<p>Development of durable icephobic coating and reduction of ice accumulation on the product surfaces has proven to be a challenging task in the past decade. Considering the challenges posted during ice storms and existing limitations to the state of the art, development of durable icephobic coating which can provide low ice adhesion strength and less ice weight increase is a critical milestone for industries and research communities. To obtain durable icephobic coating, high temperature and weather resistance Fluoro-Ethylene-Alkyl-Vinyl-Ether (FEVE) binder was selected to design a smooth and superhydrophobic coatings. These coatings were benchmarked against commercially available silicone epoxy and superhydrophobic coatings and validated its surface roughness, surface wettability and icephobic performance such as ice adhesion strength and ice accumulation. To evaluate coatings thermal durability, targeting power transmission line application, these coatings were exposed to extreme thermal ageing conditions (200 ^oC for 60 days) and retention of icephobic performance were measured. Though, commercial coatings have provided better icephobicity at unaged condition, after high temperature heat ageing these coatings icephobic performance were deteriorated significantly. However, FEVE based coating had retained its surface characteristics and icephobic properties after aggressive thermal ageing.</p>

Ice accretion on various surfaces can cause destructive effect of our lives, from cars, aircrafts, to infrastructure, power line, cooling and transportation systems. There are plenty of methods to overcome the icing problems including electrical, thermal and mechanical process to remove already accumulated ice on the surfaces and to reduce the risk of further operation. But all these process required substantial amount of energy and high cost of operation. To save the global energy and to improvement the safety issue in many infrastructure and transportation systems we have to introduce some passive anti-icing coating known as ice-phobic coating to reduce the ice-formation and ice adhesion onto the surface. Ice-phobic coatings mostly devoted to utilizing lotus-leaf-inspired superhydrophobic coatings. These surfaces show promising behavior due to the low contact area between the impacting water droplets and the surface. In this present study we investigate systematically the influence of chemical composition and functionality as well as structure of surfaces on wetting properties and later on icing behavior of surfaces. Robust anti-icing coating has been prepared by using modified silica particles as a particles film. Polymer brushes were synthesized on flat, particle surfaces by using Surface initiated ATRP. We have also investigated the effect of anti-icing behavior on the surfaces by varying surface chemistry and textures by using different sizes of particles. This approach is based on the reducing ice accumulation on the surfaces by reducing contact angle hysteresis. This is achieved by introducing nano to micro structured rough surfaces with varying surface chemistry on different substrates. Freezing and melting dynamics of water has been investigated on different surfaces by water vapour condensation in a high humidity (80%) condition ranging from super hydrophilic to super hydrophobic surfaces below the freezing point of water. Kinetics of frost formation and ice adhesion strength measurements were also performed for all samples. All these experiments were carried out in a custom humidity and temperature controlled chamber. We prepared a superhydrophobic surface by using Poly dimethyl siloxane (PDMS) modified fumed silica which display very low ice-adhesion strength almost 10 times lower than the unmodified surface. Also it has self-cleaning behavior after melting of ice since whole ice layer was folded out from the surface to remove the ice during melting. Systematic investigation of the effect of three parameters as surface energy, surface textures (structure, geometry and roughness) and mechanical properties of polymers (soft and stiff) on icing behavior has also been reported.

Ice buildup on structures leads to problems that include reduced performance, structural damage and power outages. It is therefore important to limit the energy required for removal of ice from substrates to minimize buildup. Understanding the mechanism of ice adhesion and its dependence on variables like coating thickness, stiffness, surface free energy and morphology is critical for minimizing adhesion. Despite several developments in “icephobic” coatings, which are those that have low ice adhesion, it is important to understand adhesion on the fundamental level to make way for advanced coatings. To do so, a study has been carried out that explores key variables affecting ice adhesion using a commercially available silicone, Sylgard 184®. Sylgard 184 is a two-part, platinum cured silicone elastomer available from Dow Corning with good physical and chemical stability and is used in widely diverse research studies. The thermodynamic work of ice adhesion is related to the receding contact angle θ_r of water by Equation 1. wa≈ γ_w (1+cos⁡ θ_r) Eq 1. where γ_w is the surface tension of water. Considering an elastomeric substrate and ice as a rigid cylindrical adherent, the Kendall modelcan be adapted to relate peak removal force (Pc) with work of adhesion (wa), modulus (K), thickness (t), and radius (a) according to Equation 2. Pc ∝ πa^2 ((2wa K)/t)^(1⁄2) Eq. 2 Considering these relationships, hydrophobic materials with low surface energies and high receding contact angles are generally predicted to show low adhesion. To begin to understand details, the force required to remove an ice cylinder from the silicone elastomer Sylgard 184 was investigated by focusing on three variables: coating thickness, modulus and cure temperature. “Cure” refers to the network formation or crosslinking within the material. The Wynne research group has previously established a surprising dependence of qR on Sylgard 184 cure temperature.In this thesis, the relationship among variables noted above was examined by measuring Pc for Sylgard coatings. Additionally, effects of test temperature on ice adhesion strength was studied. Surface characterization methods including ATR-IR (attenuated total reflectance infrared spectroscopy), DCA (Wilhelmy plate dynamic contact angles) and AFM (atomic force microscopy) were employed. In summary, defined processing conditions were found optimum for minimizing ice adhesion to Sylgard coatings.

Aluminum alloys are widely used materials in the aircraft industry due to their high specific strength and durability. The natural corrosion resistance of aluminum can be improved through an electrochemical anodizing process. Due to recent restrictions in the use of chromic acid with toxic hexavalent chromium as electrolyte, the industry has shifted towards the use of the functional comparable tartaric sulfuric acid (TSA). TSA anodizing provides a porous alumina layer with good corrosion resistance, yet there is a desire to tune the process to fit other purposes. For instance, ice accretion to aircraft surfaces implies a safety risk and reduced energy efficiency. Due to insufficient active anti-icing systems, aircraft manufacturers are in the search for passive anti-acing materials. The ice adhesion properties of a material are thought to be affected by wettability. In turn, the wettability is affected by the morphology of the alumina influenced by the anodizing conditions. Herein, the effects of the anodizing voltage, electrolyte temperature and anodizing time on the morphology and wettability of TSA-anodized aluminum alloy 2024-T3 were studied by scanning electron microscopy (SEM) and contact angle (CA) measurements. The morphology in relation to wettability and ice adhesion strength as well as the use of posttreatments such as hydrothermal sealing and silanization was investigated. SEM images show a clear influence by the anodizing conditions on the porosity, interpore distance and pore diameter of the porous alumina. The morphology has influence on the wettability although the relationship needs further investigation. A superhydrophobic surface obtained by silanization of a surface anodized at high voltage characterized by a rod-like morphology has potential as a passive anti-icing surface. Future work may include additional polishing pretreatments, testing of additional parameters, investigating the CA hysteresis and roll-off angle as well as measuring the adhesion strength of high-impact ice. By tuning the morphology of sustainable anodic coatings, the research area is one step closer to implementing passive anti-icing materials in aircrafts.

Ice accretion on various surfaces can cause destructive effect of our lives, from cars, aircrafts, to infrastructure, power line, cooling and transportation systems. There are plenty of methods to overcome the icing problems including electrical, thermal and mechanical process to remove already accumulated ice on the surfaces and to reduce the risk of further operation. But all these process required substantial amount of energy and high cost of operation. To save the global energy and to improvement the safety issue in many infrastructure and transportation systems we have to introduce some passive anti-icing coating known as ice-phobic coating to reduce the ice-formation and ice adhesion onto the surface. Ice-phobic coatings mostly devoted to utilizing lotus-leaf-inspired superhydrophobic coatings. These surfaces show promising behavior due to the low contact area between the impacting water droplets and the surface. In this present study we investigate systematically the influence of chemical composition and functionality as well as structure of surfaces on wetting properties and later on icing behavior of surfaces. Robust anti-icing coating has been prepared by using modified silica particles as a particles film. Polymer brushes were synthesized on flat, particle surfaces by using Surface initiated ATRP. We have also investigated the effect of anti-icing behavior on the surfaces by varying surface chemistry and textures by using different sizes of particles. This approach is based on the reducing ice accumulation on the surfaces by reducing contact angle hysteresis. This is achieved by introducing nano to micro structured rough surfaces with varying surface chemistry on different substrates. Freezing and melting dynamics of water has been investigated on different surfaces by water vapour condensation in a high humidity (80%) condition ranging from super hydrophilic to super hydrophobic surfaces below the freezing point of water. Kinetics of frost formation and ice adhesion strength measurements were also performed for all samples. All these experiments were carried out in a custom humidity and temperature controlled chamber. We prepared a superhydrophobic surface by using Poly dimethyl siloxane (PDMS) modified fumed silica which display very low ice-adhesion strength almost 10 times lower than the unmodified surface. Also it has self-cleaning behavior after melting of ice since whole ice layer was folded out from the surface to remove the ice during melting. Systematic investigation of the effect of three parameters as surface energy, surface textures (structure, geometry and roughness) and mechanical properties of polymers (soft and stiff) on icing behavior has also been reported.

This study aims to develop coatings which show wear resistant behaviour along with multiple functions such as improved ice adhesion, better freezing delay etc which help in improving the effectiveness of the wind turbine efficiency. The significance of anti-icing/de-icing solutions for wind turbines is emphasized since ice accretion can cause serious issues in generation of power and might lead to damage of blades. The use of active and passive anti-icing/de-icing technologies in wind turbine blade applications is reviewed. The discrepancy between passive anti-icing, which depends on surface treatment, coatings, de-icing fluids and active anti-icing, which uses heating devices, sensors such as actuators, transducers, is explored along with the current challenges in industry. In this study we’ve developed interesting methods for improving the anti-icing/de-icing capabilities of wind turbine blades by using gelcoat coatings in which are filler particles (boron nitride and graphene) and oils (vegetable and paraffin oil) are incorporated. Evaluating the impacts of type of fillers, oils, their concentrations on anti-icing efficacy, as well as the prospects for this technique to enhance wind energy production's reliability and productivity will be explored. In summary, this study aims to develop multi-functional polymer coatings for anti-icing/de-icing application in wind turbine blades. The coatings with boron-nitride and graphene showed an increase in the surface roughness and contact angles, while there’s no change in the chemical composition in comparison with pure gelcoat. The thermal conductivity of the coatings was increased with addition of fillers. For the wear test, the operating parameters chosen are a load of 5N and 1Hz frequency of slider, which is run for a duration of 10 min. The COF for both the coatings is lesser than baseline coatings whereas graphene provided better wear resistance. The hardness was increased for boron-nitride coatings and it remained almost same for graphene coatings. The ice adhesion strength, freezing delay and thermal analysis (TGA) for these coatings showed better performance than pure gelcoat. Whereas for coatings with vegetable and paraffin oils, the contact angles were increased and surface roughness was increased in case of paraffin oil coatings whereas it reduced for vegetable oil coatings. Both the coatings offered better wear resistance and reduced COF, whereas the hardness was reduced. The ice adhesion strength and freezing delay improved drastically and are much better than both pure gelcoat as well as coatings with boron-nitride and graphene. There is slight increase in the glass transition temperature than pure gelcoat coating.

Icing severely affects society, especially in the Nordic countries. Iceaccumulation can result in critical performance problems and safetyconcerns for instance in road, air and sea transportation, transmissionlines, marine and offshore structures, wind turbines and heat exchangers.Present active ice-combating approaches possess environmental,efficiency and cost drawbacks. Thus, fabricating icephobic surfaces orcoatings impeding ice formation (anti-icing), but facilitating ice removal(de-icing) is desired. However, different conditions in the environmentduring ice formation and growth add to the complexity of the problem.An icephobic surface that works for a certain application might not be agood candidate for another. These surfaces and the challenges are infocus in this thesis.Wetting properties are important for ice formation on surfaces fromthe liquid phase (often supercooled water), where the water repellency ofthe surfaces could enhance their anti-icing effect. Considering this,different hydrophobic and superhydrophobic surfaces with differentchemistry, morphology and roughness scale were prepared. Since anyinduced wetting state hysteresis on hydrophobic surfaces could influencetheir performance, the wetting stability was investigated. In particulardynamic wetting studies of the hydrophobic surfaces revealed whatsurface characteristics benefit a stable wetting performance. Further, theeffect of temperature, particularly sub-zero temperatures, on the wettingstate of flat and nanostructured hydrophobic surfaces was investigated.This was complemented with studies of the wetting stability of sessilewater droplets on flat to micro- and multi-scale (micro-nano) roughhydrophobic samples in a freeze-thaw cycle. To be consistent with mostapplications, all temperature-controlled experiments were performed inan environmental condition facilitating frost formation. Further, antiicingproperties of hydrophobic surfaces with different topography butsimilar chemistry were studied by freezing delay measurements.A dynamic wetting study using hydrophobic samples with similarchemistry but different topography revealed that multi-scale roughnesscould benefit the wetting stability. However, when these surfaces areutilized at low temperatures the wetting hysteresis observed during acooling/heating cycle is significant. Such a temperature-inducedhysteresis is also significant on superhydrophobic surfaces. I attributethis to condensation followed by frost formation facilitating spreading of  the supercooled water droplet. The freezing delay measurementsdemonstrate no significant effect of surface topography on anti-icingproperties of hydrophobic surfaces, however the flat surfaces showed thelongest delay. These findings are in agreement with heterogeneous icenucleation theory, suggesting preferential ice nucleation in concave sites,provided they are wetted.In the second part of this thesis, I consider the findings from theprevious part illustrating the limitations of (super)hydrophobic surfaces.The de-icing properties of hydrophilic surfaces with a hydration waterlayer, hypothesized to lubricate the interface with ice, were studied. Heretemperature-controlled shear ice adhesion measurements, down to -25oC, were performed on an adsorbed layer of a polymer, either bottle-brushstructured poly(ethylene oxide) or linear poly(ethylene oxide). The iceadhesion strength was reduced significantly on the bottle-brushstructured polymer layer, specifically at temperatures above -15 oC,whereas less adhesion reduction was observed on the layer formed by thelinear polymer. These findings are consistent with differential scanningcalorimetry (DSC) data, demonstrating that the hydration water, boundto the bottle-brush structured polymer, is in the liquid state at thetemperatures where de-icing benefit is observed. Further, continuingwith the hypothesis of the advantage of surfaces with a natural lubricantlayer for de-icing targets, I studied shear ice adhesion on the molecularlyflat basal plane of hydrophilic mica down to -35 oC. Interestingly, ultralowice adhesion strength was measured on this surface. I relate this to theproposed distinct structure of the first ice-like but fluid water layer onmica, with no free OH groups, followed by more bulk liquid-like layers.This combined with the molecularly smooth nature of mica results in aperfect plane for ice sliding. / Isbildning har en stark inverkan på samhället, speciellt i de nordiskaländerna. Isuppbyggnad kan resultera i kritiska prestandaproblem ochsäkerhetsrisker inom t.ex. väg-, luft-, och sjötransport, kraftledningar,marina- och offshorestrukturer, vindkraftverk och värmeväxlare.Nuvarande aktiva isbekämpningsmetoder uppvisar brister i avseende påmiljö, effektivitet och kostnad. Det finns därmed ett behov av attframställa ytor eller ytbeläggningar som förhindrar isbildning (antiisning)eller underlättar borttagandet av redan bildad is (avisning). Dockkompliceras problemet av de många olika förhållanden under vilka is kanbildas. En beläggning som fungerar för en viss tillämpning behöver intenödvändigtvis vara en bra kandidat för en annan. Dessa ytor ochutmaningar relaterade till dem är i fokus i denna avhandling.Vätningsegenskaper är viktiga för isbildning på ytor från vätskefas(ofta underkylt vatten), och det har visats att vattenavstötande ytor i vissasammanhang kan motverka isbildning. Med detta i åtanke framställdesolika hydrofoba och superhydrofoba ytor, med varierande kemi,morfologi och ytråhet. Eftersom en förändring i de hydrofoba ytornasvätningsegenskaper kan påverka deras funktion studerades vätningsstabilitetenför dessa ytor. I synnerhet dynamiska vätningsstudier av dehydrofoba ytorna avslöjade vilka ytegenskaper som är fördelaktiga förvätningsstabiliteten. Vidare studerades hur temperaturen, särskilt undernoll grader, påverkar vätningstillståndet på släta och nanostruktureradehydrofoba ytor. Arbetet kompletterades med studier av vätningsstabilitetenför vattendroppar på släta samt mikro- och multistrukturerade(mikro-nano) hydrofoba ytor under flera frysningsupptiningscykler.För att vara i linje med de flesta tillämpningar, utfördesalla temperaturkontrollerade mätningar i en miljö där frost kunde bildaspå ytorna. Anti-isegenskaperna hos de hydrofoba ytorna med varierandetopografi men samma kemi studerades vidare genom att studera hur långtid det dröjde innan en vattendroppe på ytan fryste vid en visstemperatur.De dynamiska vätningsstudierna på hydrofoba ytor med samma kemimen olika topografi avslöjade att en ytråhet på flera längdskalor kan haen positiv inverkan på vätningsstabiliteten. När dessa ytor är exponeradeför låga temperaturer är dock vätningshysteresen under en nedkylnings-/uppvärmnings-cykel significant. Den temperatur-inducerade hysteresenär också betydande för superhydrofoba ytor. Detta tillskriver jag  kondensation på ytan som följs av frostbildning, vilket i sin tur möjliggörspridning av den underkylda vattendroppen på ytan. Mätning avfördröjningen i frysningsförloppet påvisade ingen betydande effekt avyttopografin för hydrofoba ytor, men släta hydrofoba ytor uppvisade denlängsta fördröjningen. Dessa resultat är i överensstämmelse med rådandeheterogen iskärnbildningsteori, som visar på fördelaktig iskärnbildningpå konkava delar av ytan, förutsatt att dessa väts.I den andra delen av avhandlingen utnyttjar jag observationerna frånden första delen vilka illustrerade begränsningarna för superhydrofobaytor, och söker en annan lösning. Avisningsegenskaper för hydrofilastarkt hydratiserade ytor studerades, med hypotesen att hydratiseringkan smörja gränsskiktet med is. Temperatur-kontrolleradeisadhesionsmätningar ned till -25 °C utfördes på adsorberade skikt av enpolymer med många sidokedjor av polyetylenoxid (”bottle-brush”), såvälsom på ett skikt av linjär polyetylenoxid. Isadhesionen blev kraftigtreducerad på ”bottle-brush”-polymeren, speciellt vid temperaturer högreän -15°C. Däremot kunde knappast ingen minskad isadhesion observerasför den linjära polymeren. Dessa observationer överensstämmer meddifferentialskanningskalorimetri (DSC) data, som visar att dethydratiserade vattenskiktet, vilket är bundet till ”bottle-brush”-polymeren, är i vätskeform vid de temperaturer där avisningsfördelar ärobserverade. För att vidare undersöka hypotesen att det vore fördelaktigtmed ett naturligt smörjande skikt på ytan för att uppnå godaavisningsegenskaper, utförde jag isadhesionsmätningar på molekylärtsläta glimmerytor ner till -35 °C. Intressant nog uppmättes extremt lågisadhesion på denna yta. Detta relaterar jag till den föreslagna utprägladehydratiseringsstrukturen, bestående av ett första is-liknande vattenskiktutan fria OH-grupper, följt av ett mer bulkliknande skikt. Detta ikombination med den molekylärt släta naturen hos glimmer resulterar iett perfekt plan för isen att glida på. / <p>QC 20160504</p> / TopNano