A novel approach using differential scanning calorimetry to investigate the dissolved state in aqueous solutions of polymers used for papermaking

Yamauchi, Tatsuo; Tamai, Naoto

doi:10.1002/app.12484

Cited by 6 publications

(8 citation statements)

References 32 publications

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“…They hypothesized that low M w PEG chains are only associated with non-freezable water and as the M w increases, the polymer chains fold upon themselves allowing intermediate water molecules to form. These results agree with the observations made by Yamauchi and Tamai [ 55 ] where at M w lower than 500, intermediate water was not detected, and then slowly increased with the M w until a constant amount of about 4% of total water was reached at around M w 2200 ( Figure 9 ).…”

Section: Studies On the States Of Water On Polymers And Their Effesupporting

confidence: 92%

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Impact of the Hydration States of Polymers on Their Hemocompatibility for Medical Applications: A Review

Bag

Valenzuela

2017

IJMS

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Water has a key role in the functioning of all biological systems, it mediates many biochemical reactions, as well as other biological activities such as material biocompatibility. Water is often considered as an inert solvent, however at the molecular level, it shows different behavior when sorbed onto surfaces like polymeric implants. Three states of water have been recognized: non-freezable water, which does not freeze even at −100 °C; intermediate water, which freezes below 0 °C; and, free water, which freezes at 0 °C like bulk water. This review describes the different states of water and the techniques for their identification and quantification, and analyzes their relationship with hemocompatibility in polymer surfaces. Intermediate water content higher than 3 wt % is related to better hemocompatibility for poly(ethylene glycol), poly(meth)acrylates, aliphatic carbonyls, and poly(lactic-co-glycolic acid) surfaces. Therefore, characterizing water states in addition to water content is key for polymer selection and material design for medical applications.

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Section: Studies On the States Of Water On Polymers And Their Effesupporting

confidence: 92%

“…(•) Non-freezable water; (o) intermediate water. Reprinted from [ 55 ] with permission of John Wiley & Sons.…”

Section: Figurementioning

confidence: 99%

Impact of the Hydration States of Polymers on Their Hemocompatibility for Medical Applications: A Review

Bag

Valenzuela

2017

IJMS

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“…The number of nonfreezable water molecules around one polymeric unit in polymer E-L was considerably lower (N w = 1.24) than that in the PEG500 homopolymer with N w ≈ 9. 63 As in the case of zwitterionic copolymer Z-L, the reduction in the number of water molecules per repeating unit of PEG in the copolymer in comparison to its homopolymer could be attributed to the presence of n-BMA and IBoMA units, which limit swelling, increase chain entanglement/crowding, and reduce the availability of PEG groups to water.…”

Section: Discussionmentioning

confidence: 96%

“…This observation corresponds with that of Yamauchi and Tamai who failed to find freezable water in the PEG500 homopolymer. 63 Nonfreezable water is strongly bound to the polymer matrix and does not show thermal transitions in DSC experiments, even when cooled down to −100 °C. 64 Figure 2C,D presents the calculated ratios of the mass of nonfreezable water relative to that of the polymer and number of nonfreezable molecules around each polymeric unit.…”

Section: Discussionmentioning

confidence: 99%

Nonfreezable Water and Polymer Swelling Control the Marine Antifouling Performance of Polymers with Limited Hydrophilic Content

Kardela

Millichamp

Ferguson

et al. 2019

ACS Appl. Mater. Interfaces

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Zwitterionic chemical groups have well-documented resistance to marine fouling species when presented as homogeneous polymer brushes. These model formulations are not, however, suitable for practical fouling-control applications. It is presently unknown if a uniform film of zwitterions is required to elicit nonfouling character via the binding of interfacial water or if the incorporation of zwitterionic functionality into a more practical bulk polymer system will suffice. Here, copolymers of n-butyl methacrylate were synthesized with low incorporation levels (up to 20 mol %) of hydrophilic functionality, including zwitterionic moieties. Their antifouling (AF) properties were evaluated using barnacle cyprids (Balanus improvisus), diatom cells (Navicula incerta), and a multispecies biofilm. The laboratory assays revealed higher resistance of ionic copolymers toward cyprid settlement, which was attributed to their swelling and the presence of nonfreezable water molecules bound tightly to the polymer chains. Additionally, cells of N. incerta and the multispecies biofilm were removed more effectively on polymers containing sulfobetaine methacrylate and sulfopropyl methacrylate moieties. The results indicate that the presence of tightly bound interfacial water is not limited to model systems of pure hydrophilic homopolymers, but that this mechanism can also reduce the settlement and adhesion of fouling species via bulk copolymer systems with limited hydrophilic content. The swelling of polymers with hydrophilic content may also contribute to their AF efficacy, and such materials may therefore represent a route to translation of the well-documented nonfouling character of zwitterions into practical, industrially relevant coating formulations.

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“…Surprisingly, only a limited number of studies have addressed both the swelling behavior and detailed molecular organization of water for PEGDA-based hydrogels [ 23 , 36 ]. In contrast, the interaction of linear PEG with water has been more thoroughly studied [ 37 , 38 , 39 ], and this body of knowledge forms the basis for the present study on the water content of PEG hydrogels. Specifically, the research reported here investigates the macroscopic swelling behavior and molecular organization of water in crosslinked PEGDA as a model charge-neutral hydrogel with variable network structure and under different hydration conditions.…”

Section: Introductionmentioning

confidence: 99%

Elucidating the Molecular Mechanisms for the Interaction of Water with Polyethylene Glycol-Based Hydrogels: Influence of Ionic Strength and Gel Network Structure

2021

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The interaction of water within synthetic and natural hydrogel systems is of fundamental importance in biomaterial science. A systematic study is presented on the swelling behavior and states of water for a polyethylene glycol-diacrylate (PEGDA)-based model neutral hydrogel system that goes beyond previous studies reported in the literature. Hydrogels with different network structures are crosslinked and swollen in different combinations of water and phosphate-buffered saline (PBS). Network variables, polyethylene glycol (PEG) molecular weight (MW), and weight fraction are positively correlated with swelling ratio, while “non-freezable bound water” content decreases with PEG MW. The presence of ions has the greatest influence on equilibrium water and “freezable” and “non-freezable” water, with all hydrogel formulations showing a decreased swelling ratio and increased bound water as ionic strength increases. Similarly, the number of “non-freezable bound water” molecules, calculated from DSC data, is greatest—up to six molecules per PEG repeat unit—for gels swollen in PBS. Fundamentally, the balance of osmotic pressure and non-covalent bonding is a major factor within the molecular structure of the hydrogel system. The proposed model explains the dynamic interaction of water within hydrogels in an osmotic environment. This study will point toward a better understanding of the molecular nature of the water interface in hydrogels.

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A novel approach using differential scanning calorimetry to investigate the dissolved state in aqueous solutions of polymers used for papermaking

Cited by 6 publications

References 32 publications

Impact of the Hydration States of Polymers on Their Hemocompatibility for Medical Applications: A Review

Impact of the Hydration States of Polymers on Their Hemocompatibility for Medical Applications: A Review

Nonfreezable Water and Polymer Swelling Control the Marine Antifouling Performance of Polymers with Limited Hydrophilic Content

Elucidating the Molecular Mechanisms for the Interaction of Water with Polyethylene Glycol-Based Hydrogels: Influence of Ionic Strength and Gel Network Structure

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