Crosslinked Poly Vinyl Alcohol Research Articles

Physically Cross-Linked PVA Hydrogels as Potential Wound Dressings: How Freezing Conditions and Formulation Composition Define Cryogel Structure and Performance

Objectives: Hydrogels produced using the freeze–thaw method have demonstrated significant potential for wound management applications. However, their production requires precise control over critical factors including freezing temperature and the choice of matrix-forming excipients, for which no consensus on the optimal conditions currently exists. This study aimed to address this gap by evaluating the effects of the above-mentioned variables on cryogel performance. Methods: Mechanical properties, absorption capacity, and microstructure were assessed alongside advanced analyses using differential scanning calorimetry (DSC) and low-field nuclear magnetic resonance relaxometry (LF TD NMR). Results: The results demonstrated that fully hydrolyzed polyvinyl alcohol (PVA) with a molecular weight above 61,000 g/mol is essential for producing high-performance cryogels. Among the tested formulations, an 8% (w/w) PVA56–98 solution (Mw~195,000; DH = 98.0–98.8%) with 10% (w/w) propylene glycol (PG) provided the best balance of stretchability, durability, and low adhesion. Notably, while −25 °C is often used for cryogel preparation, freezing the gel precursor at −80 °C yielded superior results, producing materials with more open, interconnected structures and enhanced mechanical strength and elasticity—deviating from conventional practices. Conclusions: The designed cryogel prototypes exhibited functional properties comparable to or even surpassing commercial wound dressings, except for absorption capacity, which remained lower. Despite this, the cryogel prototypes demonstrated potential as wound dressings, particularly for use in dry or minimally exuding wounds. All in all, this study provides a comprehensive analysis of the physicochemical and functional properties of PVA cryogels, establishing a strong foundation for the development of advanced wound dressing systems.

The effect of NaY‐zeolite on mechanical, thermal, and spectroscopic behavior of crosslinked polyvinyl alcohol films

AbstractThe effects of sodium y zeolite (NaY‐zeolite) on crosslinked Polyvinyl alcohol (CrPVA) composite films were investigated. The spectroscopic analysis showed that crosslinks were formed between PVA, Tartaric acid (TA), and NaY‐zeolite particles. The thermal stability of the CrPVA film was improved with the addition of zeolite. Optimum thermal stability was observed for 5 wt % zeolite content. It can be seen that the mechanical properties also improved for 5 wt % zeolite‐doped CrPVA composite films when compared with CrPVA. It was observed that Young's modulus increased 54.14 to 74.49 MPa. While the degree of crystallinity of the composite film decreased from 20.42 to 14.77% due to zeolite content. This is thought to be due to the increase in the structure's crosslinking rate. The utilization of TA and NaY zeolite in membrane applications may be considered an advantage for improving the mechanical characteristics and the recyclability of membrane technology.

Eco-friendly non-fluorinated membranes for renewable energy storage

The European Union is studying the possibility of prohibiting the use of fluorinated-based materials which could limit the use of the most studied and used Nafion and Nafion-like membranes for any applications. Therefore, this study focuses on the preparation and performance evaluation of green, non-fluorinated proton exchange membranes in a chlor-alkali-based reversible electrochemical cell system for renewable energy storage applications. The membranes were prepared by casting and cross-linking of polyvinyl alcohol (PVA) with varying chitosan (CS) concentrations (5–20 wt%), followed by sulfonation using diluted sulfuric acid at room temperature. CS concentrations significantly influenced membrane's physicochemical properties, including ion exchange capacity, ionic conductivity, mechanical strength, and water uptake. Positron annihilation lifetime spectroscopy revealed a correlation between free volume properties and other membrane characteristics. A custom-designed 3D-printed electrochemical cell was developed, capable of operating in reversible mode (both electrolysis and fuel cell modes) with a zero-gap configuration. The PVA/CS (20 wt%) membrane outperformed Nafion, exhibiting a lower voltage (4 V vs. 6 V) in electrolysis mode at 50 mA cm⁻2 and a higher specific power density (2.7 vs. 1.9 mW cm⁻2 mgPt) in fuel cell mode. The obtained results demonstrate that crosslinked PVA/CS non-fluorinated based membranes can be sulfonated using diluted sulfuric acid and work effectively in reversible chlor-alkali electrochemical cells.

Low-cost and durable polyvinyl alcohol modified polyethylene separator for vanadium redox flow battery

Porous separators are considered a viable alternative to the high cost Nafion membrane for vanadium redox flow battery (VRFB) commercialization. However, the porous separators suffer from high vanadium ion crossover due to the presence of large micron size pores, which leads to decay in capacity of the VRFB system. To tackle the same, a composite separator is synthesized wherein a cross-linked polyvinyl alcohol (PVA) layer is coated on to the porous polyethylene silica separator (PE separator) to mitigate the vanadium ion crossover rate and employed in the VRFB application. Scanning electron microscopy (SEM) analysis confirmed the successful coating of the PVA film on to the PE separator. Synthesized PE-PVA separator showed a significant decrease in the vanadium ion crossover by 31.44 times compared to the pristine PE separator. Consequently, the self-discharge time increases by 8 and 1.66 times compared to the pristine PE separator and the Nafion117 membrane, respectively. VRFB cell equipped with the synthesized separator showed better capacity retention with a capacity fade rate of 0.2 % Ah·cycle−1 than the Nafion117 membrane (0.5 % Ah·cycle−1). In-situ and ex-situ oxidative stability of the separator is explored in detail and a degradation mechanism of the cross-linked PVA membrane is proposed accordingly. The synthesized single side coated PE-PVA´ separator exhibits higher coulombic efficiency of 99 % and comparable energy efficiency of 71 % at a current density of 120 mA·cm−2 and demonstrated excellent lifetime durability tested up to 1600 charge-discharge cycles at 80 mA·cm−2.

Highly efficient phosphate adsorption using calcium silicate hydrate-embedded calcium crosslinked polyvinyl alcohol thin film

The removal of phosphate from water is necessary to avoid eutrophication. In this work, a novel composite film of calcium silicate hydrate (CSH) immobilized within calcium cross-linked polyvinyl alcohol (CSH–PVA) was developed for efficient phosphate removal from water using a simple and environmentally friendly preparation method. The characterization showed that flake crystal-like CSH nanoparticles were immobilized on a PVA film (86–106 μm). Amorphous calcium phosphate and hydroxyapatite were observed after phosphate adsorption. The adsorption efficiency and capability of phosphate were examined under various conditions using batch experiments. The phosphate removal data fitted well to the pseudo-second-order kinetic model (R2 = 0.9903–0.9999) and the Langmuir isotherm model (R2 = 0.9958), which estimated a maximum removal capacity (99.01 mg g−1). Phosphate adsorption was found to be endothermic with spontaneous adsorption via chemisorption with strong affinity (ΔG° = −3.96 to −8.62 kJ mol−1, ΔH° = 65.4 kJ mol−1, and ΔS° = 232.94 J mol−1 K−1). Additionally, significant amounts of fluoride and carbonate ions affected phosphate adsorption at levels exceeding 5-fold and 20-fold that of phosphate, respectively. An excellent removal efficiency was achieved in the range of 72.06%–97.87% using phosphate-containing real samples. Therefore, the proposed CSH–PVA film showed great potential for effective phosphate removal from water, with potential for further use as a fertilizer.

Evaluation, optimization study, and life cycle assessment of novel eco-friendly PVA-based nanocomposite hydrogel adsorbents for methylene blue and paracetamol removal

In this study, an eco-friendly and novel hydrogel based on a crosslinked polyvinyl alcohol (PVA), iota carrageenan (IC) and polyvinylpyrrolidone (PVP) scaffold, containing a large amount (10–50 wt%) of nanoscale palm fronds (NPF) as additives, for water purification was demonstrated. A life cycle assessment (LCA) findings on NPF as biomass waste incorporated into PVA_PVP_IC polymer matrix was presented, and the results highlight the necessity of focused actions to reduce environmental impact and support the palm waste utilization in a sustainable manner. The multicomponent nanocomposite hydrogels were examined as adsorbents in a system work in batches for methylene blue (MB) and paracetamol (PCT) removal. The results show that, the presence of NPF, which dispersed in the hydrogel PVA_PVP_IC scaffolds containing both covalent and non-covalent cross-linking bonds, greatly enhanced the MB and PCT adsorption efficiency. A response surface methodology (RSM) model was used to find the best operating parameters of contaminant adsorption, including time, adsorbent dose, and starting concentration of pollutants. By using this statistical model, it was found that the optimal conditions for the adsorption reaction to achieve the complete removal of MB are 66.7 h adsorption time duration, 98.5 mg L−1 starting concentration, and an adsorbent dose of 5.9 mg, while for the complete removal of PCT, it is 57.6 h adsorption time duration, 80 mg L−1 starting concentration, and an adsorbent dose of 6 mg. The reusability of the nanocomposite hydrogels were tested for 5 cycles, all showed high adsorption capacity, indicating the potential for practical application of this nanocomposite hydrogel system. This study indicates that the prepared nanocomposite hydrogel raises the standard used for treatment of wastewater and also gives a solution to protect the environment and mitigate global warming.

Wearable self-powered motion sensor based on biomass carbon-dots/polyvinyl alcohol film

The functionalized polymer with scalable properties presents a promising option for flexible triboelectric nanogenerators designed for detecting human motion. In this study, a novel method to fabricate tribopositive composite film was proposed by incorporating high permittivity N-doped orange peel-based carbon dots (O-CDs) into the highly cross-linked polyvinyl alcohol (PVA). The O-CDs/PVA sensor showed elevated electrical output with the raised content of O-CDs until 1.5 wt. % with a peak voltage of 3.5 V. The response characteristics under various external force conditions were tested, and the maximum peak voltage and current reached 3.92 V and 28.6 A under the force of 50 N. Moreover, O-CDs/PVA sensors present superior high-output stability, durability, and accurate distinction to different movement states, even the vocal cord vibration. By introducing the support vector machine learning algorithm, intelligent gesture recognition was achieved. This work paves a facile, feasible, and scalable pathway to the self-powered human motion sensor device.

P16-07 Toxicological evaluation of anisotropic cross-linked polyvinyl alcohol hydrogels intended for humic substances immobilization and topical skin disease treatment

P16-07 Toxicological evaluation of anisotropic cross-linked polyvinyl alcohol hydrogels intended for humic substances immobilization and topical skin disease treatment

Research on the Thermal Aging Mechanism of Polyvinyl Alcohol Hydrogel.

Polyvinyl alcohol (PVA) hydrogels find applications in various fields, including machinery and tissue engineering, owing to their exceptional mechanical properties. However, the mechanical properties of PVA hydrogels are subject to alteration due to environmental factors such as temperature, affecting their prolonged utilization. To enhance their lifespan, it is crucial to investigate their aging mechanisms. Using physically cross-linked PVA hydrogels, this study involved high-temperature accelerated aging tests at 60 °C for 80 d and their performance was analyzed through macroscopic mechanics, microscopic morphology, and microanalysis tests. The findings revealed three aging stages, namely, a reduction in free water, a reduction in bound water, and the depletion of bound water, corresponding to volume shrinkage, decreased elongation, and a "tough-brittle" transition. The microscopic aging mechanism was influenced by intermolecular chain spacing, intermolecular hydrogen bonds, and the plasticizing effect of water. In particular, the loss of bound water predominantly affected the lifespan of PVA hydrogel structural components. These findings provide a reference for assessing and improving the lifespan of PVA hydrogels.

Experimental study for the decontamination of various surfaces from 99Mo using PVA/Borax/Al(OH)3 strippable hydrogel

Polyvinyl alcohol (PVA) is a beneficial polymer capable of forming hydrogels helpful in a wide range of applications. Hydrogels based on cross-linking of PVA with borax, and able to incorporate with a decontaminating agent have been used in the decontamination of 99Mo from contaminated surfaces. Aluminum hydroxide has been introduced in the formulations of PVA-borax, to increase the gel efficiency for 99Mo decontamination from surfaces. The formulations were investigated with glass, stainless steel, and wood as examples of different surfaces. When the hydrogel is sprayed on different surfaces, it forms rapidly and adheres well. Moreover, the hydrogel was shown to efficiently decontaminate surfaces contaminated with 99Mo by a maximum value of decontamination factor (D.F) for glass, stainless steel, and wood to be 43.5, 31.3, and 19.6 respectively.

Crosslinking of polyvinyl alcohol with di, tri, and tetracarboxylic acids: an experimental investigation

Crosslinking of polyvinyl alcohol with di, tri, and tetracarboxylic acids: an experimental investigation

Antibacterial Properties of Dandelion Extract-Based PVA/CTS/DAN/CuNP Composite Gel

Dandelion extract is a reducing agent, and CuSO4∙5H2O was used as a carrier to create copper nanoparticles (CuNPs). A novel polyvinyl alcohol–chitosan–dandelion–CuNP (PVA/CTS/DAN/CuNP) gel was acquired by cross-linking Polyvinyl alcohol (PVA) and chitosan (CTS) solution. Its structure was analyzed using Fourier transform infrared spectroscopy, Scanning electron microscopy, and X-ray diffraction. The PVA/CTS/DAN/CuNP gels manifested good stability, recycling ability, swelling properties, and biocompatibility. Using the agar diffusion method, the diameters of the inhibition zone of the composite gel against Escherichia coli, Staphylococcus aureus, and Pseudomonas aeruginosa could be over 21 mm. In conclusion, the PVA/CTS/DAN/CuNP composite gel had good antibacterial performance, which has a high potential for application in microbial contamination treatment and environmental protection.

Enhancing the performance of nanostructured PVA/SA scaffolds through incorporation of macromolecules: From synergistic effects to advanced multifunctionalities

The increasing use of biomaterial scaffolds in tissue engineering applications demands a comprehensive understanding and precise control of their overall properties. This work analyzes the synergy of naturally occurring biological macromolecules on the swelling, and thermal and mechanical properties of ionically crosslinked polyvinyl alcohol (PVA)/sodium alginate (SA) fibrous scaffolds. The presence of collagen (COL) or hyaluronic acid (HA) contributed not only to increasing the hydrogen-bond density but also to induce the crystalline PVA phase formation. Consequently, the swelling, thermal degradation, elastic modulus, and nanohardness of the scaffolds were significantly enhanced. By considering COL and HA the relevance in diverse cellular processes and tissue functions, the PVA-scaffolds here introduced are promising materials by providing advanced multifunctionalities.

Harnessing pomegranate rind waste to develop novel bioactive packaging films using citric acid crosslinked polyvinyl alcohol (PVA)/starch-based polymer matrix

Harnessing pomegranate rind waste to develop novel bioactive packaging films using citric acid crosslinked polyvinyl alcohol (PVA)/starch-based polymer matrix

Gel beads prepared by polyvinyl alcohol cross-linking with phytic acid and Fe as novel microbial carriers for simultaneous partial nitrification, anammox and denitrification

Enhancing the stability of biomass and ensuring a stable activity of anaerobic ammonia oxidizing bacteria are crucial for successful operation of the simultaneous partial nitrification, Anammox, and denitrification (SNAD) process. In this study, gel beads of polyvinyl alcohol/phytic acid (PVA/PA) and polyvinyl alcohol/phytic acid/Fe (PVA/PA/Fe) were prepared as innovative bio-carriers. Theoretical simulations and analyses revealed that these carriers are predominantly connected via hydrogen and borate bonds, with PVA/PA/Fe also featuring metal coordination bonds. The total nitrogen removal efficiency of reactors with PVA/PA/Fe and PVA/PA increased by 13.5 % and 9.0 %, respectively, compared to reactor without carriers. The iron-enriched PVA/PA/Fe carriers significantly improve SNAD by promoting Anammox, Feammox, and nitrate-dependent Fe2+ oxidation reactions, leading to faster nitrogen conversion and higher nitrogen removal rate than reactor without carriers and with PVA/PA. Using of PVA/PA and PVA/PA/Fe gel beads as bio-carriers offers benefits to the SNAD process, including cost-effective and low carbon requirement.

Coal tar pitch porous carbon-based bimolecular crosslinked hydrogel evaporator for solar-driven efficient water purification

Hydrogel evaporators have been widely used in solar-driven interfacial water evaporation due to their good thermal insulation, strong hydrophilicity, and rich internal pores. However, the occlusion pores in the hydrogel with a single molecule chain not only limit water transportation but also lead to serious salt crystallization. Hence, we developed a hydrogel evaporator (NSC-PVA/8CMC) with an abundant and open pore structure by cross-linking polyvinyl alcohol (PVA) and carboxymethyl cellulose (CMC). In which, the low-cost amorphous coal tar pitch porous carbon (NSC) is used to absorb light and improve light-to-heat conversion. The porous structure and thermal insulation (0.37 W m−1 K−1) of NSC-PVA/8CMC are conducive to excellent light absorption (≈99.02 %) and minimizing heat loss, finally leading to excellent photothermal conversion (1.44 kg m−2 h−1, 72.96 %, 1 sun). More significantly, NSC-PVA/8CMC with a strong desalination capacity can provide a self-purifying performance in seawater and brackish water. At the same time, the innovative attempt to use coal tar pitch as the photothermal conversion material has expanded the application scope of coal tar pitch.

Promoting the healing of infected diabetic wound by nanozyme-containing hydrogel with anti-bacterial inflammation suppressing, ROS-scavenging and oxygen-generating properties.

Bacterial infections already pose a significant threat to skin wounds, especially in diabetic patients who have difficulty healing wounds. However, wound or bacterial infections are known to produce excess reactive oxygen species (ROS), and hypoxia may further hinder wound healing and the development of chronic wounds. In this study, a multifunctional hydrogel for ROS scavenging and bacterial inhibition was developed by cross-linking polyvinyl alcohol (PVA) and sodium alginate (SA) with graphene oxide (GO) loaded with silver-platinum hybrid nanoparticles (GO@Ag-Pt). The PVA/SA hydrogel loaded with GO@Ag-Pt exhibited the ability to scavenge different types of ROS, generate O2, and kill a broad spectrum of bacteria in vitro. The silver-platinum hybrid nanoparticles significantly increased the antibacterial ability against Escherichia coli and Staphylococcus aureus compared with silver nanoparticles (AgNps). GO@Ag-Pt loaded hydrogel was effective in treating infections caused by S.aureus, thereby significantly promoting wound healing during the inflammatory phase. Hydrogel therapy significantly reduced the level of ROS and alleviated inflammation levels. Notably, our ROS-scavenging, antibacterial hydrogels can be used to effectively treat various types of wounds, including difficult-to-heal diabetic wounds with bacterial infections. Thus, this study proposes an effective strategy for various chronic wound healing based on ROS clearance and bacteriostatic hydrogels.

Engineering the nanozyme hydrogel beads by polyvinyl alcohol/chitosan encapsulation with recyclable and sustainable catalytic activity for visual analysis of hydrogen peroxide

BackgroundHydrogen peroxide (H2O2) plays a vital role in human health and have been regarded as a crucial analyte in metabolic processes, redox transformations, foods research and medical fields. Especially, the long-time and excessive digestion of H2O2 may even cause severe diseases. Although conventional instrumental methods and nanozymes-based colorimetric methods have been developed to accomplish the quantitative analysis of H2O2, the drawbacks of instrument dependence, cost-effectiveness, short lifespan, non-portable and unsustainable detection efficacies will limit their applications in different detection scenarios. ResultsHerein, to address these challenges, we have proposed a novel strategy for nanozyme (RuO2) hydrogel preparation by the solid support from cross-linked polyvinyl alcohol (PVA) and chitosan (CS) to both inherit the dominant peroxidase-like (POD) activity and protect the RuO2 from losing efficacies. Taking advantages from the hydrogel, the encapsulated RuO2 were further prepared as the regularly spherical beads (PCRO) to exhibit the sustainable, recyclable, and robust catalysis. Moreover, the intrinsic color interferences which originated from RuO2 can be avoided by the encapsulation strategy to promote the detection accuracy. Meanwhile, the high mechanical strength of PCRO shows the high stability, reproducibility, and cyclic catalysis to achieve the recyclable detection performance and long lifetime storage (40 days), which enables the sensitively detection of H2O2 with the detection limit as lower to 15 μM and the wide detection linear range from 0.025 to 1.0 mM. SignificanceOn the basis of the unique properties, PCRO has been further adopted to construct a smartphone detection platform to realize the instrument-free and visual analysis of H2O2 in multi-types of milk and real water samples through capturing, processing, and analyzing the RGB values from the colorimetric photographs. Therefore, PCRO with the advanced detection efficacies holds the great potential in achieving the portable and on-site analysis of targets-of-interest.

Charge-patterned nanofiltration membranes with polystyrene sulfonate particles and polyethyleneimine in cross-linked polyvinyl alcohol

Removing salinity has always been a challenge for wastewater treatment. Utilizing nanofiltration (NF) membranes is a promising approach. However, currently available NF membranes are less effective in monovalent salt removal. In this study, work toward the initial aim of fabricating charge mosaic membranes led to charge-patterned NF-selective films on polyether sulfone (PES) or polyacrylonitrile (PAN) support membranes, with similar rejection for mono- and divalent salts. The membranes were fabricated by a two-step layer assembly of first negatively charged polystyrene sulfonate (PSS) particles immobilized in a polyvinyl alcohol (PVA) layer, followed by coating a positively charged polyethyleneimine (PEI) layer. Both PVA and PEI were crosslinked using glutaraldehyde that had initially been impregnated into the support membrane. The type of support membrane, nanoparticle, PVA, and PEI concentrations during fabrication, as well as feed pH and salt concentration, play significant roles in separation performance of obtained composite membranes. Charge-patterned NF membranes fabricated using 0.5 wt.% PVA and 0.05 wt.% PSS for assembly of the first layer followed by coating 0.5 wt.% PEI solution had even somewhat higher rejection for monovalent salt (NaCl; ∼82%) compared to multivalent salts (Na2SO4, MgSO4, and MgCl2; ∼74%), at a permeance of 5.5 LMH/bar on the PES and 3.1 LMH/bar on the PAN support membrane.

Development of novel proton exchange membranes based on cross-linked polyvinyl alcohol (PVA)/5-sulfosalicylic acid (SSCA) for fuel cell applications

The proton-conducting and methanol permeation behaviors of polymeric electrolyte membranes (PEMs), as well as the expensive nature of direct methanol fuel cell (DMFC) components, pose major concerns in DMFC performance and commercialization. As a result, this research aimed to develop low-cost polyelectrolyte membranes based on cross-linked poly(vinyl alcohol)/5-sulfosalicylic acid dehydrate (PVA/SSCA) composite. Chemical cross-linkers and modifiers offer the essential chemical and mechanical stability of the developed membranes for usage as polyelectrolyte membranes (PEMs). The manufactured composite proton exchange membranes provide several benefits, including significant thermal, chemical, and mechanical stability. The results revealed that extending the SSCA molar concentration increased IEC outcomes of the synthesized membranes, reaching an elevated level of (3.31 meq g−1) compared to (0.91 meq g−1) for the Nafion 117 membrane. The proton conductivity of a composite membrane (102 μm thick) measured by impedance spectroscopy was relatively (0.078 S cm−1) and found comparable to other PVA-based composite membranes reported in the literature. Other key parameters, such as methanol permeability, were measured for constructed composite proton exchange membranes (2.52 × 10–7 cm2 s−1), which were much lower than Nafion 117 (3.39 × 10–6 cm2 s−1). The Fourier transform infrared (FT-IR), Raman scattering spectroscopy, scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) spectroscopy, elemental analysis, and thermal gravimetric analysis (TGA) were among the techniques used to characterize the synthesized membranes. These characterizations confirm the structural interaction between the membrane components’ crystalline nature, and no signs of phase separation or cracks were found; surface morphology and good membrane homogeneity, elemental analysis, and the membranes’ thermal stability (up to 290 °C). The membranes were also mechanically characterized using a universal testing machine (UTM), which revealed good mechanical stability. The findings demonstrate that a low-cost proton exchange membrane could potentially be synthesized for DMFC applications.