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High-Performance Smart Ceramic Coatings on Light Alloys

Lead Research Organisation: University of Manchester
Department Name: Materials

Abstract

The application of surface treatments is a common practice to maximize the working life of light alloys used in transport. However, traditional passive coatings only act as a physical barrier against the environment and, once damaged, no longer provide protection. From this limitation, the concept of smart coatings was born, which are defined as materials capable of interacting with the environment by responding selectively to certain triggers, such as mechanical fracture, time, temperature or pH variations. Depending on the incorporated functionality, different properties can be achieved, e.g. specific corrosion inhibition, self-healing or damage indication.

The development of smart coatings is primarily a domain of organic-based materials since the high chemical reactivity of polymers promotes the incorporation of new functionalities. However, the applicability of such materials is limited to mild environments and medium loads. The scientific question proposed in this project is whether providing smart functionalities is feasible in ceramic-based coatings that have excellent performance in extremely corrosive and abrasive environments. The active functionalisation of ceramic coatings is quite challenging given the rigid and inert nature of inorganic matrices compared to organic materials.

The scientific approach proposed in this project to achieve the active functionalisation of ceramic coatings to tackle corrosion damage, is based on the incorporation of pH-sensitive nanocontainers loaded with corrosion inhibitors. These are released into the media when detecting pH changes arisen from electrochemical activity associated with corrosion initiation. The corrosion inhibitors will act locally inhibiting corrosion propagation, while the ceramic matrix will provide wear and abrasion protection simultaneously. This project focuses on the active and dynamic behaviour of the materials rather than in the passive properties of the coatings.

Two deposition techniques are used to manufacture the ceramic coatings, namely Plasma Electrolytic Oxidation (PEO) and Aerosol Deposition (AD) method. PEO is an electrolytic surface modification technique that derives from anodising. The interest for this technique arises from the current need to replace carcinogenic electrolytes used in anodising restricted by the EU (REACH). PEO is environmentally friendly and the resulting coatings are considerably superior in terms of corrosion and wear resistance to those obtained by conventional electrolytic techniques. However, PEO requires a high-energy consumption and this limits its applicability to niche components with excellent performance. Therefore, in order expand the range of applicability and increase the potential industry impact of this research, a more cost-effective and readily available technique is also proposed: the AD method-an extremely versatile room temperature spray coating technology. The deposition principle employed in AD is based on the generation of an aerosol using submicron powder particles from the precursor, which are sprayed at high velocity towards the substrate. It results in coatings with excellent high temperature and abrasion-resistant properties.

To achieve the active functionalisation of the ceramic coatings, two manufacturing processes are proposed. The single-step process will prove more challenging, but on the other hand, it would save processing times leading to reduced economical costs. Moreover, the single-step process is expected to produce a uniform functionalisation throughout the entire thickness of the coating, which would improve the active protection properties. The double-step process requires longer times, but it is more accessible.

Successful results would increase the lifetime of Al and Mg-based components used in the transport industry that would have a direct impact on energy efficiency and would contribute to the sustainable consumption of resources.

Publications

10 25 50
 
Description Providing coatings with smart functionalities was primarily a domain for organic-based materials, this project proved that incorporating smart functionalities to ceramic coatings -which are much more resistant and robust-is also possible using encapsulated active species.
For that ceramic coatings manufactured by Plasma Electrolytic Oxidation (PEO) and the Aerosol Deposition (AD) method were functionalised following two parallel approaches, a single-step and a double-step process. The functionalisation was carried out by encapsulating a wide range of corrosion inhibitors into commercial (halloysite nanotubes and zeolites) and lab-synthesised nanocontainers (fibrous silica, layered double hydroxides and hybrid organic-inorganic hollow cerium oxide shells). In all cases, the synthesis conditions were optimised to increase the crystallinity and loading capacity and to reduce the particle size.
The single-step process aims at functionalising the surface while the coating is being synthesised, which can be challenging because there is a high risk of thermal decomposition of the nanocontainers at the location of the plasma microdischarges required for the oxide growth. This project revealed that the in-situ incorporation of zeolite and halloysite nanotubes was possible during soft sparking Plasma Electrolytic Oxidation by optimisation of electrical processing parameters that allow the control of the thermodynamics of the plasma microdischarges. Optimising the processing frequency reduced the plasma intensity allowing the incorporation of nanoparticles with complex 3D structures into the outer porous structure of the growing coating. However, it is worth noting, that although the non-reactive incorporation was achieved, the concentration of incorporated nanoparticles was not sufficient to have a significant influence on the overall corrosion performance. However, the reported findings create favourable prerequisites for the development of advanced coating systems for other functional applications (e.g. in heterogeneous catalysis and drug delivery).
The double-step process consists of a sequential treatment, where the ceramic coating is synthesised in the first step followed by a functionalisation post-treatment, which acts simultaneously as a sealing layer for the porous ceramic coating. Several organic and inorganic sealing have been evaluated on PEO coatings formed on Al and Mg-Ti substrates. This approach has shown a significant improvement (3 orders of magnitude) in the corrosion performance of PEO coatings compared to the uncoated alloy, which was associated with a combination of (i) improved barrier properties of the coating, (ii) inhibition activity provided by the encapsulated inhibitor and/or (iii) ability of the nanocontainer to trap aggressive ions from the environment.
We faced several challenges with the development of AD coatings, particularly with the adhesion properties. For that, we assessed the influence of the surface roughness and the deposition of a pre-layer by PEO. This layer was designed to be highly porous so it could act as an anchorage for the subsequent AD coating. This multilayer system showed a reduction in the internal stresses of the ceramic matrix and an improvement in the corrosion performance, which was mainly attributed to the improved sealing effect of the AD coating.
In addition to the publications reported, 5 more publications are expected to be published in the following months.
Exploitation Route The outcomes of this funding will be particularly relevant for the academic community, it will allow making informed decisions about the most appropriate combination of nanocontainer-inhibitor system, ceramic matrix and deposition technique to improve the long term corrosion performance of lightweight components. This will directly contribute to the optimisation and development of the next generation of multifunctional coatings.
Providing high performance ceramic coatings with active functionalities and corrosion protection on demand will be particularly relevant for the transport industry (automotive and aerospace) because this technology addresses the challenge of improving both the corrosion and tribological properties of light alloys commonly used to improve the energy efficiency of aeroplanes and vehicles.
Sectors Transport

 
Description This project has contributed significantly beyond academia by fostering interdisciplinary collaborations and facilitating public engagement in STEM. It has supported knowledge exchange across different disciplines, particularly in areas such as digitalised surface manufacturing and electrochemical energy devices, strengthening connections between researchers and broader scientific communities. The PI has actively promoted STEM awareness through various public engagement activities, including talks for British Science Week and the International Day of Women and Girls in Science. She also organised an annual Corrosion Photo Competition to engage wider audiences in materials science. Additionally, she co-organised the Women in STEM Conference, which attracted over 250 participants and provided a platform for knowledge sharing and networking. Furthermore, the PI's achievements have led to invitations to policy-related discussions, including participation in a UK Talent Meeting and a meeting with the Science Minister's Private Office. These opportunities allowed her to share insights on how her research connects with societal challenges, contributing to discussions on talent development and innovation strategy in the UK.
First Year Of Impact 2022
Sector Education,Transport
Impact Types Cultural

Societal

 
Description UK Talent Meeting
Geographic Reach National 
Policy Influence Type Participation in a guidance/advisory committee
 
Description Feasibility study - EPSRC NetworkPlus In Digitalised Surface Manufacturing, Digitalisation of the particulate aerosol deposition process,
Amount £18,000 (GBP)
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 12/2021 
End 07/2023
 
Description Multilevel strategies for corrosion control of magnesium-based biodegradable implants
Amount £6,000 (GBP)
Funding ID IES\R1\231345 
Organisation The Royal Society 
Sector Charity/Non Profit
Country United Kingdom
Start 08/2023 
End 08/2024
 
Description Research Recovery Fund, The University of Manchester, Tribocorrosion of light alloys
Amount £10,000 (GBP)
Organisation University of Manchester 
Sector Academic/University
Country United Kingdom
Start 12/2021 
End 08/2022
 
Description University of Manchester Interdisciplinary Research Grant
Amount £20,000 (GBP)
Organisation University of Manchester 
Sector Academic/University
Country United Kingdom
Start 01/2022 
End 07/2023
 
Description Collaboration with University of Aveiro 
Organisation University of Aveiro
Department Aveiro Institute of Materials
Country Portugal 
Sector Academic/University 
PI Contribution This collaboration has led to three grant proposals: - La Caixa Foundation Health research call - Dual action in trauma and bone disease: when smart biodegradability meets antibacterial action, 3 years (Total 791k EUR, 160k EUR for UoM) - Not Awarded - Royal Society International exchanges - Multilevel strategies for corrosion control of magnesium-based biodegradable implants, 1 year (Total 6k GBP) - Awarded The University of Manchester led the Royal Society international exchange application. If awarded researchers from both institutions will visit each other to learn complementary research techniques. - La Caixa Foundation - La Caixa Impulse- Implant failure prevention by dual-action coatings for Magnesium-based temporary orthopedic implants, 2 years (Total 50k EUR, 15k for UoM) - Under Review
Collaborator Contribution The University of Aveiro led the La Caixa Foundation Health and the La Caixa Impulse grants. They established the research consortium, wrote and submitted the proposal.
Impact This collaboration has resulted in two interdisciplinary grant applications. The topic of both grants is related to the development of smart surface treatments for temporal implants. Here we merged UoM's expertise in coating development and corrosion degradation with Aveiro's expertise in biomaterials and synthesis of nanocapsules for the smart release of antibiotics.
Start Year 2022
 
Description Collaboration with the Department of Chemical Engineering, The University of Manchester 
Organisation University of Manchester
Country United Kingdom 
Sector Academic/University 
PI Contribution This collaboration led to the award of the University of Manchester Interdisciplinary Research Institute grant which was written equally by both partners. The contribution of Dr Mingo's team to this collaboration was the synthesis of 2D nanoparticles to be used as fillers in polymeric based membranes for Electrochemical Energy Devices (EED). A member of Dr Mingo's group applied to an interdisciplinary hoping call funded by the University of Manchester (25k GBP) to spend 4 months at the collaborator's group to carry out a feasibility study. The proposal is still under review.
Collaborator Contribution The partner from the Chemical Engineering Department - Dr Perez-Page- was responsible for the development and testing of the membranes in Redox Flow Batteries. She was also responsible for writing and submitting an EPSRC grant which is still under review (Early career researcher international collaboration grant).
Impact The outputs of this collaboration are: - Award of the University of Manchester Interdisciplinary Research Institute grant, 20k GBP - Submission of EPSRC Early career researcher international collaboration grant, 200k GBP (Not awarded) - Submission of the University of Manchester Research Institute Discipline Hopping Call, 25k GBP (Not awarded) - One PhD studentship
Start Year 2021
 
Description Corrosion Awareness Day Photo Competition 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Undergraduate students
Results and Impact Dr Mingo's research group organised a competition to raise awareness of corrosion across industries and society. The competition was open to students in the UK to submit corrosion images ranging from photography to technical research images. The prize was a one-year membership to IOM3 and a £100 Amazon voucher. The pictures were published on social media. The European Federation of Corrosion highlighted this activity on their website.
Year(s) Of Engagement Activity 2021,2022,2023
URL https://www.linkedin.com/posts/beatriz-mingo-rom%C3%A1n-0698b69b_corrosionawarenessday-theuniversity...
 
Description International day of women and girls in science 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Local
Primary Audience Schools
Results and Impact Dr Mingo (2021, 2022 and 2023) and Dr Aliasghari (2023) gave a talk at Colegio Berriz Secondary School (Spain) and discussed the importance of representation and diversity in science. We also discussed our research topics and the steps to follow to become a scientist. We also talk about the University of Manchester history, courses and entry requirements.
Year(s) Of Engagement Activity 2021,2022,2023
 
Description Podcast Interview 
Form Of Engagement Activity A broadcast e.g. TV/radio/film/podcast (other than news/press)
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Media (as a channel to the public)
Results and Impact Dr Mingo was invited to the Research Beat, a science Podcast powered by Audemic, where she had the chance to share her latest progress in her research
Year(s) Of Engagement Activity 2022
URL https://audemic.io/the-research-beat/
 
Description Press release RAEng Award 
Form Of Engagement Activity A press release, press conference or response to a media enquiry/interview
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Public/other audiences
Results and Impact After the award press release several people contacted me to engage in new collaborations.
Year(s) Of Engagement Activity 2022
URL https://www.royce.ac.uk/news/beatriz-mingo-named-amongst-royal-academy-of-engineerings-five-young-en...
 
Description School visit, Springfield Primary School 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Local
Primary Audience Schools
Results and Impact Dr Mingo visited Springfield Primary school during British Science Week. She gave three talks to pupils in Year 1 (approximately 90 pupils). We talked about the different types of materials that we could spot around us and how we choose specific materials to make objects. It was a very interactive talk and the children had the chance to see and touch different materials (glass, wood, metals, plastics, etc). We also talked about the origin of materials (natural or man-made). At the end of the talk, we did an experiment to show how nappies work. The children had many questions about it.
Year(s) Of Engagement Activity 2023
 
Description Women in Engineering Day - Seminar at the Henry Royce Institute 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Local
Primary Audience Postgraduate students
Results and Impact Dr Mingo gave a talk on the occasion of Women in Engineering Day at the Henry Royce Institute. There were around 20 attendees. She talked about her journey to a career in light alloys - challenge, opportunity and achievements (professionally and personally). After the talk, the discussion focused on the main challenges faced by researchers with caring responsibilities and the support available in the university for them.
Year(s) Of Engagement Activity 2022
 
Description Women in STEM conference 2022 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach Regional
Primary Audience Undergraduate students
Results and Impact The Women in STEM Conference was a 2-day event held at The University of Manchester, whose aim was to showcase successful and inspirational women working in STEM that could serve as role models for students considering their career options. It was aimed at undergraduates, graduates, and industry experts. We secured a speaker schedule with representation from leading tech companies, CEOs of medical enterprises, IP attorneys and academics. The event was a great success with 251 registrations for the main event. It also included a commercialisation workshop, a networking event, and an exhibition with industrial partners. Sponsorship was provided from bp-ICAM, Royce and EPSRC.
Year(s) Of Engagement Activity 2022
URL https://www.eventbrite.co.uk/e/women-in-stem-tickets-388548909247?aff=ebdsoporgprofile