The wettability of industrial surfaces: Contact angle measurements and thermodynamic analysis

The water wettability of surfaces, whose surface conditions are comparable to those used in heat and mass transfer equipment, has been investigated experimentally and theoretically.In the first part, results of contact angle measurements for water on metal and non-metal surfaces are reported. With hydrophobic non-metal surfaces (e.g. Teflon) water forms large advancing and receding contact angles, and the contact angle hysteresis is small. Surface contamination is of minor influence. Hydrophilic metal surfaces (copper, nickel) are completely wetted by water only if the surfaces are extremely clean. Surface contamination reduces the wettability drastically. Under most industrial conditions advancing contact angles between 40° and 80°, and receding contact angles smaller than 20° can be expected, and the contact angle hysteresis is large. Corrosion can enhance the water wettability.In the second part, a thermodynamic analysis of the wetting of heterogeneous surfaces is presented. Equilibrium considerations for a model surface consisting of two components of different wettability provide the advancing and receding contact angles for a heterogeneous surface as a function of the equilibrium contact angles, surface fractions, and the distribution function of the two components. The advancing and receding contact angles as well as all the intermediate contact angles indicate metastable states of equilibrium of the system. The results of the model calculations give a physically based explanation for the characteristic wetting behaviour of industrial surfaces found experimentally.     

Ice adhesion on different microstructure superhydrophobic aluminum surfaces

The adhesion of ice to high -voltage overhead transmission lines should be small to ensure ease of ice shedding under small external forces. In this work, we studied the influence of the microstructure of superhydrophobic surfaces on the strength of ice adhesion at a working temperature of ?6?°C. Compared to a bare aluminum surface, the microstructure superhydrophobic aluminum surfaces did decrease ice adhesion strength. The superhydrophobic aluminum surfaces with a larger number of micro-holes produced the lowest strength of ice adhesion; its ice adhesion strength was ～163.8 times lower than that for the bare aluminum samples. Furthermore, such microstructure aluminum surfaces had water contact angles larger than 150° and water sliding angles of less than 8.2° even at a working temperature of ?6?°C. The low values of the ice adhesion strength of the above samples were mainly attributed to the superhydrophobic property, which was obtained by creating a structure of micro-nanoscale holes on the aluminum surface after treatment with a low- surface-energy fluoroalkylsilane (FAS).     

Improvement of interfacial adhesion between PBO fibers and cyanate ester matrix

Poly(p‐phenylene benzobisoxazole) (PBO) fibers were activated by the horseradish peroxidases (HRP) and then treated by 3‐Glycidoxypropyltrimethoxysilane (KH‐560) to improve the wettability and the interfacial adhesion between PBO fibers and cyanate ester matrix. The chemical compositions of PBO fibers were characterized and analyzed by FTIR and XPS. Surface morphologies of PBO fibers were examined by SEM. The wettability of PBO fibers was evaluated by the dynamic contact angle analysis test. The mechanical properties were evaluated by tensile strength and interfacial shear strength, respectively. The results demonstrated that hydroxyl groups and epoxy groups were introduced onto the surface of PBO fibers during the treatments. These treatments can effectively improve the wettability and adhesion of PBO fibers. The surface free energy of PBO fibers was increased from 31.1 mN/m to 55.2 mN/m, and the interfacial adhesion between PBO fiber and cyanate ester resin was improved to 10.77 MPa. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40204.     

Effect of sizing on interfacial adhesion of commercial high strength carbon fiber‐reinforced resin composites

The influence of sizing agent on interfacial shear strength (IFSS) of carbon fiber/epoxy (CF/EP) and carbon fiber/bismaleimide (CF/BMI) was investigated. Since sizing agent can alter physicochemical properties of CF surface, possible affecting factors, including sizing reactivity, chemical reactions between sizing and resin, wettability of fiber with resin, fiber surface roughness, and chemical composition of fiber surface, were discussed. It is found that contact angle of fiber with resin and sufficient chemical reactions between sizing and resin reveal strong correlation with the interfacial adhesion of CF/EP and CF/BMI, while the effect of surface roughness and the amount of oxygen on the fiber surface are relatively weak. Due to EP type of the composition, the sizing agent tends to improve the wettability of CF with EP, while goes against for the fiber with BMI. POLYM. COMPOS., 254–261, 2016. © 2014 Society of Plastics Engineers     

Effect of interconnect pre-oxidation on high-temperature wettability and mechanical properties of glass seals in SOFC

Metallic interconnect oxidation has a significant influence on shear strength between interconnect and sealing glass in SOFC stack operation. This is attributed to high-temperature mutual wettability. In this work, the glass having different crystallization kinetics was chosen to evaluate wettability and shear strength on Fe–16Cr alloy, which was heated treated at 750°C for 0, 50, and 100 h, forming oxide scale with a varying rough surface. Visual observation was used to quantify equilibrium contact angles between glass and substrates. The results illustrated that alloy oxidized for 50 h exhibited better wettability and shear strength, implying that thickness and roughness of the oxide scale are critical to enhancing interface joint strength. Long-term testing indicated that thermally stable glass possesses higher joint shear strength and more consistent properties. It was found that precipitated crystalline phases limited improvement of glass wettability, resulting in interfacial delamination of the glass/alloy layer over long-term operation.     

Aging of hydrophobized surfaces of ramie fibers induced by atmospheric pressure plasma treatment with ethanol pretreatment

In order to investigate hydrophilic recovery of hydrophobic treatment of cellulose fibers, ramie fibers are ethanol-pretreated followed by atmospheric pressure plasma jet (APPJ) treatment using helium as the treatment gas and age for up to 150?days in 20?°C and 65% relative humidity. Scanning electron microscopy shows the fiber surfaces of the ethanol-pretreated?+?APPJ-treated group of freshly prepared, aged for 30?days, and aged for 150?days are covered with polypropylene matrix after fiber pullout tests. X-ray photoelectron spectroscopy shows that the freshly prepared ethanol-pretreated?+?APPJ-treated group has a 31% reduction in atomic ratio of oxygen to carbon and maintains at a similar level even after 150?days of aging. Water contact angle measurement demonstrates that the wettability of fiber surface of the freshly prepared ethanol-pretreated?+?APPJ-treated group drastically decreases and remains at the same lever after aging. Interfacial shear strength test reveals that the interfacial adhesion between PP matrix and ramie fiber for the freshly prepared ethanol-pretreated?+?APPJ-treated group increases 26% and remains substantially higher than that of the control group over time. These results indicate that the ethanol pretreatment followed by APPJ treatment is a permanent surface treatment with negligible aging for at least five months.     

The effects of nanostructure and composition on the hydrophobic properties of solid surfaces

The effects of nanoroughness and chemical composition on the contact and sliding angles on hydrophobic surfaces were studied theoretically and experimentally. A theoretical model based on forces developed at the contact area between a liquid drop and hydrophobic smooth or nanoroughened surface was developed and compared with the existing models, which are based on forces developed at the periphery between the drop and the solid surface. The contact area based model gives rise to an interfacial adhesion strength parameter that better describes the drop-sliding phenomenon. Consequently, relationships were derived describing the dependence between the interfacial adhesion strength of the liquid drop to the surface of a given composition, the mass of the drop, the measured contact angles and the sliding angle. For a given surface chemistry, the sliding angle on a nanometric roughened surface can be predicted based on measurements of contact angles and the sliding angle on the respective smooth surface. Various hydrophobic coatings having different surface nanoroughnesses were prepared and, subsequently, contact angles and sliding angles on them as a function of drop volume were measured. The validity of the proposed model was investigated and compared with the existing models and the proposed model demonstrated good agreement with experimental results.     

Surface modification of armos fibers with oxygen plasma treatment for improving interfacial adhesion with poly(phthalazinone ether sulfone ketone) resin

We introduce in this article oxygen plasma treatment as a convenient and effective method for the surface modification of Armos fibers. The effects of oxygen‐plasma‐treatment power on both the Armos fiber surface properties and Armos‐fiber‐reinforced poly(phthalazinone ether sulfone ketone) composite interfacial adhesion were investigated. The Armos fiber surface chemical composition, surface morphology and roughness, and surface wettability as a function of oxygen‐plasma‐treatment power were measured by X‐ray photoelectron spectroscopy, scanning electronic microscopy, atomic force microscopy, and dynamic contact angle analysis. The results show that oxygen plasma treatment introduced a lot of reactive functional groups onto the fiber surface, changed the surface morphology, increased the surface roughness, and enhanced the surface wettability. Additionally, the effect of the oxygen‐plasma‐treatment power on the composite interfacial adhesion was measured by interlaminar shear strength with a short‐beam bending test. Oxygen plasma treatment was an effective method for improving the composite interfacial properties by both chemical bonding and physical effects. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Study on the Interfacial Behavior of Clay-Coated Carbon Fiber-Reinforced PEI Composites

In this article, based on the surface chemical treatment of carbon fiber, a clay coating process was developed for the surface modification of the carbon fiber to obtain a controlled interface between carbon fiber and polyetherimide (PEI) matrix in the composites system. SEM, XPS spectrum and contact angle measure reveal that the clay coating can improve the surface roughness of the carbon fiber surface for a favorable wettability with the matrix, which can also improve the interfacial adhesion of the composites. Experimental results show that the interlaminar shear strength (ILSS) and the three-point bending (TPB) of the composites reinforced by the carbon fiber coated with the clay have been enhanced.     

Improvement of the properties of ground tire rubber (GTR)‐filled nitrile rubber vulcanizates through plasma surface modification of GTR powder

The surface modification of ground tire rubber (GTR) powder to enhance its adhesion to nitrile rubber (NBR) vulcanizates was investigated. The hydrophobic surface of GTR powder has been transformed to a hydrophilic one through atmospheric pressure dielectric barrier discharge (DBD). The water contact angle dropped markedly from 116 to 0° after being treated for more than 10 s. Attenuated total reflectance Fourier transform infrared spectral (ATR‐FTIR) studies revealed the increase in peak intensity at 3298 and 1640 cm^?1 that correspond to O? H and C?C, respectively, on the surface of the GTR powder. The X‐ray photoelectron spectroscopic (XPS) analysis further confirmed the presence of oxygen containing polar functional groups on the surface of the GTR powder after atmospheric plasma treatment. The improvement in tensile strength and tear strength was observed for the modified GTR‐filled NBR vulcanizates, which is attributed to the enhanced interfacial interaction between modified GTR and NBR matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Wettability investigations on the cellulosic surface of alfa fibers

A wettability study was performed on samples of alfa fibers with the Wilhelmy plate technique. The set of test liquids employed in the measurement of the contact angles was composed of water, heptane, diiodomethane, α‐bromonaphthalene, and formamide. During their first immersion in high‐surface‐energy test liquids, the alfa fibers showed anisotropic behavior: they had an advancing contact angle of 67 ± 6° in one orientation of immersion and an angle of 112 ± 9.5° in the opposite one. Optical microscopy revealed the existence of fibrils on the alfa‐fiber surface. They kept almost the same orientation and were responsible for the interesting hydrophobic/hydrophilic behavior of the fibers. Contact angle measurements and investigations of the hysteresis were also performed. The various results were examined according to the heterogeneities of the fibers. The surface energy of the alfa fibers was determined with three theoretical models: the geometric model, the Good–Van Oss–Chaudhury model, and the Chang model. A comparative study of these models was undertaken. The study of the wetting properties of alfa fibers will provide essential information for optimized composites and so will help us in choosing the right chemical treatment necessary to enhance adhesion in alfa‐fiber‐based composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Adhesion of blood platelets under flow to wettability gradient polyethylene surfaces made in a shielded gas plasma

Adhesion and activation of platelets are important steps in the thrombosis of blood after contact with a biomaterial surface and are governed, in part, by the wettability of the surface. Since most implanted devices are in contact with blood under flow conditions, it is important to study the effect of wettability of device surfaces on the behavior of platelets also under flow. To this end, wettability gradient polyethylene surfaces were prepared through glow discharge with partial shielding over a length of 5 cm, with advancing water contact angles varying from 95 to 45 degrees and a contact angle hysteresis of 30 degrees. The role of blood flow on the adhesion of platelets was examined by incubating these gradient surfaces in anticoagulated, whole human blood under static conditions or in blood under a flow of 10 or 40 ml/min through a 3 mm diameter circuit or for 5 or 15 min with either the hydrophobic or hydrophilic end upstream. Generally, more platelets adhered on the hydrophilic end of the wettability gradient than on the hydrophobic end, although the increment along the wettability gradient was dependent on both the flow conditions and direction. More platelets adhered under a flow of 10 ml/min than under static conditions, due to higher mass transport. Especially when the hydrophilic end was upstream, there was a more pronounced adhesion. This can be explained in terms of immediate platelet activation by shear stress imposed at the upstream end. During flow of 40 ml/min, platelet adhesion on an upstream hydrophilic end was less than on a downstream hydrophilic end. We conclude that platelets detach from the hydrophilic end at high shear stress due to the spherical form of adhered platelets. Platelets on the hydrophobic end could withstand detachment by strong, flat shaped platelet-material contact.     

电化学氧化表面处理提高粘胶基碳纤维的界面粘结性能

通过动力学的方法研究了电化学处理前后接触角的变化 ,并用其表征碳纤维表面润湿性能的改变 ;通过拔出实验测定电化学处理前后碳纤维与树脂之间粘结性能的变化。结果表明 ,电化学处理后 ,碳纤维表面的润湿性大大改善 ,碳纤维与树脂的粘结程度提高至原来的 14 0 %～ 160 % ;研究还发现 ,不同种类的电解质电化学处理后对碳纤维表面的润湿性及其拔出强度的影响不同 ,( NH4) 2 SO4处理的碳纤维的润湿性能和拔出强度最好 ,H2 SO4处理的润湿性较之 Na OH的好 ,但拔出强度却不如 Na OH处理的高。且拔出强度越高 ,其断裂的模式趋向于单剪切断裂 ,拔出强度降低 ,其断裂变为多剪切断裂甚至为粉碎性断裂。     

Surface modification of ultra high modulus polyethylene fibers by an atmospheric pressure plasma jet

To improve their adhesion properties, ultra high modulus polyethylene (UHMPE) fibers were treated by an atmospheric pressure helium plasma jet (APPJ), which was operated at radio frequency (13.56 MHz). The surface properties of the fibers were investigated by X‐ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and contact angle measurement. The surface dyeability improvement after plasma treatments was investigated using laser scanning confocal microscopy (LSCM). The adhesion strengths of the fibers with epoxy were evaluated by microbond tests. In addition, the influence of operational parameters of the plasma treatment including power input and treatment temperature was studied. XPS analysis showed a significant increase in the surface oxygen content. LSCM results showed that the plasma treatments greatly increased fluorescence dye concentrations on the surface and higher diffusion rate to the fiber center. The tensile strength of UHMPE fiber either remained unchanged or decreased by 10–13.6% after plasma treatment. The contact angle exhibited a characteristic increase in wettability, due to the polar groups introduced by plasma treatment. The microbond test showed that the interfacial shear strengths (IFSS) increase significantly (57–139%) after plasma treatment for all groups and the optimum activation is obtained at 100°C and 5 W power input. SEM analysis showed roughened surfaces after the plasma treatments. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Design factors for reducing ice adhesion

The purpose of this study was to investigate the relationships between a type of engineering material and the ice adhesion strength while in direct application in icing conditions. Ice adhesion tests were conducted on various materials with different surface conditions. There is an identified need for systematic studies on the effects of varying surface conditions with well-characterized roughness and accurate adhesion measurement. This information is key in understanding the adhering behaviour of ice which is a necessary prerequisite for modelling the behaviour of ice adhesion to other surfaces and for icing prevention. Results show that the type of material will determine, in large, the strength of the ice adhesion between surfaces with similar roughness characteristics and the receding contact angle of water can be used as a predictor of relative ice adhesion. The adhesive strength of ice can be increased or decreased dramatically by means of adjusting the surface roughness with a uniform process. Each material tested exhibits a similar linear relationship. There was a stark contrast in the ice adhesion between the varying materials despite very similar polished surface conditions and static water contact angles. Ice bonded to the glass surface with an adhesion of 1562 ± 113 kPa, and to aluminum at 1039 ± 117 kPa, and stainless steel at 1022 ± 115 kPa, and finally Teflon at only 33 ± 52 kPa and during 80% of trials the ice/substrate interface was broken with no measured adhesion. The information gathered can be used to improve designs for a number of devices needed in cold weather climates.     

Hydrophobic recovery of repeatedly plasma-treated silicone rubber. Part 1. Storage in air

Silicone rubber is used for a wide variety of biomedical and industrial applications due to its good mechanical properties, combined with a hydrophobic surface. Frequently, however, it is desirable to alter the surface hydrophobicity of silicone rubber. Often this is done by plasma treatments but the effects are usually transient. In this study, surfaces of medical grade silicone rubber have been repeatedly modified by means of oxygen, argon, carbon dioxide, and ammonia RF plasma treatments with a 24 h time interval in between treatments. Treated samples were stored in air prior to surface characterization by water contact angle measurements, X-ray photoelectron spectroscopy (XPS), streaming potential measurements, and profilometry for surface roughness. The carbon percentage of the surfaces decreased after plasma treatment, while the silicon and oxygen percentages increased irrespective of the plasma used. The formation of Si-O-Si bridges between siloxane chains after plasma treatment was demonstrated by the appearance of a new component in the Si_2p peak but the degree to which this occurred differed per gas. Streaming potential measurements in a 10 mM potassium phosphate buffer indicated a more negatively charged surface for treated samples compared to untreated samples (-23.3 mV at pH 7.0). Surface roughness increased slightly for repeatedly plasma-treated samples from R_A = 0.35 μm to R_A = 0.46 μm, while scanning electron microscopy showed the presence of several 'cracks' spanning the surface after repeated treatment. Argon, carbon dioxide, and ammonia plasmas significantly reduced the advancing water contact angle from 115° to 58°, 72°, and 85°, respectively, on a more permanent basis (especially when the treatments were repeated after recovery). Oxygen plasma effects on water contact angles generally disappeared within 5 h, also after repeated treatment.     

Formation of a carbon fiber/polyhedral oligomeric silsesquioxane/carbon nanotube hybrid reinforcement and its effect on the interfacial properties of carbon fiber/epoxy composites

A carbon fiber/polyhedral oligomeric silsesquioxane/carbon nanotube (CF–POSS–CNT) hybrid reinforcement was prepared by grafting CNTs onto the carbon fiber surface using octaglycidyldimethylsilyl POSS as the linkage in an attempt to improve the interfacial properties between carbon fibers and an epoxy matrix. X-ray photoelectron spectroscopy, scanning electron microscopy, dynamic contact angle analysis and single fiber tensile testing were performed to characterize the hybrid reinforcements. Interlaminar shear strength (ILSS), impact toughness, dynamic mechanical analysis and force modulation atomic force microscopy were carried out to investigate the interfacial properties of the composites. Experimental results show that POSS and CNTs are grafted uniformly on the fiber surface and significantly increase the fiber surface roughness. The polar functional groups and surface energy of carbon fibers are obviously increased after the modification. Single fiber tensile testing results demonstrate that the functionalization does not lead to any discernable decrease in the fiber tensile strength. Mechanical property test results indicate the ILSS and impact toughness are enhanced. The storage modulus and service temperature increase by 11 GPa and 17 °C, respectively. POSS and CNTs effectively enhance the interfacial adhesion of the composites by improving resin wettability, increasing chemical bonding and mechanical interlocking.     

Synthesis and adhesion properties of waterborne polyurethane dispersions with long‐branched aliphatic chains

In this study, a series of waterborne polyurethanes (WPUs) with different contents of long‐branched aliphatic chains were synthesized through variation of the amount of diol chain extender trimethylol propane monooleate (TMPM). The effects of the TMPM content on the adhesion properties of the WPUs were investigated in terms of their surface tension, interfacial tension, contact angle, and adhesion strength. Fourier transform infrared and ¹H‐NMR spectra demonstrated the successful incorporation of TMPM into the polyurethanes. An increase in the TMPM content produced decreases in the surface tension of the WPUs and the interfacial tension and contact angle between the WPUs and plastic films. This indicated that the wetting properties of the WPUs on the plastic films was improved. The improved wettability enhanced the adhesion strength of the WPUs, and this showed that the long‐branched aliphatic chains could effectively improve the adhesion performance of the WPUs on the plastic films. Moreover, TMPM, with its hydrophobic aliphatic chains, increased the hydrophobicity and thermal stability of the WPU films. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41688.     

Prompt modification of styrene‐butadiene rubber surface with trichloroisocyanuric acid by increasing chlorination temperature

In this article, the surface of styrene‐butadiene rubber (SBR) was brushed with trichloroisocyanuric acid (TCI) (1 or 2 wt % in ethyl acetate) and then thermally treated under different conditions. The chemical modification was characterized by contact angle measurement and surface energy, ATR‐FTIR spectroscopy, scanning electron microscopy (SEM), and single‐lap shear test. The results revealed that the increase of the chlorination temperature was very effective for SBR surface modification by TCI, leading to enhanced surface wettability and shear strength within several minutes. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Wettability and interfacial phenomena investigations on high-density polyethylene and petroleum coke

An in-depth wettability and interfacial phenomena investigation was carried out to study interactions between high density polyethylene (HDPE) and petroleum coke. The aim is to investigate the effect of temperature and contact times on possible interactions and adhesion characteristics for partially substituting coal-tar pitch binder with waste polymers. Using a sessile drop arrangement, experimental assemblies consisting of ground HDPE and a petroleum coke substrate were heat treated in the temperature range of 150–350°C for 15–60 min. Contact angles between molten HDPE and petroleum coke surface and depth of penetration of HDPE into petroleum coke substrate were measured. The highest contact angle (131.5°) was observed at 250°C after 15 min. and lowest contact angle (30.9°) was observed at 350°C after 60 min. Highest penetration depth (75 μm) was observed at 350°C after 60 min and lowest penetration (13 μm) at 200°C after 15 min. Analysis of results showed that increasing time and temperature of heat treatment had a significant impact on the interactions of molten HDPE with petroleum coke. Longer residence time and higher temperatures increased the extent of melting of HDPE, which in turn resulted in improved wettability and deeper penetration into petroleum coke substrate. HDPE was found to bind and adhere strongly with petroleum coke. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012