Effect of temperature and strain rate on the compressive behaviour of supramolecular polyurethane

Supramolecular polyurethanes (SPUs) possess thermoresponsive and thermoreversible properties, and those characteristics are highly desirable in both bulk commodity and value-added applications such as adhesives, shape-memory materials, healable coatings and lightweight, impact-resistant structures (e.g. protection for mobile electronics). A better understanding of the mechanical properties, especially the rate and temperature sensitivity, of these materials are required to assess their suitability for different applications. In this paper, a newly developed SPU with tuneable thermal properties was studied, and the response of this SPU to compressive loading over strain rates from 10−3 to 104 s−1 was presented. Furthermore, the effect of temperature on the mechanical response was also demonstrated. The sample was tested using an Instron mechanical testing machine for quasi-static loading, a home-made hydraulic system for moderate rates and a traditional split Hopkinson pressure bars (SHPBs) for high strain rates. Results showed that the compression stress-strain behaviour was affected significantly by the thermoresponsive nature of SPU, but that, as expected for polymeric materials, the general trends of the temperature and the rate dependence mirror each other. However, this behaviour is more complicated than observed for many other polymeric materials, as a result of the richer range of transitions that influence the behaviour over the range of temperatures and strain rates tested

An effective route to the additive manufacturing of a mechanically gradient supramolecular polymer nanocomposite structure

3D Printing techniques are additive methods of fabricating parts directly from computer-aided designs. Whilst the clearest benefit is the realisation of geometrical freedom, multi-material printing allows the introduction of compositional variation and highly tailored product functionality. The paper reports a proof-of-concept additive manufacturing study to deposit a supramolecular polymer and a complementary organic filler to form composites with gradient composition to enable spatial distribution of mechanical properties and functionality by tuning the number of supramolecular interactions. We use a dual-feed extrusion 3D printing process, with feed stocks based on the supramolecular polymer and its organic composite, delivered at ratios predetermined. This allows for production of a graded specimen with varying filler concentration that dictates the mechanical properties. The printed specimen was inspected under dynamic load in a tensile test using digital image correlation to produce full-field deformation maps, which showed clear differences in deformation in regions with varying compositions, corresponding to the designed-in variations. This approach affords a novel method for printing material with graded mechanical properties which are not currently commercially available or easily accessible, however, the method can potentially be directly translated to the generation of biomaterial-based composites featuring gradients of mechanical properties

An effective route to the additive manufacturing of a mechanically gradient supramolecular polymer nanocomposite structure

3D Printing techniques are additive methods of fabricating parts directly from computer-aided designs. Whilst the clearest benefit is the realisation of geometrical freedom, multi-material printing allows the introduction of compositional variation and highly tailored product functionality. The paper reports a proof-of-concept additive manufacturing study to deposit a supramolecular polymer and a complementary organic filler to form composites with gradient composition to enable spatial distribution of mechanical properties and functionality by tuning the number of supramolecular interactions. We use a dual-feed extrusion 3D printing process, with feed stocks based on the supramolecular polymer and its organic composite, delivered at ratios predetermined. This allows for production of a graded specimen with varying filler concentration that dictates the mechanical properties. The printed specimen was inspected under dynamic load in a tensile test using digital image correlation to produce full-field deformation maps, which showed clear differences in deformation in regions with varying compositions, corresponding to the designed-in variations. This approach affords a novel method for printing material with graded mechanical properties which are not currently commercially available or easily accessible, however, the method can potentially be directly translated to the generation of biomaterial-based composites featuring gradients of mechanical properties

Fluoride-responsive debond on demand adhesives: manipulating polymercrystallinity and hydrogen bonding to optimise adhesion strength at lowbonding temperatures

This paper reports the solvent-free synthesis of a series of sixfluoride responsive debond-on-demand poly-urethane (PU) adhesives that contain a silyl functionalised degradable unit (DU). To optimise the adhesionstrength and debonding nature of the adhesives, the chemical composition of the PUs was varied according tothe structure of the polyol or the diisocyanate component in the polymer mainchain.1H NMR spectroscopy wasused to study the depolymerisation behaviour in solution state. It showed thattetra-butylammoniumfluoride(TBAF) triggered the breakdown of the DU unit without fragmenting the polyol mainchain indiscriminately. Onexposure tofluoride ions, the PUs underwent depolymerisation with reductions in Mnranging from 64 to 90% asmeasured by GPC analysis. The morphology and thermal properties of the PUs were characterised by differentialscanning calorimetry (DSC), rheology and variable temperature (VT) SAXS/WAXS analysis. Each techniquedemonstrated the reversibility of the supramolecular polymer network under thermal stimuli. PUs containingpoly(butadiene) soft segments were amorphous with glass transition and viscoelastic transition temperaturesdependent on the nature of the soft segment and diisocyanate starting materials. The PU containing a polyestersoft segment exhibited a defined melting point at 49 °C. Mechanical stress-strain analysis of the series of PUsshowed each exhibited greater than 70% reduction in toughness after treatment with TBAF for 30 min as aconsequence of the chemo-responsive degradation of the polymer mainchain. The material featuring an ester-based polyol demonstrated excellent adhesion at bonding temperatures as low as 60 °C. Moreover, this materialcould be thermally rebonded if broken by force without loss in adhesion strength over three debond-rebondcycles. Lap shear adhesion tests showed a reduction in adhesive strength of approximately 40% (from 11.4 MPato 7.3 MPa) on exposure tofluoride ion

A dynamic supramolecular polyurethane network whose mechanical properties are kinetically controlled

We report the synthesis and characterization of a kinetically controlled, thermoreversible supramolecular polyurethane whose mechanical properties depend unusually strongly on the processing history. Materials were prepared by solution casting, quenching and annealing of quenched material, allowing pronounced micro-structural evolution, which leads to rapid increases in modulus as determined by rheological analysis. Tensile tests showed that the quenched material is soft, weak and ductile (shear modulus ~ 5 MPa, elongation ~ 250 %), but after annealing, at 70 °C for one hour, it becomes stiffer, stronger and more brittle (~ 20 MPa, ~ 20 %). FTIR and NMR spectroscopic analysis, coupled with MDSC and SAXS, were performed to investigate the network’s dynamic structural changes. SAXS results suggest the presence of a lamellar structure in the sample when solution cast at high temperature, or annealed. This ordering is unique when compared to structurally-related supramolecular bisurethane and bisurea polymers, and may be the cause of the observed path dependence. These mechanical properties, which can be switched repeatedly by simple thermal treatments, coupled with its adhesion properties as determined from peel and tack tests, make it an excellent candidate as a recyclable material for adhesives and coatings

Single rod impact tests: Analytical, experimental, and modelling investigation

This work investigates the single rod impact test technique, from which wave propagation characteristics, i.e. the propagation coefficient and wave speed, can be obtained and used to identify the material modulus as a function of frequency. To accomplish this, an elastic Titanium rod and a viscoelastic Polymethyl Methacrylate (PMMA) rod have been tested. With a known modulus, the Titanium rod modulus was successfully recovered from the wave propagation coefficient in a frequency range of 5 kHz ∼ 30 kHz, which verifies the validity of this technique. The PMMA modulus identified by this technique agrees reasonably with the modulus derived from DMA tests in the range 2 kHz ∼ 20 kHz. The good agreement between the theoretical and simulation-based modulus further confirms the effectiveness of the single rod impact test in this use. It is also demonstrated that the single rod impact technique is capable of detecting the minor mechanical changes induced by temperature variations as small as 2 °C

A novel apparatus and methodology for the high frequency mechanical characterisation of ultrasoft materials

Characterising the mechanical response of ultra-soft materials is challenging, particularly at high strain rates and frequencies [1]. Time Temperature Superposition (TTS) can sometimes be used to mitigate these limitations [2], however not all materials are suitable for TTS. Biological tissues are particularly difficult to test: in addition to the extreme softness, challenges arise due to specimen inhomogeneity, sensitivity to boundary conditions, natural biological variability, and complex post-mortem changes. In the current study, a novel experimental apparatus and methodology was developed and validated using low modulus silicone elastomers as model materials. The full field visco-elastic shear response was characterised over a wide range of deformation frequencies (100-1000+ Hz) and amplitudes using Digital Image Correlation (DIC) and the Virtual Fields Method (VFM). This methodology allows for the extraction of fullfield material properties that would be difficult or impossible to obtain using traditional engineering techniques

Specimen Inertia in high strain rate tensile testing

It is well established that measurements of the dynamic mechanical response of materials are susceptible to errors due to the inertia of the specimen, which causes stresses in addition to the intrinsic material strength. A number of authors have derived equations for these stresses in compression experiments; these equations can be used as a guideline for good specimen design. However, no such equations have been presented in the literature for the equivalent effects in tensile experiments. This paper begins by considering and rationalising the equations available for compression, before producing a set of equations which can be used in design of specimens for, e.g., tensile Hopkinson bar experiments

Effects of strain rate and bond preparation for dissimilar materials in energy dispersive applications

Composite materials, typically consisting of two or more dissimilar materials adhered together in layers, are frequently used for energy absorption applications. The interface and material characteristics strongly influence the global energy absorptive capability of the composite. This research focuses on ceramic-polymer interfaces and, in particular, links between the properties of the composite, the interface and the separate materials. After characterisation of the materials, the effects of impact speed and bond condition were considered for a polymer-ceramic bond in a threepoint bend configuration. Specimens were loaded in a screw-driven machine at 0.05 mm s-1 and through projectile impact at speeds of approximately 50 m s-1. Screw-driven experiments were performed at ambient and sub ambient conditions, with the temperature chosen to simulate the expected polymer performance in the gas gun experiment, making use of the equivalence of rate and temperature for polymers

Predicting the high strain rate behaviour of particulate composites using time-temperature superposition based modelling

Polymeric particulate composites are widely used in engineering systems where they are subjected to impact loading – at a variety of temperatures – leading to high strain rate deformation. These materials are highly rate and temperature dependent, and this dependence must be well understood for effective design. It is not uncommon for many of these materials to display mechanical responses that range from glassy and brittle to rubbery and hyperelastic [1-3], due to their polymeric constituents. This makes accurate measurements and modelling not only necessary, but challenging. This is made more difficult by experimental artefacts present when traditional tools such as the split Hopkinson pressure (SHPB) or Kolsky bar are used to interrogate the high rate response of low-impedance materials. The transition from isothermal to adiabatic conditions as the rate of deformation increases also has an effect on the mechanical response, which cannot be neglected if the high rate behaviour is to be accurately predicted. In this paper, time-temperature superposition based frameworks that have enabled the high rate behaviour of neoprene rubber [4] and (plasticised) poly(vinyl chloride) [5] to be captured, will be extended to explore the high strain rate behaviour of unfilled natural rubber and several grades of glass microsphere filled natural rubber particulate composites