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Elastomers with segmental microstructure are a fascinating class of shock‐tolerant and impact‐resistant materials. However, their technological potential remains untapped due to a vague understanding of the molecular contributions to their superior mechanical behavior. Herein, in situ light‐matter interactions, to reveal the extent of microstructural mobility by temporally exploiting molecular processes during creep response, are leveraged. The segmental microstructure comprises aromatic hard domains embedded within an aliphatic soft matrix. High‐resolution digital image correlation reveals the development of strain striations, mild anisotropy, and the mechanisms responsible for domain mobility, where the rate of hard segment mobility is found to be 60% slower than that of the soft segment. Terahertz spectral analyses pinpoint the contributions of interchain hydrogen bonding of the hard segments and their significant conformational changes by observing spectral features at ≈1.2THz and ≈1.67THz. Moreover, the domain mobility is examined using experimental and computational light scattering approaches, uncovering dynamic scattering and elucidating the difference in the complex refractive index of the soft and hard segments. The study unlocks the pathway for quantitative measurements of elusive molecular mobility and conformational changes during mechanical loading and sheds light on the origin of the shock tolerance in some elastomeric polymers with segmental microstructure.

 

The core of this research is separated into three domains, the ultrahigh strain rate response of elastomeric polymers, laser‐induced shock waves , and terahertz time‐domain spectroscopy (THz‐TDS). Elastomers, e.g., polyurea, constitute an advance class of materials suitable for many applications, specifically in high impact loading scenarios, thus, a laser‐induced shock wave (LSW) experimental technique is used to investigate the mechanical response of shock‐loaded polyurea. LSW can submit samples to a strain rate exceeding 10⁶s⁻¹at low strains, enabling determination of material intrinsic failure modes. The large deformation induced during shock loading may alter the macromolecule structure, which can only be detected spectroscopically. Therefore, this research incorporated terahertz bulk spectroscopy to detect and report molecular conformational changes. Microscopy techniques were also used to elucidate changes in the microscale properties, morphology, and topography. The interpretation of the results explicated brittle failure in terms of partial and total spallation and, remarkably, ductile failure leading to plastic deformation, including plastic bulging and adiabatic shearing, not previously associated with LSW technique. Furthermore, spectral changes found in the terahertz regime substantiated the validity of terahertz spectroscopy in elucidating the underlying mechanism associated with the impact mitigating properties of dynamically loaded polyurea.

 

Abstract The residual effect of thermally and mechanically loaded polyurea samples was investigated in this study using terahertz time-domain spectroscopy (THz-TDS). Samples of different thicknesses were submerged in liquid nitrogen and allowed to reach cryogenic isothermal conditions while another set of samples were extracted from quasi-statically loaded strips. All samples were interrogated using THz-TDS since terahertz waves exhibit non-ionizing, nondestructive interactions with polymers. The time-domain terahertz signals were used to extract the optical and electrical properties as a function of sample thickness and loading conditions. The residual effect was prominent in the mechanically loaded samples compared to a nearly negligible presence in thermally loaded polyurea. On average, the results of the thermally loaded samples were subtle when compared to the virgin samples, whereas samples that were mechanically stretched showed a considerable difference in the characteristics of the time-domain signals. For example, the peak amplitude in the time-domain signal of the stretched thick sample showed a 9% difference from that of the virgin sample, whereas the thermally loaded sample saw only a 4.9% difference. Spectral analysis reported the frequency-dependent, complex refractive index of virgin and loaded polyurea as a function of thickness and spectral peaks associated with fundamental vibrational modes of the polyurea structure. The disappearance of three spectral peaks, 0.56 THz, 0.76 THz, and 0.95 THz, elucidated the residual effect of the mechanically loaded samples. In general, terahertz spectroscopy was shown to be a promising tool for future in situ and in operando investigations of field-dependent polymer responses. 

Abstract Emerging polymeric foams exhibiting unique microstructure of microspherical shells with reinforcing dense microspheres creates a new opportunity for impact-tolerant foam paddings in sport gears applications. This paper describes the static response of reinforced microcell consisting of an outer spherical shell and uniformly distributed microspheres while quantifying the stiffening effect. The distribution of the microspheres is illustrated using the Fourier series, allowing tuning of the reinforcing strategy. Expressions of the external and internal works are derived, whereas the Ritz energy method is adopted to calculate the deformations due to a compressive load distributed over a range of areas. Emphasis is given to the effect of the geometrical attributes of the microcell and the reinforcing microspheres on the resulting deformation response and stiffening effect. The framework is used to investigate the response of several case studies to elucidate the effects of relative radii ratio, reinforcement density, microcell wall thickness, and loading configurations on the stiffness. A new normalized strain energy parameter is introduced to simplify and accelerate the analysis while providing insights on the underpinnings of the observed buckling response. The results strongly suggest the viability of the newly discovered foam microstructure in managing static loads while providing an opportunity to strategically tune the mechanical response using the analytical framework presented herein. 

This paper reports the unique microstructure of polyurea foams that combines the advantages of open and closed cell polymeric foams, which were synthesized through a self-foaming process. The latter was the result of aggressive mechanical mixing of diamine curative, isocyanate, and deionized water at ambient conditions, which can be adjusted on-demand to produce variable density polyurea foam. The spherical, semi-closed microcellular structure has large perforations on the cell surface resulting from the concurrent expansion of neighboring cells and small holes at the bottom surface of the cells. This resulted in a partially perforated microcellular structure of polyurea foam. As a byproduct of the manufacturing process, polyurea microspheres nucleate and deposit on the inner cell walls of the foam, acting as a reinforcement. Since cell walls and the microspheres are made of polyurea, the resulting reinforcement effect overcomes the fundamental interfacial issue of different adjacent materials. The partially perforated, self-reinforced polyurea foam is compared to the performance of traditional counterparts in biomechanical impact scenarios. An analytical model was developed to explicate the stiffening effect associated with the reinforcing microspheres. The model results indicate that the reinforced microcell exhibited, on average, ~30% higher stiffness than its barren counterpart.