Turbidity diagrams of polyanion/polycation complexes in solution as a potential tool to predict the occurrence of polyelectrolyte multilayer deposition

Mjahed, Hajare; Voegel, Jean‐Claude; Chassepot, Armelle; Senger, Bernard; Schaaf, Pierre; Boulmedais, Fouzia; Ball, Vincent

doi:10.1016/j.jcis.2010.02.042

Cited by 43 publications

(43 citation statements)

References 87 publications

(105 reference statements)

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“…36 The formation of water soluble polyelectrolyte complexes from PEMs causing layer degradation was reviewed by Sukhishvili et al 37 and discussed by several authors. In fact, the equilibration of PECs from the multilayer to the bulk in condition of low charge density 38 or excess of charges 39 may lead to post-adsorption film rupture. As mentioned by Haynie et al, 28 both kinetics and thermodynamics favor the formation of soluble complexes, since the gain in entropy of released counterions does not compensate the loss of translational entropy by adsorbing in the multilayer phase.…”

Section: Introductionmentioning

confidence: 99%

Short versus long chain polyelectrolyte multilayers: a direct comparison of self-assembly and structural properties

Micciulla

Dodoo

Chevigny

et al. 2014

Phys. Chem. Chem. Phys.

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a Successful layer-by-layer (LbL) growth of short chain (B30 repeat units per chain) poly(sodium styrene sulfonate) (PSS)-poly(diallyl dimethylammonium chloride) (PDADMAC) multilayers is presented for the first time and compared with the growth of equivalent long chain polyelectrolyte multilayers (PEMs). A detailed study performed by quartz crystal microbalance with dissipation (QCM-D) is carried out and three main processes are identified: (i) initial mass uptake, (ii) adsorption-desorption during layer equilibration and (iii) desorption during rinsing. In contrast to the high stability and strong layer increment of high molecular weight (HMW) PEMs, layer degradation characterizes low molecular weight (LMW) multilayers. In particular, two different instability phenomena are observed: a constant decrease of sensed mass during equilibration after PDADMAC adsorption, and a strong mass loss by salt-free rinsing after PSS adsorption. Yet, an increase of salt concentration leads to much stronger layer growth.First, when the rinsing medium is changed from pure water to 0.1 M NaCl, the mass loss during rinsing is reduced, irrespective of molecular weight. Second, an increase in salt concentration in the LMW PE solutions causes a larger increment during the initial adsorption step, with no effect on the rinsing.Finally, the mechanical properties of the two systems are extracted from the measured frequency and dissipation shifts, as they offer a deeper insight into the multilayer structures depending on chain length and outermost layer. The paper enriches the field of PE assembly by presenting the use of very short PE chains to form multilayers and elucidates the role of preparation conditions to overcome the limitation of layer stability.

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Section: Introductionmentioning

confidence: 99%

Short versus long chain polyelectrolyte multilayers: a direct comparison of self-assembly and structural properties

Micciulla

Dodoo

Chevigny

et al. 2014

Phys. Chem. Chem. Phys.

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“…These observations point for very strong interactions between PAH and PSP, in a manner similar to our fi ndings for the PAH/ PSS combination of polyelectrolytes. [ 29 ] Note that phase separation occurs even from the mixtures characterized by r ≥ 0.4 when C NaCl ≥ 300 × 10 −3 M . At low ionic strength (5 and 10 × 10 −3 M ), the solutions characterized by r ≈ 1 remain turbid but no phase separation occurs even after 7 d of equilibration at 25 °C (Table 1 ).…”

Section: Pah-psp Interactions In Solutionmentioning

confidence: 99%

“…Indeed, it appears that the investigation of the polycation-polyanion interactions in solution, for instance through the establishment of phase diagrams, can be a predictive tool to predict if the deposition of polyelectrolyte multilayer fi lms by a step-by-step assembly is possible. [ 28,29 ] The poly(allylamine hydrochloride)/poly(sodium-4-styrene sulfonate) (PAH/PSS), [ 2 ] PDADMAC/PSS, [ 30 ] PAH/ PAA [ 31 ] (PAA stands for polyacrylic acid), and the PAH-PSP [32][33][34][35] (PSP stands for sodium hexametaphosphate) are representative examples of polycation/polyanion systems that have been intensively investigated from the point of view of step-by-step-deposited polyelectrolyte multilayer fi lms. The (PAH/PSP) n fi lms afforded a surprising yet reproducible set of results, among which the continuous decrease of the zeta potential with the number of deposition steps when the fi lms are deposited by the alternated spraying method.…”

Section: Introductionmentioning

confidence: 99%

Phase Diagram of Sodium Hexametaphosphate and Poly(allylamine hydrochloride) Mixtures and In Situ Monitoring of Step‐by‐Step Deposition in This Polyelectrolyte System

Ball

2014

Macro Chemistry & Physics

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The step-by-step deposition of poly(allylamine hydrochloride) (PAH) and sodium hexametaphosphate (PSP) leads to coatings displaying interesting intumescent properties and is a fascinating model system to understand the fundamental mechanism behind such a deposition process. In this investigation, the deposition kinetics of (PAH-PSP) n is followed in situ by means of a quartz crystal microbalance with dissipation monitoring, as a function of NaCl concentration. The evolution of the fi lm deposition is analyzed in detail and the data are compared with previous data obtained by ellipsometry on dried fi lms. These results are also compared with the expectations from the PAH/PSP phase diagram. The (PAH-PSP) n fi lms are also able to incorporate hexacyanoferrate anions with an amount of an incorporated redox probe refl ecting the fi lm thickness as obtained in the presence of eletrolyte solutions of increasing ionic strength. The in situ measurements and the electrochemical probe experiments reveal details of the fi lm deposition mechanism that are not accessible by dry-state characterization methods.

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“…This discussion shows that the nature of the growth regime of PEM films can be adjusted by playing on external parameters for a given combination of polyelectrolytes. Recent research shows that there is a strong relationship between interpolyelectrolyte interactions in solution, leading or not to phase separation, and the possibility or not to obtain PEM films using a step-by-step deposition strategy [50,56]. If one considers the intensity of the scattered light from a polycation-polyanion mixture in conditions where the amount of anionic sites matches the amount of cationic ones, that is, in conditions optimal for phase separation, as a function of the salt concentration, it appears that the obtained curve is almost homothetic to the PEM thickness evolution with the same polyelectrolytes.…”

Section: Interactions and Driving Forces Allowing For The Deposition mentioning

confidence: 99%

“…On the other hand, in the case where the intensity of scattered light and the thickness versus salt concentration display a maximum, the growth regime turns from linear at low salt concentration to exponential in the region of the maximum. At very low salt concentration the growth behavior of the film looks often zig-zag like, typical of an adsorption-desorption process [50].…”

Section: Interactions and Driving Forces Allowing For The Deposition mentioning

confidence: 99%

Deposition Mechanisms in Layer-by-Layer or Step-by-Step Deposition Methods: From Elastic and Impermeable Films to Soft Membranes with Ion Exchange Properties

Michel¹,

Toniazzo²,

Ruch³

et al. 2012

ISRN Materials Science

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The modification of solid-liquid interfaces with polyelectrolyte multilayer films appears as a versatile tool to confer new functionalities to surfaces in environmentally friendly conditions. Indeed such films are deposited by alternate dipping of the substrates in aqueous solutions containing the interacting species or spraying these solutions on the surface of the substrate. Spin coating is more and more used to produce similar films. The aim of this short review article is to provide an unifying picture about the deposition mechanisms of polyelectrolyte multilayer films. Often those films are described as growing either in a linear or in a supralinear growth regime with the number of deposited "layer pairs". The growth regime of PEM films can be controlled by operational parameters like the temperature or the ionic strength of the used solutions. The control over the growth regime of the films as a function of the number of deposition steps allows to control their functional properties: either hard and impermeable films in the case of linear growth or soft and permeable films in the case of supralinear growth. Such different properties can be obtained with a given combination of interacting species by changing the operational parameters during the film deposition.

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Turbidity diagrams of polyanion/polycation complexes in solution as a potential tool to predict the occurrence of polyelectrolyte multilayer deposition

Cited by 43 publications

References 87 publications

Short versus long chain polyelectrolyte multilayers: a direct comparison of self-assembly and structural properties

Short versus long chain polyelectrolyte multilayers: a direct comparison of self-assembly and structural properties

Phase Diagram of Sodium Hexametaphosphate and Poly(allylamine hydrochloride) Mixtures and In Situ Monitoring of Step‐by‐Step Deposition in This Polyelectrolyte System

Deposition Mechanisms in Layer-by-Layer or Step-by-Step Deposition Methods: From Elastic and Impermeable Films to Soft Membranes with Ion Exchange Properties

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