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In bolaform surfactants the connection is in the middle of the alkyl chain or close to the end, so that they can be considered as two polar head groups connected by a long hydrophobic chain.
If we look at the optical turbidity of the solution the trend is opposite.
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The timescales involved depend critically on the specific structure of the surfactant, in particular on the length of the hydrocarbon chain.
If we assume a typical area of 10 μm2 per microcontact, how many junctions exist between the plate and the block?
Similar dependencies on concentration are observed for the osmotic pressure or the electrical conductance of the solution.
Thermodynamics of micellization There are several approaches to derive the Gibbs free energy of micellization.
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In this case friction is determined by the viscosity of the lubricant.
With increasing temperature water becomes a less good solvent for polyethylene oxide.
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Amphiphilic molecules are present in everydays life and they are essential in many industrial processes.
Nonionic surfactants tend to show the opposite temperature effect: As the temperature is raised, a point may be reached at which large aggregates precipitate out into a distinct phase.
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Not all micelles are constituted by precisely the same number of surfactants.
Influence of temperature For ionic surfactants micellization is surprisingly little affected by temperature considering that it is an aggregation process; later we see that salt has a much stronger influence.
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Hydrodynamic lubrication prevails if the lubrication layer is thick enough to completely separate the surfaces.
Slightly below the CMC, most surfactants form monomers or low number aggregates.
Solubility and CMC versus temperature for SDS in water according to Ref.
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Trimeric or even tetrameric surfactants show properties often superior to monomeric surfactants.
Some micelles contain more, other micelles contain fewer surfactants so that there is a significant polydispersity.
The hydrocarbon chains gather inside the aggregate and the polar head groups orient towards the aqueous phase.
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To illustrate this we take one example, sodium dodecylsulfate (SDS), and see what happens when more and more SDS is added to water.
It does not like to be in water and prefers to be in an oily environment or air.
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Surfactants leave the micelle and go into solution while other surfactants enter the micelle from solution.
Cationic surfactants often pose environmental problems since they are not easily biodegradable.
At concentrations below the CMC of the surfactant, hydrophobic substances are poorly dissolved.
Above the Krafft temperature, micelle formation becomes possible and the solubility increases rapidly.
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Just as with SDS in water at neutral pH, the alkali metal dissociates as a cation so that the surfactant becomes negatively charged.
The hydrophilic part derives its water solubility from highly polar groups such as polyethylene oxide or sugars.
The right end of the plate is slowly being lifted to incline the plate until the block begins to slide.
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Anionic surfactants have a hydrophilic group, which carries a negative charge such as a carboxylate, sulfonate, or sulfate group.
The temperature at which this happens is referred to as the cloud point.
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If the plate is kept at this angle, what speed will the block have when it reaches the left end of the plate?
Examples of applications are their use in cleaning, detergency, as emulsifiers for creams in the cosmetic and pharmaceutical industry, and as flotation agents in the mining industry.
This behavior is similar to that observed for polyethylene oxide in water.
With the evolution of nanotechnology, thin film lubrication is gaining importance, where the lubrication layer thickness approaches molecular dimensions.
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The Krafft temperature is the point at which surfactant solubility equals the critical micelle concentration.
If the surfaces are only separated by adsorbed or oxide layers, boundary lubrication is acting.
There may be small systematic differences in the concentration at which the specific property abruptly changes and the CMC determined by different methods may be different.
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What is the torque we have to apply to overcome the viscous friction?
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Alkylethylene oxides, also called alkylethylene glycols, belong to the group of nonionic surfactants.
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Once the CMC is reached the monomer concentration remains almost constant and an added surfactant forms new micelles.
Lowest friction coefficients can be achieved in the case of rolling friction as, for example, in ball bearings.
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Surfactants are usually significantly less effective in most applications below the Krafft temperature.
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Amphoteric surfactants are expensive and therefore they are only used for special applications.
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Wear is the progressive loss of material caused by contact and relative motion.
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It belongs to the class of sodium alkylcarboxylates, also called fatty acids or soaps.
In parallel, a property, which is of great practical relevance, changes: the capacity to solubilize another hydrophobic substance.
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We only discuss one of them which is called the phase separation model.
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Lubricants consist of base oils that may either stem from refining of crude oil or be synthetic and a formulation of additives to achieve the desired performance of the lubricant.
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However, the general trend and the dependency on external parameters such as temperature or salt concentration is always the same.
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If A is polar and B nonpolar, the blockcopolymer will be strongly surface active and show many properties of a conventional surfactant.
For special applications the hydrocarbons might be completely or partially fluorinated.
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Since lipids are practically not soluble in water, in a strict sense they do not belong to the class of surfactants.
In systems where the thickness of the lubrication layer is of the order of the surfaces roughness and intermittent contact of the surfaces occurs, one speaks of mixed lubrication.
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At low concentration the anionic dodecylsulfate molecules are dissolved as individual ions.
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An important and widely used anionic surfactant is sodium dodecylsulfate (SDS), C12 H25 OSO3 Na, which belongs to the class of sodium alkylsulfates.
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In the following part of this chapter we concentrate on conventional surfactants.
Below the Krafft temperature the solubility is quite low and the solution appears to contain no micelles.
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Schematic distribution of surfactant aggregates as a function of the aggregation number for three different concentrations.
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In spite of the technical and economic importance, there is no general theory to describe wear, and engineers still have to rely on their extensive empirical knowledge to construct machines with low wear.
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Amphoteric (or zwitterionic) surfactants carry a positive and a negative charge so that the net charge is zero.
The phenomenon that nonionic surfactants become less soluble at elevated temperature will be important when we discuss the phase behavior of emulsions.
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