A mechanistic investigation of Pickering emulsion polymerization

Emulsion polymerization is an important industrial production method to prepare latexes. Polymer latex particles are typically 40-1000 nm and dispersed in water. The polymer dispersions find application in wide ranges of products, such as coatings and adhesives, gloves and condoms, paper textiles and carpets, concrete reinforcement, and so on.

Conventional emulsion polymerization processes make use of molecular surfactants, which aids the polymerization reaction during which the particles are made and keeps the polymer colloids dispersed in water.  We, and others, introduced Pickering emulsion polymerization a decade ago in which we replace common surfactants with inorganic nanoparticles.

In Pickering emulsion polymerization the polymer particles made are covered with an armor of the inorganic nanoparticles.  This offers a nanocomposite colloid which may have intriguing properties and features not present in conventional "naked" polymer latexes.

To fully exploit this innovation in emulsion polymers, a mechanistic understanding of the polymerization process is essential. Current understanding is limited which restricts the use of the technique in the fabrication of more complex, multilayered colloids.

In our paper, recently published in Polymer Chemistry, clarity is provided through an in-depth investigation into the Pickering emulsion polymerization of methyl methacrylate (MMA) in the presence of nano-sized colloidal silica (Ludox TM-40). Mechanistic insights are discussed by studying both the adsorption of the stabiliser to the surface of the latex particles and polymerization kinetics. The adhesion of the Pickering nanoparticles was found not to be spontaneous, as confirmed by cryo-TEM analysis of MMA droplets in water and monomer-swollen PMMA latexes. This supports the theory that the inorganic particles are driven towards the interface as a result of a heterocoagulation event in the water phase with a growing oligoradical. The emulsion polymerizations were monitored by reaction calorimetry in order to establish accurate values for monomer conversion and the overall rate of polymerizations (Rp). Rp increased for higher initial silica concentrations and the polymerizations were found to follow pseudo-bulk kinetics.

The paper can be read here: http://dx.doi.org/10.1039/C7PY00308K

Independent responsive behaviour and communication in hydrogel objects

Autonomous response mechanisms are vital to the survival of living organisms and play a key role in both biological function and independent behaviour. The design of artificial life, such as neural networks that model the human brain and robotic devices that can perform complex tasks, relies on programmed intelligence so that responses to stimuli are possible. Responsive synthetic materials can translate environmental stimuli into a direct material response, for example thermo-responsive shape change in polymer gels or light-triggered drug release from capsules. Materials that have the ability to moderate their own behaviour over time and selectively respond to their environment, however, display autonomy and more closely resemble those found in nature.

In our recent paper, published in Materials Horizons, we present soft hydrogel objects that possess an individually programmed time delay in their response to a shared environmental stimulus. We utilize the enzyme urease to programme a self-regulated change in pH, which in turn activates the designed response of gel disintegration. This design allows for independent response behaviour of a collection of hydrogel fibers which contain coloured oil droplets in a single closed system. In addition, we show that hydrogel beads can communicate with one another, hereby influencing their pre-programmed individual behaviour. 

The incorporation of responsive time control directly into soft matter objects demonstrates an advance in the field of autonomous materials.

The paper can be read at http://dx.doi.org/10.1039/C7MH00033B

Join BonLab as a PhD student in 2017

We are looking for enthusiastic and dedicated people to join the BonLab as a PhD student in October 2017. Do you have what it takes to work at the forefront in supracolloidal chemical engineering? 

You will be working under guidance of prof.dr.ir. Stefan A. F. Bon on an exciting 4 year project in collaboration with industry in the area of polymer and colloid science.

Prof.dr.ir. Stefan A. F. Bon

Prof.dr.ir. Stefan A. F. Bon

 

We study the chemistry and physics of colloidal systems in which molecular and/or colloidal entities can be assembled into more complex supracolloidal structures, with the aim to produce innovative advanced materials . The project will span synthesis of particles and macromolecules with a design tailored to provide function, the development of methods to (self)-organise colloidal matter, and the fabrication and characterization of advanced colloidal materials of use in a variety of industrial applications.

Enquiries, which should include a CV with the names of two referees, should be made to prof.dr.ir. Stefan A. F Bon (s.bon@warwick.ac.uk)

Requirements:

An eligible student must hold, or be predicted to obtain, at least a 2.1 4-year degree in Chemistry, Chemical Engineering, Physics, or an equivalent scientific discipline. Exceptional students with a 3 year BSc degree only will be considered. This studentship is open to UK and EU nationals and those of equivalent status* (fees paid, plus annum stipend). Availability is for 4 years beginning on 1st October 2017.

*Please note - ELIGIBILITY - We can only offer the stipend to UK citizens who have lived in the UK for over 3 years (e.g. as a student), or EU nationals. Applicants from outside the EU are not eligible for this post due to restrictions on funding.

 

BonLab will be at the 2017 International Polymer Colloids Group conference this summer

We at BonLab are excited and looking forward to the 2017 IPCG meeting, this time organised by prof. Prof. Jose R. Leiza from the University of the Basque Country (Spain) and Dr. Willie Lau from Oriental Yuhong (China). Prof.dr.ir. Stefan Bon will give a masterclass on polymer colloids in the preceeding Gordon Research Seminar to an international audience of postgraduate students. He will also give an invited talk in the main conference with the tentative title: Dynamic Supracolloidal Engineered Materials

The International Polymer Colloids GroupConference (IPCG2017) will bring together world leading scientists to discuss the latest developments in the area of colloidal polymer science. The talks of the invited speakers will feature a balance of traditional and emerging applications for polymer colloids, including advanced colloid monitoring techniques, morphology and film formation, hybrid colloids, colloids for life and biotechnological applications, and engineering colloids.

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The conference will take place in Arantzazu, which is a Sanctuary located in the town of Oñati in the Basque Country Region (Spain). The place benefits from the highland silence and peaceful atmosphere of the Aizkorri mountain range. The place is frequently visited by devotees (Virgin of Arantzazu) and tourists. Arantzazu is also a starting point for several mountains trails and circuits for hikers that provide access to the meadows of Urbia and on to the mountain range Aizkorri.

Stefan Bon previously chaired the 2015 IPCG meeting in New Hampshire, USA. More in this in one of our blog entries

Stefan Bon interviewed by freelance writer Chris Woolston for Nature

Prof.dr.ir. Stefan Bon had a pleasant conversation with freelance writer Chris Woolston on the UK visa and immigration policy of the UK and the impact on his research team. Stefan stressed that "the changing landscape of the UK with respect to immigration and work permits is of great concern and highly worrying. The UK is increasingly fast squandering its international reputation."

An article written by Chris was published in the scientific leading journal Nature today (02 March 2017, 543, 139–141) containing an excerpt of the discussion: "Long waits for English-proficiency tests have also vexed Stefan Bon, a chemical engineer at the University of Warwick in Coventry, UK. Last year, one of his postdocs had to travel from Germany to the Netherlands to take the test, and the whole process — scheduling it, taking it and waiting for the results — took almost six months. Bon says that principal investigators (PIs) should expect delays, and that all prospective lab members should take the test as early as possible."

 

Stefan Bon invited by ESC2017 - 16th European Student Colloid Conference

Prof.dr.ir. Stefan Bon has been invited to participate and talk at the European Students Colloid Conference, sponsored by ECIS (European Colloid & Interface Society) that will be held in Florence on June 19 - 22, 2017 (ESC2017).

He said: "I am absolutely delighted with the invitation. I am excited to participate and interact with students from all over Europe and discuss aspects of colloid science. I am very much looking forward to, what promises to be, an outstanding conference."

Prof.dr.ir. Stefan A. F. Bon 

Prof.dr.ir. Stefan A. F. Bon 

The meeting will be devoted to young physicists/chemists in the field of colloid science, and it will be a great opportunity for PhD students to present their research results and to meet their peers from different research units. 

The topics of the conference range from adsorption and interfacial phenomena, to biomaterials, to micro- and nano-structured materials... and much more. The conference program consists of oral and poster sessions, with many social events. Seven outstanding invited speakers have already confirmed their attendance.

Several prizes will be awarded for the best presentations, including the ECIS/ACIS prize for student exchange.

Abstract submission: February 1 - March 15, 2017

Notification of acceptance: April 15, 2017

Early bird registration deadline: May 15, 2017

Regular registration and bursary travel application deadline: May 29, 2017

For more information:

please visit: http://www.esc2017.it/

or email the ESC 2017 Organizing Committee: esc2017@csgi.unifi.it

Feel the sensation of emulsion polymerization

Master students at the University of Warwick registered on the Polymer MSc programmes were treated to an exciting labday by BonLab packed with polymer and colloid science. In the true spirit of "feel the sensation of emulsion polymerization", a slogan ascribed to dr. Harold Schoonbrood and originating from the research group of Anton German at the Eindhoven University of Technology in the 1990s, the students were fascinated by hands-on synthesis of a polymer latex and its particle size characterization.

Master students on the Polymer MSc programmes feel the sensation of emulsion polymerization, organized by prof.dr.ir. Stefan Bon with research members of BonLab

Master students on the Polymer MSc programmes feel the sensation of emulsion polymerization, organized by prof.dr.ir. Stefan Bon with research members of BonLab

Every student carried out their own emulsion polymerization under guidance of prof.dr.ir. Stefan Bon and two of the research members of the BonLab, Brooke Longbottom and Andrea Lotierzo. Emulsion polymerization is a process of high industrial relevance, with applications of the resulting polymer colloids in coatings/adhesives, construction, personal and household care, energy and health. The latex particles made by the participants were analysed by both dynamic light scattering, a technique relying on the random Brownian motion of the latex particles dispersed in water, and hands-on scanning electron microscopy (SEM).

Andrea Lotierzo, a PhD researcher in BonLab, works together with students on the characterization of a polymer latex with dynamic light scattering (DLS).

Andrea Lotierzo, a PhD researcher in BonLab, works together with students on the characterization of a polymer latex with dynamic light scattering (DLS).

 

The labday formed part of a postgraduate module on colloidal materials taught by prof.dr.ir. Stefan Bon. He says: "We at BonLab are delighted to give students hands-on experience in the fabrication and analysis of polymer colloids. This area is of tremendous value in the design of innovative materials, and it is key that the underlying knowledge is transferred to the next generation of scientists."  

Hands-on scanning electron microscopy training was provided by BonLab to the master students on the Polymer MSc programmes at the University of Warwick

Hands-on scanning electron microscopy training was provided by BonLab to the master students on the Polymer MSc programmes at the University of Warwick

More information:

please contact prof.dr.ir. Stefan A. F. Bon directly.

Images are courtesy of BonLab and taken by Junxin Chen (FEB2017).

Join Bonlab as a PhD student

2 PhD Studentships

Polymer and Colloid Chemical Engineering

Department of Chemistry

The University of Warwick (http://www.go.warwick.ac.uk/chemistry).

You will be working in the research group of prof.dr.ir. Stefan A. F. Bon, the BonLab (http://www.bonlab.info), on an exciting 4 year project in collaboration with industry in the area of polymer and colloid science. We study the chemistry and physics of colloidal systems in which molecular and/or colloidal entities can be assembled into more complex supracolloidal structures, with the aim to produce innovative advanced materials . Each project will span synthesis of particles and macromolecules with a design tailored to provide function, the development of methods to (self)-organise colloidal matter, and the fabrication and characterization of advanced colloidal materials of use in a variety of industrial applications.

Enquiries, which should include a CV with the names of two referees, should be made to prof.dr.ir. Stefan A. F Bon (s.bon@warwick.ac.uk)

Requirements:

An eligible student must hold, or be predicted to obtain, at least a 2.1 4-year degree in Chemistry, Chemical Engineering, Physics, or an equivalent scientific discipline. Exceptional students with a 3 year BSc degree only will be considered. This studentship is open to UK and EU nationals and those of equivalent status* (fees paid, plus annum stipend). Availability is for 4 years beginning on 1st October 2016.

*Please note - ELIGIBILITY - We can only offer the stipend to UK citizens who have lived in the UK for over 3 years (e.g. as a student), or EU nationals. Applicants from outside the EU are not eligible for this post due to restrictions on funding.

 

Join BonLab as a PhD Student

You will be working in the research team of prof. dr. ir. Stefan A. F. Bon (www.bonlab.info) on a collaborative project with industry in the area of polymer and colloid science. The project will deal with the development of stabilisers and porosity control agents for heterogeneous polymerization processes, with a focus on emulsion polymerization. 

Enquiries, which should include a CV with the names of two referees, should be made to prof. dr. ir. Stefan A. F. Bon (s.bon@warwick.ac.uk).

Requirements:

You must hold, or be predicted to obtain, a first class degree (2.1 may be considered) in Chemistry, Chemical Engineering, or Physics, ideally with some experience in polymer and/or colloid science. This studentship is open to UK and EU nationals and those of equivalent status. Applicants from outside the EU are not eligible for this post due to restrictions on funding.

Start date: As soon as possible from now.

BonLab features on the cover of Materials Horizons

Our manuscript entitled Control of vesicle membrane permeability with catalytic particles has been selected for the jan-feb 2016 cover of Materials Horizons, a premier scientific journal published by the Royal Society of Chemistry which features first reports of exceptional significance across the breadth of materials research at the cutting-edge interface with chemistry, physics, biology and engineering.

Prof.dr.ir. Stefan Bon says: "We are absolutely delighted that our research has made the cover of Materials Horizons. Rong Chen and especially Ross Jaggers worked very hard in the BonLab to fabricate giant polymer vesicles which have membrane-embedded catalytically active manganese oxide particles, hereby using droplet-based microfluidics. We demonstrate that these colloidal particles can regulate the membrane permeability of the polymersomes upon their exposure to, and catalytic reaction with, small amounts of dissolved hydrogen peroxide. Not only can we trigger complete release whereby the vesicle gets destroyed through membrane rupture by the formed oxygen bubbles as illustrated on the cover, exposure to small amounts of dissolved hydrogen peroxide leads to temporary enhanced release until all hydrogen peroxide is consumed by the catalytic particles after which the membrane permeability restores itself to its passive characteristic value." 

More on this can be read on our blog.

The paper (open access) can be read here:  http://dx.doi.org/10.1039/C5MH00093A