Mechanically interlocked polymers

Mechanically interlocked polymers ( daisy chains ) have attracted considerable interest, not just for their unique material properties but also for the synthetic challenge involve din their creation. Grubbs and coworkers [188] reportedthe synthesis of a bis-functionalized [c2] daisy-chain monomer, which was subsequently polymerized by ADMET. 

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Guidry, E.N., Li, J., Stoddart, J.F., and Grubbs, R.H. (2007) Bifunctional [C2]daisy-chains and their incorporation into mechanically interlocked polymers. Journal if the American Chemical Society, 129,8944—8945. 

Many of these features are interrelated. Finely divided soHds such as talc [14807-96-6] are excellent barriers to mechanical interlocking and interdiffusion. They also reduce the area of contact over which short-range intermolecular forces can interact. Because compatibiUty of different polymers is the exception rather than the rule, preformed sheets of a different polymer usually prevent interdiffusion and are an effective way of controlling adhesion, provided no new strong interfacial interactions are thereby introduced. Surface tension and thermodynamic work of adhesion are interrelated, as shown in equations 1, 2, and 3, and are a direct consequence of the intermolecular forces that also control adsorption and chemical reactivity. 

He concluded that for aluminium and titanium certain etching or anodization pretreatment processes produce oxide films on the metal surfaces, which because of their porosity and microscopic roughness, mechanically interlock with the polymer forming much stronger bonds than if the surface were smooth . 

In recent years there has been a renewed appreciation of potential beneficial effects of roughness on a macroscale. For example Morris and Shanahan worked with sintered steel substrates bonded with a polyurethane adhesive [61]. They observed much higher fracture energy for joints with sintered steel compared with those with fully dense steel, and ascribed this to the mechanical interlocking of polymer within the pores. Extra energy was required to extend and break these polymer fibrils. 

Portions of the sun visor arms used in automobiles can be manufactured from glass-filled thermoplastic polymers. Several visor arms contained visible blemishes on the surface. Typically, the steel insert of the visor arm is overmolded with the glass-filled thermoplastic polymer. Manufacturers sometimes utilize striations on the steel insert to provide a mechanical interlock with the over-molded thermoplastic polymer. However, in an improperly controlled environment, the mechanical process that produces the striations can also be the source of contamination and cause surface blemishes in the final product. 

Surface roughness of the substrate, needed to provide good mechanical interlocking with the polymer (6-8) ... 

Since water exposure has been shown 86) to have no substantial short-term effect on adhesive bonds in which a large degree of mechanical interlocking is present, these pretreatments have the potential to enhance the durability of aluminum/polymer adhesion systems. 

Mechanically interlocked molecular compounds, including catenanes, rotax-anes, and carceplex, are constituted of molecules composed of two or more components that cannot be separated from each other [95-98]. The development of strategy for achieving controlled self-assembling systems by non-covalent interaction enables one to prepare such attractive compounds for applications in nanoscale molecular devices. The dithiafulvene derivatives are effective electron donors, which are good candidates to form those supramolecular systems with appropriate acceptors by virtue of intermolec-ular CT interactions. In this chapter, dithiafulvene polymers forming rotax-ane structures are especially described. 

As the science of adhesion has developed, various theories of adhesion have been advocated for one material or another. With wood as a substrate, mechanical interlocking, interdiffusion of polymers, intermolecular attractive forces, and covalent chemical bonding all have been proposed, either individually or collectively, to explain adhesion. In reality, no experiments reported to date have been able to disprove the existence of any one of these mechanisms, or to quantify their relative importance. A most exasperating feature of research on adhesion to wood is that factors presumed to be independent in experiments are never totally independent. 

Exclusively mechanically interlocked linear polymer blends, typically, are not thermodynamically phase stable. Given sufficient thermal energy (Tuse>Tg), molecular motion will cause disentanglement of the chains and demixing to occur. To avoid phase separation, crosslinking of one or both components results in the formation of a semi-IPN or full-IPN, respectively. Crosslinking effectively slows or stops polymer molecular diffusion and halts the phase decomposition process. 

Surface modification of a polymer prior to metallization is widely used to improve adhesion. The most common surface modifications employed are electric discharge (corona and plasma) and, more recently, ion-beam treatments QJ- Several mechanisms have been proposed for the improved adhesion after such surface modifications (2). These include mechanical interlocking, the elimination of weak boundary layers, electrostatic attractions, and chemical bonding. All of these can play a role in adhesion depending on the surface modification used, metal/polymer system, type of metal deposition, and the extent of polymer preparation employed. However, for low power, short exposure modifications, the formation of new chemical species which can provide nucleation and chemical bonding sites for subsequent overlayers is considered to be of prime importance (3-51. 

Similarly, when intermingling of the core and shell polymers is required, in order to provide mechanical interlocking of one polymer with the other, then it is advantageous to let some of the second monomer soak into the lirst-stage particles before starting polymerization. This may be followed by semibatch polymerization of more second-stage monomer in order to produce the desired outer shell [27]. 

Mechanical Interlocking of Components. In some instances the polymers in a blend may be prevented from demixing because of numerous mutual entanglements produced by mechanical processing or the polymerization history of the blend. 

T/F plasma polymer was also selected to improve the adhesion of different spray paints to IVD Al-coated panels. As presented in Table 32.3, T/F plasma polymer [DC plasma-polymerized trimethylsilane (TMS) followed by hexafluoroethane (HFE)] gave rise to such a strong adhesion of E-coat that could not be stripped off after 24-h application of Turco solution. Since the formation of mechanical interlocking between primers and porous IVD surfaces could conceal the role of plasma treatment in enhancing adhesion, bare 7075-T6 aluminum alloy panels with smooth surfaces were first used as substrate to examine the effect of plasma treatment on the adhesion of spray paints. 

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