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Optimizing Ice-Resistant Surfaces: Unifying Self-Healing, Durability, and Functional Design for Superior Anti-/De-Icing Performance
Luleå University of Technology, Department of Engineering Sciences and Mathematics, Machine Elements.ORCID iD: 0000-0003-0477-7063
2024 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Snow and ice accumulation on critical infrastructure such as wind power turbines and power lines cause significant challenges and safety hazards in cold climate regions during wintertime. Research into anti-/de-icing technologies has been divided into two main streams, i.e., active, and passive approaches. Active technologies, including electric thermal, photothermal technologies, etc, are widely used in anti-/de-icing fields. Passive technologies, including hydrophobic and slippery surfaces, have gained increasing interest due to their low energy consumption and sustainable profile, but these passive technologies are often limited by relatively short service life and poor mechanical durability. 

A potential way of improving the anti-/de-icing performance would be to combine different technologies and create electric thermal superhydrophobic surfaces and/or photo-thermal superhydrophobic surfaces. Furthermore, the mechanical durability could be improved by developing self-healing superhydrophobic surfaces and wear-resistant electric thermal surfaces. However, some important studies of relevant mechanisms to achieve this are absent in the literature, such as the influence of self-healing on ice adhesion, and investigation on how to unify the durability and anti-/de-icing performances via molecular structure design. 

This thesis addresses these questions by focusing on enhancing the wear resistance and anti-/de-icing efficiency of anti-/de-icing materials through innovative material design. We conducted ice-phobic tests in lab environment, and long-term ice-phobic field tests, which helped us to further understand and optimize the design of ice-phobic surfaces. 

This thesis contributes to developing more durable, efficient, and sustainable anti-/de-icing solutions, addressing the critical need for reliable performance under adverse weather conditions. 

The key findings were: 

(1) A novel self-healing and low-ice adhesion poly silicon urea coating was developed, leveraging the intrinsic material structure for creating sufficient wear resistance and self-healing capabilities. The Poly silicon urea coating exhibits below 10kPa ice adhesion strength, which is far lower than the ice-phobic surface request(<100kPa). The molecular structure’s influence on self-healing and ice adhesion are specified in this work.

(2) Inspired by the low-icing bonding properties of silicon urea, a graphene-enhanced siloxane urea multi-functional coating was designed, where the low-icing properties were combined with electric and thermal conductivity to achieve both active and passive anti-/de-icing effects. This graphene enhancement coating exhibits 10 minutes of removing all ice accretion under ~570W/m2 electric power on the lab scale test. The field tests, where a graphene enhancement coating surface can keep ice-free under ~310W/m2 during the whole winter in a harsh natural environment.  

(3) To explore the influence of mechanical durability on ice-phobic, a composite coating which integrates wear resistance and thermal conductive was formulated. Graphene was proven as a suitable additive to enhance thermal conductivity and wear resistance. Compared with the blank control coating and a boron nitride composite coating, the thermal conductivity of a graphene composite coating increased around 3 times, and the anti-wear performance based on wear depth was increased around 1.5 times. The wear mechanism and wear influence on anti-/de-icing behaviour are investigated in this work. 

(4) This work also explored the impact of surface functional groups on anti-/de-icing performance, uncovering that the force interactions and steric radius of these groups significantly influence surface element distribution and material strength, thereby affecting wettability and wear behaviour. The results show that the hydrophobicity of the groups is not the only factor to influence the surface properties. A smaller steric radius and strong interactions are beneficial for reducing the van der Waals' gap between groups which can inhibit the wetting of the water molecules. The influence of five different typical groups on mechanical durability and ice adhesion is investigated in this work.

Place, publisher, year, edition, pages
Luleå: Luleå University of Technology, 2024.
Series
Doctoral thesis / Luleå University of Technology 1 jan 1997 → …, ISSN 1402-1544
Keywords [en]
Anti-/de-icing
National Category
Tribology (Interacting Surfaces including Friction, Lubrication and Wear)
Research subject
Machine Elements
Identifiers
URN: urn:nbn:se:ltu:diva-105228ISBN: 978-91-8048-556-2 (print)ISBN: 978-91-8048-557-9 (electronic)OAI: oai:DiVA.org:ltu-105228DiVA, id: diva2:1854209
Public defence
2024-06-04, E632, Luleå University of Technology, Luleå, 09:00 (English)
Opponent
Supervisors
Available from: 2024-04-24 Created: 2024-04-24 Last updated: 2024-05-14Bibliographically approved
List of papers
1. A mini-review: the ice resistance durability and mechanical durability of ice-phobic surfaces
Open this publication in new window or tab >>A mini-review: the ice resistance durability and mechanical durability of ice-phobic surfaces
(English)Manuscript (preprint) (Other academic)
National Category
Other Engineering and Technologies not elsewhere specified
Research subject
Machine Elements
Identifiers
urn:nbn:se:ltu:diva-105225 (URN)
Available from: 2024-04-24 Created: 2024-04-24 Last updated: 2024-04-24
2. Novel Intrinsic Self-Healing Poly-Silicone-Urea with Super-Low Ice Adhesion Strength
Open this publication in new window or tab >>Novel Intrinsic Self-Healing Poly-Silicone-Urea with Super-Low Ice Adhesion Strength
Show others...
2022 (English)In: Small, ISSN 1613-6810, E-ISSN 1613-6829, Vol. 18, no 22, article id 2200532Article in journal (Refereed) Published
Abstract [en]

Accumulation of snow and ice often causes problems and even dangerous situations for both industry and the general population. Passive de-icing technologies, e.g., hydrophobic, liquid-infused bionic surfaces, have attracted more and more attention compared with active de-icing technologies, e.g., electric heating, hot air heating, due to the passive de-icing technology's lower energy consumption and sustainability footprint. Using passive de-icing coatings seems to be one of the most promising solutions. However, the previously reported de-icing coatings suffer from high ice adhesion strength or short service life caused by wear. An intrinsic self-healing material based on poly-silicone-urea is developed in this work to address these problems. The material is prepared by introducing dynamic disulfide bonds into the hard phase of the polymer. Experimental results indicate that this poly-silicone-urea has a self-healing efficiency of close to 99%. More interestingly, it is found that the coating prepared from this poly-silicone-urea has a super low ice adhesion force, only 7 ± 1 kPa, which is almost the lowest value compared with previous intrinsic self-healing de-/anti-icing reports. This material can maintain low ice adhesion strength after healing. This intrinsic self-healing poly-silicone-urea can meet several practical applications, opening the door for future sustainable anti-/de-icing technologies.

Place, publisher, year, edition, pages
John Wiley & Sons, 2022
National Category
Manufacturing, Surface and Joining Technology Tribology (Interacting Surfaces including Friction, Lubrication and Wear)
Research subject
Machine Elements
Identifiers
urn:nbn:se:ltu:diva-89955 (URN)10.1002/smll.202200532 (DOI)000778739700001 ()35318812 (PubMedID)2-s2.0-85126871425 (Scopus ID)
Funder
Swedish Research Council Formas, 2019-00904Swedish Research Council, 2017-04914, 2019-04941Swedish Energy Agency, 2018-003910Interreg Nord, 20202472
Note

Validerad;2022;Nivå 2;2022-06-07 (joosat);

Available from: 2022-03-30 Created: 2022-03-30 Last updated: 2024-04-24Bibliographically approved
3. In-situ polymerized siloxane urea enhanced graphene-based super-fast, durable, all-weather elec-photo-thermal anti-/de-icing coating
Open this publication in new window or tab >>In-situ polymerized siloxane urea enhanced graphene-based super-fast, durable, all-weather elec-photo-thermal anti-/de-icing coating
2023 (English)In: Journal of Science: Advanced Materials and Devices, ISSN 2468-2284, Vol. 8, no 3, article id 100604Article in journal (Refereed) Published
Abstract [en]

Previous investigations on anti-/de-icing techniques have primarily focused on mild laboratory conditions, which have limited practical applicability due to their short service life. Consequently, there is an urgent demand for the development of durable anti-/de-icing technologies capable of withstanding complex environmental conditions. In this research endeavour, we have successfully formulated a hydrophobic coating based on graphene. To circumvent the challenges associated with environmentally unfriendly organic solvents, we utilized a graphene water slurry as the foundational material and subsequently incorporated a poly (vinyl alcohol)-water solution. The resulting solution was subjected to in situ polymerization of a siloxane urea crosslinked polymer, yielding the desired coating solution. Following a solution spraying and drying process, the ultimate product obtained was the hydrophobic conductive graphene (HCG) siloxane Coating. The HCG siloxane Coating exhibits a conductivity of 66 S/m, enabling it to melt ice droplets within a mere 10 s, whereas conventional coatings require 20–500 s for the same task. A comprehensive field test conducted during an entire winter period on a high mountain situated within the Arctic Circle in Finland demonstrated the excellent anti-icing properties of the developed coating when subjected to approximately 310 W/m2 power. Furthermore, the coating exhibited satisfactory de-icing performance under approximately 570 W/m2 power, successfully removing ice accumulations within approximately 10 min. Throughout the field test, temperatures frequently plummeted to −20 °C, accompanied by wind speeds reaching up to 12 m/s. Material characterization revealed that the micro-nano structure of the coating surface, which engenders favourable hydrophobic behaviour, was primarily attributed to the phase separation resulting from hydrophilic and hydrophobic interactions. Moreover, the semi-interpenetrating structure formed by the polyvinyl alcohol molecular chains and in-situ polymerized siloxane urea ensured the coating's strength.

Place, publisher, year, edition, pages
Elsevier, 2023
Keywords
Anti-/de-icing, Coating, Conductive, Graphene
National Category
Materials Chemistry
Research subject
Machine Elements
Identifiers
urn:nbn:se:ltu:diva-99303 (URN)10.1016/j.jsamd.2023.100604 (DOI)2-s2.0-85165422965 (Scopus ID)
Funder
Swedish Research Council Formas, 2019-00904Swedish Research Council, 2019-04941Swedish Energy Agency, 2018-003910Interreg Nord
Note

Validerad;2023;Nivå 2;2023-08-09 (hanlid)

Available from: 2023-08-09 Created: 2023-08-09 Last updated: 2024-04-24Bibliographically approved
4. Graphene-enhanced, wear-resistant and thermal-conductive, anti-/de-icing Gelcoat composite coating
Open this publication in new window or tab >>Graphene-enhanced, wear-resistant and thermal-conductive, anti-/de-icing Gelcoat composite coating
Show others...
2024 (English)In: Advanced Composites and Hybrid Materials, ISSN 2522-0128, Vol. 7, no 1, article id 9Article in journal (Refereed) Published
Abstract [en]

Wind power is considered as a sustainable and environmentally friendly energy source. However, the occurrence of icing poses significant challenges to energy production, particularly in frigid regions during the winter season. Conventional strategies employed for preventing and removing ice formation have proven inadequate due to their inability to satisfy intricate requirements or their high energy consumption. In this study, a commercial gelcoat coating was adopted as an anti-/de-icing coating by introducing different concentrations of graphene and boron nitride into the gelcoat coating through physical mixing. Extensive investigations were conducted on the correlation between anti-/de-icing, wear resistance, and thermal conductivity. Notably, the incorporation of nanoparticles induced a rise in the surface roughness, resulting in prolonged resistance to water icing on the coated surface. The wear resistance and thermal conductivity of the composite coating were enhanced through the inclusion of boron nitride and graphene. The building of thermal conductive particle networks improved thermal conductivity which can lead to improved heat transfer and heat distribution. At the same time, the enhanced gelcoat composite coating exhibited exceptional passive anti-/de-icing performance and wear resistance. This coating can replace commercial coatings to improve anti-/de-icing efficiency for the existing active heating anti-/de-icing techniques available in the market.

In this study, we aimed to enhance the wear resistance, thermal conductivity, and anti-/de-icing properties of a gelcoat composite coating by incorporating graphene and boron nitride. The gelcoat graphene coating showed better performance than the gelcoat boron nitride coating and pure gelcoat coating. The improved wear resistance of the gelcoat graphene coating can be attributed to the two-dimensional layer structure of graphene, while the addition of graphene resulted in a threefold increase in the thermal conductivity of the gelcoat composite coating compared to the pure gelcoat coating. The gelcoat composite coatings exhibited a high-water contact angle and low ice adhesive force. It was observed that as the surface roughness increased, the water contact angle also increased. The increase in ice adhesion after abrasion proves that abrasion is always detrimental to de-icing. Despite the extension of icing delay time, the large number of grooves and bumps created by wear results in stronger mechanical interlocking. It is worth mentioning that gelcoat graphene coating still demonstrated lower ice adhesive strength than gelcoat boron nitride coating and pure gelcoat coating. Overall, we successfully developed a gelcoat graphene coating with improved thermal conductivity, wear resistance, and low ice adhesive properties. This novel composite coating has the potential to significantly enhance the efficiency of existing heating technologies for anti-/de-icing applications, thereby reducing energy consumption associated with the turbine blades’ anti-/de-icing system.

Place, publisher, year, edition, pages
Springer Nature, 2024
Keywords
Graphene, Wear, Coating, Anti-/de-icing
National Category
Manufacturing, Surface and Joining Technology
Research subject
Machine Elements
Identifiers
urn:nbn:se:ltu:diva-103447 (URN)10.1007/s42114-023-00820-3 (DOI)001137939500002 ()2-s2.0-85181582111 (Scopus ID)
Funder
Swedish Research Council Formas, 2019–00904Swedish Research Council, 2019– 04941Swedish Energy Agency, 2018–003910Interreg Nord, 20202472
Note

Validerad;2024;Nivå 2;2024-04-02 (hanlid);

Full text license: CC BY 4.0

Available from: 2024-01-02 Created: 2024-01-02 Last updated: 2024-08-22Bibliographically approved
5. Effect of anti-icing coating functional groups on ice adhesion
Open this publication in new window or tab >>Effect of anti-icing coating functional groups on ice adhesion
2024 (English)In: Applied materials today, ISSN 2352-9407, Vol. 39, article id 102264Article in journal (Refereed) Published
Abstract [en]

Unwanted ice build-up is a ubiquitous phenomenon in nature, which creates a series of catastrophic impacts on a wide range of human activities. Various anti/de-icing materials have been proposed for dealing with icing issues. Superhydrophobic anti/de-icing coatings have been widely reported since it has high efficiency and can be achieved in different ways. The surface functional groups have a significant influence on surface energy which is related to surface wettability. However, the influence of the coating surfaces functional groups on the anti-/de-icing properties is still not well studied. To investigate this influence, different groups with different hydrophilicity have been introduced to 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluorooctyl acrylate (TFOA) to fabricate several branch copolymer ice-phobic coatings. The anti-icing performance and the influence of group radius and interaction were studied. The acrylic acid TFOA showed a great superhydrophobic property (over 150° water contact angle), lower ice adhesion strength (<50 kPa), and lower wear depth compared with other copolymer coatings. The mechanism was studied via the molecular dynamic calculation carried out in ChemDraw software. The interaction between hydrophobic and hydrophilic groups and the steric length of the hydrophilic groups influence the surface structure and surface element distribution, further influencing the ice adhesion strength.

Place, publisher, year, edition, pages
Elsevier, 2024
Keywords
Radius, Hydrogen bond, van der Walls gap, Ice adhesion
National Category
Manufacturing, Surface and Joining Technology
Research subject
Machine Elements
Identifiers
urn:nbn:se:ltu:diva-105227 (URN)10.1016/j.apmt.2024.102264 (DOI)2-s2.0-85194943479 (Scopus ID)
Funder
Swedish Research Council Formas, 2019–00904, 2022–01988, 2022–01047Swedish Research Council, 2019–04941
Note

Validerad;2024;Nivå 2;2024-06-10 (hanlid);

Full text license: CC BY

Available from: 2024-04-24 Created: 2024-04-24 Last updated: 2024-06-10Bibliographically approved

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