Michael R. Kessler

Autonomic healing of polymer composites

Structural polymers are susceptible to damage in the form of cracks, which form deep within the structure where detection is difficult and repair is almost impossible. Cracking leads to mechanical degradation of fibre-reinforced polymer composites; in microelectronic polymeric components it can also lead to electrical failure. Microcracking induced by thermal and mechanical fatigue is also a long-standing problem in polymer adhesives. Regardless of the application, once cracks have formed within polymeric materials, the integrity of the structure is significantly compromised. Experiments exploring the concept of self-repair have been previously reported, but the only successful crack-healing methods that have been reported so far require some form of manual intervention. Here we report a structural polymeric material with the ability to autonomically heal cracks. The material incorporates a microencapsulated healing agent that is released upon crack intrusion. Polymerization of the healing agent is then triggered by contact with an embedded catalyst, bonding the crack faces. Our fracture experiments yield as much as 75% recovery in toughness, and we expect that our approach will be applicable to other brittle materials systems (including ceramics and glasses).

In situ poly(urea-formaldehyde) microencapsulation of dicyclopentadiene

Microencapsulated healing agents that possess adequate strength, long shelf-life and excellent bonding to the host material are required for self-healing materials. Urea-formaldehyde microcapsules containing dicyclopentadiene were prepared by in situ polymerization in an oil-in-water emulsion that meet these requirements for self-healing epoxy. Microcapsules of 10–1000 μm in diameter were produced by appropriate selection of agitation rate in the range of 200–2000 rpm. A linear relation exists between log(mean diameter) and log(agitation rate). Surface morphology and shell wall thickness were investigated by optical and electron microscopy. Microcapsules are composed of a smooth 160–220 nm inner membrane and a rough, porous outer surface of agglomerated urea-formaldehyde nanoparticles. Surface morphology is influenced by pH of the reacting emulsion and interfacial surface area at the core-water interface. High yields (80–90%) of a free flowing powder of spherical microcapsules were produced with a fill co...

Self-healing structural composite materials

A self-healing fiber-reinforced structural polymer matrix composite material is demonstrated. In the composite, a microencapsulated healing agent and a solid chemical catalyst are dispersed within the polymer matrix phase. Healing is triggered by crack propagation through the microcapsules, which then release the healing agent into the crack plane. Subsequent exposure of the healing agent to the chemical catalyst initiates polymerization and bonding of the crack faces. Self-healing (autonomic healing) is demonstrated on width-tapered double cantilever beam fracture specimens in which a mid-plane delamination is introduced and then allowed to heal. Autonomic healing at room temperature yields as much as 45% recovery of virgin interlaminar fracture toughness, while healing at 80 °C increases the recovery to over 80%. The in situ kinetics of healing in structural composites is investigated in comparison to that of neat epoxy resin.

In situpoly(urea-formaldehyde) microencapsulation of dicyclopentadiene

Microencapsulated healing agents that possess adequate strength, long shelf-life and excellent bonding to the host material are required for self-healing materials. Urea-formaldehyde microcapsules containing dicyclopentadiene were prepared by in situ polymerization in an oil-in-water emulsion that meet these requirements for self-healing epoxy. Microcapsules of 10–1000 μm in diameter were produced by appropriate selection of agitation rate in the range of 200–2000 rpm. A linear relation exists between log(mean diameter) and log(agitation rate). Surface morphology and shell wall thickness were investigated by optical and electron microscopy. Microcapsules are composed of a smooth 160–220 nm inner membrane and a rough, porous outer surface of agglomerated urea-formaldehyde nanoparticles. Surface morphology is influenced by pH of the reacting emulsion and interfacial surface area at the core-water interface. High yields (80–90%) of a free flowing powder of spherical microcapsules were produced with a fill content of 83–92 wt% as determined by CHN analysis.

Self-activated healing of delamination damage in woven composites

A study of the healing of delamination damage in woven E-glass/epoxy composites is performed. With the ultimate goal of self-healing in mind, two types of healing processes are studied. In the first a catalyzed monomer is manually injected into the delamination. In the second a self-activated material is created by embedding the catalyst directly into the matrix of the composite, then manually injecting the monomer. Healing efficiencies relative to the virgin fracture toughness of up to 67% are obtained when the catalyzed monomer is injected and about 19% for the self-activated materials. Scanning electron microscopy is used to analyze the fracture surfaces and provide physical evidence of repair.

Self-healing: A new paradigm in materials design

Abstract Self-healing materials, when damaged, are designed to sense the failure and respond in an autonomous fashion to restore structural function. Inspired by biological systems, synthetic self-healing materials represent a new paradigm in the design of polymer based composites. This overview article summarizes the different strategies and approaches to achieving self-healing functionality and discusses future directions in the nascent field. The strategies are broadly classified into the following three categories: healing with an embedded liquid phase repair agent, thermally activated solid phase healing, and healing of projectile puncture.

Self-healing Polymers and Composites

Abstract Inspired by the unique and efficient wound healing processes in biological systems, several approaches to develop synthetic polymers that can repair themselves with complete, or nearly complete, autonomy have recently been developed. This review aims to survey the rapidly expanding field of self-healing polymers by reviewing the major successful autonomic repairing mechanisms developed over the last decade. Additionally, we discuss several issues related to transferring these self-healing technologies from the laboratory to real applications, such as virgin polymer property changes as a result of the added healing functionality, healing in thin films v. bulk polymers, and healing in the presence of structural reinforcements.

Green Aqueous Surface Modification of Polypropylene for Novel Polymer Nanocomposites

Polypropylene is one of the most widely used commercial commodity polymers; among many other applications, it is used for electronic and structural applications. Despite its commercial importance, the hydrophobic nature of polypropylene limits its successful application in some fields, in particular for the preparation of polymer nanocomposites. Here, a facile, plasma-assisted, biomimetic, environmentally friendly method was developed to enhance the interfacial interactions in polymer nanocomposites by modifying the surface of polypropylene. Plasma treated polypropylene was surface-modified with polydopamine (PDA) in an aqueous medium without employing other chemicals. The surface modification strategy used here was based on the easy self-polymerization and strong adhesion characteristics of dopamine (DA) under ambient laboratory conditions. The changes in surface characteristics of polypropylene were investigated using FTIR, TGA, and Raman spectroscopy. Subsequently, the surface modified polypropylene was used as the matrix to prepare SiO2-reinforced polymer nanocomposites. These nanocomposites demonstrated superior properties compared to nanocomposites prepared using pristine polypropylene. This simple, environmentally friendly, green method of modifying polypropylene indicated that polydopamine-functionalized polypropylene is a promising material for various high-performance applications.

Soy-castor oil based polyols prepared using a solvent-free and catalyst-free method and polyurethanes therefrom

Bio-based polyols from epoxidized soybean oil and castor oil fatty acid were developed using an environmentally friendly, solvent-free/catalyst-free method. The effects of the molar ratios of the carboxyl to the epoxy groups, reaction time, and reaction temperature on the polyols’ structures were systematically studied. Subsequently, polyurethane films were prepared from these green polyols. Properties of the new, soy-castor oil based polyurethane films were compared with two other polyurethane films prepared from castor oil and methoxylated soybean oil polyol, respectively. Thermal and mechanical tests showed that the polyurethane films prepared from the new polyols exhibited higher glass transition temperatures, tensile strength, Youngs modulus, and thermal stability because of the higher degree of cross-linking in the new polyols. Moreover, the novel polyols, prepared using the solvent-free and catalyst-free synthetic route, were 100% bio-based and facilitate a more environmentally friendly and economical process than conventional soy-based polyols used for polyurethane production.

Biobased Polyurethanes Prepared from Different Vegetable Oils

In this study, a series of biobased polyols were prepared from olive, canola, grape seed, linseed, and castor oil using a novel, solvent/catalyst-free synthetic method. The biobased triglyceride oils were first oxidized into epoxidized vegetable oils with formic acid and hydrogen peroxide, followed by ring-opening reaction with castor oil fatty acid. The molecular structures of the polyols and the resulting polyurethane were characterized. The effects of cross-linking density and the structures of polyols on the thermal, mechanical, and shape memory properties of the polyurethanes were also investigated.