In this study, polymer nanocomposites based on poly(lactic acid) (PLA) and organically modified layered silicates (organoclay) were prepared by melt mixing in an internal mixer. The exfoliation of organoclay could be attributed to the interaction between the organoclay and PLA molecules and shearing force during mixing. The exfoliated organoclay layers acted as nucleating agents at low content and as the organoclay content increased they became physical hindrance to the chain mobility of PLA. The thermal dynamic mechanical moduli of nanocomposites were also improved by the exfoliation of organoclay; however, the improvement was reduced at high organoclay content. The dynamic rheological studies show that the nanocomposites have higher viscosity and more pronounced elastic properties than pure PLA. Both storage and loss moduli increased with silicate loading at all frequencies and showed nonterminal behavior at low frequencies. The nanocomposites and PLA were then foamed by using the mixture of CO 2 and N 2 as blowing agent in a batch foaming process. Compared with PLA foam, the nanocomposite foams exhibited reduced cell size and increased cell density at very low organoclay content. With the increase of organoclay content, the cell size was decreased and both cell density and foam density were increased.

Summary: In order to produce modified poly(lactic acid) (PLA) resins for applications requiring high melt viscosity and elasticity (e.g., low‐density foaming, thermoforming), a commercial PLA product has been reactively modified in melt by sequentially adding 1,4‐butanediol and 1,4‐butane diisocyanate as low‐molecular‐weight chain extenders. By varying amounts of the two chain extenders associated to the end group contents of PLA, three resulted samples were obtained. They were then structurally characterized by FTIR spectroscopy and molecular structure analysis. Their thermal, dynamic mechanical thermal properties and melt viscoelastic properties were investigated and compared along with unmodified PLA. The results indicated that chemical modification may be characterized as chain scission, extension, crosslinking, or any combination of the three depending on the chain extender amounts. The increase of PLA molecular weight could be obtained by properly controlling amounts of two chain extenders. The samples with increased molecular weights showed enhanced melt viscosity and elasticity. Such property improvements promised a successful application for modified PLA in a batch foam processing by producing foams with reduced cell size, increased cell density and lowered bulk foam density in comparison with plain PLA foam.

Nanocomposites based on biodegradable polycaprolactone (PCL) and organically modified layered silicates (organoclay) were prepared by melt mixing. Their structures and properties were characterized by wide‐angle X‐ray diffraction, thermal analysis, and rheological measurements. The exfoliation of the organoclay was achieved via a melt mixing process in an internal mixer and showed a dependence on the type of organic modifier, the organoclay contents, and the processing temperature. The addition of the organoclay to PCL increased the crystallization temperature of PCL, but a high content of the organoclay could show an inverse effect. The PCL/organoclay nanocomposites showed a significant enhancement in their mechanical properties and thermal stability due to the exfoliation of the organoclay. The nanocomposites showed a much higher complex viscosity than the neat PCL and significant shear‐thinning behavior in the low frequency range. The shear storage modulus and loss modulus of the nanocomposites also exhibited less frequency dependence than the pure PCL in the low frequency range, and this was caused by the strong interactions between the organoclay layers and PCL molecules and by the good dispersion of exfoliated organoclay platelets in the PCL. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 670–678, 2003

Summary Unconventional gas resources from tight-sand and shale gas reservoirs have received great attention in the past decade around the world because of their large reserves and technical advances in developing these resources. As a result of improved horizontal-drilling and hydraulic-fracturing technologies, progress is being made toward commercial gas production from such reservoirs, as demonstrated in the US. However, understandings and technologies needed for the effective development of unconventional reservoirs are far behind the industry needs (e.g., gas-recovery rates from those unconventional resources remain very low). There are some efforts in the literature on how to model gas flow in shale gas reservoirs by use of various approaches—from modified commercial simulators to simplified analytical solutions—leading to limited success. Compared with conventional reservoirs, gas flow in ultralow-permeability unconventional reservoirs is subject to more nonlinear, coupled processes, including nonlinear adsorption/desorption, non-Darcy flow (at both high flow rate and low flow rate), strong rock/fluid interaction, and rock deformation within nanopores or microfractures, coexisting with complex flow geometry and multiscaled heterogeneity. Therefore, quantifying flow in unconventional gas reservoirs has been a significant challenge, and the traditional representative-elementary-volume- (REV) based Darcy's law, for example, may not be generally applicable. In this paper, we discuss a generalized mathematical framework model and numerical approach for unconventional-gas-reservoir simulation. We present a unified framework model able to incorporate known mechanisms and processes for two-phase gas flow and transport in shale gas or tight gas formations. The model and numerical scheme are based on generalized flow models with unstructured grids. We discuss the numerical implementation of the mathematical model and show results of our model-verification effort. Specifically, we discuss a multidomain, multicontinuum concept for handling multiscaled heterogeneity and fractures [i.e., the use of hybrid modeling approaches to describe different types and scales of fractures or heterogeneous pores—from the explicit modeling of hydraulic fractures and the fracture network in stimulated reservoir volume (SRV) to distributed natural fractures, microfractures, and tight matrix]. We demonstrate model application to quantify hydraulic fractures and transient flow behavior in shale gas reservoirs.