Smart Materials: Materials whose one or more physical properties can be significantly changed in a controlled fashion by changing the

external conditions like: stress, temperature, moisture, pH, electric or magnetic field etc. Piezoelectric Materials: When a piezoelectric material is deformed, it gives off a small but measurable electrical discharge. Alternately, when an electrical current is passed through a piezoelectric material it experiences a significant increase in size (up to a 4% change in volume). Example: Quartz, LeadTitanate (PbTiO3), SodiumNiobate, PolyVinyliDeneFluoride (PVDF): As the impact sensor in the airbag sensors in a car. The material senses the force of an impact on the car and sends an electric charge to activate the airbag. Suitably designed structures made from these materials can therefore be made that bend, expand or contract when a voltage is applied or vice versa. Piezoelectric materials are most widely used as sensors in different environments. They are often used: 1.to measure fluid compositions 2.fluid density 3.fluid viscosity 4.the force of an impact. Shape Memory Alloys: Shape memory alloys (SMA's) are metals, which exhibit two very unique properties: pseudo-elasticity, and the shape memory effect. The most effective and widely used alloys include NiTi (Nickel - Titanium), CuZnAl, and CuAlNi. Shape Memory Effect: These types of materials are those that can revert from the current shape to a previously held shape, usually due to the action of heat. A shape memory alloy possesses different properties below and above the temperature at which it is activated. Below this temperature, the alloy is easily deformed. At the activation temperature, the alloy exerts a force to return to a previously adopted shape and becomes much stiffer. The temperature of activation can be chosen by altering the ratio of nickel to titanium in the alloy. A solid state phase change is a change in which the molecular rearrangement occurrs but the substance remains a solid. The two phases, which occur in shape memory alloys, are Martensite, and Austenite. Martensite, is the relatively soft and easily deformed phase of shape memory alloys, which exists at lower temperatures. The molecular structure in this phase is twinned . Upon deformation this phase takes on the second (deformed) form Austenite, the stronger phase of shape memory alloys, occurs at higher temperatures. The shape of the Austenite structure is cubic. The un-deformed Martensite phase is the same size and shape as the cubic Austenite phase on a macroscopic scale, so that no change in size or shape is visible in shape memory alloys until the Martensite is deformed. The Shape memory effect is currently being implemented in:

1.Coffee pots / Smart showers 2.The space shuttle 3.Thermostats (safety shut off valves for fuel lines in the event of fire and air conditioning systems.) 4.Vascular Stents / Bone plates 5.Hydraulic Fittings (for Airplanes) 6.Encapsulated Bi-Gels absorb liquid at differing rates according to temperature which causes them to bend. This offers possibilities for their use as actuators in a variable insulation system. 7.Robotic Hand 8.Miniaturization of equipment and systems, decrease the number of parts required. Robotic Muscles: The bias spring shown in the upper portion of the finger would hold the finger straight, stretching the SMA wire, then the SMA wire on the bottom portion of the finger can be heated which will cause it to shorten bending the joint downwards (as in Figure 1). The heating takes place by running an electric current through the wire; the timing and magnitude of this current can be controlled through a computer interface used to manipulate the joint. Pseudo-elasticity occurs in shape memory alloys when the alloy is completely composed of Austenite. The load on the shape memory alloy is increased until the Austenite becomes transformed into Martensite simply due to the loading. The loading is absorbed by the softer Martensite, but as soon as the loading is decreased the Martensite begins to transform back to Austenite the wire springs back to its original shape. Some examples of applications in which pseudo-elasticity is used are: Eyeglass Frames Medical Tools Cellular Phone Antennae Orthodontic Arches Some of the main advantages of shape memory alloys include: Bio-compatibility Diverse Fields of Application Good Mechanical Properties (strong, corrosion resistant) There are still some difficulties with shape memory alloys that must be overcome before they can live up to their full potential. These alloys are still relatively expensive to manufacture and machine compared to other materials such as steel and aluminum. Most SMA's have poor fatigue properties; this means that while under the same loading conditions (i.e. twisting, bending, compressing) a steel component may survive for more than one hundred times more cycles than an SMA element.

Optically-Healing plastic (Nature, April 2011): Localized repair The trick to the optically-healing ability lies in the plastic's structure. Normal plastics consist of long, chain-like polymers bound together by strong covalent bonds. This plastic is made up of shorter molecules with interspersed with zinc or lanthanum ions. In solid form, these molecules are not covalently bonded, 'metal coordinate' bonds, forming long chains linked by the metal ions. When ultraviolet light shines on the plastic, it is absorbed by the metal ions and converted to heat enough to melt the local area and repair a fracture. Electro-rheostatic (ER) and magneto-rheostatic (MR) materials are fluids, which can experience a dramatic change in their viscosity. These fluids can change from a thick fluid (similar to motor oil) to nearly a solid substance within the span of a millisecond when exposed to a magnetic or electric field; the effect can be completely reversed just as quickly when the field is removed. MR fluids experience a viscosity change when exposed to a magnetic field, while ER fluids experience similar changes in an electric field. The composition of each type of smart fluid varies widely. The most common form of MR fluid consists of tiny iron particles suspended in oil, while ER fluids can be as simple as milk chocolate or cornstarch and oil. MR fluids are being developed for use in car shocks, damping washing machine vibration, prosthetic limbs, exercise equipment, and surface polishing of machine parts. ER fluids have mainly been developed for use in clutches and valves, as well as engine mounts designed to reduce noise and vibration in vehicles. Electrorheological fluids: are made by suspending particles in a liquid whose dielectric constant or conductivity is mismatched in order to create dipolar particle interactions in the presence of an ac or a dc electric field. ER fluids rapidly solidify, or at least increase their viscosity dramatically, in response to an electric field, due to the formation of particle chains that bridge the electrodes. The millisecond response of ER fluids has piqued the interest of engineers, who are now trying to incorporate these fluids into practical fast electromechanical actuators, such as fiber spinning clutches and active shock absorbers. The response is triggered due to the presence of ionisable functional groups (like -COOH, -NH2) which get ionized and acquire a charge (+/-) in a certain pH. The polymer chains now have many similarly charged groups which causes repulsion and hence the material expands in dimensions. The opposite happens when pH changes and the functional groups lose their charge hence the repulsion is gone and the material collapses back. PH-sensitive polymers: pH sensitive/responsive polymers are materials which will respond to the changes in the pH of the surrounding medium by varying their volume. Such materials swell or collapse depending on the pH of their environment. This behaviour is exhibited due to the presence of certain functional groups in the polymer chain. There are two kinds of ph sensitive materials: which have acidic group (-COOH, -SO3H) and swell in basic pH. e.g.: Polyacrylic acid

which have basic groups (-NH2) and swell in acidic pH. e.g.: Chitosan The mechanism of response is same for both, just the stimuli vary. These materials are being extensively used in controlled drug delivery systems and biomimetics (biology inspired systems). 1.pH varies along the gastrointestinal tract (GIT) between stomach and colon. This condition makes pH-sensitive polymers ideal for colon specific drug delivery. 2.Delivering insulin is different from delivering other drugs, since insulin has to be delivered in an exact amount at the exact time of need. In a glucose-rich environment, such as the bloodstream after a meal, the pH becomes 5.8. The photomechanical effect is the change in the shape of a material when it is exposed to light. The mechanical properties (such as length, shape, and stiffness) of a photomechanical material change when exposed to light. The photomechanical effect was first documented by Alexander Graham Bell in 1880. More recently, Uchino demonstrated that a photostrictive material could be used as legs in the construction of a miniature optically-powered walker. Mechanisms: 1.Photothermal Heating: This is the most common photomechanical mechanism. When energy is absorbed from a beam of light, it is converted into heat, which results in a temperature increase. For a given temperature, the change in the size of the material is proportional to the coefficient of thermal expansion. 2.Molecular Reorientation: A dye-doped polymer is made of a transparent host polymer that is impregnated with dye molecules that give the material color. These dye molecules can absorb light to generate heat, or, the molecules can change shape. The change in molecular shape stresses the polymer, which can cause the bulk material to change its shape. Possible applications: noise cancellation wallpaper reconfigurable air craft wings ultra-stable platforms for precision manufacturing or characterization reconfigurable optical filters Photomechanical materials are far from being a technology. Present research seeks to set the scientific foundations for making a novel new material that has the ability to morph in response to stress or light. Photomechanical effects are the missing ingredient for making all-optical technologies possible. Since light allows for the design of novel new architectures, and does not suffer some of the drawbacks associated with electronics Dielectric elastomers (DEs) are smart material systems which produce large strains (up to 300%) and belong to the group of electroactive polymers (EAP). Electroactive Polymers are polymers that exhibits a change in size or shape when stimulated by an electric field. Types of EAPs: 1.Dielectric EAP: actuation is caused by electrostatic forces between two electrodes which squeeze the polymer. 2.Ferroelectric Polymers 3.Electrostrictive Graft Ploymers:

4.Liquid Crystalline Polymers: Those LC polymers in which there is direct coupling of the liquid crystalline order with the conformation of the polymer. 5.Ionic EAP: the actuation is caused by the displacement of ions inside the polymer. 6.Electro-Rheological Fluids 7.Ionic-Plymer-metal Composite: Ionic polymer-metal composites consist of a thin ionomeric membrane with noble metal electrodes plated on its surface. It also has cations to balance the charge of the anions fixed to the polymer backbone. Self-healing materials are a class of smart materials that have the structurally incorporated ability to repair damage caused by mechanical usage over time. From a macromolecular perspective, stress induced damage at the molecular level leads to larger scale damage called microcracks. A microcrack is formed where neighboring polymer chains have been damaged in close proximity, ultimately leading to the weakening of the fiber as a whole. From a molecular perspective, traditional polymers yield to mechanical stress through cleavage of sigma bonds. The factors that determine how a polymer will yield include: type of stress, chemical properties inherent to the polymer, level and type of solvation, and temperature. Reversible healing polymers: For a reversible healing polymer, if the material is damaged by means such as heating and reverted to its constituents, it can be repaired or "healed" to its polymer form by applying the original condition used to polymerize it. This means we need to introduce energy into the system for repolymerization to take place. Autonomic polymer healing: Tiny capillaries or capsules of the monomer are introduced within the material. When crack reaches them they break and heal the crack. Understanding of the properties of materials results in technological breakthroughs. Till now we have managed to produce materials with controlled mechanical and electrical properties. Now the goal is to control the optical properties of the materials. Or make materials with tailored optical properties. Ex: Materials which respond to the light waves by Reflecting Confining within the specified volume Allowing the propagation only in certain directions for a set of frequencies. Fiber-optic cables only guide the light and already they are changing the telecommunication industry. So the possibilities are immense. We are looking for materials which will afford us a complete control over the light propagation. Scientists have discovered that the iridescence of various colorful creatures, from beetles to birds to butterflies, is often due to microscopic structures known as photonic crystals. Unlike pigments, which absorb or reflect certain frequencies of light as a result of their chemical composition, the way that photonic crystals reflect light is a function of their physical structure. That is, a material containing a periodic array of holes or bumps of a certain size may reflect blue light, for example, and absorb other colors even though the crystal material itself is entirely colorless. Because a crystal array looks slightly different from different angles (unlike pigments, which are the same from any angle), photonic crystals can lead to shifting shades of iridescent color

Photonic crystals are periodic optical nanostructures that are affect the motion of photons. Photonic crystals occur in nature and in various forms have been studied scientifically for the last 100 years. Crystal presents a periodic potential to an electron propagating through it. The constituents of the crystal (atoms) and the geometry (structure) of the lattice dictates the conduction properties of the crystal. The optical analogue require replacing: Atoms/molecules by macroscopic media with differing dielectric constants Periodic potential by periodic dielectric function/periodic index of refraction. If: the dielectric constants of the, materials in the crystal are sufficiently different the absorption of the light by the materials is minimal Then: refraction and reflections of light from all of the various interfaces will result in photons (behaving as waves) propagate through this structure (or not) depending on their wavelength. Wavelengths of light that are allowed to travel are known as modes, and groups of allowed modes form bands. Disallowed bands of wavelengths are called photonic band gaps. Since the basic physical phenomenon is based on diffraction, the periodicity of the photonic crystal structure has to be of the same length-scale as half the wavelength of the EM waves. E.g. for photonic crystals operating in the visible part of the spectrum the repeating regions of high and low dielectric constants have to be of 300-150 nm dimension. This makes the fabrication of optical photonic crystals cumbersome and complex. Photonic crystals: periodic dielectric structures. interact resonantly with radiation with wavelengths comparable to the periodicity length of the dielectric lattice. dispersion relation strongly depends on frequency and propagation direction distinct optical phenomena such as: Inhibition of spontaneous emission High-reflecting omni-directional mirrors Low-loss-waveguiding Guide and confine light without losses Novel environment for quantum mechanical light-matter interaction A rich variety of micro- and nano-photonics devices Photonic Crystals are artificial periodic structures that have the ability of inhibiting the linear propagation of light in all directions. One-dimensional photonic crystals In a one-dimensional photonic crystal, layers of different dielectric constant may be deposited or adhered together to form a band gap in a single direction. A Bragg grating is an example of this type of photonic crystal. Two-dimensional photonic crystals

In two dimensions, holes may be drilled in a substrate that is transparent to the wavelength of radiation that the bandgap is designed to block. Triangular and square latices of holes have been successfully employed. The Holey fiber or photonic crystal fiber can be made by taking cylindrical rods of glass in hexagonal lattice, and then heating and stretching them, the triangle-like airgaps between the glass rods become the holes that confine the modes. Photonic Crystals: Opportunities Passive devices dielectric mirrors for antennas micro-resonators and waveguides Active devices low-threshold nonlinear devices microlasers and amplifiers efficient thermal sources of light Integrated optics controlled miniaturisation pulse sculpturing A large photonic band gap for wavelengths from 8 to 20 microns proved ideally suited for suppressing broadband blackbody radiation in the infrared and has the potential to redirect thermal excitation energy into the visible spectrum This would raise the efficiency of an incandescent electric bulb from 5 percent to greater than 60 percent. It has been shown that the filaments fabricated of tungsten lattices emit remarkably more energy than solid tungsten filaments in certain bands of near-infrared wavelengths when heated. Because near-infrared is the wavelength region closest to visible light, the day may not be too distant when tungsten lattice emissions realized at visible wavelengths provide a foundation for more efficient lightingthe first significant change in Edison's light bulb since its invention. S. Y. Lin et al., Appl. Phys. Lett. (2003) Solar Cell Applications Funneling of thermal radiation of larger wavelength (orange area) to thermal radiation of shorter wavelength (grey area). Spectral and angular control over the thermal radiation.

All-optical transistor: This is analogous to an electronic transistor, where the electric currents are replaced by laser pulses. Small optically induced changes in the index of refraction of the nonlinear medium can determine important changes in the output signal. Photonic crystal all-optical transistor Probe Laser

Operating Parameters

Holding power: 10-100 nW Switching power: 50-500 pW Switching time: < 1 ps The experimental techniques used to investigate the structure of solids are of two types: 1.Diffraction based 2.Spectroscopic Diffraction based techniques: diffraction occurs when ever a wave is incident on an array of regularly spaced scatterers and the wavelength is of the same order as the spacing of the scatterers. X-rays, electrons, neutrons with wavelengths similar to the interatomic spacing of a crystal will be diffracted and provide information about structure, size, interplanner spacing, long- and short- range order and the residual lattice strain. The greatest amount of information is obtained for the crystals. Spectroscopic methods probe the electronic, vibrational, rotational and nuclear states of the matter. The spectroscopic techniques are of two types: 1.The material absorbs the electromagnetic radiation of energy equivalent to the difference in energy between particular states of matter: a) UV-Vis: transitions between adjacent electronic states b) IRAS: Vibrational transitions c) NMR: Radio waves are absorbed for nuclear transitions between states on application of Magnetic Field. 2. Scattering of the electromagnetic radiations. a) Raman Spectroscopy Principle: Generally, light is scattered elastically by an atom or molecule, i.e., there is no loss of energy due to scattering. However, some fraction of light is scattered inelastically where energy is lost or even gained upon scattering off an atom or molecule. This type of scattering is called Raman scattering. The energy lost or gained is related to the vibration of an atom or groups of atoms in the sample. We can probe the structure of gases, liquids, and solids, amorphous as well as crystalline. For the solids the transitions observed are vibrartional. Advantages: 1.Applicable to all types of materials 2.Can be used to analyze, very small quantities of material. 3.Temp and pressure can be varied. 4.Embedded materials for optically transparent matrix. Information from Raman spectroscopy of solids: 1.Strength of interatomic and intermolecular bonds 2.Mechanical strain present in a solid. 3.Composition of multicomponent matter. 4.Degree of crystallanity of solid. 5.Effects of temp and pressure on phase transformations. Semi classical approach: Raman scattering is the result of the incident radiation inducing a transition (vibrational) in the scattering entity Probability for the transition, a2mn. amn ~ m*pndV i: wave function of the ith state p = ae pi = ijj aij: polarizability matrix component ej: electric field component

For Rayleigh Scattering m=n is the vibrational ground state For Stokes Raman Scattering (winc+ wv): n is the vibrational ground state m: first vibrational excited state For anti-Stokes Raman Scattering (winc- wv): n is the first vibrational excited state m is the vibrational ground state The population of energy levels is governed by M-B distribution, so the population of the ground state is always greater than the population of the first vibrational excited state. Hence the intensity of the Stokes shifted Raman intensity is always greater than the intensity of anti-Stokes shifted Raman scattering. Raman spectrum plots the intensity of the inelsatically scattered light as a function of the shift in the wave number of the radiation (wave number = 1/wavelength). Experiment: 1. The sample is irradiated with monochromatic radiation. The light used is a single wavelength laser operating in the visible, near ultra violet, or infrared region. 2. For transparent sample most of the light is transmitted. 3. A small fraction is elastically scattered (Rayleigh). 4. A very small fraction is inelastically scattered (Raman). 5. Non-Raman scattering light is filtered out while the Raman-scattered light is collected onto a CCD area detector and dispersed. And results are presented as Raman Spectra. The information collected by the detector shows intensities and frequencies of light demonstrating Raman scattering Peak in the spectrum corresponds to one or more vibrational modes of the solid. Total number of peaks in the Raman spectrum is related to the number of symmetry allowed, Raman active modes. Some modes will be degenerate or have low intensity. Hence, no. of peaks < no. of Raman active modes. Raman activity is a function of point group symmetry of a molecule and the space group symmetry of a crystalline solid. Components: 1.Source of Radiation. 2.Optics for illuminating the sample and collecting the Raman Scattered Radiation. 3.Spectrometer for dispersing the Raman scattered radiation 4.Device for measuring the intensity of the Raman scattered light. 5.Components to control the polarization of the incident radiation and monitor the polarization of the Raman scattered radiation. Sources of Radiation: We require monochromatic source of light. 1.The strongest excitation line in the visible region (blue, 435.83 nm) of mercury arc. The power density of these sources is low so a complicated collection optics and large samples are required. 2.Lasers. In general the laser radiation is unpolarized. But the light which comes from the gas lasers capped with Brewster window is linearly polarized. Continuous wave gas lasers (argon, krypton and helium neon), provide adequately powered, monochromatic, linearly polarized (Brewster window), collimated, small diameter beams. Raman spectra for all states of matter and for a wide range of samples sizes is possible using simple system of collection optics. Data Analysis: The Raman Scattering results from the incident radiation inducing transition in electronic, vibrational and rotational states of the medium. For a solid the peaks excited by visible exciting radiation is associated with the vibrational modes of the solid. 1)Internal modes: arising from ions and molecules that make up the solid 2)External modes: arising from collective modes of the crystal Requirements:

1.The Raman transition is symmetry allowed (amn, non zero) 2.There should be a measurable Raman Intensity (amn, large enough value) The magnitude of the raman shift in wave numbers of each peak wrt the exciting laser line can be related to the energy of the vibration. If we know the mass of the atoms involved (SHO assumption), we can find the force constant of the bond associated between the atoms participating in the vibration. Changing the atom w/o changing the symmetry of the molecule will result in shift in peaks corresponding to change in the strength of the bond and the mass of the atom. This fact is responsible for providing information about the bond strength and alloying effects in solids using Raman Spectroscopy. The greatest peak broadening factor is micro crystallinity. The breadth of the peak increases dramatically as the size of the crystal decreases below 10nm. Elastic straining of the lattice will alter the spring constant of a chemical bond and hence shift the frequency of the vibrational mode associated with strained bond. The direction and magnitude of the shift in peak location will depend on the sign (tensile or conpressive) and magnitude, respectively, of the strain. Three main problems in Raman Spectroscopy are: 1.Weak intensity of the Raman scattering 2.Sample heating (due to absorption of energy during illumination with the laser beam of high power density) 3.Fluorescence (This spectrum is generally continuous and its intensity is higher than that of the Raman Scattered Radiation) Way out: 1.Switching to exciting radiation whose energy is too low to be absorbed. But since Raman scattering is light scattering process, so the intensity varies as l-4. So using longer wavelengths will reduce the intensity. Sensitivity of most PMT tubes is less for red and NIR radiations. 2. Fourier Transform Raman Spectroscopy (FTRS): We use an interferometer in place of a monochromator. The Raman scattered radiation is fed directly into a Michelson Interferrometer and then into the detector. The Raman Spectrum is obtained by taking the cosine-Fourier Transform of the intensity of light which reaches the detector. This varies in magnitude as the path difference between the moving mirror and the fixed mirror within the interferometer changes. No dispersion results in higher intensity.

Comparison between RS and IRAS Both Raman and IRAS provide information about the vibrational spectra of solids. Hence the two techniques are complimentary. Since Raman Spectroscopy uses optical radiations, it is a highly flexible technique and can probe the structures of materials wherever we can get laser light on to the sample and collect the scattered light. These include: high pressure chambers, high-temp furnaces, aqueous solutions etc. Raman scattering cross-section is much smaller than the IR absorption cross-section so the incident radiation needs to be more intense and detectors need to be more sensitive. In general some vibrational modes of a material are IR active and others are Raman active. (Rule of thumb: symmetric=Raman active, asymmetric=IR active) One of the major advantages of using Raman spectroscopy is its ability to provide detailed information of amorphous material. Raman spectrum is related to complete density of vibrational states for an amorphous materials. All metals are Raman inactive, so Raman spectroscopy cannot be used for their structural analysis.