Silicon dioxide/poly(vinyl alcohol) composite hydrogels with high mechanical properties and low swellability

Poly(vinyl alcohol) (PVA) hydrogels with tissue-like viscoelasticity, excellent biocompatibility, and hydrophilicity have been considered as promising cartilage replacement materials. However, the low mechanical properties of pure PVA hydrogels limit their applications for bearing complicated loads. Herein, we report silicon dioxide (SiO₂)/PVA composite hydrogels fabricated by fabricated cyclically freezing/thawing the aqueous mixture of PVA and methyltrimethoxysilane (MTMS). MTMS hydrolyzes and forms SiO₂ particles in situ to reinforce PVA hydrogel. Meanwhile, silanol group condenses with hydroxyl groups of PVA and chemically bonds with PVA. The resulting SiO₂/PVA hydrogels exhibit much better mechanical properties than bare PVA hydrogel. In addition, the composite hydrogels keep very low swellable property. This prepared composite hydrogels are promising in a variety of biomedical applications such as artificial articular cartilage, drug delivery, and biosensors. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46895.     

聚乙烯醇水凝胶自修复性能

高浓度聚乙烯醇（PVA）水凝胶具有一定的修复功能,但其自修复机理及制备工艺参数对其修复性能的影响缺乏研究。本文采用冷冻-解冻法制备了高浓度自修复PVA水凝胶,通过调整PVA水凝胶制备工艺参数（PVA分子量、PVA浓度、冷冻时间、解冻时间、冷冻-解冻次数、修复时间、冷冻温度等）得到了最佳工艺条件,分析了水凝胶自修复机理,并研究了PVA水凝胶的多次自修复性能。研究结果表明：相对分子质量大的PVA制备的水凝胶自修复性能好;其中冷冻时间为2h,解冻时间为1h,一次冷冻-解冻循环制备得到的水凝胶自修复性能最好,最佳修复时间为12h,能较好地进行反复自修复。指出水凝胶自修复性能主要是由其内部可逆氢键的相互作用形成的,其主要影响源于冷冻-解冻处理后水凝胶内部羟基含量及PVA分子的流动性。     

Effects of composition on the properties of dual physically cross-linked hydrogel composed of polyvinyl alcohol and poly (acrylamide-co-acrylic acid)

In previous work, we have developed a dual physically cross-linked hydrogel composed of poly (acrylamide-co-acrylic acid) (PAM-co-PAA) and polyvinyl alcohol (PVA), named as PVA/CP DN gel, by facile copolymerization and freezing/thawing. The PVA/CP DN gel is featuring both excellent mechanical properties and self-healing ability. Additionally, we have preliminarily found that the comonomer ratio for PVA/CP DN gel have great influence on the self-healing efficiency. In this research article, we will further discuss the mechanical and self-healing properties of the PVA/CP DN gel by varying the comonomer ratio of PAM-co-PAA. The results proved that the structure of DN will be loosen when the number of PAA segments exceed that of PAM. More PAA segments in copolymer make the PVA/CP DN gel have better elongation at break but weak in tensile strength and young’s modulus because of less PVA crystalline domains formed in the gel. The energy dissipation value for the double-network hydrogel decrease with the addition of PAA segments, whereas self-healing efficiency of PVA/CP DN gel increased. Anyway, this work provides more information to further understand the effects of composition on the properties of dual physically cross-linked PVA/CP DN hydrogel.     

Hybrid Hydrogels Based on Poly(vinyl alcohol) (PVA)/Agar/Poly(ethylene glycol) (PEG) Prepared by High Energy Electron Beam Irradiation: Investigation of Physico‐Mechanical and Rheological Properties

A series of hybrid hydrogels based on poly(vinyl alcohol) (PVA)/agar/poly(ethylene glycol) (PEG) prepared by a solution casting method using e‐beam irradiation are investigated to determine the effect of agar and PEG content (1, 2, and 4 wt%) on their physicomechanical and rheological properties. The gel content of the hydrogels decreases with increasing agar and PEG contents. The equilibrium swelling of PVA hydrogel decreases on blending with agar while adding PEG to PVA/agar increases the swelling by about 400%. No obvious change in the dehydration behavior of the hybrid hydrogels is observed on changing agar and PEG contents. The solid‐like rheological behavior of the hydrogels is not significantly affected by agar content, while it approaches a liquid‐like behavior at high PEG loading. The tensile strength of the hybrid hydrogels is improved by increasing agar content, while its elongation‐at‐break is decreased. On the other hand, the opposite results are found regarding the influence of PEG and its content on the mechanical properties of the hybrid hydrogels.

     

Characterization of degraded hydrogels based on poly(vinyl alcohol) grafted with poly(lactide‐co‐glycolide)

Poly(vinyl alcohol) (PVA) grafted with poly(lactide‐co‐glycolide) and cross‐linked as a material of increased hydrophobicity relative to PVA was produced. The properties were examined with respect to the mass loss, water uptake, hydrophilicity, and mechanical characteristics upon hydrolytical degradation. The hydrogels investigated display water uptake increasing with degradation time because of increasing hydrophilicity. The mass loss amounts up to 15% after eight weeks of degradation. The mechanical properties of the hydrogels are within the range of those of natural tissue, the E modulus is 18 MPa, or even 100–200 MPa, depending on the structure of material. The mechanical characteristic and their dependence degradation show the most recognizable correlation with the chemical structure. Studies of the topography of degraded samples (scanning electron microscopy) and IR measurements demonstrate the degradation to occur at slow rate due to the high degree of grafting. The mass loss is rather low and a bulk degradation mechanism takes place. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

A novel pH‐sensitive and freeze‐thawed carboxymethyl chitosan/poly(vinyl alcohol) blended hydrogel for protein delivery

BACKGROUND: Blended hydrogels are widely applied in medical fields. They can provide many advantages, such as biocompatibility and biodegradability. Many materials and methods are used to obtain blended hydrogels. In this work, carboxymethyl chitosan (CMCS) and poly(vinyl alcohol) (PVA) blended hydrogels were prepared using the freezing and thawing technique. The properties of the hydrogels prepared, i.e. gel fraction, swelling and pH‐responsive behaviors, were investigated. RESULTS: The gel fraction increased with increasing time of freezing and thawing as determined through gravimetric analysis. It was also found that the equilibrium degree of swelling improved obviously due to the addition of CMCS compared to pure PVA hydrogel. The blended hydrogel with composition CMCS/PVA 80/20 (by weight) possessed the highest swelling ratio. The results of the influence of pH values on the swelling behavior showed that minimum swelling ratios of the hydrogels occurred near the isoelectric point of CMCS. Protein release studies were performed under various pH conditions: the release was much slower under acid than under basic conditions. The release showed a burst in the first 15 h and then steadily increased. CONCLUSION: The addition of CMCS can improve the physical properties of pure PVA hydrogels and provide pH sensitivity. It is concluded that PVA hydrogels containing CMCS could be potentially applied as oral delivery systems for protein drugs. Copyright © 2009 Society of Chemical Industry     

Preparation of collagen‐immobilized poly(ethylene glycol)/poly(2‐hydroxyethyl methacrylate) interpenetrating network hydrogels for potential application of artificial cornea

To enhance the mechanical strength of poly(ethylene glycol)(PEG) gels and to provide functional groups for surface modification, we prepared interpenetrating (IPN) hydrogels by incorporating poly(2‐hydroxyethyl methacrylate)(PHEMA) inside PEG hydrogels. Formation of IPN hydrogels was confirmed by measuring the weight percent gain of the hydrogels after incorporation of PHEMA, as well as by ATR/FTIR analysis. Synthesis of IPN hydrogels with a high PHEMA content resulted in optically transparent and extensively crosslinked hydrogels with a lower water content and a 6 ～ 8‐fold improvement in mechanical properties than PEG hydrogels. Incorporation of less than 90 wt % PHEMA resulted in opaque hydrogels due to phase separation between water and PHEMA. To overcome the poor cell adhesion properties of the IPN hydrogels, collagen was covalently grafted to the surface of IPN hydrogels via carbamate linkages to hydroxyl groups in PHEMA. Resultant IPN hydrogels were proven to be noncytotoxic and cell adhesion study revealed that collagen immobilization resulted in a significant improvement of cell adhesion and spreading on the IPN hydrogel surfaces. The resultant IPN hydrogels were noncytotoxic, and a cell adhesion study revealed that collagen immobilization improved cell adhesion and spreading on the IPN hydrogel surfaces significantly. These results indicate that PEG/PHEMA IPN hydrogels are highly promising biomaterials that can be used in artificial corneas and a variety of other load‐bearing tissue engineering applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Porous boron nitride nanofibers/PVA hydrogels with improved mechanical property and thermal stability

Polyvinyl alcohol (PVA) hydrogel is a promising material possessing good chemical stability, high water absorption, excellent biocompatibility and biological aging resistant. However, the poor mechanical performance of PVA hydrogel limits its applications. Here we report the utilization of one-dimensional (1D) BN nanofibers (BNNFs) as nanofillers into PVA matrix to prepare a novel kind of BNNFs/PVA composite hydrogel via a cyclic freezing and thawing method. For comparison, the composite hydrogels using spherical BN nanoparticles i.e. BN nanospheres (BNNSs) as fillers were also prepared. The mechanical properties, thermal stabilities and swelling behaviors of the composite hydrogels were investigated in detail. Our study indicates that the mechanical properties of the hydrogels can be improved by adding of BNNFs. After loading of BNNFs into PVA with content of 0.5?wt%, the compressive strength of the composite hydrogel increases by 252% compared with that of pure PVA hydrogel. The tensile performance of BNNFs/PVA composite hydrogels has also been improved. Impressive 87.8% increases in tensile strengths can be obtained with 1?wt% BNNFs added. In addition, with the increase of BNNFs content, the thermal stability and the swelling ratio of hydrogels are increased gradually. The swelling ratio of hydrogel increases by 56.3% with only 1?wt% BNNFs added. In comparison, the improvement effects of the BNNS fillers on the mechanical strengths and swelling ratios are much weaker. The enhanced effects of BNNFs can be ascribed to the strong hydrogen bond interaction between BNNFs and PVA. The high aspect ratios of the nanofibers should also be took into account.     

Synthesis of dual physical self-healing starch-based hydrogels for repairing tissue defects

Hydrogels have the potential to simulate and permeate body tissues. They can be used in many biomedical applications, such as drug delivery, wound dressings, contact lenses, synthetic implants, biosensors, and tissue engineering. Despite recent significant advances in hydrogel fabrication, with the introduction of double network hydrogels, with ionic or hydrogen bonds, there is still the challenge of achieving optimal mechanical properties with appropriate self-healing ability. To solve the above problem, in this study, a new type of starch/chitosan/PVA/borax hydrogel was synthesized by adopting the one-pot method. The effect of concentration and ratio of raw materials on the final properties of hydrogels, such as the degree of hydrophilicity, morphology, degradation, mechanical strength, and drug release rate, was investigated. The properties of hydrogels were examined by scanning electron microscopy, thermogravimetric analysis, Fourier-transform infrared spectroscopy, X-ray diffractometry, and contact angle, which confirmed the composite synthesis and uniform distribution of HNT and curcumin. In addition, the composite hydrogel showed excellent mechanical properties. Drug release studies confirmed that the drug is slowly released from the nanocomposite hydrogels. The results showed that starch-based nanocomposite hydrogels could provide appropriate repairing potential for defects exposed to changeable parameters.     

Effect of poly(ethylene glycol)-derived crosslinkers on the properties of thermosensitive hydrogels

Three crosslinkers, poly(ethylene glycol) diacrylate (PEGDA), glycerol ethoxylate triacrylate (GETA) and citric acid-(PEG acrylate)₃ (CA-PEGTA) derived from poly(ethylene glycol) (PEG) were synthesized at first. The three series of poly (N-isopropylacrylamide) (PNIPAAm) hydrogels were prepared by photopolymerization with the crosslinkers and compared with a hydrogel based on commercial crosslinker, N,N′-methylene bis-acrylamide (NMBA). The influence of the crosslinker structures and contents on the swelling behaviour, mechanical properties, and drug release of the hydrogels was investigated. The results showed that the hydrogels based on PEGDA and NMBA exhibited the highest and the lowest swelling ratio, respectively. The content of crosslinker of all hydrogel series showed good thermosensitivity and thermo-reversibility. The critical gel transition temperature (CGTT) appeared at 32 °C for the hydrogel based on NMBA, but appeared at about 34 °C for other hydrogels due to higher hydrophilicity of the crosslinker. In the mechanical properties, three-arms crosslinker GETA and CA-PEGTA led to higher mechanical strength than a linear crosslinker PEGDA. A hydrogel based on GETA (NG6) showed the highest shear modulus of 656.9 kPa and Young’s modulus of 1655.0 kPa. The hydrogels containing higher content of crosslinker revealed lower swelling ratio and higher mechanical strength. In the drug release, the hydrogels with higher swelling ratios showed higher drug absorbed. The highest release percentage of caffeine and vitamin B12 for hydrogel based on PEGDA (NP6) could reach 68.3% and 75.4%, respectively. In addition, the bound water and toxicity of the hydrogels were also investigated.

     

Degradable natural polymer hydrogels for articular cartilage tissue engineering

Articular cartilage has poor ability to heal once damaged. Tissue engineering with scaffolds of polymer hydrogels is promising for cartilage regeneration and repair. Polymer hydrogels composed of highly hydrated crosslinked networks mimic the collagen networks of the cartilage extracellular matrix and thus are employed as inserts at cartilage defects not only to temporarily relieve the pain but also to support chondrocyte proliferation and neocartilage regeneration. The biocompatibility, biofunctionality, mechanical properties, and degradation of the polymer hydrogels are the most important parameters for hydrogel‐based cartilage tissue engineering. Degradable biopolymers with natural origin have been widely used as biomaterials for tissue engineering because of their outstanding biocompatibility, low immunological response, low cytotoxicity, and excellent capability to promote cell adhesion, proliferation, and regeneration of new tissues. This review covers several important natural proteins (collagen, gelatin, fibroin, and fibrin) and polysaccharides (chitosan, hyaluronan, alginate and agarose) widely used as hydrogels for articular cartilage tissue engineering. The mechanical properties, structures, modification, and structure–performance relationship of these hydrogels are discussed since the chemical structures and physical properties dictate the in vivo performance and applications of polymer hydrogels for articular cartilage regeneration and repair. © 2012 Society of Chemical Industry     

Imparting antifouling properties of silicone hydrogels by grafting poly(ethylene glycol) methyl ether acrylate initiated by UV light

Both hydrophilic and antifouling surfaces were prepared on silicone hydrogels with poly(ethylene glycol) methyl ether acrylate (PEGMA) grafted by UV-induced radical polymerization. The PEGMA-grafted silicone hydrogels were characterized by graft yield and static water contact angle measurements. According to the results, the graft yield reached a maximum at 8 min of UV exposure time and 20 wt% PEGMA concentration. The modified silicone hydrogels possessed hydrophilic surfaces with the lowest water contact angle of 36°. The oxygen permeability and transparency of the PEGMA-grafted silicone hydrogels were as high as the unmodified silicone hydrogel. The mechanical property of silicone hydrogels was maintained at about 95% of the tensile strength and elastic modulus after the PEGMA grafting. The in vitro single protein adsorption on the PEGMA-grafted silicone hydrogels decreased by 70–80% compared to the unmodified silicone hydrogel. The PEGMA-grafted silicone hydrogel is expected to be a novel biomaterial, which possesses excellent surface hydrophilicity, antifouling property, oxygen permeability, and mechanical property. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Boron Nitride Nanosheets Strengthened PVA/Borax Hydrogels with Highly Efficient Self-Healing and Rapid pH-Driven Shape Memory Effect

Self-healing hydrogels often possess poor mechanical properties which largely limits their applications in many fields. In this work, boron nitride nanosheets are introduced into a network of the poly(vinyl alcohol)/borax (PVA/borax) hydrogels to enhance the mechanical properties of the hydrogel without compromising the self-healing abilities. The obtained hydrogels exhibit excellent mechanical properties with a tensile strength of 0.410 ± 0.007 MPa, an elongation at break of 1712%, a Young's Modulus of 0.860 ± 0.023 MPa, and a toughness of 3.860 ± 0.075 MJ m⁻³. In addition, the self-healing efficiency of the hydrogels is higher than 90% within 10 min at room temperature. Benefiting from the excellent self-healing properties, the shapeability of the hydrogel fragments is observed using different molds. In addition, the hydrogels display rapid pH-driven shape memory effects and can recover to their original shape within 260 s. Overall, this work provides a new approach to hydrogels with integrated excellent mechanical properties, self-healing abilities, and rapid pH-driven shape memory effects.     

Investigation on the interpenetrating polymer networks (ipns) of polyvinyl alcohol and poly(N-vinyl pyrrolidone) hydrogel and its in vitro bioassessment

Poly(vinyl alcohol) (PVA) and poly(N-vinyl pyrrolidone) (PVP) composite hydrogel with interpenetrating polymer networks (IPNs) was prepared by in situ polymerization and compared with pure PVA hydrogel. The prepared IPN hydrogel was characterized by infrared spectroscopy (IR), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy. The mechanical property and cell culture were also tested. The results show that PVP can chemically bond with PVA and form uniform blend hydrogel. The content of PVP can affect the structure, crystallinity, glass transition temperature (T_g), and mechanical property of the hydrogel. The T_g of the PVA hydrogel is 2.7°C while the T_g of the IPN hydrogel is −37°C. The IPN hydrogel has lower glass transition temperature, corresponding to better elastic properties, and has better mechanical performance on stretch and compression than PVA hydrogel. The crystallinity (X_c) of PVA hydrogel and IPN hydrogel is 65.3 and 26.3%, respectively. The DMA curves and XPS analysis suggest that PVA and PVP are well miscible on a molecular level in the IPN hydrogel. The cell proliferation trend demonstrates that the addition of PVP has a positive influence on the cell growth and the IPN hydrogel may be used as a promising biomaterial for artificial cartilage substitute. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of stereoregularity and molecular weight on the mechanical properties of poly(vinyl alcohol) hydrogel

The effect of the stereoregularity and molecular weight of poly(vinyl alcohol) (PVA) on the mechanical properties of hydrogel was investigated. Compressive strength, creep behavior, and dynamic viscoelasticity were measured on hydrogels of syndiotacticity‐rich PVA derived from poly(vinyl pivalate) (D_p = 1690 diad‐syndiotacticity = 61%, D_p = 8020 diad‐syndiotacticity = 62%) and atactic PVA (D_p = 1750 diad‐syndiotacticity = 54%, D_p = 7780 diad‐syndiotacticity = 54%). Increasing the molecular weight of molecular chains constituting the gel improved the compressive strength of atactic PVA hydrogel. The stereoregularity of PVA had a greater effect than molecular weight on the strength of the hydrogel. Gel prepared from 8.8 g/dL syndiotacticity‐rich PVA had a high compressive modulus of 10 kPa, and the compressive modulus of the gel prepared from 3.3 g/dL was comparable with that of atactic PVA hydrogel prepared with more than 6 g/dL. The dynamic storage modulus of the gel derived from syndiotacticity‐rich PVA was remarkably higher than that of the atactic PVA gel and remained constant up to 60°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The synthesis,mechanisms, and additives for bio-compatible polyvinyl alcohol hydrogels: A review on current advances,trends, and future outlook

Vinyl polymers are widely used in biological, textile and industrial applications and are currently attracting research attention for specialized bio-based applications. Polyvinyl alcohol (PVA) hydrogels show great advantages as a material with high biocompatibility, permeability, hydrophilicity, and low-friction coefficient, allowing applications as smart materials, wound dressings, and flexible sensors. However, the poor mechanical properties of PVA hydrogels and biocompatibility less than natural polymers make them unsuitable in practical applications. Additives are often added to PVA hydrogels to enhance mechanical properties, endow more compatibility, functionality and expand their application range. Among them, bio-additives such as nanocellulose, natural polysaccharides and proteins are biodegradable, biocompatible, and inexpensive, broadening their applications in the biomedical and tissue engineering fields. This work reviews the synthesis of PVA hydrogels, methods to enhance their mechanical properties, types of bio-additives incorporated for biocompatibility, their mechanism of interaction with PVA and future prospects of PVA composite bio-hydrogels for application in various fields. Representative cases are carefully selected and discussed with regard to their composition and pros and cons are discussed. Finally, future requirements, as well as the opportunities and challenges of these bio-additives for improving the multifunctionality of PVA hydrogels are also presented.     

蒽改性聚乙烯醇水凝胶的制备与表征

首先以蒽甲醛和聚乙烯醇(PVA)为原料、二甲基亚砜(DMSO)为溶剂、对甲苯磺酸(TsOH)为催化剂,反应得到蒽接枝改性聚乙烯醇(AnPVA)。然后利用混合溶剂凝胶法制备AnPVA水凝胶。通过差示扫描量热法(DSC)、拉伸等测试,研究水凝胶的力学等性能。结果表明,相比于纯PVA水凝胶,AnPVA水凝胶的力学性能得到了显著提高,在水凝胶中引入疏水基团是一种十分有效提高水凝胶力学性能的手段。AnPVA水凝胶浸泡于水中加热后无明显溶胀,有着优异的耐热和耐水性能,并且该水凝胶是物理交联网络,有着良好的循环重塑性能。     

A biomimetic bilayer coating on laser-textured Ti6Al4V alloy with excellent surface wettability and biotribological properties for artificial joints

Titanium alloys with excellent mechanical properties and biocompatibility are widely used in surgical implants. However, due to its poor tribological properties, it is difficult to be used in joint bearing interfaces. Herein, mimicking the soft/hard hierarchical structure of articular cartilage/subchondral bone and the unique lubrication mechanisms of articular cartilage, a biomimetic bilayer coating consisting of a TiO₂ layer and a hydrogel layer was fabricated on laser-textured Ti6Al4V alloy by laser surface texturing, thermal oxidation and ultraviolet radiation techniques. Meanwhile, a zwitterionic polymer (SBMA) was introduced into the hydrogel layer to provide hydration lubrication. The experimental results demonstrated that the introduction of SBMA greatly improved the hydrophilicity and compressive modulus of the hydrogel layer. Compared with Ti6Al4V, the Ti6Al4V-hydrogel bearing interface exhibited a lower friction coefficient (0.06) and better wear resistance when lubricated in deionized water. More importantly, this Ti6Al4V-hydrogel bearing interface could maintain stable and low friction coefficients when lubricated in different physiological solutions for a long-term friction (4 h), and the lowest friction coefficient (0.039) was measured in phosphate buffer (PBS) solution. The outstanding biotribological performance was mainly attributed to the biphasic and hydration lubrication mechanisms of the hydrogel layer. This study provides new insights into the development of Ti6Al4V bearing interfaces for artificial joints.     

Bioprinting Via a Dual-Gel Bioink Based on Poly(Vinyl Alcohol) and Solubilized Extracellular Matrix towards Cartilage Engineering

Various hydrogel systems have been developed as biomaterial inks for bioprinting, including natural and synthetic polymers. However, the available biomaterial inks, which allow printability, cell viability, and user-defined customization, remains limited. Incorporation of biological extracellular matrix materials into tunable synthetic polymers can merge the benefits of both systems towards versatile materials for biofabrication. The aim of this study was to develop novel, cell compatible dual-component biomaterial inks and bioinks based on poly(vinyl alcohol) (PVA) and solubilized decellularized cartilage matrix (SDCM) hydrogels that can be utilized for cartilage bioprinting. In a first approach, PVA was modified with amine groups (PVA-A), and mixed with SDCM. The printability of the PVA-A/SDCM formulations cross-linked by genipin was evaluated. On the second approach, the PVA was functionalized with cis-5-norbornene-endo-2,3-dicarboxylic anhydride (PVA-Nb) to allow an ultrafast light-curing thiol-ene cross-linking. Comprehensive experiments were conducted to evaluate the influence of the SDCM ratio in mechanical properties, water uptake, swelling, cell viability, and printability of the PVA-based formulations. The studies performed with the PVA-A/SDCM formulations cross-linked by genipin showed printability, but poor shape retention due to slow cross-linking kinetics. On the other hand, the PVA-Nb/SDCM showed good printability. The results showed that incorporation of SDCM into PVA-Nb reduces the compression modulus, enhance cell viability, and bioprintability and modulate the swelling ratio of the resulted hydrogels. Results indicated that PVA-Nb hydrogels containing SDCM could be considered as versatile bioinks for cartilage bioprinting.     

Controlled mechanical and swelling properties of poly(vinyl alcohol)/sodium alginate blend hydrogels prepared by freeze–thaw followed by Ca2+ crosslinking

Poly(vinyl alcohol) (PVA)/sodium alginate (SA) blend hydrogels have immense potential for use as functional biomaterials. Understanding of influences of processing parameters and compositions on mechanical and swelling properties of PVA/SA blend hydrogels is very important. In this work, PVA/SA blend hydrogels with different SA contents were prepared by applying freeze–thaw method first to induce physical crosslinking of PVA chains and then followed by Ca²⁺ crosslinking SA chains to form interpenetrating networks of PVA and SA. The effects of number of freeze–thaw cycles, SA content and Ca²⁺ concentration on mechanical properties, swelling kinetics, and pH‐sensitivity of the blend hydrogels were investigated. The results showed that the blend hydrogels have porous sponge structure. Gel fraction, which is related to crosslink density of the blend hydrogels, increased with the increase of freeze–thaw cycles and strongly depended on SA content. The SA content exerts a significant effect on mechanical properties, swelling kinetics, and pH‐sensitivity of the blend hydrogels. The number of freeze–thaw cycles has marked impact on mechanical properties, but no obvious effect on the pH‐sensitivity of the PVA/SA blend hydrogels. Concentration of CaCl₂ aqueous solution also influences mechanical properties and pH‐sensitivity of the blend hydrogel. By altering composition and processing parameters such as freeze–thaw cycles and concentration of CaCl₂ aqueous solution, the mechanical properties and pH‐sensitivity of PVA/SA blend hydrogels can be tightly controlled. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012