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Renaissance pottery comes under the microscope

Lustre decorations were widely used in the Renaissance period and can be seen in the famous pottery found at Deruta and Gubbio in Italy (see photo). Two years ago it was discovered that the decorations consist of a thin metal-glass layer that contains silver and copper nanoparticles. These nanoparticles are between 5 and 100 nanometres in diameter and produce brilliant iridescent reflections of ‘gold’ and red. Although much has been written on the history of these objects, there is little scientific information available on the lustre technique itself.

Bruno Brunetti of the University of Perugia and colleagues from Perugia, the universities of Padova and Venice, and the European Synchrotron Radiation Facility (ESRF) in Grenoble studied original samples of Umbrian pottery using non-destructive techniques that include Rutherford backscattering spectrometry, optical absorption spectroscopy and x-ray fluorescence. Extended x-ray absorption fine structure measurements were carried out at the GILDA beamline at the ESRF.

The researchers found that the ‘gold’ colours came from silver nanoparticles and copper ions distributed in a thin layer some 60 to 120 nanometres deep. The silver and copper were present in concentrations of about 20% and 1-3 % respectively by weight. Red colours were produced by copper nanoparticles and ions present in a concentration of about 8% within a layer some 60 to 180 nanometres deep.

The Italian team believe that copper and silver were deposited using methods that are surprisingly similar to those used to make modern metal-glass composites.

Cryptography breaks 100 km barrier

“As far as we are aware, this is the first demonstration of quantum cryptography over fibres longer than 100 km,” said Shields. “The technique could be deployed in a wide range of commercial situations in less than three years.”

Communication with quantum cryptography is inherently secure because it takes advantage of the physical properties of single photons. In the technique, each transmitted bit of a cryptographic key is encoded upon a single photon. The sender and recipient each have a key to decode the photon stream, but any attempt to hack into the link and capture the key is doomed to failure as it alters the quantum state of the intercepted photons. These changes are easily detectable, revealing the presence of the hacker. In practice, attenuation in the optical fibre and noise in the detection unit limits the distance over which quantum cryptography works.

The Toshiba team was able to improve the link distance by minimizing errors due to noise in the avalanche photodiode that detects the single photons. In the future the system could be extended further by using a GaAs/AlGaAs modulation doped field effect transistor (MODFET). This device, which is under development at Toshiba, does not rely on avalanche processes and is therefore less prone to noise than conventional devices (see related story).

The previous transmission record of 87 km was set by researchers from the Japanese company Mitsubishi Electric in November last year. They also developed a novel kind of detector, which had a low dark-count probability, to extend the link distance.

Banks and government organizations are expected to be the first users of quantum cryptography systems when they become commercially available.

Water reaches new depths

The Earth is made up of a core, the mantle and the crust. Between the upper and lower mantle – a region that is 400 to 700 km deep – there are discontinuities at depths of 410 km and 660 km (figure 1). The mineralogy of the mantle changes at these discontinuities.

As much as 1500 parts per million of water can exist in the top part of the upper mantle. This water has been released from moving oceanic plates at depths shallower than 150 km. However, it is not known how much water is transported down to lower regions.

Van der Meijde and co-workers analyzed seismic waves from the plate boundary between Eurasia and Africa (figure 2). They looked specifically for waves that were created by structures in the discontinuous regions. “We found that the region at 410 km is much wider than expected,” team leader Suzan van der Lee told PhysicsWeb. “We believe that the widening – which is 20 to 30 km thick – is caused by the interaction of water molecules with the crystal structures in this region. Water has been mentioned as being related to causing deep earthquakes, so this data helps us to improve their location and understand faulting mechanisms”.

Van der Lee added that the team plans to look at other tectonic plate boundaries in the world, to see if it can find more evidence for water at such depths.

‘Gecko tape’ sticks with polymer fibres

“Geckos can run on a dirt road and then immediately climb a glass ceiling,” said Andre Geim of the University of Manchester. “But try to use scotch tape on a pavement or a sand pitch – you would not be able to attach it to anything after that. This is why the gecko tape is called self-cleaning. Moreover, adhesive tapes use glue, which eventually runs out and so they stop sticking. Gecko tape is the first without a glue (i.e. re-attachable).”

Gecko foot hairs typically have diameters of 200 to 500 nanometres. At this size of hair the geckos can exploit both van der Waals and capillary forces to climb surfaces, depending on the nature of the surface. Each hair produces a force of about 10-7 Newtons, but because so many are present in total they can produce an adhesion of roughly 10 Newtons per square centimetre.

While gecko foot hairs are made of keratin, to make their gecko tape Geim and colleagues prepared flexible fibres of the polymer polyimide on the surface of a 5 microns thick polyimide film, using electron-beam lithography and dry etching in oxygen plasma. They made fibres 2 microns long, with a diameter of around 500 nanometres and a periodicity of 1.6 microns, covering an area of roughly 1 square centimetre.

Initially, the team used a silicon wafer as a substrate for the polyimide film, but found that the tape’s sticking power increased by almost 1000 times if they used a soft bonding substrate such as scotch tape. “You never have an ideally flat surface because there are always bumps and dust,” said Geim. “Only hairs that reach these few points [the bumps and dust] stick, leaving other hairs idle. To overcome the obstacle, we eventually learnt how to place the hairs on a flexible base, a plastic ribbon like scotch tape. This compensates for the surface unevenness.”

According to Geim, although the team did consider producing enough gecko tape to hang a team member by their palm out of the window of a tall building, they felt it would be a waste of resources – costing tens of thousands of pounds for little scientific purpose. “Therefore, we limited our demonstration to a spiderman toy,” he said. Attaching gecko tape to the hand of a 15 cm high plastic spiderman figure weighing 40 grams enabled it to stick to a glass ceiling. In fact, the tape, which had a contact area of around 0.5 square centimetre with the glass, was able to carry a load of more than 100 grams.

The team still has to make the material durable, that is, re-attachable more than a few times. “You don’t want to start climbing [up a building] and after a few floors find that your gecko gloves have worn out completely,” said Geim. He reckons that means finding a different material for the hairs, perhaps keratin itself. “This is the real problem at the moment and we do not know how to deal with it,” he added.

Hydrogen goes universal

Hydrogen is widely used in the processing of electrical materials and strongly affects their electronic and structural properties. When hydrogen is added to a material – such as a semiconductor – it can bind to defects or other impurities, which prevents them from destroying the electronic properties of the material. This ‘passivation’ works by reducing the electrical conductivity of the impurities and is crucial to the performance of many devices. In 2000 Chris Van de Walle at the Palo Alto Research Center in California showed that hydrogen could also increase the electrical conductivity of certain other types of materials.


The behaviour of hydrogen, whether as a passivating agent or as a source of conductivity depends on its ‘transition energy’. Hydrogen donates electrons below this energy, and accepts electrons above it. It was thought that the transition energy depended on the host material but now, Van de Walle and a colleague, Jörg Neugebauer from the Fritz-Haber Institute der Max Planck in Germany, have calculated that it has the same value – about –4.5 electron volts – for a wide variety of different materials.

“This ‘universal alignment’ effect is not restricted to a certain class of materials but applies to materials as different as semiconductors, insulators and even liquids,” Van de Walle told PhysicsWeb. “It will allow researchers to predict the electrical behaviour of hydrogen in these different materials rather than them having to perform elaborate calculations or experiments for every possible candidate material.”

Insects stay cool with thermoelectricity

Some wasps and hornets live in parts of the world where local temperatures can reach 60 oC or more. ‘Social’ wasps live in nests and regularly go outside to forage for food. During such activities the wasp produces heat that originates in its flight muscles and then spreads throughout the rest of its body. This should make the wasps even hotter but in experiments with oriental hornets Bergman and co-workers found that the internal body temperature of the wasps could be significantly cooler than the ambient temperature.

The Israeli workers argue that the insect must possess a heat pump, which works by using power generated from electrochemical reactions in its body. They believe that additional power is generated by the photovoltaic effect in the hornet’s shell. This means that an electrical current is produced when the shell is exposed to sunlight – in a mechanism similar to that in a semiconductor p-n junction when irradiated with visible or ultraviolet light. “This could explain how hornets remain active even on very hot summer days,” Bergman told PhysicsWeb.

The researchers also took transmission and scanning electron micrographs of the shell. They observed a microstucture that was very similar to that of a practical thermoelectric heat pump – but on a different length scale (see figure).

Mars Express takes off

Mars Express is a European Space Agency mission and contains an orbiter and a lander. The orbiter carries seven instruments, including a high-resolution stereo-imaging camera as well as ultraviolet and infrared atmospheric spectrometers. The orbiter will complement the British-built lander – called Beagle 2 – that will land in the Isidis Planitia Basin, 10 degrees north of the Martian equator. Beagle 2, which is the brainchild of Colin Pillinger of the Open University, weighs less than 30kg and contains six different instruments. These include a set of ovens for heating rock and soil samples, environmental sensors, and instruments mounted on the end of a robotic arm – such as stereo cameras and spectrometers.

NASA will also launch its own mission this month called Mars Exploration, which consists of two rovers that will land on different sites on the red planet. Rover-A, scheduled for launch atop a Delta II rocket on 5 June, will land at Gusev Crater in early January next year. This crater, 15 degrees south of the equator, is thought to have once been a lake. Rover-B, meanwhile, will launch on 25 June and head for Meridiani Planum, which is 2 degrees south of the equator. Meridiani has deposits of grey hematite, an iron oxide usually produced where there is liquid water.

The two missions follow on from NASA’s Mars Odyssey orbiter and both have very complementary objectives. “The payloads on Beagle 2 and the rovers are very different to each other,” said Steve Squyres, an astronomer at Cornell University in New York and principal investigator of the NASA mission. “You’re going to have this really rich array of sensors and landers all exploring the planet at once.”

Both missions take advantage of an alignment of the Earth and Mars that minimizes the amount of fuel needed to make the trip. Such advantageous alignments occur for just a few weeks every 26 months.

In industry, seeing is believing

The old adage “seeing is believing” is as relevant today as it was 2000 years ago for the famous doubting Thomas. What we mean by seeing, however, has changed. Science would not have come as far as it has if researchers had relied solely on their eyes to study the world. But we have become used to extending our vision with all sorts of techniques, from gamma-ray astronomy to ultrasound. The resulting images or, even better, movies can enhance understanding, inspire new theories and focus discussion. And in industry, this progress can be directed to optimize a wide range of processes, from the design of jet engines to the growth of carrots.

One of the best ways to capture these images is to use tomography, which allows us to see the inside of an object without inserting probes or sensors. Tomography is an imaging technique that uses a physical phenomena, such as X-rays or a magnetic field, to produce a picture of a slice through an object. It is best known in medical applications, where the spectacular details provided by computer-assisted tomography (CAT) scanners have become valuable and widespread diagnostic tools. The aim of industrial-process tomography is to transfer similar technology to the pipes and vessels in processing plants.

Inside industry

Industrial-process tomography began in the 1930s when much attention was paid to resistivity sounding. This technique involved passing currents through the ground to determine the location of mineral deposits and geological structures, and geophysical exploration remains an important application of tomography today. But it was not until about 50 years later that people began to investigate low-cost methods to image the flows in pipes and vessels found in manufacturing. This work was pioneered by researchers at the University of Manchester Institute of Science and Technology (UMIST) in the UK and the Morgantown Energy Technology Center in the US.

The challenge of tomography is to construct an image of the contents of a target, such as a pipe, using only measurements taken from the outside. From an image of the mixture of oil, gas and water flowing in a pipeline from the North Sea, for example, we can determine how much of each component is present. Metering such multiphase flows can be incredibly difficult because each element might be travelling with a different velocity. The flows can also be turbulent, which means there is little hope of solving the necessary equations.

Tomography offers opportunities in both metering such flows and understanding their dominant physics. There is financial incentive too – global oil production is about 75 million barrels per day, which amounts to approximately $2.25bn. Just keeping track of how much is produced is a difficult task. Furthermore, in some oil wells the water that is also extracted through pipelines must be treated before it can be disposed of. Images of the proportional flow rates inside these pipes can therefore provide a crucial indicator of potential environmental damage.

Indeed, at any stage from the oil well to the consumption of petroleum spirit in a car, an increase in efficiency of just 1% would reduce costs enormously, while easing the demand on oil reserves. Hugh McCann and co-workers at UMIST are currently using tomography to map the key chemical species inside an internal combustion engine, with the aims of reducing emissions and developing more efficient engines.

But it is not just the oil industry where process tomography has applications. A uniform and consistent product is often essential for commercial success, and images from the inside of mixing vessels can determine when the contents are of even quality. On food production lines, for example, defects in fruit can be automatically detected. Tomography can also be used to improve product safety by, for example, allowing researchers to inspect jet engines or nuclear reactors for internal flaws and cracks that are not evident from their surfaces. Potentially harmful leaks from waste pipes can also be located, enabling repairs to be carried out quickly.

These applications of tomography are all well and good, but how do we actually go about achieving them? Medical imaging is very well developed, so it might appear that we can just take medical tomographs and position them round industrial vessels. But there are many barriers that prevent this simple transfer of technology. The first is skin. Humans are covered by a skin that is translucent, whereas the skin of an industrial vessel is often stainless steel or thick plastic. It is the basic physical properties of these materials that restrict our ability to take a peek inside, and which determine the imaging methods that we can use.

Ironically, it is common practice to use high-energy radiation such as X-rays and gamma rays to probe inside a human patient, where it is accepted that the gain in diagnostic information outweighs the minimal health risk. In a factory environment, however, there are strict regulations that control the use of high-energy radiation, and this adds considerable cost to the installation of X-ray or gamma-ray instruments. Although high-energy instruments are used – such as X-ray photography for imaging the concentrations of seasoning in potato-crisp factories – they are not common.

Seeing with sound

Ultrasound tomography is also well known in medical applications, particularly the wonderful pictures of babies inside the womb. Ultrasound is very safe, and the high-quality images that it produces are possible because body tissue – being largely composed of water – gives just the right amount of reflection and transmission at ultrasound frequencies. Many industrial processes also involve material that is suspended in water. In processing minerals from a mine, for example, crushed ore is suspended in water, and many food products, such as yoghurt, are ultrasound-friendly colloids or dispersions. Why, then, is ultrasound not used more?

The answer is simple. There is no need to image processes that contain a homogeneous liquid because these can be dealt with using traditional, non-tomographic instrumentation. The situation is much more interesting when there is a mixture of solids that are suspended in a liquid (a slurry). Slurries are a very convenient method of transport and form the basis of many mineral-processing plants.

Malcolm Povey in the department of food science at the University of Leeds in the UK has done much to promote the use of ultrasound in food processing, and has developed techniques to study the formation of creams and the stability of colloids. These techniques have also been exploited commercially and involve measuring the horizontal velocity and attenuation of ultrasound waves in a suspension as a function of height.

Ultrasound reflections are also used by the oil industry to image gas bubbles in a liquid. Like much of the research into industrial-process tomography, the details are commercially sensitive but the method basically involves placing transducers round a pipe. One transducer is activated to generate a signal, and the time it takes the signal to be reflected off all the other transducers is recorded. This then activates another transducer and the process is repeated, which enables the length of the signal’s flight path to be calculated. By combining all the signals, the location of air-water interfaces can be determined.

This technique works well when the number of bubbles, or interfaces, is small. But in practice there are always a great number of them, including bubbles that are too small to be seen optically. These multiple interfaces produce a much larger scattering radius for ultrasound and cause havoc with reflected-ultrasound tomography. Similarly, imaging of dense slurries and multiphase flows is not yet within practical reach because of the many interfaces of these systems. Capacitative vision

By far the best way to image industrial processes is to exploit our understanding of electromagnetism. Several electromagnetic approaches exist that are faster, cheaper and smaller than their X-ray and gamma-ray counterparts. Moreover, they do not involve ionizing radiation. To understand how these techniques work, suppose that solid particles, such as custard powder, grain or coal dust, are blown along a plastic pipe. An electrostatic field can be used to interrogate the contents of the pipe because it will be perturbed by the dielectric properties of the particles (figure 1). This is the basis for electrical-capacitance tomography, a technique brought to the fore in the mid-1980s by Maurice Beck at UMIST and Andrzej Plaskowski of Micromath in Poland.

In electrical-capacitance tomography a pipe is surrounded by a number of plate electrodes, which are contained inside an earthed shield so that only the contents of the pipe influence the measurements. The relative permittivity of the gas – which is directly related to the capacitance between the plates – can be taken as 1, while that of the solid may be 2 or more. The capacitance measured between every pair of plate electrodes in a pipe that is initially filled with air will change when a solid is introduced to the pipe. In fact, we can use Maxwell’s equations to calculate the capacitances for known configurations of air and solid, and, with the right mathematical techniques, it is possible to work in reverse. In other words, once we know the capacitances, we can work out where the solid is within the pipe.

This is known as an inverse problem, and is the central and most challenging step in tomography (see figure 2). The difficulty can be summarized as follows. Add or subtract some solid from the pipe and the capacitances change comparatively little. But a small error in a capacitance measurement could correspond to a large change in the image of the solid in the cross section. Furthermore, two small pieces of solid that are close together might be indistinguishable from a single larger piece, and resolving this problem requires taking measurements in quick succession over a long period of time.

Tomography itself can only get us so far, and to obtain better pictures we need to apply a bit of intelligence and think about what we know about the image before we consider the measurements. For example, there might only be two possible values of the permittivity, corresponding to air and solid. Or perhaps there is just one interface in the pipe, with solid at the bottom and air above. Considerations such as these allow modelling skills to be utilized to the full, which is usually tackled by multidisciplinary teams that have expertise in process engineering, physics and mathematical modelling. The more a priori knowledge we can include, the better the image we can derive.

The proof of the pudding is, of course, in the eating, and electrical-capacitance tomography has been put to work in some important process operations. High imaging rates have been used to image gas bubbles in a liquid, while Henri Tapp and co-workers at the Institute of Food Research in the UK were able to distinguish the distribution of water in the soil surrounding a carrot (figure 3). Water has a very strong permittivity contrast to soil, which makes electrical-capacitance tomography an ideal detection system. As more salts are dissolved in the water, however, its conductivity increases and currents begin to flow. These currents make it more difficult to use an electrostatic field to interrogate the system.

Impedance tomography

The physical properties of industrial processes vary considerably, and there are many situations where components conduct electrical current and cannot therefore be imaged using electrical-capacitance methods. But all is not lost. In these cases it is possible to probe the interior of a vessel by injecting currents and then measuring the voltages at its walls with electrodes. This technique is called electrical-impedance tomography, which is basically the inverse problem of determining the conductivity or permittivity of an interior from exterior measurements.

Electrical-impedance tomography is used by geophysicists to map mineral deposits and probe oil wells, and by medical physicists to image the heart and lungs. Researchers at Sheffield University in the UK and Rensslaer Polytechnic Institute in the US have been particularly active in this area since the early 1980s, and the technique has benefited from collaborations between groups working in different fields – particularly in medical and process tomography. Marko Vauhkonen and Jari Kaipio at the University of Kuopio in Finland lead a team that has transferred its skills in medical imaging to industrial applications, sometimes working with the current author.

Several studies using electrical-impedance tomography have been completed on mixing vessels – common pieces of equipment in process industries that consume a lot of power. By imaging a blob of saline as it is stirred and dispersed within a mixing tank, the rotation and spread of the saline region can be clearly seen (figure 4). This allows the performance of the mixer and the progress of the mixing to be judged.

Newer on the industrial scene is magnetic-induction tomography, which has the advantage over electrical capacitance and impedance tomography in that it does not require electrodes. Instead a magnetic field is induced within an object, where it is perturbed by small “eddy” currents. The magnetic flux is measured by external coils, from which the conductivity inside the object can be calculated. Tony Peyton at Lancaster University in the UK has developed many interesting ideas based on magnetic induction, including monitoring the flow and crystallization of molten steel during continuous casting. Along with Tapp, he is also developing a scanner for measuring body composition that combines induction tomography with an optical imaging technique called photonic scanning. This is an impressive example of sensor fusion, and the technique could be used to measure the fat composition of meat products at all stages in production, from livestock to pork pies.

A matter of cost

Industrial-process tomographs seldom produce the fine detail that is seen in medical images. While such detail would be welcomed with great enthusiasm for some aspects of processing, such as the nano-production of particles designed for drug delivery, even coarse images are a remarkable improvement on the blunt-instrument approach of bulk measurements. A low-resolution image of the distribution of contents within a vessel can still be very informative, but more importantly the image is not the final product. Monitoring and controlling a process should be undertaken automatically, which can be achieved by linking tomographic images to process-control software. High-resolution images would provide so much data that they would be difficult to handle. Ideally, tomography would provide control variables that are derived either from the image or from the signals used to form an image. In other words, the image stage could be short-circuited.

But there is a much more important reason why industrial images have lower resolution than those in medicine – cost. Tell a plant manager that they will be able to reduce their operating costs while increasing productivity and consistency and they will be interested. But mention what the necessary tomographic instrument and control system will cost and that interest will disappear. For process tomography to be widely accepted by industry it is essential that installation and operating costs are minimal. And they can be. Whereas medical scanners are known to be expensive but essential for patients’ needs, it is not so well known that industrial tomography systems are designed to be low cost.

An example of a low-cost industrial tomograph might be an electrical-impedance system that consists of a handful of electrodes. Once these were fitted, an informative image could be constructed from about 100 measurements. This contrasts with medical scanners that might use 100 x 106 X-ray intensities to form a detailed image of the human body. The key question is, can we learn enough through just a few measurements to justify low-resolution tomography? There are those of us who say yes, and we are developing and demonstrating instruments and software. But like the basic concept of tomography, further progress is very much a matter of “watch this space”.

New mass for the electron, in theory

The atomic energy scale is related to our everyday world through the equivalence of the electron’s mass and energy, E = mc2. However, while the speed of light, c, is a fixed constant by definition – it has a value of exactly 299 792 458 m s­1 – the mass of the electron is not. The mass standard in the atomic world is set by one atom of the element carbon, which is defined to be 12 atomic mass units (about 2 x 10­26 kg). All other masses in the micro-world are related to this mass standard by sophisticated experiments.

In the June issue of Physics World, Wolfgang Quint, of the GSI laboratory in Dramstdt describes how theorists are leading experimentalists in a friendly race to pin down the mass of the electron.

Ripples in a superconducting tidal pool

Waves in a pool can be excited, and their properties will depend on the depth of the water. Similarly in a metal, quasiparticles behave like waves that have a material-dependent dispersion relation between their energy and their wavevector, which specifies their direction and wavelength. This simple analogy also hints at an indirect method of measuring the dispersion relation of a metal, and hence the myriad of properties that depend on it.

Read this article in full in the June issue of Physics World. The article is by Eric Hudson in the Department of Physics at Massachusetts Institute of Technology.

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