Stiffening, strengthening, and toughening of biodegradable poly(butylene adipate-co-terephthalate) with a low nanoinclusion usage.

Simultaneous stiffening, strengthening, and toughening of biodegradable polymers, such as poly(butylene adipate-co-terephthalate) (PBAT) and others, is necessary for their use in packaging and agriculture applications. However, a high content of nanoinclusions is usually required, leading to a tradeoff between composite toughness and strength or stiffness in the reinforcement. Herein, we report an iterative reinforcement strategy that uses one nanocomposite to reinforce PBAT. An in-situ grafting polymerized cellulose nanocrystal (CNC)/PBAT (CNC-g-PBAT) nanocomposite consisting of ungrafted/free PBAT (PBATf) was used as an inclusion directly to reinforce a commercial PBAT. At an exceptionally low CNC usage of 0.02 wt.%, we achieved a simultaneous enhancement of the Young's modulus by 26 %, tensile strength by 27 %, elongation at break by 37 %, and toughness by 56 % over those for PBAT. To the best of our knowledge, such reinforcement efficiency is the highest among similar biodegradable polymer nanocomposites reported in the literature. The rheology, differential scanning calorimetry, and wide-angle X-ray diffraction measurements confirmed the mechanical reinforcement attributed to a synergistic contribution from PBATf and CNC-g-PBAT. In particular, the use of PBATf enhanced both stiffness and toughness of the composites, while the CNC-g-PBAT interacted within the polymer matrix and increased the crystallinity of the polymer matrix, leading to the strengthening and toughening effect. The strategy proposed here is greatly beneficial to producing high-performance biodegradable polymer nanocomposite films for packaging and agricultural applications using a very low amount of nanoinclusion.

Water evaporation on highly viscoelastic polymer surfaces.

Results are reported for a study on the evaporation of water droplets from a highly viscoelastic acrylic polymer surface. These are contrasted with those collected for the same measurements carried out on polydimethylsiloxane (PDMS). For PDMS, the evaporation process involves the expected multistep process including constant drop area, constant contact angle, and finally a combination of these steps until the liquid is gone. In contrast, water evaporation from the acrylic polymer shows a constant drop area mode throughout. Furthermore, during the evaporation process, the drop area actually expands on the acrylic polymer. The single mode evaporation process is consistent with formation of wetting structures, which cannot be propagated by the capillary forces. Expansion of the drop area is attributed to the influence of the drop capillary pressure. Furthermore, the rate of drop area expansion is shown to be dependent on the thickness of the polymer film.

Characterizing the distribution of sodium alkyl sulfate surfactant homologues in water-based, acrylic pressure-sensitive adhesive films.

The distributions of three sodium alkyl sulfate surfactants in dry adhesive films cast from water-based latexes were characterized using confocal Raman microscopy (CRM) and contact angle (CA) and tack measurements. Sodium dodecyl sulfate (SDS), sodium tetradecyl sulfate (STS), and sodium octadecyl sulfate (SODS) were added to dialyzed commercial adhesive latex at various concentrations. Uneven distributions were found for all three surfactants along with a tendency to enrich film-air interfaces and, to a much lesser extent, film-glass interfaces. SDS demonstrated the greatest tendency to concentrate near film surfaces followed by STS and SODS. For all three surfactants, water CA values for dried films decreased sharply with increasing concentrations in the latex, but significant differences were observed, with SDS again having the greatest impact followed by STS and SODS. Tack of dried polymer films was also found to decrease with increasing latex surfactant levels, with SDS producing the sharpest drop as well as the lowest plateau values. Results indicate that interfacial enrichment by surfactants is detectable via both CRM and CA measurements, and this enrichment can significantly affect the performance of films. Finally, surface enrichment levels are qualitatively related to measures of the surfactants' affinity for aqueous solutions, as characterized by the logarithm of their 1-octanol-water distribution coefficients (K(ow)).

Drop behavior on a thermally-stripped acrylic polymer: influence of surface tension induced wetting ridge formation on retention and running.

Results are reviewed from a study on retention and running of water and other liquids on tilted, polymer coated surfaces. The polymer is a thermally-stripped, solvent-borne acrylic composed primarily of the monomer 2-ethylhexyl acrylate, providing a soft and viscoelastic substrate absent of contaminants. It is shown that drop retention does not obey standard models, which assume dominance of capillary forces in offsetting drop weight for tilted plates. For these surfaces, maximum volumes correlate with capillary lengths, and distinct deformations, which vary in magnitude depending on location, are apparent over the entire drop perimeter. Deformation images indicate that running, which in real time appears to be continuous motion, actually proceeds through a series of steps beginning with the failure of the front edge wetting line. This produces a relatively large translation of the drop's front edge down the plate surface stretching the drop. This is followed by multiple failures at the rear edge producing a series of small translations, contracting the drop volume to a more spherical-like geometry. Repetition of this mechanism results in the appearance of propagation similar to that employed by an inchworm. The proposed mechanism is consistent with images of drop movement and deformations induced on polymer surfaces, which are apparent subsequent to the running process.

Modifications of surfactant distributions and surface morphologies in latex films due to moisture exposure.

Migration of surfactants in water-based, pressure-sensitive adhesive (PSA) films exposed to static and cyclic relative humidity conditions was investigated using confocal Raman microscopy (CRM) and atomic force microscopy (AFM). Studied PSA films contain monomers n-butyl acrylate, vinyl acetate, and methacrylic acid and an equal mass mixture of anionic and nonionic nonylphenol ethoxylate emulsifiers. A leveling of surfactant concentration distributions is observed via CRM after films stored at 50% relative humidity (RH) are exposed to a 100% RH for an extended time period, while relatively small increases in surface enrichment occur when films are stored at 0% RH. Use of CRM for binary mixtures containing anionic or nonionic surfactant and latex that has undergone dialysis to remove nonpolymeric components indicates that surfactant-polymer compatibility governs to a great extent surface enrichment, but not changes observed with humidity variations. AFM images show that upon drying latex coatings, surfactant and other additives collect in large aggregation regions, which protrude from film surfaces. These structures are absent at high humidity, which appears to result from lateral spreading across the polymer surface. When humidity is reduced, aggregation regions reform but appear to be smaller and more evenly dispersed, and by cycling humidity between 0 and 100% RH, interfacial enrichment can be seen to diminish. Presented results provide greater insights into the distribution behavior of surfactants in latex films and potential mechanisms for observed issues arising for these systems.

Characterizing the distribution of nonylphenol ethoxylate surfactants in water-based pressure-sensitive adhesive films using atomic-force and confocal Raman microscopy.

Surfactant distributions in model pressure-sensitive adhesive (PSA) films were investigated using atomic force microscopy (AFM) and confocal Raman microscopy (CRM). The PSAs are water-based acrylics synthesized with n-butyl acrylate, vinyl acetate, and methacrylic acid and two commercially available surfactants, disodium (nonylphenoxypolyethoxy)ethyl sulfosuccinate (anionic) and nonylphenoxypoly(ethyleneoxy) ethanol (nonionic). The ratio of these surfactants was varied, while the total surfactant content was held constant. AFM images demonstrate the tendency of anionic surfactant to accumulate at the film surfaces and retard latex particle coalescence. CRM, which was introduced here as a means of providing quantitative depth profiling of surfactant concentration in latex adhesive films, confirms that the anionic surfactant tends to migrate to the film interfaces. This is consistent with its greater water solubility, which causes it to be transported by convective flow during the film coalescence process. The behavior of the nonionic surfactant is consistent with its greater compatibility with the polymer, showing little enrichment at film interfaces and little lateral variability in concentration measurements made via CRM. Surfactant distributions near film interfaces determined via CRM are well fit by an exponential decay model, in which concentrations drop from their highs at interfaces to plateau values in the film bulk. It was observed that decay constants are larger at the film-air interface compared with those obtained at the film-substrate side indicating differences in the mechanism involved. In general, it is shown here that CRM acts as a powerful compliment to AFM in characterizing the distribution of surfactant species in PSA film formation.

Characterization of dynamic stick-and-break wetting behavior for various liquids on the surface of a highly viscoelastic polymer.

A thermally stripped acrylic polymer was wet with a series of liquids possessing a broad range of properties. Previously, novel wetting behavior by water was reported for the polymer, which included the formation of a wetting ridge structure substantially larger than those reported elsewhere and the complete halting of the three-phase line. This allows metastable angles ranging from 0 degrees to greater than 150 degrees to be achieved through changes in the sessile drop volume. Greater advancing angles are prevented by the collapse of the drop, producing what has been described as stick-and-break propagation. In Wilhelmy plate experiments for metal plates coated with the polymer, this mechanism produces a quasi-periodic pattern of lines composed of ridge structures. Similar behavior was observed for all liquids tested. Differences were observed in the maximum force measured with a tensiometer (pinning force) and the average distance between ridges for the formed pattern (pinning distance). These quantities are shown to be related to the height of the ridge structures. The kinematic viscosity of the liquids appears to be an important variable for the wetting process. A comparison of pinning quantities at various rates with the master curve of the polymer indicate that its viscoelastic properties govern, to a great extent, the observed rate dependencies; i.e., higher rates produce greater elastic behavior and smaller ridge heights. Also important is the polymer's tendency for creep deformation. The ridge apex is shown to be displaced a significant distance through ridge deformation, which modifies its symmetry.

Mechanical pinning of liquids through inelastic wetting ridge formation on thermally stripped acrylic polymers.

A film composed of a thermal-stripped, solvent-borne acrylic polymer is shown to completely arrest motion of the three-phase line for water as a result of ridge structure formation. This mechanism produces anomalous wetting behavior including the arbitrary selection of contact angles, formation of quasi-periodic ridge structures on surfaces, and requirement of stick and break motion for wetting line advancement, a novel mechanism reported here. The ridges are retained by the polymer subsequent to wetting, which are 2 scales larger in height than those described previously. This allows for their characterization, which shows significant detail including the hierarchical apex structure where a cutoff area is used in theoretical treatment to avoid a singularity. Results of Wilhelmy plate experiments show a spatial connection between quasi-periodic variation in force-displacement curves and the wetting ridges on plate. These results are consistent with the dominance of the viscoelastic properties of the substrate in determining wetting behavior.

Influence of ozonized kraft lignin on the crystallization of CaCO3.

Results are reviewed from a study examining how structural modifications introduced by ozonization enhance the influence of kraft lignin on the crystallization of CaCO(3). Ozone treatment of kraft lignin in an aqueous environment is shown to increase its carboxylic acid and overall oxygen content and reduce its molecular weight. Calcium concentration and temperature were monitored in heated supersaturated solutions containing ozonized kraft lignins to gauge their influence on CaCO(3) crystallization processes. The presence of kraft lignin raises the temperature necessary to induce crystallization. This effect is shown to level off at relatively low lignin concentrations and be dependent on the extent of ozone treatment the kraft lignin has undergone. A linear correlation is found between crystallization temperatures and the carboxylic acid content of ozonized lignin samples indicating the introduction of these functional groups plays an important role in enhancing its inhibitory effect. Scanning electron microscopy images of crystals grown in the presence of kraft lignins show significant morphological modifications. These are consistent with specific or pseudo specific interactions between the lignin and crystal faces of calcite to inhibit growth parallel to its c axis. The influence over crystal morphology demonstrated by modified kraft lignin increases with increasing ozonization. Also presented here are crystallization temperature data for a range of kraft lignin ultrafiltration fractions, which indicate that the optimal (nominal) molecular weight of kraft lignin for inhibiting the crystallization of CaCO(3) lies between 5000 and 10000.

Dual Reactive Domain Model for Sorption of Aqueous Organics by Wood Fiber.

An experimental study of 2,4,5-trichlorophenol (2,4,5-TCP) sorption to kraft papermaking fiber demonstrates that the dual reactive domain model (DRDM) effectively characterizes the process over a broad concentration region. Isotherm data were deconvoluted into linear partitioning and nonlinear adsorption contributions in accordance with the model demonstrating the importance of both mechanisms to the overall process. DRDM accurately fit concentration-dependent distribution coefficient, K(d)(C), data that could not be characterized with the Freundlich or Langmuir equations, and the model predicts the asymptotic movement toward a limiting K(d)(C) value at high solute or cosolute concentrations observed in experiments. Competitive effects were accounted for by modifying the adsorption portion of the model. With its limitations understood, the extended Langmuir equation was utilized and provided an effective fit of data. Langmuir fitting parameters for competitive data with five different n-alcohol homologs allowed estimates of free energy values per methylene linkage, which were in agreement with previously reported values. Also obtained from competitive data were relative sorption values for various benzene analogs, indicating that interactions in addition to those stemming from solute hydrophobicity often contribute in driving the overall sorption process. These results have implications for papermaking given the ubiquitous nature and importance of sorption in the process. Copyright 2001 Academic Press.