Browse
Submit Data
Databases
API
Help

Dataset Information

20 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Rheology of Crystallizing LLDPE.

ABSTRACT: Polymer crystallization occurs in many plastic manufacturing processes, from injection molding to film blowing. Linear low-density polyethylene (LLDPE) is one of the most commonly processed polymers, wherein the type and extent of short-chain branching (SCB) may be varied to influence crystallization. In this work, we report simultaneous measurements of the rheology and Raman spectra, using a Rheo-Raman microscope, for two industrial-grade LLDPEs undergoing crystallization. These polymers are characterized by broad polydispersity, SCB and the presence of polymer chain entanglements. The rheological behavior of these entangled LLDPE melts is modeled as a function of crystallinity using a slip-link model. The partially crystallized melt is represented by a blend of linear chains with either free or crosslinked ends, wherein the crosslinks represent attachment to growing crystallites, and a modulus shift factor that increases with degree of crystallinity. In contrast to our previous application of the slip-link model to isotactic polypropylene (iPP), in which the introduction of only bridging segments with crosslinks at both ends was sufficient to describe the available data, for these LLDPEs we find it necessary to introduce dangling segments, with crosslinks at only one end. The model captures quantitatively the evolution of viscosity and elasticity with crystallization over the whole range of frequencies in the linear regime for two LLDPE grades.

SUBMITTER: Andreev M

PROVIDER: S-EPMC8200930 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

A frequency-dependent effective medium model for the rheology of crystallizing polymers.

Project description:The rheology of crystallizing polymers is critical to polymer processing, but our current understanding of how crystallinity affects rheology during crystallization is lacking. The challenge is twofold: first, we must measure rheology simultaneously with crystallinity, and then we must develop models that can describe those measurements as well as prior phenomenological observations. Here, we further develop a generalized effective medium model to describe the frequency-dependent shear modulus of a crystallizing polymer. Through a simple model system, we show that the percolation transition in the effective medium model recovers the relaxation dynamics of a critical gel with a relaxation spectrum that can be approximated as the power mean of the initial melt and final semicrystalline material. We demonstrate the success of this model on the isothermal crystallization of polycaprolactones. From the generalized effective medium model, we can calculate the percolation fraction and power law relaxation exponent at the critical point, even when the measurement frequency range is dominated by shear thinning of the melt phase.

| S-EPMC7543060 | biostudies-literature

Rheology of crystallizing polymers: The role of spherulitic superstructures, gap height, and nucleation densities.

Project description:A longstanding goal in polymer rheology is to develop a physical picture that relates the growth of mechanical moduli during polymer crystallization to that of a structure. Here, we utilize simultaneous mechanical rheology and optical microscopy, with augmentation by deterministic reconstruction and stochastic simulations, to study isothermal crystallization in isotactic polypropylene. We observe the nucleation and growth of the surface and bulk spherulites, which are initially isolated and then impinge to form clusters and superstructures that eventually span the gap. We find that spherulitic superstructures play a critical role in the rheology, especially in the characteristic sharp upturn in moduli. Both the rheology and the spherulitic superstructures show pronounced gap dependencies, which we explain via finite-size effects in percolation phenomena and via surface-induced nucleation. The modulus-crystallinity relationship can be described through a general effective medium theory. It indicates that for thicker gaps, the viscoelastic liquid to solid transition can be described via percolation, whereas for our thinnest gap, it is best described by the linear mixing rule. We describe our results in terms of dimensionless nucleation rates and spherulite size, which enable the estimation of when gap-dependent superstructure effects can be anticipated.

| S-EPMC9706506 | biostudies-literature

Crystallizing transmembrane peptides in lipidic mesophases.

Project description:Structure determination of membrane proteins by crystallographic means has been facilitated by crystallization in lipidic mesophases. It has been suggested, however, that this so-called in meso method, as originally implemented, would not apply to small protein targets having </=4 transmembrane crossings. In our study, the hypothesis that the inherent flexibility of the mesophase would enable crystallogenesis of small proteins was tested using a transmembrane pentadecapeptide, linear gramicidin, which produced structure-grade crystals. This result suggests that the in meso method should be considered as a viable means for high-resolution structure determination of integral membrane peptides, many of which are predicted to be coded for in the human genome.

| S-EPMC2913208 | biostudies-literature

Crystallizing membrane proteins using lipidic mesophases.

Project description:A detailed protocol for crystallizing membrane proteins that makes use of lipidic mesophases is described. This has variously been referred to as the lipid cubic phase or in meso method. The method has been shown to be quite general in that it has been used to solve X-ray crystallographic structures of prokaryotic and eukaryotic proteins, proteins that are monomeric, homo- and hetero-multimeric, chromophore-containing and chromophore-free, and alpha-helical and beta-barrel proteins. Its most recent successes are the human-engineered beta(2)-adrenergic and adenosine A(2A) G protein-coupled receptors. Protocols are provided for preparing and characterizing the lipidic mesophase, for reconstituting the protein into the monoolein-based mesophase, for functional assay of the protein in the mesophase and for setting up crystallizations in manual mode. Methods for harvesting microcrystals are also described. The time required to prepare the protein-loaded mesophase and to set up a crystallization plate manually is about 1 h.

| S-EPMC2732203 | biostudies-literature

An approach to crystallizing proteins by synthetic symmetrization.

Project description:Previous studies of symmetry preferences in protein crystals suggest that symmetric proteins, such as homodimers, might crystallize more readily on average than asymmetric, monomeric proteins. Proteins that are naturally monomeric can be made homodimeric artificially by forming disulfide bonds between individual cysteine residues introduced by mutagenesis. Furthermore, by creating a variety of single-cysteine mutants, a series of distinct synthetic dimers can be generated for a given protein of interest, with each expected to gain advantage from its added symmetry and to exhibit a crystallization behavior distinct from the other constructs. This strategy was tested on phage T4 lysozyme, a protein whose crystallization as a monomer has been studied exhaustively. Experiments on three single-cysteine mutants, each prepared in dimeric form, yielded numerous novel crystal forms that cannot be realized by monomeric lysozyme. Six new crystal forms have been characterized. The results suggest that synthetic symmetrization may be a useful approach for enlarging the search space for crystallizing proteins.

| S-EPMC1637565 | biostudies-literature

Cyanoximes as effective and selective co-crystallizing agents.

Project description:The ability of cyanoxime-based synthons to act as versatile synthetic tools for the construction of co-crystals is demonstrated through the preparation and structural characterization of seven co-crystals. Cyanoximes can bind effectively to both five-membered and six-membered N-heterocyclic hydrogen-bond acceptors, and they also display selectivity towards the best acceptor (as determined using semi-empirical AM1 calculations) in ditopic compounds.

| S-EPMC2748950 | biostudies-literature

Viscosity measurements of crystallizing andesite from Tungurahua volcano (Ecuador).

Project description:Viscosity has been determined during isothermal crystallization of an andesite from Tungurahua volcano (Ecuador). Viscosity was continuously recorded using the concentric cylinder method and employing a Pt-sheathed alumina spindle at 1 bar and from 1400°C to subliquidus temperatures to track rheological changes during crystallization. The disposable spindle was not extracted from the sample but rather left in the sample during quenching thus preserving an undisturbed textural configuration of the crystals. The inspection of products quenched during the crystallization process reveals evidence for heterogeneous crystal nucleation at the spindle and near the crucible wall, as well as crystal alignment in the flow field. At the end of the crystallization, defined when viscosity is constant, plagioclase is homogeneously distributed throughout the crucible (with the single exception of experiment performed at the lowest temperature). In this experiments, the crystallization kinetics appear to be strongly affected by the stirring conditions of the viscosity determinations. A TTT (Time-Temperature-Transformation) diagram illustrating the crystallization "nose" for this andesite under stirring conditions and at ambient pressure has been constructed. We further note that at a given crystal content and distribution, the high aspect ratio of the acicular plagioclase yields a shear-thinning rheology at crystal contents as low as 13 vol %, and that the relative viscosity is higher than predicted from existing viscosity models. These viscosity experiments hold the potential for delivering insights into the relative influences of the cooling path, undercooling, and deformation on crystallization kinetics and resultant crystal morphologies, as well as their impact on magmatic viscosity.

| S-EPMC5012119 | biostudies-literature

A Hexanuclear Niobium Cluster Compound Crystallizing as Macroscopic Tubes.

Project description:Compounds with ordered structures in one or two dimensions are exciting materials and investigated intensively in many different areas of science. Many activities have been put into the preparation of low-dimensional nano-scaled structures and many compounds in this size regime are known. Contrary, the number of known compounds that have low-dimensional macroscopic sized structures that form directly in a chemical reaction is very limited. Here, we present the synthesis of the niobium cluster compound [(Et2 O)2 H]2 [Nb6 Cl18 ], crystals of which grow in form of large hexagonal empty tubes of several centimeter length and diameters in the range of 2?mm. The single-crystal X-ray structure of this compound has been refined. Under warming, the compound readily eliminates diethyl ether molecules and decomposes. From a closer look at the crystallization process a step-by-step scheme of the procedure of the tube growth is proposed. The overall conclusion from this proposal is that a crucial balance between the cluster solution concentration, the crystal growth speed and the ether diffusion speed results in the formation of macroscopic crystal tubes.

| S-EPMC6900163 | biostudies-literature

Aging in magma rheology

Project description:Aging, change in property depending on the elapsed time from preparation, is known to affect the rheological behavior of various materials. Therefore, whether magma ages must be examined to characterize potentially widespread volcanic phenomena related to the transition from rest to flow. To achieve this, we performed rheological measurements and microstructural analyses on basaltic andesite lava from the 1986 Izu-Oshima eruption. The rheology shows an initial overshoot of shear stress during start-up flow that correlates with the duration and the shear rate of a pre-rest time. This indicates that the yield stress of magma and lava increases with aging. The microstructure shows that original aggregates of crystals, which may grow during crystallization, coalesce during the pre-rest period to form clusters without changing the crystal volume fraction. We conclude that the clusters are broken by shear in the start-up flow, which induces the stress overshoot. Thus, aging in magma rheology will impact the understanding of dynamic flow.

| S-EPMC9200731 | biostudies-literature

An approach to crystallizing proteins by metal-mediated synthetic symmetrization.

Project description:Combining the concepts of synthetic symmetrization with the approach of engineering metal-binding sites, we have developed a new crystallization methodology termed metal-mediated synthetic symmetrization. In this method, pairs of histidine or cysteine mutations are introduced on the surface of target proteins, generating crystal lattice contacts or oligomeric assemblies upon coordination with metal. Metal-mediated synthetic symmetrization greatly expands the packing and oligomeric assembly possibilities of target proteins, thereby increasing the chances of growing diffraction-quality crystals. To demonstrate this method, we designed various T4 lysozyme (T4L) and maltose-binding protein (MBP) mutants and cocrystallized them with one of three metal ions: copper (Cu²?, nickel (Ni²?), or zinc (Zn²?). The approach resulted in 16 new crystal structures--eight for T4L and eight for MBP--displaying a variety of oligomeric assemblies and packing modes, representing in total 13 new and distinct crystal forms for these proteins. We discuss the potential utility of the method for crystallizing target proteins of unknown structure by engineering in pairs of histidine or cysteine residues. As an alternate strategy, we propose that the varied crystallization-prone forms of T4L or MBP engineered in this work could be used as crystallization chaperones, by fusing them genetically to target proteins of interest.

| S-EPMC3267952 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data