A Report On Size Effects in Nanomaterial Properties by Akshat Tyagi

Under the guidance of

Dr. SrinivasA Rao Nelamarri Assistant professor Department of Physics

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MALAVIYA NATIONAL INSTITUTE OF TECHNOLOGY
(Deemed University, Jaipur, RajasthaN)
J.L.N. Road, Jaipur-302017

Acknowledgement
Many people have contributed to the success of this. Although a single sentence hardly suffices, I would like to thank Almighty God for blessing us with His grace. I extend my sincere and heartfelt thanks to Dr. Srinivasa Rao Nelamarri, Department of Physics, for providing us the right ambience for carrying out this work. I am profoundly indebted to my seminar guide, Dr.Srinivasa Rao Nelamarri for innumerable acts of timely advice, encouragement and I sincerely express my gratitude to him. Last but not the least, I thank all others, and especially my classmates who in one way or another helped me in the successful completion of this work.

Akshat Tyagi 2009uec382

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electrical. properties of nanostructured materials can be tuned considerably simply by adjusting the size. mechanical and others are size dependent. optical.Abstract The question we address in this report is the question how does size matter? We discuss as to how the properties of the nanomaterials are different from the conventional bulk materials and to co relate the fact that the properties of a material can be size dependent. Many properties such as physical. 3|Page . chemical. shape or extent of agglomeration. In other words.

Table of contents Contents Acknowledgement Abstract 1.2 Aim of Report 2.1 Introduction 1. Magnetic Properties 7. Melting points and lattice constants 3. Electrical Properties 6. Chemical Properties 8. Bibliography Page No. 01 02 05 05 06 07 09 12 16 18 22 25 4|Page . Optical Properties 5. Mechanical Properties 4. Introduction 1.

and optics. The properties that we associate with these materials are averaged properties.1. many properties of materials change. At the macro. the sizes of the objects under study range from millimeters to kilometers. When measurements are made in the micrometer or nanometer range. Introduction 1. the resistivity and magnetization in electricity and magnetism. electricity and magnetism.or large-scale range ordinarily studied in traditional fields of physics such as mechanics. and ferromagnetic properties. Some physical properties of nanomaterials are related to different origins: (i) large fraction of surface atoms (surface to volume ratio increases) (ii) large surface energy (iii) spatial confinement (iv) reduced imperfections 5|Page . and the dielectric constant in optics.1 Introduction Many properties of solids depend on the size range over which they are measured. ferroelectric. Microscopic details become averaged when investigating bulk materials. such as the density and elastic moduli in mechanics. such as mechanical.

The enhancement in mechanical strength is simply due to the reduced probability of defects. However. (2) Mechanical properties of nanomaterials may reach the theoretical strength. This has important implications for the design of catalytic agents and effect on reactivity and reaction rates. electrical conductivity of nanomaterials could also be enhanced appreciably.(v) dominance of electromagnetic forces The following are just a few examples: (1) Nanomaterials may have a significantly lower melting point or phase transition temperature and appreciably reduced lattice constants. due to an increased band gap. the optical absorption peak of a semiconductor nanoparticle shifts to a short wavelength. The color of metallic nanoparticles may change with their sizes due to surface plasmon resonance. in polymeric fibrils. Metallic nanoparticles can be used as very active 6|Page . (4) Electrical conductivity decreases with a reduced dimension due to increased surface scattering. Ferromagnetism of bulk materials disappears and transfers to superparamagnetism in the nanometer scale due to the huge surface energy. due to the better ordering in microstructure. which are one or two orders of magnitude higher than that of single crystals in the bulk form. e. (6) Chemical properties : Since the electronic structure of nanoparticles depends on the size of the particle. due to a huge fraction of surface atoms in the total amount of atoms.g. For example. (5) Magnetic properties of nanostructured materials are distinctly different from that of bulk materials. the ability of the cluster to react with other species should depend on cluster size. (3) Optical properties of nanomaterials can be significantly different from bulk crystals.

semiconductors and molecular crystals are all found to have lower melting temperatures as compared with their bulk forms. such as evaporation rate (iii) the sudden change in the particle shape. inert gases. The lowering of the melting points is in general explained by the fact that the surface energy increases with a decreasing size. It is possible to make an experimental determination of the size dependence of melting temperature of nanoparticles.2 Aim of Report The aim of the report is to find the effect of size on the properties of nanomaterials. 1. Three different criteria have been explored for this determination: (i) the disappearance of the state of order in the solid (ii) the sharp variation of some physical properties. 7|Page . 2. Melting points and lattice constants Nanoparticles of metals. The decrease in the phase transition temperature can be attributed to the changes in the ratio of surface energy to volume energy as a function of particle size. Chemical sensors from nanoparticles and nanowires enhanced the sensitivity and sensor selectivity.catalysts. when the particle size decreases below 100 nm.

It is further noticed that the CdS nanoparticles with surface modification demonstrate less reduction in lattice constant than that of bare nanoparticles. 8|Page .∆θ = 2 To σ/ρLr ∆θ = Deviation of melting point from the bulk value To = Bulk melting point σ = Surface tension coefficient for a liquid-solid interface ρ = Particle density r = Particle radius L = Latent heat of fusion Lowering of the melting point is proportional to 1/r Figure below shows that the lattice constants of nanoparticles decrease linearly with an increasing reciprocal particle radius.

imperfections in crystals are highly energetic and should be eliminated from the perfect crystal structures. In addition. micro-twins. Thermodynamically. Mechanical properties The mechanical properties of materials increase with a decreasing size. etc. the less is the probability of finding in it any imperfections such as dislocations. impurity precipitates. some imperfections in bulk materials. The smaller the cross-section of a whisker or nanowires. Small size makes such elimination of imperfections possible. Such 9|Page . Two possible mechanisms have been proposed to explain the enhanced strength of nanowires or nanorods (in reality with diameters less than 10 microns). One is to ascribe the increase of strength to the high internal perfection of the nanowires or whiskers.3. such as dislocations are often created to accommodate stresses generated in the synthesis and processing of bulk materials due to temperature gradient and other inhomogeneities.

Young’s modulus is the factor relating stress and strain. near-perfect elastoelasticity was observed in pure nanocrystalline copper. and insulators. particularly in nanomaterials. semiconductors. less than 5 nm. Another mechanism is the perfection of the side faces of whiskers or nanowires.stresses are unlikely to exist in small structures. Nanostructured materials may have different elastoplasticity from that of large-grained bulk materials. For example. In general.18 shows a typical dependence of strength on the diameter of a sodium chloride whisker. and similar dependences are found in metals. 10 | P a g e . The intrinsic elastic modulus of a nanostructured material is essentially the same as that of the bulk material having micrometer-sized grains until the grain size becomes very small. Figure 8. It is particularly true when the materials are made through a bottom-up approach. prepared by means of powder metallurgy. smaller structures have less surface defects.

8 is a plot of the ratio of Young’s modulus E in nanograined iron. blocking dislocation movement. to its value in conventional grain-sized iron Eo. 11 | P a g e . as a function of grain size. Figure 6. The larger the value of Young’s modulus. the less elastic the material. The yield strength of a conventional grain-sized material is related to the grain size by the Hall-Petch equation The reason for the increase in yield strength with smaller grain size is that materials having smaller grains have more grain boundaries.It is the slope of the stress-strain curve in the linear region.

4. Optical properties 12 | P a g e .

and they shift to 13 | P a g e . One can see that the lowest energy absorption region.Figure 4. The higher energy peaks are associated with the exciton. Notice also that the intensity of the absorption increases as the particle size is reduced. Since the absorption edge is due to the band gap. this means that the band gap increases as particle size decreases. is shifted to higher energy as the particle size decreases.20 shows the optical absorption spectra of a CdSe nanoparticle at two different sizes measured at 10 K. referred to as the absorption edge.

These effects are a result of the confinement of the exciton. and the separation between the energy levels changes 14 | P a g e . the hole and the electron are forced closer together.higher energies with the decrease in particle size. Essentially. as the particle size is reduced.

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and widening and discrete of band gap 4. structural defects and dislocations. The enhancement was explained by the ordered arrangement of the polymer chains. which results in increased contribution of intramolecular conduction and reduced contribution of intermolecular conduction. would affect the electrical conductivity of nanostructures and nanomaterials. Quantized conduction including ballistic conduction 3. Since intermolecular conduction is far smaller than intramolecular conduction.5. ordered arrangement of polymers with polymer chains aligned parallel to the conduction direction would result in an increased electrical conduction. Coulomb charging and tunneling. Within nanometer fibris. Surface scattering 2.ls2 A drastic increase in electrical 16 | P a g e . EIectrical conductivity The mechanisms responsible for change in electrical conductivity can be generally grouped into four categories: 1. polymer fibers demonstrated an enhanced electrical conductivity. Change of microstructures. increased perfection. Effect of microstructure Electrical conductivity may change due to the formation of ordered microstructure. In addition. Figure 8.32 shows the electrical conductivity of polyheterocyclic fibris as a function of diameter. when the size is reduced to a nanometer scale. such as reduced impurity. For example. polymers are aligned parallel to the axis of the fibris.

conductivity with a decreasing diameter was found at diameters less than 500 nm. Also at small dimensions when the energy gaps are quantized. 17 | P a g e . Smaller the diameter. A lower synthesis temperature also favors a better alignment and thus a higher electrical conductivity.This explains why some metals become semiconductors as their size is decreased. the better alignment of polymer is expected. Quantum confinement causes the energy of the band gap to increase. the band overlap present in metals disappears and is actually transformed into a band gap.

Magnetic Properties In a polycrystalline ferroelectric. A reduction in particle size results in a high temperature crystal structure stable at low temperatures. or the ferroelectric-paraelectric transition temperature decreases with a reduced particle size. However.6. the Curie temperature. Ferromagnetic particles become unstable when the particle size reduces below a certain size. the ferroelectric properties may disappear when the particles are smaller than a certain size. When the Curie temperature drops below room temperature. nanometer sized ferro18 | P a g e . ferromagnetics become paramagnetics. and such a decrease becomes much more profound when the size is smaller than 1 micrometer. Dielectric constant or relative permittivity of ferroelectrics would increase with a decreasing grain size. ferroelectrics lose its ferroelectricity at room temperature. Such a relation could be understood considering the phase transition temperature reduces with the particle size. Consequently. since the surface energy provides a sufficient energy for domains to spontaneously switch polarization directions. As a result.

by capping the nanoparticles. as is also the case for bare Au nanoparticles. gold nanoparticles become ferromagnetic when they are capped with appropriate molecules: the charge localized at the particle surface gives rise to ferromagnetic-like behavior. More surprisingly. This observation suggested that modification of the d band structure by chemical bonding can induce ferromagnetic like character in metallic clusters. Surface atoms are not only different to bulk atoms. One can obtain magnetic nanoparticles of Pd. The large spin-orbit coupling of these noble metals can yield to a large anisotropy and therefore exhibit high ordering temperatures. Bulk gold and Pt are non-magnetic. For nanoparticles with sizes below 2 nm the localized carriers are in the 5d band. Bulk Au has an extremely low density of states and becomes diamagnetic. In the case of Pt and Pd. Surface and the core of Au nanoparticles with 2 nm in diameter show ferromagnetic and paramagnetic character. that is. respectively. it should be possible that non-ferromagnetic bulk materials exhibit ferromagnetic-like behavior when prepared in nano range. Pt and the surprising case of Au (that is diamagnetic in bulk) from non-magnetic bulk materials. but at the nano size they are magnetic. permanent magnetism was observed up to room temperature for thiol-capped Au nanoparticles.magnetic turned to paramagnetic behaves differently from the conventional paramagnetic and is referred to as superparamagnetics. 19 | P a g e . Actually. but they can also be modified by interaction with other chemical species. However. This phenomenon opens the possibility to modify the physical properties of the nanoparticles by capping them with appropriate molecules. the ferromagnetism arises from the structural changes associated with size effects.

so they repeat their magnetization curve many times a second. Such magnets are called “hard magnets. 20 | P a g e . and the widest possible hysteresis loop is desirable. causing a loss of efficiency and a rise in the temperature of the magnet.” High-saturation magnetizations are also needed in permanent magnets. which has no hysteresis at any temperature. in the case of permanent magnets used as a part of high-field systems. • A magnetic material with grain-sized single domain magnetic moments. large coercive fields are required. is said to be super-paramagnetic.” On the other hand. Magnets used in transformers and rotating electrical machinery are subjected to rapidly alternating AC magnetic fields.The diverse applications of magnets require the magnetization curve to have different properties. • Such magnets are called “soft magnetic materials. • Nanostructuring of bulk magnetic materials can be used to design the magnetization curve.

at which the magnetization saturates. • Thus. decreasing the particle size of a granular magnetic material can considerably improve the quality of magnets fabricated from it. • the magnetization increases significantly below a grain size of 20 nm. 21 | P a g e .• The size of magnetic nanoparticles has also been shown to influence the value M.

and 20) have disappeared. The Al13 and Al23. 19. peaks have increased substantially. Chemical Properties There is experimental evidence for the effect of size on the reactivity of nanoparticles. The results show that two peaks have increased substantially and certain peaks (12. Figure 4.7. The top figure is the mass spectrum of the aluminum particles before the oxygen is introduced. The bottom figure shows the spectrum after oxygen enters the chamber.13 shows the results of studies of the reaction of oxygen with aluminum particles. 14. and peaks from Al15 to Al22 have decreased. 22 | P a g e .

Nanostructured materials have some advantages: .As crystal size gets smaller.Huge surface area. the number of edges and corner sites goes up significantly .These data provide clear evidence for the dependence of the reactivity of aluminum clusters on the number of atoms in the cluster.14 plots the reaction rate of iron with hydrogen as a function of the size of the iron nanoparticles. high proportion of atoms on the surface . 23 | P a g e . more adsorptive capacity.Enhanced intrinsic chemical activity as size gets smaller which is likely due to changes in crystal shape . also surface atoms can be distorted in their bonding patterns . anion/cation vacancies can increase.Ex: When the shape changes from cubic to polyhedral. Similar size dependences have been observed for the reactivity of other metals.Enhanced solubility. thus affecting surface energy. Figure 4. The data show that particles of certain sizes such as the one with 10 atoms and sizes greater than 18 atoms are more reactive with hydrogen than others. sintering at lower T. Nanomaterials in catalysis Surface chemistry is important in catalysis.

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