Future robotic systems will be pervasive technologies operating autonomously in unknown spaces that are shared with humans. Such complex interactions make it compulsory for them to be lightweight, soft, and efficient in a way to guarantee safety, robustness and long-term operation. This set of qualities can be achieved using soft multipurpose systems that combine, integrate and commute between conventional electromechanical and fluidic drives, as well as harvest energy during inactive actuation phases for increased energy efficiency. Recent research work has shown that dielectric fluids with specific properties, can be combined with stretchable or flexible shell structures made of polymeric dielectric/electrode composite films, to implement a novel type of soft electrically-driven fluidic transducers with self-healing and self-sensing capabilities that take the name of Liquid-based Electro-Active Polymer transducers (LEAPs). These devices are similar to dielectric elastomer transducers in regards to their electrostatic working principle, but they can potentially produce larger displacements due to their lower mechanical stiffness. In this thesis a novel electrostatic transducer is presented; the transducer is made of thin polymer films and liquid dielectrics, combined with rigid stiffening elements to form a circular electrostatic bellow muscle (EBM) unit capable of out-of-plane contraction. These units are easy to manufacture and can be arranged in arrays and stacks that can be employed as contractile artificial muscles, pumps for fluid-driven soft robots, or as energy harvesters. As artificial muscles, EBMs of 20 - 40 millimeters in diameter can exert forces of up to 6 newtons, lift loads over a hundred times their own weight, and reach contractions of over 40 per cent with strain rates over 1200 per cents per second, with a bandwidth over 10 Hz. As pump drivers, EBMs produce flow rates of up 0.63 liters per minute and maximum pressure head of 6 kilopascals, whereas as generators, they reach a conversion efficiency close to 20 per cent. The compact shape, low cost, simple assembling procedure, high reliability and large contractions make the EBM a promising technology for high-performance robotic systems.

In this thesis, the results pertaining to various investigations carried out on Triglycine sulphate (TGS) single crystals, polyvinylidene fluoride (PVDF) films, lithium tantalate (LT)/PVDF nanocomposites and LT thin films are presented with emphasis on the characteristics that are crucial for their use in pyroelectric sensors. TGS single crystals (size 68 x 45 x 42 mm3), which have high pyroelectric coefficients, were grown by slow cooling method using newly designed platform technique based crystal growth work stations. The problem of slow growth rate along c-direction was overcome by placing (010) oriented seeds on the platform. The grown TGS crystals were used for the fabrication of the laser energy meter and temperature sensor. One drawback of TGS is its low Curie temperature (490C). As a consequence when the operating temperature approaches the Curie temperature, the crystals start depolarizing owing to the movement of domains. As a result the linearity of the devices gets affected and restricts the use of TGS. Therefore pyroelectric materials possessing higher Curie temperatures and larger pyroelectric coefficients than that of TGS are desirable. LT in single crystalline form having Curie temperature of ≈6000C has already been in use for pyroelectric device applications. However, growing stoichiometric LT single crystal is very difficult. On the other hand PVDF polymer films (Tc≈1800C) have low pyrolectric coefficients and difficult to pole electrically. Therefore efforts were made to prepare LT/PVDF nanocrystal composites to increase the pyroelectric coefficient of PVDF and to reduce the poling field. Nanoparticles of LT were prepared using sol-gel route. Spherical nanoparticles of size 20-40nm were prepared from sol by adding oleic acid to it. These nanoparticles were characterized using XRD, TEM, DSC and Raman spectroscopy. PVDF films with large percentage of β-phase (ferroelectric phase) were fabricated from solutions prepared using dimethylsulphoxide (DMSO) solvent. PVDF films (30µm thick), embedded with 20-40nm sized nanocrystallites of LT were fabricated to utilize them for pyroelectric sensor applications. The ferroelectric and pyrolectric properties of nano composite films were studied for sensor applications point of view. As a replacement for the single crystals of LT in pyroelectric sensors, investigations were carried out on oriented LT thin films. The studies on LT thin films yielded promising results which could be exploited for pyroelectric sensor applications.

The growth of sensors and sensing technologies have made significant impact in our day-to-day life. The five principle sensory organs of our body should perform effectively, so that we can lead a good healthy life. Apart from these natural sensors, there are man-made sensors that helps us to cope with diseases, organ failure etc. and enable us to lead a normal life. In recent years, with the prevalence of new kind of diseases, the need for new type of biomedical sensors is becoming very important. As a result, sensors used for biomedical applications have become an emerging technology and rapidly growing field of research. The aim of the present thesis work is to use the piezoelectric property of Polyvinylidene Fluoride (PVDF) film for the development of biomedical sensor and studying its application for human respiration/breathing related abnormalities. PVDF nasal sensor was designed in cantilever configuration and detailed theoretical analysis of the same was performed. Based on theoretical and experimental results, the PVDF nasal sensor dimensions were optimized. Suitable signal conditioning circuitry was designed and a measurement system for biomedical application was developed. The developed PVDF nasal sensor was calibrated using MEMS low-pressure sensor. The PVDF nasal sensor system has been applied in different biomedical applications namely, (i) to monitor human respiration pattern, (ii) to identify different Respiration Rates (RR), (iii) to evaluate Deviated Nasal Septum (DNS) in comparison with other objective method and, (vi) to clinically investigate nasal obstruction in comparison with subjective method. The thesis is divided into seven chapters. Chapter 1 This chapter gives a general introduction about biomedical sensors, piezoelectric sensing principle and PVDF polymer films along with the relevant literature survey. The brief introduction as well as literature survey of techniques used to monitor human respiration and to measure nasal obstruction is also included in this chapter. Chapter 2 This chapter gives details about the design of the PVDF nasal sensor in the cantilever configuration for sensing nasal airflow along with the relevant theoretical equations. Also, the details on the optimization of the PVDF nasal sensor dimensions based on the theoretical and experimental analysis are presented. Chapter 3 This chapter reports the designing of the necessary signal conditioning hardware along with the data acquisition unit for the PVDF nasal sensor. The signal conditioning hardware unit made consists of charge amplifier, low-pass filter and an amplifier. Besides, a complete measurement system for biomedical application was developed using PVDF nasal sensor and its merits and demerits were discussed. Chapter 4 In this chapter, an experimental set-up for measuring human respiration/breathing pressure using water U-tube manometer has been described. Also, the calibration procedure followed for the developed PVDF nasal sensor using a Micro Electro Mechanical Systems(MEMS) low pressure sensor is reported. Apart from these, the details on the measurement of deflection of the PVDF cantilever sensing element using laser displacement setup are provided. In addition, the PVDF nasal sensor was also calibrated for various air flow rates. At the end, a study has been reported on optimizing the position the PVDF nasal sensor with respect to human nose. Chapter 5 This chapter is divided into two sections, Section 5.1: This section describes the applicability of the PVDF nasal sensor using its piezoelectric property to monitor the human respiration pattern of each nostril simultaneously. The results of the PVDF nasal sensor have also been evaluated by comparing with Respiratory Inductive Plethysmograph(RIP) technique in normal subjects. Section 5.2: In this section, PVDF nasal sensor, RIP and Nasal Prongs (NP) techniques were used to measure the RR of healthy adults. The aim here was to evaluate the presently developed PVDF nasal sensor for identifying different RR compared to „Gold standard‟ RIP and NP methods. Chapter 6 This chapter is divided into two sections. Section 6.1: This section reports about the utilization of the developed PVDF nasal sensor for clinical application on the patient population. For this purpose, the performance of the PVDF nasal sensor measurements has been compared with the Peak Nasal Inspiratory Flow(PNIF) objective technique and visual analog scale (VAS). Section 6.2: This section describes about the use of PVDF nasal sensor system to measure nasal obstruction caused due to DNS objectively. Further, the results of the PVDF nasal sensor were compared with subjective techniques namely, VAS and clinician scale in patients and control group. Chapter 7 This chapter is composed of two sections. Section 7.1: This section summarizes the salient features of the work presented in this thesis. Section 7.2: This section reports a scope for carrying out further work.

Corrosion protection performance of a completely soluble polyaniline-dodecylbenzenesulfonic acid salt (PANI-DBSA) on C45 steel has been studied with electrochemical impedance and potentiodynamic measurements. Chloroform is the most suitable solvent to process the pristine PANI-DBSA because of negligible interaction of the solvent with the polyaniline (PANI) backbone. An anodic shift in the corrosion potential (<img src="http://scitation.aip.org/stockgif3/Dgr.gif" alt="Delta" align="bottom" border="0"><i>E</i>=~70&nbsp;&nbsp;mV), a decrease in the corrosion current and a significant increase in the charge transfer resistance indicate a significant anti-corrosion performance of the soluble PANI deposited on the protected steel surface. Corrosion protection follows the mechanism of formation of a passive oxide layer on the surface of C45 steel. In situ UV-Vis spectroscopy was used to investigate the differences in permeability of aqueous anions into PANI-DBSA. Preliminary results of electron diffraction studies show that PANI-DBSA possesses an orthorhombic type of crystal structure. An increase in the feed ratio of DBSA to aniline increases the tendency of aggregation of spherical particles of PANI obvious in transmission electron microscopy. PANI-DBSA slowly loses its electrochemical activity in acid free electrolyte without undergoing degradation.

A new method, probability distribution of diffusivities (time scaled square displacements between succeeding video frames), was developed to analyze single molecule tracking (SMT) experiments. This method was then applied to SMT experiments on ultrathin liquid tetrakis(2-ethylhexoxy)silane (TEHOS) films on Si wafer with 100 nm thermally grown oxide, and on thin semectic liquid crystal films. Spatial maps of diffusivities from SMT experiments on 220 nm thick semectic liquid crystal films reveal structure related dynamics. The SMT experiments on ultrathin TEHOS films were complemented by fluorescence correlation spectroscopy (FCS). The observed strongly heterogeneous single molecule dynamics within those films can be explained by a three-layer model consisting of (i) dye molecules adsorbed to the substrate, (ii) slowly diffusing molecules in the laterally heterogeneous near-surface region of 1 - 2 molecular diameters, and (iii) freely diffusing dye molecules in the upper region of the film. FCS and SMT experiments reveal a strong influence of substrate heterogeneity on SM dynamics. Thereby chemisorption to substrate surface silanols plays an important role. Vertical mean first passage times (mfpt) in those films are below 1 µs. This appears as fast component in FCS autocorrelation curves, which further contain a contribution from lateral diffusion and from adsorption events. Therefore, the FCS curves are approximated by a tri-component function, which contains an exponential term related to the mfpt, the correlation function for translational diffusion and a stretched exponential term for the broad distribution of adsorption events. Lateral diffusion coefficients obtained by FCS on 10 nm thick TEHOS films, thereby, are effective diffusion coefficients from dye transients in the focal area. They strongly depend on the substrate heterogeneity. Variation of the frame times for the acquisition of SMT experiments in steps of 20 ms from 20 ms to 200 ms revealed a strong dependence of the corresponding probability distributions of diffusivities on time, in particular in the range between 20 ms and 100 ms. This points to average dwell times of the dye molecules in at least one type of the heterogeneous regions (e.g. on and above silanol clusters) in the range of few tens of milliseconds. Furthermore, time series of SM spectra from Nile Red in 25 nm thick poly-n-alkyl-methacrylate (PnAMA) films were studied. In analogy to translational diffusion, spectral diffusion (shifts in energetic positions of SM spectra) can be studied by probability distributions of spectral diffusivities, i.e. time scaled square energetic displacements. Simulations were run and analyzed to study contributions from noise and fitting uncertainty to spectral diffusion. Furthermore the effect of spectral jumps during acquisition of a SM spectrum was investigated. Probability distributions of spectral diffusivites of Nile Red probing vitreous PnAMA films reveal a two-level system. In contrast, such probability distributions obtained from Nile Red within a 25 nm thick poly-n-butylmethacrylate film around glass transition and in the melt state, display larger spectral jumps. Moreover, for longer alkyl side chains a solvent shift to higher energies is observed, which supports the idea of nanophase separation within those polymers.

A new method, probability distribution of diffusivities (time scaled square displacements between succeeding video frames), was developed to analyze single molecule tracking (SMT) experiments. This method was then applied to SMT experiments on ultrathin liquid tetrakis(2-ethylhexoxy)silane (TEHOS) films on Si wafer with 100 nm thermally grown oxide, and on thin semectic liquid crystal films. Spatial maps of diffusivities from SMT experiments on 220 nm thick semectic liquid crystal films reveal structure related dynamics. The SMT experiments on ultrathin TEHOS films were complemented by fluorescence correlation spectroscopy (FCS). The observed strongly heterogeneous single molecule dynamics within those films can be explained by a three-layer model consisting of (i) dye molecules adsorbed to the substrate, (ii) slowly diffusing molecules in the laterally heterogeneous near-surface region of 1 - 2 molecular diameters, and (iii) freely diffusing dye molecules in the upper region of the film. FCS and SMT experiments reveal a strong influence of substrate heterogeneity on SM dynamics. Thereby chemisorption to substrate surface silanols plays an important role. Vertical mean first passage times (mfpt) in those films are below 1 µs. This appears as fast component in FCS autocorrelation curves, which further contain a contribution from lateral diffusion and from adsorption events. Therefore, the FCS curves are approximated by a tri-component function, which contains an exponential term related to the mfpt, the correlation function for translational diffusion and a stretched exponential term for the broad distribution of adsorption events. Lateral diffusion coefficients obtained by FCS on 10 nm thick TEHOS films, thereby, are effective diffusion coefficients from dye transients in the focal area. They strongly depend on the substrate heterogeneity. Variation of the frame times for the acquisition of SMT experiments in steps of 20 ms from 20 ms to 200 ms revealed a strong dependence of the corresponding probability distributions of diffusivities on time, in particular in the range between 20 ms and 100 ms. This points to average dwell times of the dye molecules in at least one type of the heterogeneous regions (e.g. on and above silanol clusters) in the range of few tens of milliseconds. Furthermore, time series of SM spectra from Nile Red in 25 nm thick poly-n-alkyl-methacrylate (PnAMA) films were studied. In analogy to translational diffusion, spectral diffusion (shifts in energetic positions of SM spectra) can be studied by probability distributions of spectral diffusivities, i.e. time scaled square energetic displacements. Simulations were run and analyzed to study contributions from noise and fitting uncertainty to spectral diffusion. Furthermore the effect of spectral jumps during acquisition of a SM spectrum was investigated. Probability distributions of spectral diffusivites of Nile Red probing vitreous PnAMA films reveal a two-level system. In contrast, such probability distributions obtained from Nile Red within a 25 nm thick poly-n-butylmethacrylate film around glass transition and in the melt state, display larger spectral jumps. Moreover, for longer alkyl side chains a solvent shift to higher energies is observed, which supports the idea of nanophase separation within those polymers.