THERMORESPONSIVE PROPERTIES OF GOLD HYBRID NANOPARTICLES OF POLY(DI(ETHYLENE GLYCOL) METHYL ETHER METHACRYLATE) (PDEGMA) AND ITS BLOCK COPOLYMERS WITH DIFFERENT ANCHORING REGIMES

Thermo-responsive materials have been of interest for many years, and have been studied mostly as thermally stimulated drug delivery vehicles. Recently acrylate and methacrylates with pendant ethylene glycol methyl ethers been studied as thermo responsive materials. This work explores thermo response properties of hybrid nanoparticles of one of these methacrylates (DEGMA) and a block copolymer with one of the acrylates (OEGA), with gold nanoparticle cores of different sizes. We were interested in the effects of gold core size, number and type of end groups that anchored the chains to the gold cores, and location of bonding sites on the thermo-response of the polymer. To control the number and location of anchoring groups we using a type of controlled radical polymerization called Reversible Addition Fragmentation Transfer (RAFT) Polymerization. Smaller gold cores did not show the thermo responsive behavior of the polymer but the gold cores did seem to self-assemble. Polymer anchored to larger gold cores did show thermo responsivity. The anchoring end group did not alter the thermoresponsivity but thiol-modified polymers stabilized gold cores less well than chains anchored by dithioester groups, allowing gold cores to grow larger. Use of multiple bonding groups stabilized the gold core. Using block copolymers we tested the effects of number of thiol groups and the distance between them. We observed that the use of multiple anchoring groups on the block copolymer with a sufficiently large gold core did not prevent thermo responsive behavior of the polymer to be detected which allows a new type of thermo-responsive hybrid nanoparticle to be used and studied for new applications.

Creep and shrinkage behavior of ultra high-performance concrete under compressive loading with varying curing regimes

This Ultra High Performance Concrete research involves observing early-age creep and shrinkage under a compressive load throughout multiple thermal curing regimes. The goal was to mimic the conditions that would be expected of a precast/prestressing plant in the United States, where UHPC beams would be produced quickly to maximize a manufacturing plant’s output. The practice of steam curing green concrete to accelerate compressive strengths for early release of the prestressing tendons was utilized (140°F [60°C], 95% RH, 14 hrs), in addition to the full thermal treatment (195°F [90°C], 95% RH, 48 hrs) while the specimens were under compressive loading. Past experimental studies on creep and shrinkage characteristics of UHPC have only looked at applying a creep load after the thermal treatment had been administered to the specimens, or on ambient cured specimens. However, this research looked at mimicking current U.S. precast/prestressed plant procedures, and thus characterized the creep and shrinkage characteristics of UHPC as it is thermally treated under a compressive load. Michigan Tech has three moveable creep frames to accommodate two loading criteria per frame of 0.2f’ci and 0.6f’ci. Specimens were loaded in the creep frames and moved into a custom built curing chamber at different times, mimicking a precast plant producing several beams throughout the week and applying a thermal cure to all of the beams over the weekend. This thesis presents the effects of creep strain due to the varying curing regimes. An ambient cure regime was used as a baseline for the comparison against the varying thermal curing regimes. In all cases of thermally cured specimens, the compressive creep and shrinkage strains are accelerated to a maximum strain value, and remain consistent after the administration of the thermal cure. An average creep coefficient for specimens subjected to a thermal cure was found to be 1.12 and 0.78 for the high and low load levels, respectively. Precast/pressed plants can expect that simultaneously thermally curing UHPC elements that are produced throughout the week does not impact the post-cure creep coefficient.

The growth response of planted red pine (Pinus resinosa Ait.) to alternative thinning regimes

Red pine (Pinus resinosa Ait.) plantations have been established in Michigan with expectations of mixed final product goals: pulpwood, boltwood and possibly sawlogs. The effects of alternative treatments on tree and stand attributes were examined in: the Atlantic Mine trial, thinned in spring 2006 with three alternatives: (1) every fifth row removal plus crown thinning, (2) every third row removal plus crown thinning and (3) every third row removal plus thinning from below; the Crane Lake trial, thinned in fall 2004 with two alternatives: (1) every third row removal and (2) every third row removal plus thinning from above; the Middle Branch East trial, thinned in fall 2004 with two alternatives: (1) every third row removal plus one in three remaining trees and (2) every third row removal plus one in five remaining trees. All trials included control plots where no thinning was applied. The trials were established in the field as a randomized complete block experiments, in which individual trees were measured in 3-4 fixed-area plots located within each treatment unit. Growth responses of diameter at breast height, height, live crown length, stand basal area and stand volume were examined along with their increments. The Tukey multiple comparison test was used to detect significant differences between treatments in their effect on tree growth response. The results showed that diameter increment increased with increasing thinning intensity and was significantly larger in thinned plots compared to unthinned. Treatments did not substantially affect average tree height increment. Stand basal area increment was significantly larger in the control plot only the year after the harvest. Volume increment was significantly larger in controls, but did not differ considerably among remaining treatments. However, the ratio of volume increment to standing volume was significantly smaller in unthinned plots compared to thinned. Since thinning treatments in all trials hardly ever differed significantly in their effect on stand growth response, mainly due to the relatively short time of the evaluation, heavier thinnings should be favored due to higher volume increment rates and shorter time needed to reach desirable diameters. Nevertheless, economic evaluation based on obtained results will be conducted in the future in order to make final decisions about the most profitable treatment.

Model to describe the mode I fracture of steel fiber reinforced ultra-high performance concrete

Ultra-high performance fiber reinforced concrete (UHPFRC) has arisen from the implementation of a variety of concrete engineering and materials science concepts developed over the last century. This material offers superior strength, serviceability, and durability over its conventional counterparts. One of the most important differences for UHPFRC over other concrete materials is its ability to resist fracture through the use of randomly dispersed discontinuous fibers and improvements to the fiber-matrix bond. Of particular interest is the materials ability to achieve higher loads after first crack, as well as its high fracture toughness. In this research, a study of the fracture behavior of UHPFRC with steel fibers was conducted to look at the effect of several parameters related to the fracture behavior and to develop a fracture model based on a non-linear curve fit of the data. To determine this, a series of three-point bending tests were performed on various single edge notched prisms (SENPs). Compression tests were also performed for quality assurance. Testing was conducted on specimens of different cross-sections, span/depth (S/D) ratios, curing regimes, ages, and fiber contents. By comparing the results from prisms of different sizes this study examines the weakening mechanism due to the size effect. Furthermore, by employing the concept of fracture energy it was possible to obtain a comparison of the fracture toughness and ductility. The model was determined based on a fit to P-w fracture curves, which was cross referenced for comparability to the results. Once obtained the model was then compared to the models proposed by the AFGC in the 2003 and to the ACI 544 model for conventional fiber reinforced concretes.