Influence of the viscosity of poly(methyl methacrylate) on the cellular structure of nanocellular materials

Three different grades of poly(methyl methacrylate) (PMMA) with different rheological properties are used for the production of nanocellular materials using gas dissolution foaming. The influences of both the viscosity of the different polymers and the processing parameters on the final cellular structure are studied using a wide range of saturation and foaming conditions. Foaming conditions affect similarly all cellular materials. It is found that an increase of the foaming temperature results in less dense nanocellular materials, with higher cell nucleation densities. In addition, it is demonstrated that a lower viscosity leads to cellular polymers with a lower relative density but larger cell sizes and smaller cell nucleation densities, these differences being more noticeable for the conditions in which low solubilities are reached. It is possible to produce nanocellular materials with relative densities of 0.24 combined with cell sizes of 75 nm and cell nucleation densities of 1015 nuclei cm−3 using the PMMA with the lowest viscosity. In contrast, minimum cell sizes of around 14 nm and maximum cell nucleation densities of 3.5 × 1016 nuclei cm−3 with relative densities of 0.4 are obtained with the most viscous one. © 2019 Society of Chemical Industr

Key Production Parameters to Obtain Transparent Nanocellular PMMA

Transparent nanocellular polymethylmethacrylate (PMMA) with relative density around 0.4 is produced for the first time by using the gas dissolution foaming technique. The processing conditions and the typical characteristics of the cellular structure needed to manufacture this novel material are discovered. It is proved that low saturation temperatures (−32 °C) combined with high saturation pressures (6, 10, 20 MPa) allow increasing the solubility of PMMA up to values not reached before. In particular, the highest CO2 uptake ever reported for PMMA, (i.e., 48 wt%) is found for a saturation pressure of 20 MPa and a saturation temperature of −32 °C. Due to these processing conditions, cell nucleation densities of 1016 nuclei cm−3 and cell sizes clearly below 50 nm are achieved. The nanocellular polymers obtained, with cell sizes ten times smaller than the wavelength of visible light and very homogeneous cellular structures, show a significant transparency

Modeling the heat transfer by conduction of nanocellular polymers with bimodal cellular structures

Nanocellular polymers are a new generation of materials with the potential of being used as very efficient thermal insulators. It has been proved experimentally that these materials present the Knudsen effect, which strongly reduces the conductivity of the gas phase. There are theoretical equations to predict the thermal conductivity due to this Knudsen effect, but all the models consider an average cell size. In this work, we propose a model to predict the thermal conductivity due to the conduction mechanisms of nanocellular materials with bimodal cellular structures, that is, with two populations of cells, micro and nanocellular. The novelty of our work is to consider not only the average cell size, but the cell size distribution. The predictions of the model are compared with the experimental conductivity of two real bimodal systems based on poly(methyl methacrylate) (PMMA), and it is proved that this new model provides more accurate estimations of the conductivity than the models that do not consider the bimodality. Furthermore, this model could be applied to monomodal nanocellular polymers. In particular, for monomodal materials presenting a wide cell size distribution and at low densities, the model predicts important variations in comparison with the current models in the literature. This result indicates that the cell size distribution must be included in the estimations of the thermal conductivity of nanocellular polymer

Nanocellular Polymers with a Gradient Cellular Structure Based on Poly(methyl methacrylate)/Thermoplastic Polyurethane Blends Produced by Gas Dissolution Foaming

Graded structures and nanocellular polymers are two examples of advanced cellular morphologies. In this work, a methodology to obtain low-density graded nanocellular polymers based on poly(methyl methacrylate) (PMMA)/ thermoplastic polyurethane (TPU) blends produced by gas dissolution foaming is reported. A systematic study of the effect of the processing condition is presented. Results show that the melt-blending results in a solid nanostructured material formed by nanometric TPU domains. The PMMA/ TPU foamed samples show a gradient cellular structure, with a homogeneous nanocellular core. In the core, the TPU domains act as nucleating sites, enhancing nucleation compared to pure PMMA and allowing the change from a microcellular to a nanocellular structure. Nonetheless, the outer region shows a gradient of cell sizes from nano- to micron-sized cells. This gradient structure is attributed to a non-constant pressure profile in the samples due to gas desorption before foaming. The nucleation in the PMMA/ TPU increases as the saturation pressure increases. Regarding the effect of the foaming conditions, it is proved that it is necessary to have a fine control to avoid degeneration of the cellular materials. Graded nanocellular polymers with relative densities of 0.16–0.30 and cell sizes ranging 310–480 nm (in the nanocellular core) are obtained

Overcoming the Challenge of Producing Large and Flat Nanocellular Polymers: A Study with PMMA

Although nanocellular polymers are interesting materials with improved properties in comparison with conventional or microcellular polymers, the production of large and flat parts of those materials is still challenging. Herein, gas dissolution foaming process is used to produce large and flat nanocellular polymethylmethacrylate samples. In order to do that, the foaming step is performed in a hot press. The methodology is optimized to produce flat samples with dimensions of 100 × 100 × 6 mm3, relative densities in the range 0.25–0.55 and cell sizes around 250 nm. Additionally, foaming parameters are modified to study their influence on the final cellular structure, and the materials produced in this paper are compared with samples produced by using a most conventional approach in which foaming step is conducted in a thermal bath. Results obtained show that an increment in the foaming temperature leads to a reduction in relative density and an increase of cell nucleation density. Moreover, differences in the final cellular structure for materials produced by both foaming routes are studied, proving that although there exist some differences, the mechanisms governing the nucleation and growing are the same in both processes, leading to the production of homogeneous materials with very similar cellular structures

Automated Purchase Negotiations in a Dynamic Electronic Marketplace

Nowadays, there is a surge of B2C and B2B e-commerce operated\ud on the Internet. However, many of these systems are often nothing\ud more than electronic product or service catalogues. Against this background,\ud it is argued that new generation systems based on automatic\ud negotiation will emerge. This paper covers a particular kind of automatic\ud negotiation systems, where a number of participants in a mobile\ud dynamic electronic marketplace automatically negotiate the purchase of\ud products or services, by means of multiple automated one-to-one bargainings.\ud In a dynamic e-marketplace, the number of buyers and sellers\ud and their preferences may change over time. By mobile we mean that\ud buyers in a commercial area may initiate simultaneous negotiations with\ud several sellers using portable devices like cell phones, laptops or personal\ud digital assistants, so these negotiations do not require participants to be\ud colocated in space. We will show how an expressive approach to fuzzy\ud constraint based agent purchase negotiations in competitive trading environments,\ud is ideally suited to work on these kind of e-marketplaces. An\ud example of mobile e-marketplace, and a comparison between an expressive\ud and an inexpressive approach will be presented to show the efficiency\ud of the proposed solution

Understanding the role of MAM molecular weight in the production of PMMA/MAM nanocellular polymers

Nanostructured polymer blends with CO2-philic domains can be used to produce nanocellular materials with controlled nucleation. It is well known that this nanostructuration can be induced by the addition of a block copolymer poly(methyl methacrylate)-poly(butyl acrylate)-poly(methyl methacrylate) (MAM) to a poly(methyl methacrylate) (PMMA) matrix. However, the effect of the block copolymer molecular weight on the production of nanocellular materials is still unknown. In this work, this effect is analysed by using three types of MAM triblock copolymers with different molecular weights, and a fixed blend ratio of 90 wt% PMMA and 10 wt% of MAM. Blends were produced by extrusion. As a result of the extrusion process, a non-equilibrium nanostructuration takes place in the blends, and the micelle density increases as MAM molecular weight increases. Micelle formation is proposed to occur as result of two mechanisms: dispersion, controlled by the extrusion parameters and the relative viscosities of the polymers, and self-assembly of MAM molecules in the dispersed domains. On the other hand, in the nanocellular materials produced with these blends, cell size decreases from 200 to 120 nm as MAM molecular weight increases. Cell growth is suggested to be controlled by the intermicelle distance and limited by the cell wall thickness. Furthermore, a theoretical explanation of the mechanisms underlying the limited expansion of PMMA/MAM systems is proposed and discussed