Stopping of crosslinking reaction in a PDMS polymer at the gel point
TL;DR: In this paper, a method was developed to stop the crosslinking reaction of a polydimethylsiloxane system without disturbing the state of the sample, and the loss modulus and the storage modulus were found to be identical over several decades of frequency and for temperatures ranging between -50°C and +180°C.
Abstract: A method has been developed to stop the crosslinking reaction of a polydimethylsiloxane system without disturbing the state of the sample. Oscillatory shear experiments on samples just before and just beyond the gelation point demonstrated the transition of the material from a viscoelastic liquid to a viscoelastic solid. At the gel point the loss modulus and the storage modulus were found to be identical over several decades of frequency and for temperatures ranging between -50°C and +180°C. Both moduli were proportional to the square root of the frequency.
Citations
More filters
TL;DR: The synthesis of novel hybrid hydrogels by stepwise copolymerization of multiarm vinyl sulfone-terminated poly(ethylene glycol) macromers and alpha-omega cysteine oligopeptides via Michael-type additions is described, and structure and properties are very sensitive to the preparation state including stoichiometry and precursor concentration and lesssensitive to the pH during cross-linking.
721 citations
TL;DR: In this article, it was shown that there is only one class of network polymers for which the gel point coincides with the crossover, and the crossover cannot be used for detecting GP.
Abstract: Dynamic mechanical measurements allow direct determination of the instant at which a network polymer gels. In such an experiment, the evolution of G′(t,ω0) and G″ (t,ω0) is measured in small amplitude oscillatory shear as a function of cross-linking time t. The frequency ω0 is kept constant throughout. At the beginning of the experiment, G″ is orders of magnitude larger than G′, and at completion of reaction, this order is reversed. It recently has been suggested by Tung and Dynes that the gel point (GP) might occur at the time at which G′ and G″ cross each other. However, there is much dispute whether GP occurs exactly at the crossover or just somewhere in its vicinity. This study resolves the dispute by modeling the rheological behavior at GP: There is only one class of network polymers for which GP coincides with the crossover. This class of polymers exhibits, when reaching GP, power law relaxation G(t) ∼ t−n with a specific exponent value n = 1/2. Examples are stoichiometrically balanced network polymers and networks with excess cross-linker, however, only at temperatures much above the glass transition. Otherwise, the power law behavior would be masked by vitrification. Power law relaxation seems to be property of polymers at GP in general. However, some polymers have a different exponent value, n ≠ 1/2, in which case the crossover occurs before GP (for n 1/2); i.e. the crossover cannot be used for detecting GP. While there are no networks known to us with n 1/2. A new method is suggested for measuring GP of these imbalanced networks.
690 citations
TL;DR: In this article, a wide variety of rheological observations of materials in the vicinity of an LST are discussed with respect to their universality, and a variety of applications for polymers near the liquid-solid transition are presented that either already exist or can be envisioned.
Abstract: Polymeric materials near the liquid-solid transition (LST) exhibit a very distinct relaxation pattern. The reference point for analyzing these patterns is the instant of LST at which relaxation becomes self-similar over wide ranges of the relaxation time. The universality of this transition and its consequences have been explored extensively during the past decade. This study will present an overview of rheological implications inherent in liquid-solid transitions of polymers. The LST can be most reliably detected in a dynamic mechanical experiment in which the frequency independence of the loss tangent marks the LST. A wide variety of rheological observations of materials in the vicinity of an LST are discussed with respect to their universality. It is shown that polymer chemistry, molecular weight, stoichiometry, temperature, inhomogeneities, etc. greatly influence the material behavior near the LST. However, the characteristic self-similar relaxation is shown by all investigated materials, independent of the nature of the LST (e.g., both, physically and chemically crosslinking polymers). Several theories predict chemical and rheological properties in the vicinity of an LST. They are briefly discussed and compared with experimental results. A variety of applications for polymers near LST are presented that either already exist or can be envisioned. The self-similar relaxation behavior which results in a power law relaxation spectrum and modulus is not restricted to materials near LST. Different classes of polymers are described that also show power law relaxation behavior. What makes the self-similar relaxation specific for materials at LST is its occurrence at long times with the longest relaxation time diverging to infinity.
669 citations
TL;DR: The unique attributes of CANs that must be considered when designing, fabricating, and characterizing these smart materials that respond to either thermal or photochemical stimuli are discussed.
Abstract: Polymer networks possessing reversible covalent cross-links constitute a novel material class with the capacity for adapting to an externally applied stimulus. These covalent adaptable networks (CANs) represent a trend in polymer network fabrication toward the rational design of structural materials possessing dynamic characteristics for specialty applications. Herein, we discuss the unique attributes of CANs that must be considered when designing, fabricating, and characterizing these smart materials that respond to either thermal or photochemical stimuli. While there are many reversible reactions which to consider as possible cross-link candidates in CANs, there are very few that are readily and repeatedly reversible. Furthermore, characterization of the mechanical properties of CANs requires special consideration owing to their unique attributes. Ultimately, these attributes are what lead to the advantageous properties displayed by CANs, such as recyclability, healability, tunability, shape changes, an...
615 citations
TL;DR: This critical review covers the literature containing rheological characterization of the physical properties of peptide and polypeptide-based hydrogels including hydrogel bulk mechanical properties, gelation mechanisms, and the behavior ofhydrogels during and after flow.
Abstract: Peptide-based hydrogels are an important class of biomaterials finding use in food industry and potential use in tissue engineering, drug delivery and microfluidics. A primary experimental method to explore the physical properties of these hydrogels is rheology. A fundamental understanding of peptide hydrogel mechanical properties and underlying molecular mechanisms is crucial for determining whether these biomaterials are potentially suitable for biotechnological uses. In this critical review, we cover the literature containing rheological characterization of the physical properties of peptide and polypeptide-based hydrogels including hydrogel bulk mechanical properties, gelation mechanisms, and the behavior of hydrogels during and after flow (219 references).
599 citations
References
More filters
Book•
01 Jan 1961
TL;DR: In this article, the authors describe the nature of Viscoelastic behavior of polymeric systems and approximate relations among the linear Viscoels and approximate interrelations among the Viscelastic Functions.
Abstract: The Nature of Viscoelastic Behavior. Illustrations of Viscoelastic Behavior of Polymeric Systems. Exact Interrelations among the Viscoelastic Functions. Approximate Interrelations among the Linear Viscoelastic Functions. Experimental Methods for Viscoelastic Liquids. Experimental Methods for Soft Viscoelastic Solids and Liquids of High Viscosity. Experimental Methods for Hard Viscoelastic Solids. Experimental Methods for Bulk Measurements. Dilute Solutions: Molecular Theory and Comparisons with Experiments. Molecular Theory for Undiluted Amorphous Polymers and Concentrated Solutions Networks and Entanglements. Dependence of Viscoelastic Behavior on Temperature and Pressure. The Transition Zone from Rubberlike to Glasslike Behavior. The Plateau and Terminal Zones in Uncross-Linked Polymers. Cross-Linked Polymers and Composite Systems. The Glassy State. Crystalline Polymers. Concentrated Solutions, Plasticized Polymers, and Gels. Viscoelastic Behavior in Bulk (Volume) Deformation. Applications to Practical Problems. Appendices. Author & Subject Indexes.
12,676 citations
79 citations