Unintended consequences: Assessing thermo-mechanical changes in vinyl nitrile foam due to micro-computed X-ray tomographic imaging.

Micro-computed X-ray tomography (µCT) is a volumetric imaging tool used to quantify the internal structure of materials. µCT imaging with mechanical testing (in situ µCT) helps visualize strain-induced structural changes and develop structure-property relationships. However, the effects on thermophysical properties of radiation exposure during in situ µCT imaging are seldom addressed, despite potential radiation sensitivity in elastomers. This work quantifies the radiation dosage effect on thermo-, chemical-, and mechanical-properties for a vinyl nitrile-based foam. Material properties were measured after (0, 1, 2, and 3) days at (8.1 ± 0.9) kGy/d. Morphological characteristics were investigated via scanning electron microscopy. Thermal transitions were assessed using differential scanning calorimetry. Viscoelasticity was measured with dynamic mechanical analysis over a range from -30 °C to 60 °C. Higher dose lead to stiffening and increased dissipation. Chemical structure was assessed with Fourier transform infrared spectroscopy and energy-dispersive X-ray spectroscopy. Soxhlet extraction was used to measure gel content. In summary, substantial changes occur in thermophysical properties, which may confound structure-property measurements. However, this also provides a modification pathway. Quantitation and calibration of the properties changes informed a finite element user material for material designers to explore tunablity and design optimization for impact protection engineers.

Enhanced durability of carbon nanotube grafted hierarchical ceramic microfiber-reinforced epoxy composites.

As carbon nanotube (CNT) infused hybrid composites are increasingly identified as next-generation aerospace materials, it is vital to evaluate their long-term structural performance under aging environments. In this work, the durability of hierarchical, aligned CNT grafted aluminoborosilicate microfiber-epoxy composites (CNT composites) are compared against baseline aluminoborosilicate composites (baseline composites), before and after immersion in water at 25 °C (hydro) and 60 °C (hydrothermal), for extended durations (90 d and 180 d). The addition of CNTs is found to reduce water diffusivities by approximately 1.5 times. The mechanical properties (bending strength and modulus) and the damage sensing capabilities (DC conductivity) of CNT composites remain intact regardless of exposure conditions. The baseline composites show significant loss of strength (44 %) after only 15 d of hydrothermal aging. This loss of mechanical strength is attributed to fiber-polymer interfacial debonding caused by accumulation of water at high temperatures. In situ acoustic and DC electrical measurements of hydrothermally aged CNT composites identify extensive stress-relieving micro-cracking and crack deflections that are absent in the aged baseline composites. These observations are supported by SEM images of the failed composite cross-sections that highlight secondary matrix toughening mechanisms in the form of CNT pullouts and fractures which enhance the service life of composites and maintain their properties under accelerated aging environments.

Connecting Molecular Exchange Dynamics to Stress Relaxation in Phase-Separated Dynamic Covalent Networks.

A suite of phase separated dynamic covalent networks based on highly tunable dynamic benzalcyanoacetate (BCA) thia-Michael acceptors are investigated. In situ kinetic studies on small molecule model systems are used in conjunction with macroscopic characterization of phase stability and stress relaxation to understand how the molecular dynamics relate to relaxation modes. Electronic modification of the BCA unit strongly impacts the exchange dynamics (particularly the rate of dissociation) and the overall equilibrium constant (Keq) of the system, with electron-withdrawing groups leading to decreased dissociation rate and increased Keq. Critically, below a chemistry-defined temperature cutoff (related to the stability of the hard phase domains), the stress relaxation behavior of these phase separated materials is dominated by the molecular exchange dynamics, allowing for networks with a tailored thermomechanical response.

A materials data framework and dataset for elastomeric foam impact mitigating materials.

The availability of materials data for impact-mitigating materials has lagged behind applications-based data. For example, data describing on-field helmeted impacts are available, whereas material behaviors for the constituent impact-mitigating materials used in helmet designs lack open datasets. Here, we describe a new FAIR (findable, accessible, interoperable, reusable) data framework with structural and mechanical response data for one example elastic impact protection foam. The continuum-scale behavior of foams emerges from the interplay of polymer properties, internal gas, and geometric structure. This behavior is rate and temperature sensitive, therefore, describing structure-property characteristics requires data collected across several types of instruments. Data included are from structure imaging via micro-computed tomography, finite deformation mechanical measurements from universal test systems with full-field displacement and strain, and visco-thermo-elastic properties from dynamic mechanical analysis. These data facilitate modeling and design efforts in foam mechanics, e.g., homogenization, direct numerical simulation, or phenomenological fitting. The data framework is implemented using data services and software from the Materials Data Facility of the Center for Hierarchical Materials Design.

Activation of Mechanophores in a Thermoset Matrix by Instrumented Scratch.

Scratches in polymer coatings and barrier layers negatively impact optical properties (haze, light transmission, etc.), initiate routes of degradation or corrosion (moisture permeability), and nucleate delamination of the coating. Detecting scratches in coatings on advanced materials systems is an important component of structural health monitoring but can be difficult if the defects are too small to be detected by the naked eye. The primary focus of the present work is to investigate scratch damage using fluorescence lifetime imaging microscopy (FLIM) and mechanical activation of a mechanophore (MP)-containing transparent epoxy coating. The approach utilizes a Berkovich tip to scratch MP-epoxy coatings under a linearly increasing normal load. The goal is to utilize the fluorescent behavior of activated MPs to enable the detection of microscale scratches and molecular scale changes in polymeric systems. Taking advantage of the amine functionality present in a polyetheramine/bisphenol A epoxy network, a modified rhodamine dye is covalently bonded into a transparent, thermoset polymer network. Following instrumented scratch application, subsequent fluorescence imaging of the scratched MP-epoxy reveals the extent of fluorescence activation induced by the mechanical deformation. In this work, the rhodamine-based mechanophore is used to identify both ductile and fracture-dominated processes during the scratch application. The fluorescence intensity increases linearly with the applied normal load and is sensitive to fracture dominated processes. Fluorescence lifetime and hyperspectral imaging of damage zones provide additional insight into the local (nanoscopic) environment and molecular structure of the MP around the fracture process zone, respectively. The mechanophore/scratch deformation approach allows a fluorescence microscope to probe local yielding and fracture events in a powerful way that enhances the optical characterization of damage zones formed by standard scratch test methods and leads to novel defect detection strategies.

Temperature-insensitive silicone composites as ballistic witness materials: the impact of water content on the thermophysical properties.

In this work, different formulations of a room-temperature silicone composite backing material (SCBM) composed of polydimethylsiloxane (PDMS), fumed silica and corn starch were investigated using different characterization techniques, i.e., differential scanning calorimetry, thermogravimetry analysis, X-ray diffraction (XRD) and small-angle X-ray scattering, as a function of controlled relative humidity. At ambient relative humidities in the range of about 20-80%, the equilibrium water content in the SCBM ranges from approximately 4-10%, which is predominantly absorbed by the corn starch. This amount of water content has been shown to have minimal effect on thermal transition temperatures (melting and glass transition) of the SCBMs. The enthalpy of melting increases with increasing relative humidity, which reflects the heterogeneous semicrystalline structure of starch granules and the role of moisture in facilitating the formation of amylopectin double helices mainly in the imperfect crystalline regions. The thermal degradation of SCBM exhibits three major mass loss steps that correspond to dehydration, decomposition of corn starch and decomposition of PDMS. The XRD patterns reveal a characteristic diffuse peak for amorphous PDMS and an A-type crystallinity for the corn starch. The XRD results show no observable changes in the crystal type and crystallinity as a function of moisture content. Results from this work help clarify the fundamental structure-property relationships in SCBMs, which are important for future development of documentary standards, especially the handling and storage specifications of next-generation ballistic witness materials for body armor testing.

Calibration Procedures for Orthogonal Superposition Rheology.

Orthogonal superposition (OSP) rheology is an advanced rheological technique that involves superimposing a small-amplitude oscillatory shear deformation orthogonal to a primary shear flow. This technique allows the measurement of structural dynamics of complex fluids under non-linear flow conditions, which is important for the understanding and prediction of the performance of a wide range of complex fluids. The OSP rheological technique has a long history of development since the 1960s, mainly through the custom-built devices that highlighted the power of this technique. The OSP technique is now commercially available to the rheology community. Given the complicated design of the OSP geometry and the non-ideal flow field, users should understand the magnitude and sources of measurement error. This study presents calibration procedures using Newtonian fluids that includes recommendations for best practices to reduce measurement errors. Specifically, detailed information on the end-effect factor determination method, sample filling procedure, and identification of the appropriate measurement range (e.g., shear rate, frequency, etc.) are provided.

Rheological Characterization of Next-Generation Ballistic Witness Materials for Body Armor Testing.

Roma Plastilina No. 1 (RP1), an artist modeling clay that has been used as a ballistic clay, is essential for evaluation and certification in standards-based ballistic resistance testing of body armor. It serves as a ballistic witness material (BWM) behind the armor, where the magnitude of the plastic deformation in the clay after a ballistic impact is the figure of merit (known as "backface signature"). RP1 is known to exhibit complex thermomechanical behavior that requires temperature conditioning and frequent performance-based evaluations to verify that its deformation response satisfies requirements. A less complex BWM formulation that allows for room-temperature storage and use as well as a more consistent thermomechanical behavior than RP1 is desired, but a validation based only on ballistic performance would be extensive and expensive to accommodate the different ballistic threats. A framework of lab-scale metrologies for measuring the effects of strain, strain rate, and temperature dependence on mechanical properties are needed to guide BWM development. The current work deals with rheological characterization of a candidate BWM, i.e., silicone composite backing material (SCBM), to understand the fundamental structure⁻property relationships in comparison to those of RP1. Small-amplitude oscillatory shear frequency sweep experiments were performed at temperatures that ranged from 20 °C to 50 °C to map elastic and damping contributions in the linear elastic regime. Large amplitude oscillatory shear (LAOS) experiments were conducted in the non-linear region and the material response was analyzed in the form of Lissajous curve representations with the values of perfect plastic dissipation ratio reported to identify the degree of plasticity. The results show that the SCBM exhibits dynamic properties that are similar in magnitude to those of temperature-conditioned RP1, but with minimal temperature sensitivity and weaker frequency dependence than RP1. Both SCBM and RP1 are identified as elastoviscoplastic materials, which is particularly important for accurate determination of backface signature in body armor evaluation. The mechanical properties of SCBM show some degree of aging and work history effects. The results from this work demonstrate that the rheological properties of SCBM, at small and large strains, are similar to RP1 with substantial improvements in BWM performance requirements in terms of temperature sensitivity and thixotropy.

Multiscale Polymer Dynamics in Hierarchical Carbon Nanotube Grafted Glass Fiber Reinforced Composites.

Carbon nanotube (CNT) grafted glass fiber reinforced epoxy nanocomposites (GFRP) present a range of stiffnesses (MPa to GPa) and length scales (µm to nm) at the fiber-matrix interface. The contribution of functionalized CNT networks to the local and bulk polymer dynamics is studied here by using a combination of torsion dynamical mechanical thermal analysis (DMTA), positron annihilation lifetime spectroscopy (PALS), and neutron scattering (NS) measurements. DMTA measurements highlight a reduction in the storage modulus (G') in the rubbery region and an asymmetric broadening of the loss modulus (G″) peak in the α-transition region. NS measurements show a suppressed hydrogen mean-square displacement (MSD) in the presence of glass fibers but a higher hydrogen MSD after grafting functionalized CNTs onto fiber surfaces. PALS measurements show greater free volume characteristics in the presence of the functionalized CNT modified composites, supporting the view that these interface layers increase polymer mobility. While NS and DMTA are sensitive to different modes of chain dynamics, the localization of functionalized nanotubes at the fiber interface is found to affect the distribution of polymer relaxation modes without significantly altering the thermally activated relaxation processes.

Lightweight, Flexible, High-Performance Carbon Nanotube Cables Made by Scalable Flow Coating.

Coaxial cables for data transmission are ubiquitous in telecommunications, aerospace, automotive, and robotics industries. Yet, the metals used to make commercial cables are unsuitably heavy and stiff. These undesirable traits are particularly problematic in aerospace applications, where weight is at a premium and flexibility is necessary to conform with the distributed layout of electronic components in satellites and aircraft. The cable outer conductor (OC) is usually the heaviest component of modern data cables; therefore, exchanging the conventional metallic OC for lower weight materials with comparable transmission characteristics is highly desirable. Carbon nanotubes (CNTs) have recently been proposed to replace the metal components in coaxial cables; however, signal attenuation was too high in prototypes produced so far. Here, we fabricate the OC of coaxial data cables by directly coating a solution of CNTs in chlorosulfonic acid (CSA) onto the cable inner dielectric. This coating has an electrical conductivity that is approximately 2 orders of magnitude greater than the best CNT OC reported in the literature to date. This high conductivity makes CNT coaxial cables an attractive alternative to commercial cables with a metal (tin-coated copper) OC, providing comparable cable attenuation and mechanical durability with a 97% lower component mass.

Imaging the Molecular Structure of Polyethylene Blends with Broadband Coherent Raman Microscopy.

Polyethylene (PE) has been widely used in a myriad of consumer products and critical infrastructure products such as underground gas and water pipes. These products are often made of blends of multiple types of PE with different molecular architectures. Although the long-term performance of these products is largely dictated by their local molecular structure, it has been studied mostly by indirect and bulk-averaging methods such as calorimetry and neutron scattering due to lack of chemical contrast for conventional imaging techniques. We demonstrate that broadband coherent anti-Stokes Raman scattering (CARS) microscopy can acquire images of the chemical composition and molecular orientation of a miscible semicrystalline PE blend with two different molecular architectures. We discuss the detailed crystal structure observed at different length scales and new insights it provides into polymer crystal morphology.

Identifying the dynamic compressive stiffness of a prospective biomimetic elastomer by an inverse method.

Soft elastomeric materials that mimic real soft human tissues are sought to provide realistic experimental devices to simulate the human body's response to blast loading to aid the development of more effective protective equipment. The dynamic mechanical behavior of these materials is often measured using a Kolsky bar because it can achieve both the high strain rates (>100s(-1)) and the large strains (>20%) that prevail in blast scenarios. Obtaining valid results is challenging, however, due to poor dynamic equilibrium, friction, and inertial effects. To avoid these difficulties, an inverse method was employed to determine the dynamic response of a soft, prospective biomimetic elastomer using Kolsky bar tests coupled with high-speed 3D digital image correlation. Individual tests were modeled using finite elements, and the dynamic stiffness of the elastomer was identified by matching the simulation results with test data using numerical optimization. Using this method, the average dynamic response was found to be nearly equivalent to the quasi-static response measured with stress-strain curves at compressive strains up to 60%, with an uncertainty of ±18%. Moreover, the behavior was consistent with the results in stress relaxation experiments and oscillatory tests although the latter were performed at lower strain levels.

Improving performance of dental resins by adding titanium dioxide nanoparticles.

OBJECTIVE: The objective of this study is to improve the performance of dental resins by adding a small amount of titanium dioxide nanoparticles (TiO2 NPs), which have outstanding mechanical properties and unique photoactivities. METHODS: Acrylic acid modified TiO2 NPs (AP25) were prepared and added to a mixture of bis-phenol-A-dimethacrylate and triethylene glycol dimethacrylate (mass ratio 1:1) at seven mass fractions. Disks made of these resins were subjected to FTIR microspectroscopy, nanoindentation, microindentation, and 3-point bending to determine the degree of vinyl conversion (DC) modulus and hardness. The shear bond strengths (SBS) of dentin adhesives containing various amount of AP25 were also examined. RESULTS: The DC increased as a function of mass fraction of AP25 and reached a plateau at 0.1%. The DC of the resin mixture was improved by ≈7% up to 91.7 ± 0.8%. The elastic modulus and hardness of the composites increased initially as more AP25 were added, and decreased after reached the maximum value at approximately 0.06% mass fraction of AP25. The maximum elastic modulus was ≈48% higher than that of the NP-free resin, and the maximum hardness was more than twice higher than that of the NP-free resin. Using these resin composites as dental adhesives, the mean SBS using resins with 0.1% mass fraction of AP25 was ≈30% higher than those using NP-free resin. SIGNIFICANCE: By adding a small amount of AP25 to the resin, the DC and the mechanical properties of resins were improved dramatically. These findings could lead to better performing dental adhesives.

Modulus and chemical mapping of multilayer coatings.

Thermoplastic olefins (TPOs) are polymeric materials utilized for interior and exterior automotive parts. These materials are often painted to protect and enhance their appearance. TPO materials possess a low surface energy because of the aliphatic backbone, and adhesion promoters (APs), such as chlorinated polyolefins, are used to increase paint adhesion and improve paint performance. The impact of the AP structure and processing conditions on the mechanical properties and degree of interpenetration was investigated on cross sectioned coatings. The AP structure was varied by the chlorine content and molecular weight for the same TPO and polyester acrylic, melamine-cured paint system. Two different processing conditions were investigated. Mechanical properties were measured using depth-sensing indentation. Long-range diffusion of coating components across each interface was verified with confocal Raman microscopy. The AP interfaces, AP/base coat and AP/TPO, were chemically and mechanically sharp at the 1 mum lateral resolution of both techniques. Depth-sensing indentation measured a modulus gradient across the top coating cross section. The free air surface of the top coat had a higher modulus than the interior. Processing conditions and polishing to prepare the cross section for measurements were found to affect only the control AP.

Effects of filler type and content on mechanical properties of photopolymerizable composites measured across two-dimensional combinatorial arrays.

Multicomponent formulations coupled with complex processing conditions govern the final properties of photopolymerizable dental composites. In this study, a single test substrate was fabricated to support multiple formulations with a gradient in degree of conversion (DC), allowing the evaluation of multiple processing conditions and formulations on one specimen. Mechanical properties and damage response were evaluated as a function of filler type/content and irradiation. DC, surface roughness, modulus, hardness, scratch deformation and cytotoxicity were quantified using techniques including near-infrared spectroscopy, laser confocal scanning microscopy, depth-sensing indentation, scratch testing and cell viability. Scratch parameters (depth, width, percent recovery) were correlated to composite modulus and hardness. Total filler content, nanofiller and irradiation time/intensity all affected the final properties, with the dominant factor for improved properties being a higher DC. This combinatorial platform accelerates the screening of dental composites through the direct comparison of properties and processing conditions across the same sample.