الفهرس 
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Abstract
The thesis aims to synthesize and characterize poly (meta phenylenediamine-co- aniline) P(mPD-co-ANI) and poly (meta phenylenediamine-co- anthranilic acid) P(mPD-co-ANTH) and their Ni, Cu, and Mn doped polymers. The copper doped poly (meta phenylenediamine-co- aniline) (Cu P(mPD-co-ANI)) and manganese doped poly (meta phenylenediamine-co-anthranilic acid) (Mn P(mPD-co-ANTH)) were used as the molecular precursors of CuO and MnO nanoparticles. The effect of doping metal ions on spectral, optical, refractive index, solubility and thermal properties of the synthesized polymers has been discussed.
The thesis contains three main chapters concerned with poly (meta phenylenediamine-co-aniline) P(mPD-co-ANI) and poly (meta phenylenediamine-co- anthranilic acid) P(mPD-co-ANTH).
The first chapter includes an introduction and a literature survey on pure and doped polyaniline derivatives with some transition metals. The effect of doping on the physical and spectral properties of the polymers was reported. The use of the doped polymers as precursors for the preparation of nanosized metal oxides (especially copper oxide and manganese oxide) and the importance of these oxides were also, presented.
The second chapter is concerned with the experimental work. It involves the methods of preparation of P(mPD-co-ANI) and P(mPD-co-ANTH) in their pure and doped forms in the presence of NiCl2, CuCl2, MnCl2 and ammonium persulphate (APS) as initiator. The synthesis of copper oxide and manganese oxide nanoparticles from (Cu P(mPD-co-ANI)) and (Mn P(mPD-co-ANTH)) respectively, was described. Some of the physical properties as solubility, density, and refractive index of the polymers under study were measured. Finally, the working procedures and apparatus (IR, UV-Vis., TGA, XRD, HR-TEM, Density and Refractive index) were described.
The third chapter of the thesis deals with the results and discussion, which includes the data obtained and the proposed polymeric structure of the pure and doped polymers. The effect of inclusion NiCl2, CuCl2 and MnCl2 on the spectral, thermal and physical properties of poly (meta phenylenediamine-co-aniline) and poly (meta phenylenediamine-co-anthranilic acid) were studied. This chapter is subdivided into two polymeric series of poly (meta phenylenediamine-co-aniline) and poly (meta phenylenediamine-co-anthranilic acid). 1
IR spectra of polymers under study indicated the bands characteristic to C=N and C=C vibrations of benzoid and quinoid moieties. IR spectra of the doped polymers indicated that the inclusion of NiCl2, CuCl2 and MnCl2 into the polymers matrix led to disturbance in the electron clouds of some functional groups of the pure copolymer.
The disturbance appears in the form of change the intensities and/or shifts in the bands of these groups. The degree of disturbance depends on the interaction between the metal ions and the azomethine nitrogen. The change in the intensity of the azomethine band suggests the participation of this group in coordination to the metal ions. The bands due to the carboxyl group (COOH) in doped P(mPD-co-ANTH) polymers changed from that of pure polymer which indicates the coordination of this group to the metal ions.
Thermal analysis measurements (TGA) have been carried out to shed more light on the effect of doping of the metal ions on the thermal stability of the polymers under study. Doping the metal ions increases thermal stability of the polymers under study.
The UV spectra indicated that Ni and Cu doped polymers exist in octahedral geometry.
The optical band gap Eg was measured from the absorption spectra. The optical band gap of the investigated doped polymers is wider than that of the free polymers. The observed values of optical band gaps revealed semi-conductivity of the doped polymers.
Cu P(mPD-co-ANI) was used as a precursor of CuO nanoparticles by its thermal decomposition at 800 ◦C. XRD analysis for the sample that produced from the thermal decomposition of Cu P(mPD-co-ANI) indicated the formation of the monoclinc crystal structures characteristic to CuO with lattice constants, a = 4.692 Å, b = 3.428 Å, and c = 5.136 Å. The particle size of the obtained oxide was calculated from the major diffraction peak by using Debye-Scherrer formula. The particle sizes were found to be around 57 nm. TEM micrographs of CuO nanoparticles were used to determine the morphology and the particle size of the obtained nanoparticles. The particle size values were found to be in good agreement with that obtained from XRD results.
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Mn P(mPD-co-ANTH) was used as a precursor of MnO nanoparticles by its thermal decomposition at 800 ◦C indicated the formation of the cubic crystal structures characteristic to MnO with lattice constant, a = 4.44 Å. The particle size of the obtained oxide was calculated from the major diffraction peak by using Debye-Scherrer formula. The particle sizes were found to be around 71 nm. TEM micrographs of MnO nanoparticles were used to determine the morphology and the particle size of the obtained nanoparticles. The particle size values were found to be in good agreement with that obtained from XRD results.
The obtained data for the solubility showed that the solubility of the polymers under study increases as the mole fraction of both ethanol and DMF increases. This indicates that the solvation process of the polymers under study increases as the mole fraction of both ethanol and DMF increases. On the other hand the results showed that the density of the solutions of polymers under study is slightly increases as the mole fraction of both ethanol and DMF increases. Also, it was noted that the solvation process of the polymers under study in DMF-water is higher than that in ethanol-water mixed solvent. This may be related to the nature of the chemical structure of DMF and ethanol which affects on the physical properties of the solvent. The higher dielectric constant and dipole moment of DMF compared with ethanol will effect on the nature of the solute-solvent interaction and then on the solvation process.
The refractive index values of the polymer solutions showed slight change compared with the pure solvents. This indicates low solvation process with respect to this property.
from studying the effect of solvent (DMF) on the UV-Vis., spectra of the polymers under study, one can note that, there is an increase in the wave length in transferring from 20% to 100% DMF-water mixtures, i.e. a blue shift takes place. Also, the results showed that there is a high change in the absorbance in transferring from 20% to 100% DMF-water mixtures. An increase in the absorption of ultraviolet light by a solution is called a hyperchromic effect. This effect may be due to the disruption of the hydrogen bonds between the polymer chains as a result of the interaction with DMF than that with water solvent molecules.