Unsupported

Film and sheet are defined as flat unsupported sections of a plastic resia whose thickness is very thin ia relation to its width and length. Films are generally regarded as being 0.25 mm or less, whereas sheet may range from this thickness to several centimeters thick. Film and sheet may be used alone ia their unsupported state or may be combined through lamination, coextmsion, or coating. They may also be used in combination with other materials such as paper, foil, or fabrics. 

Solution Casting. The production of unsupported film and sheet by solution casting has generally passed from favor and is used only for special polymers not amenable to melt processes. The use of solvents was generally very hazardous because of their flammabiUty or toxic nature. The cost of recovery and disposal of solvents became prohibitive for many lower price film appHcations. The nature of the drying operations leads to problems with solvent migration and retention that are not problems with melt-processed polymers. 

In preparation of permselective hoUow-fiber membranes, morphology must be controUed to obtain desired mechanical and transport properties. Fiber fabrication is performed without a casting surface. Therefore, in the moving, unsupported thread line, the nascent hoUow-fiber membrane must estabUsh mechanical integrity in a very short time. 

In small pieces or as inserts, laminates may be used unsupported because they are quite stiff and strong. The modulus of a high pressure decorative laminate is about 7 GPa (106 psi) at room temperature. Thick laminates range up to 25 mm and are very strong, having flexual strength of 130 MPa (19,000 psi). These products are used unsupported as toilet partitions, laboratory tops, and so forth. 

The sol—gel technique has been used mosdy to prepare alumina membranes. Figure 18 shows a cross section of a composite alumina membrane made by sHp coating successive sols with different particle sizes onto a porous ceramic support. SiUca or titanium membranes could also be made by the same principles. Unsupported titanium dioxide membranes with pore sizes of 5 nm or less have been made by the sol—gel process (57). 

The anhydride of 1,8-naphthalenedicarboxyHc acid is obtained in ca 95—116 wt % yield by the vapor-phase air-oxidation of acenaphthene at ca 330—450°C, using unsupported or supported vanadium oxide catalysts, with or without modifiers (96). 

Most catalysts for solution processes are either completely soluble or pseudo-homogeneous all their catalyst components are introduced into the reactor as Hquids but produce soHd catalysts when combined. The early Du Pont process employed a three-component catalyst consisting of titanium tetrachloride, vanadium oxytrichloride, and triisobutjlalurninum (80,81), whereas Dow used a mixture of titanium tetrachloride and triisobutylalurninum modified with ammonia (86,87). Because processes are intrinsically suitable for the use of soluble catalysts, they were the first to accommodate highly active metallocene catalysts. Other suitable catalyst systems include heterogeneous catalysts (such as chromium-based catalysts) as well as supported and unsupported Ziegler catalysts (88—90). 

Eluidized-bed reactors are highly versatile and can accommodate many types of polymerization catalysts. Most of the catalysts used for LLDPE production are heterogeneous Ziegler catalysts, in both supported and unsupported forms. The gas-phase process can also accommodate supported metallocene catalysts that produce compositionaHy uniform LLDPE resins (49—51). 

LLDPE by itself does not present any health-related hazard on account of its chemical inertness and low toxicity. Consequently, film, containers, and container Hds made from LLDPE are used on a large scale in food and dmg packaging. Some LLDPE grades produced with unsupported metallocene catalysts have an especially high purity due to high catalyst productivity and a low contamination level of resins with catalyst residue. FDA approved the use of film manufactured from these resins for food contact and for various medical appHcations (80). However, if LLDPE articles contain fillers, processing aids, or colorants, thek health factors must then be judged separately. 

Kelease Paper and Unsupported Telease Film, H-P Smith, Chicago, lU., 1981. 

Supports. The spaciag of supports is governed by the hot allowable stress of the piping materials stabiUty, ia the case of large-diameter thin-wall pipe deflection to avoid sagging or pocketing and the natural frequency of the unsupported length to avoid susceptibiUty to undesirable vibration. 

Catalysts. Nearly aU. of the industrially significant aromatic alkylation processes of the past have been carried out in the Hquid phase with unsupported acid catalysts. For example, AlCl HF have been used commercially for at least one of the benzene alkylation processes to produce ethylbenzene (104), cumene (105), and detergent alkylates (80). Exceptions to this historical trend have been the use of a supported boron trifluoride for the production of ethylbenzene and of a soHd phosphoric acid (SPA) catalyst for the production of cumene (59,106). 

Heterogeneous hydrogenation catalysts can be used in either a supported or an unsupported form. The most common supports are based on alurnina, carbon, and siUca. Supports are usually used with the more expensive metals and serve several purposes. Most importandy, they increase the efficiency of the catalyst based on the weight of metal used and they aid in the recovery of the catalyst, both of which help to keep costs low. When supported catalysts are employed, they can be used as a fixed bed or as a slurry (Uquid phase) or a fluidized bed (vapor phase). In a fixed-bed process, the amine or amine solution flows over the immobile catalyst. This eliminates the need for an elaborate catalyst recovery system and minimizes catalyst loss. When a slurry or fluidized bed is used, the catalyst must be separated from the amine by gravity (settling), filtration, or other means. 

Styrene—butadiene, acrylonitrile—butadiene, and butyl latices have also been prevulcanised, but this usually results in a lower wet gel strength. Where the mbber is to be deposited onto a fabric substrate, as in manufacture of fabric-lined gloves, the lower gel strength is not a problem. For unsupported dipped synthetic mbber products, however, the use of post-vulcanised compounds is more common. 

Equipment. A typical commercial quartz-growing autoclave is Hlustrated in Figure 1. The material of constmction for use at 17 MPa (25,000 psi) and 400°C can be a low carbon steel, such as 4140, or various types of low aHoy steel. The closure, a modified Bridgeman closure, is based on the unsupported area principle (12). That is, the pressure in the vessel is transmitted through the plunger to the steel surfaces which initially are nearly line contacts. Thus, the pressure in the seal surface gready exceeds the pressure in the vessel because most of the area of the plunger is unsupported. Hydrothermal equipment has been further discussed (10). 

Hydrogenation of Acetylenes. Complete hydrogenation of acetylenes to the corresponding alkanes, which maybe requited to remove acetylenic species from a mixture, or as a part of a multistep synthesis, may be accompHshed using <5 wt % palladium or platinum on alumina in a nonreactive solvent under very mild conditions, ie, <100°C, <1 MPa (10 atm). Platinum is preferred in those cases where it is desired to avoid isomeri2ation of the intermediate olefin. Silver on alumina also can be used in this appHcation as can unsupported platinum metal. 

In general, EPM/EPDM compounds can be extmded easily on all commercial mbber extmders. Furthermore, EPDM compounds can be calendered both as unsupported sheeting and onto a cloth substrate. 

Dipped Goods. Gloves with and without cloth support are a typical example. Unsupported appUcations involve specialty medical gloves and weather balloons. Eor CR to compete with less expensive natural mbber, it must provide added value. Natural mbber medical examination gloves contain proteins that can cause an allergic reaction in both patients and medical personnel. Polychloroprene gloves avoid the problem for those individuals, but are too expensive for general use. Natural mbber weather balloons have less lift than CR balloons and are rapidly attacked by ozone in the upper atmosphere. 

Minimum baffle spacing is generally one-fifth of the shell diameter and not less than 50.8 mm (2 in). Maximum baffle spacing is hm-ited by the requirement to provide adequate support for the tubes. The maximum unsupported tube span in inches equals 74 dP (where d is the outside tube diameter in inches). The unsupported tube span is reduced by about 12 percent for aluminum, copper, and their alloys. 

Maximum shell-side heat-transfer rates in forced convection are apparently obtained by cross-flow of the flmd at right angles to the tubes. In order to maximize this type of flow some heat exchangers are built with segmental-cut baffles and with no tubes in the window (or the baffle cutout). Maximum baffle spacing may thus equal maximum unsupported-tube span, while conventional baffle spacing is hmited to one-h f of this span. 

A typical drive-in rack consists of a steel structure to support palletized goods at the pallet edge, with the center of the pallet unsupported. The space between pallet support members is sufficient to permit a lift truck to drive in to place or retrieve a load. These racks are usually made to accommodate 12 pallets, which are positioned from the seiwice aisle to the end of the rack. Because of the rack, each pallet position has the abihty to hold 6 to 8 pallets vertically. 

Slender unsupported regions with large length to thickness ratios are highly liable to distortion during processing. 

An even more ambitious goal is to characterize an unsupported catalyst, because the surface is extremely rough and the target rapidly deteriorates under bombardment. Energy deposition leads to enormous erosion, because the substrate cannot get rid of the energy deposited, owing to the low heat conductivity. As a consequence static LEIS conditions have to be used to obtain information on the surface alone. In Fig. 3.60a we show a series of LEIS spectra obtained with 5 keV Ne" ions on a... 

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