Understanding of hydrogel network formation and its application in the architecture of significantly enhanced hydrogel

An understanding of the physical hydrogel network formation has been obtained by dynamic rheological experiments. The evidence shows that the network formation turns out to be a nucleation-controlled process. It was found that there exists a critical temperature Tc; fiber branching is greatly enhanced when the network formation is performed in the regime of T<Tc (T, the final setting temperature). This finding enables the authors to build significantly enhanced gel networks. So far G′ (elastic modulus) of the hydrogel network has been enhanced by 187% while the formation period can be greatly shortened to only 1/20 of the previous process.

Real-time observation of fiber network formation in molecular organogel : supersaturation-dependent microstructure and its related rheological property

Low-molecular mass organic gelators self-organizing into three-dimensional fiber networks within organic solvents have attracted much attention in recent years. However, to date, how the microstructure of fiber network is formed in a gelation process and the key factors that govern the topological structure of a gel network remain to be determined. In this work, we address these issues by investigating the in situ formation of the gel networks in the N-lauroyl-l-glutamic acid di-n-butylamide (GP-1)/propylene glycol (PG) system. By using optical microscopy, the time evolution of the gel network microstructure was investigated under various supersaturation conditions. It is found that supersaturation is one of the key factors that govern the topological structure of a gel network. In particular, the creation of the junctions turns out to be supersaturation-dependent. The rheological experiments further revealed the correlation between topological structure and mechanical properties. It suggests that the rheological properties can be effectively modified by tuning the microstructure topology of the gel network. Our results reported here provide new physical insight into the formation kinetics of a molecular gel. Furthermore, this work could be important in constructing and engineering a supramolecular structure for the purpose of applications.

Microengineering of soft functional materials by controlling the fiber network formation

The engineering of soft functional materials based on the construction of three-dimensional interconnecting self-organized nanofiber networks is reported. The system under investigation is an organogel formed by N-lauroyl-L-glutamic acid di-n-butylamide (GP-1) in propylene glycol. The engineering of soft functional materials is implemented by controlling primary nucleation kinetics of GP-1, which can be achieved by both reducing thermodynamic driving force and/or introducing a tiny amount of specific copolymers (i.e., poly(methyl methacrylate comethacrylic acid)). The primary nucleation rate of GP-1 is correlated to the number density of GP-1 spherulites, which determines the overall rheological properties of soft functional materials. The results show that the presence of a tiny amount of the polymer (0.01-0.06%) can effectively inhibit the nucleation of GP-1 spherulites, which leads to the formation of integrated fiber networks. It follows that with the additive approach, the viscoelasticity of the soft functional material is significantly enhanced (i.e., more than 1.5 times at 40 °C). A combination of the thermal and additive approach led to an improvement of 3.5 times in the viscosity of the gel.

Architecture of fiber network : from understanding to engineering of molecular gels

A new approach of engineering of molecular gels was established on the basis of a nucleation-initiated network formation mechanism. A variety of gel network structures can be obtained by regulating the starting temperature of the sol−gel transition. This enables us to tune the network from the spherulitic domains pattern to the extensively interconnected fibrillar network. As the consequence of fibrous network structure turning, desirable rheological and other in-use properties of the materials can be obtained accordingly. This approach of micro-/nanostructural fabrication may open up a new route for micro-/nanofunctional materials engineering in general.

Size invariance of fibrous networks of supramolecular soft materials during formation under critical volume confinement

The rheological properties of a hierarchically structured supramolecular soft material are mainly determined by the structure of its network. Controlling the thermodynamic driving force of physical gels (one type of such materials) during the formation has proven effective in manipulating the network structure due to the nature of nucleation and growth of the fiber network formation in such a supramolecular soft material. Nevertheless, it is shown in this study that such a property can be dramatically influenced when the volume of the system is reduced to below a threshold value. Unlike un-confined systems, the network structure of such a soft material formed under volume confinement contains a constant network size, independent of the experimental conditions, i.e. temperature and solute concentration. This implies that the size of the fiber networks in such a material is invariable and free from the influence of external factors, once the volume is reduced to a threshold. The observations of this work are significant in the control of the formation of fibrous networks in materials of this type.

A physarum network evolution model based on IBTM

The traditional Cellular Automation-based Physarum model reveals the process of amoebic self-organized movement and self-adaptive network formation based on bubble transportation. However, a bubble in the traditional Physarum model often transports within active zones and has little change to explore newareas.And the efficiency of evolution is very low because there is only one bubble in the system. This paper proposes an improved model, named as Improved Bubble Transportation Model (IBTM). Our model adds a time label for each grid of environment in order to drive bubbles to explore newareas, and deploysmultiple bubbles in order to improve the evolving efficiency of Physarum network.We first evaluate the morphological characteristics of IBTM with the real Physarum, and then compare the evolving time between the traditional model and IBTM. The results show that IBTM can obtain higher efficiency and stability in the process of forming an adaptive network.

A physarum-inspired vacant-particle model with shrinkage for transport network design

Physarum can form a higher efficient and stronger robust network in the processing of foraging. The vacant-particle model with shrinkage (VP-S model), which captures the relationship between the movement of Physarum and the process of network formation, can construct a network with a good balance between exploration and exploitation. In this paper, the VP-S model is applied to design a transport network. We compare the performance of the network designed based on the VP-S model with the real-world transport network in terms of average path length, network efficiency and topology robustness. Experimental results show that the network designed based on the VP-S model has better performance than the real-world transport network in all measurements. Our study indicates that the Physarum-inspired model can provide useful suggestions to the real-world transport network design.

Responding to terrorism through networks at sites of critical infrastructure : a case study of Australian airport security networks

The importance of effective multilateral security networks is widely recognised in Australia and internationally as being essential to facilitate the large-scale sharing of information required to respond to the threat of terrorism. Australian national security agencies are currently constructing networks in order to bring the diverse national and international security agencies together to achieve this. This paper examines this process of security network formation in the area of critical infrastructure protection, with particular emphasis on airport security. We address the key issues and factors shaping network formation and the dynamics involved in network practice. These include the need for the networks to extend membership beyond the strictly defined elements of national security; the integration of public and private ‘nodes’ in counter-terrorism ‘networks’; and the broader ‘responsibilisation’ of the private sector and the challenges with ‘enabling’ them in counter-terrorism networks. We argue that the need to integrate public and private agencies in counter-terrorism networks is necessary but faces considerable organisational, cultural, and legal barriers.

Dielectric properties of conducting polymer

The dielectric properties of conducting polymer composites containing polypyrrole (PPy) crushed films, PPy powder, polyaniline (PAn) base and acid powders as the dispersants and silicone rubber and vinyl ester as matrix materials have been investigated in the frequency range 2-18 GHz. The dielectric parameters such as the real part, epsiprime, and imaginary part, epsiPrime, of the permittivity and loss tangent, tandelta, increase with increasing conductivity and concentration of the dispersant. The geometrical shape of the dispersant governs the ability of conductive network formation which is indicated by a large drop in the resistivity of the composite. Also, dispersant/matrix interactions and physical properties of the matrix influence the agglomeration of the dispersant phase which, in turn, affects the dielectric properties of the composites. Flakes of PPy obtained by crushing highly conductive films and large PAn powder aggregates were unable to form a conducting network. The composites without a network of dispersant exhibit low dielectric parameters. On the other hand, high values of tan delta ranging from 0.7–1.1 were achieved for the PPy powder (15 parts)/silicone rubber composites where a conducting network was observed.

Reactive block copolymer modified thermosets : highly ordered nanostructures and improved properties

A highly ordered poly(dimethyl siloxane)-poly(glycidyl methacrylate) (PDMS-PGMA) reactive diblock copolymer was synthesized and used to modify bisphenol A-type epoxy resin (ER). The PDMS-PGMA block copolymer consisted of epoxy-miscible PGMA blocks and an epoxy-immiscible PDMS block. The PGMA reactive block of the block copolymer formed covalent bonds with cured epoxy and was involved in the network formation, and the PDMS block phase separated to give different ordered and disordered nanostructures at different blend compositions. The solvent cast PDMS-PGMA diblock copolymer showed ordered hexagonal cylindrical morphology. A highly ordered morphology consisting of hexagonal cylinders inside the lamellar morphology was observed in the cured PDMS-PGMA block copolymer. In the cured ER/PDMS-PGMA blends, a variety of morphologies including lamellar, cubic and worm-like and spherical nanostructures were detected depending on the blend composition. Moreover, the addition of this reactive diblock copolymer significantly increases the hydrophobicity and the glass transition temperature. It also improves the tensile strength and tensile ductility of the nanostructured thermosets at low diblock copolymer contents.

Engineering molecular self-assembled fibrillar networks by ultrasound

The architecture of self-organized three-dimensionally interconnected nanocrystal fibrillar networks has been achieved by ultrasound from a solution consisting of separate spherulites. The ultrasound stimulated structural transformation is correlated to the striking ultrasonic effects on turning nongelled solutions or weak gels into strong gels instantly, with enhancement of the storage modulus up to 3 magnitudes and up to 4 times more gelling capability. The basic principle involved in the ultrasound-induced structural transformation is established on the basis of the nucleation-and-growth model of a fiber network formation, and the mechanism of seeding multiplication, aggregation suppressing, and fiber distribution and growth promotion is proposed. This novel technique enables us to produce self-supporting gel functional materials possessing significantly modified macroscopic properties, from materials previously thus far considered to be “useless”, without the use of chemical stimuli. Moreover, it provides a general strategy for the engineering of self-organized fiber network architectures, and we are consequently able to achieve the supramolecular functional materials with controllable macroscopic properties.

Kinetically controlled homogenization and transformation of crystalline fiber networks in supramolecular materials

Supramolecular materials with three-dimensional fiber networks have applications in many fields. For these applications, a homogeneous fiber network is essential in order to get the desired performance of a material. However, such a fiber network is hard to obtain, particularly when the crystallization of fiber takes place nonisothermally. In this work, a copolymer is used to kinetically control the nucleation and fiber network formation of a small molecular gelling agent, N-lauroyl-L-glutamic acid di-nbutylamide (GP-1) in benzyl benzoate. The retarded nucleation and enhanced mismatch nucleation of the gelator by the additive leads to the conversion of a mixed fiber network into a homogeneous network consisting of spherulites only. The enhanced structural mismatch of the GP-1 during crystallization is quantitatively characterized using the rheological data. This effect also leads to the transformation of an interconnecting (single) fiber network of GP-1 into a multidomain fiber network in another solvent, isostearyl alcohol. The approach developed is significant to the production of supramolecular materials with homogeneous fiber networks and is convenient to switch a single fiber network to a multidomain network without adjusting the thermodynamic driving force.

Architecture of supramolecular soft functional materials: from understanding to micro-/nanoscale engineering

This article gives an overview of the current progress of a class of supramolecular soft materials consisting of fiber networks and the trapped liquid. After discussing the up-to-date knowledge on the types of fiber networks and the correlation to the rheological properties, the gelation mechanism turns out to be one of the key subjects for this review. In this concern, the following two aspects will be focused upon: the single fiber network formation and the multi-domain fiber network formation of this type of material. Concerning the fiber network formation, taking place via nucleation, and the nucleation-mediated growth and branching mechanism, the theoretical basis of crystallographic mismatch nucleation that governs fiber branching and formation of three-dimensional fiber networks is presented. In connection to the multi-domain fiber network formation, which is governed by the primary nucleation and the subsequent formation of single fiber networks from nucleation centers, the control of the primary nucleation rate will be considered. Based on the understanding on the the gelation mechanism, the engineering strategies of soft functional materials of this type will be systematically discussed. These include the control of the nucleation and branching-controlled fiber network formation in terms of tuning the thermodynamic driving force of the gelling system and introducing suitable additives, as well as introducing ultrasound. Finally, a summary and the outlook of future research on the basis of the nucleation-growth-controlled fiber network formation are given.

Chromate replacement in coatings for corrosion protection of aerospace aluminium alloys

Mixed rare earth organophosphates have been investigated as potential corrosion inhibitors for AA2024-T3 with the aim of replacing chromate-based technologies. Cerium diphenyl phosphate (Ce(dpp) 3) and mischmetal diphenyl phosphate (Mm(dpp) 3) were added to epoxy coatings applied to AA2024-T3 panels and they were effective in reducing the amount and rate of filiform corrosion in high humidity conditions. Ce(dpp) 3 was the most effective and characterisation of the coating formulations showed approximately a factor of 5 reduction in both the number of corrosion filaments initiated as well as the length of these. Mm(dpp) 3 appeared to reduce the corrosion growth rate by a factor of 2 although it was the more effective inhibitor in solution studies. Spectroscopic characterisation of the coatings indicated that the cerium based inhibitor may disrupt network formation in the epoxy thus resulting in a coating that absorbed more water and allowed greater solubilisation of the corrosion inhibiting compound.