Cross-linked Systems Research Articles

FABRICATION AND CHARACTERIZATION OF Β-CYCLODEXTRIN-BASED NANO SPONGES FOR DELIVERY OF ABIRATERONE ACETATE

Abiraterone acetate is a steroidal progesterone derivative that inhibits the enzymes CYP17A1, CYP11B1, and the androgen receptor antagonist. It is clinically used in adrenal, testicular, and prostatic cancer. Abiraterone has limited use, due to poor water solubility and low oral bioavailability (<10%). The current study focused on the enhancement of water solubility of abiraterone using β-cyclodextrin nano sponges, which are a hyper cross-linked novel nano-drug delivery system. Design and optimization of β-cyclodextrin nano sponges were carried out, using the modified solvent method. Polymer to cross-linker ratio, solvent volume, and reaction time were defined as critical parameters for optimization. Fourier-transform Infrared spectroscopy, differential scanning calorimetry, scanning electron microscopy, Zeta sizer, and powdered X-ray diffraction technique were used for characterization. Drug entrapment and In-vitro dissolution studies were performed and samples were analyzed using reverse phase high performance liquid chromatography. Optimized β-cyclodextrin nano sponges were porous para-crystalline particles (25.3%) with an average particle size of 463.4 nm. High drug entrapment leads to enhancement of solubility by 17.33 folds and a 3-fold increase in drug dissolution profile. The present approach offers the best way to increase the solubility of abiraterone by formulating a nano-size hyper cross-linked βcyclodextrin nano sponges which can tend to the improvement of abiraterone oral bioavailability.

Environmentally Sound Approach for Fabrication of Antibacterial/Anti-UV/Anti-crease and Fragrant Denim Fabrics

A green approach for imparting multifunctional properties namely antibacterial, anti-UV, anti-crease and fragrance property to indigo dyed cotton denim fabrics using environmentally benign finishing, hosting and bioactive agents was investigated. In the current work, pre-loading of MCT-βCD, as a hosting agent, via ester-crosslinking using CA/SHP, as formaldehyde-free crosslinking system using pad-dry-cure method, followed by post-treatment with selected bio active agents namely Clove oil, Lavender oil, Tulsi oil and Vanillin R were carried out to add new, durable and desirable functional properties. The obtained results demonstrated that the variation in the efficacy and durability of the imparted functional properties is governed by extent of loading the modified βCD, number and availability of hydrophobic hosting-cavities, type and chemical constituents of the guest molecule and its extent of inclusion into the created cavities via formation of host-guest complex, as well as its retention or release during the washing process. The remarkable improvement in antibacterial activity against the pathogenic bacteria followed the decreasing order: Tulsi≥ Clove> Vanillin> Lavender>> None. The obtained results also demonstrated that, the imparted anti-UV capability of post-loaded denim samples follows the descending order: Vanillin>Tulsi>Clove>Lavender>>None. The imparted functional properties showed a high durability even after 15 washes.

Hydroxypropylmethyl cellulose (HPMC) crosslinked keratin/hydroxyapatite (HA) scaffold fabrication, characterization and in vitro biocompatibility assessment as a bone graft for alveolar bone regeneration

Wool derived keratin has garnered significant advancements in the field of biomaterials for hard tissue regeneration. The main limitation of keratin-based biomaterials for bone tissue engineering is their fragile nature. This paper proposes the development of a novel hydroxypropyl methylcellulose (HPMC) crosslinked keratin scaffold, containing hydroxyapatite as a major inorganic component by freeze drying technique for alveolar bone regeneration. The prepared keratin/hydroxyapatite/HPMC (K/HA/HPMC) scaffold was characterized to study its chemical, physical, and mechanical properties by Scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), Energy dispersive X-ray spectroscopy (EDX), X-Ray diffractometric (XRD) analysis. The SEM images of the scaffolds showed highly porous interconnected architecture with average pore size of 108.36 ± 22.56 while microcomputed tomographic analysis measured total porosity as 79.65 %±. Energy dispersive X-ray spectroscopic (EDX) analysis confirmed that inorganic component of scaffold was mainly composed of calcium and phosphorous ions having Ca/P molar ration of 1.6. The maximum compressive strength was found to be in the range of 0.841 ± 0.37 MPa. Furthermore, the K/HA/HPMC scaffold was structurally stable and weight loss of about 26% was observed when soaked in phosphate buffered solution (PBS) for 28 days. In vitro biocompatibility testing showed that K/HA/HPMC scaffold was cytocompatible and supported the attachment, proliferation of osteoblast (Saos-2) cells. Thus, the development of a non-toxic chemical cross-linking system with HPMC was investigated to fabricate K/HA/HPMC scaffold and our results showed great potential of these scaffolds to regenerate alveolar bone due to their structural similarity and excellent in vitro biocompatibility.

Systematic Literature Review of the Effect of Layered Double Hydroxides on the Mechanical Properties of Rubber.

Layered double hydroxides (LDHs) have attracted interest as reinforcing fillers in elastomers due to their ease of synthesis and customisability. A systematic review was performed on the effect of LDHs on the mechanical properties of elastomers using the Scopus database. Of the 61 articles relevant to the search criteria, the majority were published on polyurethane (PU) and nitrile butadiene rubber (NBR). Mg-Al LDH was used in most of the studies and Zn-Al LDH was used second most common. LDH can act as a reinforcing filler, typically increasing tensile strength even at low concentrations, so it could be used as an alternative to traditional reinforcing fillers for elastomers. LDH can also be made a functional filler by selecting the right metals and interlayer anions. It was found that Mg-Al LDH and Zn-Al LDH can both participate in crosslinking reactions and can replace MgO and ZnO, respectively. Less Zn ions are required for crosslinking when LDH is used than when ZnO is used, making LDH more environmentally friendly. Organic modification is usually required to improve compatibility with the elastomer matrix, especially in non-polar elastomers. It enables exfoliation of the LDH and intercalation of polymer chains into the LDH interlayer to occur. Organic modifiers can also be used to functionalise the LDH. Stearic acid used in crosslinking systems can be replaced by stearate anions from stearate-modified LDH.

Three-dimensional bioprinting of polysaccharide-based self-healing hydrogels with dual cross-linking.

Three-dimensional (3D) bioprinting technique is useful to fabricate constructs with functional and biological structures for various biomedical applications. Oxidized hyaluronate (OHA) and glycol chitosan (GC) can form autonomous self-healing hydrogels when adipic acid dihydrazide (ADH) is used. We demonstrate that hyaluronate-alginate hybrid (HAH) polymers can be used for secondary physical cross-linking of OHA/GC/ADH hydrogel with calcium ions after 3D printing. The molecular weight of hyaluronate can be varied while keeping the molecular weight of alginate in HAH. The mechanical stiffness and stability of gels after 3D printing are strongly dependent on the molecular weight of HAH at the same cross-linking density. In vitro chondrogenic differentiation of ATDC5 cells encapsulated in 3D-printed constructs is dependent on the molecular weight of HAH in gels. This dual cross-linking system consisting of naturally occurring biocompatible polysaccharides may have potential in the 3D bioprinting of custom-made scaffolds for tissue engineering applications.

Thermally tunable hydrogel crosslinking mediated by temperature sensitive liposome

Hydrogel crosslinking by external stimuli is a versatile strategy to control and modulate hydrogel properties. Besides photonic energy, thermal energy is one of the most accessible external stimuli and widely applicable for many biomedical applications. However, conventional thermal crosslinking systems require a relatively high temperature (over 100 °C) to initiate covalent bond formation. To our knowledge, there has not been a thermally tunable hydrogel crosslinking system suitable for biological applications. This work demonstrates a unique approach to utilize temperature sensitive liposomes to control and modulate hydrogel crosslinking over mild temperature range (below 50 °C). Temperature sensitive liposomes were used to control the release of chemical crosslinkers by moderate temperature changes. The thermally controlled crosslinker release resulted in tunable mechanical and transport properties of the hydrogel. No significant inflammable response observed in the histology results ensured the biocompatibility of the liposome-mediated crosslinkable hydrogel. This work opens new opportunities to implement thermal energy system for control and modulate hydrogel properties.

Development of sustainable, cost effective foam finishing approach for cellulosic textile employing succinic acid/xylitol crosslinking system

Clothing is an essential human need that must fulfil the purpose of protecting against weather in addition to satisfying the functional and aesthetic need without sacrificing serviceability and comfort. The escalating awareness about personal hygiene and environmental concerns, especially in the current frenzied world with a pandemic, has generated a huge demand for functional, ironing-free clothing with impeccable hygiene while maintaining the true spirit of sustainability in all three aspects i.e. performance, chemical, and process domains. Conventional textile processing is highly unsustainable in terms of the excessive use of water, energy, and toxic chemicals. In this study, we introduced a sustainable foam processing method for the development of easy-care textile with improved physical, aesthetic, and comfort performance while maintaining zero toxicity in the finishing formulation. Foam of the succinic acid crosslinker was systematically optimized using natural thickeners as the stabilizing agents. Xylitol was introduced in the recipe as an extender to promote crosslinking. The finished sample of the optimized foam formulation showed remarked improvement of 32% in strength and 13% in stiffness with comparable easy-care performance as that of the conventional padded sample. The unparallel dominancy and sustainability of the foaming process were established through a detailed cost and effectiveness index which heralded the rapid adaptation and industrialization.

Screen Printing Tissue Models Using Chemically Cross-Linked Hydrogel Systems: A Simple Approach To Efficiently Make Highly Tunable Matrices.

In vitro models provide a good starting point for drug screening and understanding various cellular mechanisms corresponding to different conditions. 3D cultures have drawn significant interest to mimic the in vivo microenvironment better and overcome the limitations of the 2D monolayered cultures. We previously reported a technique based on the screen printing process to pattern live mammalian cells using gelatin as the bioink. Even though gelatin is an inexpensive scaffolding material with various tissue engineering applications, it might not be the ideal hydrogel material to provide various mechanical and chemical cues to the cells. In this paper, we discuss the synthesis and characterization of two synthetic chemically cross-linked hydrogel systems based on poly(ethylene glycol) (PEG) and poly-l-lysine (PLL) to be used as the bioink in the screen printing process. These hydrogels are suitable as the bioinks for the screen printing process and serve as the barebone materials that can be tuned mechanically and augmented chemically to create a suitable in vitro microenvironment for the cells. This paper presents the synthesis, mechanical testing, and characterization of the hydrogel systems and their applications in the screen printing process.

Biobased Stimuli-Responsive Hydrogels That Comprise Supramolecular Interpenetrating Networks and Exhibit Programmed Behaviors

In this paper, a hierarchical design of supramolecular hydrogels comprising two individual supramolecular networks that are capable of exhibiting reversible and programmed behaviors is described. Both component networks are established by (i) conformational transformation of natural polysaccharides and (ii) host–guest interaction between separate polymer chains. Sequential formation of each orthogonal network generates an interpenetrated structure, which results in the formation of biobased, completely noncovalent, double-network hydrogels. Owing to the intrinsic advantages of the cross-linking system, the hydrogel materials demonstrated the reversibility of physical properties in response to heat or light and exhibited macroscopic performance such as self-healing or injectable properties without calamitous structural collapse. In particular, it was possible to demonstrate the superstructured hydrogels as a responsive vector. Selected dye or drug molecules were loaded during the formation of the networks, and sustained release behavior was achieved around body temperature, which could be fairly enhanced upon UV-light irradiation. Also, we were able to develop a three-dimensional, bioprinted, large-scale pattern using the hydrogels as a bioink. We envisage that the designed hydrogels can be further advanced by employing other cargo molecules or supramolecular chemistries, which would create emerging, autonomous materials suitable for bioengineered scaffolds or coating layers that are implantable and highly sensitive to physiological signals.

The Use of the ATD Technique to Measure the Gelation Time of Epoxy Resins.

In this paper, we investigated the thermodynamics of the resin curing process, when it was a part of composition with graphite powder and cut carbon fibers, to precisely determine the time and temperature of gelation. The material for the research is a set of commercial epoxy resins with a gelation time not exceeding 100 min. The curing process was characterized for the neat resins and for resins with 10% by weight of flake graphite and cut carbon fibers. The results recorded in the analysis of temperature derivative (ATD) method unequivocally showed that the largest first derivative registered during the test is the gel point of the resin. The innovative approach to measuring the gelation time of resins facilitates the measurements while ensuring the stability of the curing process compared to the normative tests that introduce mechanical interaction. In addition, it was found during the research that the introduction of 10% by weight of carbon particles in the form of graphite and cut carbon fibers rather shortens the gelation time and lowers the temperature peak due to the effective absorption and storage of heat from the cross-linking system. The inhibiting (or accelerating) action of fillers is probably dependent on chemical activity of the cross-linking system.

Porous Materials Based on Poly(methylvinylsiloxane) Cross-Linked with 1,3,5,7-Tetramethylcyclotetrasiloxane in High Internal Phase Emulsion as Precursors to Si-C-O and Si-C-O/Pd Ceramics

Polysiloxane networks were prepared by hydrosilylation of poly(methylvinylsiloxane) (V3 polymer) with 1,3,5,7-tetramethylcyclotetrasiloxane (D4H) at various Si-Vinyl: Si-H groups molar ratios in water-in-oil high internal phase emulsion (HIPE). Curing the emulsions followed by removal of water led to foamed cross-linked polysiloxane systems differing in the cross-linking degrees, as well as residual Si-H and Si-Vinyl group concentrations. Treatment of thus obtained materials in Pd(OAc)2 solution in tetrahydrofuran resulted in the formation of porous palladium/polymer nanocomposites with different Pd contents (1.09–1.70 wt %). Conducted investigations showed that pyrolysis of the studied materials at 1000 °C in argon atmosphere leads to porous Si-C-O and Si-C-O/Pd ceramics containing amorphous carbon and graphitic phases. Thermogravimetric (TG) analysis of the starting cross-linked polymer materials and those containing Pd nanoparticles revealed that the presence of palladium deteriorates thermal stability and decreases ceramic yields of preceramic networks. The extent of this effect depends on polymer cross-linking density in the system.

Novel Crosslinking System for Poly-Chloroprene Rubber to Enable Recyclability and Introduce Self-Healing.

The introduction of dynamic bonds capable of mediating self-healing in a fully cross-linked polychloroprene network can only occur if the reversible moieties are carried by the cross-linker itself or within the main polymer backbone. Conventional cross-linking is not suitable for such a purpose. In the present work, a method to develop a self-healable and recyclable polychloroprene rubber is presented. Dynamic disulfide bonds are introduced as part of the structure of a crosslinker (liquid polysulfide polymer, Thiokol LP3) coupled to the polymer backbone via thermally initiated thiol-ene reaction. The curing and kinetic parameters were determined by isothermal differential scanning calorimetry and by moving die rheometer analysis; tensile testing was carried to compare the tensile strength of cured compound, healed compounds and recycled compounds, while chemical analysis was conducted by surface X-ray Photoelectron Spectroscopy. Three formulations with increasing concentrations of Thiokol LP-3 were studied (2, 4, 6 phr), reaching a maximum ultimate tensile strength of 22.4 MPa and ultimate tensile strain of 16.2 with 2 phr of Thiokol LP-3, 11.7 MPa and 10.7 strain with 4 phr and 5.6 MPa and 7.3 strain with 6 phr. The best healing efficiencies were obtained after 24 h of healing at 80 °C, increasing with the concentration of Thiokol LP-3, reaching maximum values of 4.5% 4.4% 13.4% with 2 phr, 4 phr and 6 phr, respectively, while the highest recycling efficiency was obtained with 4 phr of Thiokol LP-3, reaching 11.2%.

Fabrication of a state of the art mesh lock polymer for water based solid free drilling fluid

Polymers are used widely in various kinds of drilling fluid to maintain the proper rheological properties. However, most of them are not available for high-temperature or salt solutions due to poor temperature and salt resistance. To ameliorate the temperature and salt resistance of polymer used in the solid-free water-based drilling fluid, a novel polymer with a kind of "Mesh-Lock" reinforced network cross structure, named PLY-F [main monomer acrylic acid (AA), acrylamide (AM), functional monomers 2-acrylamide-2-methylpropanesulfonic acid (AMPS) N-vinylpyrrolidone (NVP) and C16DMAAC] were prepared through free radical polymerization of an aqueous solution of organic cross-linking agent pentaerythritol triallyl ether (PTE) as a cross-linking system, Potassium persulfate (KPS) and sodium bisulfite as the initiator for the first time. The surface morphology, crosslinking architecture and temperature and salt resistance of the PLY-F were fully characterized with several means including SEM, FT-IR, 13CNMR, dynamic rheology, and long-term thermal stability. The SEM observation indicated that the PLY-F exhibits a regular “Mesh-Lock” reinforced network cross structure. FT-IR, 13CNMR analysis indicated that the characteristic functional groups of each monomer such as AM, AA, AMPS and NVP were all together in the polymer. The results show that the apparent viscosity retention rate of the PLY-F in the potassium formate solution (with a density of 1.3 g/cm3) was more than 80% after heat rolling for 72 h at 200 °C and the plastic viscosity retention rate reached 90.3%. Moreover, the salt resistance of the polymer can reach the density of 1.4 g/cm3 (potassium formate solution) under 200 °C and the temperature resistance can reach 220 °C under the density of 1.3 g/cm3 (potassium formate solution). Besides, the PLY-F still has good rheological properties in other saturated solutions (NaCl, HCOONa) under 210 °C.

A new method for plugging the dominant seepage channel after polymer flooding and its mechanism: Fracturing–seepage–plugging

AbstractAfter polymer flooding, a low-resistant dominant seepage channel forms at the bottom of the high-permeability reservoir, which is extremely disadvantageous for further enhanced oil recovery. In this study, we proposed a new method to plug the dominant seepage channel after polymer flooding, through fracturing–seepage–plugging using a solid-free plugging agent, which can achieve deeper and further regional plugging. This method involved dissolving the crosslinking agent and stabilizer in the water-based fracturing fluid (hereinafter referred to as the fracturing plugging agent) and transporting it to the target reservoir through hydraulic fractures. The fracturing plugging agent percolated into the deep part of the reservoir under the action of fracture closure pressure and gelled with the residual polymer in the formation to achieve deep regional plugging of the advantageous channel. To study the percolation law of fracturing plugging agent in the dominant channel, high-pressure displacement experiments were conducted using natural cores under different permeability and concentration conditions of the fracturing plugging agent. The results showed that the percolation rate of the fracturing plugging agent was almost linearly related to reservoir permeability. Due to the formation of micro-fractures and crosslinking reactions, the percolation rate first increased and then decreased to a stable state. After a certain period, the pores were blocked, resulting in a sharp decrease in the percolation rate and then decayed. In addition, the higher the concentration of fracturing plugging agent, the better the core plugging performance. Moreover, when the concentration of fracturing plugging agent injected into the core exceeded 3,000 mg/L, the core permeability increased, and the breakthrough pressure evidently increased three to four times. On the basis of this, rheometer tests, scanning electron microscopy (SEM) observations, and mercury intrusion tests were performed to evaluate gelation performance, shear effect, and pore retention morphology of the crosslinking system made by mixing the injected plugging agent and residual polymer in the reservoir. The results showed that the shear action could reduce the gelling property, and the concentration of fracturing plugging agent should be >3,000 mg/L to meet the requirements of gelling. Furthermore, the viscosity of the crosslinking system reached the peak value at approximately 72 h, forming a network space structure of layered superposition, thereby increasing viscosity by 40–50 times. Finally, SEM images revealed that after the fracture plugging agent was injected into the core, the micelles were mostly concentrated in the front and middle sections. The average pore radius of the core decreased by 8.620 μm, and the average porosity decreased by 54.85%.

3D Printing of Polysaccharide-Based Self-Healing Hydrogel Reinforced with Alginate for Secondary Cross-Linking.

Three-dimensional (3D) bioprinting has been attractive for tissue and organ regeneration with the possibility of constructing biologically functional structures useful in many biomedical applications. Autonomous healing of hydrogels composed of oxidized hyaluronate (OHA), glycol chitosan (GC), and adipic acid dihydrazide (ADH) was achieved after damage. Interestingly, the addition of alginate (ALG) to the OHA/GC/ADH self-healing hydrogels was useful for the dual cross-linking system, which enhanced the structural stability of the gels without the loss of their self-healing capability. Various characteristics of OHA/GC/ADH/ALG hydrogels, including viscoelastic properties, cytotoxicity, and 3D printability, were investigated. Additionally, potential applications of 3D bioprinting of OHA/GC/ADH/ALG hydrogels for cartilage regeneration were investigated in vitro. This hydrogel system may have potential for bioprinting of a custom-made scaffold in various tissue engineering applications.

A multi-physics approach on modeling of hygrothermal aging and its effects on constitutive behavior of cross-linked polymers

A multi-physics model is proposed to predict the changes in the constitutive behavior of cross-linked polymeric systems due to damages induced by deformation, oxidation, moisture, and temperature. Coupling the concept of network evolution, hydrolysis, and thermo-oxidation aging, we hypothesize that the synergized effects of deformation-induced damage, as well as different environmental factors such as humidity, temperature, and oxygen, can be taken into account through a generic model. Deformation-induced damage is due to the chain breakage while hygrothermal aging results from the interaction of elastomeric components with moisture in the presence of oxygen and temperature. Results indicate that hygrothermal aging can be considered as a consequence of damage accumulation of two concurrent aging mechanisms, namely; (i) thermo-oxidative, and (ii) hydrolytic aging. In order to capture the mutual effects of thermo-oxidative and hydrolytic aging, the assumption has been made that each of the aging phenomena can be superimposed upon each other. In fact, each of them acts independently, and as a result, they can propagate hygrothermal aging in collaboration. In view of multiple kinetics involved in hygrothermal aging, its effect has been induced by the concurrent effects of three micro-mechanisms; (i) chain scission due to the presence of temperature, (ii) reduction of cross-links attributed to the attendance of water, and (iii) formation of cross-links as a repercussion of oxygen present in the environment. Utilizing the theory of network decomposition, all phenomena and their correlation were modeled, and thus, the strain energy function of the polymer matrix is written with respect to four independent mechanisms; (i) the shrinking original matrix that has neither been attacked by water nor oxygen, (ii) conversion of the first network to two new networks due to reduction and formation of cross-links, and (iii) energy loss from network degradation due to water attrition to polymer active agents. The proposed model cannot consider variation in oxygen density since it has been derived for cases where there is abundant oxygen. In this respect, the model is valid for a slow aging process that occurs in super-thin samples. Finally, the model is validated with respect to extensive sets of our experimental data. In view of its interoperability, precision, and deep insight it provides into the nature of the aging phenomenon, the model is a good choice for advanced implementation in FE applications.

Water-Preserving and Salt-Resistant Slow-Release Fertilizers of Polyacrylic Acid-Potassium Humate Coated Ammonium Dihydrogen Phosphate.

Polyacrylic acid (PAA) has high water absorbency but poor salt resistance. Humic acid (HA) extracted from lignite was introduced into the cross-linked copolymer systems of AA to improve the water absorbency and salt-tolerance. A polyacrylic acid-potassium humate (PAA-KHA) coated ammonium dihydrogen phosphate (ADP) fertilizer with water-preserving, salt-resistant and slow-release properties was prepared. The main properties of HA extracted from lignite oxidized by H2O2 were studied. Furthermore, the synthesis process, water absorbency of PAA-KHA in deionized water and in NaCl solution, morphologies of PAA-KHA, and the slow-release performance of the fertilizer (ADP@PAA-KHA) were investigated. The results showed PAA-KHA had a layered interpenetrating network, which can provide sufficient storage space for water and nutrients. The salty water absorbency of PAA-KHA increased by about 3 times compared to PAA. Both the PO43− and NH4+ cumulative release of ADP@PAA-KHA with a coating rate of 10% in deionized water, were less than 20% within 24 h, and were 55.71% and 28.04% after the 15th day, respectively. The weight change of ADP@PAA-KHA before and after absorbing water was about 53 times in deionized water and about 4 times in 1 wt% of NaCl salty water. The results show that ADP@PAA-KHA has excellent properties of water retention, salt resistance and slow-release. This will efficiently improve the utilization of fertilizer and reduce the irrigation water consumption at the same time.

Influence of different curing regimes on properties of new copolymer of chloroprene and acrylonitrile

The curing system plays a vital role in designing rubber compounds for various industrial applications. Therefore, it is paramount to establish viable curing strategies for any new elastomer to explore its application potentials and commercial significance. Impacts of different curing regimes on the properties of a recently developed copolymer of chloroprene and acrylonitrile (acrylonitrile-chloroprene rubber, NCR) are reported here. Several primary accelerators (four from thiourea- and one from thiazolene product families) were used for curing the new rubber along with fixed loadings of zinc oxide (5 phr) and magnesium oxide (4 phr). Besides, curatives based on sulfur and peroxide were also evaluated. The influence of different curing systems on the rheological and physical properties of the copolymer was explored. It has been seen that the properties of the copolymer are considerably influenced by the different curing systems used. While ethylene thiourea (ETU) and propylene thiourea (PTU), as primary accelerators, provide the highest state of cure but may cause scorch. The use of trimethyl thiourea (TMU), on the other hand, results in the fastest rate and the most stable state of cure, good scorch safety, bin stability, and an overall good balance of properties. The sulfur-based crosslinking system induces good mechanical properties but causes limited bin stability, poor high-temperature compression set, and impaired heat resistance properties. As a curing agent, peroxide delivers the best bin stability in the rubber stocks but yields higher stiffness and limited aging resistance in the vulcanizates.

Novel Bionic Soy Protein-Based Adhesive with Excellent Prepressing Adhesion, Flame Retardancy, and Mildew Resistance.

Soy protein (SP)-based adhesives can replace traditional aldehyde-based adhesives for the manufacturing of wood-based panels. However, developing a SP-based adhesive with excellent prepressing bonding strength, flame retardancy, and mildew resistance remains a challenge. Herein, an inorganic crystal cross-linked hybrid SP adhesive was developed inspired by the "secreting-hardening" process of the mussel adhesive protein and the organic-inorganic hybrid adhesive system of the oyster. Calcium sulfoaluminate (CSA) was introduced into the adhesive mixture of SP and acrylic acid to induce the in situ polymerization of acrylic acid to achieve adhesive gelation. The generation of the inorganic crystals by hydration of CSA not only contributed to the formation of a stable cross-linked hybrid adhesive system for strong cohesion but also provided strong interfacial adhesion between the adhesive layers and the plywood veneers. As anticipated, the prepared plywood sample bonded with the hybrid adhesive gel had an excellent prepressing bonding strength of 544 kPa, representing a significant increase compared to that of the pure SP adhesive (19 kPa). Moreover, the generated inorganic crystals endowed the adhesive with excellent mildew resistance and flame retardancy. This study provides a novel and effective strategy for the preparation of high-performance SP-based adhesives.

Self-Healable Biocomposites Crosslinked with a Combination of Silica and Quercetin

In this publication, novel bio-based composites made of epoxidized natural rubber with 50 mol% of epoxidation (ENR-50) are presented. The obtained materials, partially cured with a totally environmentally friendly crosslinking system consisting of natural ingredients, including quercetin and silica, exhibit a self-healing ability resulting from the self-adhesion of ENR-50 and reversible physical forces between the curing agent and the matrix. The impact of natural components on the crosslinking effect in uncured ENR-50 matrix was analyzed based on rheometric measurements, mechanical tests and crosslinking density. The partially crosslinked samples were next cut into two separate pieces, which were instantly contacted together under a small manual press, left at room temperature for a few days for the healing process to occur and finally retested. The healing efficiency was estimated by measuring mechanical properties before and after the healing process and was also confirmed by photos taken using optical and scanning electron microscope (SEM). According to the results, a combination of silica and quercetin is a totally safe, natural and effective crosslinking system dedicated to epoxidized natural rubber. The novel composites containing ingredients safe for human beings exhibit promising self-healing properties with a healing efficiency of up to 45% without any external stimuli and stand a chance of becoming innovative biomedical materials.