Innovation in Emulsion Polymerization process opens window to Janus and patchy particles

Emulsion polymerization is of pivotal importance as a route to the fabrication of water-based synthetic polymer colloids. The product is often referred to as a polymer latex and plays a crucial role in a wide variety of applications spanning coatings (protective/decorative/automotive), adhesives (pressure sensitive/laminating/construction), paper and inks, gloves and condoms, carpets, non-wovens, leather, asphalt paving, redispersible powders, and as plastic material modifiers.

Since its discovery in the 1920s the emulsion polymerization process and its mechanistic understanding has evolved. Our most noticeable past contributions include the first reversible-deactivation nitroxide-mediated radical emulsion polymerization (Macromolecules 1997: DOI 10.1021/ma961003s), and the development and mechanistic understanding of Pickering mini-emulsion (Macromolecules 2005: DOI 10.1021/ma051070z) and emulsion polymerization processes (J. Am. Chem. Soc. 2008: DOI 10.1021/ja807242k). The latest on nano-silica stabilized Pickering Emulsion Polymerization from our lab can be found here.

One quest in emulsion polymerization technology that remains challenging and intriguing is control of the particle morphology. It is of importance as the architecture of the polymer colloid influences its behavioural properties when used in applications. We now report in ACS Nano an elegant innovation in the emulsion polymerization process which makes use of nanogels as stabilizers and allows us to fabricate Janus and patchy polymer colloids.

False coloured SEM images of emulsion polymerizations using nanogels as stabilizers (N1) at 2.8 wt% wrt monomer in which the pH was adjusted to 8.8 (A), 5.5 (B), 5.0 (C) and 4.5 (D) prior to polymerization. Scale bars: 100 nm.

The use of the nanogels in the emulsion polymerization leads to anisotropic Janus and patchy colloids, where a latex particle is decorated with a number of patches on its surface. In the paper we show that control of particle size and patch density can be achieved by tailoring the reaction conditions.

Proposed mechanism for the formation of Janus and patchy particles in the emulsion polymerization of styrene carried out in presence of nanogel particles.

The work was carried out by a team of talented scientists from the BonLab, Andrea Lotierzo, Brooke Longbottom, and Wai Hin Lee. Prof.dr.ir. Stefan Bon says: “ I am absolutely delighted that our work is published in the internationally leading journal ACS Nano. It is a great achievement of the team who have worked tremendously hard in the realisation of this new innovative technology. It shows that the area of emulsion polymerization is very much alive and kicking!”

The link to the paper is here: DOI: 10.1021/acsnano.8b06557

BonLab joins the Bio Electricity Group and the Bio Electrical Engineering (BEE) Hub

The BonLab at Warwick University specialises in the fabrication of colloidal and macromolecular materials for a wide range of applications, including coatings/adhesives, personal/household care products, and confectionary. BonLab's recent scientific activity in the fields of autonomous and programmable colloidal gels and active colloidal matter drew attention from researchers in life sciences.

Prof.dr.ir. Stefan Bon says: "We are delighted with the invitation to join the bio electricity group and the bio electrical engineering (BEE) hub, hosted at Warwick University. We hope that our scientific portfolio and know-how will provide a synergistic angle and will help innovate in this exciting area of science"

Information on the Bio Electricity Group:

Despite the early works of Luigi Galvani in the 18th century, the experimental inquiry into the biological systems has never fully taken an electrical viewpoint. Galvani’s, and subsequently Alessandro Volta’s, studies led to the discovery of the electrical battery and the birth of electrochemistry, but the biological thread have been largely neglected outside of neurosciences.

At Warwick, we have taken on this neglected thread and have identified biological electricity as a key research direction. In particular, we believe that electrical forces, and the ability to control them, are fundamental in organising living systems across the scales (see publications). To better understand these forces and develop means to measure and control them, we undertake an interdisciplinary approach that brings together expertise from biology, physics, engineering, and chemistry.

Our research in this area is currently conducted through several collaborative PhD and postdoctoral projects. In addition, we have recently launched a Bio Electrical Engineering (BEE) Innovation Hub with funds from a BBSRC Innovation Accelarator Award provided to the University of Warwick.

Current membership (and interest areas) in the Warwick BioElectricity group include; Munehiro Asally (electrical patterns in cellular organisation), Orkun Soyer (electrical interfaces to cells), Murray Grant (electrical signals in plants), Pat Unwin (electrobiochemical measurements), Marco Polin (electrotaxis), Rob Cross (sub-cellular electrical fields), and Stefan Bon (electrical stimuli in colloidal biomaterials)
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BonLab develops technology to program hydrogels

A hydrogel is a solid object predominantly composed of water. The water is held together by a cross-linked 3D mesh, which is formed from components such as polymer molecules or colloidal particles. Hydrogels can be found in a wide range of application areas, for example food (think of agar, gelatine, tapioca, alginate containing products), and health (wound dressing, contact lenses, hygiene products, tissue engineering scaffolds, and drug delivery systems).  

In Nature hydrogels can be found widely in soft organisms. Jellyfish spring to mind. These are intriguing creatures and form an inspiration for an area called soft robotics, a discipline seek to fabricate soft structures capable of adaptation, ultimately superseding mechanical hard-robots. Hydrogels are an ideal building block for the design of soft robots as their material characteristics can be tailored. It is however, challenging to introduce and program responsive autonomous behaviour and complex functions into man-made hydrogel objects.

Ross Jaggers and prof.dr.ir. Stefan Bon at BonLab have now developed technology that allows for temporal and spatial programming of hydrogel objects, which we made from the biopolymer sodium alginate. Key to its design was the combined use of enzyme and metal-chelation know-how.

This video shows a programmed hydrogel tree. The hydrogel is made from sodium alginate and cross-linked with Calcium ions. Two scenarios are shown. In a tree of generation 1 the leaves contain a pH sensitive dye and the enzyme urease. The enzyme is trapped into the hydrogel leaves. The tree is floating in water of acidic pH. The water contains urea as trigger/fuel. After a dormant time period the leaves change colour from yellow to blue. This happens as the enzyme decomposes urea into ammonia and carbon dioxide. The bell-shaped activity curve of the enzyme is key to program the time delay in colour change. In a tree of generation 2, the leaves contain emulsion droplets of oil which are coloured red. Again they contain the enzyme urease. In this case, however, the system also contains the compound EDTA, which is a great calcium chelator at higher pH values. After a certain dormant time period, the pH in the leaves rises sufficiently (as a result of the enzymatic reaction decomposing urea into ammonia and carbon dioxide) that EDTA does its job. This results in spatial disintegration of the hydrogel leaves.

This video shows a programmed hydrogel object containing the numbers 1, 2 and 3. The hydrogel is made from sodium alginate and cross-linked with Calcium ions. The numbers contain emulsion droplets of oil which are coloured blue, red and yellow respectively. Each hydrogel number is loaded with a different amount of the enzyme urease. The enzyme is trapped into the gel. Number 1 contains the highest amount, number 3 the lowest. The hydrogel object is floating in water of acidic pH. The water contains urea as trigger/fuel. The system also contains the compound EDTA, which is a great calcium chelator at higher pH values. After a certain programmed dormant time period (dependent on enzyme loading), the pH in each of the numbers rises sufficiently (as a result of the enzymatic reaction decomposing urea into ammonia and carbon dioxide) that EDTA does its job. This results in spatial and temporal disintegration of the numbers.

Details of the study can be found in our paper "temporal and spatial programming in soft composite hydrogel objects" which was published in the Journal of Materials Chemistry B (DOI: 10.1039/C7TB02011B).

The study forms part of a wider program to develop technology to design hydrogels that can be programmed and communicate. As part of this series we reported earlier in 2017 in Materials Horizons a study on the design of hydrogel fibres and beads with autonomous independent responsive behaviour and have the ability to communicate (DOI: 10.1039/C7MH00033B).

Roughening up polymer microspheres and their diffusion in a liquid

Spherical microparticles that are roughened up, so that their surfaces are no longer smooth, are intriguing. You can wonder that when we place a large number of these particles in a liquid, it may show interesting rheological behaviour. For example, would they behave like cornstarch in that when we apply a lot of shear it thickens? You can imagine that spiky spheres can interlock and jam. Biologists are interested in how microparticles interact with cells and organisms, and have started to show that the shape of the particle can play an important role. Similarly, these small particles of intricate shape may show fascinating behavior at deformable surfaces, for example is there a cheerio effect?, and may show unexpected motion. This sounds all fun, but how do we make rough microparticles, as for polymer ones this is not easy?

Fig. 1 Transmission electron microscopy (TEM) images of poly(styrene) microspheres deformed at 110 °C within a dried colloidal inorganic matrix for approximate time periods of 10, 30, 60 and 120 min (a–d), (e–h), (i–l). The inorganic particles utilized were cigar-shaped calcium carbonate (a–d), large, rod-shaped calcium carbonate (e–h) and small, spherical/oblong-shaped zinc oxide (i–l). Scale bars = 1.0 μm.

In our paper published in Soft Matter we report an easy and versatile method to morph spherical microparticles into their rough surface textured analogues. For this, we embed the particles into an inorganic matrix of intricate shape and heat them up above the temperature at which the particles become a polymer melt. Capillary imbibition imprints the inorganic texture into the particles, turning them rough. We also look at how the particles move through a liquid, by tracking their motional behavior. Rough particles appear bigger, than their smooth precursors.  

You can read the paper here: DOI:10.1039/C7SM00589J

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

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.

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."

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

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).

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

More information:

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

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

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