Ingmar
Polenz
*a,
Quentin
Brosseau
a and
Jean-Christophe
Baret
ab
aMax-Planck Institute for Dynamics and Self-Organization, Am Fassberg 17, Göttingen, Germany. E-mail: Ingmar.polenz@ds.mpg.de; Tel: +49 551 5176 291
bCNRS, Univ. Bordeaux, CRPP, UPR 8641, Soft Micro Systems, 115 Avenue Schweitzer, 33600 Pessac, France. E-mail: jean-christophe.baret@u-bordeaux.fr
First published on 16th February 2015
We use microfluidic polydimethylsiloxane (PDMS) devices to measure the kinetics of reactive encapsulations occurring at the interface of emulsion droplets. The formation of the polymeric shell is inferred from the droplet deformability measured in a series of expansion–constriction chambers along the microfluidic chip. With this tool we quantify the kinetic processes governing the encapsulation at the very early stage of shell formation with a time resolution of the order of the millisecond for overall reactions occurring in less than 0.5 s. We perform a comparison of monomer reactivities used for the encapsulation. We study the formation of polyurea microcapsules (PUMCs); the shell formation proceeds at the water–oil interface by an immediate reaction of amines dissolved in the aqueous phase and isocyanates dissolved in the oil phase. We observe that both monomers contribute differently to the encapsulation kinetics. The kinetics of the shell formation process at the oil-in-water (O/W) experiments significantly differs from the water-in-oil (W/O) systems; the component dissolved in the continuous phase has the largest impact on the kinetics. In addition, we quantified the retarding effect on the encapsulation kinetics by the interface stabilizing agent (surfactant). Our approach is valuable for quantifying in situ reactive encapsulation processes and provides guidelines to generate microcapsules with soft interfaces of tailored and controllable interfacial properties.
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Fig. 1 (a) Schematic of reactive encapsulations and selected examples and (b) illustration of a batch processes for reactive encapsulations. |
In this article, we report on a microfluidic tool for the direct visualization of the encapsulation kinetics of interfacial polymerizations. We use as a marker of the polymerization progress the change in the droplet deformability while a polymeric shell is forming at the interface. We insert sudden planar expansions in the channel geometry that cause identical hydrodynamic shear stresses acting at the emulsion droplet interface causing a transversal droplet deformation. A consecutive arrangement of these expansion chambers allows for a systematic monitoring of the droplet deformability and, hence, of the encapsulation reaction process. The method of the deformation chambers is inspired by concepts of previous works on droplet deformations in external hydrodynamic flow fields26,27 and was previously used to measure the dynamics of surfactant adsorption at liquid–liquid interfaces.28 We show that our measurement results contain both information on specific material properties of the shell and – due to the time resolution of the experiment – their variations over time.
We study the polyurea microencapsulation. The generation of polyurea follows a polyaddition mechanism of amines and isocyanates. No side products are formed which simplifies the characterization of this encapsulation. A schematic of the polyurea formation as well as isocyanates and amines used in our investigations is given in Fig. 2.
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Fig. 2 (a) Schematic of the polyurea formation process as well as of the (b) isocyanates, amines and surfactants used in this study. |
The amine is dissolved in the aqueous phase and the isocyanate is in the oil phase. The interfacial polymerization process is initiated when both phases are brought into contact. Our method enables us to investigate both water-in-oil (W/O) and oil-in-water (O/W) encapsulations. We gain deeper insights into the shell formation mechanisms at the early stage of the polyurea microcapsules (PUMCs). An encapsulation rate vE is introduced in this work based on the standard principles of polymerization kinetics.29 Here, it is derived from a measurement of the time-dependent deformability of droplets over while the polymeric shell is being formed. With this kinetic approach we are able to express reactivity trends of certain amines and isocyanates with different chemical structures.30–32 In addition, we quantify the retardation of the encapsulation by surface stabilizing agents (surfactant). We obtain kinetic data of reactive microencapsulation for a wide range of experimental conditions.
The polyurea microencapsulation is performed in situ. As soon as both phases get in contact, the polymerisation starts. To avoid clogging of the device by polymerisation at the stagnation points of the flow, we first produce droplets in an reactant-free continuous phase. We add the reactant using an additional set of channels, downstream of the droplet production nozzle (Fig. 3). We use KMC oil 113 (Fisher Scientific, ρ = 0.89 g cm−3, η = 9.8 cP; γoil–water = 37 mN m−1), which is a mixture of 1,7- and 2,6-diisopropyl naphthalene, as oil for its solubility properties for isocyanates and its non-swelling properties of the PDMS channels. Amines are dissolved in the aqueous phase and isocyanates are in the oil phase. The emulsification and encapsulation are decoupled at the microfluidic chip to prevent an immediate clogging of the device at the nozzle region by the rapid polymer formation. First, emulsion droplets of the dispersed phase (D) containing the first monomer (0.001–30 wt%) in the appropriate continuous phase (CF1) are generated at a flow-focusing T-junction with dimensions of 100 μm in height and width. CF1 is either a pure fluid or contains surfactant (0.25–5 wt%). Emulsion droplets are then flown into a V-shaped flow-focusing junction using continuous phase CF2 that consists of the second monomer for the shell production (0.5–20 wt%) in the same fluid as CF1. In total, the device is run with three fluid streams and the flow rates of D, CF1 and CF2 are held constant at 100, 2450 and 1050 μL·h−1.
The controlled deformation of the emulsion droplets is achieved in the 34 successive expansion chambers (500 × 300 μm, see Fig. 3) that are separated by microfluidic channels of dimensions 500 × 100 μm. The droplet deformations are recorded using high speed imaging (Phantom) and the droplet contour is detected by image processing.
Amines 1,6-hexamethylenediamine (HMDA), ethylenediamine (En), tetraethylenepentamine (TEPA), polyethyleneimine ((En)n, MN = 600 g mol−1), as well as surfactant sodium dodecyl sulphate (SDS) and isocyanates 2,4-toluene diisocyanate (TDI) and 1,6-hexamethylene diisocyanate (HDI) are purchased from Sigma Aldrich and used as received. Surfactant Abil Em 90 is purchased from Evonik Industries and the HDI isocyanurate HDI3 from BASF SE and used as received.
![]() | (1) |
The time evolution of δ within a given chamber is shown in Fig. 3b; the time-dependence of the deformation in the chamber results from the hydrodynamic shear stress acting on the droplet and are a coupling of the following events: when the droplets enter the planar expansion of the chamber, they deform transversally to the flow direction and reach a maximum (δmax) before relaxing to a spherical shape (L = l; δ = 0). While entering the constriction the droplet deforms longitudinally (δ decreases) until it reaches a minimum value which is defined by the lateral confinement in the constriction. In the further context we use the maximum deformation δmax as an indicator for the polymer shell response to the tensile stress acting on the droplet.
The deformation profile of the reactive emulsion droplets is recorded in 34 consecutively arranged expansion chambers. With the channel height and flow rates of D, CF1 and CF2 used here, we monitor reactive encapsulation in a time range between 5 and 620 ms (Fig. 3b). As the flow conditions are identical in all the expansions, monitoring the deformation along the chip provides a measurement of evolution of the shell growth in time. Our microfluidic system has several advantages: it provides (i) a continuous mode of operation through the continuous production and flow of droplets; (ii) a versatile method to tune the experimental parameters such as flow rates or volume fractions and (iii) a reproducible production of polyurea microcapsules usable to obtain statistically relevant information on large amount of capsules.
At the initial state of the experiment (t = 0) no polymer film covers the emulsion droplet. Among other factors, the deformation is mainly defined by the interfacial tension and the droplet size as described by the capillary number Ca as it has been found in previous studies.28 At increasing chamber count (reaction time) we detect that the prolate deformation of the droplet, induced by the channel geometry, is not fully relaxing within the expansion (see Fig. 3b) as a result of the growth of the polymer film at the interface region. As a consequence of the rigidification of the oil–water interface by the polymer film, the deformation of the particle is dominated by the viscoelastic properties of the polymer shell leading to the decrease in δmax in the experiment.
We start our investigations with the water-in-oil (W/O) experiments. As an example, the variation of δmax over time for a set of W/O polyurea microencapsulations using the combination TDI/HMDA at varying HMDA concentration without surfactant are illustrated in Fig. 4. At the initial stage (chamber counts 1–4) for most of the experiments we detect no mentionable change in δmax; obviously, at this stage the whole encapsulation kinetics are limited by the diffusion of the TDI to the water–oil interface. Subsequently after this stage, a notable decrease in δmax is recorded – shell formation proceeds at the W/O-interface. The δmax decrease is fitted to an exponential relaxation. δmax reaches a plateau at −0.135 which is visible for the HMDA concentrations 0.5, 0.25 and 0.1 wt% (Fig. 4). We observed that in particular the absolute value of this plateau is a function of the initial droplet size and the channel width at the constriction.
The decrease of δmax is faster with increasing HMDA concentration (see Fig. 4): the time-scale of the exponential relaxations systematically decreases indicating faster reactions. These findings encouraged us to apply basic principles of step growth polymerization kinetics29 for the definition of the encapsulation dynamics. The polyaddition rate vP of an isocyanate IC and amine AM at the interface reads
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![]() | (3) |
The introduction of this apparent rate law is motivated by the link that can be made between the maximum deformation and the material mechanical properties. The deformation is directly connected to both the Young's modulus E and the shell thickness h which measures the polymer formed (eqn (4)). As a note, it was shown previously that the stress T1 required for an elastic transversal deformation of a membrane of thickness h ≪ R along an emulsion droplet equals
![]() | (4) |
We therefore restrict our analysis to the apparent rate law derived from the variation of the maximum deformation. The rate of the reaction is found to depend on the reagents concentration and surfactant additives. For a complete description of the encapsulation kinetics, the reaction orders α, β and γ have to be determined which are the slopes of the reaction rate in a double logarithmic representation of the experimental data. We then obtain the complete description of the encapsulation kinetics through the reaction orders α, β and γ that are now all experimentally accessible.
In our approach, the apparent rate vE is the change of the maximum deformation of the droplet over time and is measured as the slope of δmax over time (Fig. 4). We measure vE at the initial stage of the encapsulation according to the determination of polymerization kinetics;29 gelling effects and transition reactions can be neglected at this region. The initial stage of encapsulation is the region where a first notable decrease in δmax is recorded. The concentration-independent rate constant kE in eqn (4) can furthermore be considered for the quantification of various polyaddition systems. Experimental results of the order determinations for the W/O polyurea microencapsulations are presented in Fig. 5. Thus, the shape of the encapsulation rate law for W/O-PUMCs finally reads
![]() | (5) |
Due to the fact that the surfactant is not directly involved in the reaction of polymerization, we replace kE by k*E. The shape of eqn (5) reveals interesting insights into the encapsulation mechanism.
The isocyanate of the continuous phase, has the dominating impact on vE; an increase of the IC concentration by a factor of eight increases vE by eight whereas the same increase of the AM amount solely leads to an encapsulation rate growth by a factor of two. The amine has a weaker effect on the kinetics. Interestingly, independent from the functionality of the reactant we obtain the same encapsulation orders, which means that the principal early shell formation mechanism is not a function of the latent property of the monomer to undergo cross-linking reactions.
In addition, eqn (5) enables a precise quantification of the influence of the surfactant on the encapsulation kinetics which, up to nowadays, cannot be found in literature. A significant retardation of the encapsulation dynamics is measured in our experiments when working with Abil EM 90; the encapsulation rate constant of the surfactant-containing system is reduced by a factor of five compared to the non-surfactant containing encapsulations. We tested the surfactant adsorption dynamics of Abil EM 90. With the experiment conditions used an equilibrium interfacial tension has been reached; the retardation of the encapsulation is caused by the blocking of reactive sites (at the interface and by entrapping of reactants in surfactant micelles) by the surfactant which reduces the probability of AM–IC impacts. The surfactant is assembled at the water–oil interface and, further on, interacts with the polyurea causing changes in the shell morphology which was also discussed recently.36
We find a similar apparent rate relationship with different exponents
![]() | (6) |
We also find, similarly to the W/O-encapsulation, that the reactant of the continuous fluid (amine) dominates the encapsulation dynamics. The retardation effect of the surface stabilizing agent at the O/W-encapsulations is remarkable. O/W-encapsulations performed without SDS are faster by a factor of 10 compared to the SDS containing systems. A stronger inhibition of the encapsulation by the SDS is indicated. Obviously, SDS blocks the reactive sites and components for the shell formation more efficiently than Abil EM 90.
Amine | Isocyanate | k E(W/O)rel | k E(O/W)rel |
---|---|---|---|
a There is no reliable information on absolute reaction rate constants of HDI and TDI with amines. However, trends in conversions of isocyanates with alcohols can be directly compared even though that they react slower than the conversion with amines by a factor of 100–1000. The values correspond to the reaction with the second isocyanate function of the molecule. | |||
En | TDI | 1 | 1 |
HMDA | 4.98 | 36.47 | |
TEPA | 5.99 | 50.94 | |
(En)n | 10.21 | 244.21 | |
Secondary AM | Primary isocyanate | 1 (ref. 30–32) | |
Primary AM | 2–5 (ref. 30–32) | ||
HMDA | HDI | 1 | 1 |
HDI3 | 6.52 | 0.72 | |
TDI | 9.07 | 40.83 | |
HDI | n-Butyl alcohol | 1a30–32 | |
TDI | 66.4a30–32 |
A higher reactivity of aromatic isocyanates (TDI) compared to aliphatic (HDI, HDI3) isocyanates is detected as it is known for these compounds;30–32 the trend is more significant for the O/W encapsulations. However, the tendency is significantly lower compared to the literature known reaction rates which possibly indicates the limitation of the encapsulation by the diffusion of the monomer.
A contrary result is found for the amines. Primary amines react faster with isocyanates than secondary amines by a factor of 2–5.30–32 However, the encapsulation rate constants kE of TEPA and (En)n are larger than those of En and HMDA by a factor of 6–244. The trend is more significant for the O/W-microencapsulations. The results can be explained by an increased amount of reactive sites at polyurea that is formed from TDI/TEPA and TDI/(En)n. First, the probability of monomer addition to this polymer is increased and, secondly, cross-linking reactions occur that result in polymer networks with high elastic moduli E. The polyurea chains, generated from the combinations TDI/En and TDI/HMDA, where the amines only bear two NH2 functions, are linear leading to materials with small elastic modulus E. According to eqn (2), the deformation of a capsule is directly linked to the Young's modulus E of the polymeric membrane. Consequently, multiply cross-linked polymer networks with high elastic moduli E require a higher tensile stress for deformation than polymers without knots that have comparatively lower E. The encapsulation rate constant kE therefore reflects the development of the mechanical properties of the polyurea that is formed at the water–oil interface. This observation is furthermore confirmed by the experiments with an isocyanate that has more than two NCO groups. HDI3 that generally has the same chemical reactivity as HDI has a significant higher kE(W/O)rel (see Table 1). At the HDI3/HMDA encapsulations multiply cross-linked polyurea with high E-values is formed, obviously compared to the not cross-linking HDI/HMDA system.
Our microfluidic tool provides a direct monitoring of reactive encapsulations. It is usable to study encapsulation dynamics but also to study the time-evolution of mechanical properties of thin polymer films at soft reactive interfaces. A further step – which is beyond the scope of the present study – would be to quantitatively relate the mechanics of deformation of the capsule to its material properties and obtain rate constants in terms of material production rather than deformation variations.
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