Effects of network structures on the tensile toughness of copper-catalyzed azide-alkyne cycloaddition (CuAAC)-based photopolymers.

In the present study, the photo-initiated copper-catalyzed azide-alkyne cycloaddition (CuAAC) polymerization was utilized to form structurally diverse glassy polymer networks. Systematic alterations in the monomer backbone rigidity (e.g., cyclic or aliphatic groups with a different length of backbone) and the reactive functional group density (e.g., tetra-, tri-, di-, and mono-functional azide and alkyne monomers) were used to provide readily tailorable network structures with crosslink densities (estimated from the rubbery modulus) varying by a factor of over 20. All eight of the resultant networks exhibited glass transition temperatures (Tg) between 50 and 80 °C with tensile toughness ranging from 28 to 61 MJ m-3. A nearly linear dependence of yield stress and elongation at break (broadly defined as strength and ductility, respectively) on the Tg and rubbery modulus was established in these triazole networks. When a flexible di-alkyne monomer (5 carbon spacing between alkynes) was incorporated in a network composed of a tri-alkyne and di-azide monomer, the elongation at break was improved from 166 to 300 %, while the yield stress was reduced from 36 to 23 MPa. Additionally, the polymer ductility was also varied by incorporating mono-functional azides as chain ends in the network - replacing a sterically hindered stiff mono-azide with a more flexible mono-azide increased the elongation at break from 24 to 185 % and the tensile toughness from 6 to 28 MJ m-3.

Light-Activated Stress Relaxation, Toughness Improvement, and Photoinduced Reversal of Physical Aging in Glassy Polymer Networks.

A covalent adaptable network (CAN) with high glass transition temperature (Tg ), superior mechanical properties including toughness and ductility, and unprecedented spatio-temporally controlled dynamic behavior is prepared by introducing dynamic moieties capable of reversible addition fragmentation chain transfer (RAFT) into photoinitiated copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC)-based networks. While the CuAAC polymerization yields glassy polymers composed of rigid triazole linkages with enhanced toughness, the RAFT moieties undergo bond exchange leading to stress relaxation upon light exposure. This unprecedented level of stress relaxation in the glassy state leads to numerous desirable attributes including glassy state photoinduced plasticity, toughness improvement during large deformation, and even photoinduced reversal of the effects of physical aging resulting in the rejuvenation of mechanical and thermodynamic properties in physically aged RAFT-CuAAC networks that undergo bond exchange in the glassy state. Surprisingly, when an allyl-sulfide-containing azide monomer (AS-N3 ) is used to form the network, the network exhibits up to 80% stress relaxation in the glassy state (Tg  - 45 °C) under fixed displacement. In situ activation of RAFT during mechanical loading results in a 50% improvement in elongation to break and 40% improvement in the toughness when compared to the same network without light-activation of RAFT during the tensile testing.

Stress Relaxation via Covalent Dynamic Bonds in Nanogel-Containing Thiol-Ene Resins.

Functional nanogels are attractive additives for use in polymer composites. In this study, nanogels with internal allyl sulfide moieties throughout their network structure were prepared via a thiol-Michael addition reaction. The excess thiol-functionalized nanogels were less than 60 nm as discrete particles but act as room-temperature liquids in the bulk state. The reactive nanogels can be dispersed in and swollen by a thiol-ene matrix resin, which upon photopolymerization yields dramatically decreased levels of polymerization shrinkage stress. Furthermore, the postcured nanogel-modified polymers effectively relaxed applied stresses as well as enhanced toughness during exposure to a UV light source that activated the addition-fragmentation as a means for dynamic bond exchange. These nanogels provide a generic approach to introduce adaptable network performance that significantly improves a number of key properties of glassy cross-linked polymer.

Dynamic covalent chemistry (DCC) in dental restorative materials: Implementation of a DCC-based adaptive interface (AI) at the resin-filler interface for improved performance.

OBJECTIVE: Dental restorative composites have been extensively studied with a goal to improve material performance. However, stress induced microcracks from polymerization shrinkage, thermal and other stresses along with the low fracture toughness of methacrylate-based composites remain significant problems. Herein, the study focuses on applying a dynamic covalent chemistry (DCC)-based adaptive interface to conventional BisGMA/TEGDMA (70:30) dental resins by coupling moieties capable of thiol-thioester (TTE) DCC to the resin-filler interface as a means to induce interfacial stress relaxation and promote interfacial healing. METHODS: Silica nanoparticles (SNP) are functionalized with TTE-functionalized silanes to covalently bond the interface to the network while simultaneously facilitating relaxation of the filler-matrix interface via DCC. The functionalized particles were incorporated into the otherwise static conventional BisGMA/TEGDMA (70:30) dental resins. The role of interfacial bond exchange to enhance dental composite performance in response to shrinkage and other stresses, flexural modulus and toughness was investigated. Shrinkage stress was monitored with a tensometer coupled with FTIR spectroscopy. Flexural modulus/strength and flexural toughness were characterized in three-point bending on a universal testing machine. RESULTS: A reduction of 30% in shrinkage stress was achieved when interfacial TTE bond exchange was activated while not only maintaining but also enhancing mechanical properties of the composite. These enhancements include a 60% increase in Young's modulus, 33% increase in flexural strength and 35% increase in the toughness, relative to composites unable to undergo DCC but otherwise identical in composition. Furthermore, by combining interfacial DCC with resin-based DCC, an 80% reduction of shrinkage-induced stress is observed in a thiol-ene system "equipped" with both types of DCC mechanisms relative to the composite without DCC in either the resin or at the resin-filler interface. SIGNIFICANCE: This behavior highlights the advantages of utilizing the DCC at the resin-filler interface as a stress-relieving mechanism that is compatible with current and future developments in the field of dental restorative materials, nearly independent of the type of resin improvements and types that will be used, as it can dramatically enhance their mechanical performance by reducing both polymerization and mechanically applied stresses throughout the composite lifetime.

Enabling Applications of Covalent Adaptable Networks.

The ability to behave in a fluidlike manner fundamentally separates thermoset and thermoplastic polymers. Bridging this divide, covalent adaptable networks (CANs) structurally resemble thermosets with permanent covalent crosslinks but are able to flow in a manner that resembles thermoplastic behavior only when a dynamic chemical reaction is active. As a consequence, the rheological behavior of CANs becomes intrinsically tied to the dynamic reaction kinetics and the stimuli that are used to trigger those, including temperature, light, and chemical stimuli, providing unprecedented control over viscoelastic properties. CANs represent a highly capable material that serves as a powerful tool to improve mechanical properties and processing in a wide variety of polymer applications, including composites, hydrogels, and shape-memory polymers. This review aims to highlight the enabling material properties of CANs and the applied fields where the CAN concept has been embraced.

Dynamic Covalent Chemistry at Interfaces: Development of Tougher, Healable Composites through Stress Relaxation at the Resin-Silica Nanoparticles Interface.

The interfacial region in composites that incorporate filler materials of dramatically different modulus relative to the resin phase acts as a stress concentrator and becomes a primary locus for composite failure. A novel adaptive interface (AI) platform formed by coupling moieties capable of dynamic covalent chemistry (DCC) is introduced to the resin-filler interface to promote stress relaxation. Specifically, silica nanoparticles (SNP) are functionalized with a silane capable of addition fragmentation chain transfer (AFT), a process by which DCC-active bonds are reversibly exchanged upon light exposure and concomitant radical generation, and copolymerized with a thiol-ene resin. At a fixed SNP loading of 25 wt%, the toughness (2.3 MJ m-3) is more than doubled and polymerization shrinkage stress (0.4 MPa) is cut in half in the AI composite relative to otherwise identical composites that possess a passive interface (PI) with similar silane structure, but without the AFT moiety. In situ activation of the AI during mechanical loading results in 70% stress relaxation and three times higher fracture toughness than the PI control. When interfacial DCC was combined with resin-based DCC, the toughness was improved by 10 times relative to the composite without DCC in either the resin or at the resin-filler interface.

Fully recoverable rigid shape memory foam based on copper-catalyzed azide-alkyne cycloaddition (CuAAC) using a salt leaching technique.

This study is the first to employ the use of the copper-catalyzed azide-alkyne cycloaddition (CuAAC) polymerization to form a tough and stiff, porous material from a well-defined network possessing a high glass transition temperature. The effect of the network linkages formed as a product of the CuAAC reaction, i.e., the triazoles, on the mechanical behavior at high strain was evaluated by comparing the CuAAC foam to an epoxy-amine-based foam, which consisted of monomers with similar backbone structures and mechanical properties (i.e., Tg of 115 °C and a rubbery modulus of 1.0 MPa for the CuAAC foam, Tg of 125 °C and a rubbery modulus of 1.2 MPa for the epoxy-amine foam). When each foam was compressed uniformly to 80% strain at ambient temperature, the epoxy-amine foam was severely damaged after only reaching 70% strain in the first compression cycle with a toughness of 300 MJ/m3. In contrast, the CuAAC foam exhibited pronounced ductile behavior in the glassy state with three times higher toughness of 850 MJ/m3 after the first cycle of compression to 80% strain. Additionally, when the CuAAC foam was heated above Tg after each of five compression cycles to 80% strain at ambient temperature, the foam completely recovered its original shape while exhibiting a gradual decrease in mechanical performance over the multiple compression cycles. The foam demonstrated almost complete shape fixity and recovery ratios even through five successive cycles, indicative of "reversible plasticity", making it highly desirable as a glassy shape memory foams.

Light-Stimulated Permanent Shape Reconfiguration in Cross-Linked Polymer Microparticles.

Reconfiguring the permanent shape of elastomeric microparticles has been impossible due to the incapability of plastic deformation in these materials. To address this limitation, we synthesize the first instance of microparticles comprising a covalent adaptable network (CAN). CANs are cross-linked polymer networks capable of reconfiguring their network topology, enabling stress relaxation and shape changing behaviors, and reversible addition-fragmentation chain transfer (RAFT) is the corresponding dynamic chemistry used in this work to enable CAN-based microparticles. Using nanoimprint lithography to apply controllable deformations we demonstrate that upon light stimulation microparticles are able to reconfigure their shape to permanently fix large aspect ratios and nanoscale surface topographies.

Reduced shrinkage stress via photo-initiated copper(I)-catalyzed cycloaddition polymerizations of azide-alkyne resins.

OBJECTIVES: Polymerization shrinkage stress and factors involved in the stress development such as volumetric shrinkage and modulus were investigated in photo-CuAAC (photo-initiated copper(I)-catalyzed azide-alkyne cycloaddition) polymerization and compared with conventional BisGMA-based methacrylate polymerization for their use as alternative dental resins. METHODS: Tri-functional alkyne and di-functional azide monomers were synthesized for photo-CuAAC polymerization. Conversion kinetics, stress development and polymerization shrinkage were determined with FTIR spectroscopy, tensometery, and with a linometer, respectively, for CuAAC and BisGMA-based monomer mixtures using a camphorquinone/amine visible light photoinitiator system. Thermo-mechanical properties for the cured polymer matrices were characterized by dynamic mechanical analysis and in three-point bending on a universal testing machine. Polymerization kinetics, polymerization shrinkage stress, dynamic volumetric shrinkage, glass transition temperature (Tg), flexural modulus, flexural strength, and flexural toughness were compared between the two different resin systems. RESULTS: A glassy CuAAC polymer (Tg=62°C) exhibited 15-25% lower flexural modulus of 2.5±0.2GPa and flexural strength of 117±8MPa compared to BisGMA-based polymer (Tg=160°C) but showed considerably higher energy absorption around 7.1MJ×m-3 without fracture when strained to 11% via three-point bend compared to the flexural toughness of 2.7MJ×m-3 obtained from BisGMA-based polymer. In contrast to BisGMA-based polymers at 75% functional group conversion, the CuAAC polymerization developed approximately three times lower shrinkage stress with the potential to achieve quantitative conversion under ambient temperature photocuring conditions. Moreover, relatively equivalent dynamic volumetric shrinkage of around 6-7% was observed via both CuAAC and dimethacrylate polymerization, suggesting that the low shrinkage stress of CuAAC polymerization was due to delayed gelation along with slower rate of polymerization and the formation of a more compliant network structure. SIGNIFICANCE: CuAAC crosslinked networks possessed high toughness and low polymerization shrinkage stress with quantitative conversion, which eliminated obstacles associated with BisGMA-based dental resins including limited conversion, unreacted extractable moieties, brittle failure, and high shrinkage stress.

Effects of oxygen on light activation in covalent adaptable network polymers.

Light activated polymers are a novel group of active materials that deform when irradiated with light at specific wavelengths. This paper focuses on the understanding and evaluation of light activated covalent adaptable networks formed by radical polymerization reactions, which have potential applications as novel actuators, surface patterning, and light-induced bending and folding. In these polymer networks, free radicals are generated upon light irradiation and lead to evolution of the polymer network structure through bond exchange reactions. It is well known that oxygen is an important inhibitor in radical-based chemistry as oxygen reacts with free radicals and renders them as inactive species towards further propagation and reaction. However, it is unclear how radical depletion by oxygen may affect the light-induced actuation. This paper studies the effects of oxygen on both stress relaxation and bending actuation. Light induced stress relaxation experiments are conducted in an environmental chamber where the concentration of oxygen is controlled by the nitrogen flow. A constitutive model that considers oxygen diffusion, radical termination due to oxygen, and the polymer network evolution is developed and used to study the stress relaxation and bending, and the model predictions agree well with experiments. Parametric studies are conducted to identify the situations where the effects of oxygen are negligible and other conditions where they must be considered.

Photo-induced bending in a light-activated polymer laminated composite.

Light activated polymers (LAPs) have attracted increasing attention since these materials change their shape and/or behavior in response to light exposure, which serves as an instant, remote and precisely controllable stimulus that enables non-contact control of the material shape and behavior through simple variation in light intensity, wavelength and spatially controlled exposure. These features distinguish LAPs from other active polymers triggered by other stimuli such as heat, electrical field or humidity. Previous examples have resulted in demonstrations in applications such as surface patterning, photo-induced shape memory behavior, and photo-origami. However, in many of these applications, an undesirable limitation has been the requirement to apply and maintain an external load during light irradiation. In this paper, a laminated structure is introduced to provide a pre-programmed stress field, which is then used for photo-induced deformation. This laminated structure is fabricated by bonding a stretched elastomer (NOA65) sheet between two LAP layers. Releasing the elastomer causes contraction and introduces a compressive stress in the LAPs, which are relaxed optically to trigger the desired deformation. A theoretical model is developed to quantitatively examine the laminated composite system, allowing exploration of the design space and optimum design of the laminate.

Creating a mentoring partnership model: a university-department of health experience.

The purpose of this project was to increase the number of students participating in public health nursing experiences at Vermont Department of Health through creation of a mentoring partnership model. The model targeted preceptor needs, including roles and responsibilities when working with students; educational needs of faculty, particularly related to evolving roles of public health nurses; and creation of additional clinical opportunities for students. Outcomes included improved working relationships among students, faculty, and public health mentors as measured by narrative evaluative comments of project participants; a 150% increase in the number of students participating in public health nursing clinical experiences; expanded involvement of Vermont Department of Health district offices and central office, with the addition of two new clinical sites and increased numbers of students in sites used prior to this project. Guidelines for preceptors working with students were also developed.