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Lamellae forming polystyrene‐b‐poly‐2‐vinylpyridine diblock copolymer melts are investigated with linear shear rheology and Fourier transformation rheology (FT rheology) to quantify their nonlinear behavior under oscillatory shear via mechanical higher harmonic contributions such as I3/1(ω1, γ0). The determination of the zero‐shear nonlinearity (3Q0(ω)≡limγ0→0I3/1/γ02$^3Q_0(\omega)\equiv \lim _{\gamma _0 \rightarrow 0}I_{3/1}/\gamma _0^2$) by a variation of γ0 is hindered by the increasing domain alignment at increasing γ0. Thus, an approach for determining 3Q0(T) by a variation of the temperature is developed and used. This approach allows obtaining insights on the nonlinear behavior directly at temperature‐dependent phase transitions, such as at the order‐disorder transition temperature TODT of block copolymers. The maximum of 3Q0 is found to be close to TODT. The nonlinearity originating from the connection of the unequal polymer blocks is shown to dominate the overall nonlinearity, and the maximum of 3Q0(T) correlates to domain alignment for T < TODT. [ABSTRACT FROM AUTHOR]

The cumulative nonlinearity (Qf) is proposed as a new parameter to quantify mechanical fatigue. The parameter Qf represents the (cycle number) integral of the ratio of the third harmonic to the fundamental one (I3/1), obtained via Fourier transform of the stress (torque), normalized by the square of the strain amplitude (γ0). The validation is performed on different polymers: polystyrene (PS) with different molecular weights, styrene‐acrylonitrile (SAN), polymethylmethacrylate (PMMA), and polytertbuthylmethacrylate (PtBMA) under strain controlled fatigue tests in a torsion rectangular set‐up. A power‐law correlation between the number of cycles to failure (Nf) and the cumulative nonlinearity was found for Nf > 1000 cycles, and the results were compared with well‐established failure criteria such as the cumulative stress and the dissipated energy density. It was found that the cumulative nonlinearity has superior prediction ability since it can quantify material changes during a test. [ABSTRACT FROM AUTHOR]

The fatigue behavior of polystyrene (PS) in strain controlled torsion rectangular oscillatory tests was analyzed via Fourier transform (FT) to better understand the time evolution of linear and nonlinear mechanical parameters, and to establish fingerprints related to failure onset. The tests were performed under large amplitude oscillatory shear (LAOS), so the stress response was no longer perfectly sinusoidal and higher harmonics could be detected and quantified in the FT spectra as a function of time or number of cycles N . A linear parameter, the storage modulus ( G′(N) ), was analyzed, as well as nonlinear parameters of the ratios of the second ( I 2 (N) ) and the third ( I 3 (N) ) harmonics over the fundamental one ( I 1 (N) ). The nonlinear parameter I 2/1 (N) is very low for undamaged samples, but its intensity was found to increase when defects were created in the structure to a point where cracks became visible in the sample. On the other hand, the I 3/1 (N) parameter increased steadily during a test up to a local maximum where a macroscopic crack occurs in the sample. Both parameters I 2/1 (N) and I 3/1 (N) are proposed as new criteria to detect the onset of part failure under the conditions tested and can be used as safety limits for partial damage. [ABSTRACT FROM AUTHOR]

Hyphenated low-field NMR techniques are promising characterization methods for online process analytics and comprehensive offline studies of soft materials. By combining different analytical methods with low-field NMR, information on chemical and physical properties can be correlated with molecular dynamics and complementary chemical information. In this review, we present three hyphenated low-field NMR techniques: a combination of near-infrared spectroscopy and time-domain NMR (TD-NMR) relaxometry, online 1H-NMR spectroscopy measured directly after size exclusion chromatographic (SEC, also known as GPC) separation and a combination of rheometry and TD-NMR relaxometry for highly viscous materials. Case studies are reviewed that underline the possibilities and challenges of the different hyphenated low-field NMR methods. Copyright © 2015 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Different carbon-based fillers such as carbon nanotubes (CNTs), graphite, and thermally reduced graphene oxide (TrGO) are melt mixed with an isotactic poly(propylene) (iPP) and the mechanical properties of the resulting composites in the solid and melt state are analyzed. The Young's modulus of composites is increased around 25% relative to the neat iPP at concentrations above 10 wt% of CNTs or graphite whereas composites with TrGO are increased around 40% at similar concentrations. These results are compared with theoretical models showing that the filler agglomeration and surface area are key parameters. The rheological results of the composites under oscillatory shear conditions at the melt state show that the viscous raw polymer melt experiences a solid-like transition at a threshold concentration that strongly depends on the filler used. This transition appears at 10 wt% for CNTs, 8 wt% for TrGO, and 40 wt% for graphite. The viscosity of iPP/TrGO composites is further increased by adding CNTs particles, although the Young's modulus does not increase. [ABSTRACT FROM AUTHOR]

In this work, the effect of multi-walled carbon nanotube (CNT) and montmorillonite nanoclay on polymer chain dynamics is investigated around the percolation concentration for systems based on ethylene vinyl acetate (EVA) copolymer. Then, the results obtained are compared with literature data to determine if, regardless of particle characteristics, a universal rheological behavior can be detected at percolation. To do so, rheological analyses are performed under small amplitude oscillatory shear (SAOS), large amplitude oscillatory shear (LAOS), and transient shear step. SAOS data showed that, while the dynamics related to the Rouse relaxation time ( τ) were not significantly influenced, the reptation relaxation time ( τ) was strongly increased by the presence of nanoparticles. In step shear transient tests, the critical shear rate $$ \left({\dot{\upgamma}}_{\mathrm{cr}}\right) $$ for overshoot appearance was decreased due to chain confinement, and the formation of particle network strongly increased the level of stress overshoot. Particle networks increased significantly the nonlinear parameters ( I/ I and Q) obtained under LAOS and quantified by FT-rheology. In all measurements, due to the higher surface area associated to its size and density as well as hollow structure, CNT showed stronger effects compared to clay. Moreover, while the percolation concentration was different for CNT and clay, both systems showed similar behavior at percolation: a 0.5 scaling for G′ indicating a Rouse-dominated behavior. [ABSTRACT FROM AUTHOR]

Strain-controlled large amplitude oscillatory shear (LAOStrain) experiments on a polyisoprene melt and a polyisobutylene solution were conducted on four different rheometers. The results are compared using nonlinear quantities such as the normalized intensity of the third harmonic ( I) and the intrinsic nonlinearity in order to assess the reproducibility of the experiments. Two of the investigated instruments were strain-controlled rheometers, another two, were advanced stress-controlled rheometers. Since the stress-controlled rheometers are able to conduct strain-controlled tests when employing an active deformation control loop, the two different rheometer types could be compared. Experimental details like the gain of the deformation control loop, and the method of temperature control have been shown to play crucial roles in achieving reasonable reproducibility across the different instruments. Furthermore, deviations from the quadratic scaling of I with the strain amplitude and the influence of instrument inertia on nonlinear quantities were observed for one of the stress-controlled instruments. The standard deviation of the intrinsic nonlinearity Q( ω) at a specific angular frequency as determined by measurements on the same instrument was found to be 8 % or lower. The relative deviations of Q across different instruments were instead up to 12 % in the investigated frequency range with an exception for a specific instrument and one of the samples, where the deviation was considerably larger. [ABSTRACT FROM AUTHOR]

As a first remark, it should be noted that large portions of the archives of Karlsruhe University were lost during World War II (WWII) so that official documents about, e.g., the hiring process and the departure of Staudinger do not exist any longer (K. Nippert, July 2013, personal communication). [ABSTRACT FROM AUTHOR]

Eine spezielle Konstruktion eines Entropiemotors besteht aus zwei exzentrisch angeordneten Rädern deren einer Teil in einem warmen Wasserbad liegt. Auf diese Weise können Elastomerfilamente benutzt werden, um aus thermischer Energie bei niedriger Temperatur mechanische Energie zu gewinnen. Dabei durchlaufen die Elastomerfilamente eine reversible Änderung ihrer molekularen Konformation. [ABSTRACT FROM AUTHOR]

Following a theoretical proposal [M. Farhat et al., Phys. Rev. Lett. 103, 024301 (2009)], we design, fabricate, and characterize a cloaking structure for elastic waves in 1 mm thin structured polymer plates. The cloak consists of 20 concentric rings of 16 different metamaterials, each being a tailored composite of polyvinyl chloride and polydimethylsiloxane. By using stroboscopic imaging with a camera from the direction normal to the plate, we record movies of the elastic waves for monochromatic plane-wave excitation. We observe good cloaking behavior for carrier frequencies in the range from 200 to 400 Hz (one octave), in good agreement with a complete continuum-mechanics numerical treatment. This system is thus ideally suited for demonstration experiments conveying the ideas of transformation optics. [ABSTRACT FROM AUTHOR]

Abstract: Dynamic oscillatory shear tests are common in rheology and have been used to investigate a wide range of soft matter and complex fluids including polymer melts and solutions, block copolymers, biological macromolecules, polyelectrolytes, surfactants, suspensions, emulsions and beyond. More specifically, small amplitude oscillatory shear (SAOS) tests have become the canonical method for probing the linear viscoelastic properties of these complex fluids because of the firm theoretical background and the ease of implementing suitable test protocols. However, in most processing operations the deformations can be large and rapid: it is therefore the nonlinear material properties that control the system response. A full sample characterization thus requires well-defined nonlinear test protocols. Consequently there has been a recent renewal of interest in exploiting large amplitude oscillatory shear (LAOS) tests to investigate and quantify the nonlinear viscoelastic behavior of complex fluids. In terms of the experimental input, both LAOS and SAOS require the user to select appropriate ranges of strain amplitude (γ 0) and frequency (ω). However, there is a distinct difference in the analysis of experimental output, i.e. the material response. At sufficiently large strain amplitude, the material response will become nonlinear in LAOS tests and the familiar material functions used to quantify the linear behavior in SAOS tests are no longer sufficient. For example, the definitions of the linear viscoelastic moduli G′(ω) and G″(ω) are based inherently on the assumption that the stress response is purely sinusoidal (linear). However, a nonlinear stress response is not a perfect sinusoid and therefore the viscoelastic moduli are not uniquely defined; other methods are needed for quantifying the nonlinear material response under LAOS deformation. In the present review article, we first summarize the typical nonlinear responses observed with complex fluids under LAOS deformations. We then introduce and critically compare several methods that quantify the nonlinear oscillatory stress response. We illustrate the utility and sensitivity of these protocols by investigating the nonlinear response of various complex fluids over a wide range of frequency and amplitude of deformation, and show that LAOS characterization is a rigorous test for rheological models and advanced quality control. [Copyright &y& Elsevier]

Abstract: The paper introduces a novel procedure to determine the non-linear parameter of the Giesekus model, in relation to the characterization of the non-linear oscillatory shear regime of viscoelastic polymer solutions based on polyacrylamide. Instead of using the shear-thinning viscosity as the representative non-linear effect, the third harmonic in the Fourier spectrum of the shear stress response signal is considered for computing the mobility factor. The fluid is subjected to large amplitude oscillatory shear (LAOS) and its response is recorded. Deviations of this signal from the sinusoidal form are specific to each material and gives both qualitative and quantitative measures of the non-linearity. By fitting the material response with the corresponding numerical solutions of the n-modes Giesekus constitutive relation, one can extract the values of the non-linear α i -parameters that describe the fluid rheology. It is demonstrated that this procedure, which can be successfully applied to semi-concentrated polymer solutions, provides better results than the classical viscosity-fit method. [Copyright &y& Elsevier]

Abstract: The mechanical and structural properties of κ/ι-hybrid carrageenan gels obtained at various concentrations in the presence of 0.1 m KCl were studied with Fourier Transform rheology (FTR) and cryoSEM imaging. FTR data show that gels formed at concentration below 1.25 wt% exhibit a strain hardening behavior. The strain hardening is characterized by a quadratic increase of the scaled third harmonic with the strain and a third harmonic phase angle of zero degree. Both features are weakly depending on the concentration and conform to predictions from a strain hardening model devised for fractal colloidal gels. However, the phase angle of the third harmonic reveals that κ/ι-hybrid carrageenan gels obtained at higher concentrations show shear thinning behavior. Colloidal gel models used to extract structural information from the concentration scaling of gel equilibrium shear modulus G 0 and the strain dependence of FTR parameters suggest that κ/ι-hybrid carrageenan gels are built from aggregating rod-like strands (with fractal dimension x = 1.13) which essentially stretch under increasing strain. The mechanically relevant structural parameters fairly match the gel fractal dimension (d = 1.66) obtained from the cryoSEM analysis. [Copyright &y& Elsevier]

The understanding of long chain branched homopolymer melts in shear flow is of significant interest to polymer science and critical to ensure stable processing. We report on the startup shear flow at a constant shear rate of well-defined pom-pom shaped polymer melts. Pom-poms consist of two stars covalently connected by a single backbone. For low-arm numbers and short arms, a single stress overshoot followed by a steady state is observed, similar to linear and star shaped melts. For one highly branched pom-pom with entangled branches, a double stress overshoot during the startup shear flow could be observed before reaching the steady state viscosity. Additionally, we find that the Cox–Merz rule, which relates the complex viscosity η * ω to the steady state shear viscosity η γ ̇ , fails at high-shear rates, if the backbone is not self-entangled. [ABSTRACT FROM AUTHOR]

The determination of molar masses and their distributions is crucial in polymer synthesis and design. This work presents the current performance and limitations of diffusion‐ordered spectroscopy (DOSY) on a low‐field (benchtop) NMR spectrometer (at 90 MHz) as an alternative to size exclusion chromatography (SEC) for determining diffusion coefficient distributions (DCDs) and molar mass distributions (MMDs). After optimization for narrowly distributed homopolymers, MMDs obtained with inverse Laplace transformation (ILT) and log‐normal distribution are compared with average molar masses obtained with mono‐ and bi‐exponential fits, as well as MMDs obtained from SEC. This approach enables ILT to determine DCDs and MMDs even for bimodal homopolymers with fully spectrally overlapping signals and block copolymers with various chemical compositions, for which chemical composition profiles are determined. The feasibility of low‐field diffusion NMR with samples dissolved in non‐deuterated solvents is further demonstrated and methods for solvent suppression are discussed. [ABSTRACT FROM AUTHOR]

Polymer topology highly impacts rheological melt and foaming properties. Grafting sidechains onto a linear polymer typically results in shear thinning and strain hardening in elongation flow. To study the influence of an increasing number of covalently connected polystyrene (PS) stars s with a linear PS chain (Mw,PS = 90 kg mol−1), low‐disperse branched polymers with s ranging from one to four are synthesized. Each star contains approximately 12 sidechains with a length of Mw,a≈ 25 kg mol−1. Oscillatory shear measurements indicated that the zero‐shear viscosity η0 scales with η0 ≈ Mw,t3.9$M_{w,t}^{3.9}$ at Tref = 180 °C. Moreover, uniaxial elongation rheology allows determining the strain hardening factor SHF, which varies between SHF = 2–135, with increasing s. Foaming experiments revealed that combining viscosity reduction with the improvement of stretchability promotes higher volume expansion ratios (VER = 3.21–10.41) and the formation of larger cells (D = 4.8–14.8 µm). [ABSTRACT FROM AUTHOR]

This work investigates the phenomena of self-heating, also called intrinsic heating, and thermoelastic coupling during non-linear dynamic mechanical fatigue testing via surface temperature measurement coupled with the mechanical behavior of polymers. Static tensile tests and dynamic strain controlled fatigue tests under tension/tension were performed at a frequency of ω 1 /2π = 5 Hz, as well as in the low cycle fatigue regime at ω 1 /2π = 0.2 Hz, on six polymers: high density polyethylene (HDPE), low density polyethylene (LDPE), ultra high molecular weight polyethylene (UHMWPE), polyamide 6 (PA6), and two grades of polypropylene (PP). In dynamic testing, the surface temperature rises to a plateau value (ΔT) when an equilibrium between the viscous/plastic dissipated energy and heat convection is reached. Power-law correlations were found between the strain amplitude (ε 0) and ΔT , as well as between ε 0 and the calculated dissipated energy density (W diss,p) obtained from the mechanical stress response, with similar exponents for both correlations. Thermoelastic coupling is firstly investigated in uniaxial tension, revealing a linear relation between the strain rate and the rate of temperature decrease, which is more distinct with decreasing polymer chain mobility. In dynamic fatigue testing, the surface temperature was found to oscillate with an amplitude T 1 , which was analyzed via Fourier transform. A direct relation between T 1 and ε 0 at small deformations was observed. At large strain amplitudes, T 1 (ε 0) follows a similar trend as the complex modulus E*(ε 0). At low frequencies and large strain amplitudes, additional higher harmonics at two (T 2) and three (T 3) times the fundamental frequency were also detected as fingerprints of plastic deformation, resulting in additional heat dissipated during the loading half cycle. From the results obtained, the advantages of the calculated dissipated energy density over the surface temperature analysis was analyzed to predict the fatigue behavior. This analysis is believed to be valid for all materials due to the mathematical/physical principles involved. The results are thus expected to hold for other materials such as composites, rubbers, ceramics and metals. [Display omitted] • Intrinsic heating follows mechanical nonlinearity quantified by the loss modulus. • Onset of mechanical nonlinearity correlates with 106 cycles lifetime for polypropylene. • Thermoelastic coupling is proportional to the nonlinear behavior of the complex modulus. • Plastic deformation results in higher harmonics in thermoelastic coupling at low frequency. • Higher harmonics in thermoelastic coupling can be quantified via Fourier transform. [ABSTRACT FROM AUTHOR]

In response to nutrients, intestinal L‐ and K‐cells naturally secrete glucagon‐like peptide 1 (GLP‐1). GLP‐1 regulates postprandial blood glucose by increasing insulin secretion, slowing down gastric emptying and inducing satiety. A selection of specifically developed collagen hydrolysates was screened for their ability to enhance natural GLP‐1 production in vitro. The best performing hydrolysate, H80 (Nextida GC), was orally administered at different doses to lean, normoglycemic mice and overweight, prediabetic mice. Lean mice were acutely challenged 45 min before an oral glucose load. While daily supplemented for 6 weeks, prediabetic mice were acutely challenged at day 21 and 34. Oral glucose tolerance, plasma insulin and GLP‐1 levels were assessed, and a gastric emptying assay performed in prediabetic mice. H80 significantly lowered the blood glucose response in lean and prediabetic mice, at a 4 g/kg dose (−25% and −36%, respectively), compared to vehicle. In chronically supplemented, prediabetic mice, acute H80 administration slowed down gastric emptying (−60%) after 21 days and increased plasma insulin (+166%) after 35 days of supplementation. H80 increased plasma active GLP‐1 in lean (+217%) and prediabetic (+860%) mice. Overall, the data indicate that the specific collagen hydrolysate, H80, has significant GLP‐1‐mediated effects on oral glucose tolerance in lean and prediabetic mice. Furthermore, effects on postprandial glucose tolerance were evaluated in a small, human, proof of concept study. H80 reduced the postprandial glucose response at a 5 g dose in healthy, normoglycemic and prediabetic participants. Oral supplementation with H80 might thus be a promising strategy to maintain normal glucose tolerance. [ABSTRACT FROM AUTHOR]

Electrochemically exfoliated graphene (EEG) is compounded with copolyamide 6/66 (PA6/66) to investigate the influence of the carbonaceous filler material on the thermal, rheological, and mechanical properties of the composite. Toward that end, the environmentally friendly electrochemical exfoliation in aqueous solution is further developed to furnish graphene in large quantities. Separating the exfoliation process from the incorporation into the polymer matrix by wet phase inversion (WPI) allowed in‐depth characterization of the EEG by scanning electron microscopy (SEM), atomic force microscopy (AFM), and Raman spectroscopy. The crystallinity of copolyamide 6/66‐EEG is significantly changed, as revealed by differential scanning calorimetry (DSC). Likewise, the new composite materials exhibit different flow properties, as well as increased mechanical reinforcement with additive concentration. This is proven by dynamic shear rheology and three‐point stress tests compared to the neat polymer. [ABSTRACT FROM AUTHOR]

Organogels are polymer networks extended by a liquid organic phase, offering a wide range of properties due to the many combinations of polymer networks, solvents, and shapes achievable through 3D printing. However, current printing methods limit solvent choice and composition, which in turn limits organogels' properties, applications, and potential for innovation. As a solution, a method for solvent‐independent printing of 3D organogel structures is presented. In this method, the printing step is decoupled from the choice of solvent, allowing access to the full spectrum of solvent diversity, thereby significantly expanding the range of achievable properties in organogel structures. With no changes to the polymer network, the 3D geometry, or the printing methodology itself, the choice of solvent alone is shown to have an enormous impact on organogel properties. As demonstrated, it can modulate the thermo‐mechanical properties of the organogels, both shifting and extending their thermal stability range to span from ‐30 to over 100 °C. The choice of solvent can also transition the organogels from highly adhesive to extremely slippery. Finally, the method also improves the surface smoothness of prints. Such advances have potential applications in soft robotics, actuators, and sensors, and represent a versatile approach to expanding the functionality of 3D‐printed organogels. [ABSTRACT FROM AUTHOR]

3D printing technologies have matured to produce complex structures, still they are often limited to static materials. Introducing alkoxyamine bonds into 3D printed structures offers unprecedented possibilities for post‐synthetic modification through nitroxide exchange reaction and nitroxide‐mediated polymerization. This study provides a comprehensive molecular and macroscopic characterization of 3D‐printed alkoxyamine‐containing dynamic covalent adaptable networks. The study provides new insights into their dynamic structural and mechanical alterations, making them promising candidates for advanced applications ranging from biomedical engineering to flexible electronics. [ABSTRACT FROM AUTHOR]

The mechanical nonlinear visco-hyper-elastic behavior of elastomers via Fourier transform (FT) of the stress during cyclic sinusoidal strain controlled fatigue in tension/tension is investigated. FT allows to quantify the nonlinear contributions in the stress, changing due to ongoing fatigue, i.e., its deviation from a purely sinusoidal waveform via the intensities of the second (I2/1) and third (I3/1) normalized higher harmonics. Two commercial resins, ethylene–vinyl-acetate (EVA) and poly(ethylene-co-octene), a polyolefin elastomer (POE), are used. The nonlinear contributions in the stress depend on the strain amplitude, so strain sweep tests with different deformation ratio R (ratio of the minimum (εmin) over maximum (εmax) strain, R = εmin/ εmax), are performed, to understand and predict the FT spectra at the beginning of each fatigue test. Linear and nonlinear mechanical parameters are compared to those computed via Neo-Hooke, Mooney-Rivlin, Ogden, and Arruda-Boyce models. A modified Neo-Hookean model is proposed to fit the nonlinear visco-hyper-elastic mechanical behavior, covering the nonlinear contributions detectable for large strain amplitudes (I2/1 or I3/1 > 10−3), and the linear stress response (I2/1 and I3/1 < 10−3) occurring at very large strain amplitudes and R ratios. Finally, changes in the visco-hyper-elastic material behavior due to fatigue are detected and quantified via FT, showing that I2/1 and I3/1 are more sensitive parameters towards fatigue than storage (E') and loss (E") moduli. The I2/1 intensity is found to decrease to a minimum before increasing fast at failure for time-dependent measurements. This I2/1 minimum can be correlated to changes of the hyper-elastic material behavior from strain softening to strain hardening, occurring in the high cycle fatigue regime after about 50% and 70% of the total fatigue lifetime for POE and EVA, respectively. [ABSTRACT FROM AUTHOR]

A series of well‐defined symmetric poly(methyl methacrylate)‐b‐poly(sodium methacrylate)‐b‐poly(methyl methacrylate) (PMMA‐b‐PSMA‐b‐PMMA) triblock copolymers with various block compositions is synthesized. The amphiphilic ABA triblock copolymers form polyelectrolyte hydrogels in water by self‐assembly. The hydrophobic PMMA endblocks act as physical cross‐links in the form of frozen micelles, while the hydrophilic PSMA midblocks span the 3D network. The influence of various synthetic parameters on the self‐assembly and the macroscopic properties of these hydrogels is systematically investigated by water absorbency, oscillatory shear rheology, and small‐angle X‐ray scattering. The polymer concentration during the hydrogel formation affects the ratio between looping and bridging chains. The number of MMA units per endblock (nA) determines the size and the relaxation rates of the physical cross‐links and thus, the mechanical stability of the hydrogels. More SMA units in the midblock (nB) increase the water absorbency, while the mechanical moduli decrease. Even lower G‐moduli are achieved by partly exchanging the symmetric ABA triblock with AB diblock copolymers, which can only form non‐elastic dangling ends. [ABSTRACT FROM AUTHOR]

This article presents a fast, straightforward synthesis approach to polymerize alternating multiblock copolymers, ultra‐high molecular weight (UHMW) (homo)polymers as well as precursors for complex macromolecular topologies such as comb or barbwire architectures. The one‐pot synthesis strategy proposed in this work is based on anionic polymerization via a bifunctional initiator and the subsequent linking of macro dianions with a bifunctional linker, additionally overcoming the limitations associated with the monomer reactivity. Thus, the synthetic route guarantees the repeating size of polymer blocks and an equal distribution of functional groups in precursors for complex topologies. Dianions of polystyrene (PS), polyisoprene‐b‐polystyrene‐b‐polyisoprene, and poly‐2‐vinylpyridine‐b‐polystyrene‐b‐poly‐2‐vinylpyridine are linked with α,α′‐dibromo‐para‐xylene to UHMW and multiblock copolymers. Multiblock copolymers with on average up to 50 well‐defined alternating A and B blocks are accessible within 15 min. [ABSTRACT FROM AUTHOR]

The plant Santa herba (Eriodictyon californicum) contains high flavonoids, thus potentially exerting beneficial effects in context of obesity, often accompanied by inflammation and metabolic imbalance. The study assessed the impact of Santa herba on oxidative stress, energy metabolism, weight reduction, and eating behavior, combining in vitro models with clinical data. Santa herba binding of the adenosine receptor A2A (ADORA2A) was assessed using a radioligand binding assay. A Caenorhabditis elegans model was used to determine mobility boosting effects, and Santa herba oxygen radical absorbance capacity (ORAC) values were determined in comparison to antioxidative plants. Clinical data, that is, body weight and appetite-related parameters, were obtained from overweight and obese women receiving either Santa herba or placebo for 12 weeks. Results showed that Santa herba extract binds to ADORA2A, stimulates C. elegans motility (+7.5%) and locomotion, and yields high antioxidative capacities (ORAC: 819 trolox equivalent). Clinical data, obtained from 24 overweight and 25 obese women (mean: 47.5 years), demonstrated a reduced body weight (P = .042) and body fat (P = .044), and by trend reduced leptin levels (P = .065) in women with obesity after Santa herba consumption compared to placebo. In conclusion, Santa herba extract has energizing and antioxidative properties and may aid in weight management of people with obesity. ClinicalTrials.gov Identifier: NCT03853603. [ABSTRACT FROM AUTHOR]

We consider the elongational rheology of model polystyrene topologies with 2, 3 and 4 stars, which are connected by one (2-star or "Pom-Pom"), two (3-star) and three (4-star) linear backbone chains. The number of arms of each star varies from qa = 3 to 24, the molecular weight of the arms from Mw,a = 25 kg/mol to 300 kg/mol, and the backbone chains from Mw,b = 100 kg/mol to 382 kg/mol. If the length of the arm is shorter than the length of the backbone, i.e. Mw,a < Mw,b, and despite the vastly different topologies considered, the elongational stress growth coefficient can be modeled by the Hierarchical Multi-mode Molecular Stress Function (HMMSF) model, based exclusively on the linear-viscoelastic characterization and a single nonlinear parameter, the dilution modulus. If the length of the arms of the stars is similar or longer than the length of the backbone chain (Mw,a ≥ Mw,b) connecting two stars, the impact of the backbone chain on the rheology vanishes and the elongational stress growth coefficient is dominated by the star topology showing similar features of the elongational stress growth coefficient as those of linear polymers. [ABSTRACT FROM AUTHOR]

The fatigue behavior of 28 amorphous and semi‐crystalline thermoplastic polymers and elastomers is tested under strain controlled sinusoidal tension‐tension (TT) and torsion (T) at room temperature and analyzed via strain‐life (total strain amplitude versus fatigue lifetime) and crack propagation rate versus total strain amplitude curves, analogous to Paris' law. Investigating fatigue is extremely time‐ and resources consuming, so universal relationships between the exponents of the strain‐life power‐law and material properties are of high importance. For a brittle failure mechanism (I), the strain‐life curves are found to have fixed exponents of BTT,I = −0.27 and BT,I = −0.22, respectively, while the crack propagation versus strain amplitude in TT has an exponent of mda/dN,I = 4. For ductile failure (II), fixed strain‐life curve exponents in TT of BTT,II = −0.35 and in torsion of BT,II = −0.48 with mda/dN,II = 2.8 are obtained. In torsion, most semi‐crystalline polymers show brittle and ductile failure depending on the applied strain amplitude, so the strain‐life curve exponent changes accordingly. The universal exponents for strain‐life and crack growth‐strain amplitude curves offer a significant simplification to rapidly estimate, predict, and simulate the fatigue behavior of polymers. [ABSTRACT FROM AUTHOR]

Polymer gels, consisting of cross‐linked polymer network systems swollen by a solvent, show great potential in biomedicine, flexible electronics, and artificial muscles, due to their tissue‐like mechanical properties. Due to the presence of a large amount of solvent, the improvement of the mechanical properties of the polymer gel is a challenge. Moreover, combining high toughness with useful properties, such as 3D printability or shape‐memory, in one polymer gel system is even more challenging. In this study, a simple and efficient method is developed for the fabrication of tough polymer gels by polymerizing 2‐hydroxyethyl methacrylate (HEMA) in a mixture of poly(ethylene glycol) (PEG) and poly(propylene glycol) (PPG). The polymerized elastic networkpresents distinct compatibility with PEG (compatible) and PPG (poorly compatible), resulting in in‐situ phase separation at the microscale. The resulting phase‐separated gel demonstrates high strength (8.0 MPa), favorable fracture strain (430%), and large toughness (17.0 MJ m−3). The separated hard phasewith a high glass transition temperature (75 °C) endows the whole soft polymer gel with the property of shape memory at room temperature. Finally, the fabrication of tunable tough PEGgels is combined with 3D printing as well as with shape memory properties, demonstrating the use of PEGgels for 4D printing. [ABSTRACT FROM AUTHOR]

Strain hardening of long-chain branched polymers in elongational flow occurs due to the stretch of the backbone chain between branch points. With an increasing number of side arms, the length of the backbone chain segment between two branch points of a comb decreases. Of particular interest is the case when the number Nb of arms per entanglement length of the polymer is larger than one. This leads not only to larger strain hardening but also to hyperstretching, i.e., the elongational stress growth shows an enhanced increase with strain. We consider elongational data reported by Abbasi et al. [Macromolecules 50(15), 5964–5977 (2017)] and Faust et al. [Macromol. Chem. Phys. 224(1), 2200214 (2023)] on a series of comb and branch-on-branch polystyrene (PS) melts with the average number Nb of branches per entanglement segment of the backbone ranging from Nb = 0.2 to Nb = 9.5. In addition, we present measurements of the elongational viscosity of two PS combs with Nb = 4.7 as well as of blends consisting of 5 to 50 wt. % of a PS comb and a monodisperse linear PS. Analysis by the hierarchical multimode molecular stress function model shows that while backbone chains of loosely grafted combs with Nb < 1 are stretched affinely in elongational flow, backbone chains of more densely grafted combs with Nb > 1 show increasing hyperstretching with increasing Nb. The elongational data of the comb/linear blends confirm that hyperstretching is an intrinsic property of the comb macromolecule with Nb > 1, independent of its concentration in the blend. While this is of considerable interest from a modeling point of view, hyperstretching causing an enhanced increase of the elongational stress growth can also have a significant impact on the processability of polymers, and quantification of this effect is, therefore, important. [ABSTRACT FROM AUTHOR]

Silica as one the most important fillers for rubber material is routinely modified by silane to improve its compatibility with the rubber matrix. Silanization of the silica particle affects both the linear and nonlinear rheological behaviors of the compounds. Their rheological nonlinearity, however, is mostly analyzed in an indirect way from linear rheological parameters, e.g. G′(ω1, γ0) and G″(ω1, γ0), which lose their physical meaning in the nonlinear viscoelastic regime. In the present work, the nonlinearity is directly quantified by the Fourier-transform rheology (FT-Rheology) technique in terms of I3/1(ω1, γ0), the third relative higher harmonic, for unvulcanized styrene butadiene rubber compounds filled with a fixed amount of silica, but varying dosages of silane. With the proposed model for I3/1(γ0), the contributions toward nonlinearity from the filler networks at a low strain amplitude and the one from the polymer networks at high strain amplitude can be successfully separated for filled systems. The utmost nonlinearity contribution from the filler networks decreases with the silane content, which is assigned to the weakening interparticle interaction of the filler. With increasing silanization of silica, the utmost nonlinearity contribution from the polymer networks is found to increase. This nonlinear mechanical response is attributed to the enhanced interfacial interaction between the filler and polymer. [ABSTRACT FROM AUTHOR]

Low folate status is a risk factor for birth defects. We studied concentrations of red blood cell (RBC)- and serum folate in 198 German women in relation to information on dietary folate intake, demographic and lifestyle factors. Median serum- and RBC-folate levels were; (14.7 and 589 nmol/L, respectively. Serum < 7.0 nmol/L or RBC-folate < 405 nmol/L were observed in 3.5% and 18.7% of the women, respectively. Three per cent of the women had both lowered serum and RBC-folate. Whereas RBC-folate > 952 nmol/L (optimal levels around conception) were observed in 9.6%. Serum- and RBC-folate were positively associated; they showed the expected correlations with homocysteine, but only weak correlations with folate intake. Younger age, lower fibre and higher carbohydrate intakes were associated with lower blood folate. Thus, folate intake of approximately 278 µg/d was not sufficient to achieve optimal folate status in young women. In conclusion, in the absence of fortification with folic acid, the majority of the women did not achieve folate status that is optimal for prevention of birth defects. [ABSTRACT FROM AUTHOR]

During the processing of elastomeric compounds under high flow rates, significant pressure drops (106–108 Pa) are encountered. Under such conditions, the viscosity of these compounds is significantly affected by pressure and viscous heating. Moreover, strong flow rates may cause these systems to slip at the wall, violating the classical no-slip boundary condition of fluid mechanics. To determine the slip velocity by the well-known Mooney method, the effects of pressure and viscous heating should be considered. In this work, an experimental methodology is developed to determine the slip velocity of styrene–butadiene compounds in capillary flow corrected for the effects of pressure and viscous heating. First, the temperature increase due to viscous heating is measured during the extrusion process and accounted for in correcting the experimental data to infer the slip velocity. Consequently, the corrected experimental data for the effects of pressure and viscous heating are used to calculate the slip velocity from the deviation of the linear viscoelastic behavior (deviation from the Cox–Merz rule). The Mooney method is also used to confirm the calculated slip velocity of the elastomeric compounds. [ABSTRACT FROM AUTHOR]

Purpose: Folate required to achieve desirable red blood cell (RBC) folate concentrations within 4-8 weeks pre-pregnancy is not known. We studied the effect of supplementation with 400 or 800 µg/day folate in achieving RBC-folate ≥906 nmol/L.Methods: Non-pregnant women were randomized to receive multinutrient supplements containing 400 µg/day (n = 100) or 800 µg/day (n = 101) folate [folic acid and (6S)-5-CH3-H4folate-Ca (1:1)]. The changes of folate biomarkers were studied after 4 and 8 weeks in the 198 women who returned at least for visit 2.Results: At baseline, 12 of the 198 participants (6.1%) had RBC-folate <340 nmol/L, but 88% had levels <906 nmol/L. The RBC-folate concentrations increased significantly in the 800 µg/day (mean ± SD = 652 ± 295 at baseline; 928 ± 330 at 4 weeks; and 1218 ± 435 nmol/L at 8 weeks) compared with the 400 µg/day [632 ± 285 at baseline (p = 0.578); 805 ± 363 at 4 weeks (p < 0.001); 1021 ± 414 nmol/L at 8 weeks (p < 0.001)]. The changes of RBC-folate were greater in the 800 µg/day than in the 400 µg/day at any time (changes after 8 weeks: 566 ± 260 vs. 389 ± 229 nmol/L; p < 0.001). Significantly more women in the 800 µg group achieved desirable RBC-folate concentrations at 4 weeks (45.5 vs. 31.3%; p = 0.041) or 8 weeks (83.8 vs. 54.5%; p < 0.001) compared with the 400 µg group. RBC-folate levels below the population median (590 nmol/L) were associated with a reduced response to supplements.Conclusions: 88% of the women had insufficient RBC-folate to prevent birth defects, while 6.1% had deficiency. Women with low RBC-folate were unlikely to achieve desirable levels within 4-8 weeks, unless they receive 800 µg/day. The current supplementation recommendations are not sufficient in countries not applying fortification.Trials register: The trial was registered at The German Clinical Trials Register: DRKS-ID: DRKS00009770. [ABSTRACT FROM AUTHOR]

The foaming structure and rheological properties of four different isotactic homo-polypropylenes with various molecular weights and an isotactic long chain branched polypropylene were investigated to find a suitable rheological fingerprint for PP foams. The molecular weight distribution and thermal properties were measured using GPC-MALLS and differential scanning calorimetry, respectively. Small amplitude oscillatory shear data and uniaxial extensional experiments were analyzed using the frameworks of van Gurp-Palmen plot (δ vs. |G*|) and the molecular stress function model, respectively. These analyses were used to find a correlation between the molecular structure, rheological properties and foaming structures of linear and long chain branching polypropylenes. Two linear viscoelastic characteristics, |G*| at δ = 60° and |η*| at ω = 5 rad/s were used as criteria for foamability of these polymers, where decreasing of both parameters by increasing the long chain branching content results in smaller cell size and higher cell density. The molecular stress function model was able to quantify the strain hardening properties of long chain branching blends using small amplitude oscillatory shear data and two nonlinear material parameters, 1 ≤ β ≤ 2.2 and 1 ≤ fmax 2 ≤ 600, where the minimum and maximum values of these parameters belong to the linear and long chain branched polypropylene, respectively. Increasing the long chain branched polypropylene content of the PP blends increased strain hardening, and therefore improved the foaming characteristics significantly by suppressing the coalescence of cells. Dilution of linear PP with only 10 wt% of long chain branched polypropylene enhanced the cell density from 5.7 × 106 to 2.7 × 107 cell/cm3 and reduced the average cell diameter from 58 to 26 µm, respectively, while their volume expansion ratio remained in the same range of 2–3. Increasing of long chain branching to 50 and 100 wt% enhanced the V.E.R. to 6.2 and 7.8, respectively. [ABSTRACT FROM AUTHOR]

Purpose: The aim of this trial was to investigate the influence of a dietetic product consisting of a unique combination of l-arginine with the vitamins B6, folic acid and B12 (Telcor® Arginin plus) on endothelial dysfunction.Methods: Subjects aged 40-65 years with mild to moderate blood pressure (BP) elevation not treated with anti-hypertensive drugs were randomly assigned to either the dietetic product (n = 40) or a matching placebo (n = 41) for 3 months with open follow-up for a further 3 months. Postprandial change in endothelial function was assessed using the validated reactive hyperaemia index (RHI) at 3 months compared to the study onset (RHI post-pre, visit 3-visit 1; ΔΔRHI). Secondary parameters included BP and plasma homocysteine concentration.Results: The primary efficacy analysis revealed superiority of the nutritional intervention over placebo (p = 0.0349) in reducing the deterioration of endothelial function. While in the active group ΔΔRHI increased (0.371 ± 0.122), almost no change could be detected in the placebo group (0.031 ± 0.100), thus demonstrating a significant improvement in vascular function in the intervention group. Moreover, the intervention reduced BP and homocysteine levels. Non-serious adverse events were equally distributed in both groups, and none of the events were assessed as possibly intervention-related by the investigators.Conclusions: This trial confirmed the effective and safe use of dietary management with l-arginine in combination with B vitamins. The primary efficacy analysis demonstrated a statistically significant superiority of the combination of l-arginine with B vitamins over placebo in improving and restoring impaired endothelial function and lowering BP in patients with mild to moderate blood pressure elevation. [ABSTRACT FROM AUTHOR]

The rheological behavior of styrene–butadiene rubber (SBR) compounds filled with silica is investigated as a function of silica volume fraction. To predict the mechanical response, a continuum model for entangled polymer melts filled with nanoparticles is herein introduced. This model is capable of describing the rheological response in both the linear and nonlinear viscoelastic regimes in the context of non-equilibrium thermodynamics to guarantee its thermodynamic admissibility. The constitutive model describes the polymer nanocomposite melts at a mesoscopic level of description by considering the conformation tensor between successive entanglement points, and the orientation tensor for the, in general, spheroidal nanoparticles that describes their average orientation. Evolution equations are developed for nanoparticles with an arbitrary shape but are eventually specified to the case of spherical ones. The multimode version of the new constitutive model provides a very accurate prediction of the rheological behavior of the processability range of SBR/silica nanocomposites. Thus, the new model is a tool able to provide answers to the several difficulties that rubber-producing manufacturers face when processing rubber compounds. [ABSTRACT FROM AUTHOR]

The elongational rheology of blends of a polystyrene (PS) Pom-Pom with two linear polystyrenes was recently reported by Hirschberg et al. (J. Rheol. 2023, 67:403–415). The Pom-Pom PS280k-2x22-22k with a self-entangled backbone (Mw,bb = 280 kg/mol) and 22 entangled sidearms (Mw,a = 22 kg/mol) at each of the two branch points was blended at weight fractions from 75 to 2 wt% with two linear polystyrenes (PS) having Mw of 43 kg/mol (PS43k) and 90 kg/mol (PS90k), respectively. While the pure Pom-Pom shows strong strain hardening in elongational flow (SHF > 100), strain hardening (SHF > 10) is still observed in Pom-Pom/linear blends containing only 2 wt% of Pom-Pom. The elongational start-up viscosities of the blends with Pom-Pom weight fractions above 10 wt% are well described by the Molecular Stress Function (MSF) model, however, requiring two nonlinear fit parameters. Here we show that quantitative and parameter-free modeling of the elongational viscosity data is possible by the Hierarchical Multi-mode Molecular Stress Function (HMMSF) model based on the concepts of hierarchical relaxation and dynamic dilution. In addition, we investigated the elongational viscosity of a blend consisting of 20 wt% Pom-Pom PS280k-2x22-22k and 80 wt% of a PS star with 11 arms of Mw,a = 25 kg/mol having a similar span molecular weight as PS43k and similar Mw,a as the Pom-Pom. This work might open up possibilities toward polymer upcycling of less-defined polymers by adding a polymer with optimized topology to gain the intended strain hardening, e.g., for film blowing applications. [ABSTRACT FROM AUTHOR]

Time-domain NMR is a well known tool for assessing the molecular dynamics in soft matter by measuring the excitation and subsequent decay of 1H nuclear magnetization. It is widely used, e.g., to quantify the composition of heterogeneous soft matter systems like semicrystalline polymers or emulsions. Further applications, known from academic research and industrial application, include measuring the moisture content in solids, the residual magnetic dipolar coupling for quantifying molecular motion in crosslinked systems, or diffusometry. We report the integration of a permanent magnet based pulsed NMR spectrometer into a modern, commercially available high-end shear rheometer. The setup allows for the first time to simultaneously conduct time-domain 1H NMR and steady shear or dynamic rheological measurements on one sample and to directly correlate the results from both, without concerns about differences in the sample history or temperature calibration. Moreover, the new in-situ combination allows the full usage of the rheometer to apply nonlinear deformation, under steady shear or large amplitude oscillatory shear, and directly measure the effect on the time evolution of the sample properties. This publication introduces the technical setup of this novel instrument combination and describes the shear induced crystallization of polyolefins to demonstrate its capabilities. Further potential applications are outlined. [ABSTRACT FROM AUTHOR]

The present study highlights a range of surface and volume extrudate patterns that can be detected during the extrusion flow of long‐chain branched polymers. Thus, four linear low‐density polyethylenes (LDPEs) have been extruded using a single‐screw extruder coupled to an inline optical imaging system. The selected LDPEs are selected to outline the influence of molecular weight and long‐chain branching on the types of melt flow extrusion instabilities (MFEI). Through the inline imaging system, space–time diagrams are constructed and analyzed via Fourier‐transformation using a custom moving window procedure. Based on the number of characteristic frequencies, peak broadness, and whether they are surface or volume distortions, three main MFEI types, distinct from those typically observed in linear and short‐chain branched polymers, are identified. The higher molecular weight, low long‐chain branching LDPEs exhibited all three instability types, including a special type volume instability. Independently of the molecular weight, higher long‐chain branching appeared to have a stabilizing effect on the transition sequences by suppressing volume extrudate distortions or limiting surface patters to a form of weak intensity type. [ABSTRACT FROM AUTHOR]

A Pom-Pom polymer with qa side chains of molecular weight Mw,a at both ends of a backbone chain of molecular weight Mw,b is the simplest branched polymer topology. Ten nearly monodisperse polystyrene Pom-Pom systems synthesized via an optimized anionic polymerization and a grafting-onto method with Mw,b of 100 to 400 kg/mol, Mw,a of 9 to 50 kg/mol, and qa between 9 and 22 are considered. We analyze the elongational rheology of the Pom-Poms by use of the hierarchical multi-mode molecular stress function (HMMSF) model, which has been shown to predict the elongational viscosity of linear and long-chain branched (LCB) polymer melts based exclusively on the linear-viscoelastic characterization and a single material parameter, the so-called dilution modulus GD. For the Pom-Poms considered here, we show that GD can be identified with the plateau modulus G N 0 = G D , and the modeling of the elongational viscosity of the Pom-Poms does therefore not require any fitting parameter but is fully determined by the linear-viscoelastic characterization of the melts. Due to the high strain hardening of the Pom-Poms, brittle fracture is observed at higher strains and strain rates, which is well described by the entropic fracture criterion. [ABSTRACT FROM AUTHOR]

Quantification of diffusion coefficient distribution (DCD) and correlation with molecular weight distribution (MWD) of polymers is still an issue in pulsed field-gradient nuclear magnetic resonance (PFG-NMR). The conventional scaling law utilized so far to relate diffusion coefficient and molecular weight only holds true for the determination of MWD at sufficiently low concentrations. To extend measurement limits and to get a good signal-to-noise ratio, an exponential correlation is introduced to describe the effect of polymer concentration on diffusion in PFG-NMR. Two model polymers (polystyrene and poly(methyl methacrylate)) dissolved in deuterated chloroform are studied at different concentrations in the range of 0.16-8 wt%. The DCDs are determined by modeling the measured signal attenuation with three methods (gamma distribution, log normal distribution, and tailored norm regularization). It is shown that the proposed method applies to the PFG-NMR measurements on polymer solutions over a wide concentration range, providing almost the same MWDs as those obtained at low concentrations. The MWDs retrieved from NMR experiments agree well with those by size exclusion chromatography. [ABSTRACT FROM AUTHOR]

The development of a high sensitivity polymer melt extrusion flow instability detection die capable of estimating the normal stress differences of polymer melts during capillary rheometry tests via the ’hole effect’ is presented here as proof-of-principle. Two polymer melts, a low density polyethylene (branched topology) and a high density polyethylene (linear topology), were tested in a variety of experimental configurations with the purpose of determining optimal conditions for performing normal stress difference measurements. The data was compared with rotational rheometry oscillatory shear measurements analyzed via the Laun rule. It is shown that it is possible to estimate the first normal stress difference in the capillary die, whereas the second normal stress difference cannot be determined within the experimental errors using the current configuration design. Furthermore, the influence of the induced streamline curvature via the ’hole effect’ on the onset and development of melt flow instabilities is simultaneously assessed. It is shown that the hole depth has a stabilizing influence, i.e. the onset of instabilities occurs at higher shear rates, in the long chain branched polymer tested, whereas for the linear polymer tested it has a destabilizing effect on the stick-slip instability i.e. the onset of stick-slip occurs at lower shear rates. [ABSTRACT FROM AUTHOR]

The article "Potential of Benchtop NMR for the Determination of Polymer Molar Masses, Molar Mass Distributions, and Chemical Composition Profiles by Means of Diffusion-Ordered Spectroscopy, DOSY" published in Macromolecular Rapid Communications discusses the use of Diffusion-Ordered Spectroscopy (DOSY) on a 90 MHz NMR spectrometer for polymer analysis. The study focuses on method optimization for fast molar mass determination, validation of polymer samples, and obtaining diffusion coefficient distributions, molar mass distributions, and chemical composition profiles. The article also explores the application of DOSY to samples dissolved in protonated solvents. [Extracted from the article]

The influence of topology on the strain hardening in uniaxial elongation is investigated using monodisperse comb and dendrigraft model polystyrenes (PS) synthesized via living anionic polymerization. A backbone with a molecular weight of Mw,bb = 310 kg mol−1 is used for all materials, while a number of 100 short (SCB, Mw,scb = 15 kg mol−1) or long chain branches (LCB, Mw,lcb = 40 kg mol−1) are grafted onto the backbone. The synthesized LCB comb serves as precursor for the dendrigraft‐type branch‐on‐branch (bob) structures to add a second generation of branches (SCB, Mw,scb ≈ 14 kg mol−1) that is varied in number from 120 to 460. The SCB and LCB combs achieve remarkable strain hardening factors (SHF) of around 200 at strain rates greater than 0.1 s−1. In contrast, the bob PS reach exceptionally high SHF of 1750 at very low strain rates of 0.005 s−1 using a tilted sample placement to extend the maximum Hencky strain from 4 to 6. To the best of the authors' knowledge, SHF this high have never been reported for polymer melts. Furthermore, the batch foaming with CO2 is investigated and the volume expansions of the resulting polymer foams are correlated to the uniaxial elongational properties. [ABSTRACT FROM AUTHOR]

This publication is concerned with the development of a novel high sensitivity instability detection die for a laboratory size extruder. The high sensitivity system consists of piezoelectric transducers placed along the die length to monitor local pressure fluctuations, having temporal and pressure resolution of up to Δ t ≈ 10−3 s and Δ p ≈ 10−5 bar, at a nominal pressure of 500 bar. The system is tested on short chain branched polyethylenes, namely on the detection and characterization of the sharkskin instability. It is shown that the determined instabilities are related to characteristic peaks in the corresponding in situ pressure Fourier-transform spectra and that other peaks are caused by different, but defined, sources. The in situ results obtained are validated through optical image analysis of the instabilities. [ABSTRACT FROM AUTHOR]

The extrusion flow instabilities of commercial polybutadiene (PBD) are investigated as a function of the different extrusion die geometries, such as round capillary, slit, and complex cross‐section profile slit dies via capillary rheology. Qualitative models are used to fit the experimental data for the spatial characteristic wavelength (λ) of the appearing extrusion flow instabilities. A new qualitative model for the slit die geometry, rectangular cross‐section, is derived based on the theoretical concept of the "two layers" extrudate and the force balance at the die exit region. The proposed qualitative model for the slit die geometry is used to predict the spatial characteristic wavelength (λ) for extrudates obtained by complex cross‐section profile slit die geometries similar to industrial manufacturing. Correlation between the ratio of the extensional (Ys) and shear (σx) stress at the die exit area and the characteristic dimension, height H for slit dies and diameter D for round capillary dies, is presented. Moreover, a geometry‐dependent model is used to predict the spatial characteristic wavelength (λ) of the extrusion flow instabilities from a round capillary die to a slit die and vice versa. [ABSTRACT FROM AUTHOR]

We investigate yielding in a colloidal gel that forms a heterogeneous structure, consisting of a twophase bicontinuous network of colloid-rich domains of fractal clusters and colloid-poor domains. Combining large amplitude oscillatory shear measurements with simultaneous small and ultra-small angle neutron scattering (rheo-SANS/USANS), we characterize both the nonlinear mechanical processes and strain amplitude-dependent microstructure underlying yielding. We observe a broad, three-stage yielding process that evolves over an order of magnitude in strain amplitude between the onset of nonlinearity and flow. Analyzing the intracycle response as a sequence of physical processes reveals a transition from elastic straining to elastoplastic thinning (which dominates in region I) and eventually yielding (which evolves through region II) and flow (which saturates in region III), and allows quantification of instantaneous nonlinear parameters associated with yielding. These measures exhibit significant strain rate amplitude dependence above a characteristic frequency, which we argue is governed by poroelastic effects. Correlating these results with timeaveraged rheo-USANS measurements reveals that the material passes through a cascade of structural breakdown from large to progressively smaller length scales. In region I, compression of the fractal domains leads to the formation of large voids. In regions II and III, cluster-cluster correlations become increasingly homogeneous, suggesting breakage and eventually depercolation of intercluster bonds at the yield point. All significant structural changes occur on the micron-scale, suggesting that large-scale rearrangements of hundreds or thousands of particles, rather than the homogeneous rearrangement of particle-particle bonds, dominate the initial yielding of heterogeneous colloidal gels. [ABSTRACT FROM AUTHOR]

In this work, three different cyclic carbonates are obtained from renewable diols and transformed into carbamates by reacting them with renewable 11‐amino undecanoic acid methyl ester to synthesize non‐isocyanate poly(ester urethane)s in a sustainable manner. A procedure using 2,3‐butanediol (2,3‐BDO) as a renewable starting material to synthesize a cyclic carbonate with dimethyl carbonate (DMC) is introduced, catalyzed by 1,5,7‐triazabicylco[4.4.0]dec‐5‐ene (TBD). Three purification strategies, i.e., column chromatography, extraction, and distillation, are compared regarding their E‐Factors. Propylene glycol (PG) and ethylene glycol (EG) are used as alternative starting materials to broaden the substrate scope and compare material properties, their cyclic carbonates likewise react to carbamates with 11‐amino undecanoic acid methyl ester. All carbamates are then polymerized in a bulk polycondensation reaction, yielding non‐isocyanate polyurethanes (NIPUs), specifically poly (ester urethane)s, with molecular weights (Mn) up to 10 kDa. Complete characterization is reported using differential scanning calorimetric (DSC), size exclusion chromatographic measurements (SEC), 1H‐NMR as well as IR spectroscopy. The rheological properties of the poly(ester urethane)s are investigated in the framework of small amplitude oscillatory shear (SAOS) and uniaxial elongation. [ABSTRACT FROM AUTHOR]