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Tuning High and Low Temperature Foaming Behavior of Linear and Long-Chain Branched Polypropylene via Partial and Complete Melting.

ABSTRACT: While existing foam studies have identified processing parameters, such as high-pressure drop rate, and engineering measures, such as high melt strength, as key factors for improving foamability, there is a conspicuous absence of studies that directly relate foamability to material properties obtained from fundamental characterization. To bridge this gap, this work presents batch foaming studies on one linear and two long-chain branched polypropylene (PP) resins to investigate how foamability is affected by partial melting (Method 1) and complete melting followed by undercooling (Method 2). At temperatures above the melting point, similar expansion was obtained using both foaming procedures within each resin, while the PP with the highest strain hardening ratio (13) exhibited the highest expansion ratio (45 ± 3). At low temperatures, the foamability of all resins was dramatically improved using Method 2 compared to Method 1, due to access to lower foaming temperatures (<150 °C) near the crystallization onset. Furthermore, Method 2 resulted in a more uniform cellular structure over a wider temperature range (120-170 °C compared to 155-175 °C). Overall, strong extensional hardening and low onset of crystallization were shown to give rise to foamability at high and low temperatures, respectively, suggesting that both characteristics can be appropriately used to tune the foamability of PP in industrial foaming applications.

SUBMITTER: Kweon MS

PROVIDER: S-EPMC8747320 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Improved Cell Morphology and Surface Roughness in High-Temperature Foam Injection Molding Using a Long-Chain Branched Polypropylene.

Project description:Long-chain branched polypropylene (LCB PP) has been used extensively to improve cell morphologies in foaming applications. However, most research focuses on low melt flow rate (MFR) resins, whereas foam production methods such as mold-opening foam injection molding (MO-FIM) require high-MFR resins to improve processability. A systematic study was conducted comparing a conventional linear PP, a broad molecular weight distribution (BMWD) linear PP, and a newly developed BMWD LCB PP for use in MO-FIM. The effects of foaming temperature and molecular architecture on cell morphology, surface roughness, and mechanical properties were studied by utilizing two chemical blowing agents (CBAs) with different activation temperatures and varying packing times. At the highest foaming temperatures, BMWD LCB PP foams exhibited 887% higher cell density, 46% smaller cell sizes, and more uniform cell structures than BWMD linear PP. Linear PP was found to have a surface roughness 23% higher on average than other resins. The BMWD LCB PP was found to have increased flexural modulus (44%) at the cost of decreased toughness (-88%) compared to linear PP. The branched architecture and high molecular weight of the BMWD LCB PP contributed to improved foam morphologies and surface quality in high-temperature MO-FIM conditions.

| S-EPMC8348131 | biostudies-literature

Engineering linear, branched-chain triterpene metabolism in monocots.

Project description:Triterpenes are thirty-carbon compounds derived from the universal five-carbon prenyl precursors isopentenyl diphosphate (IPP) and dimethylallyl diphosphate (DMAPP). Normally, triterpenes are synthesized via the mevalonate (MVA) pathway operating in the cytoplasm of eukaryotes where DMAPP is condensed with two IPPs to yield farnesyl diphosphate (FPP), catalyzed by FPP synthase (FPS). Squalene synthase (SQS) condenses two molecules of FPP to generate the symmetrical product squalene, the first committed precursor to sterols and most other triterpenes. In the green algae Botryococcus braunii, two FPP molecules can also be condensed in an asymmetric manner yielding the more highly branched triterpene, botryococcene. Botryococcene is an attractive molecule because of its potential as a biofuel and petrochemical feedstock. Because B. braunii, the only native host for botryococcene biosynthesis, is difficult to grow, there have been efforts to move botryococcene biosynthesis into organisms more amenable to large-scale production. Here, we report the genetic engineering of the model monocot, Brachypodium distachyon, for botryococcene biosynthesis and accumulation. A subcellular targeting strategy was used, directing the enzymes (botryococcene synthase [BS] and FPS) to either the cytosol or the plastid. High titres of botryococcene (>1 mg/g FW in T0 mature plants) were obtained using the cytosolic-targeting strategy. Plastid-targeted BS + FPS lines accumulated botryococcene (albeit in lesser amounts than the cytosolic BS + FPS lines), but they showed a detrimental phenotype dependent on plastid-targeted FPS, and could not proliferate and survive to set seed under phototrophic conditions. These results highlight intriguing differences in isoprenoid metabolism between dicots and monocots.

| S-EPMC6335073 | biostudies-literature

Structure and Properties of a Metallocene Polypropylene Resin with Low Melting Temperature for Melt Spinning Fiber Application.

Project description:An isotactic polypropylene (iPP-1) resin with low melting temperature (Tm) is synthesized by a metallocene catalyst and investigated for melt-spun fiber applications. The structure, thermal and mechanical properties, and feasibility of producing fibers of a commercial metallocene iPP (iPP-2) and a conventional Ziegler-Natta iPP (iPP-3) are carefully examined for comparison. Tm of iPP-1 is about 10 °C lower than the other two samples, which is well addressed both in the resin and the fiber products. Besides, the newly developed iPP-1 possesses higher isotacticity and crystallinity than the commercial ones, which assures the mechanical properties of the fiber products. Thanks to the addition of calcium stearate, its crystal grain size is smaller than those of the two other commercial iPPs. iPP-1 shows a similar rheological behavior as the commercial ones and good spinnability within a wide range of take-up speeds (1200-2750 m/min). The tensile property of fibers from iPP-1 is better than commercial ones, which can fulfill the application requirement. The formation of the mesomorphic phase in iPP-1 during melt spinning is confirmed by the orientation and crystallization investigation with wide angle X-ray diffraction (WAXD), which is responsible for its excellent processing capability and the mechanical properties of the resultant fibers. The work may provide not only a promising candidate for the high-performance PP fiber but also a deep understanding of the formation mechanism of the mesomorphic phase during fiber spinning.

| S-EPMC6523879 | biostudies-literature

Improving Rheological and Mechanical Properties of Various Virgin and Recycled Polypropylenes by Blending with Long-Chain Branched Polypropylene.

Project description:Blends of two long-chain branched polypropylenes (LCB-PP) and five linear polypropylenes (L-PP) were prepared in a single screw extruder at 240 °C. The two LCB-PPs were self-created via reactive extrusion at 180 °C by using dimyristyl peroxydicarbonate (PODIC C126) and dilauroyl peroxide (LP) as peroxides. For blending two virgin and three recycled PPs like coffee caps, yoghurt cups and buckets with different melt flow rate (MFR) values were used. The influence of using blends was assessed by investigating the rheological (dynamic and extensional rheology) and mechanical properties (tensile test and impact tensile test). The dynamic rheology indicated that the molecular weight as well as the molecular weight distribution could be increased or broadened. Also the melt strength behavior could be improved by using the two peroxide modified LCB-PP blends on the basis of PODIC C126 or PEROXAN LP (dilauroyl peroxide). In addition, the mechanical properties were consistently enhanced or at least kept constant compared to the original material. In particular, the impact tensile strength but also the elongation at break could be increased considerably. This study showed that the blending of LCB-PP can increase the investigated properties and represents a promising option, especially when using recycled PP, which demonstrates a real "up-cycling" process.

| S-EPMC8038188 | biostudies-literature

Single-chain magnet behavior in a finite linear hexanuclear molecule.

Project description:The careful monitoring of crystallization conditions of a mixture made of a TbIII building block and a substituted nitronyl-nitroxide that typically provides infinite coordination polymers (chains), affords a remarkably stable linear hexanuclear molecule made of six TbIII ions and five NIT radicals. The hexanuclear units are double-bridged by water molecules but ab initio calculations demonstrate that this bridge is inefficient in mediating any magnetic interaction other than a small dipolar antiferromagnetic coupling. Surprisingly the hexanuclears, despite being finite molecules, show a single-chain magnet (SCM) behavior. This results in a magnetic hysteresis at low temperature whose coercive field is almost doubled when compared to the chains. We thus demonstrate that finite linear molecules can display SCM magnetic relaxation, which is a strong asset for molecular data storage purposes because 1D magnetic relaxation is more robust than the relaxation mechanisms observed in single-molecule magnets (SMMs) where under-barrier magnetic relaxation can operate.

| S-EPMC8356920 | biostudies-literature

Strain-dependent photoluminescence behavior of CdSe/CdS nanocrystals with spherical, linear, and branched topologies.

Project description:The photoluminescence of CdSe/CdS core/shell quantum dots, nanorods, and tetrapods is investigated as a function of applied hydrostatic and non-hydrostatic pressure. The optoelectronic properties of all three nanocrystal morphologies are affected by strain. Furthermore, it is demonstrated that the unique morphology of seeded tetrapods is highly sensitive to non-isotropic stress environments. Seeded tetrapods can thereby serve as an optical strain gauge, capable of measuring forces on the order of nanonewtons. We anticipate that a nanocrystal strain gauge with optical readout will be useful for applications including sensitive optomechanical devices and biological force investigations.

| S-EPMC2768666 | biostudies-literature

Metabolic engineering of microbes for branched-chain biodiesel production with low-temperature property.

Project description:BACKGROUND:The steadily increasing demand for diesel fuels calls for renewable energy sources. This has attracted a growing amount of research to develop advanced, alternative biodiesel worldwide. Several major disadvantages of current biodiesels are the undesirable physical properties such as high viscosity and poor low-temperature operability. Therefore, there is an urgent need to develop novel and advanced biodiesels. RESULTS:Inspired by the proven capability of wax ester synthase/acyl-coenzyme A, diacylglycerol acyltransferase (WS/DGAT) to generate fatty acid esters, de novo biosynthesis of fatty acid branched-chain esters (FABCEs) and branched fatty acid branched-chain esters (BFABCEs) was performed in engineered Escherichia coli through combination of the (branched) fatty acid biosynthetic pathway and the branched-chain amino acid biosynthetic pathway. Furthermore, by modifying the fatty acid pathway, we improved FABCE production to 273 mg/L and achieved a high proportion of FABCEs at 99.3 % of total fatty acid esters. In order to investigate the universality of this strategy, Pichia pastoris yeast was engineered and produced desirable levels of FABCEs for the first time with a good starting point of 169 mg/L. CONCLUSIONS:We propose new pathways of fatty acid ester biosynthesis and establish proof of concept through metabolic engineering of E. coli and P. pastoris yeast. We were able to produce advanced biodiesels with high proportions FABCEs and BFABCEs. Furthermore, this new strategy promises to achieve advanced biodiesels with beneficial low-temperature properties.

| S-EPMC4483204 | biostudies-literature

Rheological Behavior of Blends of Metallocene Catalyzed Long-Chain Branched Polyethylenes. Part I: Shear Rheological and Thermorheological Behavior.

Project description:Long-chain branched metallocene-catalyzed high-density polyethylenes (LCB-mHDPE) were solution blended to obtain blends with varying degrees of branching. A high molecular LCB-mHDPE was mixed with low molecular LCB-mHDPE at varying concentrations. The rheological behavior of those low molecular LCB-mHDPE is similar but their molar mass and molar mass distribution are significantly different. Those blends were characterized rheologically to study the effects of concentration, molar mass distribution, and long-chain branching level of the low molecular LCB-mHDPE. Owing to the ultra-long relaxation times of the high molecular LCB-mHDPE, the blends exhibited a clearly more long-chain branched behavior than the base materials. The thermorheological complexity analysis showed an apparent increase in the activation energies Ea determined from G', G″, and especially δ. Ea(δ), which for LCB-mHDPE is a peak function, turned out to produce even more pronounced peaks than observed for LCB-mPE with narrow molar mass distribution and also LCB-mPE with broader molar mass distribution. Thus, it is possible to estimate the molar mass distribution from the details of the thermorheological complexity.

| S-EPMC7864184 | biostudies-literature

Partial purification and properties of branched-chain 2-oxo acid dehydrogenase of ox liver.

Project description:1. A branched-chain 2-oxo acid dehydrogenase was partially purified from ox liver mitochondria. 2. The preparation oxidized 4-methyl-2-oxopentanoate, 3-methyl-2-oxobutyrate and D- and L-3-methyl-2-oxopentanoate. The apparent Km values for the oxo acids and for thiamin pyrophosphate, CoA, NAD+ and Mg2+ were determined. 3. The oxidation of each oxo acid was inhibited by isovaleryl (3-methylbutyryl)-CoA (competitive with CoA) and by NADH (competitive with NAD+); Ki values were determined. 4. The preparation showed substrate inhibition with each 2-oxo acid. The oxidative decarboxylation of 4-methyl-2-oxo[1-14C]pentanoate was inhibited by 3-methyl-2-oxobutyrate and DL-3-methyl-2-oxopentanoate, but not by pyruvate. The Vmax. with 3-methyl-2-oxobutyrate as variable substrate was not increased by the presence of each of the other 2-oxo acids. 5. Ox heart pyruvate dehydrogenase did not oxidize these branched-chain 2-oxo acids and it was not inhibited by isovaleryl-CoA. The branched-chain 2-oxo acid dehydrogenase activity (unlike that of pyruvate dehydrogenase) was not inhibited by acetyl-CoA. 6. It is concluded that the branched-chain 2-oxo acid dehydrogenase activity is distinct from that of pyruvate dehydrogenase, and that a single complex may oxidize all three branched-chain 2-oxo acids.

| S-EPMC1184023 | biostudies-other

FabH selectivity for anteiso branched-chain fatty acid precursors in low-temperature adaptation in Listeria monocytogenes.

Project description:Gram-positive bacteria, including Listeria monocytogenes, adjust membrane fluidity by shortening the fatty acid chain length and increasing the proportional production of anteiso fatty acids at lower growth temperatures. The first condensation reaction in fatty acid biosynthesis is carried out by beta-ketoacyl-acyl carrier protein synthase III (FabH), which determines the type of fatty acid produced in bacteria. Here, we measured the initial rates of FabH-catalyzed condensation of malonyl-acyl carrier protein and alternate branched-chain precursor acyl-CoAs utilizing affinity-purified His-tagged L. monocytogenes FabH heterologously expressed in Escherichia coli. Listeria monocytogenes FabH showed a preference for 2-methylbutyryl-CoA, the precursor of odd-numbered anteiso fatty acids, at 30 degrees C, which was further increased at a low temperature (10 degrees C), suggesting that temperature-dependent substrate selectivity of FabH underlies the increased formation of anteiso branched-chain fatty acids during low-temperature adaptation. The increased FabH preferential condensation of 2-methylbutyryl-CoA could not be attributed to a significantly higher availability of this fatty acid precursor as acyl-CoA pool levels were reduced similarly for all fatty acid precursors at low temperatures.

| S-EPMC2818224 | biostudies-literature

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