Chain cohesion

Using surface pressure (u)-area (A) isotherms for sodium octadecyl sulfate (C18 sulfate) and octadecyl trimethylam-monium bromide (C18 TAB) monolayers spread at the air/water (A/W) and n-heptane/water (O/W) interfaces, we show that the Davies-Guastalla and Davies surface equations of state are not followed over a wide range of temperature and salt concentration. We attribute the discrepancies to Davies incorrect estimate of the chain-cohesion term at the A/W interface, the inadequacy of the electrical contribution to n at all but the highest A studied, and a possible chain-cohesion term at the O/W interface. 

A larger area of polyether chain cohesion in the interfacial layer. This increase in cohesion area should result in an increase in cohesion energy per molecule and therefore, at surface saturation, a higher surface viscosity. 

In organic polymer fibres the intra-chain bonding is always covalent, a strong bond, but the nature of the inter-chain bonding is weaker in polyolefines the chains are linked by van der Waals bonds, and in polyamides and polyesters inter-chain cohesion is augmented by hydrogen bridging. 

Asphaltenes are obtained in the laboratory by precipitation in normal heptane. Refer to the separation flow diagram in Figure 1.2. They comprise an accumulation of condensed polynuclear aromatic layers linked by saturated chains. A folding of the construction shows the aromatic layers to be in piles, whose cohesion is attributed to -it electrons from double bonds of the benzene ring. These are shiny black solids whose molecular weight can vary from 1000 to 100,000. 

Additives acting on the pour point also modify the crystal size and, in addition, decrease the cohesive forces between crystals, allowing flow at lower temperatures. These additives are also copolymers containing vinyl esters, alkyl acrylates, or alkyl fumarates. In addition, formulations containing surfactants, such as the amides or fatty acid salts and long-chain dialkyl-amines, have an effect both on the cold filter plugging point and the pour point. 

The behavior of insoluble monolayers at the hydrocarbon-water interface has been studied to some extent. In general, a values for straight-chain acids and alcohols are greater at a given film pressure than if spread at the water-air interface. This is perhaps to be expected since the nonpolar phase should tend to reduce the cohesion between the hydrocarbon tails. See Ref. 91 for early reviews. Takenaka [92] has reported polarized resonance Raman spectra for an azo dye monolayer at the CCl4-water interface some conclusions as to orientation were possible. A mean-held theory based on Lennard-Jones potentials has been used to model an amphiphile at an oil-water interface one conclusion was that the depth of the interfacial region can be relatively large [93]. 

Polyolefins with branched side chains other than P4MP1 have been prepared Figure 11.14). Because of their increased cohesive energy, ability for the molecules to pack and the effect of increasing chain stiffness some of these polymers have very high melting points. For example, poly-(3-methylbut-l-ene) melts at about 240°C and poly-(4,4-dimethylpent-l-ene) is reported to have a melting point of between 300 C and 350°C. Certain cyclic side chains can also... 

The aim of this chapter is to describe the micro-mechanical processes that occur close to an interface during adhesive or cohesive failure of polymers. Emphasis will be placed on both the nature of the processes that occur and the micromechanical models that have been proposed to describe these processes. The main concern will be processes that occur at size scales ranging from nanometres (molecular dimensions) to a few micrometres. Failure is most commonly controlled by mechanical process that occur within this size range as it is these small scale processes that apply stress on the chain and cause the chain scission or pull-out that is often the basic process of fracture. The situation for elastomeric adhesives on substrates such as skin, glassy polymers or steel is different and will not be considered here but is described in a chapter on tack . Multiphase materials, such as rubber-toughened or semi-crystalline polymers, will not be considered much here as they show a whole range of different micro-mechanical processes initiated by the modulus mismatch between the phases. 

Step 3. The set of fracture properties G(t) are related to the interfaee structure H(t) through suitable deformation mechanisms deduced from the micromechanics of fracture. This is the most difficult part of the problem but the analysis of the fracture process in situ can lead to valuable information on the microscopic deformation mechanisms. SEM, optical and XPS analysis of the fractured interface usually determine the mode of fracture (cohesive, adhesive or mixed) and details of the fracture micromechanics. However, considerable modeling may be required with entanglement and chain fracture mechanisms to realize useful solutions since most of the important events occur within the deformation zone before new fracture surfaces are created. We then obtain a solution to the problem. 

These types of polar monomer provide sites for hydrogen bonding which increase the cohesive strength of the PSA because of strong inter-chain interaction, and they can also allow for hydrogen bonding or other polar interactions with some substrates. 

As the amount of acrylic acid in the polymer increases, the degree of hydrogen bonding between polymer chains also increases causing the cohesive strength to improve without the need for crosslinking. Very similar observations can be made for other polar monomers, such as acrylamide. 

After this treatment the surface energy of the fibers is increased to a level much closer to the surface energy of the matrix. Thus, a better wettability and a higher interfacial adhesion are obtained. The polypropylene (PP) chain permits segmental crystallization and cohesive coupling between modified fiber and PP matrix [40]. The graft copolymerization method is effective, but complex. 

High degree of chain-to-chain attraction as a result of polarity (high cohesive energy density) results in chain stiffness and immobility... 

Fig. 2. The hardness of a poiymer crystal is related to the critical stress required to overcome the cohesive forces between chain molecules. Different modes arise depending on the direction of the applied force...

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