UNDERSTANDING THE STABILITY AND PROPERTIES OF BULK NANOBUBBLES

Lead Research Organisation: University of Birmingham
Department Name: Chemical Engineering

Abstract

Bulk nanobubbles are a novel type of nanoscale bubble system. They are spherical with a typical diameter of 100-200 nanometres and they exist in bulk liquid. The most peculiar characteristic of these bulk nanobubbles is their extraordinary longevity. Whilst the lifetime of macrobubbles (> 1 mm) is on the order of seconds and that of microbubbles (1-1000 microns) is on the order of minutes, nanobubbles do last for weeks and months. Existing theories, however, predict a huge inner gas pressure (typically around 30 atm) and, consequently, molecular diffusion theory would predict that they would dissolve extremely quickly - on a timescale of about 1 microsecond.

The existence of bulk nanobubbles has been reported by a number of academic researchers but due to their unusual behaviour there is still some controversy around the subject. In a preliminary study in collaboration with the IDEC Corporation in Osaka (Japan), we have managed to generate nanobubbles via two different techniques and, using advanced instrumentation, we have been able to visualise them and measure their size distribution.

Because of their unusual longevity bulk nanobubbles are already attracting a lot of industrial attention and many potential applications have been identified or tested, especially in Japan and USA. Thus, there is immense scope for nanobubbles to impact and even revolutionise many current industrial processes such as water treatment, industrial cleaning and the production of chemicals, biofuels, food as well as other important high value added applications including healthcare technologies.

There is, however, little academic or industrial activity taking place within Europe and the UK. As such, there is an urgent need for research on this subject so as to enable the UK to keep up with this emerging scientific field and so that UK industry can benefit from the vast potential of this novel technology.

From a scientific point of view, the mystery behind the longevity of bulk nanobubbles has led to many different speculations as to the reasons for this phenomenon. However, reports are sparse, and in the main conflicting and have not been independently validated. An aspect to be considered is that nanobubbles are not macroscopic systems and so everyday thermodynamics is not reliable. Furthermore, atomistic simulations on this scale are only now becoming feasible. To fully exploit the potential benefits of bulk nanobubbles, our understanding of the fundamental rules governing their existence and behaviour needs to be substantially improved.

Our hypothesis is that bulk nanobubbles do exist, they are filled with gas and they persist for a timescale at least ten orders of magnitude longer than expected. The aim of this proposal is to explore and study the underlying mechanisms by which they come to exist and persist, and to help explain some of the reported unusual properties of bulk nanobubble suspensions using a combination of experimental, theoretical and computational tools.

The work will address questions concerning the formation of nanobubbles, their coalescence, dynamic behaviour and stability, including their apparent immunity to the destabilising process of coarsening or disproportionation, also known as Ostwald ripening. The effects of liquid properties, gas properties, shear and temperature will be studied experimentally, modelled theoretically and simulated computationally by molecular dynamics. The practical aim of the present project is to develop robust predictive tools based on the knowledge gained from the experimental and modelling work, as an aid to industrial practitioners. These tools will provide a description of the structural and dynamical properties of bulk nanobubbles in terms of the liquid and gas intrinsic properties as well as external parameters like pressure and temperature. We will also work with our industrial partners to help them explore and develop novel applications.

Planned Impact

Bulk nanobubbles challenge our understanding of bubble physics and behaviour. Their extraordinary persistence and their generally puzzling behaviour require us to revisit many aspects of existing bubble science. The issues at stake engage both academic researchers looking to probe, understand and model these entities, and industrialists seeking to exploit their remarkable properties to develop new applications or to enhance existing ones based on understanding rather than via trial and error.

Previous gas-liquid research at Birmingham has made substantial academic impact and has led to many national and international collaborations. The Atomistic Simulation Centre at QUB has generated a number of significant advances in the understanding of materials at the atomic scale by means of theory and computer simulation, whilst STFC Daresbury Laboratory has been a key international player in the development of advanced software for materials simulation. We expect that the combination of our strengths will result in new interdisciplinary views and tools for the study of gas-liquid systems and multiphase systems in general, delivering high impact fundamental research across disciplinary boundaries between several EPSRC areas, e.g. Fluid Dynamics, Process Engineering, Computational and Theoretical Physical Sciences, Particle Technology, Complex Fluids and Rheology, and Innovative Production Processes. This work also spans multiple EPSRC themes, e.g. Engineering, Manufacturing the Future, Physical Sciences, and Healthcare Technologies.

The computational methods used and developed in this project are generic and are thus applicable to other types of two-phase nanoscale systems, e.g. surface nanobubbles, nanoparticles and nanodroplets. In addition, we will further develop a range of new enhanced sampling methodologies introduced by one of us (Tribello), which are applicable to a very wide range of phenomena in biochemistry, chemistry, and materials science. These promising methods have not yet been adopted widely, mostly because they have only been tested on model systems. Here, we have an opportunity to use them to study a real complex problem of industrial relevance and to ensure that they work for system sizes that challenge both the software and the infrastructure of the UK's largest HPC resource.

There is immense scope for bulk nanobubbles to impact and revolutionise many current industrial processes, as reported by the 'Fine Bubbles Industries Association' in Japan (FBIA-Japan), including water treatment, industrial cleaning and the production of chemicals, biofuels, food and pharmaceuticals as well as other important high value added applications such as in the biotechnology and medical fields. This research has the potential to impact all these industries by improving our understanding of these nanobubble systems and by giving us the ability to predict their behaviour and, hence, to provide guidance to industrial practitioners involved in developing innovative applications.

Two of us (Barigou and Pacek) have been involved through FBIA-Japan and the BSI in the creation of the new ISO Technical Committee on Fine Bubble Technologies (ISO/TC281), and are currently involved in the creation of FBIA-Europe, to promote fine bubble technologies in Europe.

More specifically, this research is supported by Unilever (food/personal care), PepsiCo (food/drinks), Mondelez (confectionery/coffee), who are keen to explore and develop novel applications; Particle Technology, an SME who are keen to incorporate nanobubbles in their cleaning techniques for the aerospace, medical, pharmaceutical and telecommunications industries; and Malvern Instruments who are keen to enhance/develop instrumentation for nanoparticle characterisation. During the project, we will share results and ideas with all of them and we will also engage with them to help them evaluate and develop industrial applications specific to their own businesses.
 
Description - Existence of bulk nanobubbles: we have fulfilled one of the main and crucial objectives of the research by establishing beyond any reasonable doubt that bulk nanobubbles do exist and they are stable, therefore, hopefully ending the debate about their existence as well as their unusual longevity. We have also identified a number of analytical techniques which can distinguish nanobubbles from other nanoscale contamination. Characterisation of bulk nanobubbles: we have demonstrated the size, the long-term stability and the electrical surface charge of bulk nanobubbles. We have established that the surface charge is the primary factor behind the longevity of these entities. We have also studied the behaviour of bulk nanobubbles in various physical (e.g. temperature) and chemical environments (acidic, basic, salt, surfactants, pH, conductivity). Bulk nanobubble generation: we have developed a number of techniques for generating bulk nanobubble suspensions: (i) method based on the use of high-intensity ultrasound; (ii) electrochemical method based on water electrolysis; (iii) method which uses a microfluidiser based on forcing water to flow under high pressure (300-1500 bar) through a narrow (75 micron) diameter channel. In addition, we have tested other techniques: (iv) the NanoGalf nanobubble generator invented by the IDEC corporation (Japan), supplied to us by the manufacturer who is a collaborator on this project; this device produces nanobubbles by varied pressure levels of liquid flow through a series of tubes of different diameters ending in a nozzle; (v) flow through a venturi; (vi) mechanical high-shear rotor-stator device in both batch and continuous modes. More recently (2018-19), we have developed a solvent-water mixing method for spontaneous generation of bulk nanobubbles. We have also characterised and compared the performance of all these techniques. Production of concentrated nanobubble suspensions: we have demonstrated two techniques (albeit both energy intensive and, hence, not economically viable) by which nanobubble suspensions can be concentrated, i.e. the number of nanobubble per unit volume is enhanced: (i) by vaporization of water either via boiling or under vacuum; and (ii) by nano-filtration. The interesting point here is that boiling/vacuum does not affect the integrity of the nanobubbles.

- Important new research questions which have arisen and which need to be addressed in future projects include: (i) how to efficiently and economically produce large bubble number densities to give significant gas holdups of at least a few percent so that industrial applications can become attractive (e.g. food), which is currently not doable; (ii) the effect of very high pressure on nanobubbles: this may be important for experimental estimation of the actual (unknown) pressure inside the nanobubbles and, hence, for shedding more light on their stability mechanism.

- Negative results highlighted by the work include the inadequacy of well-known analytical methods (e.g. chromatography, mass spectrophotometry, FTIR, NMR, raman spectrometry) to quantify the type of gas inside nanobubbles and its volume concentration.

- The grant enabled the training of two postdoctoral research fellows and three PhD students and many engineering graduates in the field of bulk nanobubbles and nanotechnolgy. We have developed a number of collaborations including with: the School of Dentistry, the School of medicine, Malvern instruments for the use and analysis of nanobubbles.
Exploitation Route The experimental and theoretical methodologies developed here will be applied to the study of nanobubbles, but they are generic and therefore applicable to other types of two-phase systems. Through our scientific publications and conference communications, academics working in a variety of themes such as food formulations, cleaning, nanoemulsions, nanoparticles and foams, fuel cells, biofuels, two-phase flow, catalysis, and gas-liquid reactors, will benefit from these findings. Similarly, academics in other institutions in the UK and worldwide will equally benefit.

The knowledge developed from theory, modelling and experiment, will directly benefited to world leading companies: e.g. Unilever (food, person care product), Mondelez (confectionery, coffee), Particle Technology (surface cleaning), and PepsiCo (food, beverages), they can use these finding to develop novel applications of bulk nanobubbles in their own areas of interest.
Sectors Agriculture, Food and Drink,Chemicals,Energy,Environment,Healthcare,Manufacturing, including Industrial Biotechology,Pharmaceuticals and Medical Biotechnology

 
Description Comparison of different analysis techniques of nanobubbles in collaboration with Malvern Instruments Ltd. (Archimedes, Nanosight, Zetasizer); this led to new plans for further developments of the novel Archimedes instrument; a new variant of the novel Archimedes instrument has been developed based on a nano-scale sensor instead of micro-scale sensor. Collaboration with Oxfiniti Ltd. has led to the development of pilot and lab scale test rigs for studying the application of bulk nanobubbles to a superoxygenation process for water purification.
First Year Of Impact 2016
Sector Creative Economy,Manufacturing, including Industrial Biotechology,Other
Impact Types Economic

 
Description First RSE Conference - 15-16 September 2016 @ Manchester
Geographic Reach Multiple continents/international 
Policy Influence Type Membership of a guideline committee
Impact I was elected at the first voted for UK RSE Executive Committee to advise on its own future and work towards the recognition and professionalisation of software development work within research environments; as UK and USA academia and other research institutions, as well as advise and influence EPSRC and NSFon these needs, the path to and implications when addressing them.
URL https://ukrse.github.io/conf2016
 
Description EPSRC Doctoral Training Account
Amount £60,000 (GBP)
Funding ID PhD student: Georgios Papagiannidis 
Organisation University of Birmingham 
Sector Academic/University
Country United Kingdom
Start 11/2018 
End 11/2021
 
Description EPSRC Doctoral Training Account
Amount £55,000 (GBP)
Funding ID PhD student: Leslie Labarre 
Organisation University of Birmingham 
Sector Academic/University
Country United Kingdom
Start 09/2015 
End 09/2018
 
Description EPSRC Doctoral Training Account
Amount £55,000 (GBP)
Funding ID PhD student: Gianluca Ferraro 
Organisation University of Birmingham 
Sector Academic/University
Country United Kingdom
Start 09/2016 
End 09/2019
 
Description Campden BRI 
Organisation Campden BRI
Country United Kingdom 
Sector Private 
PI Contribution Intellectual input; Expertise; Data
Collaborator Contribution Intellectual input; Expertise; Data
Impact Collaboration is multi-disciplinary: chemical engineering; food processing
Start Year 2016
 
Description Dental cleaning application of bulk nanobubbles 
Organisation University of Birmingham
Department School of Dentistry
Country United Kingdom 
Sector Academic/University 
PI Contribution Intellectual input, expertise, data, experimental techniques and nanobubble samples
Collaborator Contribution Intellectual input, expertise, data, experimental techniques, dental cleaning samples
Impact Collaboration is inter-disciplinary: chemical engineering; dentistry. One joint review paper so far.
Start Year 2018
 
Description IDEC Corporation 
Organisation IDEC Global
Department IDEC Corporation Japan
Country Global 
Sector Private 
PI Contribution Evaluation of equipment for nanobubble generation (intellectual input; expertise; data)
Collaborator Contribution Provision of Nanogalf generation-3 equipment for nanobubble generation, access to data, expertise, staff time
Impact Evaluation of Nanogalf generation-3 equipment for nanobubble generation which led to development of new generation-4 equipment multi-disciplinary: Chemical Engineering; Environmental; Instrumentation
Start Year 2015
 
Description LBI/50 Fine Bubble Technology (FBT) 
Organisation British Standards Institute (BSI Group)
Country United Kingdom 
Sector Charity/Non Profit 
PI Contribution Intellectual input, expertise and data to ISO/TC 281: standards on fine bubble technology. Prof. Barigou has been nominated as expert member of the Committee: LBI/50 Fine Bubble Technology (FBT).
Collaborator Contribution Intellectual input
Impact Collaboration is multi-disciplinary: chemical engineering; physics; chemistry; colloid science; material science; food processing; environmental; instrumentation No outcome so far.
Start Year 2015
 
Description Malvern 
Organisation Malvern Instruments
Country United Kingdom 
Sector Private 
PI Contribution Intellectual input; expertise; experimental data
Collaborator Contribution Free loan of equipment; training of staff and research students; use of instruments and facilities in company labs; Large discount on Malvern ZSP Zetasizer for characterising nanobubbles (value approximately £40,000)
Impact Comparison of different analysis techniques of nanobubbles (Archimedes, Nanosight, Zetasizer); this led to new plans for further developments of the novel Archimedes instrument; a new variant of the novel Archimedes instrument has been developed based on a nano-scale sensor instead of micro-scale sensor. Collaboration is multi-disciplinary: Chemical Engineering; Instrumentation
Start Year 2015
 
Description Medical applications of nanobubbles 
Organisation University of Birmingham
Department School of Clinical and Experimental Medicine Birmingham
Country United Kingdom 
Sector Academic/University 
PI Contribution Intellectual input, expertise, data, experimental techniques and nanobubble samples
Collaborator Contribution Intellectual input, expertise, data, experimental techniques and models, experimental trials
Impact Collaboration is multi-disciplinary: chemical engineering; medicine; pharmacy
Start Year 2016
 
Description Oxfiniti Super Oxygenation System 
Organisation Oxfiniti
Country United Kingdom 
Sector Private 
PI Contribution Intellectual input; expertise; experimental data
Collaborator Contribution Industrial expertise on use of bulk nanobubbles for water purification
Impact Building of a pilot scale and Lab scale test rigs for a superoxygentation water purification system using bulk nanobubbles.
Start Year 2018
 
Description DL_POLY'S 25TH ANNIVERSARY SPECIAL MEETING- 3rd November 2017 @ Chicheley Hall 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact The event was organised to celebrate the DL_POLY project anniversary and its successes with former and current project contributors and stakeholders.

Molecular Simulation Special Issue

To celebrate the project anniversary we have organised a Molecular Simulation special issue "DL_POLY: Twenty five years of molecular dynamics evolution". The papers will be refereed and will focus on modelling, methodology or numerical/algorithm/software developments related to or carried out with the help of DL_POLY (or its spinoffs DL_MULTI, DL_MESO_DPD). We are looking for high standard unpublished research as well as new angle reflections and summaries of recently published research (with appropriate citations and acknowledgements to originally published work)

Submission Site
Information for authors
The submission deadline is at the end of January 2018.

PROGRAMME
3 November 2017

08.30-09.00 Registration with Tea/Coffee

09.00-09.05 Official opening (Ilian Todorov)

Chair: Ilian Todorov

09.05-09.35 Prof. Martin Dove (QMUL) - Molecular dynamics simulations of carbon capture by porous hybrid materials

09.40-10.10 Dr. Patrice Bordat (University of Pau) - Solvation and free energy module implemented in DL_POLY: Study for a preferential CO2/CH4 adsorption in silica monoliths

10.15-10.35 Tea/Coffee Break

Chair: Tim Forester

10.40-11.10 Prof. John Harding (University of Sheffield) - Understanding biomineralisation: what has DL_POLY ever done for us?

11.15-11.45 Dr. Simone Melchionna (ISC-CNR) - Proteins and multiscale biology: the long time legacy of DL_POLY

11.50-12.20 Prof. Richard Catlow (UCL/University of Cardiff) - Molecular dynamics in Catalytic systems

12.25-13.25 Lunch

Chair: Maurice Leslie

13.30-14.00 Dr. Kostya Trachenko (QMUL) - Using DL_POLY to understand radiation damage effects and soft matter (glasses, liquids, supercritical fluids)

14.05-14.35 Dr. P.-L. Chau (Institut Pasteur) - General Anaestheics and Membrane Interactions

14.40-15.10 Dr. David Quigley (University of Warwick) - The Hackademic Approach to Simulations with DL_POLY

15.10-15.30 Tea/Coffee Break

Chair: Neil Allan

15.35-16.05 Prof. Steve Parker (University of Bath) - Atomistic Simulations of Oxide and Mineral Interfaces

16.10-16.40 Prof. Martyn Guest (University of Cardiff) - DL_POLY - A Performance Overview; Analysing, Understanding and Exploiting available HPC Technology

16.45-17.25 Closing Remarks by Prof. William Smith - A Short History of DL_POLY
Year(s) Of Engagement Activity 2017
URL https://www.ccp5.ac.uk/events/dl_poly_25
 
Description ISO Committee Meeting 
Form Of Engagement Activity A formal working group, expert panel or dialogue
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Industry/Business
Results and Impact Meeting of ISO Committee (LBI/50 Fine Bubble Technology (FBT) ) to discuss proposal for new standard on fine bubble technology; University of Birmingham, 05 October 2015.
Year(s) Of Engagement Activity 2015
URL http://standardsproposals.bsigroup.com/Home/Proposal/5100