Ultraviolet processing

One of the most efficient methods for rapid generation of highly crosslinked polymers is by exposing multifunctional monomers to UV radiation in the presence of a photoinitiator. A liquid resin can be transformed within a fraction of a second into a solid polymer that is very resistant to chemical, heat and mechanical treatments. A review of UV curing of polymers is presented by Decker (1989).  

Quality-control tests and important process variables 

Important material and process variables for UV processing include 

UV-irradiation power curing temperature the material s cure kinetics and the material s chemoviscosity 

Typical systems include unsaturated polyesters (relatively slow cure used in the woodfinishing industry), thiolene systems (which are useful for coatings, adhesives and sealants). 

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Ultraviolet processing has been restricted to lab-scale studies however, many authors have examined kinetic cure modelling of these systems during the development of new UV-cure materials. 

The use of the ultraviolet process as a means of disinfecting water to meet the bacteriological requirements of the Public Health Service Drinking Water Standards is acceptable provided the equipment used meets the criteria described herein. 

Systems, Public Health Service Publication No. 24.) The ultraviolet process of disinfecting water will not change the chemical and physical characteristics of the water. Additional treatment, if otherwise dictated, will still be required, including possible need for residual disinfectant in the distribution system. 

In absorption spectroscopy a beam of electromagnetic radiation passes through a sample. Much of the radiation is transmitted without a loss in intensity. At selected frequencies, however, the radiation s intensity is attenuated. This process of attenuation is called absorption. Two general requirements must be met if an analyte is to absorb electromagnetic radiation. The first requirement is that there must be a mechanism by which the radiation s electric field or magnetic field interacts with the analyte. For ultraviolet and visible radiation, this interaction involves the electronic energy of valence electrons. A chemical bond s vibrational energy is altered by the absorbance of infrared radiation. A more detailed treatment of this interaction, and its importance in deter-... 

Diffraction gratings may be made by a holographic process, but blaze characteristics cannot be controlled and their efficiency is low in the infrared. They are mostly used for low-order work in the visible and near-ultraviolet. 

Figure 8.1 Processes occurring in (a) ultraviolet photoelectron spectroscopy (UPS), (b) X-ray photoelectron spectroscopy (XPS) and (c) Auger electron spectroscopy (AES)...

Instead of using a laser operating in the vacuum-ultraviolet region a laser operating at half the energy may be used. Then the ionization process in Figure 9.50(b) involves the... 

Figure 9.50 Processes involved in obtaining (a) an ultraviolet photoelectron spectrum, (b) a zero kinetic energy photoelectron (ZEKE-PE) spectrum by a one-photon process and (c) a ZEKE-PE spectrum by a two-photon process in which the first photon is resonant with an excited electronic state of the molecule...

Photopolymerization and Plasma Polymerization. The use of ultraviolet light alone (14) as well as the use of electrically excited plasmas or glow discharges to generate monomers capable of undergoing VDP have been explored. The products of these two processes, called plasma polymers, continue to receive considerable scientific attention. Interest in these approaches is enhanced by the fact that the feedstock material from which the monomer capable of VDP is generated is often inexpensive and readily available. In spite of these widespread scientific efforts, however, commercial use of the technologies is quite limited. 

Oxidation. Acetaldehyde is readily oxidised with oxygen or air to acetic acid, acetic anhydride, and peracetic acid (see Acetic acid and derivatives). The principal product depends on the reaction conditions. Acetic acid [64-19-7] may be produced commercially by the Hquid-phase oxidation of acetaldehyde at 65°C using cobalt or manganese acetate dissolved in acetic acid as a catalyst (34). Liquid-phase oxidation in the presence of mixed acetates of copper and cobalt yields acetic anhydride [108-24-7] (35). Peroxyacetic acid or a perester is beheved to be the precursor in both syntheses. There are two commercial processes for the production of peracetic acid [79-21 -0]. Low temperature oxidation of acetaldehyde in the presence of metal salts, ultraviolet irradiation, or osone yields acetaldehyde monoperacetate, which can be decomposed to peracetic acid and acetaldehyde (36). Peracetic acid can also be formed directiy by Hquid-phase oxidation at 5—50°C with a cobalt salt catalyst (37) (see Peroxides and peroxy compounds). Nitric acid oxidation of acetaldehyde yields glyoxal [107-22-2] (38,39). Oxidations of /)-xylene to terephthaHc acid [100-21-0] and of ethanol to acetic acid are activated by acetaldehyde (40,41). 

Optical Lithography. Optical Hthography uses visible or ultraviolet light as the exposure media, and is the dominant Hthographic process used for patterning IC wafers. The linewidth limit is near 0.4 p.m, although some narrower features may be possible (34). The masks typically are made from patterned, opaque chromium films on glass. 

Binders and Resins. The choice of binder is the most important ingredient choice in the formulation process because the binder affects the performance properties of a paint more than any other single ingredient (3). The physical properties of binders required for paints include the abiHty to dry or cure under various ambient conditions, good adhesion to various substrates, abrasion resistance, washabiHty, flexibiHty, water resistance, and ultraviolet light resistance. The balance of these required properties is mosdy dependent on whether the paint is being developed for interior or exterior appHcations. 

A more energy-efficient variation of photohalogenation, which has been used since the 1940s to produce chlorinated solvents, is the Kharasch process (45). Ultraviolet radiation is used to photocleave ben2oyl peroxide (see Peroxides and peroxide compounds). The radical products react with sulfuryl chloride (from SO2 and CI2) to Hberate atomic chlorine and initiate a radical chain process in which hydrocarbons become halogenated. Thus, for Ar = aryl,... 

The diacid components for the manufacture of poly(y -phenyleneisophthalamide) and poly(p-phenyleneterephthalamide) are produced by one of two processes. In the first, the diacid chlorides are produced by the oxidation of / -xylene [108-38-3] or -xylene [106-42-3] followed by the reaction of the diacids with phosgene [75-44-5]. In the second, process m- or -xylene reacts with chlorine initiated by ultraviolet light to form the m- or Nhexachloroxylene. This then reacts with the respective aromatic dicarboxyUc acid to form the diacid chloride. 

Ultraviolet Aging. Nylon parts exposed to sunlight and uv rays undergo a similar free-radical aging process. Again, this can be reduced with appropriately stabilized materials. 

Curing with Ultraviolet, Visible, and Infrared Processing Equipment... 

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