Synopsis of the proposed Ph.

D Thesis on

Dielectric and Conductivity Studies on CCTO : PVC and CCTO : PET 0-3 Connectivity Ceramic Polymer Composites
FOR THE AWARD OF

DOCTOR OF PHILOSOPHY
IN CHEMISTRY

Institute of Engineering & Technology, Mangalayatan University, Aligarh

Research Scholar

Supervisor

Ajay Pratap Singh Lecturer (Chemistry) I.E.T. Mangalayatan University, Aligarh

Dr. Shipli Saxena Lecturer (Chemistry) I.E.T. Mangalayatan University, Aligarh

Introduction
Recently CaCu3Ti4O12 (CCTO) was discovered, and it was found to possess one of the largest static dielectric constants ever measured, reaching nearly 80000 for single-crystal samples and 10000 for ceramic samples at room temperature[13]. Remarkably, the enormous static susceptibility is almost constant over a wide temperature range ( 0500 K). Moreover, measurements of the dynamic susceptibility
[3]

shows that the relative permittivity,r falls from its huge static value to a more

conventional 100 with increasing frequency, and that this crossover shows a Debye -like frequency dependence . However, the physical origins of the enormous r and the related Debye relaxation process remain mysterious. It is tempting to classify a solid exhibiting such a prodigious dielectric response as a relaxor or a ferroelectric, mounting empirical evidence tends to exclude CCTO from either category. The low-temperature static dielectric response of perovskite ferroelectrics can surpass 1000[4] rising rapidly above this value with increasing temperature and peaking near the ferroelectric phase transition temperature. However, this peak in response is generally confined to a limited temperature range around the transition, whereas that seen in CCTO appears quite temperature independent at fixed low frequency over a much wider range. Furthermore, high-resolution x-ray and neutron powder diffraction measurements on CCTO reveals a centrosymmetric crystal structure space group Im3 persisting down to 35 K, ruling out a conventional ferroelectric phase transition. The Debye-Waller factors are also found to be normal over a wide temperature range, from 35 K to beyond room temperature,
[1]

inconsistent with random local polar displacements of the magnitude

typical in ferroelectrics or their disordered paraelectric phases. Nanodomains or disorder effects, common to relaxor materials, are notably absent: neither super-structure peaks nor strong diffuse scattering are observed in diffraction experiments. Single-crystal samples were described to be mainly twinned, i.e., containing nanoscale domains [1] differing in the sign of the rotation of the TiO6 octahedra. The presence of the associated and other domain boundaries may have important consequences for the dielectric properties. The crystal structure of CCTO is body-centered cubic with four ATiO3 perovskite type formula units per primitive cell where A is either Ca or Cu. CCTO ceramics although possesses large dielectric constant the loss tangent values are quite high ~ 0.1, this limits its use as a material for capacitors in the electronic industry. It is envisaged that a composite

with an appropriate passive phase can render this material useful for this purpose. Poly Vinyl Chloride (PVC) and Poly Ethylene Teraphthalate (PET) with its universal presence and integrability with other materials can be an excellent matrices for CCTO ceramics. Injection moulding and extrusion of PVC and PET into different sizes and shapes is an industry spread all over the globe. CCTO ceramic when added into PVC / PET as a filler material in appropriate quantity along with matching interphase material can add to the functionality of PVC / PET, which otherwise are considered an electrically passive materials. We envisage a symbiotic relation between the two phases, since CCTO will render the material to be highly dielectric, while PVC /PET will act as a supporting scaffold against brittle fracture and render mechanical toughness to the composite.

Relevance of the study

As mentioned above the mechanism of the high dielectric constant exhibited by the material is of primary importance, Secondly the need for a method or process to integrate the material into microelectronic devices, and to find a way to bring down the cost and dielectric loss, makes the study all the more relevant. The high electrical resistivity of PVC and PET may bring down the dielectric loss to acceptable values. Of course there is a flurry of activities going on in the country and abroad towards the goal, yet there is lot of scope in investigation of the material and its composites, since there is lack of proper understanding of the mechanism involved. Although the literature is replete with novel synthesis of CCTO ceramics and its modified versions, not much work has been done in the direction (composites), in the manner mentioned above, as of today.

Preparation of the samples

The preparation method to be used in synthesizing the ceramic is the conventional oxide route. In this method oxides are weighed precisely according to stoichiometric ratios, i.e. Copper oxide, Calcium oxide, and Titanium oxide, and balled milled in a mill lined with rubber and containing zirconia balls of different sizes. This is to bring down the particle size of the constituent oxides. The ball milling is carried out for at least 40 hours with acetone as the dispersant. The dried ball milled powder is then sieved using a m mesh. Since the particle size of the constituent oxides play a major part in the physical properties of the ceramic as well as the composite, It is planned to double sieve the powder

before calcinations and sintering using a high temperature furnace (1200oC). It can also lead to good control on the uniformity of particle distribution leading to a sharp sintering temperature. X-ray diffractogram of the sintered powder shall yield the theoretical density. It should be seen that the sample should exhibit at least 95% of the x-ray density implying a ceramic with proper stoichiometry, lesser densities would mean an imbalance in stoichiometry. Aging of the ceramic is yet another crucial factor which characterizes a device grade ceramic/composite. Hence it is planned that the physical properties of every composition of the the composite shall be monitored at equally spaced intervals of time (i.e. after every week ). It is also planned to subject the prepared samples to temperature cycles at equal intervals to accelerate the process of aging. The sintered powder has to be then again ball milled with measured quantities of PVC and PET powder. It is expected that the PVC / PET gets distributed evenly within the ceramic powder. It is also assumed that the PVC / PET fraction will not react with the CCTO fraction. The powders has to be then made into pellets using a steel die applying pressure of about 25 tons and then heated with the pressure on, at a relatively low temperature (100 to 200oC). The PVC / PET now softens and a three dimensional matrix of PVC / PET is formed with CCTO particles distributed evenly within the polymer matrix. The volume percentage of PVC (/PET) / CCTO is varied and series of samples are made for characterization. An optimal ratio shall be elucidated in view of the subsequent analysis of the results, which follows after characterization.

Methodology
The prepared samples shall be characterized as follows.

A)

Density measurement All the composite samples shall be weighed in air and then in water to determine the specific gravity by Archimedes principal. The density of the sample shall indicate the percentage ratio of ceramic to PVC and also to an extent, the porosity of the composite.

B)

Electrical conductivity :- The conductivity studies of the composite sample is of utmost importance since that decides whether these material can be used in Electronic applications or not. It also gives the mechanism of conduction and the species of charge

carriers responsible for conduction[5]. Since in ceramics the mechanism of conduction varies with its stoichiometry and the impurities it may possess. To carry on with these studies the sample has to be first electroded by vacuum coating silver electrodes on to the flat sides after the sample after it has been lapped and polished. The current vs. voltage graphs at various temperatures shall be noted, also the current at different temperature for a constant potential difference is also determined. The apparatus to be used is a conductivity cell whose temperature can be maintained to an accuracy of

0.5oC.

Generally the current is measured using Keithley 610 C Electro meter or any higher versions available.

C)

XRD:- XRD studies of the sample are taken to ensure the formation of the crystal structure[6] and proper sintering of ceramics as well as the composite. The XRD peaks also indicate the grain size and grain size distribution of this ceramic. Here Debye Scherer formula shall be used to calculate grain size.

D)

Dielectric Studies: - The sample shall be subjected to dielectric studies. This study also known as the dielectric spectroscopy is the most important of all the studies planned[7,8,9,10]. The relative permittivity of the samples as a function of temperature at a constant frequency as well the permittivity with respect to frequency at a constant temperature shall be measured.

E)

SEM Studies:- There are conducted to find grain size distribution of the ceramic as well as to confirm the connectivity of various fractions in the sample[11, 12]. The SEM studies can also reveal the morphological parameters of the composite.

Possible Applications of the study

There can be a variety of applications for high dielectric materials, one being extra miniature capacitors, dielectric resonators etc. On integrating with microdevices one can envision ultrafast FETs, DRAMS and other devices. Due to the plasticity of PVC/PET one can also make the devices in desired shapes and sizes. CCTO ceramics and composites can be used as dielectric medium for high

capacitance application due to its good frequency & temperature independence. The composite can be configured into soft nano composites with enhanced electro mechanical response. It finds great use in bio-medical implantable applications. The present work is significant as CCTO :PVC and CCTO:PET ceramic polymer composites are materials where conflicting mechanical properties are compromised to give rise to soft, flexible, high dielectric constant and tough substance, which otherwise , can not be realized with pure phases . Therefore one can primarily, predict the use of these materials in high dielectric applications like capacitors, which can be designed in to various shapes and sizes. Considering other properties of the material like the ability to form very thin sheets, one can also envision their use in microelectronic devices as microstrip resonator antennas as well. Since the material is devoid of toxic elements like lead etc. one can gauge its environmental friendliness as compared to other similar perovskite materials and its composites. Last but not the least is its use in nano technology. Nano composites and nano devices can be fabricated with ease since the matrix of the composite is polymer, therefore one can control the fabrication of the devices like nano capacitors and integrate them with micro circuits using large scale integrating facilities. The applications mentioned above are not exhaustive, one may also come up with ideas and innovations as the research work progresses, we expect more ramifications of the study as the results of the work starts to emerge.

References [1] M.A. Subramanian, L. Dong, N. Duan, B.A. Reisner, A.W. Sleight, High Dielectric Constant in ACu3Ti4O12 andACu3Ti3FeO12 Phases. J. Solid State Chem. 151 (2000) 323.

[2]

C.C. Homes, T. Vogt, S.M. Shapiro, S. Wakimoto, A.P. Ramirez, Optical Response of HighDielectric-Constant Perovskite-Related Oxide Science 293 (2001) 673.

[3]

T.B. Adams, D.C. Sinclair, A.R. West, Giant barrier layer capacitance effects in CaCu3Ti4O12 ceramics. Adv. Mater. 14 (2002) 1321.

[4]

P. Lunkenheimer, V. Bobnar, A.V. Pronin, A.I. Ritus, A.A. Volkov, A. Loidl, Origin of apparent colossal dielectric constants. Phys. Rev. B 66 (2002) 052105

[5].

Homes, C.C., Vogt, T., Shapiro, S.M., Wakimoto, S., Subramanian, M.A. and Ramirez, A.P. (2003). Charge transfer in the high dielectric constant materials CaCu3Ti4O12 and CdCu3Ti4O12. Physical Review B, Vol. 67, 0921061-0921064.

[6].

Almeida, A.F.L., de Oliveira, R.S., Goes, J.C., Sasaki, J. M., Filho, A.G.S., Filho, J.M. and Sombra, A.S.B.(2002). Structural properties of CaCu3Ti4O12 obtained by mechanical alloying. Materials Science and Engineering B, Vol. 96, 275-283.

[7]

He, L., Neaton, J.B., Vanderbilt, D. and Cohen, M.H. (2003). Lattice dielectric response of CdCu3Ti4O12 and of CaCu3Ti4O12 from first principles. Physical Review B, Vol. 67, 01213110121034. Ramirez, A.P., Subramanian, M.A., Gardel, M.,Blumberg, G., Li, D., Vogt, T. and Shapiro, S.M.(2000). Giant dielectric constant response in a coppertitanate. Solid State Communications, Vol. 115, 217- 220.

[8]

. [9]

Almeida, A.F.L., Fechine, P.B.A., Goes, J.C., Valente, M.A., Miranda, M.A.R. and Sombra, A.S.B. (2004). Dielectric properties of BaTiO3 (BTO)- CaCu3Ti4O12 (CCTO) composite screen-printed thick films for high dielectric constant devices in the medium frequency range. Materials Science and Engineering B, Vol. 111, 113-123

. [10] Chiodelli, G., Massarotti, V., Capsoni, D., Bini, M., Azzoni, C.B., Mozzati, M.C. and Lupotto, P. (2004). Electric and dielectric properties of pure and doped CaCu3Ti4O12 perovskite materials. Solid StateCommunications, Vol. 132, 241-246.

[11]

Seunghwa Kwon, Chien-Chih Huang, M.A. Subramanian and David P. Cann Effects of cation stoichiometry on the dielectric properties of CaCu3Ti4O12 Journal of Alloys and Compounds Volume 473, Issues 1-2, 3 April 2009, Pages 433-436

[12]

Li Tao, Chen Zhenping, Su Yuling, Su Lei, Zhang Jincang, Effect of grain size and Cu-rich phase on the electric properties of CaCu3Ti4O12 ceramics. Journal of Material Science, vol. 44, n22, pp. 6149-6154 (2009)