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

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 Abstract

Present thesis reports the results of research work done on synthesis of nanoparticles of

CaCO3, CaSO4, Ca3(PO4)2 and Mg (OH) 2 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) 2

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 X-

ray 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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