Abstract:Formation of homo-interpenetrating polymer networks (homo-IPNs) of poly(2-hydroxyethyl methacrylate) (PHEMA) and their capacity for calcification are investigated. A sequential method is established to generate IPNs of rank I and II, containing two or three crosslinked networks. Although the networks are chemically identical, thermo-mechanical analysis (DSC, DMA) suggests some phase separation. Calcification of PHEMA hydrogels, thought to be controlled by the free volume pathways accessible to calcium ions, is… Show more
“…The cosolvency of monomer‐water mixtures has an important impact on phase separation occurring during polymerization in the presence of diluent because the dissolution ability of monomer‐water mixtures for PHEMA gets first better and after passing through a maximum it decreases again reaching its minimum when all monomer has been polymerized. HEMA monomer is a better solvent for PHEMA than water contrary to the statement in ref . There is an important feature of the system that the swelling degree is independent of the crosslinker concentration in the range of about ≤1%.…”
Section: Resultsmentioning
confidence: 58%
“…HEMA monomer is a better solvent for PHEMA than water contrary to the statement in ref. [25] There is an important feature of the system that the swelling degree is independent of the crosslinker concentration in the range of about 1%. How the situation develops for PHEMA-water systems is illustrated by Figure 4.…”
Section: Resultsmentioning
confidence: 99%
“…Since PHEMA offers excellent biocompatibility its use in materials research for bioengineering has been vital . In ophthalmology, the great effort has been put on development of hydrogels for artificial cornea, vitreous substitute, biomimetic hydrogels resistant to calcium uptake including several studies of crosslinked PHEMA hydrogel owing to its excellent compatibility with living tissues (c.f., refs. ν‐syneresis).…”
Section: Introductionmentioning
confidence: 99%
“…It was found that a PHEMA/PHEMA DN took up somewhat less calcium when used as implant than a single PHEMA gel. [25] As network B, HEMA was used to reinforce poly (ethylene glycol) gels [35] ; however, the material was optically clear only for gels with>90 wt.-% PHEMA. To improve the adhesion, collagen was added.…”
Summary
The interpenetrating network structure was used to control mechanical properties of hydrogels based on poly(2‐hydroxyethyl methacrylate) (PHEMA) (first network (A) or second network (B)) and poly(glycerol methacrylate) (PGMA) (network B). In order to understand the structure, mechanical and swelling properties of sequentially made IPN hydrogels, the swollen PHEMA network microstructure and its formation was investigated by means of swelling and SWAXS experiments. Visually clear and microscopically homogenous hydrogel networks based on poly(2‐hydroxyethyl methacrylate) revealed presence of domains of size 1–10 nm formed during polymerization in the presence of water. The study was carried out to understand conditions under which the hydrophobic interactions are operative and their effect on the microstructure as well as how they change when the double network structure is introduced. The morphologies of network A ranged from homogenous, non‐porous, and optically clear gels, to macroporous gels resulting from phase separation and offering fused‐sphere morphology. A cryogel characterized by large elongated and partially interconnected pores of tens to hundreds micrometers were another object for comparison. In most cases, an increase of tensile moduli and improvement of ultimate tensile properties was achieved. A surprisingly high increase in true strength (by a factor of 10 – 30) was achieved when the macroporous PHEMA network A was reinforced by weak PHEMA or PGMA networks B. All these weakly crosslinked IPN gels were optically clear.
“…The cosolvency of monomer‐water mixtures has an important impact on phase separation occurring during polymerization in the presence of diluent because the dissolution ability of monomer‐water mixtures for PHEMA gets first better and after passing through a maximum it decreases again reaching its minimum when all monomer has been polymerized. HEMA monomer is a better solvent for PHEMA than water contrary to the statement in ref . There is an important feature of the system that the swelling degree is independent of the crosslinker concentration in the range of about ≤1%.…”
Section: Resultsmentioning
confidence: 58%
“…HEMA monomer is a better solvent for PHEMA than water contrary to the statement in ref. [25] There is an important feature of the system that the swelling degree is independent of the crosslinker concentration in the range of about 1%. How the situation develops for PHEMA-water systems is illustrated by Figure 4.…”
Section: Resultsmentioning
confidence: 99%
“…Since PHEMA offers excellent biocompatibility its use in materials research for bioengineering has been vital . In ophthalmology, the great effort has been put on development of hydrogels for artificial cornea, vitreous substitute, biomimetic hydrogels resistant to calcium uptake including several studies of crosslinked PHEMA hydrogel owing to its excellent compatibility with living tissues (c.f., refs. ν‐syneresis).…”
Section: Introductionmentioning
confidence: 99%
“…It was found that a PHEMA/PHEMA DN took up somewhat less calcium when used as implant than a single PHEMA gel. [25] As network B, HEMA was used to reinforce poly (ethylene glycol) gels [35] ; however, the material was optically clear only for gels with>90 wt.-% PHEMA. To improve the adhesion, collagen was added.…”
Summary
The interpenetrating network structure was used to control mechanical properties of hydrogels based on poly(2‐hydroxyethyl methacrylate) (PHEMA) (first network (A) or second network (B)) and poly(glycerol methacrylate) (PGMA) (network B). In order to understand the structure, mechanical and swelling properties of sequentially made IPN hydrogels, the swollen PHEMA network microstructure and its formation was investigated by means of swelling and SWAXS experiments. Visually clear and microscopically homogenous hydrogel networks based on poly(2‐hydroxyethyl methacrylate) revealed presence of domains of size 1–10 nm formed during polymerization in the presence of water. The study was carried out to understand conditions under which the hydrophobic interactions are operative and their effect on the microstructure as well as how they change when the double network structure is introduced. The morphologies of network A ranged from homogenous, non‐porous, and optically clear gels, to macroporous gels resulting from phase separation and offering fused‐sphere morphology. A cryogel characterized by large elongated and partially interconnected pores of tens to hundreds micrometers were another object for comparison. In most cases, an increase of tensile moduli and improvement of ultimate tensile properties was achieved. A surprisingly high increase in true strength (by a factor of 10 – 30) was achieved when the macroporous PHEMA network A was reinforced by weak PHEMA or PGMA networks B. All these weakly crosslinked IPN gels were optically clear.
“…Images of a leather sample before and after removal of a weight that adhered onto this material with the aid of HEMA/AAm hydrogels: original state with the applied weight (a); during removal of the weight (b); and after removal of the weight (c). Also shown is an image of the leather after it had been washed with water, showing a clean surface (d) hydrogels were in the range of 50-145°C 41 . However, the self-healing properties of conventional PHEMA hydrogels differed significantly from those reported herein.…”
Section: Rheological Behavior Of the Hydrogelsmentioning
Without the introduction of new functional groups, altering the properties of a substance, such as by changing from a non-self-healing to a rapidly self-healing material, is often difficult. In this work, we report that the properties of 2hydroxyethyl methacrylate and acrylamide (HEMA/AAm) hydrogels can be easily altered from non-self-healing to rapidly self-healing by simply tuning the reaction temperature. Notably, the hydrogels that are prepared at room temperature do not exhibit self-healing behavior, while those treated at an elevated temperature show automatic selfhealing performance within~15 s. Interestingly, in contrast with the previous self-healing HEMA-based polymeric hydrogels, which function only above their glass transition temperatures (T g), the hydrogels prepared herein exhibit rapid self-healing properties at room temperature, which is below their T g. In addition, the stretching capabilities of the hydrogels can be greatly enhanced by up to 30-fold. The hydrogels also exhibit good adhesive performance and can adhere strongly onto various substrates, such as wood, glass, fabric, paper, leather, porcelain, and steel. For example, a 10 kg weight could be suspended from a wooden substrate with the aid of these hydrogels. These results may provide valuable insight regarding the design of self-healing hydrogels and their large-scale production.
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