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308119 Photographic silver halide emulsions. preparations. addenda, processing and systems INDEX I. Emulsion preparation and types II. Emulsion washing III. Chemical sensitization IV. Spectral sensitization and desensitization V. Brighteners VI. Antifoggants and stabilizers VII. Color materials VIII. Absorbing and scattering materials IX. Vehicles and vehicle extenders X. Hardeners XI. Coating aids XII. Plasticizers and lubricants XIII. Antistatic layers XIV. Methods of addition XV. Coating and drying procedures XVI. Matting agents XVII. Supports XVIII. Exposure XIX. Processing XX. Developing agents XXI. Development modifiers XXII. Physical development systems XXIII. Image-transfer systems XXIV. Dry development systems XXV. Printing and lithography XXVI. Printout XXVII. Direct-print Photographic silver halide emulsions, preparationsT addenda, processing and systems I.Emulsion preparation and types A The silver halide emulsions can be comprised of silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver bromoiodide, silver chlorobromoiodide or mixtures thereof. The emulsions can include coarse, medium or fine silver halide grains and can be prepared by a variety of techniques-e.g., single-jet, double-jet (including continuous removal techniques), accelerated flow rate and interrupted precipitation techniqiies as illustrated by Trivelli and Smith, The Photographic Journal, Vol. LXXIX, May, 1939, pp. 330-338, T. H. James, The Theory p_f the. Photographic Process. 4th Ed., Macmillan, 1977, Chapter 3, Terwilliger et al Research Disclosure. Vol. 149, September 1976, Item 14987, as well as Nietz et al U.S. Patent 2,222,264, Wilgus German OLS 2,107,118, Lewis U.K. Patents 1,335,925, 1,430,465 and 1,469,480, Irie et al U.S. Patent 3,650,757, Kurz U.S. Patent 3,672,900, Morgan U.S. Patent 3,917,485, Musliner U.S. Patent 3,790,387, Evans U.S. Patent 3,761,276 and Oilman et al U.S. Patent 3,979,213. Although silver halide emulsion crystals favor {100} (cubic) and {111} (octahedral) surface faces, all of the seven theoretical crystallographic forms for cubic crystal lattice materials can be prepared, as summarized by Maskasky U.S. Patent 4,643,966. Crystals bounded by combinations of these faces can also be formed (e.g., cubo-octahedral grains). Lattice irregularities such as twin planes or screw dislocations can lead to further diversity in silver halide grain shapes. The emulsions can a high proportion of tabular-grain emulsions, as described by Abbott et al U.S. Patent 4,425,426; Wilgus et al U.S. Patent 4,434,226, Solberg et al U.S. Patent 4,433,048, Kofron et al U.S. Patent 4,439,520, Daubendiek et al U.S. Patent 4,414,310, Wey U.S. Patent 4,399,215, Evans et al U.S. Patent 4,504,570, Maskasky U.S. Patents 4,400,463 and 4,435,501, Wey et al U.S. Patent 4,414,306, Mignot U.S. Patent 4,386,156, and Research Disclosure, Vol.225, January 1983, Item 22534, and Vol. 232, August 1983, Item 23212. Thin silver iodide tabular-grain emulsions can be prepared as described by Maskasky U.S. Patent 4,459,353 and House U.S. Patent 4,490,458. The emulsion grain shapes can be further varied with epitaxial depositions, as described by Maskasky U.S. Patents 4,094,684, 4,142,900, 4,435,501, and 4,463,087, and Koitabashi et al U.K. Patent Application 2,053,499A and U.S. Patent 4,349,622. Also, the faces of the emulsion grains can be decorated with protrusions or "ruffles", as described by Maskasky U.S. Patent 4,643,966. B In silver haloiodide emulsions, the iodide can be uniformly distributed among the emulsion grains, as described by Maternaghan U.S. Patent 4,184,878 and Koitabashi et al Japanese Patent Application JA 48/65,925, or iodide level can be varied among the grains as described by Ogawa et al U.S. Patent 4,617,259. Within a single emulsion grain, the iodide can be uniformly distributed or can be varied as described by Daubendiek et al U.S. Patent 4,414,310 and Wilgus et al U.S. Patent 4,434,226. Iodide concentration can be highest in the core area, as described by Wall, Photographic Emulsions, American Photographic Publishing Co., Boston, 1929, p.37ff, Ketellaper, Journal of Photographic Science. Vol.26, 1978, p.189, Falxa et al U.S. Patent 4,259,438, Koitabashi et al U.S. Patent 4,444,877, Matsuzaka et al U.S. Patent 4,497,895, Takiguchi et al European Patent Application EP 97,720, Takada et al U.S. Patent 4,668,614, Shibahara Japanese Patent Application JA 60/143,332, and Shibahara et al U.S. Patent 4,728,602. Iodide concentration can be varied gradually or abruptly through the emulsion grain leading to zones of high or low iodide, as described by Klein et al U.K. Patent 1,027,146, Beckett et al U.S. Patent 3,505,068, Corben U.S. Patent 4,210,450, Solberg et al U.S. Patent 4,433,048, Becker et al U.S. Patent 4,636,461, Sugimoto et al U.S. Patent 4,665,012, Matsuzaka et al European Patent Application 202,784, and Aida et al European Patent Application 264,954. As discussed by Solberg et al, cited above, placement of the iodide can be determined by judicious gradual or abrupt adjustments in the amount of iodide added at each stage of emulsion precipitation. Techniques can vary from the continuous presence of fine silver iodide grains throughout the precipitation for uniform distribution as described by Maternaghan U.S. Patent 4,150,994, to the abrupt additions of iodide solution at various stages in the precipitation as described by Breslav et al, Zfaurjial Nauchnoi i Prikladnoi Fotografii i Kinematografii. Vol.17, No.3 (1972), p.217, in Japanese Patent Application JA 53/66,218 and by Yoshida et al European Patent Application 243,099. C The halide composition of the emulsion grains as precipitated can be modified by halide conversion, i.e., the displacement of a more soluble silver halide salt by a less soluble salt as described by Allentoff et al U.S. Patent 3,477,852. The halide conversion can be limited to specific positions on the silver halide grains, e.g., to the locations of epitaxial deposits, as described by Maskasky U.S. Patent 4,142,900, or to corners or edges of the grains as described by Hasebe et al European Patent Applications EP 273,429 and 273,430 and Yamada et al German OLS 3,819,241. D Compounds of metals such as copper, thallium, lead, mercury, bismuth, zinc, cadmium, rhenium, and Group VIII metals (e.g., iron, ruthenium, rhodium, palladium, osmium, iridium, and platinum) can be present during precipitation of the silver halide emulsion, as illustrated by Arnold et al U.S. Patent 1,195,432; Hochstetter U.S. Patent 1,951,933; Trivelli et al U.S. Patent 2,448,060; Overman U.S. Patent 2,628,167; Mueller et al U.S. Patent 2,950,972; McBride U.S. Patent 3,287,136; Sidebotham U.S. Patent 3,488,709; Rosecrants et al U.S. Patent 3,737,313; Spence et al U.S. Patent 3,687,676; Gilman et al U.S. Patent 3,761,267; Ohkubo et al U.S. Patent 3,890,154; Iwaosa et al U.S. Patent 3,901,711; Habu et al U.S. Patent 4,173,483; Atwell U.S. Patent 4,269,927; Janusonis et al U.S. Patent 4,835,093; B. H. Carroll, "Iridium Sensitization: A Literature Review", Photographic Science and Engineering. Vol.24, No. 6, Nov./Dec.1980, pp.265-267; and Grzeskowiak et al European Patent Application EP 264,288. The metals introduced during grain nucleation and/or growth can enter the grains as dopants to modify photographic properties, depending on their level and location within the grains. When the metal forms a part of a coordination complex, such a hexacoordination complex or a tetracoordination complex, the ligands can also be occluded within the grains. Coordination ligands, such as halo, aquo, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo, and carbonyl ligands are contemplated and can be relied upon to vary emulsion properties further. E The reactants can be added to the reaction vessel in the form of solutions of silver and halide salts, or in the form of preformed silver halide nuclei or fine grains, as described by Mignot U.S. Patent 4,334,012, Saito U.S. Patent 4,301,241, Solberg et al U.S. Patent 4,433,048, and Maternaghan U.S. Patent 4,150,994. The individual reactants can be added through surface or subsurface delivery tubes by gravity feed or by delivery apparatus for maintaining control of the rate of delivery and the pH and/or pAg of the reaction vessel contents, as illustrated by Culhane et al U.S. Patent 3,821,002, Oliver U.S. Patent 3,031,304 and Claes et al Photographische Korrespondenz. 102 Band, No. 10, 1967, p.162. To obtain rapid distribution of the reactants within the reaction vessel, specially constructed mixing devices can be employed as illustrated by Audran U.S. Patent 2,996,287, McCrossen et al U.S. Patent 3,342,605, Frame et al U.S. Patent 3,415,650, Porter et al U.S. Patent 3,785,777, Saito et al German OLS 2,556,885 and Saito et al German OLS 2,555,364. An enclosed reaction vessel can be employed to receive and mix reactants upstream of the main reaction vessel as illustrated by Forster et al U.S. Patent 3,897,935 and Posse et al U.S. Patent 3,790,386. Formation of silver halide grain nuclei by reacting silver and halide salts in solution can be continued during grain growth, or nucleation and grain growth may be carried out as separate steps in either the same reaction vessel or separate reaction vessels, as described by Posse et al U.S. Patent 3,790,386, Saito U.S. Patent 4,242,445, and Mignot U.S. Patent 4,334,012. The volume of the emulsion in the reaction vessel can be allowed to increase as the reactants are added, or can be controlled by such methods as continuous removal of the emulsion as described in U.K. Patent 1,302,405 and by Terwilliger et al U.S. Patent 4,046,576, or separation of a portion of the dispersing medium as described by Mignot, cited above. The reactant solutions or dispersions can be added at a constant rate, or their rate of addition or concentration can be varied continuously or stepwise as described by Hirata et al, Bulletin o_ the Society of Scientific Photography of Japan. No. 16, 1969, p. 1, Irie et al U.S. Patent 3,650,757, Wilgus German OLS 2,107,118 and Saito U.S. Patents 4,242,445 and 4,301,241. F The silver halide emulsions can be either monodispersed or polydispersed as precipitated. The grain size distribution of the emulsions can be controlled by various techniques such as silver halide grain separation or blending silver halide emulsions of differing grain sizes, by controlled ripening as described in Research Disclosure. Vol. 232, August, 1983, Item 23212, or by continuously introducing silver halide grains as additional host grains as described by Wey et al U.S. Patent 4,552,838. The emulsions can include Lippmann emulsions and ammoniacal emulsions as illustrated by Glafkides, Photographic Chemistry. Vol. 1, Fountain Press, London, 1958, pp. 365-368 and pp. 301-304; excess halide ion-ripened emulsions as described by G.F. Duffin, Photographic Emulsion Chemistry, Focal Press, Ltd., London, 1966, pp. 60-72; thiocyanate-ripened emulsions as illustrated by Illingsworth U.S. Patent 3,320,069; thioether-ripened emulsions as illustrated by McBride U.S. Patent 3,271,157, Jones U.S. Patent 3,574,628 and Rosecrants U.S. Patent 3,737,313, or emulsions containing weak silver halide solvents such as ammonium salts, as illustrated by Perignon U.S. Patent 3,784,381 and Research Disclosure. Vol.134, June, 1975, Item 13452. G The emulsions can be surface-sensitive emulsions-i.e., emulsions that form latent images primarily on the surfaces of the silver halide grains (as typically occurs absent intentional grain modification) or internal latent image-forming emulsions-i.e., emulsions that form latent images predominantly in the interior of the silver halide grains (typically achieved by internal crystal irregularities or dopant incorporation), as illustrated by Knott et al U.S. Patent 2,456,953, Davey et al U.S. Patent 2,592,250, Porter et al U.S. Patents 3,206,313 and 3,327,322, Berriman U.S. Patent 3,367,778, Bacon et al U.S. Patent 3,447,927, Evans U.S. Patent 3,761,276, Morgan U.S. Patent 3,917,485, Gilman et al U.S. Patent 3,979,312 and Miller U.S. Patent 3,767,413. H The emulsions can be negative-working emulsions such as surface-sensitive emulsions or unfogged internal latent image-forming emulsions, or direct-positive emulsions of the surface-fogged type, as illustrated by Kendall et al U.S. Patent 2,541,472, Shouwenaars U.K. Patent 723,019, Illingsworth U.S. Patent 3,501,307, Berriman U.S. Patent 3,367,778, Research Disclosure. Vol. 134, June, 1975, Item 13452, Kurz U.S. Patent 3,672,900, Judd et al U.S. Patent 3,600,180 and Taber et al U.S. Patent 3,647,463, or of the unfogged, internal latent image-forming type, which are positive-working with fogging development, as il...