scholarly journals Low-Temperature-Meltable Elastomers Based on Linear Polydimethylsiloxane Chains Alpha, Omega-Terminated with Mesogenic Groups as Physical Crosslinker: A Passive Smart Material with Potential as Viscoelastic Coupling. Part II—Viscoelastic and Rheological Properties

Polymers ◽  
2020 ◽  
Vol 12 (12) ◽  
pp. 2840
Author(s):  
Sabina Horodecka ◽  
Adam Strachota ◽  
Beata Mossety-Leszczak ◽  
Maciej Kisiel ◽  
Beata Strachota ◽  
...  
Keyword(s):  
Phase Separation ◽  
Low Temperature ◽  
Smart Materials ◽  
Volume Fraction ◽  
Mechanical Strain ◽  
Polymer Networks ◽  
Building Blocks ◽  
Self Healing ◽  
Structure Property ◽  
Mechanical Coupling

Rheological and viscoelastic properties of physically crosslinked low-temperature elastomers were studied. The supramolecularly assembling copolymers consist of linear polydimethylsiloxane (PDMS) elastic chains terminated on both ends with mesogenic building blocks (LC) of azobenzene type. They are generally and also structurally highly different from the well-studied LC polymer networks or LC elastomers: The LC units make up only a small volume fraction in our materials and act as fairly efficient physical crosslinkers with thermotropic properties. The aggregation (nano-phase separation) of the relatively rare, small and spatially separated terminal LC units generates temperature-switched viscoelasticity in the molten copolymers. Their rheological behavior was found to be controlled by an interplay of nano-phase separation of the LC units (growth and splitting of their aggregates) and of the thermotropic transitions in these aggregates (which change their stiffness). As a consequence, multiple gel points (up to three) are observed in temperature scans of the copolymers. The physical crosslinks also can be reversibly disconnected by large mechanical strain in the ‘warm’ rubbery state, as well as in melt (thixotropy). The kinetics of crosslink formation was found to be fast if induced by temperature and extremely fast in case of internal self-healing after strain damage. Thixotropic loop tests hence display only very small hysteresis in the LC-melt-state, although the melts show very distinct shear thinning. Our study evaluates structure-property relationships in three homologous systems with elastic PDMS segments of different length (8.6, 16.3 and 64.4 repeat units). The studied copolymers might be of interest as passive smart materials, especially as temperature-controlled elastic/viscoelastic mechanical coupling.

scholarly journals Low-Temperature Meltable Elastomers Based on Linear Polydimethylsiloxane Chains Alpha, Omega-Terminated with Mesogenic Groups as Physical Crosslinkers: A Passive Smart Material with Potential as Viscoelastic Coupling. Part I: Synthesis and Phase Behavior

Polymers ◽  
2020 ◽  
Vol 12 (11) ◽  
pp. 2476 ◽  
Author(s):  
Sabina Horodecka ◽  
Adam Strachota ◽  
Beata Mossety-Leszczak ◽  
Beata Strachota ◽  
Miroslav Šlouf ◽  
...  
Keyword(s):  
Low Temperature ◽  
Smart Materials ◽  
Self Assembly ◽  
Lamellar Structure ◽  
Volume Fraction ◽  
Polymer Networks ◽  
Polarized Light ◽  
Building Blocks ◽  
Structure Property ◽  
Mechanical Coupling

Physically crosslinked low-temperature elastomers were prepared based on linear polydimethylsiloxane (PDMS) elastic chains terminated on both ends with mesogenic building blocks (LC) of azobenzene type. They are generally (and also structurally) highly different from the well-studied LC polymer networks (light-sensitive actuators). The LC units also make up only a small volume fraction in our materials and they do not generate elastic energy upon irradiation, but they act as physical crosslinkers with thermotropic properties. Our elastomers lack permanent chemical crosslinks—their structure is fully linear. The aggregation of the relatively rare, small, and spatially separated terminal LC units nevertheless proved to be a considerably strong crosslinking mechanism. The most attractive product displays a rubber plateau extending over 100 °C, melts near 8 °C, and is soluble in organic solvents. The self-assembly (via LC aggregation) of the copolymer molecules leads to a distinctly lamellar structure indicated by X-ray diffraction (XRD). This structure persists also in melt (polarized light microscopy, XRD), where 1–2 thermotropic transitions occur. The interesting effects of the properties of this lamellar structure on viscoelastic and rheological properties in the rubbery and in the melt state are discussed in a follow-up paper (“Part II”). The copolymers might be of interest as passive smart materials, especially as temperature-controlled elastic/viscoelastic mechanical coupling. Our study focuses on the comparison of physical properties and structure–property relationships in three systems with elastic PDMS segments of different length (8.6, 16.3, and 64.4 repeat units).

Elastomeric Polyether-Ester Block Copolymers. I. Structure-Property Relationships of Tetramethylene Terephthalate/Polyether Terephthalate Copolymers

1977 ◽  
Vol 50 (4) ◽  
pp. 688-703 ◽  
Author(s):  
J. R. Wolfe
Keyword(s):  
Phase Separation ◽  
Melting Point ◽  
Block Copolymers ◽  
Low Temperature ◽  
Chain Length ◽  
Chemical Structure ◽  
High Water ◽  
Structure Property ◽  
Tear Strength ◽  
Structure Property Relationships

Abstract The properties of elastomeric tetramethylene terephthalate/polyether terephthalate copolymers have been related to the chemical structure, chain length, and concentration in the copolymers of the PTMEG-, PEG-, and PPG-derived polyether units. Low-temperature properties and tear strength are dependent on all three polyether-related variables. Melting point, hardness, and stress at 100% elongation appear to be independent of polyether structure. Polyether glycols of low MW volatilize during copolymer preparation. High-MW polyethers tend to crystallize when present in the copolymers. Polyether glycols of intermediate MW (∼ 1000) yield copolymers with the best resistance to low-temperature stiffening. Copolymer synthesis is most difficult with PPG as the polyether glycol. Inherent viscosities are low, and phase separation occurs at lower polyether MW than with PTMEG or PEG. The PEG-based copolymers exhibit high water swell, particularly at intermediate and high PEG MW. The PTMEG-based copolymers are easiest to synthesize and exhibit the best overall combination of properties.

scholarly journals Design Strategy for Self-Healing Epoxy Coatings

Coatings ◽  
2020 ◽  
Vol 10 (1) ◽  
pp. 50 ◽  
Author(s):  
Dian Yuan ◽  
Vahab Solouki Bonab ◽  
Ammar Patel ◽  
Talha Yilmaz ◽  
Richard A. Gross ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Phase Separation ◽  
Thermoplastic Polyurethane ◽  
Polymeric Materials ◽  
Secondary Phase ◽  
Diglycidyl Ether ◽  
Self Healing ◽  
Structure Property ◽  
Chain Entanglement ◽  
Epoxy Network

Self-healing strategies including intrinsic and extrinsic self-healing are commonly used for polymeric materials to restore their appearance and properties upon damage. Unlike intrinsic self-healing tactics where recovery is based on reversible chemical or physical bonds, extrinsic self-healing approaches rely on a secondary phase to acquire the self-healing functionality. Understanding the impacts of the secondary phase on both healing performance and matrix properties is important for rational system design. In this work, self-healing coating systems were prepared by blending a bio-based epoxy from diglycidyl ether of diphenolate esters (DGEDP) with thermoplastic polyurethane (TPU) prepolymers. Such systems exhibit polymerization induced phase separation morphology that controls coating mechanical and healing properties. Structure–property analysis indicates that the degree of phase separation is controlled by tuning the TPU prepolymer molecular weight. Increasing the TPU prepolymer molecular weight results in a highly phase separated morphology that is preferable for mechanical performances but undesirable for healing functionality. In this case, diffusion of TPU prepolymers during healing is restricted by the epoxy network rigidity and chain entanglement. Low molecular weight TPU prepolymers tend to phase mix with the epoxy matrix during curing, resulting in the formation of a flexible epoxy network that benefits TPU flow while decreasing Tg and mechanical properties. This work describes a rational strategy to develop self-healing coatings with controlled morphology to extend their functions and tailor their properties for specific applications.

scholarly journals Dually Crosslinked Polymer Networks Incorporating Dynamic Covalent Bonds

Polymers ◽  
2021 ◽  
Vol 13 (3) ◽  
pp. 396
Author(s):  
Larissa Hammer ◽  
Nathan J. Van Zee ◽  
Renaud Nicolaÿ
Keyword(s):  
Physical Properties ◽  
Dimensional Stability ◽  
Dynamic Networks ◽  
Polymer Networks ◽  
Polymeric Materials ◽  
Self Healing ◽  
Structure Property ◽  
Covalent Bonds ◽  
Design Structure ◽  
Increasing Demand

Covalent adaptable networks (CANs) are polymeric networks containing covalent crosslinks that are dynamic under specific conditions. In addition to possessing the malleability of thermoplastics and the dimensional stability of thermosets, CANs exhibit a unique combination of physical properties, including adaptability, self-healing, shape-memory, stimuli-responsiveness, and enhanced recyclability. The physical properties and the service conditions (such as temperature, pH, and humidity) of CANs are defined by the nature of their constituent dynamic covalent bonds (DCBs). In response to the increasing demand for more sophisticated and adaptable materials, the scientific community has identified dual dynamic networks (DDNs) as a promising new class of polymeric materials. By combining two (or more) distinct crosslinkers in one system, a material with tailored thermal, rheological, and mechanical properties can be designed. One remarkable ability of DDNs is their capacity to combine dimensional stability, bond dynamicity, and multi-responsiveness. This review aims to give an overview of the advances in the emerging field of DDNs with a special emphasis on their design, structure-property relationships, and applications. This review illustrates how DDNs offer many prospects that single (dynamic) networks cannot provide and highlights the challenges associated with their synthesis and characterization.

Bulk standards for low-temperature biological x-ray microanalysis

1984 ◽  
Vol 42 ◽  
pp. 282-283
Author(s):  
P. Echlin ◽  
M. McKoon ◽  
E.S. Taylor ◽  
C.E. Thomas ◽  
K.L. Maloney ◽  
...  
Keyword(s):  
Phase Separation ◽  
Low Temperature ◽  
Analytical Method ◽  
Salt Solutions ◽  
Absolute Concentration ◽  
Cooling Process ◽  
X Ray ◽  
The Absolute ◽  
Analytical Procedures ◽  
Electrical Conductors

Although sections of frozen salt solutions have been used as standards for x-ray microanalysis, such solutions are less useful when analysed in the bulk form. They are poor thermal and electrical conductors and severe phase separation occurs during the cooling process. Following a suggestion by Whitecross et al we have made up a series of salt solutions containing a small amount of graphite to improve the sample conductivity. In addition, we have incorporated a polymer to ensure the formation of microcrystalline ice and a consequent homogenity of salt dispersion within the frozen matrix. The mixtures have been used to standardize the analytical procedures applied to frozen hydrated bulk specimens based on the peak/background analytical method and to measure the absolute concentration of elements in developing roots.

Porous Gel Coatings Obtained by Phase Separation in ORMOSIL System

2000 ◽  
Vol 628 ◽  
Author(s):  
Kazuki Nakanishi ◽  
Souichi Kumon ◽  
Kazuyuki Hirao ◽  
Hiroshi Jinnai
Keyword(s):  
Phase Separation ◽  
Reaction Time ◽  
Volume Fraction ◽  
Sol Gel ◽  
Reaction Times ◽  
Dip Coating ◽  
Coating Solution ◽  
Coating Method ◽  
Gel Phase ◽  
Dip Coating Method

ABSTRACTMacroporous silicate thick films were prepared by a sol-gel dip-coating method accompanied by the phase separation using methyl-trimethoxysilane (MTMS), nitric acid and dimethylformamide (DMF) as starting components. The morphology of the film varied to a large extent depending on the time elapsed after the hydrolysis until the dipping of the coating solution. On a glass substrate, the films prepared by early dipping had inhomogeneous submicrometer-sized pores on the surface of the film. At increased reaction times, relatively narrow sized isolated macropores were observed and their size gradually decreased with the increase of reaction time. On a polyester substrate, in contrast, micrometer-sized isolated spherical gel domains were homogeneously deposited by earlier dippings. With an increase of reaction time, the volume fraction of the gel phase increased, then the morphology of the coating transformed into co-continuous gel domains and macropores, and finally inverted into the continuous gel domains with isolated macropores. The overall morphological variation with the reaction time was explained in terms of the phase separation and the structure freezing by the forced gelation, both of which were induced by the evaporation of methanol during the dipping operation.

scholarly journals Initial mechanical conditions within an optimized bone scaffold do not ensure bone regeneration – an in silico analysis

2021 ◽  
Author(s):  
Camille Perier-Metz ◽  
Georg N. Duda ◽  
Sara Checa
Keyword(s):  
Bone Regeneration ◽  
In Silico ◽  
Volume Fraction ◽  
Computer Modelling ◽  
Mechanical Strain ◽  
In Silico Analysis ◽  
Bone Volume ◽  
Mechanical Stimuli ◽  
Design Strategies ◽  
Scaffold Design

AbstractLarge bone defects remain a clinical challenge because they do not heal spontaneously. 3-D printed scaffolds are a promising treatment option for such critical defects. Recent scaffold design strategies have made use of computer modelling techniques to optimize scaffold design. In particular, scaffold geometries have been optimized to avoid mechanical failure and recently also to provide a distinct mechanical stimulation to cells within the scaffold pores. This way, mechanical strain levels are optimized to favour the bone tissue formation. However, bone regeneration is a highly dynamic process where the mechanical conditions immediately after surgery might not ensure optimal regeneration throughout healing. Here, we investigated in silico whether scaffolds presenting optimal mechanical conditions for bone regeneration immediately after surgery also present an optimal design for the full regeneration process. A computer framework, combining an automatic parametric scaffold design generation with a mechano-biological bone regeneration model, was developed to predict the level of regenerated bone volume for a large range of scaffold designs and to compare it with the scaffold pore volume fraction under favourable mechanical stimuli immediately after surgery. We found that many scaffold designs could be considered as highly beneficial for bone healing immediately after surgery; however, most of them did not show optimal bone formation in later regenerative phases. This study allowed to gain a more thorough understanding of the effect of scaffold geometry changes on bone regeneration and how to maximize regenerated bone volume in the long term.

Self-healing Polymeric Hydrogels: Toward Multifunctional Soft Smart Materials

2021 ◽  
Author(s):  
Xiao-Ling Zuo ◽  
Shao-Fan Wang ◽  
Xiao-Xia Le ◽  
Wei Lu ◽  
Tao Chen
Keyword(s):  
Smart Materials ◽  
Self Healing ◽  
Polymeric Hydrogels

scholarly journals Cold-Active β-Galactosidases: Insight into Cold Adaption Mechanisms and Biotechnological Exploitation

Marine Drugs ◽  
2021 ◽  
Vol 19 (1) ◽  
pp. 43
Author(s):  
Marco Mangiagalli ◽  
Marina Lotti
Keyword(s):  
Low Temperature ◽  
Molecular Mechanisms ◽  
Building Blocks ◽  
Cold Active ◽  
Cold Adaption ◽  
Glycosyl Donor ◽  
Pharmaceutical Industries ◽  
Biotechnological Processes ◽  
Hydrolysis Of ◽  
Insight Into

β-galactosidases (EC 3.2.1.23) catalyze the hydrolysis of β-galactosidic bonds in oligosaccharides and, under certain conditions, transfer a sugar moiety from a glycosyl donor to an acceptor. Cold-active β-galactosidases are identified in microorganisms endemic to permanently low-temperature environments. While mesophilic β-galactosidases are broadly studied and employed for biotechnological purposes, the cold-active enzymes are still scarcely explored, although they may prove very useful in biotechnological processes at low temperature. This review covers several issues related to cold-active β-galactosidases, including their classification, structure and molecular mechanisms of cold adaptation. Moreover, their applications are discussed, focusing on the production of lactose-free dairy products as well as on the valorization of cheese whey and the synthesis of glycosyl building blocks for the food, cosmetic and pharmaceutical industries.

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