sharp contrast with the previous results on HCl doped PANI, jozefowicz  which show that the delocalized carriers and therefore, $`\chi _P`$ are mainly associated with the crystalline domains in doped PANI. It is possible that the absence of any counterions in BF3-PANI, as opposed to the protonated PANI, may be responsible for these qualitative changes.

Though we have analyzed the magnetic data in terms of $`\chi =\chi _P+C/T`$, close inspection of the temperature dependence suggests interesting deviations from this behavior at $``$ 200 K. For systems obeying the above equation, $`\chi `$$`T`$ is linear in temperature. However, $`\chi `$$`T`$ for the BF3 doped PANI shown in Fig. 2b exhibits an increase in the slope above 210 K, indicating a slight increase in $`\chi _p`$ and a simultaneous decrease in $`C`$. While this increase in Pauli susceptibility component is not evident in the $`\chi `$ vs. $`T`$ plot shown in Fig. 2a, $`ln\chi `$ vs. $`lnT`$ plot in Fig. 2b accentuates a small but gradual increase in the free carrier susceptibility above about 200 K. This enhancement of $`\chi _P`$ at the cost of $`C`$ with increasing $`T`$ suggests that these changes are possibly a consequence of the thermal activation of the localized spins into free carriers, indicating that the trapping potential is in the scale of the thermal energy in this system.

We find that the ESR signals from BF3-doped PANI have homogenously broadened Lorentzian shape, which suggests a three dimensional delocalization of the charge carriers eprlor  as well as a negligible contribution from the hyperfine and dipolar interactions. PRBv45  The ESR linewidth of a sample is determined by various relaxation processes that influence the lifetime of the spin carriers. We present the temperature dependence of the peak-to-peak linewidth of the ESR signal ($`\mathrm{\Delta }`$$`H_{pp}`$) for BF3-PANI in 4-300 K range in Fig. 3. Although the lineshape remained essentially Lorentzian in the entire temperature range, the linewidth shows different variations in three different temperature regimes, marked in the figure as A, B and C. In systems where the scattering between the localized and the delocalized spins determines the relaxation rates, the relaxation time and therefore the linewidth are given by the Korringa relation, korringa  $`\mathrm{\Delta }`$$`H_{pp}`$ $``$ $`N^2(E_F)T`$. Between 50 K and 230 K (region B), we indeed find the linewidth to increase linearly with T. Since the slope is directly proportional to $`N^2(E_F)`$, we compare the slope in our sample with that of a previously published result on HCl doped PANI films, PRBv45  for which the $`N(E_F)`$ is known to be 1.6 states eV-1 (2-rings)-1. From the ratio of the slopes, the calculated $`N(E_F)`$ for BF3-PANI is 15.2 states eV-1 (2-rings)-1; this value matches well with that obtained from the susceptibility results, once again establishing an order of magnitude improvement in the intrinsic conductivity. At further lower temperatures (region A), the linewidth is essentially temperature independent. This is possibly due to a partial localization of the mobile spins, thereby increasing the concentration of fixed spins and compensating the thermally induced changes in the ESR linewidth. More pronounced effect has been observed PRBv45 ; prb98  in the case of powdered HCl doped PANI, where the ESR linewidth actually begins to increase with decreasing temperature below 190 K. In more ordered samples like stretched films of HCl-doped PANI, the ESR linewidth at lower temperatures becomes temperature independent, prb98  as observed here. It is therefore quite intriguing to note that despite being amorphous, the effect of localization is so weak in the case of BF3-PANI. It would appear that the energy difference between the chemical potential and the mobility edge in BF3-doped PANI is very small, though the system is extremely disordered. At higher temperatures (region C), we observe a sharp decrease in the ESR linewidth. Since the localized spins are primarily responsible for the relaxation process in ESR, this observation suggests that the number of localized spins decreases at these higher temperatures. This is consistent with the conclusions based on the magnetic susceptibility data (Fig. 2b) that the delocalized spins increasingly become mobile above $``$ 210 K, leading to an increase of the $`\chi _P`$ component at the expense of the $`C`$ value.

In summary, we report an interesting class of conducting polyaniline doped with electron deficient boron trifluoride. The intrinsic conductivity is at least an order of magnitude higher compared to all other polyaniline samples. This is remarkable in view of the fact that the polymer remains amorphous even on doping, representing a highly conducting amorphous state, at least above $``$ 50 K. This is in sharp contrast to proton doped PANI where the conductivity is associated with the crystalline domains. The energy scales associated with the trap potential for localizing spins was found to be small, in order of the thermal energy scale. These distinctive behaviors suggest that the present sample belongs to an interesting class of amorphous and yet highly conducting polymers.

We are grateful to the Council for Scientific and Industrial Research (CSIR) for providing the financial support.


text:
# Theory of the quantification of the redshifts.

## 1 Introduction

The “Coherent Raman Effect on Incoherent Light”(CREIL)  explains a lot of properties of the quasars

Creil is a light-matter parametric interaction which has the following properties:

\- CREIL redshifts the frequencies of the natural incoherent light, transferring the corresponding energy to the thermal radiation.

\- CREIL keeps the widths of the lines, there is no blur of the spectra.

\- The relative frequency shift $`\mathrm{\Delta }\nu /\nu `$ is nearly independent on $`\nu `$.

\- As CREIL is a space-coherent process, it does not blur the images.

\- CREIL requires a low pressure gas which is not excited, acting as a catalyst; to be active in CREIL, a gas must have Raman resonances in the megaHerz range (or lower).

In astrophysics, H$`{}_{}{}^{+}{}_{2}{}^{}`$ has the convenient resonances. To get them, atomic H needs to be excited by a Lyman transition; for low values of the principal quantum number $`n`$, the fine, hyperfine and Lamb energies are too high (gigaHerz range), so that a Zeeman splitting is necessary.

## 2 Propagation of light in a halo made of atomic hydrogen.

Consider a nearly homogeneous halo made of low pressure atomic hydrogen in a low magnetic field.

If the intensity of the nearly thermal spectrum emitted by a strong source does not depend on the frequency, supposing that the redshifting power of the gas is constant, the pumping of the Lyman lines is constant, so that the constancy of the redshifting power is verified. As absorption and redshift are simultaneous, the width of the absorption lines is equal to the redshift, so that the absorptions are spread, weak, invisible.

Suppose that, at some place, the pressure is higher than 100 Pascals, or that the magnetic field disappears locally, so that there is no CREIL: the Lyman lines are written into the spectrum.

Then the CREIL appears, spreads the lines, making their absorption invisible. However, if an absorbed, shifted and strong (low $`n`$), Lyman line coincides with an other strong Lyman line, the decrease of CREIL stabilises the frequencies, all absorption lines are written into the spectrum; in particular the absorption of the shifted, previously written line is increased. Thus the Lyman absorption patterns become stronger and are linked by superpositions of shifted and unshifted frequencies.

## 3 Application to the quasars and galaxies.

The quasars are surrounded by a halo of atomic hydrogen observed by the Lyman absorption and magnetic fields are deduced from polarisations. Therefore the previous conditions apply

Using the Rydberg approximation, the coincidence of Lyman $`\alpha `$ and $`\beta `$ lines occurs for a shift $`z_{\alpha \beta }=5/27=0.185=30.0617`$. For the $`\alpha `$ and $`\gamma `$ lines, $`z_{\alpha \gamma }=1/4=40.0625`$. By a combination of successive links of patterns, one may obtain $`z_f=2z_{\alpha \beta }+z_{\alpha \gamma }=0.620`$. $`z=.062`$ may be obtained too.

These features are observed experimentally . They apply to the galaxies.

This building of the composed pattern shows that the complexity of the spectrum; the density of lines increases with the redshift, an observed property too.

## 4 Conclusion.

There are few hypothesis, which correspond to standard physics and to observations. It is difficult to suppose, as the standard theory does, that there are lots of galaxies along the paths of all quasars, and that the redshifts of these galaxies obey a single law. The older hypothesis, dark matter or high speed clouds do not work better.

Therefore the CREIL origin of the largest part of the redshifts of the quasars seems proved. Why not the remainder to get the “cosmological redshift ”by a CREIL interaction of the light with H$`{}_{}{}^{+}{}_{2}{}^{}`$ which could provide the 2.7K radiation?


text:
# The X-ray jet and central structure of the active galaxy NGC 315

## 1 Introduction

X-ray studies of the kpc-scale radio jets of active galaxies can test whether their electrons are accelerated to high energies. Fast synchrotron energy losses of high-energy electrons allow X-ray maps to pinpoint the acceleration sites. Nearby, low-power jets of the Fanaroff & Riley (1974) class I (FRI) have large projected angular sizes, and provide the best opportunity for measuring X-ray substructure.

The high spatial resolution and sensitivity of Chandra have been crucial to extending X-ray jet studies beyond Cen A and M 87, the only FRI radio galaxies for which resolved X-ray jets had been detected prior to its launch (Schreier et al. 1979; Schreier, Gorenstein & Feigelson 1982). In this paper we report the detection of an X-ray jet in the inner parts of the giant FRI radio galaxy NGC 315, at $`z=0.0165`$.

The observation was made as part of our Chandra programme of imaging and spectroscopy of FRI radio galaxies from the B2 bright sample (Colla et al. 1975; Ulrich 1989), aimed at studying the validity of the unification of B2 radio galaxies and BL Lac objects and at testing physical and dynamical models for the X-ray and radio-emitting structures. NGC 315 is one of the X-ray brightest B2 sources studied with ROSAT (Canosa et al. 1999), and consequently only a short Chandra exposure time was needed to meet our criterion of uniform data quality for the sample.

NGC 315 has a two-sided radio structure extending roughly one degree on the sky (Bridle et al. 1979). On milliarcsec scales, the sidedness asymmetry and proper motions suggest the jet bulk motion is relativistic ($`v>0.75c`$), possibly accelerating between 3 and 10 pc from the nucleus, with an angle to the line of sight between 30 and 40 degrees (Cotton et al. 1999; Giovannini et al. 1994, 2001). The north-west radio jet remains dominant on a scale of a few tens of arcsec. A transition from supersonic to turbulent transonic flow, with deceleration by entrainment, is likely to occur at about 17 arcsec from the core, where there is a sudden change in jet opening angle (Bicknell 1986). Bicknell (1994) shows from the application of conservation laws that an entraining jet which is initially relativistic will have a speed between $`0.3`$ and $`0.7c`$ at the flare point, and he demonstrates how such a model is consistent with the radio data from NGC 315.

Resolved jet emission from NGC 315 remains unseen in the optical from ground-based (Butcher et al. 1980) and HST (Verdoes Kleijn et al. 1999) measurements. The HST observations detect an unresolved nuclear source surrounded by an inclined, regular, circum-nuclear disk of radius about 1 arcsec and extinction about 0.25 magnitudes, whose axis is aligned to within a few degrees of the north-west radio jet (Verdoes Kleijn et al. 1999; de Ruiter et al. 2002).

In this paper we adopt a value for the Hubble constant of $`H_o=70`$ km s-1 Mpc-1. 1 arcsec corresponds to 335 pc at NGC 315. The J2000 position of the radio nucleus is $`\alpha =00^{}57^{}48^{\prime \prime }.8834`$. $`\delta =+30^\mathrm{h}21^\mathrm{m}08^\mathrm{s}.812`$ (Xu et al. 2000). The Galactic column density to the source obtained from 21 cm measurements is $`5.92\times 10^{20}`$ cm-2 (Dickey & Lockman 1990), and local absorption through this gas is included in all our spectral models.

## 2 Chandra Observations and Results

We observed NGC 315 with the back-illuminated CCD chip, S3, of the Advanced CCD Imaging Spectrometer (ACIS) on board Chandra on 2000 October 8. Details of the instrument and its modes of operation can be found in the Chandra Proposers’ Observatory Guide, available from http://cxc.harvard.edu/proposer. The observation was made in the VFAINT data mode, with a 128-row subarray (giving a 1 by 8 arcmin field of view, with the source roughly centred in the 1 arcmin direction and at a 3:1 offset position in the 8 arcmin direction). The use of the subarray was to reduce the readout time to 0.44 s in order to guard against the effects of pile-up should much of the flux detected with ROSAT (Worrall & Birkinshaw 1994) be unresolved to Chandra. Results presented here all use ciao v2.3 and the caldb v2.20 calibration database. The data have been re-calibrated and analysed, with random pixelization removed and taking advantage of VFAINT background cleaning, following the software ‘threads’ from the Chandra X-ray Center (http://cxc.harvard.edu/ciao). Events with grades 0,2,3,4,6 are used. All X-ray spectra are binned to a minimum of 20 counts per bin, and the time-dependent decline in quantum efficiency is taken into account using the recommended methods. After the VFAINT background cleaning, there were no time intervals which needed to be excluded because of anomalously high background, and the calibrated data have an observation duration of 4.67 ks.

### 2.1 The X-ray image and resolved jet

Fig. 1 shows the 0.5–5 keV Chandra X-ray data together with contours outlining the inner radio emission. In the figure, the X-ray core is burned out and the low-surface-brightness emission is suppressed in order to emphasize small-scale extended emission.

X-ray emission from the core is extended with a similar ellipticity and position angle to the optical emission from NGC 315. We have used the IRAF STSDAS task ELLIPSE to measure the ellipticity of a Kitt Peak 4 m R-band image (Birkinshaw and Davies, private communication), and find position angles between 40 and 46 degrees and ellipticities between 0.16 and 0.26 for most of the galaxy. For example, at a semi-major axis of 10 arcsec, the ellipticity is $`0.251\pm 0.002`$ and the position angle is $`45.2\pm 0.2`$ degrees. We find an ellipticity of $`0.29\pm 0.03`$ and a position angle of $`49\pm 3`$ when similar procedures are applied to the 0.5-5 keV X-ray image smoothed with a Gaussian of $`\sigma =1.3`$ arcsec, masking out the region of the resolved jet.

Resolved X-ray emission from the NW radio jet is clearly evident at a position angle roughly perpendicular to the semi-major axis of the galaxy. The X-ray emission is particularly strong at the base of the first radio enhancement. We find $`55\pm 9`$ net counts in the energy range $`0.55`$ keV from the jet as measured in a rectangular box of length 12 arcsec and width 6 arcsec, starting 3 arcsec from the nucleus, taking a corresponding box diametrically opposite the nucleus to measure the background.

### 2.2 Radial-Profile Analysis

In order to separate unresolved and galaxy emission, avoiding resolved jet emission, we extracted a source-centred 0.4–7 keV radial profile excluding a pie slice of position angle between $`295^{}`$ and $`325^{}`$. We fitted the profile with models convolved with the Point Response Function (PRF), using home-grown software whose algorithms are described in Birkinshaw (1994). Our procedure for finding the appropriate energy-weighted PRF follows that described in Worrall et al. (2001), except that we used a revised functional form for the third additive component in order to give an improved description of bright point sources (see http://cxc.harvard.edu/cal/Hrma/psf): for the energy distribution of the counts in our NGC 315 observation we find this third component to be proportional to $`(1+\theta /0.021)^{2.1}`$, for $`\theta 5`$ arcmin.

The ROSAT PSPC measured thermal X-ray emission associated with NGC 315’s atmosphere out to a radius of 2 arcmin, and we expect this emission to dominate over the background throughout part of the field of view of our Chandra observation. A rectangular box of size 1 arcmin by 2 arcmin as far from NGC 315 as possible but still in the field of view (i.e. all being 4 arcmin or more away from the nucleus of NGC 315) contains $`0.007\pm 0.001`$ cts arcsec-2, 0.4–7 keV, consistent with time-averaged results available from http://cxc.harvard.edu/cal/Acis/Cal\_prods/bkgrnd/current. We use this as a measure of the background in the observation for all the analyses presented here. As a check, we have also performed the radial analysis allowing our fitting to find the best-fitting source and background contributions to an annulus of radii 40 and 62 arcsec, and the results for the background and the model parameters agree with those using the rectangular-box background.

The radial profile gives unacceptable fits to single-component models of a point source or a $`\beta `$ model (used to describe gas in hydrostatic equilibrium), but the fit to the combination of the two is good, as shown in Fig. 2. Parameter values and uncertainties are given in Table 1.

### 2.3 X-ray Spectrum

Our radial-profile analysis separates the 313 counts111Counts refer to 0.4–7 keV throughout §2.3. within a source-centered circle of radius 1 arcsec into contributions of 90 per cent from unresolved emission and 10 per cent from the extended component. Spectral analysis supports the dominance of non-thermal emission in the unresolved component. The data give a good fit to a single-component absorbed power law, as shown in Fig. 3. While the statistics are inadequate for fitting a two-component model, a single-component thermal model gives unrealistic results: a best-fitting temperature of 25 keV, an intrinsic absorption of $`N_\mathrm{H}=4\times 10^{21}`$ cm-2, and a 0.5 – 7 keV luminosity of $`3\times 10^{41}`$ ergs s-1 which is unreasonably high for the X-ray binary population within 335 pc of NGC 315’s centre.

To measure the spectrum of the extended emission we have fitted a Raymond-Smith thermal model to the 511 counts from a core-centred annulus of radii 2 arcsec and 45 arcsec, excluding a pie slice of position angle between $`295^{}`$ and $`325^{}`$, to avoid the resolved jet emission and the majority of counts from the unresolved emission. The best fit gives $`kT0.6`$ keV and a small intrinsic absorption of $`N_\mathrm{H}=5\times 10^{20}`$ cm-2 (comparable to Galactic absorption), although the uncertainties are such that the additional absorption is consistent with being zero. There is marginal improvement in the fit (an $`F`$ test giving a 7 per cent probability of the improvement in $`\chi ^2`$ being by chance) if a thermal bremsstrahlung component (best-fitting $`kT=4.2`$ keV) is included in the model. In this case the minimum $`\chi ^2`$ is 20.8 for 17 degrees of freedom, and a 0.5–7 keV luminosity of $`6\times 10^{40}`$ ergs s-1 (about 20 per cent of the total luminosity from the region) is in the bremsstrahlung component. Although this is a factor of a few higher than expected for the composite emission from X-ray binaries in the NGC 315 galaxy, the uncertainties are large. The abundance of the thermal gas increases from about 0.2 solar to more reasonable values between about 0.5 and 1.0 solar when the bremsstrahlung component is included. A consistent temperature is found for the thermal gas, whether or not the bremsstrahlung component is included, and the statistical uncertainties dominate the errors. The best-fit value and 90 per cent confidence uncertainties (for one interesting parameter) are estimated to be $`kT=0.62\pm 0.06`$ keV.

Our spectral fitting to the total 920 counts in the central 2 arcsec radius core plus the region of the previous paragraph finds a two-component power-law plus thermal model to be acceptable. The statistical quality of the data is insufficient to require more complex spectral models, such as the addition of a bremsstrahlung component. The results are insensitive to the gas abundance (which we set to be 0.5 times solar) and intrinsic absorption in front of the thermal emission (which we set to be zero). The $`\chi ^2`$ contours of power-law slope versus gas temperature are shown in Fig. 4. For the best-fit parameters, the number of counts in the power-law component is $`438\pm 38`$ ($`1\sigma `$ statistical error only). This is in reasonable agreement with the results from the radial-profile analysis (Table 1). In the remainder of this paper the radial-profile analysis is used to separate the counts into unresolved emission, which we characterize by a power law of photon spectral index $`1.4\pm 0.4`$, from the resolved emission which we characterize by a thermal model with $`kT=0.6\pm 0.1`$ keV.

With so few counts, the spectrum of the resolved jet emission is poorly constrained. However, the distribution of counts suggests a spectrum which is steeper than that of the core. A formal fit (of the counts in four energy bins) with no intrinsic absorption gives a photon spectral index of $`2.5\pm 0.7`$ ($`1\sigma `$ uncertainty).

### 2.4 Physical Parameters of the X-ray Components

In this short observation we have measured resolved jet emission between about 3 and 15 arcsec from the nucleus. The counts are converted into a 0.4-5 keV luminosity in Table 2 assuming a power law of photon spectral index 2.5. The 1 keV flux density is then 4.3 nJy. The 5 GHz radio flux from a matched region in the map of Fig. 1 is 68 mJy. The two-point rest-frame 5-GHz to 1-keV spectral index is therefore $`\alpha _{\mathrm{rx}}=0.94\pm 0.01`$, where the error is dominated by the 16 per cent uncertainty in the X-ray counts (§2.1).

With regard to the core emission, the spectral index of the power-law component (Fig. 3) is highly correlated with the intrinsic absorption. Our results suggest a somewhat flatter spectral index and lower absorption than found by Matsumoto et al. (2001; spectral index of $`2.02_{0.32}^{+0.37}`$, $`N_\mathrm{H}=0.9_{0.5}^{+0.6}\times 10^{22}`$ cm-2) in a two-component thermal and power-law fit to ASCA data, but the results are consistent with a similar correlation of spectral index and intrinsic absorption. Table 2 gives the best-fit 0.4–5 keV luminosity of the power-law component. This is comparable with the luminosities of two other low-power radio galaxies from the B2 sample in which Chandra has found unresolved X-ray cores and resolved jets, B2 0206+35 at $`2.9\times 10^{41}`$ ergs s-1 and B2 0755+37 at $`1.9\times 10^{42}`$ ergs s-1 (Worrall et al. 2001). The 2–10 keV luminosity of NGC 315’s power-law component is $`6.8\times 10^{41}`$ ergs s-1, larger than the ASCA value of $`3.1\times 10^{41}`$ ergs s-1 (Matsumoto et al. 2001) and possibly supporting variability similar to that reported between ROSAT PSPC and HRI observations by Worrall & Birkinshaw (2000). The interpolation to a 0.2–1.9 keV luminosity further supports variability of a factor of about 3 when compared with the ROSAT PSPC results (Worrall & Birkinshaw 2000), with ROSAT being higher, but this is highly dependent on the spectral index used for the interpolation, and a spectrum closer to the ASCA result removes the requirement for variability. The 2 keV core flux density from the Chandra observation is 40 nJy. Since this is the same value as adopted by Giovannini et al. (1994), their conclusions concerning relativistic beaming based on synchrotron self-Compton emission in the VLBI core would be unchanged.

Values for physical parameters of the X-ray-emitting gas are listed in Table 2. Chandra’s high spatial resolution finds a smaller core radius (Table 1) and a density gradient within 10 arcsec of the centre to which the ROSAT PSPC was insensitive, but the gas pressure at 10 arcsec is in remarkable agreement with the ROSAT results (compare Table 2 with figure 9 of Worrall & Birkinshaw 2000). When the best-fit Chandra results are extrapolated to estimate the gas luminosity for $`\theta <3`$ arcmin and 0.2–2.5 keV, we find a value of $`5.3\times 10^{41}`$ ergs s-1, which is in excellent agreement with the value of $`(5.4\pm 0.2)\times 10^{41}`$ ergs s-1 from ROSAT, and the gas temperature (see Fig. 4) is also in good agreement with the value of $`kT=0.62_{0.1}^{+0.09}`$ keV from ROSAT (Worrall & Birkinshaw 2000). Our results for the temperature are lower than $`kT=0.8_{0.06}^{+0.04}`$ keV found from ASCA data by Matsumoto et al. (2001). While there is no obvious explanation for the difference, we note that while the ASCA data have more counts, the gas and AGN emission were both unresolved in the ASCA beam so that there was no ability to measure the spectrum of the gas uncontaminated by AGN emission, as is possible with Chandra. NGC 315’s 0.4–5 keV gas luminosity within a radius of 15 kpc is similar to the values of $`2.6\times 10^{41}`$ ergs s-1 and $`4.2\times 10^{41}`$ ergs s-1 found for B2 0206+35 and B2 0755+37, respectively (Worrall et al. 2001).

## 3 Discussion

Chandra has

1. made the first detection of resolved X-ray jet emission in the nearby radio galaxy NGC 315,
2. confirmed, with high spatial resolution, results from ROSAT and ASCA that the bulk of the X-ray emission is comprised of a combination of galaxy-scale emission, principally from a hot X-ray-emitting atmosphere, and unresolved emission which fits a power-law spectrum, and
3. found evidence that the resolved X-ray jet is of steeper spectrum than the core, and that the jet emission is brightest close to the core, in particular at the base of the first bright radio knot.

The resolved jet emission has properties similar to those seen in deep observations of some other FRI sources. For example, the power-law energy spectral index of the X-ray emission, $`\alpha _x=1.5\pm 0.7`$, is consistent with the two-point radio to X-ray spectral index of 0.94, supporting a synchrotron origin with either a broken or unbroken spectrum, depending on the radio spectrum in this region. Such a synchrotron spectrum would be consistent with Butcher et al. (1980)’s optical upper limit on jet emission of $`1\mu `$Jy per kpc. The inverse Compton arguments applied to 3C 66B by Hardcastle et al. (2001) give similar results for NGC 315 in underpredicting the X-ray emission under reasonable assumptions for orientation, beaming, and available photon fields. The strong X-ray emission at the base of the first radio enhancement is a behaviour similar to that seen in 3C 66B (Hardcastle et al. 2001) and Cen A (Kraft et al. 2002).

When we compare the X-ray flux density of the unresolved emission with the total VLBI 5 GHz radio flux density of $`477\pm 5`$ mJy from Venturi et al. (1993), we find a two-point rest-frame 5 GHz to 1 keV spectral index of $`\alpha _{\mathrm{rx}}0.86`$. The uncertainties are dominated by possible variability, with the factor of three discussed in §2.4 leading to an uncertainty in $`\alpha _{\mathrm{rx}}`$ of about $`\pm 0.06`$. The value of $`\alpha _{\mathrm{rx}}`$ is within the range of 0.8 to 0.93 found for three other B2 bright-sample FRI radio galaxies observed with Chandra (Worrall et al. 2001). Similar values of $`\alpha _{\mathrm{rx}}`$ for galaxies of different fluxes would support a relationship between the core radio and X-ray components, as argued statistically for the B2 bright sample based on ROSAT data by Canosa et al. (1999). The core two-point spectral index is somewhat flatter than that inferred for the resolved jet, possibly lending support to a different (inverse Compton) origin for the core emission (e.g., Giovannini et al. 1994, Hardcastle & Worrall 2000).

The nuclear X-ray emission of NGC 315 is seen through a moderate intrinsic column density (Fig. 3) of $`N_\mathrm{H}=(5_{2.7}^{+3.2})\times 10^{21}`$ cm-2 (90 per cent confidence uncertainty for 1 interesting parameter). Chandra typically finds intrinsic column densities below $`10^{22}`$ cm-2 in FRI radio-galaxy nuclei (e.g., Worrall et al. 2001; Hardcastle et al. 2001, 2002; Wilson & Yang 2002). Nuclear optical emission, now commonly detected with HST, has been shown by Chiaberge, Capetti & Celotti (1999) to correlate with the VLA-scale core radio emission. This optical emission is generally associated with extinction at a level compatible with the X-ray absorption (e.g., Ferrarese & Ford 1999), suggesting that both the X-ray and optical emission are associated with the sub-kpc-scale radio jets (Hardcastle & Worrall 2000).

It is unclear whether FRI radio galaxies contain a dense torus of gas and dust of the type required by models which unify powerful radio sources (Barthel 1989). Cen A and NGC 4261 are the clearest cases where column densities of order $`10^{23}`$ cm-2 are required by the X-ray data (Kraft et al. 2003, in preparation; Zezas et al. 2003). Both objects are closer than NGC 315, with the advantage that the nuclear emission is better separated from kpc-scale, radio-related, X-rays. However, M 87 is also nearby and does not require a heavily-absorbed component (Wilson & Yang 2002). Even if central tori exist in FRI radio galaxies, most of the X-ray emission may be associated with structures on larger scales, since there is at least one good case where the nucleus is known to be radiatively inefficient (Di Matteo et al. 2003). Little or no excess nuclear absorbing column would then be seen, except in cases (such as NGC 4261) where the jets lie almost in the plane of the sky. If this is the case, the low X-ray column density of NGC 315, whose jets may lie $`35^{}`$ from the line of sight (see §1), says little about the presence or absence of a nuclear torus, although a second, heavily-absorbed, component might appear in a deeper X-ray observations.

We have compared the pressure in the radio jet with that in the external X-ray emitting gas, assuming an equipartition magnetic field. At 10 arcsec from the core the FWHM of the radio jet is roughly 1.3 arcsec. Using the radio flux density in a cylinder of length 1 arcsec, modelling the electron spectrum above $`\gamma _{\mathrm{min}}=10`$ with a synchrotron spectrum consistent with the distribution of radio, X-ray, and optical (upper limit) flux densities over the surrounding 12-arcsec length of jet, assuming no relativistic protons, a filling factor of unity, no relativistic bulk motions, and a jet on the plane of the sky, we find a pressure of about $`6\times 10^{12}`$ Pa, which is a reasonable match to the external pressure of $`(4\pm 1)\times 10^{12}`$ Pa (Table 2) given the measurement and model uncertainties. Such a model would be appropriate if the radio source is intrinsically one-sided. If at 10 arcsec from the core the jet is inclined at $`\theta =35`$ degrees to the line of sight, and has a bulk velocity of $`0.7c`$ (see §1), then the bulk relativistic beaming factor, $`\delta =1/\gamma (1\beta \mathrm{cos}\theta )=1.67`$. The minimum pressure in the jet will now be reduced, by a factor of roughly $`\delta ^{10/7}(\mathrm{sin}\theta )^{4/7}`$ (Bicknell 1994), i.e., to $`2\times 10^{12}`$ Pa. Projection effects mean that the jet is longer. The pressure in a $`\beta `$-model external atmosphere scales as $`(\mathrm{cos}\theta )^{3\beta }`$ at large distances from the core radius, i.e., to give $`2.9\times 10^{12}`$ Pa, such that a match between minimum jet pressure and external pressure can still be claimed given the uncertainties. Pressure balance between the external medium and the minimum pressure in the jet at about 100 arcsec from the core (on the reasonable assumption that the jet is now sufficiently slow that beaming can be ignored) has previously been reported based on ROSAT PSPC data by Worrall & Birkinshaw (2000), who point out that NGC 315 appears to be rather different from other B2 bright sample radio galaxies in remaining in pressure balance (at minimum pressure) over a large length of radio jet, without requiring an additional component of internal pressure.


text:
# A new necessary and sufficient condition for the Riemann hypothesis

## 1. Introduction and Preliminairies

In this note we shall prove the following theorem:

###### Theorem 1.1.

Let

(1.1)
$$c_k:=\underset{j=0}{\overset{k}{}}(1)^j\left(\genfrac{}{}{0pt}{}{k}{j}\right)\frac{1}{\zeta (2j+2)},$$

then the Riemann hypothesis is true if and only if

(1.2)
$$c_kk^{\frac{3}{4}+ϵ},(ϵ>0).$$

###### Remark 1.1.

It will be seen below that unconditionally

(1.3)
$$c_kk^{\frac{1}{2}}.$$

###### Remark 1.2.

It is quite obvious how one can trivially modify the proof of the theorem to obtain a more general result:

###### Theorem 1.2.

A necessary and sufficient condition for $`\zeta (s)0`$ in the half-plane $`\mathrm{}(s)>2(1\alpha )`$ is

(1.4)
$$c_kk^{\alpha +ϵ},(ϵ>0).$$

However we shall eschew such gratuitous generalizing at this stage.

Necessary and sufficient conditions for the Riemann hypothesis depending only on values of $`\zeta (s)`$ at positive integers have been known for a long time, e.g. those of M. Riesz  and Hardy-Littlewood . M. Riesz’s criterion, for example, states that the Riemann hypothesis is true if and only if

$$\underset{k=1}{\overset{\mathrm{}}{}}\frac{(1)^{k+1}x^k}{(k1)!\zeta (2k)}=O(x^{\frac{1}{4}+ϵ}),(x+\mathrm{}).$$

We believe our condition is new and it is definitely simpler, as it only involves finite rational combinations of the values $`\zeta (2h)`$, and seems well posed for numerical calculations. This work however did not originate as an attempt to simplify Riesz’s criterion. It arose rather as a consequence of our note  on Maslanka’s expression of the Riemann zeta function (,) in the form

$$(s1)\zeta (s)=\underset{k=0}{\overset{\mathrm{}}{}}A_kP_k\left(\frac{s}{2}\right).$$

Here the $`P_k(s)`$ are the Pochhammer polynomials

(1.5)
$$P_k(s):=\underset{r=1}{\overset{k}{}}\left(1\frac{s}{r}\right),$$

which will appear prominently in the proof of Theorem 1.1. Two elementary facts about them shall be needed: firstly

(1.6)
$$(1)^k\left(\genfrac{}{}{0pt}{}{\frac{s}{2}1}{k}\right)=P_k\left(\frac{s}{2}\right),$$

which is essentially a matter of notation, and secondly a standard estimate given here without proof:

###### Lemma 1.1.

For every circle $`|s|<r<\mathrm{}`$ there is a positive constant $`C_r`$ such that

(1.7)
$$|P_k(s)|C_rk^{\mathrm{}(s)}.$$

## 2. Sufficiency of the condition

The sufficiency of the condition (1.4) follows from writing $`(\zeta (s))^1`$ as a series of Pochhammer polynomials.

###### Proposition 2.1 (Sufficiency of the condition).

If $`c_kk^{\frac{3}{4}+\frac{1}{2}ϵ}`$ for any $`ϵ>0`$, then

(2.1)
$$\frac{1}{\zeta (s)}=\underset{k=0}{\overset{\mathrm{}}{}}c_kP_k\left(\frac{s}{2}\right),(\mathrm{}(s)>\frac{1}{2}),$$

where the series converges uniformly on compact subsets of the half-plane.

###### Remark 2.1.

Since it shall be shown that actually $`c_kk^{\frac{1}{2}}`$ it follows modifying trivially the above argument that the representatiom (2.1) for $`(\zeta (s))^1`$ is unconditionally valid at least in the half-plane $`\mathrm{}(s)>1`$.

We need a lemma before proving Proposition 2.1.

###### Lemma 2.1.

Define

(2.2)
$$q_k:=\underset{n=1}{\overset{\mathrm{}}{}}\frac{1}{n^2}\left(1\frac{1}{n^2}\right)^k,$$

then

(2.3)
$$q_kk^{\frac{1}{2}}.$$

###### Proof.

Let $`\overline{B_1}(x)=x[x]\frac{1}{2}`$. By the Euler-MacLaurin formula we have for $`k1`$

$`q_k`$ $`=`$ $`{\displaystyle _1^{\mathrm{}}}{\displaystyle \frac{1}{x^2}}\left(1{\displaystyle \frac{1}{x^2}}\right)^k𝑑x+{\displaystyle _1^{\mathrm{}}}\overline{B_1}(x){\displaystyle \frac{d}{dx}}{\displaystyle \frac{1}{x^2}}\left(1{\displaystyle \frac{1}{x^2}}\right)^k𝑑x`$
$`=`$ $`\sqrt{\pi }{\displaystyle \frac{\mathrm{\Gamma }(k+1)}{\mathrm{\Gamma }(k+\frac{3}{2})}}+{\displaystyle _1^{\mathrm{}}}\overline{B_1}(x){\displaystyle \frac{d}{dx}}\left({\displaystyle \frac{1}{x^2}}\left(1{\displaystyle \frac{1}{x^2}}\right)^k\right)𝑑x.`$
Clearly

(2.5)
$$\frac{\mathrm{\Gamma }(k+1)}{\mathrm{\Gamma }(k+\frac{3}{2})}k^{\frac{1}{2}},$$

and, letting $`V(f(x))`$ denote the total variation of $`f(x)`$ in $`[1,\mathrm{})`$, we see that

(2.6) $`\left|{\displaystyle _1^{\mathrm{}}}\overline{B_1}(x){\displaystyle \frac{d}{dx}}\left({\displaystyle \frac{1}{x^2}}\left(1{\displaystyle \frac{1}{x^2}}\right)^k\right)𝑑x\right|`$ $``$ $`{\displaystyle _1^{\mathrm{}}}\left|{\displaystyle \frac{d}{dx}}\left({\displaystyle \frac{1}{x^2}}\left(1{\displaystyle \frac{1}{x^2}}\right)^k\right)\right|𝑑x`$
$`=`$ $`V\left({\displaystyle \frac{1}{x^2}}\left(1{\displaystyle \frac{1}{x^2}}\right)^k\right)`$
$`=`$ $`2\underset{1x<\mathrm{}}{\mathrm{max}}{\displaystyle \frac{1}{x^2}}\left(1{\displaystyle \frac{1}{x^2}}\right)^k`$
$`=`$ $`{\displaystyle \frac{2}{k+1}}\left(1{\displaystyle \frac{1}{k+1}}\right)^kk^1.`$
Hence, (2),(2.5) and (2.6) achieve (2.3). ∎

###### Proof of Proposition 2.1.

First note that

$`c_k`$ $`=`$ $`{\displaystyle \underset{j=0}{\overset{k}{}}}(1)^j\left({\displaystyle \genfrac{}{}{0pt}{}{k}{j}}\right){\displaystyle \frac{1}{\zeta (2j+2)}}`$
$`=`$ $`{\displaystyle \underset{j=0}{\overset{k}{}}}(1)^j\left({\displaystyle \genfrac{}{}{0pt}{}{k}{j}}\right){\displaystyle \underset{n=1}{\overset{\mathrm{}}{}}}{\displaystyle \frac{\mu (n)}{n^{2j+2}}}`$
$`=`$ $`{\displaystyle \underset{n=1}{\overset{\mathrm{}}{}}}{\displaystyle \frac{\mu (n)}{n^2}}{\displaystyle \underset{j=0}{\overset{k}{}}}(1)^j\left({\displaystyle \genfrac{}{}{0pt}{}{k}{j}}\right){\displaystyle \frac{1}{n^{2j}}}`$
$`=`$ $`{\displaystyle \underset{n=1}{\overset{\mathrm{}}{}}}{\displaystyle \frac{\mu (n)}{n^2}}\left(1{\displaystyle \frac{1}{n^2}}\right)^k.`$
Starting now with $`\mathrm{}(s)>1`$ we have

(2.8) $`{\displaystyle \frac{1}{\zeta (s)}}={\displaystyle \underset{n=1}{}}{\displaystyle \frac{\mu (n)}{n^s}}`$ $`=`$ $`{\displaystyle \underset{n=1}{\overset{\mathrm{}}{}}}{\displaystyle \frac{\mu (n)}{n^2}}\left({\displaystyle \frac{1}{n^2}}\right)^{\frac{s}{2}1}`$
$`=`$ $`{\displaystyle \underset{n=1}{\overset{\mathrm{}}{}}}{\displaystyle \frac{\mu (n)}{n^2}}\left(1\left(1{\displaystyle \frac{1}{n^2}}\right)\right)^{\frac{s}{2}1}`$
$`=`$ $`{\displaystyle \underset{n=1}{\overset{\mathrm{}}{}}}{\displaystyle \frac{\mu (n)}{n^2}}{\displaystyle \underset{k=0}{\overset{\mathrm{}}{}}}(1)^k\left({\displaystyle \genfrac{}{}{0pt}{}{\frac{s}{2}1}{k}}\right)\left(1{\displaystyle \frac{1}{n^2}}\right)^k`$
$`=`$ $`{\displaystyle \underset{n=1}{\overset{\mathrm{}}{}}}{\displaystyle \frac{\mu (n)}{n^2}}{\displaystyle \underset{k=0}{\overset{\mathrm{}}{}}}P_k\left({\displaystyle \frac{s}{2}}\right)\left(1{\displaystyle \frac{1}{n^2}}\right)^k.`$
These summations can be interchanged because calling

$$S=\underset{n=1}{\overset{\mathrm{}}{}}\underset{k=0}{\overset{\mathrm{}}{}}\frac{1}{n^2}\left|P_k\left(\frac{s}{2}\right)\right|\left(1\frac{1}{n^2}\right)^k,$$

we see from Lemma 1.1 and Lemma 2.2 that

$`S`$ $`=`$ $`{\displaystyle \underset{k=0}{\overset{\mathrm{}}{}}}\left|P_k\left({\displaystyle \frac{s}{2}}\right)\right|{\displaystyle \underset{n=1}{\overset{\mathrm{}}{}}}{\displaystyle \frac{1}{n^2}}\left(1{\displaystyle \frac{1}{n^2}}\right)^k`$
$`=`$ $`{\displaystyle \underset{k=0}{\overset{\mathrm{}}{}}}\left|P_k\left({\displaystyle \frac{s}{2}}\right)\right|q_k{\displaystyle \underset{k=1}{\overset{\mathrm{}}{}}}k^{\frac{\mathrm{}(s)}{2}\frac{1}{2}}<\mathrm{}.`$
Thus we proceed to interchange summations in (2.8), taking into account (2), to obtain unconditionally for $`\mathrm{}(s)>1`$,

(2.9) $`{\displaystyle \frac{1}{\zeta (s)}}`$ $`=`$ $`{\displaystyle \underset{k=0}{\overset{\mathrm{}}{}}}P_k\left({\displaystyle \frac{s}{2}}\right){\displaystyle \underset{n=1}{\overset{\mathrm{}}{}}}{\displaystyle \frac{\mu (n)}{n^2}}\left(1{\displaystyle \frac{1}{n^2}}\right)^k`$
$`=`$ $`{\displaystyle \underset{k=0}{\overset{\mathrm{}}{}}}c_kP_k\left({\displaystyle \frac{s}{2}}\right).`$
But Lemma 1.1 together with the hypothesis $`c_k<<k^{\frac{3}{4}+\frac{1}{2}ϵ}`$ implies that the above series converges uniformly on compacts of the half-plane $`\mathrm{}(s)>\frac{1}{2}+ϵ`$. This means that the series extends $`(\zeta (s))^1`$ analytically to the half-plane $`\mathrm{}(s)>\frac{1}{2}`$. ∎

## 3. Necessity of the condition

###### Proof of the necessity of the condition.

Assume now that the Riemann hypothesis is true. If as usual we write

$$M(x):=\underset{nx}{}\mu (n),$$

we then have

$$M(x)x^{\frac{1}{2}+2ϵ},(ϵ>0).$$

We can transform the second expression for $`c_k`$ in (2) summing it by parts to obtain

$`c_k`$ $`=`$ $`{\displaystyle _1^{\mathrm{}}}M(x){\displaystyle \frac{d}{dx}}\left({\displaystyle \frac{1}{x^2}}\left(1{\displaystyle \frac{1}{x^2}}\right)^k\right)𝑑x`$
$`=`$ $`2{\displaystyle _0^1}M\left({\displaystyle \frac{1}{x}}\right)(1x^2)^k((k+2)x^3x)𝑑x.`$
Therefore

$$|c_k|2(k+2)_0^1\left|M\left(\frac{1}{x}\right)\right|x^3(1x^2)^k𝑑x+_0^1\left|M\left(\frac{1}{x}\right)\right|x(1x^2)^k𝑑x,$$

but (on the Riemann hypothesis)

$$M\left(\frac{1}{x}\right)<<x^{\frac{1}{2}2ϵ},(x0),$$

so that

(3.1)
$$c_kk_0^1x^{\frac{5}{2}2ϵ}(1x^2)^k𝑑x+_0^1x^{\frac{1}{2}2ϵ}(1x^2)^k𝑑x.$$

On the other hand, for $`\mathrm{}(\lambda )>1`$ a classical beta integral result is

$$_0^1x^\lambda (1x^2)^k𝑑x=\mathrm{\Gamma }\left(\frac{\lambda +1}{2}\right)\frac{\mathrm{\Gamma }(k+1)}{\mathrm{\Gamma }(k+\frac{1}{2}(\lambda +3))}k^{\frac{1}{2}\frac{\lambda }{2}},$$

so that (3.1) becomes

$$c_kk^{\frac{3}{4}+ϵ}.$$

## 4. Results of some calculations

A test for the first $`c_k`$ up to $`k=1000`$ shows a very pleasant smooth curve which, on the meager strength of so limited a calculation, would seem to indicate that

$$c_kk^{\frac{3}{4}}\mathrm{log}^2k$$

tends to a finite limit in a very regular way.

Luis Báez-Duarte
Departamento de Matemáticas
Instituto Venezolano de Investigaciones Científicas
Apartado 21827, Caracas 1020-A
Venezuela