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Over the past 25 years, IRIS has become an integral resource in materials laboratories around the world, bringing together stimulating communities of rheology experimentalists and theoreticians, rheological experts, and experts from other fields, and even making rheology accessible to non-rheologists. The calculational tools of IRIS interface data from different experimental findings with predictions from rheology theories. Since its beginning, many theory groups used IRIS to share their original codes for rheology predictions. We demonstrate this in two examples, (1) the detailed analysis of small amplitude oscillatory shear data (SAOS) and predictions thereof and (2) a theory, newly implemented in IRIS, that elegantly unites dynamical quantities from small amplitude oscillatory shear (SAOS) with data from filament stretching rheometry and predictions of transient shear. IRIS supports this convergence with a standardizing data (Dealy et al., J Rheol 39:253-265, 1995 ), which makes data sharing easy and independent of instrument brand-specific and laboratory-specific coding.

Elongational viscosity data of well-characterized solutions of 3–50% weight fraction of monodisperse polystyrene PS-820k (molar mass of 820,000 g/mol) dissolved in oligomeric styrene OS8.8 (molar mass of 8800 g/mol) as reported by André et al. (Macromolecules 54:2797–2810, 2021) are analyzed by the Extended Interchain Pressure (EIP) model including the effects of finite chain extensibility. Excellent agreement between experimental data and model predictions is obtained, based exclusively on the linear-viscoelastic characterization of the polymer solutions. The data were obtained by a filament stretching rheometer, and at high strain rates and lower polymer concentrations, the stretched filaments fail by rupture before reaching the steady-state elongational viscosity. Filament rupture is predicted by a criterion for brittle fracture of entangled polymer liquids, which assumes that fracture is caused by scission of primary C-C bonds of polymer chains when the strain energy reaches the bond-dissociation energy of the covalent bond (Wagner et al., J. Rheology 65:311–324, 2021).

The data set of steady and transient shear data reported by Santangelo and Roland Journal of Rheology 45: 583–594, ( 2001 ) in the nonlinear range of shear rates of an unentangled polystyrene melt PS13K with a molar mass of 13.7 kDa is analysed by using the single integral constitutive equation approach developed by Narimissa and Wagner Journal of Rheology 64:129–140, ( 2020 ) for elongational and shear flow of Rouse melts. We compare model predictions with the steady-state, stress growth, and stress relaxation data after start-up shear flows. In characterising the linear-viscoelastic relaxation behaviour, we consider that in the vicinity of the glass transition temperature, Rouse modes and glassy modes are inseparable, and we model the terminal regime of PS13K by effective Rouse modes. Excellent agreement is achieved between model predictions and shear viscosity data, and good agreement with first normal stress coefficient data. In particular, the shear viscosity data of PS13K as well as of two polystyrene melts with M = 10.5 kDa and M = 9.8 kDa investigated by Stratton Macromolecules 5 (3): 304–310, ( 1972 ) agree quantitatively with the universal mastercurve predicted by Narimissa and Wagner for unentangled melts, and approach a scaling of Wi −1/2 at sufficiently high Weissenberg numbers Wi . Some deviations between model predictions and data are seen for stress growth and stress relaxation of shear stress and first normal stress difference, which may be attributed to limitations of the experimental data, and may also indicate limitations of the model due to the complex interactions of Rouse modes and glassy modes in the vicinity of the glass transition temperature. Graphical abstract

Plasticulture, the practice of using plastic materials in agricultural applications, consumes about 6.7 million tons of plastics every year, which is about 2% of the overall global annual plastics production. For different reasons, plastic material used for agriculture is difficult to recycle. Therefore, most of it is either buried in fertile soils, thereby significantly causing deterioration of their properties, or, at best case, end in landfills where its half-life is measured in decades and even centuries. Hence, developing biodegradable plastic materials that are suitable for agricultural applications is a vital and inevitable need for the global human society. In our labs, two types of potentially biodegradable plastic polymer films were prepared and characterized imidazolium in terms of their bio-degradability. In the first approach, polymers made of ionic liquid monomers were prepared using photo radical induced polymerization. The second approach relies on formation of polyethylene-like n-alkane disulfide polymers from 1,ω-di-thiols through thermally activated air oxidation. These two families of materials were tested for their biodegradability in soils by using a simulation system that combines a controlled environment chamber equipped with a respirometer and a proton-transfer-reaction time of flight mass spectrometer (PTR-TOF-MS) system. This system provides a time-dependent and comprehensive fingerprint of volatiles emitted in the degradation process. The results obtained thus far indicate that whereas the ionic-liquid based polymer does not show significant bio-degradability under the test conditions, the building block monomer, 1,10-n-decane dithiol, as well as its disulfide-based polymer, are bio-degradable. The latter reaching, under basic soil conditions and in room temperature, ∼20% degradation within three months. These results suggest that by introduction of disulfide groups into the polyethylene backbone one may be able to render it biodegradable, thus considerably shortening its half-life in soils. Principal component analysis, PCA, of the data about the total volatiles produced during the degradation in soil indicates a distinctive volatile “fingerprint” of the disulfide-based bio-degradable products which comes from the volatile organic compounds portfolio as recorded by the PTR-TOF-MS. The biodegradation volatile fingerprint of this kind of film was different from the “fingerprint” of the soil background which served as a control. These results can help us to better understand and design biodegradable films for agricultural mulching practices.

The study of commercial low-density polyethylenes (LDPEs) has always focused on the effects of the molecular architecture of the polymer on its shear and extensional rheological properties due to their direct influence on manufacturability. However, the complex morphology of industrial-grade LDPEs also affects the crystallization kinetics and dynamic mechanical properties of the polymers, which are key to the processibility and applications. Therefore, a comprehensive investigation was conducted into the areas of crystallization kinetics, crystallinity, dynamic mechanical, and linear and non-linear shear rheological properties of two industrial-grade LDPEs to build a cohesive insight into the influence of morphology on these material properties. We further analyzed the steady-state and transient shear viscosity data obtained from the two LDPEs in comparison with constitutive model predictions using the hierarchical multi-mode molecular stress function (HMMSF) and found excellent agreement within experimental accuracy between predictions by the HMMSF model and shear stress as well as normal stress data of the LDPEs investigated.

The Hierarchical Multi-mode Molecular Stress Function (HMMSF) model predicts the elongational and multiaxial extensional viscosities of polydisperse linear polymer melts based exclusively on their linear viscoelastic characterization and a single nonlinear material parameter, the so-called dilution modulus G D . For long-chain branched (LCB) polymer melts such as low-density polyethylene (LDPE), the HMMSF model describes quantitatively the elongational stress growth coefficient up to the maximum of the elongational viscosity but fails to predict the existence of the maximum and the following steady-state viscosity. By taking into account branch point withdrawal in elongational flow of LCB melts, we extend the HMMSF model and show that the maximum of the elongational viscosity can be characterized by a single additional parameter, the characteristic stretch λ ¯ m , while the steady-state tensile stress and the elongational viscosity depend only on the dilution modulus G D as in the case of linear polydisperse melts. Comparison of predictions of the Extended Hierarchical Multi-mode Molecular Stress Function (EHMMSF) model to experimental data of 5 LDPE melts with widely different molecular weights, polydispersities and densities, and a model polystyrene pom-pom polymer shows good agreement within experimental accuracy in constant elongational-rate flow as well as stress relaxation after steady and reversed elongational flow. For the LCB melts considered, we report differences in the specific Hencky strain at the maximum of the tensile stress as quantified by the characteristic stretch λ ¯ m , and we discuss correlations between polydispersity, dilution modulus G D , and strain hardening potential of the LDPE melts. We also extend the fracture criterion for brittle fracture of monodisperse polymer melts to the case of polydisperse polymers and find reasonable agreement with experimental evidence.

Samples of two commercial low-density polyethylene melts were investigated with respect to their fracture behavior in controlled uniaxial extensional flow at constant strain rate in a filament stretching rheometer. In order to assess the possible influence of grain boundaries on fracture, the samples were prepared by three different types of pre-treatment: by compression molding of (1) virgin pellets used as received, (2) pellets homogenized in a twin-screw extruder, and (3) pellets that were milled into powder by cryogenic grinding under liquid nitrogen. The elongational stress growth data were analyzed by the Extended Hierarchical Multi-mode Molecular Stress Function (EHMMSF) model developed by Wagner et al. (Rheol. Acta 61, 281-298 (2022)) for long-chain branched (LCB) polymer melts. The EHMMSF model quantifies the elongational stress growth including the maximum in the elongational viscosity of LDPE melts based solely on the linear-viscoelastic relaxation spectrum and two nonlinear material parameters, the dilution modulus G D and a characteristic stretch parameter λ ¯ m . Within experimental accuracy, model predictions are in excellent agreement with the elongational stress growth data of the two LDPE melts, independent of the preparation method used. At sufficiently high strain rates, the fracture of the polymer filaments was observed and is in general accordance with the entropic fracture criterion implemented in the EHMMSF model. High-speed videography reveals that fracture is preceded by parabolic crack opening, which is characteristic for elastic fracture and which has been observed earlier in filament stretching of monodisperse polystyrene solutions. Here, for the first time, we demonstrate the appearance of a parabolic crack opening in the fracture process of polydisperse long-chain branched polyethylene melts.

The transient elongational data set obtained by filament-stretching rheometry of four commercial high-density polyethylene (HDPE) melts with different molecular characteristics was reported by Morelly and Alvarez [Rheologica Acta 59, 797–807 (2020)]. We use the Hierarchical Multi-mode Molecular Stress Function (HMMSF) model of Narimissa and Wagner [Rheol. Acta 54, 779–791 (2015), and J. Rheology 60, 625–636 (2016)] for linear and long-chain branched (LCB) polymer melts to analyze the extensional rheological behavior of the four HDPEs with different polydispersity and long-chain branching content. Model predictions based solely on the linear-viscoelastic spectrum and a single nonlinear parameter, the dilution modulus GD for extensional flows reveals good agreement with elongational stress growth data. The relationship of dilution modulus GD to molecular characteristics (e.g., polydispersity index (PDI), long-chain branching index (LCBI), disengagement time τd) of the high-density polyethylene melts are presented in this paper. A new measure of the maximum strain hardening factor (MSHF) is proposed, which allows separation of the effects of orientation and chain stretching.

Morelly et al. (Macromolecules 52:915-922, 2019) reported transient and steady-state elongational viscosity data of monodisperse linear polymer melts obtained by filament-stretching rheometry with locally controlled strain and strain rate and found different power law scaling of the elongational viscosities of polystyrene, poly(tert-butylstyrene) and poly(methyl-methacrylate). Very good agreement is achieved between data and predictions of the extended interchain pressure (EIP) model (Narimissa et al. J. Rheol. 64, 95-110 (2020)), based solely on linear viscoelastic characterization and the Rouse time τ R of the melts. The analysis reveals that both the normalized elongational viscosity and the normalized elongational stress are dependent on the number of entanglements ( Z ) and the ratio of entanglement molar mass M em to critical molar mass M cm of the melts in the linear viscoelastic regime through η E 0 / G N τ R ∝ M em / M cm 2.4 Z 1.4 and σ E 0 / G N ∝ M em / M cm 2.4 Z 1.4 W i , while in the limit of fast elongational flow with high Weissenberg number Wi = τ R ε ̇ , both viscosity and stress become independent of Z and M em / M cm , and approach a scaling which depends only on Wi , i.e. η E /( G N τ R ) ∝  Wi −1/2 and σ E / G N  ∝  Wi 1/2 . When expressed by an effective power law, the broad transition from the linear viscoelastic to the high Wi regime leads to chemistry-dependent scaling at intermediate Wi depending on the number of entanglements and the ratio between entanglement molar mass and critical molar mass.

In-extruder measurements of shear viscosity and normal stresses are important as these measurement techniques allow determining the rheological state of the polymer melt at processing conditions up to high shear rates. However, validation of viscosity and normal stress data obtained by in-line slit rheometers at high shear rates is difficult due to a lack of overlap of the in-line data and the off-line measurements by rotational rheometers limited to lower shear rates. Here, shear viscosity and normal stress data measured in-line at large shear rates during extrusion and off-line at low shear rates are compared to predictions of the Doi-Edwards model and the Hierarchical Multi-Mode Molecular Stress Function (HMMSF) model using linear-viscoelastic off-line small amplitude oscillating shear data of two polystyrenes and a low-density polyethylene as input parameters. For polystyrene, the results of this investigation do not only validate the experimental data obtained by rotational as well as slit-die rheometry, but also demonstrate the agreement between experiments and models up to very high shear rates, which were not experimentally accessible earlier. The low-density polyethylene shows a more complex behaviour, which follows the HMMSF model at low shear rates, but approaches the Doi-Edwards model at high shear rates.