Phenolics Fillers

Sphere, flow across, 15 72 It Sphere-of-influence (SOI), 19 355-356, 358 Spherical bubbles, in foams, 12 7-8 Spherical fillers, phenolic resin,... 

Resin Filler Phenolic resin Wood flour = Cellulose = type 51 Textile fiber = Textile chips =... 

Wheat (Triticum vulgare) starch Zinc stearate filler, phenolic Aluminum calcium silicate filler, photographic paper Barium carbonate filler, plastic foams Barium sulfate filler, plastic prods. 

Chemical resistance, however, is influenced by the type and amount of fillers. Phenolic resins filled with organic materials are more resistant than those with... 

Chemically, limestone is also a feedstock for forming calcium carbide, which is used to manufacture acetylene, a feedstock for acetylene black filler, phenol acetylene tackifier resins, and other rubber chemical additives. 

At first glance it appears that these systems do conform fully to the discussion above this is an oversimplification, however. The ortho and para hydrogens in phenol are not equal in reactivity, for example. In addition, the technology associated with these polymers involves changing the reaction conditions as the polymerization progresses to shift the proportions of several possible reactions. Accordingly, the product formed depends on the nature of the catalyst used, the proportions of the monomers, and the temperature. Sometimes other additives or fillers are added as well. 

Furfural has been used as a component in many resin appHcations, most of them thermosetting. A comprehensive review of the patent Hterature describing these uses is beyond the scope of this review. A few, selected recent patents and journal articles have been referenced. Resins prepared from the condensation products of furfural with urea (47), formaldehyde (48), phenols (49,50), etc, modified by appropriate binders and fillers are described in the technical Hterature for earlier appHcations, see reference 1, which contains many references in an appendix. 

Phenol—formaldehyde (PF) was the first of the synthetic adhesives developed. By combining phenol with formaldehyde, which has exceptional cross-linking abiHties with many chemicals and materials, and a small amount of sodium hydroxide, a resin was obtained. The first resins soHdified as they cooled, and it was discovered that if it was ground to a powder with a small amount of additional formaldehyde and the appHcation of more heat, the mixture would Hquify and then convert to a permanently hard material. Upon combination of the powdered resin mixture with a filler material such as wood flour, the result then being placed in a mold and pressed under heat and pressure, a hard, durable, black plastic material was found to result. For many years these resulting products were called BakeHte, the trade name of the inventor. BakeHte products are still produced today, but this use accounts for only a small portion of the PF resins used. 

Although the use of simple diluents and adulterants almost certainly predates recorded history, the use of fillers to modify the properties of a composition can be traced as far back as eady Roman times, when artisans used ground marble in lime plaster, frescoes, and po22olanic mortar. The use of fillers in paper and paper coatings made its appearance in the mid-nineteenth century. Functional fillers, which introduce new properties into a composition rather than modify pre-existing properties, were commercially developed eady in the twentieth century when Goodrich added carbon black to mbber and Baekeland formulated phenol— formaldehyde plastics with wood dour. 

Different phenoHc resins are used for different types of wood for example, plywood adhesives contain alkaline-catalyzed Hquid resole resins. Extension with a filler reduces cost, minimizes absorption, and increases bond strength. These resins have an alkaline content of 5—7% and are low in free phenol and formaldehyde. Because many resins have a high water content and limited storage stabiHty, they are frequently made at or near the mill producing the plywood product. The plywood veneers are dried, coated with resin, stacked for pressing, and cured at 140—150°C. 

Spheres. HoUow spherical fillers have become extremely useflil for the plastics industry and others. A wide range of hoUow spherical fillers are currently available, including inorganic hoUow spheres made from glass, carbon, fly ash, alumina, and 2h conia and organic hoUow spheres made from epoxy, polystyrene, urea—formaldehyde, and phenol—formaldehyde. Although phenol—formaldehyde hoUow spheres are not the largest-volume product, they serve in some important appHcations and show potential for future use. 

The C-4 alcohols are preferably stored ia baked phenolic-lined steel tanks. However, plain steel tanks can also be employed provided a fine porosity filler is iastaHed to remove any contaminating mst (34). 

Glassy, or vitreous, carbon is a black, shiny, dense, brittle material with a vitreous or glasslike appearance (10,11). It is produced by the controUed pyrolysis of thermosetting resins phenol—formaldehyde and polyurethanes are among the most common precursors. Unlike conventional artificial graphites, glassy carbon has no filler material. The Hquid resin itself becomes the binder. 

This includes wire enamels on a base of polyvinyl formal, polyurethane or epoxy resins as well as moulding powder plastics on phenol-formaldehyde and similar binders, with cellulose fillers, laminated plastics on paper and cotton cloth base, triacetate cellulose films, films and fibres of polyethylene terephthalate. 

Woodflour, a fine sawdust preferably obtained from softwoods such as pine, spruce and poplar, is the most commonly used filler. Somewhat fibrous in nature, it is not only an effective diluent for the resin to reduce exotheim and shrinkage, but it is also cheap and improves the impact strength of the mouldings. There is a good adhesion between phenol-formaldehyde resin and the woodflour and it is possible that some chemical bonding may occur. 

The chemical resistance of the mouldings depends on the type of filler and resin used. Simple phenol-formaldehyde materials are readily attacked by aqueous sodium hydroxide solution but eresol- and xylenol-based resins are more resistant. Provided the filler used is also resistant, phenolic mouldings are resistant to acids except 50% sulphurie aeid, formic acid and oxidising acids. The resins are stable up to 200°C. Some reeently developed grades of moulding compounds are claimed to be capable of exposure to 300°C for short periods. 

Whilst the injection moulding process has now been widely accepted for phenolics the transition from compression moulding has been less extensive with U-F materials. The basic reason for this is that the U-F materials are more difficult to mould. This has been associated with filler orientation during moulding, which can lead to stress peaks in the finished product which the somewhat brittle resin in less able to withstand than can a phenolic resin. 

Industrial grade materials employ fillers such as asbestos, silica and glass fibre. These are incorporated by dry-blending methods similar to those used with woodflour-filled phenolic compositions. 

The second path in Fig. 3 outlines the approach to a more robust tape designed by Drew [21]. Here the milled rubber and filler are combined with tackifiers and other additives/stabilizers in an intensive dispersing step, such as a Mogul or Banbury mixer. Next, a phenolic resin or an alternative crosslinker is added and allowed to react with the rubber crosslinker to a point somewhat short of crosslinking. The compounded mixture is then charged to a heavy duty chum and dissolved in a suitable solvent like mineral spirits. To prepare a masking tape. 

By far the preponderance of the 3400 kt of current worldwide phenolic resin production is in the form of phenol-formaldehyde (PF) reaction products. Phenol and formaldehyde are currently two of the most available monomers on earth. About 6000 kt of phenol and 10,000 kt of formaldehyde (100% basis) were produced in 1998 [55,56]. The organic raw materials for synthesis of phenol and formaldehyde are cumene (derived from benzene and propylene) and methanol, respectively. These materials are, in turn, obtained from petroleum and natural gas at relatively low cost ([57], pp. 10-26 [58], pp. 1-30). Cost is one of the most important advantages of phenolics in most applications. It is critical to the acceptance of phenolics for wood panel manufacture. With the exception of urea-formaldehyde resins, PF resins are the lowest cost thermosetting resins available. In addition to its synthesis from low cost monomers, phenolic resin costs are often further reduced by extension with fillers such as clays, chalk, rags, wood flours, nutshell flours, grain flours, starches, lignins, tannins, and various other low eost materials. Often these fillers and extenders improve the performance of the phenolic for a particular use while reducing cost. 

Cured phenolics are universally brittle in nature. This is true of both resoles and novolacs and does not depend much on the source of methylene used to promote cure. Consequently, the fillers used in molded articles are highly important to the design of the manufactured product. With resoles, the fiber or filler are usually the primary component of the final composite, with the resole acting as a binder or impregnating agent. With novolacs the resin may be the major component in the molded part. Poly-silanes and other organic polymers are also added in some applications to promote impact resistance and toughness [192]. 

Phenol-formaldehyde (phenolic) plastics The chemical resistance is affected by the phenol used, cresols giving the best acid resistance whilst xylenols are often used to obtain the best alkali resistance. For chemical-resistant applications the fillers used in moulding powder and reinforcing material in laminates should be inorganic, e.g. asbestos or glass. The resins are usually dark in colour. 

Phenolics Excellent Includes the addition of mineral fillers. 

Between 250 and 450°F (121 and 232°C), plastics used include glass or mineral-filled phenolics, melamines, alkyds, silicones, nylons, polyphenylene oxides, polysulfones, polycarbonates, methylpentenes, fluorocarbons, polypropylenes, and diallyl phthalates. The addition of glass fillers to the thermoplastics can raise the useful temperature range as much as 100°F and at the same time shortens the molding cycle. 

Chlorinated polyether is formulated particularly for products requiring, good chemical resistance. Other materials exhibiting good chemical resistance include all of the fluorocarbon plastics, ethylpentenes, polyolefins, certain phenolics, and diallyl phtha-late compounds. Additives such as fillers, plasticizers, stabilizers, colorants, and type catalysts can decrease the chemical resistance of unfilled plastics. Certain chemicals in cosmetics will affect plastics, and tests are necessary in most cases with new formulations. Temperature condition is also very important to include in the evaluation. Careful tests must be made under actual use conditions in final selection studies. 

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