The thermal decomposition of hydroxyl-terminated generation-4 polyamidoamine dendrimer (G4OH) films deposited on Au surfaces has been compared with decomposition of the same dendrimer encapsulating an approximately 40-atom Pt particle (Pt-G4OH). Infrared absorption reflection spectroscopy studies showed that, when the films were heated in air to various temperatures up to 275 degrees C, the disappearance of the amide vibrational modes occurred at lower temperature for the Pt-G4OH film. Dendrimer decomposition was also investigated by thermogravimetric analysis (TGA) in both air and argon atmospheres. For the G4OH dendrimer, complete decomposition was achieved in air at 500 degrees C, while decomposition of the Pt-G4OH dendrimer was completed at 400 degrees C, leaving only platinum metal behind. In a nonoxidizing argon atmosphere, a greater fraction of the G4OH decomposed below 300 degrees C, but all of the dendrimer fragments were not removed until heating above 550 degrees C. In contrast, Pt-G4OH decomposition in argon was similar to that in air, except that decomposition occurred at temperatures approximately 15 degrees C higher. Thermal decomposition of the dendrimer films on Au surfaces was also studied by temperature programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS) under ultrahigh vacuum conditions. Heating the G4OH films to 250 degrees C during the TPD experiment induced the desorption of large dendrimer fragments at 55, 72, 84, 97, 127, 146, and 261 amu. For the Pt-G4OH films, mass fragments above 98 amu were not observed at any temperature, but much greater intensities for H(2) desorption were detected compared to that of the G4OH film. XPS studies of the G4OH films demonstrated that significant bond breaking in the dendrimer did not occur until temperatures above 250 degrees C and heating to 450 degrees C caused dissociation of C=O, C-O, and C-N bonds. For the Pt-G4OH dendrimer films, carbon-oxygen and carbon-nitrogen bond scission was observed at room temperature, and further decomposition to atomic species occurred after heating to 450 degrees C. All of these results are consistent with the fact that the Pt particles inside the G4OH dendrimer catalyze thermal decomposition, allowing dendrimer decomposition to occur at lower temperatures. However, the Pt particles also catalyze bond scission within the dendrimer fragments so that decomposition of the dendrimer to gaseous hydrogen is the dominant reaction pathway compared to desorption of the larger dendrimer fragments observed in the absence of Pt particles.
The trend towards miniaturization has brought about strong demand for increasingly smaller precision‐molded plastic components. In order to control metering accuracy and homogeneity of the very small quantities of melt in the micro molding process, new micro molding machines that use an injection system comprising a screw extruder and a plunger injection unit have been developed. By use of such injection systems, standard plastic granules can be handled by the screw extruder and melt accuracy can be achieved by the electrically driven injection plunger. The objective of this work is to investigate the effects of the process parameters on the micro molding process and part quality. A series of micro gears were molded using a polyoxymethylene resin in a set of statistically designed experiments. Micro component inspection, characterization, and data analysis work was carried out to study the molded gears. It was found that metering size and holding pressure time are the process parameters that have the most significant effects on part quality, and that the process is also significantly affected by the interaction of these two parameters. There is an optimum metering size range in which the hold pressure can act together with the metering size to properly fill micro mold cavities.
This work describes the use of atomic force microscopy (AFM) to measure the size of dendrimer-stabilized Pt nanoparticles (Pt DNs) deposited from aqueous solutions onto mica surfaces. Despite considerable previous work in this area, we do not fully understand the mechanisms by which PAMAM dendrimers template the formation of Pt DNs. In particular, Pt DN sizes measured by high-resolution transmission electron microscopy (HRTEM) are reported to be larger than expected if one assumes that each PAMAM molecule templates one spherical Pt nanoparticle. AFM provides a vertical height measurement that complements the lateral dimension measurement from HRTEM. We show that AFM height measurements can distinguish between "empty" PAMAM and Pt DNs. If the complexation of Pt precursor with PAMAM is prematurely terminated, AFM images and feature height distributions show evidence of arrested precipitation of Pt colloids. In contrast, sufficient Pt-PAMAM complexation time leads to AFM images and height distributions that have relatively narrow, normal distributions with mean values that increase with the nominal Pt:PAMAM ratio. The surface density of features in AFM images suggest that these Pt DNs reside on the mica surface as two-dimensional surface aggregates. These observations are consistent with an intradendrimer templating mechanism for Pt DNs. However, we cannot determine if the mechanism obeys a fixed loading law because we do not have definitive information about Pt DN shape. A second peak in the Pt DN height distribution appears when the Pt loading exceeds about 66% of PAMAM's theoretical capacity for Pt. Excluding these secondary particles, the dependence of mean feature height on the Pt:PAMAM ratio follows a power-law relationship. Also considering the magnitudes of the measured mean height values, the data suggest that Pt DNs exist as ramified, noncompact aggregates of Pt atoms interspersed within the PAMAM framework.
Evapotranspiration is an important component of the water and energy balance. It is dependent on climate. Precipitation, solar radiation, temperature, humidity, and wind all contribute to the rate of evapotranspiration. In this study, the temporal trends of reference evapotranspiration (ET ref ) and four main ET ref drivers, namely, mean air temperature (T a ), wind speed (u 2 ), net radiation (R n ) and actual vapour pressure (e a ) from 1970 to 2009, were calculated based on 75 meteorological stations on the Tibetan Plateau. The results showed that the ET ref on the Tibetan Plateau decreased on average by 0.6909 mm a -1 a -1 from 1970 to 2009. T a and e a showed an increasing trend, whereas u 2 and R n exhibited a decreasing trend. To explore the underlying causes of the ET ref variation, an attribution analysis was performed to quantify the contribution of T a , u 2 , R n and e a , which showed that the changes in u 2 , R n and e a produced the negative effect, whereas T a produced the positive effect on ET ref rates. The changes in u 2 were found to produce the largest decrease (À0.7 mm) in ET ref , followed by e a (À0.4 mm) and R n (À0.1 mm). Although the significant increase in T a had a large positive effect (0.51 mm) on ET ref rates, changes in the other three variables each reduced ET ref rates, resulting in an overall negative trend in ET ref .
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