Declaration

DECLARATION

I hereby declare that the matter embodied in the thesis entitled “Studies on Synthesis of Mineral Nano Filler and their Effect of Their Mechanical and Thermal Properties of Polymer” is a result of investigation carried out by me under the guidance of Prof. Satyendra Mishra at University Department of Chemical Technology, North Maharashtra University, Jalgaon, MS, India 425 001. I further declare that this work has not been submitted in part or full to any other University or Institute for the award of any other degree.

Place: Jalgaon

(Mr. Shriram S. Sonawane)

Date:

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NORTH MAHARASHTRA UNIVERSITY, JALGAON P. B. NO. 80, Umavi Nagar, Jalgaon, MS, India 425 001

Prof. Satyendra Mishra Head, University Department of Chemical Technology North Maharashtra University, Jalgaon

CERTIFICATE This is to certify that the work entitled “Studies on Synthesis of Mineral Nano Filler and their Effect of Their Mechanical and Thermal Properties of Polymer” incorporated in this thesis is a original work carried out by Mr. Shriram Shaligram Sonawane under my guidance and supervision for the award of degree of Doctor of Philosophy in chemistry. The work embodied has not been submitted in part or full to any other University or Institution for the award of any other degree. Material obtained from other sources has been duly acknowledged.

Prof. Satyendra Mishra (Research Guide)

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Acknowledgement It is my great pleasure to express deep sense of gratitude & sincere thanks to Prof. Satyendra Mishra, with whom I had privilege of completing my Ph.D dissertation. His devotion to research, teaching and dedication to the Nanotechnology petriclarly polymer Nanocomposites subject has always been moral support to me. Prof S. Mishra’s efforts to carry out something new and taking the planned work towards success shall be source of inspiration for me. I express my sincere thanks towards Prof D G Hundiwale (Director, School of Chemical Sciences), Prof U R Kapadi Ex Professor (School of Chemical Sciences), for providing instrumental facility during my research tenure. I would like to express my thanks towards faculty of UDCT for their co-operation during my research tenure. I express my thanks to non-teaching staff and technical staff of UDCT for their assistance during my research tenure. The generous help extended by Dr.Navinchandra Shimpi in the department is greatly appreciated. I express my thanks to Mr. Ujjwal Patil for his valuable support and being consistently with me during my research tenure. I especially grateful to my Parents, brother Shivaji, my Sister’s Ratna and Jyoti for their constant inspiration, who made me to reach in such a great position. Thanks are also due to the constant support of my wife for the completion of this work. Finally I express my thanks to Prof.C.M.Netkar who has been involved with me and always give boosting support during my research work.

Mr. Shriram Shaligram Sonawane Research Scholar iii

Abstract Present thesis reports the results of research work done on synthesis of nanoparticles of CaCO3, CaSO4, Ca3(PO4)2 and Mg (OH)

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in the various sizes by matrix mediated growth

technique. For synthesis of nano inorganic particles, water-soluble polymer such as polyethylene glycol (m.wt 6000) was used; variation in its molar ratio was done to reduce the nano sizes of CaCO3, CaSO4, Ca3(PO4)2 and Mg (OH).

Three different nano sizes were

synthesized. Nano sizes were confirmed using X-ray diffractomer, calculated by Scherer’s formula which are CaCO3 of (23, 17, and 11nm), nano Mg(OH)2 (24, 20, and 11 nm), nano CaSO4 (23, 17, and 11nm) and Ca3(PO4)2 . The reduction in nano size is due to vigorous stirring at molecular level and also due to increase in viscosity of the medium. The shape and sizes are also confirmed using TEM. The polyamide/ CaCO3, CaSO4, Ca3(PO4)2 and Mg (OH)

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nanocomposites were prepared via melt intercalation on twin-screw extruder. It was also tried to investigate the morphological property relationship using scanning electron microscope, and Xray diffraction. Thermal properties of these nanocomposites were studied using DSC and TGA. Nano CaCO3, CaSO4, Ca3(PO4)2 and Mg (OH) 2 was added from 1 to 4-wt % in the polyamide. Properties such as tensile strength, elongation at break, hardness, and flame retardency were studied. These results were compared with respective commercial filler filled composites. There was propounding effect observed on properties of polyamide nanocomposites due to uniform dispersion of nano particles over the commercial filler polymer. Extent of dispersion of nano particles was studied along with micro cracks generated during tensile testing using AFM and SEM. It was found that nano particle filled composites are thermally more stable compared to that of commercial fillers. The effect of nano CaSO4 on polyamide composites was also investigated. The shape of nano CaSO4 particles is needle like or fiber like, which has been confirmed by TEM. The reduction of

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nano CaSO4 leads to increment in mechanical and thermal properties of polyamide nanocomposites as compared to commercial CaSO4 polyamide composites. Substantial improvements in mechanical properties are obtained by addition of smaller amount of Mg(OH)2.

Tensile strength, young’s modulus, modulus at 300% elongation were more

pronounced as compared to commercial Mg(OH)2. The improvements in mechanical properties are due to uniform dispersion of nano particles through out the matrix.

Flame retarding

properties of Mg(OH)2. polyamide composites are found to be more effective compared to commercial Mg(OH)2. The improvement in flammability is due to the nano scale inorganic filler in the polyamide nanocomposites that promotes formation of the char layer, which acts as an excellent insulator and mass transfer barrier. This effect drastically improves the burning resistance and absorbs the heat of burning. The structural effect of CaSO4 (needle like structure) nanoparticles on polyamide nanocomposites leads to uniform transfer of heat by uniform dispersion of nanoparticles during formation of nanocomposites with melt intercalation, which agrees with theoretical prediction and shows enhancement in modulus. The effect of organically modified (OMMT) clay on polyamide nanocomposites was also studied. OMMT/polyamide nanocomposites were prepared through direct melt compounding on a conventional twin screw extruder. The polymer chains get exfoliated in between the two plates of OMMT and disperse uniformly. The mechanical testing results of the composites showed an increase in the Young’s modulus, elongation at break and tensile strength with increase in wt % loading of OMMT in polyamide,. The increases in properties were found to be more appreciable at 4 wt % loading of OMMT. 1 wt % loading of OMMT/ polyamide composites resulted in 11 % increment in elongation at break compared to virgin polymer, while 4 wt % loading of OMMT/ polyamide composite showed 13 % increment in elongation at break. Besides that, effect of

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OMMT in polyamide was found to be significant in Young’s modulus (30 %) at 4 wt % loading. Moreover, rheological data like torque, fusion time, viscosity and shear rate were also recorded on Brabender Plasticorder. The data obtained on Brabender Plasticorder were correlated with M= CS a and ô =K (ã)n , which gave power law index (n). This value indicates pseudo plastic nature of the polyamide/OMMT, since n<1. The torque of OMMT/polyamide nanocomposites decreases with increase in wt % loadings this is due to soft nature of OMMT, which acts as a lubricating agent. This improvement in mechanical properties with increase in amount of OMMT loading is evidenced from reduction in shear viscosity and torque.

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