\r\n\t
\r\n\tSince they involve very small amounts of energy, high sound pressure levels are increasingly simpler and cheaper to emit. Noise is everywhere - it can be emitted as an energy waste by traffic or factories, but also by teenagers looking for loneliness in an overpopulated world.
\r\n\t
\r\n\tWhen the noise emission ends, it will not be possible to find its footprint in the environment, hence it is necessary to be in the right place at the right time to measure it. Moreover, having adequate instruments, updated protocols and trained personnel are mandatory to achieve that. Even then, decision makers must clearly understand the reported situation to decide the need and importance of taking further actions.
\r\n\t
\r\n\tThis book will address issues of noise in the city, in the neighborhood or at work, aspects about management and consequences of exposure to high sound pressure levels ranging from the auditory, extra-auditory and psychophysics effects to the addiction to noise and the loss of solidarity.
\r\n\t
\r\n\tThe book aims to provide a various points of view and analysis of cases regarding this omnipresent pollutant.
Pickering emulsions are defined as the dispersion of one liquid into another, with which it is immiscible and stabilized by solid particles. These solid particles adsorb at the interface between the two phases. They exist in nature with, for example, fat crystals in butter or casein particles in milk [1]. Their anchoring at this interface is almost irreversible and the inhibition of coalescence is very effective. Ramsden has shown that emulsions or bubbles can be permanently stabilized by means of fine solid or highly viscous particles placed at the interface of two liquids [2]. Pickering\'s work published in 1907 describes these phenomena more fully and shows that these particles, having a greater affinity with the aqueous phase than with the oily phase, are alternatives, often more advantageous than surfactants to obtain easily very stable O/W emulsions [3]. After many years, Pickering emulsions have been studied again since the 2000s and are of increasing interest to researchers. According to Scopus, 17 publications containing the terms “Pickering emulsion” in the title, keywords or abstract were published in 2005, 100 in 2011 and 220 in 2014.
There are various nature and shape of the particles used, such as spherical, cubic, in the form of rods, silica, titanium, melamine-formaldehyde, polystyrene, clays, spores or bacteria. The most common are nano spherical silica particles. Their size must be adapted to the desired emulsion, because an emulsion with droplets of at least a few micrometers is obtained from particles of 1–100 nm and an emulsion with drops of the order of a millimeter with particles of about 100 nm [4]. However, as in the case of surfactants, to allow them to be anchored at the interface, they must be partially wetted by each of the two phases. In general, the particles used are hydrophobic (such as carbon black) or hydrophilic (such as silica). If they are too hydrophilic or hydrophobic, they do not sufficiently stabilize the emulsion, the drops obtained are large (>100 μm) and unstable toward coalescence [5]. A grafting of molecules giving them their affinity with the water-oil interfaces is therefore carried out [6, 7, 8, 9, 10, 11, 12]. This is the case, for example, with pyrogenic, hydrophilic silica particles. Pure, 100% of their groups are hydrophilic Si-OH silanols, so they are unable to stabilize the interface except with certain oils. The grafting of hydrocarbon chains, such as dimethyl silyl, reduces their affinity with the aqueous phase, the most hydrophobic ones containing 14% silanols [4, 5].
By adjusting the grafting rate, it is possible to obtain particles of varying wettability. Since the distribution of hydrophilic and hydrophobic groups on the surface of particles is relatively homogeneous, they are not considered to be amphiphilic, unlike surfactants, although they have surface action (except for Janus particles, which have a hydrophilic and hydrophobic part, they have surface activity and are amphiphilic) [5]. The wettability of some particles may vary with pH, and reactive emulsions can be obtained [13, 14, 15]. They can also be “modified” by adsorption of surfactants to their surface [16]. Emulsions can also be stabilized with microgels, liquid crystals, spores or bacteria [17, 18, 19]. Finally, as with surfactants, it is possible to use a mixture of hydrophilic particles of different types and sizes to stabilize an emulsion [20]. Depending on the ratio between the hydrophilic and hydrophobic groups of their surfaces or their affinity with each of the two phases, emulsions obtained can be direct (O/W), inverse (W/O) or multiple [21, 22, 23, 24].
Pickering emulsions are extremely stable. They are of interest for food, pharmaceutical and cosmetic formulations as well as for their coupling with an encapsulation process [25, 26, 27]. They also provide good stability for multiple emulsions that are very difficult to stabilize with surfactants that diffuse in the system and can destabilize the system, unlike solid particles. In addition, the use of these nanoparticles can also participate in the formulation of sunscreen creams. Indeed, they help protect against ultraviolet radiation by limiting the use of surfactants [28].
In order to adsorb at the interface, the particles must be partially wetted by each of the two phases. This wetting is characterized by the contact angle measured on the aqueous side between the interface and the tangent to the particle at the point of contact between the three elements (if the gravitational forces are negligible in relation to the capillary forces, which are generally the case for nanoparticles). The angle of contact depends on the interfacial energies between the solid and the two phases and is given by Young\'s law (Eq. (1)).
When the contact angle is less than 90°, the particles are known as hydrophilic, and when it is greater than 90°, they are called hydrophobic [21, 29, 30]. To facilitate the choice of particles used, a parallel can be made with the hydrophilic lipophilic balance theory, the angles below 90° correspond to an HLB between 9 and 15 and the angles above 90° correspond to an HLB between 3 and 7 [4]. In addition, as in the case of surfactants, Pickering emulsions generally follow the Bandcroft law, according to which the continuous phase is that for which the particle has the most affinity [31]. This is the case for silica particles, when 65% of their surface groups are silanols, the particles are mainly hydrophilic, their affinity is greater for the aqueous phase and the favored emulsion is direct. Several models describe this phenomenon. The most commonly accepted method is based on the spontaneous curvature dependence of the interface on the particle contact angle. In addition, in this case, the particles inhibit more effectively the coalescence and Ostwald ripening, their sterically hindered being greater. There are also amphiphilic particles, whose distribution of hydrophilic and hydrophobic groups are not homogeneous but separated into two distinct regions, one hydrophilic and the other hydrophobic. They are produced by chemically modifying part of the particle to change its wettability. These particles are called Janus particles and are three times more effective at a 90° contact angle than conventional particles and maintain interfacial activity even at 0 and 180° contact angles [32].
Since the particles used in Pickering emulsions are generally nanometric, it is difficult to measure their contact angle. In the literature, several studies present methods of measuring particle contact angle at the interface. However, they can only be used for particles with a diameter higher than 20 μm and are subject to uncertainties or require special equipment. It is also possible to use the data available in the literature to select a particle type. The type of the particle-stabilized emulsion depends mainly on this contact angle. Other parameters such as particle size and shape, the phase into which the particles are introduced, their concentration, the volume fraction of the dispersed phase, the polarity of the oil, the viscosity of each of the two phases, the presence of additives such as electrolytes, surfactants or flocculating agents and the method of operation also influence the direction of the emulsion obtained. Indeed, it is better to introduce particles into the external phase to promote the formation and stability of the emulsion [5, 33, 34]. This phenomenon is related to the difference in hydrophobia of particles wetted by water or oil. In fact, the feed angles (from oil to water) are larger than the feed angles (from water to oil) at the interface. The particles therefore have a more hydrophobic behavior when introduced into the oil and preferentially induce the E/H type and they are more hydrophilic when placed in the aqueous phase enhancing H/E emulsions [35]. As with surfactants, the type of oil, and in particular its polarity and the volume ratio between the two phases influence the type of emulsion obtained with the same particle [33, 36].
Once the particle is placed at the interface, the stability of the emulsion depends on its anchoring. The more force required to remove the particle from the interface, the more stable the emulsion is. For small particles (less than a few micrometers in diameter), gravity can be considered negligible. Clint and Taylor defined the particle-water contact area as 2π r2(1−cos2θ) and the flat area of water surface missing πr2 sin2θ = πr2(1−cos2θ), where R is the radius of the particle [37]. By replacing the air with the oily phase, the free energy needed to remove the particle from the interface is defined by Eq. (2).
Young\'s equation (Eq. (1)) allows simplification to obtain Eq. (3).
Binks completed these results by defining the energy needed to remove the particle from the interface in Eq. (4) with the negative sign corresponding to the particle removal from the interface to the aqueous phase and the positive sign to the oily phase [5].
According to this equation, the particle is strongly anchored at the interface for =90° and the extraction force decreases rapidly on each side of the interface to become weak between 0 and 20° and between 160 and 180° for a pyrogenic silica particle at the water/toluene interface. Moreover, this energy is much lower for tiny particles (r=2 nm) than for “big” ones (r = 8 nm) for which it reaches 1000 × kT at 90° (kT representing the thermal energy expressed as a function of Boltzman constant k and temperature T), the adhesion can then be considered irreversible. The adhesion energy is strongly dependent on size and varies according to the square radius. Thus the very small particles, having a size comparable to that of surfactants (<0.5 nm), are very easily removed from the interface, they are therefore not good emulsion stabilizers [5]. However, the particle size must be submicronic to obtain a satisfactory emulsion. The adhesion energy also depends on particle size and contact angle. The interfacial tension between the two phases has little influence on these results. The anchoring at the interface of particles with a diameter of about 10 nm with a contact angle of between 20 and 180° is therefore almost irreversible, which gives these emulsions an infinite stability.
The structural particle arrangement at the interface of the Pickering emulsions varies. Various configurations can be observed, that is, (a) the hexagonal configuration forming a monolayer completely overlapping the interface, (b) the two-dimensional gel structure, (c) the dense aggregates which slightly overlapping the surface and (d) the hexagonal structure forming a two-layer or multilayer covering the interface. The recovery rate does not depend on the quantity of particles introduced, but may be partial even if it is sufficient [38]. Midmore has shown that covering at least 29% of the droplet surface is required to stabilize the emulsion [39]. The type of structure obtained and the stability of the emulsion depend on the competition between repulsion and attraction forces between the particles, linked to van der Waals forces, electrostatic and capillary interactions. Unlike surfactants, particles adsorbed at the interface do not necessarily decrease the interfacial tension between the two phases [40, 41]. The stabilization of the emulsion is attributed, in the case of fully coated particles, to the presence of a mechanical barrier (static repulsion) between the two interfaces hindering the coalescence and Ostwald ripening. Electrostatic repulsion phenomena can also occur [4, 42].
In the case of droplets with an incomplete overlap, several phenomena are observed. In the first case, the emulsion is not stable as it stands and the drops coalesce until they are completely covered which leads to an increase in droplet size and a decrease in the interface area [43, 44, 45]. The size of the emulsion droplets depends directly on the amount of particles introduced (and therefore likely to cover the interface). The size distribution of the drops obtained in this way is narrow. Chevalier and Bolzinger described three regimes depending on the quantity of particles introduced [4]. In the first regime, there are too few and the stabilization of the emulsion fails. In the second, they are all anchored at the interface and the size is proportional to the quantity introduced. In the latter, size is controlled by agitation parameters and the excess particles remain agglomerated in the continuous phase leading to an increase in the viscosity of the medium. In this case, since the final size is no longer the result of the limited coalescence but of the shearing of the drops, the size distribution is much wider. In general, in order to obtain an emulsion containing 20% oily phase with a size between 10 and 100 μm, 1–6% in weight of partially hydrophobic silica particles must be dispersed in water [46].
In the second case of incomplete overlap, the emulsions are stable despite the not completely covered interface. The phenomena involved are not well understood but are based on the interactions between particles. This stabilization can be explained by two main hypotheses. These can form a dense structure that allows bridging between the drops and avoids contact between the interfaces. This hypothesis is in accordance with the observations of Destribats et al. who noted that particles preferentially place themselves at the zones of junctions between droplets and attributes these phenomena to electrostatic interactions [47]. It is also possible that particles may move at the interface and that their movements are sufficiently significant to allow redistribution [13, 48]. It is usual for particles to occur in solution and at the interface as aggregates, contributing to steric hindered between the drops and without affecting the stabilization of the interface. As for surfactants, it is possible to use a mixture of particles with different contact angles to stabilize the emulsions. In this case, it is also possible to induce phase inversion by adding hydrophilic particles in a W/O emulsion or hydrophobic particles in an O/W emulsion or by modifying the volume ratio between phases [5].
The studies of Velev and his team in 1996 and 1997, showing the potential of Pickering emulsions for microencapsulation and the development of advanced materials in general, were one of the reasons for the renewed interest of the scientific community in Pickering emulsions in the 1990s [49, 50, 51]. Thereafter, Weitz, Bon and their collaborators in the 2000s prepared capsules from Pickering emulsions with controlled size, permeability and mechanical properties [52, 53, 54, 55].
Pickering emulsions are already a way to encapsulate the core [52]. However, it is necessary to reinforce this protective layer to obtain mechanically resistant capsules. Several methods can be used. A chemical crosslinking agent can be used to bind particles together [46, 56, 57, 58, 59, 60]. It is also possible to use thermofusible nanoparticles that soften above their glass transition temperature to form a polymer film around the droplet [53, 61, 62]. Pickering emulsions can also be combined with traditional encapsulation processes.
The processes used are mainly physicochemical and chemical. Layer-by-layer processes (with pairs of alginate, chitosan and whey polymers, e.g. methoxylated pectins) over stabilized emulsions with silica nanospheres or clays (laponite) make it possible to obtain controlled porosity capsules depending on the number of layers and the affinity between the electrolytes used in the synthesis conditions for controlled release applications, in particular in the medical field [63, 64]. Several studies also deal with coacervation, particularly on the inner side, to form a polymeric film solidifying the Pickering emulsion [14, 65]. Many studies employ chemical encapsulation processes. Thus, styrene or methyl methacrylate mixed with an initiator can also be polymerized on the outer or inner face of a Pickering W/O or O/W emulsion, respectively [66, 67]. One of the main applications is thermal energy storage with the use of phase change materials (PCMs). In this case, the stabilizing particles can have several functions. They inhibit radical reactions in the aqueous phase [68]. The initiators of Atom Transfer Radical Polymerization (ATRP) can be located by grafting on nanoparticles [69]. They can also be used as a nucleation point for polymerization, as in the case of the emulsion of a styrene and AIBN (azobisisobutryonitrile, a primer) mixture in water stabilized by silica nanoparticles functionalized with methacryloxypropyltrimethoxy silane (MPTMS). The presence of MPTMS double bonds C=C allows copolymerization with styrene during radical polymerization. In situ melamine formalin (MF) polymerization processes are also described in the literature. Thus, the use of organo-modified silica nanoparticles increases the encapsulation efficiency of PCM by improving emulsion stability and providing a precipitation site for MF membrane formation [70]. The use of certain particles such as hydroxyapatite, a mineral species of the phosphates family, coupled with Artemisia argyi, a Chinese medicinal plant, allows the preparation of microcapsules having antimicrobial properties [71]. Furthermore, Pickering emulsions can also be coupled with sol-gel processes [72]. For example, a Pickering W/O emulsion stabilized with poly(methyl methacrylate) nanoparticles (PMMA) encapsulates hydrophilic substances (live organisms, drugs, enzymes, and bacteria) and protects them from both precursor and catalyst. The emulsion droplets are functionalized with an amphiphilic catalyst to direct the sol-gel reaction from TEOS. The amount of precursors added allows the porosity of the membrane to be adjusted [73]. A Pickering W/O emulsion stabilized by silica nanoparticles, mostly hydrophobic after hexadecylsilane grafting, followed by continuous phase sol-gel gelling, produces a controlled porosity foam [1]. The W/O/W emulsion is stabilized by hydrophobic silica for the first W/O emulsion and then hydrophilic silica functionalized with cetyltrimethylammonium (CTAB, a cationic surfactant) for the second H/E emulsion. The interface is then mineralized via a sol-gel process, the nucleation is directed to the interface by CTAB. It also solubilizes TEOS, which does not require prehydrolysis. The oily phase is wax, with a high rate of expansion at around 37°C, allowing thermal controlled release of the internal aqueous phase [24].
These last years, sol-gel microencapsulation approach has gained increasing interest to develop specific applications with high added values. The silicone membranes allow the physical and chemical protection of various types of active ingredient such as dyestuffs [74], drugs [75], enzymes or bacteria [76], flame retardants [77], etc. The polysiloxane membranes possess adequate mechanical properties [78], and chemically and thermally stable due to their amorphous structure [79]. In addition, they are compatible with most medical or pharmaceutical formulations, biocompatible, non-toxic, and have been approved as an inactive ingredient in pharmacopeia by the Food and Drug Administration.
During the encapsulation of active ingredients by sol-gel, it is necessary to control the formulation and the experimental conditions to obtain materials with the desired properties. The first step is to select the appropriate precursor(s). The chemical properties of the precursor(s) and active ingredient(s), as well as the environmental conditions are the main parameters to take in account for the selection of the possible solvent and catalyst. Furthermore, appropriate surfactant(s) should be used. Silica microcapsules can be obtained from organosilane monomer, mainly tetraethoxysilane (TEOS) as silica precursor, or mixtures in mild conditions either by a one step process or by a multi-stage process. The shell formation mechanism is relatively complex and depends mainly on the pH adjustment during the various synthesis steps. For a starting system from an oil in water emulsion, a major key of this process is the self assembly of silica precursor on the organic droplets under elaborate conditions, which required for a reasonably rapid hydrolysis reaction to eventually form the silica shell. In syntheses of silica nanoparticles or microcapsules by sol-gel route, gelation is not observed. Indeed, when the size of the particles are sufficiently important, electrostatic repulsions stabilize them and prevent the condensation of particles between them without hindering the condensation of monomers in solution onto their surface [80]. It is generally carried out in diluted aqueous medium. Kortesuo et al. also showed that an increase in the amount of water, exudation and encapsulated allow to decrease the release of the core substance despite particle agglomeration and therefore the formation of clusters [81].
Considering a hydrophobic active substance, the first step is the realization of the oil in water emulsion, with the use of surfactants. Ionic surfactants such as CTAB or sodium dodecyl sulfate (SDS) provide a small pore size (2–4 nm), while non-ionic surfactants such as Tween® (polysorbates) induce the formation of bigger pores (approximately 10 nm) and a thinner membrane [79]. Thus, according to the design of the microcapsules, the release behavior of the active substance can be well controlled. However, according to Ciriminna et al., the “impermeable” encapsulation of lipophilic products by a silica shell resulting from a sol-gel process is complex [82]. Indeed, complex emulsion processes (O/W/O) using a high amount of surfactants and/or high shearing rate have been developed to obtain tiny droplets (0.1–3 μm) to allow the formation of homogeneous particles and avoid migration of the active ingredient.
One of the first approaches to encapsulating lipophilic active ingredients has been developed by Magdassi et al [83]. It is based on the mixture of active and alkoxysilane emulsified in a solution of water and surfactants. The catalyst (acid or base) is added at the end of the emulsion to allow the capsules to formation by polycondensation at the interface with the aqueous phase. As many hydrophobic substances are solubilized, at least partially in TEOS, MTES or MTMS, many processes are based on the mixing of the active ingredient with the precursor (s) that then constitutes the dispersed organic phase. However, in this type of process, the hydrolysis of the precursors is more difficult and the capsule remains loaded with precursors that do not participate in the formation of the membrane.An alternative is the use of Pickering emulsions, which have been studied by Detribats et al. for the encapsulation of waxes to be released under thermal stress [84]. They have the advantage of allowing control of capsule size and act as a nucleating agent when the capsules are synthesized (they have been previously functionalized with a cationic surfactant, CTAB). Moreover, they are stable for several months and limit the exudation of the active ingredient. Barbe et al. have shown that for pH less than 2, although the structure formed is rather open, it condenses during drying and gives a dry microporous structure with pore sizes of about 1 nm [85]. When the pH increases, the network has a superior mechanical strength and higher rigidity due to crosslinking, drying leads to cracks formation and increases pores size. At pH 7, they range from 2 to 20 nm and at pH 11, the average size is 9 nm. Moreover, the diffusion of the active ingredient is not carried out or only slightly through the micropores, the increase in pH leads to an increase in the release rates of the active ingredient.
To obtain encapsulation with few or no exudation of the active ingredient, it is also required to incorporate a sufficient amount of silanes. Zhang et al. obtain a reduced release for a ratio of active mass to silane 50/50 [86]. Similarly, according to Aster et al., incorporating 5–20 mol% (preferably 8–15%) of alkyl groups in the structure results in slightly porous capsules containing hydrophobic products, the affinity between the silica shell and the active ingredient is increased by the presence of lipophilic alkyl groups. For an amount less than 2%, the capsules are porous and for a amount more than 25%, capsule formation is made difficult and requires the use of specific emulsifiers and catalysts. In addition, Sullivan et al. showed that to some extent, the addition of organo-modified silanes, dimethyldiethoxyysilane in the study, increases the thickness of the membrane and results in a decrease of the release [87]. Microcapsules prepared in basic pH are formed from silica nanoparticles that clump together to form the membrane [88]. The porosity of the membrane is therefore important and the tightness limited. On the contrary, a synthesis in an acidic medium promotes the formation of microcapsules that reduce exudation of the active substance. The recommended pH is generally between 2 and 3 [86]. Indeed, they synthesized spherical microcapsules with a well-defined, low-porous membrane at a pH of 2.89. The synthesis has a duration of 48 h at 35°C [89]. When they pre-hydrolyzed the silane, it was reduced to 24 h and the decrease of the pH to 2.45 further limited the exudation of the active ingredient. To minimize these duration of the synthesis to 4/5 h, it is possible to carry out a double catalysis.
Sol-gel process was used to entrap a liposoluble flame retardant compound, that is, bisphenol A bis(diphenyl phosphate) (BDP) from Devan chemicals (Belgium). In a microencapsulation process, the first step is the emulsion step, which can be described as a limiting one since it determines the mean diameter and size distribution of obtained microparticles. The emulsion need to be remained stable during the formation of the shell from the condensation of the reactive species, used as monomers. The originality of this work is the use of nanosilica particles to promote the formation of a Pickering emulsion. In our previous attempts, we have observed that the use of a non-ionic surfactant such as Tween® 20 during the process leads to a decrease of the thermal stability of the microcapsules, and it was difficult to obtain the desired size range, that is, from 10 to 100 μm, to use these microcapsules for a specific textile application.
In this study, nanosilica particles, Aerosil R816 (Safic Alcan, France), have been used to realize the first process step. Thus, emulsion has been prepared with 10 wt.% of BDP in a aqueous solution containing 0.5, 1 and 3 wt.% of Aerosil R816 previously dispersed in 100 ml of water. The agitator used is mobile with four inclined blades rotating at 1000 rpm for 30 min. The emulsion obtained is sufficiently stable, if its droplets have an average diameter of about 30 μm. The preparation of microcapsules as depicted in Figure 1, was realized with the addition of 0.5 of CTAB (Sigma Aldrich, France) after the formation of the emulsion, and 100 ml of 10 wt.% of tetraethoxysilane (TEOS, Sigma Aldrich, France), hydrolyzed at pH 2.8 in a formic acid solution was added dropwise in the solution. The mixture is kept under stirring during 1 day at 45°C to promote silane condensation. Thereafter, sodium hydroxide solution (10 wt.%) is added up to pH 6 to form a thick shell around the droplet. After, a maturing step for 1 h, the particles are washed and filtered to be dried at 50°C during 24 h. CTAB was used to initiate migration of hydrolysed silanol molecules to the droplet surface.
Schematic representation and optical microscopy at the various step of the sol-gel encapsulation. Reprinted from Ref [90] with permission from Elsevier.
The shear rate step was monitored by optical microscopy (Axioskos Zeiss equipped with a camera, IVC 800 12S) every 5 min for 1 h to follow the emulsion size distribution (Figure 2). At the beginning of the emulsion, most droplets have an average diameter between 100 and 500 μm, and few droplets are smaller than 100 μm. A decrease in droplet diameter is observed during the first 25 min. Indeed, after 5 min of shearing, the largest droplets have a size of about 500 μm, to reach 300 μm after 20 min. After half an hour, their diameters decrease to 200 μm. In addition, small droplets (mean diameter less than 100 μm) begin to form after about 20 min. Between 30 min and 1 h, the size distribution does not change. The balance between shear and coalescence is therefore reached after 30 min of agitation for the quantity of nanoparticles used and the droplet size is satisfactory (mainly between 10 and 100 μm).
Optical micrographs of the emulsion with 1 wt.% of Aerosil R816 versus time. Reprinted from Ref [90] with permission from Elsevier.
Figure 3 shows the optical micrographs obtained by optical microscopy of emulsions made with 10 g of dispersed phase sheared for 30 min with 3.1 and 0.5 wt.% of silica nanoparticles. After stopping the stirring, samples were taken at different times between 5 min and 1 week to check the stability of emulsions stabilized with silica nanoparticles. A re-dispersion is achieved by manual agitation. In all cases, droplets of a few micrometers to 500 μm are observed. For both active ingredients, the largest diameters are visible with 0.5 wt.% of nanoparticles. There are few variations in size between 1 and 3 wt.% and the droplets are mostly smaller than 100 μm. For emulsions with 0.5 wt.% nanoparticles, the average diameter is larger and the size distribution is wider. Emulsion size tends to decrease with the quantity of nanoparticles up to a limit size [91].
Stability of the emulsion according to the amount of nanoparticles (magnification by 10).
In each case, the stability is satisfactory, since after 1 week of storage, the phases remain separated with very few rearrangements and size variations. Size does not increase with storage time. Thus, no coalescence or Ostwald ripening is observed after this aging period. No limited coalescence is observed after 5 min. As a result, the droplet coverage by nanoparticles is reached, and size is determined by the efficiency of the agitation process, that is, a limited coalescence occurs in less than 5 min. Considering the study conducted by Chevalier and Bolzinger [4], describing three distinct regimes according to the silica nanoparticle content of oil-in-water emulsions, it can be established that with 0.5 wt.% of particles the second regime is reached, while with 1 and 3 wt.% it is the third one. To avoid thickening of the solution and interactions between silanols and excess particles during shell synthesis, the smaller excess particles are favored.
The “infinite” stability of Pickering emulsions for the system studied in this study has been observed. Despite the creaming and sedimentation, the emulsion stabilized by nanoparticles of silica remains stable for more than a week without the observation of phenomena of irreversible destabilization such as coalescence or Ostwald ripening. Manual agitation is sufficient to disperse the droplets in the medium. The mechanical agitation required during membrane formation is therefore sufficient. Emulsions stabilized using 1 wt.% of nanoparticles and stirred for 30 min are selected for further study. In fact, they allow to obtain droplets with an average diameter of about 3 μm and a size distribution of between 10 and 60 μm.
The silica particles were prepared by sol-gel encapsulation from the previous emulsions. The sol-gel polymerization is carried out in two stages, that is, the hydrolysis of the silica precursors is followed by their condensation in order to initiate the formation of the Si-O-Si network. Hydrolysis allows the formation of silanol species in presence of water, which are at a later stage involved in the reaction to create a Si-O-Si bridge with the release of a water molecule during the condensation. Even if, hydrolysis can be realized under acidic and basic conditions with a minimum pH value at pH 7 and an exponential increase for low and high pH, low pH increases the hydrolysis rate and inhibits condensation, which is the limiting step in these conditions. And, the basic state favors rapid condensation, which leads to the formation of inhomogeneous shells and aggregates. The result is a small and uniform growth of the capsules, resulting in dense and homogeneous polymeric shells. Therefore, the choice of pH allows to control the size and shape of the particles.
Thus, in this work, the shell polymerization was first performed under acidic conditions for 24 h to promote controlled shell growth before pH neutralization, resulting in rapid condensation and hardening of the shell. In addition, CTAB was added after emulsion completion and prior to the addition of hydrolysed TEOS in the medium to facilitate silanols migration at the droplet interface prior to condensation.
Optical microscopy was also performed during particle synthesis and photographs are presented for each step in Figure 1. No significant morphological changes are observed during the first 24 h of shell formation. On the contrary, as expected, pH neutralization leads to rapid shell formation and aggregation of particles in clusters. This aggregation should even be accentuated by the presence of the cationic surfactant.
After, the formation of the shell, microcapsules were hardened, washed, filtered and cried at 50°C during 24 h to obtain a thin powder. The use of water to clean the capsules allows removal of silica species that did not react and also ethanol molecules released during the hydrolysis. The SEM observations of the obtained powder show the formation of aggregates with a mean size from several micrometers up to 500 μm (Figure 4). The may be related to interconnected silica capsules, formed by coagulation and/or crosslinking reactions between reactive groupments of the silica shells during the synthesis, and more specially during the increase of the pH in the solution. In fact, the pH modification leads to uncontrolled and heterogeneous condensation of silanols in the continuous medium. Furthermore during this step, the existence of depolymerization mechanism coupled to a weak formed interface leads to the breakage of particles before the mechanically strong silica layer was formed from TEOS. Thereafter, the formation of tiny droplets was further stabilized by the presence of CTBA molecules in the water. Thus, this particle networking could be even magnified by the huge amount of cationic surfactant used to foster silanols migration toward the interface.
SEM micrographs of microcapsules.
Microencapsulated FRs typically consists of core materials, that is, FRs, entrapped in a shell material to form a core-shell structure. According to the required effect, the choice of a particular process is mainly determined by the physico-chemical properties of the FR compounds, and the desired thermo-mechanical properties of the polymeric shell. Thus, it could endow especial properties with the core materials by forming a solid shell. Since the last decade, microencapsulation via sol-gel route has been recognized as a promising method in various application fields to protect active substance. These types of particles are biocompatible with a limited toxicity and have good properties in terms of chemical and thermo-mechanical stabilities. Silica microcapsules can be obtained from organosilane monomer, mainly tetraethoxysilane (TEOS) as silica precursor, or mixtures in mild conditions either by a one step process or by a multi-stage process. The shell formation mechanism is relatively complex and depends mainly on the pH adjustment during the various synthesis steps. It has been shown that the use of Pickering emulsion with nanoparticles provides more highly stable emulsions and can promote silica shell formation. The formation of a template by O/W Pickering emulsion is a delicate interplay between the emulsion stability, oil polarity and sol-gel reaction kinetics. Furthermore, morphology of capsules produced with Pickering emulsion is smooth, dense and aggregated.
This work was supported by research grants FUI 13 n° F1205008VFOMOTEX program supported by Techtera, Up-Tex and with Fibroline company (Ecully, France) as lead manager. The authors thank the FEDER funds (European Union), and the Nord Pas-de-Calais region for their financial support.
One in three women at age of 60 years in the USA have undergone a hysterectomy, it is the second most common major surgical procedure performed in women worldwide [1]. Also, it is the leading reason for non-obstetric surgery among women in many high-income settings [2, 3, 4]. Fibroids, dysfunctional uterine bleeding, uterine prolapse and chronic pelvic pain are the most indication for this surgery [5]. So, the majority of hysterectomies are performed on benign indications to improve quality of life with few complications post-operative.
In recent years, an increasing number of studies have shown long-term adverse effects of hysterectomy on the pelvic floor and some studies have demonstrated unwanted effects on other health aspects. Long-term effects of hysterectomy on the pelvic floor that should be considered in surgical decision making are: pelvic organ prolapse, urinary incontinence, bowel dysfunction, sexual function and pelvic organ fistula formation. These outcomes are particularly relevant as life expectancy has increased and sequel may occur a long time after the surgical procedure and severely [1]. The surgery can take an emotional toll on woman as well. These effects might be very personal; she may feel differently than others, this leads her to depression. Losing the ability to become pregnant is hard for many women in worldwide and especially in Arabic countries, where the reproductively in considered the main reason for marriage. Some women feel “changed.” They may also mourn the loss of their fertility [6]. Fears of looking less “womanly” Younger women who have a hysterectomy sometimes are anxious about whether the surgery will change their appearance. They worry that it will make them more masculine [6]. A lot of Women who are the power of the community depressed, as a result of this operation, because of losing a something that a part of her femininity, make their body image and self -esteem disrupted, feelings that their different from others women who can childbearing, and she is not, all of that make them isolated from the community, when this community need for their power and productivity. In next section authors will highlighted on women perspective on her body, and focus on factors that might directly and indirectly influence these perspectives that includes religious, cultural, economic, political and psycho-social aspects based on review.
In this part, author will offer a narrative review that present a group of studies, to see the experiences and results of previous studies that discuss the experience of women who had done hysterectomy. As well as discuss the role of health care profession and recommended strategies to overcome these problem. This section will include four themes which are quality of life; physical and psychological changes; sexuality; Cultural and religious aspects; finally the review conclusion and recommendations.
Sexuality is written as separate theme not under physical and psychological theme due to its important and effects based on Maslow hierarchy. Another point is the sensitivity of talking in this subject in conservative Arabic culture even from health care profession themselves. If I ask myself if any of health care profession provided women with health education about her sexuality after hysterectomy, the answer is obviously clear. Might be there is no time to provide that after operation but the important point the negligence of this type of education. This indicates that health care professions are playing a big role to solve or complicate this issue. They have to deliver a competent health care for women based of her needs. This is the woman’s right not luxury, especially for ethnic minorities group.
Improvements of quality of life and decrease gynecologic symptoms are the main reason of any decision that taken by women for undergoes hysterectomy. In a systematic review study, authors investigated and analyzed six studies which evaluated QOL after hysterectomy. The authors concluded that a significant improvement above baseline in QOL scores [7]. However, many evidence as illustrated in this review showed the suffer of women physically and psychologically post-operative.
Hysterectomy is the one of surgery that needs more physical & psychological support by nurses in hospitals or/and outpatient clinics. Also provide a full background or knowledge for women who will do a hysterectomy that help to avoid the impact of hysterectomy [8]. There are four major subjects relating to the participant’s experience were identified by Valerie Fleming [9], doubts and justifications, pain, embodiment and sense of bitterness. In addition there are three domains must to integrate biophysical care of women, psychological, sociological, and spiritual domains [10]. Both of these study spotlight on the importance of provider training and education, also efforts must be directed to the community to enlighten men and families about hysterectomy by dispelling myths and providing current health information related to women’s gynecological health and alternatives to, indications for, and types of hysterectomy.
As a result of study that examined by Gul Pinar et al., there is a relationships between hysterectomy and body image, self-esteem, and dyadic adjustment, which appears significantly in the scores, lower than the healthy women [11]. This indicates for the reduction of psychological support from community in general and family in specific. The most impact of hysterectomy as discussed on previous study [12], is the emotional side, seven themes that divided from this side, fear; pain; death and dying; numbness or delay in emotional reaction; bonding with baby; communication; and the need for information. Something that must to focus on managing it by enhances the quality of life or to avoid it before happened by providing correct health information by care providers. Like study which discussed in relation to the importance of information provision by gynecologists and its effects on women’s decision-making about hysterectomy [13]. So gynecologists must initiate a comprehensive discussion about other treatments and their advantages and disadvantages. To explain the differences in complications between women after surgery, there are factors can determine this complication, Lifestyle factors (smoking and body mass index) and co-morbidity status, occupation and educational level [14].
The patients need for expressed their emotions and feelings after the major event that had happened in their life, otherwise, physical and psychological changes might be exaggerated. In previous qualitative study on Palestinian women, the most physical changes occur after hysterectomies were including pain, insomnia, eating disorder and immobility. One of the participants described pain as saying: “I had never felt like this pain in my life”. As a consequence of the pain, patients also suffer disturbances at night and changes in the sleep cycle. Also, Changes in the patients’ appetite were reported in this study and it differs from one woman to another. Some of the participants expressed that their appetite increased and others reported the opposite. Another problem that reported was the immobility which affected the daily performance and routine activities at home [15].
Depression, accompanied by anxiety, de-socialization, and aggression, is the most common complication that reported by women after hysterectomy. The depression was figure as the most common psychological complication of hysterectomy [15, 16].
Also psychological and emotional stress was evident in previous study and shown a negative emotional outcome after hysterectomy. It has been suggested that early detection and immediate action by healthcare providers may prevent these negative impacts on the psychological wellbeing of these women. This is especially so in younger women in whom the psychological impacts are the greatest. Furthermore, because the main reason for the psychological impact was related to the immediate postmenopausal status after surgery, younger women appear to be more vulnerable, thus emphasizing the need for proper counseling in younger women undergoing hysterectomy [17].
The most coping mechanism and adaptation technique that used by women after operation from literature were praying, the Holy Quran, music, and other activities such as walking, sports (yoga) [15]. While, other study found that the operation affects patients’ emotional reactions. As a result, they used these techniques to cope with their new condition and accept it [17].
Another issue that should be highlighted in this review is the role and effect of environment as cultural and religious on the perception of women who undergo hysterectomy. The woman is not presented on isolation; she interacted with surrounding that affect her status and view to her body and problem. It is important to figure that uterus is representing woman’s femininity and fertility.
The woman is not totally responsible for her body from legal and cultural aspect, it is partially. In Arabic countries as in Saudi Arabia and Palestine the health care system ask the husband’s consent for any medical procedure that affects the reproductive ability of his wife. In recent study that disuses this practice in Saudi Arabia, author recommended that “arguments advocating for discontinuing the requirement are offered along with measures to implement in order to overcome this social artifact” [18].
However, Islamic law closely regulates and governs the life of every Muslim. The basic principle is that it is impermissible for a woman to have her uterus removed because this entails permanent sterilization, and this conflicts with one of the most important higher objectives of the Sharee‘ah – fruitfulness in procreation. Anas ibn Maalik narrated that the Prophet, sallallaahu ‘alayhi wa sallam, said: “Marry fertile affectionate women, for I will be proud of your numbers in front of the Prophets on the Day of Judgment.” [19].
However, if there is concern of real or prevalent harm to the woman’s health if the uterus is not removed, or it is feared that it could cause her death or bring about considerable hardship beyond her ability to endure, and it is necessary, according to the advice of reliable and experienced doctors, for the uterus to be removed to ward off such harm, then it is permissible for the woman to have her uterus removed. This is based on the well-established principles that “elimination of harm takes precedence to realization of benefit” and “necessity makes something prohibited permissible”. Allaah The Exalted says (what means): {…while He has explained in detail to you what He has forbidden you, excepting that to which you are compelled.} [Quran 6:119].
Moreover, the Prophet, sallallaahu ‘alayhi wa sallam, said: “There shall be no harm or reciprocal harm.” [Musnad Ahmad and Al-Muwatta’] [19]. According to catholic a hysterectomy by choice over medical necessity would be a sin because it would cause permanent sterilization.
It is obviously clear here the gap between the cultural practice and religions aspect, what presented in religion in not translate totally to reality and practice. The women should have the total freedom to decide what she wants on her body. The powering women and taking her responsibilities will help her to cope well and accept any change to her body and soul.
From literature, other culture as presented in Indian, the author found the term “normalization of hysterectomy” was mentioned in many studies. The women are preferred to do hysterectomy as treatment for any menstrual or uterine problem instead of receiving medical or pharmacological treatment. This term underscores “the complex negotiations between women’s agency and medically un indicated procedures, as well as the ethical obligations of providers—both of which require further consideration in the Indian context” [20]. However, this term is not presented in Arabic context; in contrast the family likes to have more children as highlighted above from religious and cultural side. Arabic families like to have more male children because they considered that in Arabic term “Ozwa” as a positive point and they will help them in future when parents become old. The more male children the women have delivered the more respect will receive from their culture, husband family and mother in law. So, we can imagine the scope of problem, how the effect of remove part of her women body “uterus” on her self-image.
It is recognized that effects of hysterectomy on women’s sexuality are debated and controversial from literature [17]. A Socio-cultural construction is main factor that influenced the sexuality that involves many factors such as gender, identity, sexual orientation, pleasure, intimacy, and reproduction [22]. Many previous studies reported that the majority of women and their partners reported zero negative impact on sexual satisfaction after abdominal hysterectomy, regardless of the surgery was subtotal or total to [23], for example the majority of Norwegian women and their partners reported no negative impact on sexual satisfaction after abdominal hysterectomy, regardless of whether the hysterectomy was subtotal or total [23]. While From the literature, some of the studies are inconsistent with these findings [15, 21, 22, 23, 24, 25, 26, 35].
Other study reported that only one fourth of the women reported decreased sexual arousal, while the majority had experienced higher sexual arousal after abdominal and vaginal hysterectomy [27]. Various measures are used in these studies so comparing the degree of improvement in sexual is difficult. Guliz et al. mentioned in his study that advanced age, women’s attitude towards sexuality, and type of hysterectomy are the main elements that determine sexual functioning after hysterectomy. Depression has a negative effect on sexual functioning [28]. A negative sexual experience before hysterectomy will be a strong predictor of having a negative sexual experience of partners after operation [23]. A survey conducted in Jordan, which is one of Arab countries found that sexual performance after hysterectomy was their most significant concern, and there was a significant improvement in sexual function for women undergoing this procedure [26].
When looking to change in sexual changes, Literature review reveals that dyspareunia, and a change in orgasm and/or less sex are happened to approximately 10 to 20% of the women who underwent a hysterectomy [29], and in post operatively sexual dysfunction [30, 31, 32, 33], then after two years of operation the sexual dysfunction stabilized [24]. The main reason for sexual annoyances were included the modified self-image perception after surgery and decrease in vaginal lubrication a [34].
One of study revealed the negative impact of hysterectomy on the sexual life, which lead to increased depression and anxiety, with sexual dissatisfaction [35]. The counseling and discussion prior hysterectomy for potential sexual changes after surgery is crucial and may enhance the situation [36]. Another problem that might occur is the urinary problems after the operation or hysterectomy for sexually active and healthy women, they resulted in sexual dysfunction and increase in depression. The age, educational status, working condition and family structure is also important in this case [37].
In the other study, that is titled by” Women’s attitudes about sexuality”. In the third month after hysterectomy 49.5% of the women had begun to have sexual intercourse again, 34.3% of those were determined to have a decrease in sexual functions. It was also found that level of depression was less in the postoperative period compared to the preoperative period. Three months after hysterectomy, sexual functioning had significantly decreased. A clear resolution in symptoms of depression was seen after hysterectomy. It was determined that sexual functioning after hysterectomy was affected by advanced age, a women’s attitude about sexuality, and the type of hysterectomy [28].
It is indicated in this review that sexual function is a major cause of women’s concern for scheduled hysterectomy; therefore, it is important to spread awareness among women and let them know that most probably they will neither lose their sexual desire after hysterectomy, nor they will lose their feminine shape or style [26]. It is important to figure if ethnicity, socioeconomic status and sexual function are taken into account; it is easily to manage the physical and psychological changes [17].
The health care profession should have insight regards the perception of women of her body after hystrectomy. In order to provide a competent health care for women based of her needs. Women’s sexuality fractioning is essence and concern of women after hysterectomy, this topic is debated and controversial from literature. It is important here to highlight that uterus has symbolic values related to femininity as mentioned previously and evidence by many studies [38]. This problem among Arabian women is apparent and clear, where the womb of a woman is considered everything for her it represent it femininity and fertility, it means a lot for her. The woman inside herself felt of “deficient being” in the eyes of herself and her extended family, taking into consideration the presented of conservative culture that women’s have and early marriage practice that aimed to protect women and produce more children from cultural lenses view. This leads us the significant to power women by increase her awareness pre-operative, follow up post-operative and having a good support system.
Educational programs for women undergoing hysterectomy will promote better self-care behavior, reduce postoperative anxiety and pain, and mitigate some of the negative influences of hysterectomy. So, interventions may not affect the actual incidence of the side-effects; they may help patients cope with adverse outcomes better, thus emphasizing the importance of the adaptation process to accept this condition with a positive thought.
The results of this review reveal that hysterectomy had significant argumentative effects on women’s’ quality of life, physically, psychological and sexually. For effective handling of this problem, healthcare profession must be aware of these potentially problematic issues and use effective intervention pre-post operation. Multidisciplinary teams have to work together, nurses have to lead the work to ensure of using the holistic approach that cover women’s needs that included physical, psychological, spiritually, culturally and be individually. One size not fit all.
The important point here, that we could not change the culture or the mistake in the interpretation of religion. So, the practical solution is to involve the family into the therapeutic plan, identifying and addressing the psychosocial problems of the particularly high-risk groups is another critical point and referred them.
Based on the findings from this review, recommendations can be made to nurses working at gynecological departments. Nurses could also help the patients explore current coping mechanisms and support systems after hysterectomy. Another recommendation is to conduct a future study that examine the current education that provides to women pre-post operatively and it suitability based on her ethnicity and needs where ever the women is presented in her home country or diaspora.
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