Hard and soft colloids at fluid interfaces: Adsorption, interactions, assembly & rheology.

Soft microgel particles inherently possess qualities of both polymers as well as particles. We review the similarities and differences between soft microgel particles and stiff colloids at fluid-fluid interfaces. We compare two fundamental aspects of particle-laden interfaces namely the adsorption kinetics and the interactions between adsorbed particles. Although it is well established that the transport of both hard particles and microgels to the interface is driven by diffusion, the analysis of the adsorption kinetics needs reconsideration and a proper equation of state relating the surface pressure to the adsorbed mass should be used. We review the theoretical and experimental investigations into the interactions of particles at the interface. The rheology of the interfacial layers is intimately related to the interactions, and the differences between hard particles and microgels become pronounced. The assembly of particles into the layer is another distinguishing factor that separates hard particles from soft microgel particles. Microgels deform substantially upon adsorption and the stability of a microgel-stabilized emulsion depends on the conformational changes triggered by external stimuli.

[1]  S. Barman,et al.  Simultaneous interfacial rheology and microstructure measurement of densely aggregated particle laden interfaces using a modified double wall ring interfacial rheometer. , 2014, Langmuir : the ACS journal of surfaces and colloids.

[2]  D. Reich,et al.  Interfacial hydrodynamic drag on nanowires embedded in thin oil films and protein layers. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[3]  G. Franks,et al.  The role of particles in stabilising foams and emulsions. , 2008, Advances in colloid and interface science.

[4]  W. Richtering,et al.  Influence of cross-link density on rheological properties of temperature-sensitive microgel suspensions , 2000 .

[5]  Peter Lindner,et al.  Are thermoresponsive microgels model systems for concentrated colloidal suspensions? A rheology and small-angle neutron scattering study. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[6]  J. van der Gucht,et al.  Capillarity-induced ordering of spherical colloids on an interface with anisotropic curvature , 2013, Proceedings of the National Academy of Sciences.

[7]  W. Richtering,et al.  The compressibility of pH-sensitive microgels at the oil-water interface: higher charge leads to less repulsion. , 2014, Angewandte Chemie.

[8]  L. Liggieri,et al.  Effect of nanoparticles on the interfacial properties of liquid/liquid and liquid/air surface layers. , 2006, The journal of physical chemistry. B.

[9]  P. Pieranski,et al.  Two-Dimensional Interfacial Colloidal Crystals , 1980 .

[10]  Justin D. Debord,et al.  Synthesis and characterization of pH-responsive copolymer microgels with tunable volume phase transition temperatures , 2003 .

[11]  Walter Richtering,et al.  Temperature sensitive microgel suspensions: Colloidal phase behavior and rheology of soft spheres , 1999 .

[12]  Thomas G. Mason,et al.  New fundamental concepts in emulsion rheology , 1999 .

[13]  B. Binks,et al.  Stability of oil-in-water emulsions stabilised by silica particles , 1999 .

[14]  P. Cicuta,et al.  On the relation between hierarchical morphology and mechanical properties of a colloidal 2D gel system , 2012 .

[15]  Lenore L. Dai,et al.  Structure of microparticles in solid-stabilized emulsions. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[16]  K. Danov,et al.  Capillary forces between particles at a liquid interface: general theoretical approach and interactions between capillary multipoles. , 2010, Advances in colloid and interface science.

[17]  F. Ortega,et al.  Interfacial microrheology: Particle tracking and related techniques , 2010 .

[18]  V. Schmitt,et al.  Materials based on solid-stabilized emulsions. , 2004, Journal of colloid and interface science.

[19]  H. Kawaguchi,et al.  Thermosensitive pickering emulsion stabilized by poly(N-isopropylacrylamide)-carrying particles. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[20]  Daphne Weihs,et al.  Bio-microrheology: a frontier in microrheology. , 2006, Biophysical journal.

[21]  W. Barnes,et al.  Capillary forces between soft, elastic spheres , 2010 .

[22]  K. Nagayama,et al.  Capillary interactions between particles bound to interfaces, liquid films and biomembranes. , 2000, Advances in colloid and interface science.

[23]  A. Yodh,et al.  Capillary interactions between anisotropic colloidal particles. , 2005, Physical review letters.

[24]  G. Fuller,et al.  Thin film formation of silica nanoparticle/lipid composite films at the fluid-fluid interface. , 2010, Langmuir.

[25]  To Ngai,et al.  Novel emulsions stabilized by pH and temperature sensitive microgels. , 2005, Chemical communications.

[26]  W. Richtering,et al.  Influence of microgel architecture and oil polarity on stabilization of emulsions by stimuli-sensitive core-shell poly(N-isopropylacrylamide-co-methacrylic acid) microgels: Mickering versus Pickering behavior? , 2011, Langmuir : the ACS journal of surfaces and colloids.

[27]  P. Kralchevsky,et al.  Latex-particle-stabilized emulsions of anti-Bancroft type. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[28]  B. Cabane,et al.  Why are hydrophobic/water interfaces negatively charged? , 2012, Angewandte Chemie.

[29]  F. MacKintosh,et al.  Microrheology : Rheology and rheological techniques , 1999 .

[30]  P. Warszyński,et al.  ROLE OF ELECTROSTATIC INTERACTIONS IN PARTICLE ADSORPTION , 1996 .

[31]  T. Emrick,et al.  Adsorption energy of nano- and microparticles at liquid-liquid interfaces. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[32]  A. Law Structure and interactions of colloidal particles at fluid interfaces , 2011 .

[33]  D. Johannsmann,et al.  Long-range attraction between colloidal spheres at the air-water interface: the consequence of an irregular meniscus , 2000, Physical review. E, Statistical physics, plasmas, fluids, and related interdisciplinary topics.

[34]  Hans-Jürgen Butt,et al.  Capillary forces: influence of roughness and heterogeneity. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[35]  D. Zang,et al.  An ellipsometry study of silica nanoparticle layers at the water surface. , 2009, Physical chemistry chemical physics : PCCP.

[36]  J. Vermant,et al.  Weak electrolyte dependence in the repulsion of colloids at an oil-water interface. , 2014, Langmuir : the ACS journal of surfaces and colloids.

[37]  G. Fuller,et al.  Tracking the interfacial dynamics of PNiPAM soft microgels particles adsorbed at the air–water interface and in thin liquid films , 2013, Rheologica Acta.

[38]  D. E. Tambe,et al.  Factors Controlling the Stability of Colloid-Stabilized Emulsions: II. A Model for the Rheological Properties of Colloid-Laden Interfaces , 1994 .

[39]  K. Danov,et al.  Surface pressure isotherm for a monolayer of charged colloidal particles at a water/nonpolar-fluid interface: experiment and theoretical model. , 2014, Langmuir : the ACS journal of surfaces and colloids.

[40]  Günter Brenn,et al.  Interactions between particles with an undulated contact line at a fluid interface: capillary multipoles of arbitrary order. , 2005, Journal of colloid and interface science.

[41]  To Ngai,et al.  Environmental Responsiveness of Microgel Particles and Particle-Stabilized Emulsions , 2006 .

[42]  V. Schmitt,et al.  Water-in-oil emulsions stabilized by water-dispersible poly(N-isopropylacrylamide) microgels: understanding anti-Finkle behavior. , 2011, Langmuir.

[43]  M. C. Stuart,et al.  Equation of state and adsorption dynamics of soft microgel particles at an air-water interface. , 2014, Soft matter.

[44]  D. Weitz,et al.  Tracer microrheology in complex fluids , 1998 .

[45]  K. Kremer,et al.  Fluorescence Correlation Spectroscopy Study of Molecular Probe Diffusion in Polymer Melts , 2009 .

[46]  C. Rao,et al.  Interfacial rheology of an ultrathin nanocrystalline film formed at the liquid/liquid interface. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[47]  David M. Kaz,et al.  Physical ageing of the contact line on colloidal particles at liquid interfaces. , 2012, Nature materials.

[48]  Zbigniew Adamczyk,et al.  Particle adsorption and deposition: role of electrostatic interactions , 2003 .

[49]  J. Vermant,et al.  Heterogeneity of the electrostatic repulsion between colloids at the oil–water interface , 2010 .

[50]  J. Basu,et al.  Interfacial microrheology as a tool to study viscoelastic transitions in nanoconfined soft matter. , 2010, Physical review. E, Statistical, nonlinear, and soft matter physics.

[51]  E. Dickinson Faraday research article. Structure and composition of adsorbed protein layers and the relationship to emulsion stability , 1992 .

[52]  J. Fransaer,et al.  Finite ion-size effects dominate the interaction between charged colloidal particles at an oil-water interface. , 2010, Physical review letters.

[53]  Stephan Barcikowski,et al.  Cytotoxicity and ion release of alloy nanoparticles , 2012, Journal of Nanoparticle Research.

[54]  S. Dietrich,et al.  Dynamics of colloidal particles with capillary interactions. , 2010, Physical review. E, Statistical, nonlinear, and soft matter physics.

[55]  D. Heyes,et al.  Interactions between microgel particles , 2009 .

[56]  Yongjun Zhang,et al.  PNIPAM microgels for biomedical applications: from dispersed particles to 3D assemblies , 2011 .

[57]  M. Kawaguchi,et al.  Surface dilational moduli of latex-particle monolayers spread at air-water interface. , 2013, Journal of colloid and interface science.

[58]  Vinothan N. Manoharan,et al.  Colloidal self-assembly at an interface , 2010 .

[59]  F. Ortega,et al.  Surface rheology: macro- and microrheology of poly(tert-butyl acrylate) monolayers , 2011 .

[60]  D. Langevin,et al.  Influence of interfacial rheology on foam and emulsion properties. , 2000, Advances in colloid and interface science.

[61]  A. R. Bausch,et al.  Electric-field-induced capillary attraction between like-charged particles at liquid interfaces , 2002, Nature.

[62]  E. Furst,et al.  Optical trapping forces for colloids at the oil-water interface. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[63]  D. Langevin,et al.  Effect of particle hydrophobicity on the properties of silica particle layers at the air-water interface. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[64]  V. Starov,et al.  Particle laden fluid interfaces: dynamics and interfacial rheology. , 2014, Advances in colloid and interface science.

[65]  Siyoung Q. Choi,et al.  Interfacial microrheology of DPPC monolayers at the air–water interface , 2011 .

[66]  D. Zang,et al.  Influence of the contact angle of silica nanoparticles at the air–water interface on the mechanical properties of the layers composed of these particles , 2011 .

[67]  Jérôme Bibette,et al.  Emulsions: basic principles , 1999 .

[68]  C. P. Whitby,et al.  Some general features of limited coalescence in solid-stabilized emulsions , 2003, The European physical journal. E, Soft matter.

[69]  M. Ioannidis,et al.  Effects of temperature, pH, and ionic strength on the adsorption of nanoparticles at liquid–liquid interfaces , 2012, Journal of Nanoparticle Research.

[70]  Angus A. Gray-Weale,et al.  Oil/Water interface charged by hydroxide ions and deprotonated fatty acids: a comment. , 2012, Angewandte Chemie.

[71]  A. Yodh,et al.  Wetting and contact lines of micrometer-sized ellipsoids. , 2006, Physical review letters.

[72]  S. Roke,et al.  Surface impurities are not responsible for the charge on the oil/water interface: a comment. , 2012, Angewandte Chemie.

[73]  Force balance of particles trapped at fluid interfaces. , 2006, The Journal of chemical physics.

[74]  E. Guzmán,et al.  Wide-frequency dilational rheology investigation of mixed silica nanoparticle–CTAB interfacial layers , 2011 .

[75]  Curtis W. Frank,et al.  An Interfacial Stress Rheometer To Study Rheological Transitions in Monolayers at the Air-Water Interface , 1999 .

[76]  B. Binks Particles as surfactants—similarities and differences , 2002 .

[77]  L. Torres,et al.  Preparation of o/w emulsions stabilized by solid particles and their characterization by oscillatory rheology , 2007 .

[78]  Pietro Cicuta,et al.  Microrheology: a review of the method and applications. , 2007, Soft matter.

[79]  T. Hellweg,et al.  New “smart” poly(NIPAM) microgels and nanoparticle microgel hybrids: Properties and advances in characterisation , 2009 .

[80]  N. Kovalchuk,et al.  Fast dynamic interfacial tension measurements and dilational rheology of interfacial layers by using the capillary pressure technique , 2012 .

[81]  S. Rice,et al.  Static and dynamic evanescent wave light scattering studies of diblock copolymers adsorbed at the air/water interface , 1993 .

[82]  M. Ioannidis,et al.  Irreversible adsorption-driven assembly of nanoparticles at fluid interfaces revealed by a dynamic surface tension probe. , 2014, Langmuir : the ACS journal of surfaces and colloids.

[83]  M. Oettel,et al.  Charged particles at fluid interfaces as a probe into structural details of a double layer. , 2011, Physical chemistry chemical physics : PCCP.

[84]  L. Tordai,et al.  Time‐Dependence of Boundary Tensions of Solutions I. The Role of Diffusion in Time‐Effects , 1946 .

[85]  V. Prasad,et al.  Two-dimensional to three-dimensional transition in soap films demonstrated by microrheology. , 2009, Physical review letters.

[86]  S. O. Lumsdon,et al.  Influence of Particle Wettability on the Type and Stability of Surfactant-Free Emulsions† , 2000 .

[87]  T. Mayer,et al.  The polymer/colloid duality of microgel suspensions. , 2012, Annual review of physical chemistry.

[88]  R. Miller,et al.  Dilational surface elasticity of spread monolayers of polystyrene microparticles. , 2014, Soft matter.

[89]  P. Wilde,et al.  Proteins and emulsifiers at liquid interfaces. , 2004, Advances in colloid and interface science.

[90]  I. Banerjee,et al.  Micro- and Nanoscale Hydrogel Systems for Drug Delivery and Tissue Engineering , 2009, Materials.

[91]  Lenore L. Dai,et al.  Influences of surfactant and nanoparticle assembly on effective interfacial tensions. , 2008, Physical chemistry chemical physics : PCCP.

[92]  B. A. Rosen,et al.  Microgels as stimuli-responsive stabilizers for emulsions. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[93]  N. Wagner,et al.  Colloidal Suspension Rheology: Frontmatter , 2011 .

[94]  Bernard P. Binks,et al.  Emulsions stabilised solely by colloidal particles , 2003 .

[95]  B. Binks Colloidal particles at liquid interfaces. , 2008, Physical chemistry chemical physics : PCCP.

[96]  F. Stillinger Interfacial Solutions of the Poisson‐Boltzmann Equation , 1961 .

[97]  M. Ioannidis,et al.  Adsorption kinetics of alkanethiol-capped gold nanoparticles at the hexane–water interface , 2011 .

[98]  V. Schmitt,et al.  Pickering emulsions: what are the main parameters determining the emulsion type and interfacial properties? , 2014, Langmuir : the ACS journal of surfaces and colloids.

[99]  W. Richtering,et al.  Poly(N-isopropylacrylamide) microgels at the oil–water interface: adsorption kinetics , 2013 .

[100]  B. Binks,et al.  Inversion of emulsions stabilized solely by ionizable nanoparticles. , 2005, Angewandte Chemie.

[101]  S. Melle,et al.  Pickering emulsions with controllable stability. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[102]  L. Liggieri,et al.  Liquid–liquid interfacial properties of mixed nanoparticle–surfactant systems , 2008 .

[103]  Immersion of charged nanoparticles in a salt solution/air interface. , 2008, The journal of physical chemistry. B.

[104]  S. Sacanna,et al.  Thermodynamically stable pickering emulsions. , 2007, Physical review letters.

[105]  Michael Berhanu,et al.  Aggregation of frictional particles due to capillary attraction. , 2011, Physical review. E, Statistical, nonlinear, and soft matter physics.

[106]  P. Kralchevsky,et al.  On the thermodynamics of particle-stabilized emulsions: curvature effects and catastrophic phase inversion. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[107]  Mukul M. Sharma,et al.  Factors controlling the stability of colloid-stabilized emulsions. IV. evaluating the effectiveness of demulsifiers , 1995 .

[108]  J. S. Pedersen,et al.  Small-angle neutron scattering study of structural changes in temperature sensitive microgel colloids. , 2004, The Journal of chemical physics.

[109]  Johan Sjöblom,et al.  Encyclopedic Handbook of Emulsion Technology , 2001 .

[110]  J. He,et al.  On the kinetics of nanoparticle self-assembly at liquid/liquid interfaces. , 2007, Physical chemistry chemical physics : PCCP.

[111]  D. Ross,et al.  Experimental and Theoretical Analysis of the Limited Coalescence Process: Stepwise Limited Coalescence , 1995 .

[112]  T. P. Lockhart,et al.  Pickering Emulsions: Interfacial Tension, Colloidal Layer Morphology, and Trapped-Particle Motion , 2003 .

[113]  Strain-rate frequency superposition: a rheological probe of structural relaxation in soft materials. , 2006, Physical review letters.

[114]  H. Diamant,et al.  Dynamic surface tension of aqueous solutions of ionic surfactants: role of electrostatics. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[115]  V. N. Paunov,et al.  Compression and Structure of Monolayers of Charged Latex Particles at Air/Water and Octane/Water Interfaces , 2000 .

[116]  Roie Shlomovitz,et al.  Measurement of monolayer viscosity using noncontact microrheology. , 2013, Physical review letters.

[117]  S. Armes,et al.  Is latex surface charge an important parameter for foam stabilization? , 2007, Langmuir : the ACS journal of surfaces and colloids.

[118]  L. Mahadevan,et al.  The “Cheerios effect” , 2005 .

[119]  T. Waigh Microrheology of complex fluids , 2005 .

[120]  C. Vega,et al.  Freezing transition and interaction potential in monolayers of microparticles at fluid interfaces. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[121]  J. Vermant,et al.  Interfacial layers of stimuli-responsive poly-(N-isopropylacrylamide-co-methacrylicacid) (PNIPAM-co-MAA) microgels characterized by interfacial rheology and compression isotherms. , 2010, Physical chemistry chemical physics : PCCP.

[122]  B. Vincent,et al.  Microgel particles as model colloids : theory, properties and applications , 1999 .

[123]  A. Hurd The electrostatic interaction between interfacial colloidal particles , 1985 .

[124]  W. Richtering,et al.  Unraveling the 3D localization and deformation of responsive microgels at oil/water interfaces: a step forward in understanding soft emulsion stabilizers. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[125]  Regine von Klitzing,et al.  Disjoining pressure in thin liquid foam and emulsion films—new concepts and perspectives , 2003 .

[126]  J. Vermant,et al.  Micro and macrorheology at fluid-fluid interfaces. , 2014, Soft matter.

[127]  K. Danov,et al.  Particles with an Undulated Contact Line at a Fluid Interface: Interaction between Capillary Quadrupoles and Rheology of Particulate Monolayers , 2001 .

[128]  M. Michel,et al.  Composite interfacial layers containing micro-size and nano-size particles. , 2006, Advances in colloid and interface science.

[129]  V. Schmitt,et al.  Soft microgels as Pickering emulsion stabilisers: role of particle deformability , 2011 .

[130]  D. Grier,et al.  Methods of Digital Video Microscopy for Colloidal Studies , 1996 .

[131]  W. Richtering Responsive emulsions stabilized by stimuli-sensitive microgels: emulsions with special non-Pickering properties. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[132]  F. Monroy,et al.  Molecular weight dependence of the shear rheology of poly(methyl methacrylate) Langmuir films: a comparison between two different rheometry techniques. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[133]  P. Chaikin,et al.  Ion partitioning at the oil-water interface as a source of tunable electrostatic effects in emulsions with colloids. , 2007, Physical chemistry chemical physics : PCCP.

[134]  D. van den Ende,et al.  Capillary forces between spherical particles floating at a liquid-liquid interface. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[135]  W. Richtering,et al.  Emulsions stabilized by stimuli-sensitive poly(N-isopropylacrylamide)-co-methacrylic acid polymers: microgels versus low molecular weight polymers. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[136]  F. Monroy,et al.  Fourier-transform rheology of polymer Langmuir monolayers: analysis of the non-linear and plastic behaviors. , 2006, Advances in colloid and interface science.

[137]  E. Dickinson Hydrocolloids as emulsifiers and emulsion stabilizers , 2009 .

[138]  D. Langevin,et al.  Foams stabilised by mixtures of nanoparticles and oppositely charged surfactants: relationship between bubble shrinkage and foam coarsening. , 2014, Soft matter.

[139]  D. Langevin,et al.  Particle-stabilised foams: an interfacial study , 2009 .

[140]  M. Oettel,et al.  Colloidal particles at fluid interfaces: Effective interactions, dynamics and a gravitation–like instability , 2013 .

[141]  Jayant P. Rane,et al.  Adsorption kinetics of asphaltenes at the oil-water interface and nanoaggregation in the bulk. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[142]  Marcus,et al.  Self-diffusion in dilute quasi-two-dimensional hard sphere suspensions: Evanescent wave light scattering and video microscopy studies. , 1996, Physical review. E, Statistical physics, plasmas, fluids, and related interdisciplinary topics.

[143]  S. O. Lumsdon,et al.  Pickering Emulsions Stabilized by Monodisperse Latex Particles: Effects of Particle Size , 2001 .

[144]  Mukul M. Sharma,et al.  Factors Controlling the Stability of Colloid-Stabilized Emulsions: I. An Experimental Investigation , 1995 .

[145]  T C Lubensky,et al.  Rheological microscopy: local mechanical properties from microrheology. , 2003, Physical review letters.

[146]  W. Ramsden,et al.  Separation of solids in the surface-layers of solutions and ‘suspensions’ (observations on surface-membranes, bubbles, emulsions, and mechanical coagulation).—Preliminary account , 1904, Proceedings of the Royal Society of London.

[147]  Reinhard Miller,et al.  Dilational and shear rheology of adsorption layers at liquid interfaces , 1996 .

[148]  Hui Zhao,et al.  The influence of particle size and residual charge on electrostatic interactions between charged colloidal particles at an oil-water interface. , 2014, Soft matter.

[149]  I. Hénaut,et al.  Adsorption Kinetics of Asphaltenes at Liquid Interfaces , 2002 .

[150]  S. Botchway,et al.  Measurement of long-range repulsive forces between charged particles at an oil-water interface. , 2002, Physical review letters.

[151]  D. E. Tambe,et al.  The effect of colloidal particles on fluid-fluid interfacial properties and emulsion stability , 1994 .

[152]  D. Zang,et al.  Viscoelastic properties of silica nanoparticle monolayers at the air-water interface , 2010, The European physical journal. E, Soft matter.