Graduation Year

2011

Document Type

Dissertation

Degree

Ph.D.

Degree Granting Department

Chemistry

Major Professor

Julie P. Harmon, Ph.D.

Committee Member

Xiao Li, Ph.D

Committee Member

Norma A. Alcantar, Ph.D.

Committee Member

Jianfeng Cai, Ph.D.

Keywords

elatomer, hardness testing, microstructure, tensile testing, thermal analysis

Abstract

Synthesis of high molar mass polycarbonate polyurethanes using a novel polyol is described. The resulting elastomers demonstrate excellent mechanical properties as well as the capability to re-heal after rupture without the addition of additives or imbedded healing agents. The self-healing functionality is shown to greatly improve with the addition of up to 1% single and multi-walled carbon nanotubes. The interface of the carbon nanotubes and self-healing polymer are probed using Raman techniques and provide an insight into how the self-healing actions are improved with the addition of carbon nanotubes.

Synthesis of polycarbonate polyurethanes and carbon nanotube composites using a novel casting method is described and compared to the more traditional solution casting method. The dispersion of the carbon nanotubes is evaluated as well as the effect of effective dispersion on the composites through tensile testing, rheometry and hardness testing. Although complete agglomeration avoidance could not be achieved, significant size decrease was observed. Over 200% improvement in tensile strength is shown with conventional solution casting method which is further improved by the described novel solution casting method.

Contact angle measurements on our novel self-healing poly (carbonate urethane) and CNTs composites show that surface energies are drastically changed when CNTs are used. The most revealing finding is that f×svp increases in CNT composite materials from ~30% of the surface energy on average for the samples tested, to ~80%. We have shown that surface free energies increase most likely as a result of exposing hydrogen bonding sites typically found within the bulk in polyurethanes. Our polyurethane differs from traditional polyurethanes in that it has both novel soft segments made from a novel polycarbonate polyol discussed in chapter 2 and relatively soft ¡§hard¡¦ segments resulting from the use of H12MDI, all leading to increased ability to hydrogen bond within the material. The availability of the hydrogen bonding sites is demonstrated by FTIR absorbance bands for associated and unassociated hydrogen bonding sites, which do not seem to be accessible to a large until the PCPU¡¦s surface is disrupted. Once disrupted, the exposed hydrogen bonding sites are able to bond with other bonding sites of adjacent ruptured surfaces. This would explain why our material is non-blocking, e.g. won¡¦t stick to itself, until the surface is ruptured. It would also explain why any two ruptured surfaces of our material will reheal, even if they were not attached previously.

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