Tailoring of Mechanical Properties of Diisocyanate Crosslinked Gelatin-Based Hydrogels

2013 ◽  
Vol 1569 ◽  
pp. 3-8 ◽  
Author(s):  
Axel T. Neffe ◽  
Tim Gebauer ◽  
Andreas Lendlein

ABSTRACTPolymer network formation is an important tool for tailoring mechanical properties of polymeric materials. One option to synthesize a network is the addition of bivalent crosslinkers reacting with functional groups present in a polymer. In case of polymer network syntheses based on biopolymers, performing such a crosslinking reaction in water is sometimes necessary in view of the solubility of the biopolymer, such as gelatin, and can be beneficial to avoid potential contamination of the formed material with organic solvents in view of applications in biomedicine. In the case of applying diisocyanates for the crosslinking in water, it is necessary to show that the low molecular weight bifunctional crosslinker has fully reacted, while tailoring of the mechanical properties of the resulting hydrogels is possible despite the complex reaction mechanism. Here, the formation of gelatin-based hydrogel networks with the diisocyanates 2,4-toluene diisocyanate, 1,4-butane diisocyanate, and isophorone diisocyanate is presented. It is shown that extensive washing of materials is required to ensure full conversion of the diisocyanates. The use of different diisocyanates gives hydrogels covering a large range of Young’s moduli (12-450 kPa). The elongations at break (up to 83%) as well as the maximum tensile strengths (up to 410 kPa) of the hydrogels described here are much higher than for lysine diisocyanate ethyl ester crosslinked gelatin reported before. Rheological investigations suggest that the network formation in some cases is due to physical interactions and entanglements rather than covalent crosslink formation.

Author(s):  
Philipp Knospe ◽  
Patrick Böhm ◽  
Jochen Gutmann ◽  
Michael Dornbusch

AbstractNowadays, coating materials must meet high demands in terms of mechanical, chemical and optical properties in all areas of application. Amongst others, amines and isocyanates are used as crosslinking components for curing reactions, meeting the highly demanding properties of the coatings industry. In this work, a new crosslinking reaction for coatings based on oxazoline chemistry is investigated with the objective to overcome disadvantages of established systems and fulfill the need for sustainable coating compounds. The oxazoline-group containing resin, synthesized from commercially available substances, undergoes cationic self-crosslinking polymerization to build up a network based on urethane and amide moieties. NMR-, IR- and ES-mass spectroscopy are suitable techniques to characterize the synthesized oxazoline monomers, which are linked to polyisocyanates and polymerized afterwards via self-polymerization. The progress of crosslinking is followed by changes in IR spectra and by rheological measurements to calculate time dependent values for storage and loss modulus. The glass transition temperature of the resulting coating is determined, too. Furthermore, sol–gel-analysis is performed to determine the degree of crosslinking. After application on steel and aluminium panels, application tests are performed. In addition to excellent adhesion to the substrate, the polymer network shows promising mechanical properties and with that it could represent a new technology for the coatings industry.


2013 ◽  
Vol 1569 ◽  
pp. 15-20 ◽  
Author(s):  
Tim Gebauer ◽  
Axel T. Neffe ◽  
Andreas Lendlein

ABSTRACTGelatin can be covalently crosslinked in aqueous solution by application of diisocyanates like L-lysine diisocyanate ethyl ester in order to form hydrogels. Reaction of isocyanate groups with water is however a limiting factor in hydrogel network formation and can strongly influence the outcome of the crosslinking process. Here, diisocyanates with different water solubility and reactivity were applied for the formation of gelatin-based hydrogel networks and the mechanical properties of the hydrogels were investigated to gain a better understanding of starting material/ hydrogel property relations. L-Lysin diisocyanate ethyl ester (LDI), 2,4-toluene diisocyanate (TDI), 1,4-butane diisocyanate (BDI), and isophorone diisocyanate (IPDI) were selected, having different solubility in water ranging from 10-4 to 10-2 mol·L-1. BDI and LDI were estimated to have average reactive isocyanates groups, whereas TDI is highly reactive and IPDI has low reactivity. Formed hydrogels showed different morphologies and were partially very inhomogeneous. Gelation time (1 to 50 minutes), water uptake (300 to 900 wt.-%), and mechanical properties determined by tensile tests (E-moduli 35 to 370 kPa) and rheology (Shear moduli 4.5 to 19.5 kPa) showed that high water solubility as well as high reactivity leads to the formation of poorly crosslinked or inhomogeneous materials. Nevertheless, diisocyanates with lower solubility in water and low reactivity are able to form stable, homogeneous hydrogel networks with gelatin in water.


Polymers ◽  
2019 ◽  
Vol 11 (11) ◽  
pp. 1845 ◽  
Author(s):  
Lei ◽  
Zhou ◽  
Liu

Existing theories cannot predict the mechanical property changes of polyacrylamide hydrogels with different water content because of the absence of side chains. In this study, polyacrylamide hydrogels are prepared and tested to investigate the side chain effect on their mechanical properties. First, the comparison between the effective chain density and total chain density provides proof of the large amount of side chains in the polymer network of PAAm hydrogel. We propose a practical chain density fraction to measure the side chain fraction. Then, the abnormal Young’s moduli-polymer volume fraction relationship reveals that side chains affect the mechanical properties of hydrogel through the insufficient lubrication of water. Water confined in narrow space within a molecular-level size can bear shear force to provide extra deformation resistance. A constitutive mode considering the effect of the insufficient lubrication of water is proposed. Combining this constitutive model with experimental results, we find that this insufficient lubrication of water exists even in equilibrium PAAm hydrogel. Molecular dynamics simulations reveal that this insufficient lubrication of water comes from the constraint of polymer chains. It also demonstrates that when there is insufficient lubrication, the rearrangement of water molecules leads to the persistent energy dissipation in the Mullins effect of PAAm hydrogel.


2020 ◽  
Vol 67 (2) ◽  
pp. 115-120
Author(s):  
Raisa A. Alekhina ◽  
Victoriya E. Slavkina ◽  
Yuliya A. Lopatina

The article presents options for recycling polymers. The use of biodegradable materials is promising. This is a special class of polymers that can decompose under aerobic or anaerobic conditions under the action of microorganisms or enzymes forming natural products such as carbon dioxide, nitrogen, water, biomass, and inorganic salts. (Research purpose) The research purpose is in reviewing biodegradable materials that can be used for the manufacture of products used in agriculture. (Materials and methods) The study are based on open information sources containing information about biodegradable materials. Research methods are collecting, studying and comparative analysis of information. (Results and discussion) The article presents the advantages and disadvantages of biodegradable materials, mechanical properties of the main groups of biodegradable polymers. The article provides a summary list of agricultural products that can be made from biodegradable polymer materials. It was found that products from the general group are widely used in agriculture. Authors have found that products from a special group can only be made from biodegradable polymers with a controlled decomposition period in the soil, their use contributes to increasing the productivity of crops. (Conclusions) It was found that biodegradable polymer materials, along with environmental safety, have mechanical properties that allow them producing products that do not carry significant loads during operation. We have shown that the creation of responsible products (machine parts) from biodegradable polymers requires an increase in their strength properties, which is achievable by creating composites based on them. It was found that the technological complexity of their manufacture and high cost are the limiting factors for the widespread use of biodegradable polymers at this stage.


2012 ◽  
Vol 26 (3) ◽  
pp. 249-255
Author(s):  
Boniek Castillo Dutra Borges ◽  
Fabrício Lopes da Rocha Pereira ◽  
Roberta Caroline Bruschi Alonso ◽  
Rodivan Braz ◽  
Marcos Antônio Japiassú Resende Montes ◽  
...  

Biomolecules ◽  
2020 ◽  
Vol 10 (10) ◽  
pp. 1456
Author(s):  
Isabel Matos Oliveira ◽  
Cristiana Gonçalves ◽  
Myeong Eun Shin ◽  
Sumi Lee ◽  
Rui Luis Reis ◽  
...  

Rheumatoid arthritis is a rheumatic disease for which a healing treatment does not presently exist. Silk fibroin has been extensively studied for use in drug delivery systems due to its uniqueness, versatility and strong clinical track record in medicine. However, in general, natural polymeric materials are not mechanically stable enough, and have high rates of biodegradation. Thus, synthetic materials such as gellan gum can be used to produce composite structures with biological signals to promote tissue-specific interactions while providing the desired mechanical properties. In this work, we aimed to produce hydrogels of tyramine-modified gellan gum with silk fibroin (Ty–GG/SF) via horseradish peroxidase (HRP), with encapsulated betamethasone, to improve the biocompatibility and mechanical properties, and further increase therapeutic efficacy to treat rheumatoid arthritis (RA). The Ty–GG/SF hydrogels presented a β-sheet secondary structure, with gelation time around 2–5 min, good resistance to enzymatic degradation, a suitable injectability profile, viscoelastic capacity with a significant solid component and a betamethasone-controlled release profile over time. In vitro studies showed that Ty–GG/SF hydrogels did not produce a deleterious effect on cellular metabolic activity, morphology or proliferation. Furthermore, Ty–GG/SF hydrogels with encapsulated betamethasone revealed greater therapeutic efficacy than the drug applied alone. Therefore, this strategy can provide an improvement in therapeutic efficacy when compared to the traditional use of drugs for the treatment of rheumatoid arthritis.


Forests ◽  
2021 ◽  
Vol 12 (8) ◽  
pp. 968
Author(s):  
Dong Xing ◽  
Xinzhou Wang ◽  
Siqun Wang

In this paper, Berkovich depth-sensing indentation has been used to study the effects of the temperature-dependent quasi-static mechanical properties and creep deformation of heat-treated wood at temperatures from 20 °C to 180 °C. The characteristics of the load–depth curve, creep strain rate, creep compliance, and creep stress exponent of heat-treated wood are evaluated. The results showed that high temperature heat treatment improved the hardness of wood cell walls and reduced the creep rate of wood cell walls. This is mainly due to the improvement of the crystallinity of the cellulose, and the recondensation and crosslinking reaction of the lignocellulose structure. The Burgers model is well fitted to study the creep behavior of heat-treated wood cell walls under different temperatures.


Molecules ◽  
2021 ◽  
Vol 26 (4) ◽  
pp. 773
Author(s):  
Ahmad Safwan Ismail ◽  
Mohammad Jawaid ◽  
Norul Hisham Hamid ◽  
Ridwan Yahaya ◽  
Azman Hassan

Polymer blends is a well-established and suitable method to produced new polymeric materials as compared to synthesis of a new polymer. The combination of two different types of polymers will produce a new and unique material, which has the attribute of both polymers. The aim of this work is to analyze mechanical and morphological properties of bio-phenolic/epoxy polymer blends to find the best formulation for future study. Bio-phenolic/epoxy polymer blends were fabricated using the hand lay-up method at different loading of bio-phenolic (5 wt%, 10 wt%, 15 wt%, 20 wt%, and 25 wt%) in the epoxy matrix whereas neat bio-phenolic and epoxy samples were also fabricated for comparison. Results indicated that mechanical properties were improved for bio-phenolic/epoxy polymer blends compared to neat epoxy and phenolic. In addition, there is no sign of phase separation in polymer blends. The highest tensile, flexural, and impact strength was shown by P-20(biophenolic-20 wt% and Epoxy-80 wt%) whereas P-25 (biophenolic-25 wt% and Epoxy-75 wt%) has the highest tensile and flexural modulus. Based on the finding, it is concluded that P-20 shows better overall mechanical properties among the polymer blends. Based on this finding, the bio-phenolic/epoxy blend with 20 wt% will be used for further study on flax-reinforced bio-phenolic/epoxy polymer blends.


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