This dissertation studies physical properties and technological applications of engineered heterogenous polymer gels. Such gels are synthesized based on modulation of gel chemical nature in space. The shape memory gels have been developed in this study by using the modulated gel technology. At room temperature, they form a straight line. As the temperature is increased, they spontaneously bend or curl into a predetermined shape such as a letter of the alphabet, a numerical number, a spiral, a square, or a fish. The shape changes are reversible. The heterogenous structures have been also obtained on the gel surface. The central idea is to cover a dehydrated gel surface with a patterned mask, then to sputter-deposit a gold film onto it. After removing the mask, a gold pattern is left on the gel surface. Periodical surface array can serve as gratings to diffract light. The grating constant can be continuously changed by the external environmental stimuli such as temperature and electric field. Several applications of gels with periodic surface arrays as sensors for measuring gel swelling ratio, internal strain under an uniaxial stress, and shear modulus have been demonstrated. The porous NIPA gels have been synthesized by suspension technique. Microstructures of newly synthesized gels are characterized by both SEM and capillary test and are related to their swelling and mechanical properties. The heterogenous porous NIPA gel shrink about 35,000 times faster than its counterpart--the homogeneous NIPA gel. Development of such fast responsive gels can result in sensors and devices applications. A new gel system with built-in anisotropy is studied. This gel system consists of interpenetrated polymer network (IPN) gels of polyacrylamide (PAAM) and N-isopropylacrylamide (NIPA). The swelling property of the anisotropy IPN gels along the pre-stressing direction is different from that along other directions, in contrast to conventional gels which swell isotropically. It is found that the ratio (L/D) of length (L) and diameter (D) of IPN samples has step-wise changes as the samples are heated from below the volume phase transition temperature to the above. A theoretical model is proposed and is in good agreement with the experimental results.

Homogeneous hydrogels made of an interpenetrating network of poly(N-isopropylacrylamide) (PNIPAm) and poly(acrylic acid) (PAAc) are synthesized by a two-step process; first making PNIPAm hydrogels and then interpenetrating acrylic acid throughout the hydrogel through polymerization. The kinetic growth of the IPN is plotted and an equation is fitted to the data. When diluted to certain concentrations in water, the hydrogels show reversible, inverse thermal gelation at about 34°C. This shows unique application to the medical field, as the transition is just below body temperature. A drug release experiment is performed using high molecular weight dyes, and a phase diagram is created through observation of the purified, concentrated gel at varying concentrations and temperatures.

The assembly of poly(N-isopropylacrylamide-co-acrylic acid) (pNIPAm-co-AAc) microgel thin films into disordered and ordered arrays was investigated. Disordered pNIPAm-co-AAc microgel arrays were assembled based on electrostatic attractions between polyanionic pNIPAm-co-AAc microgels and polycationic poly(allylamine hydrochloride) (PAH). These interactions were studied in solution and subsequently used to assemble thin films following a Layer-by-Layer assembly protocol. Thin films were assembled as a function of pNIPAm-co-AAc microgel solution temperature and the resultant film thermoresponsivity characterized as a function of microgel layer number and pH. The response of assembled thin films to pH 3.0 and 6.5 exposure was then characterized by quartz crystal impedance and surface plasmon resonance spectroscopy, which showed that the thin film solvation was highly dependent on the pH of the solution it was in. Assembled thin films were also shown to be useful as controlled drug delivery platforms, where it was found that small molecules could be released from the films in a temperature regulated fashion. Microgel thin films also exhibited unique optical properties and were used as microlens arrays, which were able to focus pattern in air as well as in solution and had focal lengths that could be tuned in response to pH and temperature changes. Ordered microgel arrays were assembled following a thermal annealing process, in order to make light diffracting materials. These ordered arrays were photopolymerized and exhibited temperature dependent Bragg diffraction properties.