Tack of Entangled Molecular Bottlebrushes.

Polymer softness (i.e., low elastic modulus) is a known requirement for good tack in adhesives. We assess the tack performance of α-olefin molecular bottlebrushes having an elastic modulus from 4 to 30 times lower than a linear polyolefin (polypropylene). Monotonic increases of the tack parameters are observed as the bottlebrush side chain length (Nsc) increases and the modulus decreases. All-atom molecular dynamics simulations reveal that the monomeric bonding energy increases with Nsc due to a strong van der Waals interaction between the side chains and the aluminum sheet, which overcomes the energy penalty imposed by side-chain bending.

Local and Global Stretching of Polymer Chains during Startup of Extensional Flow.

The nonlinear rheological response to extensional flows in entangled polymers is related to the segmental chain stretching and to the chemical identity of the monomeric units. The latter has a strong effect on the drag coefficients, and therefore, quantification of molecular conformation changes in the subnanometer scale (at the monomer level) are crucial to fully understand nonlinear viscoelastic behavior in polymer melts. We report in situ time-resolved extensional rheo-small-angle neutron scattering (tEr-SANS) and wide-angle X-ray scattering (tEr-WAXS) during startup of uniaxial flow on a monodisperse polystyrene melt. Flow-induced segmental alignment was quantified with tEr-SANS, whereas local alignment of the backbone-backbone and phenyl-phenyl interactions were measured with tEr-WAXS. Linear relations between the three alignment factors and stress were observed at low stresses, which confirmed the validity of simple stress-SANS and stress-WAXS rules (SSR and SWR, respectively). Significant differences in SSR and SWR coefficients, as well as the stress values for failure of the two rules suggest very different correlations between global (at the segmental level) and local (at the monomer level) conformations with stress.

Enhanced Foamability with Shrinking Microfibers in Linear Polymer.

Strain hardening has important roles in understanding material structures and polymer processing methods, such as foaming, film forming, and fiber extruding. A common method to improve strain hardening behavior is to chemically branch polymer structures, which is costly, thus preventing users from controlling the degree of behavior. A smart microfiber blending technology, however, would allow cost-efficient tuning of the degree of strain hardening. In this study, we investigated the effects of compounding polymers with microfibers for both shear and extensional rheological behaviors and characteristics and thus for the final foam morphologies formed by batch physical foaming with carbon dioxide. Extensional rheometry showed that compounding of in situ shrinking microfibers significantly enhanced strain hardening compared to compounding of nonshrinking microfibers. Shear rheometry with linear viscoelastic data showed a greater increase in both the loss and storage modulus in composites with shrinking microfibers than in those with nonshrinking microfibers at low frequencies. The batch physical foaming results demonstrated a greater increase in the cell population density and expansion ratio with in situ shrinking microfibers than with nonshrinking microfibers. The enhancement due to the shrinkage of compounded microfibers decreasing with temperature implies that the strain hardening can be tailored by changing processing conditions.

Extensional Strain Hardening in Highly Entangled Molecular Bottlebrushes.

The highly strained conformation in dense molecular bottlebrushes (DB) has profound effects on the dynamics of these type of macromolecules. Understanding of such effects in both their linear and nonlinear viscoelastic responses is crucial for their design and processing. The nonlinear response of poly(1-octadecene), a highly entangled α-olefin DB with linear side chains sixteen carbons long, is studied here and compared to the nonlinear response of a linear polyolefin (polypropylene) with equivalent linear viscoelastic response. We found that the DB shows remarkably larger extensional strain hardening (SH) and extensibility than the linear polyolefin. The strong SH is attributed to a strain-induced increase in friction drag between adjacent chains resulting from side-chain interdigitation and alignment perpendicular to the flow. The higher extensibility of DBs compared to linear counterparts has been predicted previously [Daniel et al., Nat. Mater. 15, 183 (2015)NMAACR1476-1122] and confirmed here for the first time in DB melts.

Iono-Elastomer-Based Wearable Strain Sensor with Real-Time Thermomechanical Dual Response.

An ultrastretchable iono-elastomer with resistance sensitive to both elongation strain and temperature has been developed by hierarchical self-assembly of an end functionalized triblock copolymer in a protic ionic liquid (ethylammonium nitrate) followed by cross-linking. Small-angle X-ray scattering experiments in situ with uniaxial elongation reveal a nanoscale microstructural transition of the hierarchically self-assembled cross-linked micelles that is responsible for the material's remarkable mechanical and ionic conductivity responses. The results show that the intermicelle distance extends along the deformation direction while the micelles organize into a long-range ordered face-centered-cubic structure during the uniaxial elongation. Besides good cyclability and resistance to selected physical damage, the iono-elastomer simultaneously achieves an unprecedented combination of high stretchability (340%), highly linear resistance vs elongation strain ( R2 = 0.998), and large temperature gauge factor (Δ R/ R = 3.24%/°C@30 °C). Human subject testing demonstrates that the iono-elastomer-based wearable thermomechanical sensor is able to effectively and accurately register both body motion and skin temperature simultaneously.

Extensional Strain Hardening Induced by π-π Interactions in Barely Entangled Polymer Chains: The Curious Case of Poly(4-vinylbiphenyl).

Aromatic π-π interactions between phenyl groups of adjacent chains in poly(4-vinylbiphenyl) (PVBP) have profound effects on the dynamics of this polymer. We report two unexpected nonlinear viscoelastic responses of PVBP when subjected to uniaxial flow. One is the unprecedented observation of extensional strain hardening (SH) in a barely entangled polymer melt. An even more intriguing finding is that SH of lightly (or even barely) entangled melts occurs at strain rates one order of magnitude below the coil-stretch transition predicted by Rouse theory (ϵ[over ˙]_{H}=0.5/τ_{R}).We postulate that this behavior is due to a molecular rearrangement mechanism (supported by x-ray diffraction measurements) that involves flow-induced π-π stacking of the phenyl groups, which results in an enhancement of the friction coefficient between polymer chains.

Ultrastretchable Iono-Elastomers with Mechanoelectrical Response.

The emerging technologies involving wearable electronics require new materials with high stretchability, resistance to high loads, and high conductivities. We report a facile synthetic strategy based on self-assembly of concentrated solutions of end-functionalized PEO106-PPO70-PEO106 triblock copolymer in ethylammonium nitrate into face-centered cubic micellar crystals, followed by micelle corona cross-linking to generate elastomeric ion gels (iono-elastomers). These materials exhibit an unprecedented combination of high stretchability, high ionic conductivity, and mechanoelectrical response. The latter consists of a remarkable and counterintuitive increase in ion conductivity with strain during uniaxial extension, which is reversible upon load release. Based on in situ SAXS measurements of reversible crystal structure transformations during deformation, we postulate that the origin of the conductivity increase is a reversible formation of ion nanochannels due to a novel microstructural rearrangement specific to this material.

Microstructural evolution of a model, shear-banding micellar solution during shear startup and cessation.

We present direct measurements of the evolution of the segmental-level microstructure of a stable shear-banding polymerlike micelle solution during flow startup and cessation in the plane of flow. These measurements provide a definitive, quantitative microstructural understanding of the stages observed during flow startup: an initial elastic response with limited alignment that yields with a large stress overshoot to a homogeneous flow with associated micellar alignment that persists for approximately three relaxation times. This transient is followed by a shear (kink) band formation with a flow-aligned low-viscosity band that exhibits shear-induced concentration fluctuations and coexists with a nearly isotropic band of homogenous, highly viscoelastic micellar solution. Stable, steady banding flow is achieved only after approximately two reptation times. Flow cessation from this shear-banded state is also found to be nontrivial, exhibiting an initial fast relaxation with only minor structural relaxation, followed by a slower relaxation of the aligned micellar fluid with the equilibrium fluid's characteristic relaxation time. These measurements resolve a controversy in the literature surrounding the mechanism of shear banding in entangled wormlike micelles and, by means of comparison to existing literature, provide further insights into the mechanisms driving shear-banding instabilities in related systems. The methods and instrumentation described should find broad use in exploring complex fluid rheology and testing microstructure-based constitutive equations.

Spatiotemporal stress and structure evolution in dynamically sheared polymer-like micellar solutions.

The complex, nonlinear flow behavior of soft materials transcends industrial applications, smart material design and non-equilibrium thermodynamics. A long-standing, fundamental challenge in soft-matter science is establishing a quantitative connection between the deformation field, local microstructure and macroscopic dynamic flow properties i.e., the rheology. Here, a new experimental method is developed using simultaneous small angle neutron scattering (SANS) and nonlinear oscillatory shear rheometry to investigate the spatiotemporal microstructure evolution of a polymer-like micellar (PLM) solution. We demonstrate the novelty of nonlinear oscillatory shear experimental methods to create and interrogate metastable material states. These include a precursory state to the shear banded condition as well as a disentangled, low viscosity state with an inhomogeneous supra-molecular microstructure flowing at high shear rates. This new experimental evidence provides insight into the complexities of the shear banding phenomenon often observed in sheared complex fluids and provides valuable data for quantitatively testing non-equilibrium theory.

Spontaneous thermoreversible formation of cationic vesicles in a protic ionic liquid.

The search for stable vesicular structures is a long-standing topic of research because of the usefulness of these structures and the scarcity of surfactant systems that spontaneously form vesicles in true thermodynamic equilibrium. We report the first experimental evidence of spontaneous formation of vesicles for a pure cationic double tail surfactant (didodecyldimethylammonium bromide, DDAB) in a protic ionic liquid (ethylammonium nitrate, EAN). Using small and ultra-small angle neutron scattering, rheology and bright field microscopy, we identify the coexistence of two vesicle containing phases in compositions ranging from 2 to 68 wt %. A low density highly viscous solution containing giant vesicles (D ~ 30 µm) and a sponge (L(3)) phase coexists with a dilute high density phase containing large vesicles (D ~ 2.5 µm). Vesicles form spontaneously via different thermodynamic routes, with the same size distribution, which strongly supports that they exist in a true thermodynamic equilibrium. The formation of equilibrium vesicles and the L(3) phase is facilitated by ion exchange between the cationic surfactant and the ionic liquid, as well as the strength of the solvophobic effect in the protic ionic liquid.

Dynamics of melting and recrystallization in a polymeric micellar crystal subjected to large amplitude oscillatory shear flow.

Shear-induced structural transitions of a micellar cubic phase during large amplitude oscillatory shear flow is studied with time-resolved oscillatory rheological small angle neutron scattering. This technique allows us to resolve the structural changes within a cycle of oscillation. By applying a strain rate near the critical melting shear rate, melting and recrystallization occurs in a cyclic mode. The maximum degree of order is observed when the shear stress reaches a plateau value during the large amplitude oscillatory shear cycle, whereas melting is maximized at the strain rate wave peaks. This structural evolution confirms the cyclic mechanism of sticking and sliding of 2D hexagonal close-packed layers [I. W. Hamley et al., Phys. Rev. E 58, 7620 (1998)].

Structural transitions of CTAB micelles in a protic ionic liquid.

Micellar solutions of hexadecyltrimethylammonium bromide (CTAB) in a protic ionic liquid, ethylammonium nitrate (EAN), are studied by shear rheology, polarizing optical microscopy (POM), conductivity measurements, and small angle neutron scattering (SANS). Three concentration regimes are examined: A dilute regime (with concentrations [CTAB] < 5 wt %) consisting of noninteracting spherical micelles, a semidilute regime (5 wt % ≤ [CTAB] ≤ 45 wt %) where micelles interact via electrostatic repulsions, and a concentrated regime (45 wt % < [CTAB] ≤ 62 wt %) where a reversible, temperature-dependent isotropic (L(1)) to hexatic (Hex) phase transition is observed. The L(1)-Hex transition, which has been predicted but not previously observed, is characterized by (1) a sharp increase in the shear viscosity, (2) the formation of focal conical birefringence textures (observed by POM), and (3) enhancement of the crystalline order, evidenced by the appearance of Bragg reflections in the SANS profiles. Ionic conductivity is not sensitive to the L(1)-Hex transition, which corroborates the absence of topological transitions.

Sponge-to-lamellar transition in a double-tail cationic surfactant/protic ionic liquid system: structural and rheological analysis.

The self-assembly of didodecyldimethylammonium bromide (DDAB) in a protic ionic liquid, ethylammonium nitrate (EAN), in the high surfactant concentration regime is studied using five different experimental techniques. A thermoreversible first-order sponge (L(3)) to lamellar (L(α)) transition occurring at [DDAB] > 80 wt % was identified by (1) a sharp increase in the elastic and viscous moduli, (2) a transition peak recorded by differential scanning calorimetry, (3) formation of Maltese cross birefringence textures observed via polarizing optical microscopy, (4) a decrease in the interbilayer mean distance measured by small angle neutron scattering, and (5) an abrupt increase in the conductivity obstruction factor. In contrast to aqueous DDAB solutions, this surfactant forms a stable L(3) phase in EAN in a wide window of compositions and temperatures, which is potentially useful for the synthesis of nanoporous materials. To the best of our knowledge, this is the first evidence of the formation of the L(3) phase in an ionic liquid.

Measurement of geometrical parameters in cocontinuous polymer blends: 3D versus 2D image analysis.

Formulae of stereology are used to estimate 3D geometrical parameters of cocontinuous structures measured from 2D micrographs of polymer blends. 3D images of symmetric and nonsymmetric polymer blends made of fluorescently labelled polystyrene and styrene-ran-acrylonitrile copolymer were obtained with laser scanning confocal microscopy. Geometrical parameters of the blend interface, specifically volume fraction, surface area per unit volume (S (V) ) and average of local mean curvature were measured directly from the 3D images and compared to the values estimated from analysis of a number of 2D slices combined with stereological relations. When the total length of phase boundary considered in the analysis of the 2D slices (L(Tot) ) was at least 6000 times bigger than the characteristic length of the microstructure (S(-1) (V) ), the standard deviation for all the parameters measured became negligible. However, considerable discrepancies between the average values computed from 3D and 2D images were observed for any value of L(Tot) . The mean curvature distribution was also measured from both the 3D images and the 2D slices. The distribution was estimated from the 2D slices but with a width about 2.4 times that of the true value obtained from the 3D images.

Direct measurement of interface anisotropy of bicontinuous structures via 3D image analysis.

A very important morphological parameter in two-phase fluids is the interface anisotropy, which can be quantified using the interface tensor, q(ij). However, the computation of this tensor for complex interfaces is not straightforward. A novel method (the local cross product method, LCPM) to compute the interface tensor of two-phase fluids using 3D imaging coupled with differential geometry is presented here. The method was used to evaluate the degree of anisotropy of phase separated systems with bicontinuous morphologies subjected to uniaxial and shear deformation fields. A model bicontinuous structure (i.e., the gyroid surface) was used to assess the accuracy and precision of the method. The method was then used to track the anisotropy changes of an immiscible polymer blend with cocontinuous morphology, during uniaxial deformation and subsequent retraction. It was found that the dependence of the anisotropy on the Hencky strain of both the gyroid surface and the cocontinuous blend follow the same trend. The retraction of the blend after uniaxial extension is accompanied by an exponential decay of the second invariant of q(ij), which obeys the relation: |II(q)|/Q(2) approximately e(-0.129t).

Characterizing interface shape evolution in immiscible polymer blends via 3D image analysis.

The coordinate transformation (CT) method was applied to measure the local curvature of the interface of an immiscible polymer blend made of fluorescently labeled polystyrene (FLPS) and styrene-ran-acrylonitrile copolymer (SAN). The CT method involves the local parametrization of the interface by a quadratic polynomial to compute the local values of the mean (H) and the Gaussian (K) curvatures. Distributions of the curvatures at different annealing times were obtained by measuring H and K at many (typically 10(7)) points on the interface. Coarsening of a symmetric (50/50 w/w FLPS/SAN) and a nonsymmetric (35/65 w/w) blend was monitored. For the symmetric blend, two regimes of surface evolution were identified: in the early stage, the probability densities of the curvatures at various times were successfully scaled by a time-dependent characteristic length, i.e., interface area per unit volume (Q). This behavior has been previously observed in blends with morphologies created by a different mechanism, namely spinodal decomposition. In the late stage, the dynamic scaling failed and the time evolution of the interface slowed down. For the nonsymmetric blend, the domains of the minor phase (FLPS) were more elongated and they eventually broke up producing a composite microstructure with islands of drops within cocontinuous domains. We defined a "scaled" genus (G) to quantify the topology evolution of the blends during coarsening. Loss of connectivity was evidenced by a decrease of G with time for the nonsymmetric blend, while a constant value of this parameter indicated no change in topology during coarsening for the symmetric blend.