Monte Carlo Renormalization Group for Entanglement Percolation

We use a large cell Monte Carlo Renormalization procedure, to compute the critical exponents of a system of growing linear polymers. We simulate the growth of non-intersecting chains in large MC cells. Dense regions where chains get in each others' way, give rise to connected clusters under coarse graining. At each time step, the fraction of occupied bonds is determined in both the original and the coarse grained configurations, and averaged over many realizations. Our results for the fractal dimension on three dimensional lattices are consistent with the percolation value.Comment: 5 pages, 5 figure

Modeling the effect of the curing conversion on the dynamic viscosity of epoxy resins cured by an anhydride curing agent

Published curing profiles of epoxy resins mixed with an anhydride curing agent and subsequently crosslinked were reanalyzed with a modified sigmoidal model to describe the dynamic viscosity accompanying resin curing. The sigmoidal analysis yielded two kinetic parameters, one relating to the induction time required to observe meaningful viscosity changes and one relating to the rate of viscosity rise in the rapidly polymerizing zone. Both of these kinetic factors decreased with increasing polymerization temperature. The analysis also led to the interpretation of the upper limit in viscosity in the model that correlated with a higher network density at higher temperatures. The initial viscosity was fixed in our model. The sigmoidal analysis led to a closer representation of the dynamic viscosity data than the Williams–Landel–Ferry (WLF)-based analysis presented with the original data sets and, although from a more semiempirical basis, might be both easier and more adaptable for incorporating into other flow models. As a final observation, the induction time identified by the log–sigmoidal model correlated closely with the gelation time identified with a modified-WLF-based model by Ivankovic et al. (J Appl Polym Sci 2003, 90, 3012); this suggested a similar activation energy threshold for curing advancement. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/64448/1/31148_ftp.pd

A New Era in Engineering Plastics: Compatibility and Perspectives of Sustainable Alipharomatic Poly(ethylene terephthalate)/Poly(ethylene 2,5-furandicarboxylate) Blends

The industrialisation of poly(ethylene 2,5-furandicarboxylate) for total replacement of poly(ethylene terephthalate) in the polyester market is under question. Preparation of high-performing polymer blends is a well-established strategy for tuning the properties of certain homopolymers and create tailor-made materials to meet the demands for a number of applications. In this work, the structure, thermal properties and the miscibility of a series of poly(ethylene terephthalate)/poly(ethylene 2,5-furandicarboxylate) (PET/PEF) blends have been studied. A number of thermal treatments were followed in order to examine the thermal transitions, their dynamic state and the miscibility characteristics for each blend composition. Based on their glass transition temperatures and melting behaviour the PET/PEF blends are miscible at high and low poly(ethylene terephthalate) (PET) contents, while partial miscibility was observed at intermediate compositions. The multiple melting was studied and their melting point depression was analysed with the Flory-Huggins theory. In an attempt to further improve miscibility, reactive blending was also investigated

Chemorheology of photopolymerizable acrylates using a modified Boltzmann sigmoidal model

Experiments were conducted to evaluate the influence of ambient photoconversion on rheology for a range of photopolymerizable urethane dimethacrylate (UDMA) resins containing varying amounts of three comonomers including 1,6 hexane diol-dimethacrylate (HDDMA), an alkoxylated cyclohexane dimethanol diacrylate monomer (CD-582), and hydroxyethyl methacrylate (HEMA). Experiments were performed both as a function of composition and time-dependent dose varying the intensity using a photorheometer. A semilog-based sigmoidal model allowed the determination of four physical model parameters to define the relationship between reaction kinetics and its dynamic influence on viscosity. We have observed induction times and viscosity changes associated with the model that shows a trend in reaction kinetics in the following order from most to least reactive: UDMA > CD582 > HDDMA > HEMA. With increasing amounts of reactive diluent included in the formulation, the kinetics of reaction was more sluggish. The value of this sigmoidal model is that it could help define formulation and process conditions most likely to control crosslinking to maximize dimensional stability or other thermophysical properties. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2319–2325, 2008Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/61230/1/21563_ftp.pd

Increasing the Dissolution Rate of Polystyrene Waste in Solvent-Based Recycling

Solvent-based recycling of plastic waste is a promising approach for cleaning polymer chains without breaking them. However, the time required to actually dissolve the polymer in a lab environment can take hours. Different factors play a role in polymer dissolution, including temperature, turbulence, and solvent properties. This work provides insights into bottlenecks and opportunities to increase the dissolution rate of polystyrene in solvents. The paper starts with a broad solvent screening in which the dissolution times are compared. Based on the experimental results, a multiple regression model is constructed, which shows that within several solvent properties, the viscosity of the solvent is the major contributor to the dissolution time, followed by the hydrogen, polar, and dispersion bonding (solubility) parameters. These results also indicate that cyclohexene, 2-pentanone, ethylbenzene, and methyl ethyl ketone are solvents that allow fast dissolution. Next, the dissolution kinetics of polystyrene in cyclohexene in a lab-scale reactor and a baffled reactor are investigated. The effects of temperature, particle size, impeller speed, and impeller type were studied. The results show that increased turbulence in a baffled reactor can decrease the dissolution time from 40 to 7 min compared to a lab-scale reactor, indicating the importance of a proper reactor design. The application of a first-order kinetic model confirms that dissolution in a baffled reactor is at least 5-fold faster than that in a lab-scale reactor. Finally, the dissolution kinetics of a real waste sample reveal that, in optimized conditions, full dissolution occurs after 5 min

Sigmoidal Chemorheological Models of Chip-Underfill Materials Offer Alternative Predictions of Combined Cure and Flow

Prior rheology results on chip-underfill epoxy resins have been re-analyzed by a sigmoidal model that contains three variable physical parameters, including the terminal cured viscosity of the gel, an induction or dwell time and a time factor associated with the speed of conversion as viscosity undergoes large dynamic changes during rapid crosslinking. The analyses were conducted with resins that were originally cured between 150 and 180 °C and show obvious non-linearity, even on a semi-log plot of dynamic viscosity. The sigmoidal models more accurately represent a wider range of dynamic viscosity than power-law-based rheological models, which are both more common and more generally accepted for practical application. If total flow is the critical design parameter in terms of chip underfill, perhaps these alternative sigmoidal models need to be more thoroughly evaluated to gauge their practical use and validity.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/61221/1/832_ftp.pd

Exploring Next-Generation Engineering Bioplastics: Poly(alkylene furanoate)/Poly(alkylene terephthalate) (PAF/PAT) Blends

Polymers from renewable resources and especially strong engineering partially aromatic biobased polyesters are of special importance for the evolution of bioeconomy. The fabrication of polymer blends is a creative method for the production of tailor-made materials for advanced applications that are able to combine functionalities from both components. In this study, poly(alkylene furanoate)/poly(alkylene terephthalate) blends with different compositions were prepared by solution blending in a mixture of trifluoroacetic acid and chloroform. Three different types of blends were initially prepared, namely, poly(ethylene furanoate)/poly(ethylene terephthalate) (PEF/PET), poly(propylene furanoate)/poly(propylene terephthalate) (PPF/PPT), and poly(1,4-cyclohenedimethylene furanoate)/poly(1,4-cycloxehane terephthalate) (PCHDMF/PCHDMT). These blends’ miscibility characteristics were evaluated by examining the glass transition temperature of each blend. Moreover, reactive blending was utilized for the enhancement of miscibility and dynamic homogeneity and the formation of copolymers through transesterification reactions at high temperatures. PEF–PET and PPF–PPT blends formed a copolymer at relatively low reactive blending times. Finally, poly(ethylene terephthalate-co-ethylene furanoate) (PETF) random copolymers were successfully introduced as compatibilizers for the PEF/PET immiscible blends, which resulted in enhanced miscibility