Surfaces polymer blends

The development of instruments that enhance human perception has gone hand in hand with the advances of science. Several advances in the area of colloids, surfaces, polymers, blends, and composites were made through the use of microscopes, which are essentials tools for modem science. 

Finally, similar effects can be seen in miscible polymer blends where the surface tension correlates with the enrichment of the lower-energy component at the surface as monitored by x-ray photoelectron spectroscopy [104],... 

Flammiche A, Flourston D J, Pollock FI M, Reading M and Song M 1996 Scanning thermal microscopy sub-surface imaging, thermal mapping of polymer blends, localised calorimetry J. Vac. Sol. Technol. B 14 1486... 

Additives. Because of their versatility, imparted via chemical modification, the appHcations of ethyleneimine encompass the entire additive sector. The addition of PEI to PVC plastisols increases the adhesion of the coatings by selective adsorption at the substrate surface (410). PEI derivatives are also used as adhesion promoters in paper coating (411). The adducts formed from fatty alcohol epoxides and PEI are used as dispersants and emulsifiers (412). They are able to control the viscosity of dispersions, and thus faciHtate transport in pipe systems (413). Eatty acid derivatives of PEI are even able to control the viscosity of pigment dispersions (414). The high nitrogen content of PEIs has a flame-retardant effect. This property is used, in combination with phosphoms compounds, for providing wood panels (415), ceUulose (416), or polymer blends (417,418) with a flame-retardant finish. 

Another example of static SIMS used in a more quantitative role is in the analysis of extmded polymer blends. The morphology of blended polymers processed by extrusion or molding can be affected by the melt temperature, and pressure, etc. The surface morphology can have an effect on the properties of the molded polymer. Adhesion, mechanical properties, and physical appearance are just a few properties affected by processing conditions. 

In a molded polymer blend, the surface morphology results from variations in composition between the surface and the bulk. Static SIMS was used to semiquan-titatively provide information on the surface chemistry on a polycarbonate (PC)/polybutylene terephthalate (PBT) blend. Samples of pure PC, pure PBT, and PC/PBT blends of known composition were prepared and analyzed using static SIMS. Fn ment peaks characteristic of the PC and PBT materials were identified. By measuring the SIMS intensities of these characteristic peaks from the PC/PBT blends, a typical working curve between secondary ion intensity and polymer blend composition was determined. A static SIMS analysis of the extruded surface of a blended polymer was performed. The peak intensities could then be compared with the known samples in the working curve to provide information about the relative amounts of PC and PBT on the actual surface. 

In a fundamental sense, the miscibility, adhesion, interfacial energies, and morphology developed are all thermodynamically interrelated in a complex way to the interaction forces between the polymers. Miscibility of a polymer blend containing two polymers depends on the mutual solubility of the polymeric components. The blend is termed compatible when the solubility parameter of the two components are close to each other and show a single-phase transition temperature. However, most polymer pairs tend to be immiscible due to differences in their viscoelastic properties, surface-tensions, and intermolecular interactions. According to the terminology, the polymer pairs are incompatible and show separate glass transitions. For many purposes, miscibility in polymer blends is neither required nor de-... 

Fig. la —c. Schematic drawing of some specific examples of polymer molecules at an interface (a) the free surface of a homopolymer, (b) the surface enrichment of one component in a miscible polymer blend, and (c) the interface between polymers of different molecular weight and/or chemical composition... 

When dealing with polymer blends or blockcopolymers, surface enrichment or microstructures may be observed as already discussed in Sect. 3.1. Quite similar effects may be expected for buried interfaces e.g. between polymer and substrate where one component may be preferentially enriched. In a system of PS, PVP and diblock copolymer PS-6-PVP it has been shown by FRS that the copolymer enrichment is strongly concentration dependent [158]. In a mixed film of PS(D) and end-functionalized PS on a silicon wafer the end-functionalized chains will be attached to the silicon interface and can be detected by NR [159],... 

A surface is that part of an object which is in direct contact with its environment and hence, is most affected by it. The surface properties of solid organic polymers have a strong impact on many, if not most, of their apphcations. The properties and structure of these surfaces are, therefore, of utmost importance. The chemical stmcture and thermodynamic state of polymer surfaces are important factors that determine many of their practical characteristics. Examples of properties affected by polymer surface stmcture include adhesion, wettability, friction, coatability, permeability, dyeabil-ity, gloss, corrosion, surface electrostatic charging, cellular recognition, and biocompatibility. Interfacial characteristics of polymer systems control the domain size and the stability of polymer-polymer dispersions, adhesive strength of laminates and composites, cohesive strength of polymer blends, mechanical properties of adhesive joints, etc. 

The data of Zink et al. (1998) illustrate the measurement by NRA of near-surface composition profiles in isotopically labelled polymer blends. If a mixture of polymers is adjacent to a phase interface (e.g. a solid or an air surface), often one of the components is preferentially attracted to the surface and will segregate to it, and this phenomenon will influence the tribological behaviour the interface (lubrication, wear and adhesion). 

Transparency is often required. This is achieved by arranging that the particle size of the modifier to be below that of the wavelength of visible light (0.4-0.8 pm). This can normally be achieved by emulsion polymerisation, e.g., polybutadiene, polystyrene. Adhesion and surface compatibility between the polymer and modifier can be achieved by surface grafting of polar groups, e.g., acrylonitrile, various acrylates, onto the impact modifier surface before blending. 

As already indicated above, what one may consider a surface depends on the property under consideration. Adhesion is very much an outer atomic layer issue, unless one is dealing with materials like fibreboard in which the polymer resin may also be involved in mechanical anchoring onto the wood particles. Gloss and other optical properties are related to the penetration depth of optical radiation. The latter depends on the optical properties of the material, but in general involves more than a few micrometer thickness and therewith much more than the outer atomic layers only. It is thus the penetration depth of the probing technique that needs to be suitably selected with respect to the surface problem under investigation. Examples selected for various depths (< 10 nm, 10 s of nm, 100 nm, micrometer scale) have been presented in Chapter 10 of the book by Garton on Infrared Spectroscopy of Polymer Blends, Composites and Surfaces... 

This topic has been mentioned in Section V, Failure, Defect and Contaminant Analysis, in Chapter 15, where a number of typical practical problem invetsigations were presented. Obviously the potential list of examples exhibiting different characteristics and requiring a different type of analysis is lengthy. When the sample is heterogeneous, e.g., a polymer blend or a composite, the study of the surface of a failed piece of material may reveal whether the problem is the interface of the components or that failure occurred within one of these. In particular in the case of crazing or necking orientation may have been induced, the way this can be analysed is discussed in Chapter 8. 

Recent developments have allowed for more detailed studies of polymer surface morphology by ESCA. Angle-resolved ESCA (ARXPS) allows for providing chemical compositions from shallower depths. By varying the angle of incidence different depths can be probed, and procedures have been developed to arrive at three-dimensional reconstruction of the surface. An example is shown in Figure 2, where a PVC/PMMA polymer blend has been analysed using such an approach [9]. 

A.Garton, Infrared spectrosocpy of polymer blends, Composites and Surfaces, Hanser Publishers, Munich, 1992. 

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