Lichao Gao

Bio: Lichao Gao is an academic researcher from University of Massachusetts Amherst. The author has contributed to research in topics: Contact angle & Wetting. The author has an hindex of 17, co-authored 18 publications receiving 3849 citations.

Contact angle hysteresis explained

Abstract: A view of contact angle hysteresis from the perspectives of the three-phase contact line and of the kinetics of contact line motion is given. Arguments are made that advancing and receding are discrete events that have different activation energies. That hysteresis can be quantified as an activation energy by the changes in interfacial area is argued. That this is an appropriate way of viewing hysteresis is demonstrated with examples.

How Wenzel and Cassie were wrong

Abstract: We argue using experimental data that contact lines and not contact areas are important in determining wettability. Three types of two-component surfaces were prepared that contain "spots" in a surrounding field: a hydrophilic spot in a hydrophobic field, a rough spot in a smooth field, and a smooth spot in a rough field. Water contact angles were measured within the spots and with the spot confined to within the contact line of the sessile drop. Spot diameter and contact line diameter were varied. All of the data indicate that contact angle behavior (advancing, receding, and hysteresis) is determined by interactions of the liquid and the solid at the three-phase contact line alone and that the interfacial area within the contact perimeter is irrelevant. The point is made that Wenzel's and Cassie's equations are valid only to the extent that the structure of the contact area reflects the ground state energies of contact lines and the transition states between them.

The “Lotus Effect” Explained: Two Reasons Why Two Length Scales of Topography Are Important

Abstract: Surfaces containing 4 × 8 × 40 μm staggered rhombus posts were hydrophobized using two methods. One, using a dimethyldichlorosilane reaction in the vapor phase, introduces a smooth modified layer, and the other, a solution reaction using methyltrichlorosilane, imparts a second (nanoscopic) length scale of topography. The smooth modified surface exhibits contact angles of θA/θR = 176°/156°. Arguments are made that the pinning of the receding contact line by the post tops (with θA/θR = 104°/103°) is responsible for the hysteresis. The second level of topography raises the contact angles of the post tops and the macroscopic sample to θA/θR = >176°/>176° and eliminates hysteresis. The increase in Laplace pressure due to the increase in the advancing contact angle of the post tops is a second reason that two length scales of topography are important.

A Perfectly Hydrophobic Surface (θA/θR = 180°/180°)

Abstract: A perfectly hydrophobic surface with both advancing and receding water contact angles of 180° was prepared using a facile method on a silicon wafer. Phase separation of a toluene-swollen covalently attached methylsilicone results in a nanoscale network structure that is responsible for the superhydrophobicity. A method for testing extreme hydrophobicity was devised to distinguish between surfaces exhibiting contact angles of 180 and 179°.

Wetting 101 degrees.

Abstract: We review our 2006-2009 publications on wetting and superhydrophobicity in a manner designed to serve as a useful primer for those who would like to use the concepts of this field. We demonstrate that the 1D (three-phase, solid/liquid/vapor) contact line perspective is simpler, more intuitive, more useful, and more consistent with facts than the disproved but widely held-to-be-correct 2D view. We give an explanation of what we believe to be the reason that the existing theoretical understanding is wrong and argue that the teaching of surface science over the last century has led generations of students and scientists to a misunderstanding of the wetting of solids by liquids. We review our analyses of the phenomena of contact angle hysteresis, the lotus effect, and perfect hydrophobicity and suggest that needlessly complex theoretical understandings, incorrect models, and ill-defined terminology are not useful and can be destructive.

Designing Superoleophobic Surfaces

Abstract: Understanding the complementary roles of surface energy and roughness on natural nonwetting surfaces has led to the development of a number of biomimetic superhydrophobic surfaces, which exhibit apparent contact angles with water greater than 150 degrees and low contact angle hysteresis. However, superoleophobic surfaces-those that display contact angles greater than 150 degrees with organic liquids having appreciably lower surface tensions than that of water-are extremely rare. Calculations suggest that creating such a surface would require a surface energy lower than that of any known material. We show how a third factor, re-entrant surface curvature, in conjunction with chemical composition and roughened texture, can be used to design surfaces that display extreme resistance to wetting from a number of liquids with low surface tension, including alkanes such as decane and octane.

Wetting and Spreading

Abstract: Wetting phenomena are ubiquitous in nature and technology. A solid substrate exposed to the environment is almost invariably covered by a layer of fluid material. In this review, the surface forces that lead to wetting are considered, and the equilibrium surface coverage of a substrate in contact with a drop of liquid. Depending on the nature of the surface forces involved, different scenarios for wetting phase transitions are possible; recent progress allows us to relate the critical exponents directly to the nature of the surface forces which lead to the different wetting scenarios. Thermal fluctuation effects, which can be greatly enhanced for wetting of geometrically or chemically structured substrates, and are much stronger in colloidal suspensions, modify the adsorption singularities. Macroscopic descriptions and microscopic theories have been developed to understand and predict wetting behavior relevant to microfluidics and nanofluidics applications. Then the dynamics of wetting is examined. A drop, placed on a substrate which it wets, spreads out to form a film. Conversely, a nonwetted substrate previously covered by a film dewets upon an appropriate change of system parameters. The hydrodynamics of both wetting and dewetting is influenced by the presence of the three-phase contact line separating "wet" regions from those that are either dry or covered by a microscopic film only. Recent theoretical, experimental, and numerical progress in the description of moving contact line dynamics are reviewed, and its relation to the thermodynamics of wetting is explored. In addition, recent progress on rough surfaces is surveyed. The anchoring of contact lines and contact angle hysteresis are explored resulting from surface inhomogeneities. Further, new ways to mold wetting characteristics according to technological constraints are discussed, for example, the use of patterned surfaces, surfactants, or complex fluids.

Antifouling coatings: recent developments in the design of surfaces that prevent fouling by proteins, bacteria, and marine organisms.

Abstract: The major strategies for designing surfaces that prevent fouling due to proteins, bacteria, and marine organisms are reviewed. Biofouling is of great concern in numerous applications ranging from biosensors to biomedical implants and devices, and from food packaging to industrial and marine equipment. The two major approaches to combat surface fouling are based on either preventing biofoulants from attaching or degrading them. One of the key strategies for imparting adhesion resistance involves the functionalization of surfaces with poly(ethylene glycol) (PEG) or oligo(ethylene glycol). Several alternatives to PEG-based coatings have also been designed over the past decade. While protein-resistant coatings may also resist bacterial attachment and subsequent biofilm formation, in order to overcome the fouling-mediated risk of bacterial infection it is highly desirable to design coatings that are bactericidal. Traditional techniques involve the design of coatings that release biocidal agents, including antibiotics, quaternary ammonium salts (QAS), and silver, into the surrounding aqueous environment. However, the emergence of antibiotic- and silver-resistant pathogenic strains has necessitated the development of alternative strategies. Therefore, other techniques based on the use of polycations, enzymes, nanomaterials, and photoactive agents are being investigated. With regard to marine antifouling coatings, restrictions on the use of biocide-releasing coatings have made the generation of nontoxic antifouling surfaces more important. While considerable progress has been made in the design of antifouling coatings, ongoing research in this area should result in the development of even better antifouling materials in the future.

Wetting and Roughness

Abstract: We discuss in this review how the roughness of a solid impacts its wettability. We see in particular that both the apparent contact angle and the contact angle hysteresis can be dramatically affected by the presence of roughness. Owing to the development of refined methods for setting very well-controlled micro- or nanotextures on a solid, these effects are being exploited to induce novel wetting properties, such as spontaneous filmification, superhydrophobicity, superoleophobicity, and interfacial slip, that could not be achieved without roughness.

Candle Soot as a Template for a Transparent Robust Superamphiphobic Coating

Abstract: Coating is an essential step in adjusting the surface properties of materials. Superhydrophobic coatings with contact angles greater than 150° and roll-off angles below 10° for water have been developed, based on low-energy surfaces and roughness on the nano- and micrometer scales. However, these surfaces are still wetted by organic liquids such as surfactant-based solutions, alcohols, or alkanes. Coatings that are simultaneously superhydrophobic and superoleophobic are rare. We designed an easily fabricated, transparent, and oil-rebounding superamphiphobic coating. A porous deposit of candle soot was coated with a 25-nanometer-thick silica shell. The black coating became transparent after calcination at 600°C. After silanization, the coating was superamphiphobic and remained so even after its top layer was damaged by sand impingement.