Thesis (PhD (Chemistry and Polymer Science))--University of Stellenbosch, 2009. / Due to numerous accidents involving munitions, recent interest has focused on the development and use of insensitive munitions (IM). Polymeric materials are used in insensitive munitions as binders or plasticizers. Most of the polymeric binders used are based on polycondensation reaction via using urethane linkages. The main aim of this study was the synthesis and characterization of selected energetic thermoplastic elastomers binder based on utilizing controlled free radical polymerization. This was achieved by using hydroxyl terminated poly (epichlorohydrin) (PECH-diol) and hydroxyl terminated glycidyl azide polymer (GAP-diol) as starting materials, and the subsequent synthesis of different macroinitiators. These macro-initiators were used to polymerize methyl methacrylate (MMA) to obtain thermoplastic elastomers. PECH-diol was prepared by cationic ring-opening polymerization (CROP) based on using borontrifluoride etherate (BF3-etherate) as catalyst and a low molecular weight diol as initiator. GAP-diol was synthesized by the reaction of PECH-diol with sodium azide in organic solvent.. Poly(epichlorohydrin-methyl methacrylate) (PECH-PMMA) and poly(glycidyl azidemethyl methacrylate) (GAP-PMMA) block copolymers were prepared by free radical polymerization of MMA monomer in presence of PECH and GAP macro-azoinitiator (MAI). The MAIs were prepared by the polycondensation reaction of hydroxyl terminated groups of elastomer with 4,4' azobis (4-cyanopentanoyl chloride) (ACPC). The phase behavior of blends of amorphous PMMA/PECH-diol and PMMA/GAP-diol was also investigated. Poly(epichlorohydrin-methyl methacrylate) (PECH-PMMA) and poly(glycidyl azidemethyl methacrylate) (GAP-PMMA) graft copolymers were synthesized by photopolymerization of MMA in presence of PECH and GAP with pendant N,Ndiethyldithiocarbamate groups as macro-photoiniferters. . Photopolymerization of MMA proceeded in a controlled fashion. A macro RAFT agent, based on the reaction of PECH with pendent dithiobenzoate was prepared. The macro-RAFT agent was used in the controlled thermal bulk polymerization of methyl methacrylate. Finally, living/controlled radical polymerization of MMA with four different photoiniferters, namely benzyl diethyl dithiocarbamate (BDC), 2-(N,N-diethyldithiocarbamyl) propionic acid (PDC), 2-(N,Ndiethyldithiocarbamyl) isobutyric acid (DTCA), and diethyl dithiocarbamateepichlorohydrin was achieved.

Title from PDF of title page (University of Missouri--Columbia, viewed on Feb 18, 2010). The entire thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file; a non-technical public abstract appears in the public.pdf file. Thesis advisor: Dr. Stephen Lombardo. Includes bibliographical references.

Thesis (M.S.)--University of Nevada, Reno, 2007. / "May, 2007." Includes bibliographical references (leaves 45-46). Online version available on the World Wide Web.

Dissertation (Ph.D.)--Auburn University, 2005. / Abstract. Includes bibliographic references (p.82-87).

Thesis (Ph. D.)--University of Missouri-Columbia, 2007. / The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file (viewed on October 16, 2007) Vita. Includes bibliographical references.

The objectives of this work are to discuss multiscale models that are used to characterize the constitutive relations of the granular composite materials with dual functions. This is accomplished by the use of ab initio methods to obtain the constitutive relations of the structural energetic materials without conducting tests. First, it is necessary to study the quantum many body problem to quantitatively determine the internal energy of the material when subjected to different strain conditions. It is impossible to obtain an exact solution to the quantum many body problem that is modeled by the Schrödinger's equations with the current technology. It is possible to solve these equations approximately by the density functional theory which yields only energies at absolute 0ºK. Thus it becomes necessary to add both the lattice thermal contributions and electron thermal contribution. Then, resulting energy is used to bridge to the continuum level and obtain the constitutive equations. This is the procedure that is used in this work. The issues of the constitutive equations form the focus of this thesis. More specifically, the scope of the thesis is further restricted to analyze the constitutive equations of specific mixtures of nickel, aluminum with PTFE or Teflon as the binder. It is to be noted that the equations of state forms only a part of the complete constitutive relationships. This thesis presents solutions to the following problems: (1) Determination of the thermodynamically complete equation of state of the binder and the energetic material PTFE or Teflon, from ab initio methods based on the density functional theory. (2) Determination of the equations of state of the granular composite or the mixture of nickel, aluminum and PTFE from ab initio methods. (3) Determination of the complete constitutive equation of aluminum, from ab initio methods, under conditions of finite deformations, with principle of objectivity, material symmetry conditions and polyconvexity of the strain energy. All results are compared to test results whenever they are available.

Thesis (Ph. D.)--Florida State University, 2005. / Advisor: Joseph B. Schlenoff, Florida State University, College of Arts and Sciences, Dept. of Chemistry and Biochemistry. Title and description from dissertation home page (viewed Feb. 1, 2006). Document formatted into pages; contains xvii, 167 pages. Includes bibliographical references.