Co-reporter:Bingqian Zheng, Surita R. Bhatia
Colloids and Surfaces A: Physicochemical and Engineering Aspects 2017 Volume 520(Volume 520) pp:
Publication Date(Web):5 May 2017
DOI:10.1016/j.colsurfa.2017.02.027
•Dynamics of colloidal clay dispersions with adsorbing polymer chains are explored via dynamic light scattering.•Results show diffusive behavior for both fast and slow relaxation processes at early aging times.•DLS consistent with formation of large particle clusters at early aging times.We report the dynamics of aqueous dispersions of the disk-shaped colloidal clay laponite® with poly(ethylene oxide) (PEO) chains of moderate molecular weight, explored via angle-dependent dynamic light scattering (DLS) and rheology. The PEO chains adsorb onto the laponite® surfaces, causing interesting dynamic behavior, including transitions from arrested states to liquid states as the concentration and molecular weight of PEO is increased. This re-entrant behavior has been attributed to formation of particle clusters induced free PEO chains. Our DLS results are consistent with a slow diffusive dynamic process, suggesting the formation of large particle clusters, in samples at aging times <75 days. By contrast to behavior observed in laponite® dispersions with a non-adsorbing polymer, poly(acrylic acid) (PAA), diffusion coefficients of these clusters in the laponite®-PEO systems continue to decrease with aging time until samples reach an arrested state.Download high-res image (135KB)Download full-size image
Co-reporter:Wendy L. Hom, Surita R. Bhatia
Polymer 2017 Volume 109() pp:170-175
Publication Date(Web):27 January 2017
DOI:10.1016/j.polymer.2016.12.058
•A nanocomposite of alginate, clay, and temperature-sensitive copolymer is reported.•Addition of PEO-PPO-PEO greatly enhances storage moduli of alginate-clay gels.•Varying composition provides a tool for tuning mechanical properties of the gel.The mechanical properties of a new type of nanocomposite gel, consisting of varying concentrations of the biopolymer alginate and the synthetic clay Laponite®, together with the temperature-sensitive copolymer poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO, trade name Pluronic® F127), are reported. These “ALP” gels (alginate-Laponite®-Pluronic®) were prepared and studied using rheology. Gels with multiple networks and gelation mechanisms have been explored as one strategy to strengthen and stiffen conventional hydrogels, which usually consist of a single polymer network. This work shows that the ALP gels exhibit significantly higher storage and loss modulus (G′, G″) values than gels composed of only alginate and Laponite®. Moreover, the interaction between the components appears to be synergistic; that is, the resulting multicomponent hydrogels are much more elastic than the additive effects of individual components. For example, the G′ of one series of the nanocomposite gels containing F127 Pluronic® experiences two orders of magnitude enhancement compared to its respective control containing only alginate and Laponite®. Furthermore, the ALP gels show a 20-40x enhancement in storage modulus, with values as high as 10,000–20,000 Pa, over the 30–55 °C temperature range. The large degree of enhancement in the storage modulus of the ALP gels with addition of Pluronic® is quite remarkable, compared to alginate-Laponite® gels on their own at comparable concentrations and temperatures, which form relatively weak gels. These results provide a simple strategy for significantly increasing the mechanical properties of polymer hydrogels used in biomaterials applications.
Co-reporter:Sunita Srivastava;Suhasini Kishore;Suresh Narayanan;Alec R. Sy;Surita R. Bhatia
Journal of Polymer Science Part B: Polymer Physics 2016 Volume 54( Issue 7) pp:752-760
Publication Date(Web):
DOI:10.1002/polb.23973
ABSTRACT
We present an X-ray photon correlation spectroscopy (XPCS) study of dynamic transitions in an anisotropic colloid-polymer dispersion with multiple arrested states. The results provide insight into the mechanism for formation of repulsive glasses, attractive glasses, and networked gels of colloids with weakly adsorbing polymer chains. In the presence of adsorbing polymer chains, we observe three distinct regimes: a state with slow dynamics consisting of finite particles and clusters, for which interparticle interactions are predominantly repulsive; a second dynamic regime occurring above the saturation concentration of added polymer, in which small clusters of nanoparticles form via a short-range depletion attraction; and a third regime above the overlap concentration in which dynamics of clusters are independent of polymer chain length. The observed complex dynamic state diagram is primarily governed by the structural reorganization of a nanoparticle cluster and polymer chains at the nanoparticle-polymer surface and in the concentrated medium, which in turn controls the dynamics of the dispersion. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 752–760
Co-reporter:Suhasini Kishore, Sunita Srivastava, Surita R. Bhatia
Polymer 2016 Volume 105() pp:461-471
Publication Date(Web):22 November 2016
DOI:10.1016/j.polymer.2016.07.091
•Microstructural changes in laponite®-polymer systems are reported using USAXS.•Characteristic sizes vary with chain length, concentration and colloid fraction.•Disks with long chains (Rg/R ≫ 1) result in the formation of large scale structures.•No large scale structure is observed for disks with smaller chains (Rg/R < 1).•Formation of intermediate-sized structures depend on electrostatics and colloid fraction.Structural arrest in an aging colloid-polymer mixture of charged colloidal disks and weakly interacting polymers is primarily governed by the spatial arrangement of microstructural domains in the system. Here we present a detailed ultra-small angle x-ray scattering (USAXS) study of the polymer induced microstructural changes occurring in systems containing laponite® and poly(ethylene oxide) (PEO). Laponite® suspensions are known to transition from a homogeneous fluid to an arrested phase as a function of time. USAXS results show that when polymer chains are added to this colloidal system, the microstructural changes are found to depend on (i) polymer-colloid size ratio, (ii) particle and polymer concentration. Large length scale structures (300–1000 nm) of non-uniformly varying size appear with increasing concentration of high molecular weight PEO (Rg/R ∼ 2.4). However with shorter PEO chains (Rg/R ∼ 0.5), we observe the formation of intermediary structures with a characteristic length scale of 50–60 nm. With increasing particle concentration, we observe a more compact structure for the high molecular weight PEO and no signature of a percolating network in the case of the low molecular PEO. We believe that these results add to our understanding of the complex aging behavior of clay-polymer systems.
Co-reporter:Xiao Liu;Surita R. Bhatia
Polymers for Advanced Technologies 2015 Volume 26( Issue 7) pp:874-879
Publication Date(Web):
DOI:10.1002/pat.3514
Hydrogels of the synthetic clay Laponite® and Laponite®-poly (ethylene oxide) (PEO) have long been studied as model systems to understand fundamental aspects of colloidal disks and colloid-polymer systems. More recently, these systems have been explored for a variety of biomedical applications. However, there is limited information in the literature on the fundamental properties of Laponite and Laponite-polymer gels at pH < 9. Here, we report the rheological behavior of Laponite and Laponite-PEO systems at biologically relevant conditions (e.g. physiological pH and ionic strength) and examine the effect of phosphate-buffered saline on the properties of the gel. Our results show that the elastic modulus of both Laponite and Laponite-PEO gels increases dramatically, in some cases by one order of magnitude or more, after immersing gels in phosphate-buffered saline. This may be due to an enhanced edge–face interaction between particles in buffered solutions, which would promote a long-lasting network structure of clay particles. These results are relevant to the design of clay-polymer gels and nanocomposites hydrogels for biomaterials applications. Copyright © 2015 John Wiley & Sons, Ltd.
Co-reporter:Suhasini Kishore, Yingzhu Chen, Pradeep Ravindra, Surita. R. Bhatia
Colloids and Surfaces A: Physicochemical and Engineering Aspects 2015 Volume 482() pp:585-595
Publication Date(Web):5 October 2015
DOI:10.1016/j.colsurfa.2015.06.056
•Dynamics of polymer–clay dispersions are reported at varying polymer concentration.•Colloidal re-entrant behavior is observed when the polymer medium is dilute.•A second critical transition is observed at higher polymer concentrations.•Dispersions at the second critical exhibit slower aging dynamics.Particle-scale rearrangements occurring in mixtures containing anisotropic disk-shaped colloids and polymers often lead to the development of unusual viscoelastic features that can play a crucial role in applications. Here, we report the early aging behavior of a series of mixtures containing laponite, a model disk-shaped colloid, and poly(ethylene oxide) (PEO) chains of three different molecular weights, 35 kg/mol, 20 kg/mol and 4.6 kg/mol. The concentrations of PEO were varied within their respective dilute and semi-dilute un-entangled regions. Rheological experiments were utilized to describe the effects of chain number and length on the macroscopic behavior of suspensions and dynamic light scattering (DLS) was used as a tool to establish a correlation between the macroscopic behavior and dynamics seen at smaller length scales. For dilute concentrations of PEO, the rheology is consistent with a glass–liquid–glass phase transition, a trend that resembles the re-entrant behavior observed in many colloid–polymer systems. However, in more concentrated PEO solutions, samples re-stabilize and remain stable for a longer period of time. Interestingly, at lower length scales the stabilization that is seen in the concentrated region is characterized by an increase in the first and second relaxation timescales, suggesting that tightly bound stable clusters diffuse through the medium. To our knowledge, this type of behavior in an anisotropic colloid–polymer system has not been previously observed.
Co-reporter:Erika M. Saffer, Melissa A. Lackey, David M. Griffin, Suhasini Kishore, Gregory N. Tew and Surita R. Bhatia
Soft Matter 2014 vol. 10(Issue 12) pp:1905-1916
Publication Date(Web):07 Jan 2014
DOI:10.1039/C3SM52395K
Polymer networks are critically important for numerous applications including soft biomaterials, adhesives, coatings, elastomers, and gel-based materials for energy storage. One long-standing challenge these materials present lies in understanding the role of network defects, such as dangling ends and loops, developed during cross-linking. These defects can negatively impact the physical, mechanical, and transport properties of the gel. Here we report chemically cross-linked poly(ethylene glycol) (PEG) gels formed through a unique cross-linking scheme designed to minimize defects in the network. The highly resilient mechanical properties of these systems (discussed in a previous publication) [J. Cui, M. A. Lackey, A. E. Madkour, E. M. Saffer, D. M. Griffin, S. R. Bhatia, A. J. Crosby and G. N. Tew, Biomacromolecules, 2012, 13, 584–588], suggests that this cross-linking technique yields more homogeneous network structures. Four series of gels were formed based on chains of 35000 g mol−1, (35k), 12000 g mol−1 (12k) g mol−1, 8000 g mol−1 (8k) and 4000 g mol−1 (4k) PEG. Gels were synthesized at five initial polymer concentrations ranging from 0.077 g mL−1 to 0.50 g mL−1. Small-angle neutron scattering (SANS) was utilized to investigate the network structures of gels in both D2O and d-DMF. SANS results show the resulting network structure is dependent on PEG length, transitioning from a more homogeneous network structure at high molecular weight PEG to a two phase structure at the lowest molecular weight PEG. Further investigation of the transport properties inherent to these systems, such as diffusion, will aid to further confirm the network structures.
Co-reporter:Joseph C. White;Megan E. Godsey;Surita R. Bhatia
Polymers for Advanced Technologies 2014 Volume 25( Issue 11) pp:1242-1246
Publication Date(Web):
DOI:10.1002/pat.3296
A major limitation of current soft biomaterials for tissue engineering and cell encapsulation is inadequate transport of oxygen to cells and tissues. Oxygen transport is a challenge in nearly all aqueous hydrogel biomaterials. Here, we report the effective diffusivity of oxygen in alginate-based hydrogels containing stable perfluorocarbon (PFC) emulsions. Incorporation of 7% perfluorooctyl bromide into the alginate gels was found to increase oxygen permeability by a factor of three. Our work also demonstrates that the increase in oxygen transport is largely due to improved oxygen solubility in PFC-containing gels. Although promising, this improved oxygen transport comes with a trade-off in terms of mechanical robustness. This must be carefully considered in future development of PFC-containing hydrogels for biomedical devices. Copyright © 2014 John Wiley & Sons, Ltd.
Co-reporter:Whitney L. Stoppel;Joseph C. White;Sarena D. Horava;Anna C. Henry;Susan C. Roberts;Surita R. Bhatia
Journal of Biomedical Materials Research Part B: Applied Biomaterials 2014 Volume 102( Issue 4) pp:877-884
Publication Date(Web):
DOI:10.1002/jbm.b.33070
Abstract
Terminal, or postprocessing, sterilization of composite biomaterials is crucial for their use in wound healing and tissue-engineered devices. Recent research has focused on optimizing traditional biomaterial formulations to create better products for commercial and academic use which incorporate hydrophobic compounds or secondary gel networks. To use a hydrogel in a clinical setting, terminal sterilization is necessary to ensure patient safety. Lyophilization, gamma-irradiation, and ethylene oxide treatment all have negative consequences when applied to alginate scaffolds for clinical use. Here, we aim to find alternative terminal sterilization methods for alginate and alginate-based composite hydrogels which maintain the structure of composite alginate networks for use in biomedical applications. A thorough investigation of the effect of common sterilization methods on swollen alginate-based hydrogels has not been reported and therefore, this work examines autoclaving, ethanol washing, and ultraviolet light as sterilization techniques for alginate and alginate/Pluronic® F68 composite hydrogels. Preservation of structural integrity is evaluated using shear rheology and analysis of water retention, and efficacy of sterilization is determined via bacterial persistence within the hydrogel. Results indicate that ethanol sterilization is the best method of those investigated because ethanol washing results in minimal effects on mechanical properties and water retention and eliminates bacterial persistence. Furthermore, this study suggests that ethanol treatment is an efficacious method for terminally sterilizing interpenetrating networks or other composite hydrogel systems. © 2013 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 102B: 877–884, 2014.
Co-reporter:Joseph C. White, Erika M. Saffer, and Surita R. Bhatia
Biomacromolecules 2013 Volume 14(Issue 12) pp:
Publication Date(Web):October 22, 2013
DOI:10.1021/bm401373j
Stimuli-responsive hydrogels with high strength and toughness have received significant interest in recent years. Here, we report thermally active composite hydrogels comprising alginate and one of two poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymers. Temperature-sensitive structural and mechanical changes are probed using calorimetry, neutron scattering, shear rheology, unconfined compression, and fracture. Below the lower gelation temperature, LGT, the mechanical properties are dominated by alginate. As the LGT is reached, the contribution of PEO-PPO-PEO to the mechanical properties is activated, resulting in order-of-magnitude increases in elastic modulus. Under compression, we show the evolution of plasticity for the composite hydrogels as the LGT is approached and surpassed, resulting in dramatic increases in fracture stress compared to neat alginate hydrogels. Plasticity was observed above the LGT and may be attributed to restructuring from the sliding of packed micelles and strain-hardening due to stress concentration on alginate cross-links and junction zones, ultimately leading to fracture.
Co-reporter:Anand K. Atmuri and Surita R. Bhatia
Langmuir 2013 Volume 29(Issue 10) pp:3179-3187
Publication Date(Web):February 18, 2013
DOI:10.1021/la304062r
Formation of stable, dense nanoparticle clusters is interesting due to both the underlying physics and use of nanoclusters in applications such as digital printing, imaging and biosensing, and energy storage. Here, we explore formation of nanoparticle clusters in dispersions of the model disk-shaped colloid Laponite. Under basic conditions, the model disk-shaped colloid Laponite forms a repulsive glass in water due to strong electrostatic interactions. Addition of a nonadsorbing polymer, the sodium salt of poly(acrylic acid) (PAA), induces a depletion attraction between particles. Through dynamic light scattering (DLS) and rheology, we see that the polymer initially causes a transition from the glassy phase to an ergodic fluid. Samples at higher particle concentration age to a weak nonergodic state, while samples at lower Laponite remain as fluids. As the strength of attraction between particles is increased, we find an increase in the fast relaxation time measured via dynamic light scattering (e.g., slowing of the short-time diffusion of a single particle). While this may in part be attributed to an increase in the ionic strength, the aging behavior and glass-fluid transition we observe appear to be unique to the presence of polymer, suggesting that depletion plays an important role. DLS data on the fluid samples were consistent with two widely spaced diffusive relaxation modes, corresponding to motion of single particles and motion of large clusters, although other slow dynamic processes may be present. On the basis of the estimated volume fraction and depletion attraction, we believe the Laponite-PAA suspensions to be either fluids of stable clusters or glasses of clusters, although it is possible that the nonergodic state we observe is instead a gel of clusters. Additionally, the cluster size was found to be stable for at least 120 days and was directly related to the polymer concentration. This may serve as an important means of tuning cluster size in products and processes based on dense nanoparticle assemblies.
Co-reporter:Anand K. Atmuri, Michael A. Henson, Surita R. Bhatia
Colloids and Surfaces A: Physicochemical and Engineering Aspects 2013 Volume 436() pp:325-332
Publication Date(Web):5 September 2013
DOI:10.1016/j.colsurfa.2013.07.002
•Formation of stable finite-sized clusters observed in charged colloidal dispersions.•A population balance equation (PBE) model was developed to capture this phenomenon.•Model successfully predicts aggregation regimes and final aggregate size.Forming stable clusters or aggregates of nanoparticles is of interest in a number of emerging applications. While formation of unstable fractal aggregates and flocs has been well-studied with both experiments and theory, the conditions that lead to stable, finite-sized clusters is not as well understood. Here, we present an integrated experimental and modeling study to explore aggregation in concentrated attractive colloidal suspensions. A population balance equation (PBE) model is used to predict the aggregation dynamics of quiescent colloidal suspensions. A DLVO (Derjaguin–Landau–Verwey–Overbeek) type potential is used to describe the interparticle potential, with attractive interactions arising from van der Waals forces and long-range repulsive interactions caused by electrostatics. The PBE model includes a full calculation of stability ratio variations as a function of aggregate size, such that the energy barrier increases with increasing size. As the ionic strength is decreased, the model predicts three regimes of behavior: uncontrolled aggregation into large flocs, controlled aggregation into stable clusters, and no aggregation. The model is tested experimentally using latex particles at different salt concentrations and particle concentrations. When the Hamaker constant and surface potential are fit to aggregate size measurements collected at one salt concentration, the model accurately predicts the final mean aggregate size and regimes of aggregation at other salt concentrations and the same particle concentration. This result suggests that van der Waals and electrostatic forces are the dominant particle interactions in determining the final aggregate state. The mean aggregate size and aggregation regimes at different particle concentrations could be accurately predicted by adjusting the surface potential. This parameter adjustment is consistent with the expectation that increasing colloid weight fractions cause aggregates to have a more fractal nature and hence have a lower effective repulsion. However, the model predicts much faster aggregation rates than what are observed experimentally. This discrepancy may be due to hydrodynamic effects or another slow dynamical process which is not accounted for in the model. Nevertheless, this study presents the first PBE model that can successfully predict stable aggregate size and aggregation regimes of charged colloidal particles over a range of salt concentrations and particle concentrations.