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A

MINOR PROJECT

ON

“POLYMER IN CHEMICAL SENSORS ALONG WITH ITS FABRICATION”

Submitted By: BADAL LODHARI & YASH PATEL (10BCH011) (10BCH067)

Guided By: Prof.NEHA PATNI.

CHEMICAL ENGINEERING DEPARTMENT INSTITUTE OF TECHNOLOGY NIRMA UNIVERSITY

CERTIFICATE
This is to certify that Mr. BADAL VINODKUMAR LODHARI & YASH SUMULBHAI PATEL, students of Chemical Engineering, 7th semester, of Nirma University, has satisfactorily completed the seminar on “POLYMER IN CHEMICAL SENSORS ALONG WITH ITS FABRICATION” as a partial fulfillment towards the degree of B. Tech. in Chemical Engineering.

Date: Place:

Prof. Neha Patni.

Dr. S. S. Patel Head of Department

INDEX
Page no. Acknowledgement Abstract Content List of figures List of tables I II III IV V

Neha Patni for his constant support. We would like to thank my guide Prof. We would like to thank my parents and my friends for helping me.S.Patel and the whole Chemical Department for their guidance. I .S. We would also like to thank our HOD Dr. We would like to thank the Library of Nirma University for providing me all the essential resources.ACKNOWLEDGEMENTS First of all.

ion-selective sensors. Better selectivity and rapid measurements have been achieved by replacing classical sensor materials with polymers involving nano technology and exploiting either the intrinsic or extrinsic functions of polymers. II . The developing role of polymers as gas sensors. Semiconductors. humidity sensors. Polymers used in sensor devices either participate in sensing mechanisms or immobilize the component responsible for sensingthe analyte. biosensor devices. and organic semiconductors have been the classical materials for sensor devices. rapid and reliable means for the detection and quantitation of specific chemical species. and provided a basis for the development of intelligent instrumentation systems. Polymers are used in chemical sensors Because their chemical and physical properties may be tailored over a wide range of characteristics. ionic membranes. Finally. During the last 5 years. semiconducting metal oxides. the use of polymers is finding a permanent place in sophisticated electronic measuring devices such as sensors. This technology has enabled the continuous measurement of a marker substance. etc.. are reviewed and discussed in this paper. polymers have gained tremendous recognition in the field of artificial sensor in the goal of mimicking natural sense organs. Both intrinsically conducting polymers and nonconducting polymers are used in sensor devices.ABSTRACT Chemical sensors have become an important technology in chemical measurement. pH sensors. These analytical devices provide a simple. Chemical Sensors combine a molecular recognition element with a transducer in order to produce an electronic signal in the presence of a particular analyte. solid electrolytes. current trends in sensor research and also challenges in future sensor research are discussed.

1 GAS SENSORS 3. 5.1. 10. III .1 RECEPTORS 1. 26. Title INTRODUCTION 1. 3. 1.3.1 SENSORS PHSICS 2.3 SENSOR TECHNOLOGY POLYMERS IN CHEMICAL SENSORS 3.1 CHEMICAL EQUILIBRIUM 2.3 ION SELECTIVE SENSORS 3. 24. 21.1 THE TERM SENSOR 1.2 TRANSDUCERS 1.CONTENT Chapter No. 1.1 SOLIDS 2. 7.2 PH SENSORS 3.3 ELEMENTS OF CHEMICAL SENSORS 1. 6.4 ALCOHOL SENSORS CONCLUSION REFERENCES Page No. 7.4 PARAMETERS OF CHEMICAL SENSORS FUNDAMENTALS 2. 1.2 CHARACTERISTICS OF A CHEMICAL SENSOR 1. 3. 6. 2.3. 6. 5. 10. 5. 2. 19. 4. 9. 4.2.2 SENSOR CHEMISTRY 2. 27.

Title 1.1 3. 3. 18. 2.2 Two sources in the development of chemical sensors Scheme of a typical chemical sensor system Basic Representation of a crystaquartz crystal microbalance(QCM) sensor Layout of a Single Acoustic Aperture Wave (SAW) Page No. 18. No. 2. . 4.3 3.LIST OF FIGURES Sr. IV.2 1. 4. 1.

19.LIST OF TABLES Sr No. 16. 4. 2. V. . 3. Adsorption of strychnine (a pesticide) and b-ionene (an odor) at 45 8C by various films immobilized on a QCM surface 5. Structures of some ionophores used in ion selective sensor devices Page No. 23. 1. Title 2 Various sensors and their applications 3 Polymers used in various gas sensors 4. 11.

etc. there is broad agreement about attributes of sensors. A chemical sensor furnishes information about its environment and consists of a physical transducer and a chemically selective layer [1]. They can be used in many other fields besides just intelligent machines. as recognition agent. A modern definition should be comprehensive. monitoring toxic gases and vapors in the workplace or contaminants in natural waters by industrial effluents and runoff from agriculture fields. Actually. Sensor devices have been made from classical semiconductors. • Be cheap. bacteria. chemical and biological environment.1THE TERM SENSOR It would not be sufficient to see sensors merely as some kind of technical sensing organs.1. Although a majority of polymers are unable to conduct electricity. metals and catalytic materials. During the last 20 years. they gained importance in the construction of sensor devices. and the number of active researchers. giving birth to a large number of sensor devices for medical and environmental technology. Sensors should: • Be in direct contact with the investigated subject. e. the published literature. there is still no generally accepted definition of the term. Either an intrinsically conducting polymer is being used as a coating or encapsulating material on an electrode surface. • Be small. a near revolution is apparent in sensor research. global research and development (R&D) on the field of sensors has expanded exponentially in terms of financial investment. On the other hand. • Transform non-electric information into electric signals. A survey of the literature reveals that polymers also acquired a major position as materials in various sensor devices among other materials. It is well known that the function of a sensor is to provide information on our physical. however. differences regarding whether the receptor alone is a sensor or whether the term encompasses the complete unit containing receptor plus transducer. or non-conducting a polymer is being used for immobilization of specific receptor agents on the sensor device. their insulating properties are utilized in the electronic industry. insulators. 1. whereas a chemical sensor does not contain these agents.g. Legislation has fostered a huge demand for the sensors necessary in environmental monitoring. 1. solid electrolytes.We find. • Operate continuously or at least in repeated cycles. antibody. • Respond quickly. Since the chemical and physical properties of polymers may be tailored by the chemist for particular needs. tissue. it seems to be rather clear what we mean when we talk about a sensor. . Regardless of such differences. A biosensor contains a biological entity such as enzyme. INTRODUCTION. Thus.

Figure 1. Initially. especially about the occurrence and amount of constituents including information about their spatial distribution and their temporal changes’ (Danzer et al. however. Two sources in the development of chemical sensors 2. 1976). On the other hand. There are two obvious sources for the formationof sensor science as an independent field. chemists hesitated to deal with sensors. instrumental form. The latter by definition aims to ‘ obtain information about substantial matter. the field is given little space in analytical chemistry textbooks. Figure 1. that chemical sensors comprise a branch of analytical chemistry. above all as a result of mass production. One of these sources is the above-mentioned development of microtechnologies. Up to now. which stimulated a demand for sensing organs. chemical expertise was necessary to design chemical sensors. This is true mainly in European textbooks. Sensors do not fit smoothly into traditional concepts and appear to belong to an unrelated field. . Indeed. but later their interest in them grew.2. CHARACTERISTICS OF A CHEMICAL SENSOR The term ‘chemical sensor’ stems not merely from the demand for artificial sensing organs.2 attempts to outline the formation of sensor science as a bona fide branch of science. they have not been a typical constituent of analytical chemistry lectures in Europe.It seems astonishing that sensors are expected to be cheap. 1. Such an expectation can be understood as the expression of the self-evident requirement that sensors be available in large quantities.2. The second source is a consequence of the evolution of analytical chemistry which brought about a growing need for mobile analyses and their instrumentation. There is no doubt. The field of chemical sensors has been adapted and is now largely considered a significant subdiscipline of analytical chemistry. Such expertise is the subject of analytical chemistry in its modern.

The resulting mass change can be measured as a frequency change in an electrical oscillator circuit. ELEMENTS OF CHEMICAL SENSORS Section 1. . in particular units for signal amplification and for signal conditioning.g. Thismeans that low concentration values should be detected.e. one and the same physical object acts as receptor and as transducer. the postulation of a low detection limit. This is expressed typically in statements like the following (IUPAC 1999): Chemical sensors usually contain two basic components connected in series: a chemical (molecular) recognition system (receptor) and a physicochemical transducer. The above list could be extended with. many pragmatic descriptions exist in the literature. 1. In some cases. The receptor is formed by a sensitive layer at the crystal surface. its physical properties are changed in such a way that the appending transducer can gain an electrical signal. It means that sensor signals should not ‘freeze’ but respond dynamically to changes in sample concentration in the course ofmeasurement.g. or a high sensitivity. The attribute of reversibility is considered important by many authors. Consider the following definition by Wolfbe is (1990): Chemical sensors are small-sized devices comprising are cognition element. or at least be selective to a group of analytes. As a result. e. and a signal processor capable of continuously and reversibly reporting a chemical concentration. a transduction element. into an analytically useful signal. 3. • Be specific. • Respond rapidly.a definition was given by IUPAC in 1991:[4] A chemical sensor is a device that transforms chemical information. • Be small. In the majority of chemical sensors.3. This is the case e. the receptor interacts with analyte molecules. they should respond exclusively to one analyte. In other documents. • Be cheap. additional elements are considered to be necessary. ranging from concentration of a specific sample component to total composition analysis.. 1. A typical arrangement is outlined in Fig. • Maintain their activity over a long time period. This is rather general. i. receptor and transducer are represented by different physical objects. The following characteristics of chemical sensors are generally accepted. Chemical sensors should: • Transform chemical quantities into electrical signals. A piezoelectric quartz crystal acts as transducer. Thus. In mass sensitive sensors.1 showed that the functions of a chemical sensor can be considered to be tasks of different units. The latter is capable of absorbing gas molecules. however.3. in metallic oxide semiconductor gas sensors which change their electrical conductivity in contact with some gases Conductivity change itself is a measurable electrical signal.

3. Typical for biosensors is that molecules are recognized by their size or their dimension. 4. Instead of equilibrium.e.1. . The term molecular recognition is used to describe this behaviour. or participate in a chemical equilibrium together with the analyte. Primarily these phenomena act at the interface between analyte and receptor surface. i.most important for chemical sensors are adsorption. Receptor layers can respond selectively toparticular substances or to a group of substances. Scheme of a typical chemical sensor system 1. RECEPTORS The receptor function is fulfilled in many cases by a thin layer which is able to interact with analyte molecules. a chemical reaction may also become the source of information. catalyse a reaction selectively. ion exchange and liquid–liquid extraction (partition equilibrium). Among the processes of interaction. where both are in an equilibrium state.3. by steric recognition.Figure 1.

current or resistance. in electrochemical sensors where receptor and analyte are partners of the same redox couple. Among the examples given are those that develop their sensor function only in combination with an additional receptor layer. • Sensitivity: change in the measurement signal per concentration unit of the analyte. for example. • Linearity: the relative deviation of an experimentally determined calibration graph from an ideal straight line. i. In what follows. 1981). • Detection limit: the lowest concentration value which can be detected by the sensor in question.3. Usually values for linearity are specified for a definite concentration range. . It is base on a scheme developed by electronics engineers but has not been applied to sensors till now (Malmstadt et al. Following the quantity appearing at the transducer output.e. Quantitative expressions of selectivity exist for different types of sensors. signals are processed nearly exclusively by means of electrical instrumentation. The pool of transducers can be classified in different ways. ‘voltage transducer’ etc. the slope of a calibration graph. • Selectivity: an expression ofwhether a sensor responds selectively to a group of analytes or even specifically to a single analyte. under definite conditions.We find this. an attempt is made to find a classification scheme which reflects the inner function of the transducers using only a few transducer principles.4 PARAMETERS OF CHEMICAL SENSORS[3] The following list contains static as well as dynamic parameters which can be used to characterize the performance of chemical sensors. every sensor should include a transducing function. the actual concentration value. in receptors where a catalyst accelerates the rate of an analyte reaction somuch that the released heat from the reaction creates a temperature change that can be transduced into an electrical signal. there exists no systematic concept for classification. Processes at the receptor-analyte interface can be classified into interaction equilibria and chemical reaction equilibria. Procedures for evaluation of the detection limit depend on the kind of sensor considered.must be transformed into an electric quantity voltage. In the international literature. receptor operation is an inherent function of the transducer. The differences are not significant for work with sensors. In other types. for example. • Dynamic range: the concentration range between the detection limit and the upper limiting concentration. A true chemical equilibrium is formed.2. anon-electric quantity. 1. we encounter types like ‘current transducer’. Whether or not the analyte can be quantified at the detection limit is not determined. 1.e. Accordingly. 5. i. TRANSDUCERS Today.

Every ion tends to be surrounded as uniformly as possible by oppositely charged counterions.1. The different sorts of solids are characterized preferably by the type of chemical bonding that predominates. In an ionic solid.e. These components. 2. The latter can be specified either for continuous operation or for repeated on-off cycles. Usually specified as the time to rise to a definite ratio of the final value. the signal variation for zero concentration. • Hysteresis: the maximum difference in output when the value is approached with (a) an increasing and (b) a decreasing analyte concentration range.1.g. FUNDAMENTAL 2. In solidswith an atomic lattice. • Life cycle: the length of time over which the sensor will operate. This parameter is important chiefly for detectors in flowing streams. the value of t99 represents the time necessary to reach 99 percent of the full-scale output. Metallic bonding brings about a rigid but ductile structure. e.Amorphous substances like glasses or polymers are not considered to be solids. atoms or molecules. In metallic solids. thus forming an electrically neutral structure. The crystal structure forms as a result of the attempt of spherical atoms to approximate each other as close as possible and to form a package of maximum density. Thus. • Stability: the ability of the sensor to maintain its performance for a certain period of time. free electrons are delocalized in a framework of regularly arranged cations.1 SOLIDS Many phenomena occurring at the surface of solids are important for sensors. i. SENSORS PHSICS 2. . The maximum storage time (shelf life) must be distinguished from the maximum operating life.• Resolution: the lowest concentration difference which can be distinguished when the composition is varied continuously. It is given as a percentage of fullscale output. • Response time: the time for a sensor to respond from zero concentration to a step change in concentration. although they have some properties of solid bodies. 6. As a measure of stability. are fixed by bonding forces so that they form regions with a regular lattice structure. atoms are connected by covalent bonding forces forming a regular network involving the complete crystal. drift values are used. The variety of existing structures is a result of the fact that ions often have quite different radii and often are not shaped like a ball. ions of opposite charge are held together by Coulomb forces. e. The components of solids are typically arranged regularly.g. The time which has elapsed until 63 percent of the final value is reached is called the time constant.

The conductivity of metallic conductors decreases with increasing temperature. This means. For quantitation of mixtures of substances. or to the number of molecules in 2g hydrogen gas. The most important basis of analytical chemistry is the theory of chemical equilibrium. independent of the kind of substance. whereas semiconductors showthe opposite behaviour. χ = nB/nA+Nb c χ 7. This corresponds to the number of atoms in 12g carbon or in 197g gold. preferably denoted in terms of molarity (the number of moles per volume of solution in litres c = n/v). They can be classified following the type of temperature dependence of their electric conductivity. Solids withmobile electrons are electronic conductors. and whereas a certain amount of products is formed. c = 1mol/L = 1M. the concentration of solutions. When molecules react. Their conductivity tends to increase with temperature. Elements like silicon or germanium as well as compounds like gallium arsenide are typical semiconductors. first of all. For example. For ca. The vast majority of organic solids are molecular crystals. One mole means a very large number of particles. they form new products. The diamond structure is a typical example of an atomic lattice. . measured in the SI unit mol (mole). In a system which is in equilibrium. Both approaches result in the same mathematical relationships. For a theoretical description of chemical equilibrium and to derive its inherent laws. 350 years chemists have been performing chemical operations with the intention obtaining information about chemical composition. utilizing the laws and the relationships describing chemical equilibria. where the index B denotes the solvent). In the diamond crystal. This denotes the number of moles of dissolved substance nB as a proportion of the total number of moles ina solution (nA + nB. One mole always indicates the same number of particles. Their temperature dependence is higher than that of metals. It is advantageous to give a substance amount not by its mass but by the number of moles. Solids with an atomic lattice often are very hard and chemically inert. Substances with a very low conductivity (e.022 · 1023 pieces. diamond) are isolators. namely 6.1 CHEMICAL EQUILIBRIUM.The crystal structure is now determined by the tendency of orbitals to overlap rather than to follow geometric principles. Such forces are much weaker than chemical bonding forces. reactions do not stop.g.2 SENSOR CHEMISTRY 2. every carbon atom is interconnected with four equal neighbours in the formof a tetrahedron. like those of semiconductors. and the products are decomposed again. 2. even if no movement is visible for an external observer. namely the thermodynamic approach and the kinetic approach. Crystals with molecular lattices are formed by molecules interconnected by intermolecular forces. the mole fraction (molar fraction). Chemical equilibrium is a dynamic equilibrium.2. simultaneously an equal amount of the original reactants is generated as a result o the consumption of the products. Generally they are soft and have a low melting point. the following quantities are important: n the amount of substance. Each atom is in an sp3 hybridization state and forms four σ bonds. there exist two fundamentally different models.

measured inmol s−1. The chemical driving force has a name. When we write a chemical equation for a reaction in equilibrium. respectively. . They depend only on temperature.and finally K =c2(HI) c(I2) · c(H2). 2. For low values of c. denoted by the symbol ΔRG. ΔRGθ and R are constants. is of strict validity regardless of the actual shape of reaction-rate equations. As in electric engineering. Just the opposite behaviour can be expected for the backward reaction. the rate of forward reaction initially must be high but decrease more and more in the course of reaction (Fig.22). Alternatively. Obviously. This very important quantity is a function of all reacting species appearing in a chemical reaction scheme: ΔRG = ΔRGθ + R · T ln f · ciνi (2.13) In this equation. where the current is the result of the ‘driving force’ voltage.a the activity a = f · c is a concentration where the activity coefficient f is some kind of ‘correcting factor’. Activity values in electrolyte solutions strongly depend on the concentrations of all the species present in solution and of their charge numbers. The result.12) Equation (2.12) is well known under the historical name law of mass action. Since these concentrations decrease in the course of the reaction. H2 + I2 → 2HI we can write r = k · c(H2) · c(I2) whereas for the opposite direction 2HI → H2 + I2 the rate is r = k · c2(HI) The terms_k and_k are the rate constants of the forward and backward reactions. In some cases. Starting with a given ‘stock’ of reactant molecules. a driving force should exist. The chemical reaction rate r = dn/dt. The derivation of this law given above is not really a strict one. it makes sense towrite the double arrow‘→←’ instead of a ‘=’. this chemical driving force depends on reactant concentrations. for other reactions with different stoichiometric factors (the numbers which appear in chemical equations left from the chemical formula symbols).g. the law of mass action can be derived on the basis of the assumption that for a definite initial state (a given set of reactants each with given concentration). depends on the concentrations of reactants as well as on the concentrations of products. a can be calculated using the ionic strength I. however. the law may look different from the example given in Eq. both reaction rates are equal: r = k · c(H2) · c(I2) = _k · c2(HI) . in chemistry the reaction rate can be considered the result of a ‘chemical driving force’. Under conditions of equilibrium. It is the so-called change of free Gibbs energy. the driving force must also decrease. For a simple reaction. and finally approach zero. approximately a ≈ c and f ≈ 1.12). (2. e. 8. the reaction of iodine vapour with hydrogen gas. (2. Of course. since the dynamic character of chemical equilibria is symbolized in this way: H2 + I2 ←→ 2HI. Activity is measured using the same unitsas concentration c. if all the partners are in a gaseous state.

The efficiency of such techniques can be illustrated by considering modern integrated electronic circuits where millions of transistors are located on a single silicon chip. extreme resolution is attainable and complex threedimensional structures can be realized. the field of sensors has formed in the course of the rapid development of microtechnologies.The stoichiometric coefficients νi appear with a positive sign for products generated and with a negative sign for reactants consumed in the course of reaction.3 SENSOR TECHNOLOGY Chemical sensors are products of quite different fields of science and technology. The operator π means ‘multiply all the following numbers’. Microelectronic structures can be two or three dimensional. the receptor. The paste is fired and sintered in the next manufacturing step. The common design of a chemical sensor includes an interface in direct contact with the sample. the most important element for sample recognition. Layers of equal material and in equal order can be fabricated by thin-film as well as by thick-film techniques. devices for signal processing and many other types of units. The latter are fundamental for new technological fields like micromechanics and microfluidics. In thick-film technology. Examples of multilayer sensors are polycrystalline semiconductor gas sensors. Consequently. The latter can also be produced by sputtering. the predominant technique in microelectronics. i. Another example is a gas sensor type where a paste of fine oxide particles is deposited on a ceramic substrate. Very often the receptor represents a thin layer located at the surface of an inert carrier. 2.Thin layers are generated by vapour deposition. where the sensitive tin dioxide or titanium dioxide layer is spread by sputtering on the surface of a conductive layer designed to be a heater.e. The transducer. With thin films on silicon wafers. Techniques for generating structures have reached a high degree of perfection and are very important for microelectronics. . different layers are screen-printed on the surface of a carrier. depending on the kind of sensor. consisting either of platinum or of ruthenium dioxide. Thin-film technology. It is useful to have a closer look at design details characteristic of chemical sensors. A combination of thick-film and thin-film technologies can also be found in sensors. only rough structures can bemade. and these technologies have strongly influenced the design of chemical sensors. The next element cannot be described by a simple rule. On the other hand. there exist quite differentmanufacturing techniqes. construction details have emerged with sensors which cannot be found in any other field of analytical chemistry. also plays an important role for sensors.With thick films. sputtering or chemical vapour deposition (CVD). There are electric contacts. can be manufactured by different means. In this way. They strongly vary with respect to resolution. 9.

85 V versus Ag/AgCl without serious interference from oxidizable species. A very low concentration of nitric oxide (20 nM–50 mM) could be measured with these sensors at 0. To detect HCl in sub-ppm levels. etc. The changes in the Soret-and Q-bands with HCl gas in ppm levels have been examined. They achieved a higher and preferable sensitivity to sub-ppm levels of HCl using polyhexylmethacrylate matrix in the composite.1. complete miniature laboratories (lab-on-the chip) can be assembled. As a result. There have been improvements using a catalytic micro-reactor in the gas flow leading to the amperometric sensors. Hydrogen chloride (HCl) is not only the source of dioxin produced in the incineration of plants and acid rain. PMMA. Amperometric sensors have been fabricated by Mizutani for the determination of dissolved oxygen and nitric oxide using a perm selective polydimethylsiloxane (PDMS) (II) membrane. Variation in the electrodes and the electrode potentials can be utilized to identify the gases present.Chemical sensors can be integrated into such devices. but it also has been identified as a workplace hazard with a short-term exposure limit of 5 ppm. have been used to detect hazardous gases and vapors. 10. such as L-ascorbic acid. showed optochemical detection of HCl gas using a mono-substituted tetraphenylporphin–polymer composite films. Conducting polymers showed promising applications for sensing gases having acid–base or oxidizing characteristics.10. Amperometric sensors consisting of an electrochemical cell in a gas flow. The sensor response and recovery behavior is improved if the matrix has a glass transition temperature below the sensing temperature. . composites of alkoxy substituted tetraphenylporphyrin– polymer composite films were developed by Nakagawa. Conducting polymer composites with other polymers such as PVC.15. and hence increases sensitivity to HCl. Highly complex instruments like liquid chromatographs also are becoming available in miniaturized form. A hydrophobic polymer layer with a porous structure is useful for the selective permeation of gases. which respond to electrochemically active gases and vapors. polymers with active functional groups and SPEs are also used to detect such gases. Some applications of gas sensors are included in Table 2. nitrogen oxide and toxic gases from related industries has become a serious environmental concern. GAS SENSORS The emission of gaseous pollutants such as sulphur oxide. uric acid and acetaminophen. Sensors are needed to detect and measure the concentration of such gaseous pollutants. It has been found that high selectivity to sub ppm levels of HCl gas was achieved using a 5. 3. In fact analytical gas sensors offer a promising and inexpensive solution to problems related to hazardous gases in the environment.20-tetra (40-butoxyphenyl)porphyrin-butylmethacrylate [TP (OC4 H9)PH2-BuMA] composite film Supriyatno et al. POLYMER IN SENSOR DEVICES 3. Such a reactor with a heated filament of platinum causes the analyte to undergo oxidation so that previously electrochemically unreactive species can be detected. The alkoxy group imparts basicity to the material.

Gases permeate easily through the pores to reach the electrode surface. . Being perm selective.They prepared the electrode by dip coating from an emulsion of PDMS. the polymer coating is capable of discriminating between gases and hydrophobic species. 11. whereas the transport of the hydrophilic compounds is strongly restricted. which co-exist in the samples to be measured.

.12.

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which make them attractive candidates for gas sensing elements. and polypyrrole (X ¼ N–H). PCl3. Polyacetylene is doped with iodine on exposure to iodine vapor. The authors also claimed excellent stability for this sensor. Exposure of this normally resistive polymer to iodine vapor altered the conductivity by up to 11 orders of magnitude. Lyon. thiophene. polythiophene (X ¼ S). It was observed that nucleophilic gases (ammonia and methanol. SO2) having the opposite effect.Chou.8 ppm. Polyacetylene (III) is known to be the first organic conducting polymer (OCP). These physical property changes can be observed at room temperature. Above approximately 2% doping. when they are doped/dedoped by some chemical agent. when they are exposed to lowerconcentrations of the chemicals. ethanol vapors) cause a decrease in conductivity. 14. followed by a detailed paper in 1985. . It is a very good sensor for detecting DO in water. with electrophilic gases (NOx. with Nafion as the SPE. The performance of the sensor was linear at room temperature with higher concentrations (0. Persaud and Pelosi reported conducting polymer sensor arrays for gas and odor sensing based on substituted polymers of pyrrole.5– 5%). the carriers are free to move along the polymer chains resulting in metallic behavior. indole and others in 1984 at the European Chemoreception Congress (ECRO). aniline. polyaniline and their composites. Then. responding within a matter of minutes. which retain the p-system of polyacetylene but include heteroatom bonded to the chain in a five membered ring were developed. Ng and Wang prepared a Au-SPE sensor for detecting dissolved oxygen (DO) in water. Most of the widely studied conducting polymers in gas sensing applications are polythiophene and its derivatives. with a lower limit of 3. Such heterocyclic OCPs (IV) include polyfuran (X ¼ O). Later heterocyclic polymers. polypyrroles. charge transfer occurs from polyacetylene chain (donor) to the iodine (acceptor) leads to the formation of charge carriers. The intrinsically conducting polymers are p-conjugated macromolecules that show electrical and optical property changes. Nylander investigated the gas sensing properties of polypyrrole by exposing polypyrroleimpregnated filter paper to ammonia vapor.

since the conductivity is strongly dependent on the doping level. with the consequence of reducing the number of holes in the polypyrrole and increasing the resistivity of the submicrometer film. The NH3 sensitivity was detected by the change in resistance of the polypyrrole film.10 ppm). 15. These polymers have characteristics of low powerconsumption. polystyrene and polycarbonates. 1. respectively.Electrically conducting polyacrylonitrile(PAN) /polypyrrole(PPY) . optimum performance at low to ambient temperature. In NO2 sensing. . viz. polypyrrole/polycarbonate composites were prepared by electropolymerization of the conducting polymers into the matrix of the insulating polymers PAN.polythiophene /polycarbonate. The interaction of this polymer with gas molecules decreases the polaron density in the band-gap of the polymer. The NH3-sensing mechanism was based on dedoping of PAN by basic ammonia. whereas the nanocomposite of polyaniline and isopolymolybdic acid (PMA) showed a decrease of relative response with the increase in ammonia concentration. Electroactive nanocomposite ultrathin films of polyaniline (PAN) and isopolymolybdic acid (PMA) for detection of NH3 and NO2 gases were fabricated by alternate deposition of PAN and PMA following Langmuir–Blodgett (LB) and self-assembly techniques. It was observed that PANI–PMMA composite coatings are sensitive to very low concentrations of NH3 gas (. NO2 played the role of an oxidative dopant. They observed the sensor response in terms of the dc electric resistance on exposure to ammonia. causing an increase in the conductivity when emeraldine base is exposed to NO2. found that the optical and electrical properties of p-conjugated polyaniline change due to interaction of the emeraldine salt (ES) (V) with NH3 gas. They explained the decrease in resistance on the basis of removal of a proton from the acrylic acid dopant by the ammonia molecules.polythiophene /polystyrene. Acrylic acid doped polyaniline showed a sharp increase in relative response for around 10 ppm ammonia and subsequently remained constant beyond 500 ppm. sensor responseproportional to analyte concentration and rapid adsorption/desorption kinetics. low poisoning effects. The change in resistance was found to increase linearly with NH3 concentration up to 58 ppm and saturates thereafter. Yadong reportedthat submicrometer polypyrrole film exhibits a useful sensitivity to NH3. They interpreted the resistance change of the film in terms of the formation of a positively charged electric barrier of NH4 þ-ion in the submicrometer film. A plot of the variation of relative response of the ammonia gas sensor with increase in the concentration of ammonia gas is shown in Fig. thereby rendering free conduction sites in the polymer matrix. 1–600 ppm. The process was based on dopinginduced deposition effect of emeraldine base. Chabukswar synthesized acrylic acid doped polyaniline for use as an ammonia vapor sensor over a broad range of concentrations. polypyrrole/polystyrene. The electrons of the NH3 gas act as the donor to the p-type semiconductor polypyrrole. A polypyrrole–poly(vinyl alcohol)(PVA) composite prepared by electropolymerizing pyrrole in a cross-linked matrix of pyrrole was found to posses significant NH3 sensing capacity.

16. .

The oscillations are applied to the sensor through a set of metallic electrodes formed on the piezoelectric surface. will alter the resonant frequency of the wave. Quartz Crystal Microbalance (QCM) sensors are a kind of piezoelectric quartz crystal with a selective coating deposited on the surface to serve as an adsorptive surface. These devices operate at ultrahigh frequencies (gigahertz range). The QCM is a very stable device. Such evidence supports the idea that polypyrrole undergoes a reversible redox reaction when ammonia is detected at submillimolar concentrations. frequency and phase shift. polymer–ceramic composite. For example. for example. LiNbO3 . Table 4 shows how exposure of 19 ppm strychnine (a pesticide) or b-ionine (an odor) affects the absorption masses of QCM coated with various chemically sensitive films. The natural resonant frequency of the QCM is disturbed by a change in mass from the adsorption of molecules onto the coating. e. capable of measuring an extremely small mass change. The electric field distorts the lattice of the piezoelectric material beneath the electrode.Similar to QCM sensors. the alkanes having no such hydrogen bonding capacity.g. hydrogen bond forming acidic volatiles was best detected by hydrogen bond forming basic polymers. epoxy resin for estimation of ethanol in commercial liquors and cellulose. due to the change in mass of the coating on the sensor by an absorbing species. including phthalocyanine .over which a selective coating is deposited. The general trend observed shows that polymer-coated QCMs are most sensitive towards volatiles possessing a complimentary physicochemical character. giving them the capability to sense as little as 1 pg of material. A number of materials have been investigated as coatings for QCM sensors. Fig. 2 presents a schematic diagram for a QCM. When the wave arrives at the other end.The ammonia sensing mechanism of the polypyrrole electrode has been addressed. 3 shows that the acoustic wave is created by an AC voltage signal applied to a set of interdigited electrodes at one end of the device. . Fig. with evidence that a mobile counter ion may be required for proper sensor operation. 17. The signal can be monitored in terms of amplitude. fluoropolymers for sensing of a pollutant organophosphorus gas and commercially available gas chromatography phases as coating for sensing toluene in dry air. a duplicate set of interdigited electrodes generate an AC signal as the acoustic wave passes underneath them. If a piezoelectric substance is incorporated in an oscillating electronic circuit a surface acoustic wave (SAW) is formed across the substance. a shift in resonance frequency of 1 Hz can easily be measure for an AT-cut quartz plate with a resonance frequency of 5 MHz. Alkanes could be distinguished from alkenes by the use of strongly hydrogen bond forming acidic polymers that could interact with the weak hydrogen bond basicity of the alkenes. the coating on the sensor determines the selectivity of the SAW device. causing a SAW to propagate toward the other end through a region of the crystal known as the acoustic aperture. Any change in velocity of these waves. which corresponds to a change in mass of just 17 ng/cm2.

2: Layout of a Single Acoustic Aperture Wave (SAW) 18. this can be overcome by the use of a reference cell. . Fig 3.In these sensors the response times can be of the order of 1 s.1 : Basic Representation of a crystaquartz crystal microbalance(QCM) sensor Fig 3. Although SAW sensors are very sensitive to physical changes in the sample matrix.

Munkhol used photochemically polymerized copolymer of acrylamide-methylenebis(acrylamide) containing fluoresceinamine covalently attached to an optical fiber surface (core dia 100 mm) in a pH sensor device. the measurement and control of pH is very important in chemistry. Since the solution pH has a significant effect on chemical reactions. Others have also developed optical pH sensors based on polyaniline for measurement of pH in the range 2–12. While they prepared polyaniline films by chemical oxidation at room temperature. Demarcos and Wolfbeis developed an optical pH sensor based on polypyrrole by oxidative polymerization. They reported that the polyaniline films synthesized within a time span of 30 min are very stable in water. the immobilization step for an organic dye during preparation of the sensor layer was not required. The use of conducting polymers in the preparation of optical pH sensor has eliminated the need for organic dyes. polyaniline has been found as most suitable for pH sensing in aqueous medium. biochemistry. they improved the stability of the polyaniline film significantly by increasing the reaction time up to 12 h. Jin reported an optical pH sensor based on polyaniline (Table 2). Since the polymer film has suitable optical properties for optical pH sensor. clinical chemistry and environmental science. The pH indicates the amount of hydrogen ion in a solution. .2 PH SENSORS.3. Amongst various organic materials. The film showed rapid reversible color change upon pH change. 19.

8. 50. and their electrical resistance varied in the range 2. They used weak acid (acetic acid) and weak base (ammonium hydroxide) as analytes. Solid contact electrodes with N. The optical pH sensors could be kept exposed in air for over 1 month without any deterioration in sensor performance.dialkylbenzylethylenediamine (alkyl ¼ butyl.76 MV. decyl) were prepared. Solid contact electrodes and coated wire electrodes had been fabricated from polymer cocktail solutions based on N.0–13. whereas ammonium hydroxide was analyzed only in aqueous medium.37–2.0 V versus Ag/AgCl. They showed that the response range and slopes were influenced by the alkyl chain length.5–13. 3. The 90% response time was . The acetic acid was analyzed in both aqueous and dry acetonitrile. The light yellow color polymer modified electrode was characterized by scanning electron microscopy (SEM). 51.5 M tetraphenyl borate at 2.6. 4.2 8C. Other pH sensor devices using polymers have also been developed. Hydrogen ion selective solid contact electrodes based on N. Ferguson used a poly(hydroxyethyl methacrylate) (IX) hydrogel containing acryloyl fluorescein as pH indicator. especially when compared with coated wire electrodes. 20. .4–13.0.2–13. Shakhsher and Seitz exploited the swelling of a small drop of aminated polystyrene (quaternized) on the tip of a single optical fiber as the working principle of a pH sensor.2. Leiner developed a commercial blood pH sensor in which the pH-sensitive layer was obtained by reacting aminoethylcellulose fibers with 1-hydroxy-pyrene-3. The effect of pH on the change in electronic spectrum of polyaniline polymers was explained by the different degree of protonation of the imine nitrogen atoms in the polymer chain.0 and 3. with Nernstian slopes of 49. Solid contact electrodes showed linear selectivity to hydrogen ion in the pH ranges 4. octyl.1. and subsequently.N0dialkylbenzylethylenediamine (alkyl ¼ butyl.7 mV pH21 at 20 ^ 0.N0. The senso was derived from polymer-modified electrode obtained from electrochemical polymerization of aniline in dry acetonitrile containing 0.The solution pH could be determined by monitoring either absorption at a fixed wavelength or the maximum absorption wavelength of the film.2 s. hexyl. urea sensor. Pandey and Singh reported the pH sensing function of polymermodified electrode (a novel pH sensor) in both aqueous and non-aqueous mediums. respectively.7. Stability was also improved.5 and 53.N0-didecylbenzylethylenediamine showed the best selectivity and reproducibility of e.f. followed by attachment of the sensitive layer to the surface of a polyester foil. hexyl.8-trisulfochloride. and embedding the composite in an ionpermeable polyurethane (PU) based hydrogel material. Later. decyl). octyl.m. Pandey developed a solid state poly(3cyclohexyl)thiophene treated electrode as pH sensor.

plasticizer (. Silicone rubber-based membrane containing a modified calyx (4) arene was used for detection of Naþ in body fluids.0–2 wt%). 21. which in turn is transmitted as an electronic signal for display. functioning by host–guest interactions. polymers have been utilized to entrap the sensing elements. Ion sensors find wide application in medical. and ionic additives (.65 wt%). charged carriers and neutral carriers—doped in polymeric membranes. Teixeira studied the potentiometric response of a l-MnO2-based graphite-epoxy electrode for determination of lithium ions. The response time of the proposed electrode was lower than 30 s and its lifetime greater than 6 months. Potentiometric ISEs for copper ions have been prepared by screen-printing. some ionic exchange/interaction occurs. The chemical structures of some ionophores are shown in Table 5. When such systems come in contact with analytes to be sensed. are used as neutral carriers. such as antibiotics. environmental and industrial analysis. Further. In ion-selective sensors. The response and selectivity of an ion-selective device depend on the composition of the membrane.1–5 wt%). which are entrapped in polymer films for the detections of different ions.3. they discussed the possibility of miniaturization of the electrode by putting the composite inside a capillary tube. In addition to organic salts. the selective membrane across which an activity-dependent potential difference develops.3. Generally. Table 6 describes various sensor components. 15% graphite and 50% epoxy resin. with the screen-printing paste composed of methyl and butyl methacrylate copolymer. Ion selective electrodes (ISE) are suitable for determination of some specific ions in a solution in the presence of other ions. and their sensing characteristics.copper sulphides and graphite (Table 2). ion carrier (. Polyvinyl chloride (PVC) is the most commonly used as polymeric matrix. . The best potentiometric response was obtained for an electrode composition of 35% l-MnO2. or as a matrix for the conducting system. The quantitative analysis of ions in solutions by ISEs is a widely used analytical method. with which all chemists are familiar. Commercial potentiometric devices of varying selectivity for both cations and anions are common in most laboratories. The polymeric membrane-based device consists of an internal electrode and reference solution. Such an electrode requires a conditioning time in a Liþ solution prior to the measurement of its equilibrium potential. A typical membrane composition for the usual cations and anions consists of polymer (33 wt%). Silicone rubber and a PU/PVC copolymer were reported to be good screen-printable ion selective membranes for sensing arrays. ion sensors have been developed taking the polymer as theconductive system/component. ION SELECTIVE SENSORS There is a vast literature covering the theory and design of ion selective devices. and an external reference electrode to which the membrane potential is compared in the potential measurement.Ion-sensitive chemical transduction is based on ion selectivity conveyed by ionophore—ion-exchange agents. several macrocyclics. They are also used in measuring the hardness of water. crown ethers and calixerenes.

these polymers are compatible with the photolithographic fabrication techniques in microelectronics. The authors claimed their results to be well correlated with those obtained by standard methods. such as the gate surfaces of ion selective field effect transistors (ISFETs). .1. Membranes sensitive to calcium ions were optimized according to the type of plasticizer and the polymer/plasticizer ratio. TDMACl) or anionic (potassium tetraki (4chlorophenyl) borate. dioctyl phenylphosphonate (DOPP) and cationic (tridodecylmethylammonium chloride. 22. A new Ca2þ-selective polyaniline (PANI)-based membrane has been developed for all-solid-state sensor applications. KTpClPB) as lipophilic additives. it is possible that the first layer of epoxy resin on the electrode surface absorb the Liþ solution. and provide better adhesion to silanized semiconductor surfaces. PANI is used as the membrane matrix. The membrane is made of electrically conducting PANI containing bis [4-(1. and thus time is necessary to attain equilibrium. Artigas described the fabrication of a calcium ion-sensitive electrochemical sensor.Since the epoxy resin absorbs significant amount of water. and the resulting sensitivities were quasi-Nernstian (26–27 mV/dec) in a range of 5 £ 1026–8 £ 1022 M. Such sensors are stable for more than 8 months. These sensors were used to measure calcium activity in water samples extracted from agricultural soils. which transforms the ionic response to an electronic signal. This sensor device consists of a photocurable polymer membrane based on aliphatic diacrylated polyurethane instead of PVC.3.3tetramethylbutyl) phenyl] phosphoric acid (DTMBP-PO4H). Moreover.

.23.

4 ALCOHOL SENSORS. Polypyrrole incorporated with dodecyl benzene sulfonic acid (DBSA) and ammonium persulfate (APS) showed a linear change in resistance when exposed to methanol vapor in the range 87–5000 ppm.60%) for short chain alcohols. Ukeda presented a new approach in the coimmobilization of alcohol dehydrogenase and nicotinamide adenine dinucleotide (NAD) using acetylated cellulose membrane on glutaraldehyde activated Sepharose and its application to the enzymatic analysis of ethanol.3 dimethyl aniline). Polyaniline doped with camphor sulphonic acid (CSA) also showed a good response for alcohol vapors. methanol.3. but none of them are suitable for long chain alcohols. Polyaniline and its substituted derivatives (XI) such as poly(o-toluidine).5 dimethyl aniline) and poly(diphenyl amine) were found by Athawale and Kulkarni to be sensitive to various alcohols such as methanol. poly(N-ethyl aniline). at concentrations up to 3000 ppm. ethanol. ethanol and propanol. The polypyrrole was also studied as a sensing layer for alcohols. viz. poly(oanisidine). butanol and heptanol vapors (Table 2). poly(N-methyl aniline). The response is rapid and reversible at room temperature. poly(2. such as methanol. Bartlett also detected methanol vapor by the change in resistance of a polypyrrole film. All the polymers showed measurable responses (sensitivity . The determination of alcohol is important in industrial and clinical analyses. Since conducting polymers gained popularity as competent sensor material for organic vapors. These reports discussed the sensing mechanism on the basis of the crystallinity of polyaniline. . The change in resistance of the polymers on exposure to different alcohol vapors was attributed to their chemical structure. 24. an opposite trend in the change of resistance was observed with butanol and heptanol vapors. propanol. They explained the results based on the vapor-induced change in the crystallinity of the polymer. All the polymers respond to the saturated alcohol vapors by undergoing a change in resistance. chain length and dielectric nature. poly(2. ethanol and propanol. few reports are available describing the use of polyaniline as a sensor for alcohol vapors. While the resistance decreased in presence of small chain alcohols. as well as in biochemical applications.

this limitation was overcome by adjusting the pH of the sample solution. The sensor layers respond to aqueous ethanol with a color change from green to blue with increasing ethanol content. These layers also exhibit strong sensitivity to acetic acid.1% v/v. 25.They investigated the effects of methanol concentration. However. . with a linear calibration function up to 20% v/v ethanol and a detection limit of 0. which affects effective measurements on beverages. Blum prepared an alcohol sensor in which two lipophilic derivatives of Reichardt’s phenolbetaine were dissolved in thin layers of plasticized poly(ethylene vinylacetate) copolymer coated with micro porous white PTFE in order to facilitate reflectance (transflectance) measurements. Mayes reported a liquid phase alcohol sensor based on a reflection hologram distributed within a poly(hydroxyethyl methacrylate) (IX) film as a means to measure alcohol induced thickness changes. operating temperature and film thickness on the response. The highest signal changes are observed at a wavelength of 750 nm.

While some polymers are intrinsically responsible for a sensor function.4. The majority of sensor devices utilize many polymers with definite roles. either in the sensing mechanism or through immobilizing the species responsible for sensing of the analyte component.CONCLUSION. The collaboration of polymer scientists and technologists in sensor research will accelerate the availability of durable and cheap artificial sensor devices for human consumption. . multiple sensor arrays. 26. other polymers are made to augment the sensing operation through modification of the polymer by functionalization. This has become possible only because polymers may be tailored for particular properties. are easily processed. and may be selected to be inert in the environment containing the analyte. Polymeric thin film deposition technology and the design of more active and sensorspecific polymers will lead to successful miniature.

Anal Chem 1988. [3] Danzer K.May 2004.ELSEVIER . Than E.Textbook of chemical sensors(Introduction for scientist and engineers) :ISBN978-3-540-45742-8. Sarmishtha Majumdar Polymers in sensor applications. Jorg Reinbold. KGaA. Andreas Katerkamp. Akademische Verlagsgesellschaft Geest & Portig K. Weinhei. . Bezegh A. Reinhard Renneberg. REFERENCES : [1] Janata J.Chemical and Biochemical Sensors 2012. Molch D (1976) Analytik – systematischer Überblick. [2] Peter Gründler.60: 62R–74R.5. Bernd Ross. [6] Basudam Adhikari. Wiley-VCH Verlag GmbH & Co. Bernd Grundig. [5] Karl Cammann. Leipzig [4] IUPAC (1991) Pure Appl Chem 63:1247–1250. 27.-G. Chemical sensors.