SPE Library

Nanofibrillated cellulose (NFC) has properties ideal for applications in the packaging and medical industries. To understand if cellulose-based polymers could become a replacement for synthetic polymers in these fields, NFC suspensions were repeatedly exposed to elevated shear stresses to simulate industrial processing procedures and allow for observation of changes in material properties. A capillary rheometer was used to run aqueous NFC suspensions of 10 wt% at room temperature at shear rates beyond 30,000 s-1. Due to repeated shear rate exposure, a decrease in volume resulting from unavoidable water loss informed the observable increase in apparent viscosity and suggested that this increasing trend was not caused by a change in material morphology. Noisy data as a result of flocs was detrimental to the analysis of material behavior during rheological testing. Once preprocessing procedures are successfully designed to reduce noise in the data, material behavior at high shear rates will be further defined.

After nearly 80 years of research in constitutive modeling of polymeric fluids, simple yet capable models are still sought after today. In this work, we provide an explicit constitutive equation where the extra stress tensor is an explicit function of the objective velocity gradient while finite stretch of polymer chains are considered. With this model, the basic rheological functions in uniaxial extensional, planar extension and simple shear can all be obtained as closed-form analytical solutions with only elementary mathematical functions involved. The new model demonstrates excellent fitting to some sear and extensional data in the literature, and is able to simultaneously predict the major rheological functions in steady-state shear and extension.

Multi-wall carbon nanotubes (MWCNTs), graphene nanoplates (GNPs), and hybrid fillers (MWCNTs/GNPs) filled thermoplastic polyurethane (TPU) nanocomposites are prepared via melt mixing. The effects of filler (contents of 1, 2, and 3 wt%) and temperature are investigated on the rheological behavior of the TPU nanocomposites. The results demonstrate that the TPU/MWCNT nanocomposites exhibit stronger polymer-filler and filler-filler interactions than TPU/GNP and TPU/GNP/MWCNT nanocomposites. It is found that the nanocomposites with 2 and 3 wt% MWCNTs (2CNT and 3CNT) and 3 wt% MWCNTs/GNPs (3Hybrid) exhibit anomalous rheological behavior. As rising the temperature from 180 to 190 ℃, the complex viscosity values slightly increase in the low frequency region (< 0.4 rad/s) for the 2CNT and 3Hybrid samples, and more significantly increases over a wider frequency range (up to about 10 rad/s) for the 3CNT sample. The Fourier transform infrared spectroscopy spectra demonstrate that the anomalous rheological behavior is not caused by hydrogen bonding in the TPU nanocomposites. The results of scanning electron microscopy observation, time sweep tests, and volume electrical conductivity measurements reveal that the anomalous rheological behavior is attributed to physical contact of the MWCNTs under low shear.

The purpose of this study was to investigate the feasibility of in-situ foaming in fused filament fabrication (FFF) process. Development of unexpanded filaments loaded with thermally expandable microspheres, TEM is reported as a feedstock for in-situ foam printing. Four different material compositions, i.e., two grades of polylactic acid, PLA, and two plasticizers (polyethylene glycol, PEG, and triethyl citrate, TEC) were examined. PLA, TEM and plasticizer were dry blended and fed into the extruder. The filaments were then extruded at the lowest possible barrel temperatures, collected by a filament winder, and used for FFF printing process. The results showed that PLA Ingeo 4043D (MFR=6 g/10min) provides a more favorable temperature window for the suppression of TEM expansion during extrusion process, compared to PLA Ingeo 3052D (MFR=14 g/10min). TEC plasticizer was also found to effectively lower the process temperatures without adversely interacting with the TEM particles. Consequently, unexpanded filaments of PLA4043D/TEM5%/TEC2% was successfully fabricated with a density value of 1.16 g/cm3, which is only ~4.5% lower than the theoretical density value. The in-situ foaming in FFF process was then successfully demonstrated. The printed foams revealed a uniform cellular structure, reproducible dimensions, as well as less print marks on the surface, compared to the solid counterparts.

A simulation of an imprinting process using Smoothed Dissipative Particle Dynamics is shown. Cavity filling modes and their dependence on die parameters is demonstrated for single and multicavity die, showing results consistent with FEM simulations and experimental data. Particle-based simulation methods can allow for modeling of more complex fluid behaviors.

For several decades, the Tait model has been used in simulation software to describe the volumetric mechanical behavior of thermoplastic polymers as they cool. It is used to compute the residual strains and stresses of the polymer as it solidifies, but there is a problem. Many data sets have coefficients where there exists a discontinuity at the transition between the molten and solid domains. This paper outlines some basic checks that can be done to detect this problem and a procedure to fit the coefficients to data so that this problem does not arise.

This paper presents a process for fitting corrected viscosity data to constituent and temperature dependent data to a range of two-equation models. The process tests different models to determine the best fit model for each. Rheometer data for polymer melts, after corrections for shear rate and entrance pressure losses, may fit one model better than another, and as such the following constituent models are reviewed in the form as they are commonly applied in commercial software today: 1) Cross Model, 2) Modified Cross Model, and 3) Carreau-Yasuda. Once the constituent model is fit, the following temperature dependent models are compared: 1) WLF, Exponential, Arrhenius, and Masuko-Magill. The differences between the models are presented in order to highlight the need to compare different models to obtain a best fit. Lastly, a solution is presented to the problem of convergent viscosities with respect to shear rate as compared across a range of temperatures as no existing model in common use today can capture this specific behavior.

Tracking the cure progress of slow reacting, uncatalyzed polyurethane systems is a tedious, time consuming process that has been largely neglected due to the availability of catalysts. The use of catalysts has enabled quick, nonisothermal studies to dominate the field of research, but when catalysis is not an option, these methods become impractical. In this context, we can use chemorheology to correlate viscoelastic data to several previously developed cure models. The models presented here examine viscosity buildup, reaction rate progress, and thermodynamic behavior, while emphasizing the importance of interpretation during data analysis. These chemorheological techniques focus on the development of thermally curing networks during subjection to flow fields, and apply to a vast array of thermosetting polymeric materials.

Rheological testing of new material formulations can require significant quantities, specifically when considering development of new chemistries at the laboratory scale. In order to minimize the quantity of material required for evaluation, we are developing approaches suitable for characterization of high solids content formulations using micro-capillary rheometry. The goal of this investigation is to design and produce a micro-capillary rheometer capable of characterizing basic rheological properties, such as viscosity and shear-thinning behavior, while requiring the least amount of sample possible. In our current design, we implement a micro-dispensing approach combined with calibrated force transducers. With this approach we can further elucidate an understanding of the differences between typical capillary rheometry and behavior at reduced dimension flow fields. Issues such as pressure relaxation and free volume compaction can therefore be studied through readily modified geometries and testing rates. This design will lead to a better understanding of micro-capillary rheometer design and enable a unique approach for rheology measurements for new chemistries and formulations, including high solids content formulations (up to 60+ vol%). Additionally, this framework will facilitate the study of a variety of flow geometries applicable to a wide range of applications including precision dispensing of adhesives and sealants, and direct ink write additive manufacturing.

The shear rate-dependent viscosity of natural rubber and three types of synthetic rubber was measured using the Rubber Screw Rheometer. Viscosity values with Mooney viscometer, which has traditionally measured rubber viscosity, have a high correlation with the values of RSR shear rate 10 [1/s]. Thus the Mooney Viscosity value can be estimated using the RSR shear viscosity measurement. Also, in the case of virgin rubber, the accuracy of the measured value increases when it has a pre-shear history. It was confirmed that the viscosity measurement value was a measurement value having a deviation within +3% when comparing the three times repeated measurements. The measured value was correlated to Mooney Viscosity successfully with a first- order equation.

Ethylene-octane copolymer (EOC) with high octane content (45 wt.%) was cross-linked via electron beam irradiation at different dosages (30, 60, 90, and 120 kGy). Effect of irradiation dosage on thermal and mechanical properties was studied. When compared to low density polyethylene, EOC exhibited higher degree of cross-linking reflected in increased gel content, higher elastic modulus (G’), and lower tan obtained by rheology measurement at 150 °C. Cross-linking caused improvement in high temperature creep and also in elastic properties at room and elevated temperatures. Differential scanning calorimetry revealed that e-beam irradiation has caused a gradual reduction in crystallinity and a presence of a fraction with higher melting temperature. In the case of EOC, as the extent of cross-linking increased, stress at break showed an increasing trend whereas irradiation dosage had an inverse effect on elongation at break which could be aroused from the formation of crosslink networks. Radiation dosage has positive effect on thermal stability estimated by thermogravimetric analysis. After 30 min of thermal degradation at 220 °C, slightly higher C=O peak for cross-linked sample was found by Fourier transform infrared spectroscopy while for room temperature samples no C=O peak was detected.

The complex viscosity of planar star-branched polymers has been derived from general rigid bead-rod theory, but only for singly-beaded arms. Here, we explore the respective roles of branch functionality, arm length of non-planar arrangements, analytically from general rigid bead-rod theory. For non-planar, we include polyhedral, both regular and irregular. We fit the theory to complex viscosity measurements on polybutadiene solutions, one quadrafunctional star-branched, the other unbranched, of the same molecular weight. We learn that when general rigid bead-rod theory is applied to quadrafunctional polybutadiene, a slightly irregular center-beaded tetrahedron of interior angle 134º is required (with 1,360,000 g/gmol per bead) to describe its complex viscosity behaviour.