Mechanical cross-link

Figure 2 Pass Ale types ofpolymers based upon catenane architecures A Linear mechanically-linked polymers B mechanically cross-linked polymers C stars with a flexible, potentially switchable, catenane core D combs with catenarw linkages E main chain catenanes with switchable surface properties F highly mechani-cally-crosslinked networks G poly- or [n]catenanes. Only examples of types A and F have thus far been prepared...

Humidity sensors using cross-linked styrene-sulfonate have been developed by Pope [41] using this mechanism. Cross-linked copolymers prepared from styrene-sulfonate are fabricated on polystyrene substrates furnished with Ag electrodes. This sensor responds to water vapor at temperatures below 100 °C and rinsing the element is enough to restore the sensor characteristics in case of contamination. A similar sensor which consists of polystyrene-sulfonate containing 4-10% divinylbenzene, has been developed by Musa [42]. This sensor exhibits extremely low hysteresis, 3% r.h., but the long term stability is poor. 

The amorphous supercooled melt obtains shape stability by chemical or mechanical cross-links and then behaves like an isotropic rubber with low elastic modulus and high recoverable or even reversible strain. The cross-links transform the melt into a network of N individual chain links per volume which yield a restoring force coefficient... 

A simpler class of mechanical cross-link is completely new both in... 

Figure 19. Mechanical cross-links a) tying knots between molecules b) molecular sheaves c) a molecular braid d) a molecular weave.

B. Likozar, Z. Major, Morphology, mechanical, cross-linking, thermal, and tribological properties of nitrile and hydrogenated nitrile rubber/multi-walled carbon nanotubes composites prepared by melt compounding the effect of acrylonitrile content and hydrogenation, Applied Surface Science, ISSN 0169 332 257 (2) (November 1, 2010) 565-573. http //dx.doi.Org/10.1016/j.apsusc.2010.07.034. 

These monomers provide a means for introducing carboxyl groups into copolymers. In copolymers these acids can improve adhesion properties, improve freeze-thaw and mechanical stability of polymer dispersions, provide stability in alkalies (including ammonia), increase resistance to attack by oils, and provide reactive centers for cross-linking by divalent metal ions, diamines, or epoxides. 

If the concentration of junction points is high enough, even branches will contain branches. Eventually a point is reached at which the amount of branching is so extensive that the polymer molecule becomes a giant three-dimensional network. When this condition is achieved, the molecule is said to be cross-linked. In this case, an entire macroscopic object may be considered to consist of essentially one molecule. The forces which give cohesiveness to such a body are covalent bonds, not intermolecular forces. Accordingly, the mechanical behavior of cross-linked bodies is much different from those without cross-linking. 

No polymer is ever 100% crystalline at best, patches of crystallinity are present in an otherwise amorphous matrix. In some ways, the presence of these domains of crystallinity is equivalent to cross-links, since different chains loop in and out of the same crystal. Although there are similarities in the mechanical behavior of chemically cross-linked and partially crystalline polymers, a significant difference is that the former are irreversibly bonded while the latter are reversible through changes of temperature. Materials in which chemical cross-linking is responsible for the mechanical properties are called thermosetting those in which this kind of physical cross-linking operates, thermoplastic. 

Polymers with the mechanical and chemical properties we have discussed in this section are called elastomers. In the next couple of sections we shall examine the thermodynamic basis for elasticity and then apply these ideas to cross-linked polymer networks. 

It has been hypothesized that cross-linked polymers would have better mechanical properties if interchain bridges were located at the ends rather than the center of chains. To test this, low molecular weight polyesters were synthesizedf... 

We noted above that the presence of monomer with a functionality greater than 2 results in branched polymer chains. This in turn produces a three-dimensional network of polymer under certain circumstances. The solubility and mechanical behavior of such materials depend critically on whether the extent of polymerization is above or below the threshold for the formation of this network. The threshold is described as the gel point, since the reaction mixture sets up or gels at this point. We have previously introduced the term thermosetting to describe these cross-linked polymeric materials. Because their mechanical properties are largely unaffected by temperature variations-in contrast to thermoplastic materials which become more fluid on heating-step-growth polymers that exceed the gel point are widely used as engineering materials. 

Uses. Furfuryl alcohol is widely used as a monomer in manufacturing furfuryl alcohol resins, and as a reactive solvent in a variety of synthetic resins and appHcations. Resins derived from furfuryl alcohol are the most important appHcation for furfuryl alcohol in both utihty and volume. The final cross-linked products display outstanding chemical, thermal, and mechanical properties. They are also heat-stable and remarkably resistant to acids, alkaUes, and solvents. Many commercial resins of various compositions and properties have been prepared by polymerization of furfuryl alcohol and other co-reactants such as furfural, formaldehyde, glyoxal, resorcinol, phenoHc compounds and urea. In 1992, domestic furfuryl alcohol consumption was estimated at 47 million pounds (38). 

The second limitation stems from the insolubilization mechanism operant in these resists. Photoinitiated cross-linking converts the polymer film... 

Bulk Polymerization. The bulk polymerization of acryUc monomers is characterized by a rapid acceleration in the rate and the formation of a cross-linked insoluble network polymer at low conversion (90,91). Such network polymers are thought to form by a chain-transfer mechanism involving abstraction of the hydrogen alpha to the ester carbonyl in a polymer chain followed by growth of a branch radical. Ultimately, two of these branch radicals combine (91). Commercially, the bulk polymerization of acryUc monomers is of limited importance. 

Thermal Oxidative Stability. ABS undergoes autoxidation and the kinetic features of the oxygen consumption reaction are consistent with an autocatalytic free-radical chain mechanism. Comparisons of the rate of oxidation of ABS with that of polybutadiene and styrene—acrylonitrile copolymer indicate that the polybutadiene component is significantly more sensitive to oxidation than the thermoplastic component (31—33). Oxidation of polybutadiene under these conditions results in embrittlement of the mbber because of cross-linking such embrittlement of the elastomer in ABS results in the loss of impact resistance. Studies have also indicated that oxidation causes detachment of the grafted styrene—acrylonitrile copolymer from the elastomer which contributes to impact deterioration (34). 

Rocket Propellants. SoHd rocket propellants are mostly based on chemically cross-linked polymeric elastomers to provide the mechanical properties required in launchings and the environmental conditions experienced in storage, shipment, and handling (see Elastomers, synthetic). Double-and triple-based nitrocellulose propellants are also employed as rocket propellants. 

Polymer-based rocket propellants are generally referred to as composite propellants, and often identified by the elastomer used, eg, urethane propellants or carboxy- (CTPB) or hydroxy- (HTPB) terrninated polybutadiene propellants. The cross-linked polymers act as a viscoelastic matrix to provide mechanical strength, and as a fuel to react with the oxidizers present. Ammonium perchlorate and ammonium nitrate are the most common oxidizers used nitramines such as HMX or RDX may be added to react with the fuels and increase the impulse produced. Many other substances may be added including metallic fuels, plasticizers, stabilizers, catalysts, ballistic modifiers, and bonding agents. Typical components are Hsted in Table 1. 

In poly(ethylene terephthalate) (14—16) and poly(methyl methacrylate) (17—19), the mechanism of action of phosphoms flame retardants is at least partly attributable to a decrease in the amount of combustible volatiles and a corresponding increase in nonvolatile residue (char). In poly(methyl methacrylate), the phosphoms flame retardant appears to cause an initial cross-linking through anhydride linkages (19). 

Thermal Properties. Modified ETFE copolymer has a broad operating temperature range up to 150°C for continuous exposure (24). Cross-linking by radiation improves the high temperature capabiUty further. However, prolonged exposure to higher temperatures gradually impairs the mechanical properties and results in discoloration. 

Other PDMS—sihca-based hybrids have been reported (16,17) and related to the ceramer hybrids (10—12,17). Using differential scanning calorimetry, dynamic mechanical analysis, and saxs, the microstmcture of these PDMS hybrids was determined to be microphase-separated, in that the polysiUcate domains (of ca 3 nm in diameter) behave as network cross-link junctions dispersed within the PDMS oligomer-rich phase. The distance between these... 

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