Glass functionalisation and decoration with nanoparticles: A challenging way to induce new applications

  • Acronym: Glass
  • Project Code: PN-III-P1-1.1-TE-2021-1242
  • Contract Number: 95TE
  • Start: 15/05/2022
    End: 13/09/2024
  • Duration: 28 months
  • Budget: 445.000,00  Lei
  • Contracting Agency:: Executive Agency for Higher Education, Research, Development and Innovation Funding

  • Coordinating Institution: : National University for Science and Technology POLITEHNICA Bucharest – National Research Center for Micro and Nanomaterials

    Address: Spl. Independentei 313, Sector 6, Bucharest, Romania
    Phone: +4021.402.9465

Coordinator – University POLITEHNICA of Bucharest

Project Manager: Prof. Habil. PhD. Eng. Anton FICAI

Researcher PhD. Ionela-Andreea NEACȘU

PhD Stud. Ludmila MOTELICA

PhD. Stud.  Cornelia-Ioana ILIE

PhD. Stud. Georgiana DOLETE

PhD. Stud. Alexa Maria CROITORU

PhD. Stud. Alexandra Cătălina BÎRCĂ

PhD. Stud. Georgiana Mădălina Lemnaru (POPA)

PhD. Stud. Valentin George SĂFTOIU

The project scope is to generate new valences of the glass supports by functionalisation and immobilisation of nanoparticles and also by functionalisation with specific functional groups. Currently, self-cleaning is assured to the glass windows especially due to the presence of a thin coating of TiO2 – according to a photocatalytic mechanism. In this proposal, we are going to develop some organic coatings able to maintain clean surface due to a biomimetic approach that involves the surface functionalisation with (poly)ethylene glycol-like molecules which assure a biomimetic self-cleaning mechanism, similar to the wings of many flies and butterflies and leaves of plants. The generated (coated/functionalised) glasses can be important tools in sample preparation and advanced analysis, which can be useful even in the evaluation of traces because these innovative surfaces can assure a concentration of the analytes onto their surfaces. The proposed solutions are feasible. The team already has proven expertise in glass or silica functionalisation, nanoparticles synthesis, sorption and desorption of analytes, etc.

The aim of this project is to expand the uses of glass and prove its versatility through advanced functionalization. Glass is a highly used material due to its inert nature which makes it suitable for various applications, from construction to domestic or niche applications, including electronics, automotive, etc. An important aspect that must be mentioned is the discovery of conductive glasses or bioactive glasses. The project proposal assumed some very well-identified applications (for example, functionalization to increase compatibility with polymers – and not only being known the expanding of the applications of composite materials, including construction; development of reactive surfaces capable of binding a wide range of species such as heavy metals, drugs, pesticides, toxic compounds, etc; or to ensure, on the contrary, to develop of anti-fingerprint surfaces (even if the sebum and ions are not removed, their arrangement is disturbed so that the hill/valley structure to be not recognizable), the development of sensory surfaces capable of selectively binding the compounds of interest; etc.). These desires were achieved by chemical functionalization, and the most suitable method is based on silanization with proper silanisation agent. The support is the key factor, so that of all the materials available and studied, glass was chosen, due to its very good stability and the possibility of functionalization by means of silanol groups. Within the project, the modification and characterization processes of the modified glass surfaces were developed starting from flat borosilicate glass surfaces (standard microscope slides) with various functionalizing agents to induce the varied properties required for very wide fields of applications: medical, environmental, sensorial, etc. The modification of the surfaces was carried out by chemical techniques, in an aqueous medium, in order to decorate the surface with various functional groups: amino, thio, hydroxy, etc., or by decorating with Ag nanoparticles capable of subsequently bind other molecules of interest through a direct, simple or by self-assembling approach.

The project was designed in two major scientific topics, one related to the surface modification with functional groups and the second by decoration of the glass surfaces with nanoparticles. In fact, the second major objective is based on the first one, the nanoparticles being attached on the surface via the thiolic groups which can assure a strong binding and thus a long-lasting effect. The surface modification with functional groups was proved to be suitable and, based on the patent application several potential applications were identified. The modification was done directly, by silanisation (and in this case alkyl, aminopropyl, mercaptopropyl, … moieties were easily introduced but also, by a self-assembling methodology, in this case the optimization should be based on the complementarity between the length and nature of the moiety chemically bonded within the silanisation process and the overall characteristics of the mobile layer. Good results in this case were obtained with the APTMS/PEG pair when anti-fingerprint surfaces were obtained. The decoration with Ag nanoparticles were done using mercapropropyl followed by AgNPs absorption while these nanoparticles can be further used in the absorption of specific agents, especially mercapto-derivatives (from many classes, drugs, pesticides, …) with potential applications as specific sorbent for sampling but also as sensors.

As potential perspectives, we can list the further extension of these studies using conductive glasses and respectively active glasses so that the above-mentioned surface modifications affect the electrical conductivity of conductive glasses and thus can be used directly in sensoristics and respectively to work with bioactive glasses with greater reactivity and which could ensure a greater degree of functionalization (and implicitly the attachment of a greater number of functional groups of interest) or, their use in a complex manner, in which the adsorption of the analytes of interest is controlled by the resorption of the support, thus being able to highlight the presence of some analytes, especially above certain concentrations.

As a result of the strong applicative character, an application for an invention patent based on the modification of the glass surface was submitted within the project, an invention patent that was otherwise already appreciated in invention salons or professional conferences, obtaining numerous distinctions (2 gold medals, one silver medal as well as 4 special prizes awarded by the participating official delegations (IRAN, Canada, Croatia) obtained at the invention salons in Chisinau, Moldova; Iași, Romania and Toronto, Canada. Currently, there are 3 Q1/Q2 articles published and 2 more articles are under review (also in Q1/Q2 journals), according to the report. Furthermore, some of the mentioned perspectives are included in a PTE project application.

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Scientific Papers:

  1. Gabriela DANILIUC; Cornelia ILIE; Angela SPOIALA; Ludmila MOTELICA; Constantin MIREA; Denisa FICAI, Anton FICAI; Developing Anti-Fingerprint (Mobile) Glass Surfaces by Silanization and Self-Assembling; Applied Surface Science; under review
  2. Cornelia-Ioana Ilie, Angela Spoială, Ludmila Motelica, Liliana Marinescu, Zeno Ghizdăveț, Doina-Roxana Trușcă, Ovidiu-Cristian Oprea, Denisa Ficai, Anton Ficai; Ag NPs-decorated glass surfaces for sensing in medical applications; Microchemical Journal; under review
  3. V. Saftoiu, C. Constantin, A.I. Nicoara, G. Pelin, D. Ficai, A. Ficai, Glass Fibre-Reinforced Composite Materials Used in the Aeronautical Transport Sector: A Critical Circular Economy Point of View, Sustainability-Basel 16(11) (2024).
  4. L. Mîrt, D. Ficai, O.C. Oprea, G. Vasilievici, A. Ficai, Current and Future Perspectives of Bioactive Glasses as Injectable Material, Nanomaterials-Basel 14(14) (2024).
  5. I. Ilie, A. Spoiala, L. Motelica, L. Marinescu, G. Dolete, D.R. Trusca, O.C. Oprea, D. Ficai, A. Ficai, M.J. Fabra, Decoration of a Glass Surface with AgNPs Using Thio-Derivates for Environmental Applications, Coatings 14(1) (2024).
  6. V. Saftoiu, C. Constantin, A.I. Nicoara, G. Pelin, D. Ficai, A. Ficai, Glass Fabrics Functionalization for the Development of High-Performance Sandwich Structures, U Politeh Buch Ser B 85(1) (2023) 17-28.

Patent application:

  1. Cornelia-Ioana ILIE, Angela SPOIALA, Ludmila MOTELICA, Denisa FICAI, Ovidiu-Cristian OPREA; Anton Ficai, Procedeu de modificare strat cu strat a suprafeței de sticlă; A00797/06/12/2022

Dissemination at conferences and invention and innovation fairs / awards

  1. Cornelia-Ioana ILIE, Angela SPOIALA, Ludmila MOTELICA, Denisa FICAI, Ovidiu-Cristian OPREA; Anton Ficai, Process of glass surface modification by a layer by layer approach / Procedeu de modificare strat cu strat a suprafeței de sticlă; A00797/06/12/2022; 9th International Invention Innovation Competition in Canada – ICan 2024; August 24, Toronto, Canada
  • Gold medal awarded by the International Jury of the International Salon
  • International Special Award awarded by The First Institute of Inventors and Researchers in I.R. IRAN (FIRI)
  • Canadian Special Award awarded by Innovation Initiative Co-operative Inc. “The Inventors Circle”
  1. Cornelia Ioana ILIE, Ludmila MOTELICA, Angela SPOIALĂ, Denisa FICAI, Ovidiu Cristian OPREA, Anton FICAI; Glass functionalization and decoration with nanoparticles: a challenging way to induce new applications; Patent application No. A100797/06.12.2022; International Salon of Invention and Innovative Entreprenorship, 12-13 Octomber 2023, Chisinau, Moldova
  • Silver medal awarded by the International Jury of the International Salon
  1. Cornelia Ioana ILIE, Ludmila MOTELICA, Angela SPOIALĂ, Denisa FICAI, Ovidiu Cristian OPREA, Anton FICAI; Glass functionalization and decoration with nanoparticles: a challenging way to induce new applications; Patent application No. A100797/06.12.2022; 15th European Exhibition of Creativity and Innovation-EuroInvent 2023, 13 May 2023, Iaşi, Romania
  • Gold medal awarded by the International Jury of the International Salon
  • Certificate of Excellence awarded by the University POLITEHNICA of Timişoara
  • Special Award Croatian Inventors Network
  • Excellence Diploma awarded by Asociatia Justin Capra
  1. George Valentin SAFTOIU, Ludmila MOTELICA, Georgiana DOLETE, Roxana TRUSCA, Denisa FICAI, Ovidiu Cristian OPREA, Ecaterina ANDRONESCU, Anton FICAI; Functional glass surfaces for emerging applications sasa; RICCCE 22; 7-9 Septembrie, Sinaia, România
  2. Gabriela DANILIUC, Cornelia ILIE, George Valentin SĂFTOIU, Ludmila MOTELICA, Angela SPOIALA, Denisa FICAI, Anton FICAI; Glass, a material with tunable properties / Sticla, un material cu proprietăţi accordabile; Conferinţa AGEPI (National Intellectual Property Agency of Moldova); 27.04.2023; Chisinau, Moldova;
  3. Cornelia ILIE, Ludmila MOTELICA, Denisa FICAI, Roxana Doina TRUSCA, Ovidiu Cristian OPREA, Anton FICAI; New perspectives of the silicates based materials: from classical to emerging applications of glasses; 8th International Conference on Nanotechnology: Fundamentals and applications (ICNFA’23); 9-11.08.2024; London.
  4. Anton Ficai, Gabriela Daniliuc, Cornelia-Ioana Ilie, Angela Spoială, Ludmila Motelica, Georgiana Dolete, Doina-Roxana Trușcă, Denisa Ficai and Ovidiu-Cristian Oprea; Self assembling processes on glass surfaces: a strategy to generate new functionalities; 6th EuChemS Inorganic Chemistry Conference; 03 – 07.09.2023; Viena
  5. Cornelia Ioana ILIE, Ludmila MOTELICA, Angela SPOIALĂ, Denisa FICAI, Ovidiu Cristian OPREA, Anton FICAI; Anti-fingerprint glass surface developed by advanced chemical modification based on chemical modification with aminopropyl moieties followed by self-assembling; 15th International Conference on Nanotechnology: Fundamentals and Applications (ICNFA 2024); 25-27.08.2024; Barcelona, Spain;
  6. Anton FICAI; Rolul Chimiei în Contextul secolului XXI; 20.05.2024 (conference aimed to popularize science among pre-university chemistry students and teachers).

In addition to these indicators, professional training of some young people was carried out within the project, among which I mention:

Gabriela Daniliuc defended her dissertation Antifingerprint glass surfaces for special applications; within the Master Program: Applications of Chemistry in Forensic Science;

Luiza Mirţ is a doctoral student with a doctoral thesis in the field of active glasses, being a doctoral student under the international co-supervision with Friedriche-Alexander Universitat, Erlangen Germany (professor Aldo Boccaccini).

Currently, there is a project application within “Centers of Excellence” call on the societal impact area 1.5. Circular economy (of which I am the project director and which also includes an oxide materials component, from the point of view of circularity and performance improvement) but also a PTE project to advance the TRL scale towards product(s).

The project proposal “Microfluidics-Based Ex Vivo Mimetic System for Facultative-Anaerobic Microbiota”, registered at HORIZON-HLTH-2024-TOOL-05-two-stage and containing an important component related to the modification of the glass/polymer surface from which we would realize the microfluidic device was selected in the second evaluation phase (one of the 15 projects out of the 198 submitted, A. Ficai being the director of the submitted H2024 project) but was not funded in the end.