RAW MATERIALS
`
`IN THE
`
`GLASS INDUSTRY
`
`PART II - Minor Ingredients
`
`Compiled by
`Alexis G. Pincus
`Ceramics Department, Rutgers University
`and
`David H. Davies
`Certain-Teed Corporation
`
`A collection of articles on raw materials used for commercial silicate glasses published in THE
`GLASS INDUSTRY magazine since its inception in 1920. Part II has sections on fining agents,
`colorants and decolorizers, opacifiers, and cullet.
`An extensive bibliography prepared especially for these two volumes and a subject index ap(cid:173)
`pear at the back of this part II.
`
`ASHLEE PUBLISHING CO., INC.
`
`Books for the Glass Industry Division
`
`310 Madison Avenue, New York, N.Y. 10017
`
`O-I Glass, Inc.
`Exhibit 1021
`Page 001
`
`

`

`Library of Congress Number 83-70137
`
`ISBN Number0-911993·02·9
`
`Copyright© 1983 by Ashlee Publishing Co., Inc.
`
`l .I
`
`O-I Glass, Inc.
`Exhibit 1021
`Page 002
`
`

`

`Table of Contents
`
`PART I-Major Ingredients
`
`Preface ....................................................................................... III
`Introduction ................................................................................... IX
`
`Section
`Chapter
`
`I.
`1.
`
`2.
`
`3.
`
`4.
`
`5.
`
`6.
`
`7.
`
`8.
`
`9.
`
`General
`Raw Materials of the Glass Industry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
`J. B. Krak (Apr. 1925)
`German War Efforts in Replacing Glass Raw Materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
`Oscar Knapp (Aug. 1947)
`Raw Materials Procurement Problems in the Glass Industry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
`C. L. Rice (Apr. 1948)
`Better Raw Materials for the Glass Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
`Axel Ottoson (May 1948)
`Glass-Making Raw Materials of California . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
`W. A. Seitz (Sept. 1957)
`Problems in Sampling and Sieve Testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23,
`Paul Close (Dec. 1962, Jan. 1963)
`Raw Materials for the Specialty Glass Industry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
`G. H. Edwards and J. G. Copley, Jr. (Mar., Apr. 1977)
`Raw Materials for Glass Manufacture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
`Harry N. Mills (Nov. 1977)
`The West Coast Raw Material Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
`Henry Moore (June 1978)
`
`Section n.
`Chapter 10.
`
`11.
`
`12.
`
`13.
`
`14.
`
`15.
`
`16.
`
`Sources of Silica-Glass Sands
`The Chieflngredient of Glass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
`Anon. (Feb. 1921)
`A voiding Errors in the Analysis of Glass Sand . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
`J.B. Krak (June 1923)
`The Geology of Glass Sands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
`Howard West Elkington (Dec. 1923)
`Glass Division Votes on Sand Specifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
`Anon. (Feb. 1926)
`Should Glass Sand be Used Wet or Dry? .............................................. 55
`D. E. Berger (Jan. 1935)
`Glass Sands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
`S. R. Scholes (Sept. 1937)
`Dredge Improves Sand-Mining Operation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
`Anon. (Feb. 1965)
`
`Ill
`
`O-I Glass, Inc.
`Exhibit 1021
`Page 003
`
`

`

`III.
`Section
`Chapter 17.
`
`18.
`
`19.
`
`20.
`
`21.
`
`22.
`
`23.
`
`24.
`
`25.
`
`26.
`
`27.
`
`28.
`
`29.
`
`30.
`
`31.
`
`IV.
`Section
`Chapter 32.
`
`33.
`
`34.
`
`35.
`
`36.
`
`37.
`
`38.
`
`39.
`
`40.
`
`41.
`
`42.
`
`43.
`
`44.
`
`45.
`
`46.
`
`Sources of Alkalis
`NotesonSodaAsh ................................................................ 68
`Anon. (Nov. 1920)
`Use of Light Soda Ash in the Production of Flint Bottle Glass ............................ 69
`C. A. Cole (Dec. 1920)
`The Comparative Cost of Soda Ash and Salt Cake in the Manufacture of Window Glass . . . . . . 72
`J.B. Krak (Jan. 1922)
`Salt Cake and Soda Ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
`J. B. Krak (June, July 1925)
`Note on Use of Caustic Alkali in Glass Batches . .. . . .. . .. . .. . . . . . . . . .. . . . . . . . . . . . . .. . .. . 78
`A. E. Badger and L. M. Doney (Mar. 1939)
`Outlook for Soda Ash in the Glass Industry .. . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . .. . . . . . 79
`Melvin E. Clark (June 1948)
`Alkalis and Glass: Allied Industries . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . 84
`H. W. Harrington and R. V. Yount (Sept. 1954)
`NewSodaAshPlant. .............................................................. 88
`Anon. (Aug. 1962)
`Fundamentals of Caustic Soda . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . • . . . . . . . . . . . . . . . . . . . . 90
`Jim Moss (Nov. 1969)
`Natural Soda Ash ................................................................. 94
`Wyman L. Taylor (Nov. 1972)
`TronaMine-SodaAshProduction ............................•.................... 96
`James E. McLeod (Aug. 1975)
`Lithium Development and Expansion ............................................... . 100
`H. E. Simpson (Jan. 1955)
`Lithium ......................................................................... 107
`Albert E. Schreck (Oct. 1961)
`Removal oflron from Spodumene Concentrates by Chlorination ......................... 113
`L. S. Richardson and J. H. Fishwick (July 1968)
`Lithia Reduces Viscosity Melting and Fining Times ..................................... 116
`John H. Fishwick (Sept., Oct. 1972)
`
`Sources of Bivalent Oxides
`The Relative Advantages and Disadvantages of Limestone, Burnt Lime, and Slaked Lime •... 122
`F. W. Rodkin and W. E. S. Turner (Oct. 1921)
`Bureau of Standards' Recommended Specification for Limestone, Quicklime
`and Hydrated Lime ........................................................... 125
`Anon. (Mar. 1922)
`American Society of Testing Materials' Recommended Specifications for
`Quicklime and Hydrated Lime .................................................. 127
`Anon. (Apr. 1922)
`Lime for Glass Making ............................................................. 128
`R.R. Shively (Aug. 1922, Jan. 1924)
`Burnt Lime or Limestone-Some Random Observations ................................ 130
`Irving E. Adams (Jan. 1923)
`Limestone, Burnt and Hydrated Lime ................................................ 132
`J.B. Krak (Sept. 1925)
`TheUseofLimeinGlass ........................................................... 138
`George 0. Smith (Dec. 1925)
`The Function of Lime in Glass ...................................................... 140
`D. J. McSwiney (Aug. 1926)
`Limestone, Burnt Lime or Hydrated Lime ............................................ 144
`Anon. (Jan. 1928)
`The Rejuvenation of Raw Lime in Glass Making ....................................... 145
`R. Frink (Feb. 1934)
`Status of Lime in Container Batches ................................................. 147
`Anon. (Mar. 1936)
`Specifications for Limestone for Making Colorless Glass ................................ 149
`S. R. Scholes (Dec. 1937)
`The Technical Valuation of Lead, Zinc and Barium Compounds .......................... 151
`J. B. Krak (June 1921)
`The Action of Barium in Glass ...................................................... 152
`Anon. (June 1925)
`The Use of Barite in Soda Lime Flint Glasses .......................................... 153
`D. J. McSwiney (May 19_28)
`
`IV
`
`O-I Glass, Inc.
`Exhibit 1021
`Page 004
`
`

`

`47. Technology and Valuation of Lead Oxides ............................................ 155
`Anon. (Aug. 1926)
`48. Red Lead for the Glassmaker ....................................................... 157
`R. L. Hallows (Dec. 1928)
`49. The Valuation of Zinc Oxide ........................................................ 161
`Anon. (Sept. 1926)
`
`Section V. Sources of Alumina
`Chapter 50. Aluminum Compounds ............................................................ 164
`J.B. Krak (Aug. 1921)
`51. Use of Alumina in Glass ............................................................ 165
`R. R. Shively (Sept. 1924)
`52. The Use of Alumina in Glass ........................................................ 167
`D. J. McSwiney (Apr. 1925)
`53. Feldspar as a Source of Alumina in Glass ........................... : .................. 171
`George 0. Smith (Aug. 1925)
`54. Valuation of Aluminum-Bearing Materials ............................................ 173
`Anon. (June 1926)
`55. Aluminum Hydroxide for the Manufacture of Opaque Glass ............................. 174
`Robert Schneider (Mar. 1927)
`56. Feldspar and Feldspar Production in North Carolina ................................... 176
`Jasper L. Stuckey (Nov. 1927)
`57. Comparative Tests on Alumina and Feldspar as Sources of Alumina in Glass ................ 179
`R. K. McBerty (Oct. 1928)
`58. Feldspar in North Carolina ......................................................... 182
`R. Carl Moore (Oct. 1929)
`59. Feldspar Grinders' Institute, Inc., Gets Going ......................................... 184
`Anon. (Oct. 1929)
`60. Commercial Standard for Ground Feldspar ........................................... 187
`Anon. (Jan. 1930)
`61. Feldspar Development in North Carolina ............................................. 189
`B. c .. Burgess (Mar., Apr. 1930)
`62. Feldspar Producers Meet Changing Demands ......................................... 198
`E.W. Koenig (Mar. 1930)
`63. Relation of Particle Size to the Melting of Feldspar ..................................... 200
`A. K. Lyle (Sept. 1930)
`64. Granular Glasspar ................................................................ 202
`B. C. Burgess (Sept. 1930)
`65. Feldspar-Jt.s Effect in Glass ....................................................... 204
`E.W. Koenig (Nov. 1930)
`66. Bureau of Mines Infonnation Circular on Feldspar ..................................... 206
`Anon. (Nov. 1930)
`67. Preparation ofFeldspathic Flux for Glass and Porcelain ................................. 208
`Anon. (May 1932)
`68. The Cost of Alumina from Feldspar .................................................. 209
`S. R. Scholes (Sept. 1934)
`69. Kyanite as a Source of Alumina ..................................................... 211
`S. R. Scholes (Dec. 1934)
`70. Volcanic Ash as a Constituent of Glass Batches ........................................ 212
`Anon. (Apr. 1935)
`71. Alumina in Glass Batches .......................................................... 213
`Hugo Kuehl (May 1935)
`72. Use of Feldspar in the Glass Industry ................................................. 215
`Wilhelm Schmidt (July 1935)
`73. Milling and Classification ofFeldspar ................................................ 218
`V. V. Kelsey (Oct. 1936)
`74. Nepheline Syenite-A New Batch Material ............................................ 221
`Anon. (Mar. 1936)
`75. Nepheline Syenite ................................................................. 222
`R. R. Ladoo (June 1937)
`76. Unusual Sources of Alumina in Glass Manufacture ..................................... 225
`R. W. Hopkins (May 1957)
`77. Feldspar by Flotation ............................................................... 229
`Anon. (Dec. 1961)
`
`V
`
`O-I Glass, Inc.
`Exhibit 1021
`Page 005
`
`

`

`Section VI.
`Chapter 78.
`
`79.
`
`80.
`
`81.
`
`82.
`
`83.
`
`84.
`
`Sources of Boric Oxide
`Properties, Technology and Valuation of Boron Compounds ......•..................... 232
`J. B. Krak (July 1921)
`Borax and Boric Acid .............................................................. 233
`J. B. Krak (May 1925)
`Boric Acid in Glass Manufacture ............. , ...................................... 236
`W. E. S. Turner (Sept. 1929)
`Developments in the Use of Borax ................................................... 239
`Anon. (Jan. 1931)
`A New Borax Product ............................................................. 240
`W. Ronald Lester (July 1935)
`Boric Oxide-Its Chemistry and Role in Glass Technology ............................... 243
`W. A. Weyl (May-Oct. 1948, selected portions)
`Borates in the Glass Industry ........................................................ 249
`M. H. Pickard (Feb. 1954)
`
`Part II-Minor Ingredients
`
`Section VII. General
`Chapter 85. Rarer Elements in the Glass Industry ................................................. 256
`H. Conrad Meyer (Mar. 1930)
`86. The Theory and Practice Concerning the Use of Minor Constituents in Glass ............... 257
`Richard M. Wiker (Aug. 1956)
`87. The Rare Earths .................................................................. 260
`Clifford A. Hampel (Jan., Feb., Mar. 1960)
`
`Section VIII. Fining Agents
`Chapter 88. Technology and Analysis of Salt Cake ................................................ 280
`J.B. Krak (Mar. 1921; Mar. 1924)
`89. Sodium Nitrate and Calcium Sulphate as Substitutes for Salt Cake
`in Plate and Sheet Glass ........................................................ 281
`Anon. (May 1924)
`90. Western Deposit of Sodium Sulphate Now Being Developed Commercially ................. 284
`Anon. (June 1927)
`91. Sulfates in Glass .................................................................. 286
`Addison R. Scholes (Mar. 1941)
`92. The Role of Sodium Sulphate in Glass Manufacture .................................... 291
`Woldemar A. Weyl (Jan., Feb., Mar. 1943)
`93. Reduction of Sodium Sulfate in Glass Manufacture ..................................... 303
`N. I. Kitaigorodskii, G. G. Sentyurin and V. A. Rishina (Dec. 1947)
`94. Use of Sulfates in Glass ............................................................ 304
`W. H. Manring (Mar. 1958)
`95. Comments and Rebuttal ............................................................ 309
`Larry Penberthy and A. R. Conroy, D. D. Billings, W. H. Manring and W. C. Bauer
`(Dec. 1963 and Feb. 1964)
`96. Blast Furnace Slag as a Raw Material for Glass Melting and Refming ...................... 311
`Rune Persson (Oct. 1966)
`97. Clarifiers ........................................................................ 315
`J.B. Krak (Oct. 1921)
`98. Arsenic as an Ingredient in Glass ..................................................... 316
`William Bloch and D. E. Sharp (July 1930)
`99. TheUseofArsenicinGlassBatches .................................................. 320
`Anon. (Feb. 1935)
`100. The Use of Arsenic in the Glass Industry .............................................. 322
`Woldemar A. Weyl (July 1942)
`101. AntimonyinGlass ................................................................ 328
`Tryggve Baak and E. J. Hornyak (July, Aug. 1966)
`
`IX. Colorants and Decolorizers
`Section
`Chapter 102. Selenium-from a Notebook ....................................................... 338
`Chester L. Sharp (Dec. 1920)
`103. Manganese Ores in Glass Making .................................................... 340
`Anon. (Jan. 1921)
`
`VI
`
`O-I Glass, Inc.
`Exhibit 1021
`Page 006
`
`

`

`109.
`
`104. Decolorizers ..................................................................... 342
`J.B. Krak (Nov. 1921)
`Decolorizing Glass
`Asher Blum (Nov. 1921)
`105. Colored Glasses .................................................................. 344
`J.B. Krak (Dec. 1921)
`106. TheUseofSeleniumasaDecolorizer ................................................. 347
`R. R. Shively (Feb. 1924)
`107. Notes on the Purity of Cadmium Sulphide ............................................ 349
`H. V. Huber (Nov. 1925)
`108. Note on the Use of Uranium Compounds ............................................. 350
`Theodore Lenchner (Aug. 1926)
`Iron and Its Compounds as Coloring Agents for Glass .................................. 351
`Erich Felsnet (Feb. 1927)
`110. Technology, UsesandAnalysisofSelenium ........................................... 354
`J.B. Krak (July 1928)
`111. Cerium and Manganese Dioxides for Decolorizing ....................................... 356
`Anon. (Mar. 1930)
`112. Use of Electrochemical By-Products in Glass Making: Arsenic, Selenium, Tellurium ......... 358
`Alexander Silverman (Aug. 1932)
`113. UseofSeleniumforDecolorizingGlass ............................................... 363
`Anon. (Sept. 1935)
`114. The Effect of Some Batch Materials on the Decolorization of Glass by Selenium ............. 368
`William Horak (Nov. 1936)
`115. Decolorization of Manganese and Sulfur in Glass with Application
`to Use of Furnace Slags ........................................................ 371
`A. E. Badger (June 1939)
`116. ProcessingandUseofSelenium ..................................................... 374
`Anon. (July 1946)
`117. Research on Utilization of Spinet with Lower Valent Aluminum Ion
`as a Reducing Reagent of Glass .................................................. 376
`Goro Yamaguchi (Feb. 1955)
`118. ThePlatinumMetalsinGlass ....................................................... 379
`M. G. Hawes (Aug. 1957)
`119. Use of Cerium Concentrates for Decolorizing Soda-Lime Glasses ......................... 382
`Allan P. Herring, R. W. Dean and J. L. Drobnick (July, Aug., Sept. 1970)
`
`Section X. Opacifiers
`Chapter 120. TheValuationofOpacifyingMaterials .............................................. .400
`Anon. (May 1926)
`121. Fluorspar-Its Mining and Markets .................................................. 402
`E. L. Brokenshire (May 1927)
`122. Valuation ofFluorspar .... · ......................................................... 404
`Anon. (June 1927)
`123. The Use of Topaz as a Glass Opacifier ................................................ 407
`Samuel B. Meyer, Jr. (May 1942)
`124. Effect of Fluorides on Infrared Transmittance of Certain Silicate Glasses (abstract) .......... 409
`G. W. Cleek and T. G. Scuderi (Feb. 1960)
`
`Section XI. Cullet
`Chapter 125. TheManufactureandUseofCullet ................................................. .412
`D. J. McSwiney (Mar. 1926)
`126. The Use of Cullet in Glass Manufacture .............................................. .414
`Erich Felsner (July 1926)
`127. TheUseofCullet-AReview ....................................................... 416
`Anon. (Feb. 1942)
`128. Glass Containers as a Factor in Municipal Solid Waste Disposal ......................... .420
`John H. Abrahams, Jr. (May 1970)
`129. Recycling Waste-Closing the Loop ................................................ .424
`Anon. (Dec. 1971; Jan., Feb. 1972)
`130, Waste Glass Beneficiation by Dense Media Separation .................................. 432
`Michael W. Stewart, Thomas J. Shiple and John P. Cumings (Apr., May 1974)
`
`Bibliography .................................................................................. 436
`Index ........................................................................................ . 452
`
`VII
`
`O-I Glass, Inc.
`Exhibit 1021
`Page 007
`
`

`

`Chapter 115
`ecolorization of Manganese and Sulfur
`In Glass with Application to Use
`Of Furnace Slags
`
`Jf ABSTRACT-The purple color of glasses caused by trivalent
`rt ;lllanganese may be prevented by adding zinc sulfide or cad(cid:173)
`JF''.inium sulfide to the glass batch. Excess of zinc sulfide pro(cid:173)
`';;r>ouces amber colors, while excess cadmium sulfide causes a
`:,;{>tanary-yellow color. The use of slags in glass batches usually
`}{;produces amber or black glasses due to the sulfur, man(cid:173)
`;";8 ·ganese, and iron contained in the slag. The color due to
`;Ji[ sulfur and manganese may be prevented by adding zinc oxide
`}1; io the glass batch. For the slag used in these experiments,
`'';/ ~ut one part of zinc oxide is necessary to decolorize one
`;JJ'part of slag, the color of the glass being green!sh due !o the
`r{'., h-on content. The amber- -color caused by mtroducmg 5
`\ff- jjier cent of slag in a glass hatch may he prevented also by
`,;i: fhe use of arsenic or antimony oxide2, which act a& high(cid:173)
`t· lemperatures oxidizers of the sulfur in the slag.
`1!J.
`'[{" latroduetion
`When glasses containing manganese are melted under
`•oxidizing conditions, a purple color due to trivalent man·
`ganese is produced. This appears black if enough man·
`ganese is presenL If the glass is melted under reducing
`t:onditions, the manganese is in the divalent form and
`the glass is practically colorless. This reduction of man-
`. ganese may be effected by contact with furnace gases or
`. by means of a reducing agent mixed in with the glass
`hatch.
`The following experiments were made on a small scale.
`Application of results to commercial practice should be
`made with caution since conditions of time, temperature,
`and furnace atmosphere would be altered markedly.
`
`'i/'
`
`-Use ef Zlae or Cadmium SuUide as a Reducing
`A«eat fer M-g-ese la GI~
`The decolorization of manganese in glasses may he
`made by means of various reducing agents in the batch.
`The following experiments utilized zinc sulfide or cad(cid:173)
`mium sulfide as a reducing agent. In the use of the
`former the following reaction would be expected, namely,
`3 Mn20 8 + ZnS = 6 MnO + ZnO + S02, the weights of
`Mn20 3 and ZnS being in the proportion of about 5 to I.
`The reduction in valence of the manganese would pro·
`duce a nearly colorless glass from the original purple.
`In order to study this effect, a series of borax glasses
`( equivalent to 0.44 per
`containing 0.5 per cent Mn0 2
`l'ent cent Mn 20 3 in the glass) with additions of zinc sol-
`
`fide varying up to 2 per cent ZnS was melted in platinum
`It was found that the glass batch containing
`crucibles.
`0.5 per cent MnO,, was nearly black and that this glass
`could be decolorized by the addition to the hatch of
`.075 per cent ZnS. A similar decolorizing action was
`possessed by cadmium sulfide. Glasses containing more
`than .075 per cent ZnS tended towards amber colors,
`while that with 2 per cent ZnS was opaque due to the
`large excess of this material. The weights of Mn 20,,
`and ZnS in the colorless glass were in the proportion of
`0.44 to .075 or about 6 to l, which is satisfactory agree(cid:173)
`ment with the predicted ratio of 5 to I.
`The action of zinc sulfide as a decolorizer for man(cid:173)
`ganese, which was shown in the melts of borax glasses,
`was checked in a soda-lime-silica glass of the composi(cid:173)
`tion 72 per cent Si02, 12 per cent CaO, 16 per cent
`Na~O, to which 0.5 per cent Mn0 2 was added. Meltings
`were made in small porcelain crucibles. The batch con(cid:173)
`sisted of sand, calcium carbonate, soda, and manganese
`dioxide. To this batch the following various amounts
`. of zinc sulfide or of cadmium sulfide were added, the
`colors of the resulting glasses being noted also:
`
`.057,_ ZnS ( amethyst glass)
`.10% ZnS (amethyst glass)
`.25 % ZnS ( colorless glass)
`.507,, ZnS ( colorless glass)
`l.007,, ZnS ( very faint amber glass)
`2.00% ZnS (light amber)
`4.00% ZnS (light amber)
`0.5 % CdS ( colorless glass)
`1.0 % CdS (very faint yellow)
`2.0 % CdS ( canary yellow)
`These results show that the purple color produced hy
`the addition ol 0.5 per cent Mn02 was decolorized 1y
`the use of from 0.25 to 0.50 per cent of zinc sulfide
`(see Fig. l, Glasses M, N, P, R), the sulfide of cadmium
`acting similarly. This amount of ZnS necessary to de·
`colorize these soda-lime-silica glasses is greater than
`that in the borax glasses since the silicate melts were
`held at a high temperature and some ZnS was lost by
`oxidation. The addition of 2 per cent of ZnS or of
`CdS formed pleasing amber or canary yellow colors,
`
`371
`
`O-I Glass, Inc.
`Exhibit 1021
`Page 008
`
`

`

`respectively.
`Larger amounts of manganese can be reduced to form
`nearly colorless glasses by using greater quantities of
`zinc sulfide. In one series of tests, a glass batch contain(cid:173)
`ing 6 per cent of Mn0 2 was decolorized by the use of
`3 per cent ZnS.
`
`Slag as a Raw Material for Glass-making
`The utilization of furnace slags in glass batches is
`advantageous due to the low cost of this material. The
`relatively large quantities of sulfur, manganese, and iron
`
`Fig. I. Series A to F shows the effect of additions of
`zinc oxide to an amber gla88 containing 5 % slag.
`Glass A is made without additions of ZnO and is amber
`in color.
`Glasses B to F contain I to 5% ZnO, respectively, and
`a progressive lightening in color is produced,
`Glass G shows the decolorizing action of 0.4 % arsenic
`oxide when added to Glass A, while Glass H shows the
`similar effect of antimony oxide.
`Series M, N, P, and R shows the effect of adding ZnS
`in the amounts of 0.05%, 0.25%, 1.0%, and 4.0%, re(cid:173)
`spectively, to a purple glass containing 0.5% MnO,. Small
`additions decolorize the purple color, while larger amounts
`form amber glasses.
`
`372
`
`l
`)
`which s?ch slags usually contain restrict its use to {t1
`production of colored ware or, for colorless "flints/;:4
`such small amounts in the batch that only a faint (:()]J
`is produced.
`
`Effeet of Zlne Oxide on Color
`from Batehes eontalnlng Slag
`For preliminary tests on the color produced by slag1
`glass batches, a series of glasses consisting of 5 pij
`borax ~ 1 pa~t slag + _l part of various ma~eria1$:~
`melted m platmum crucibles and cast on an rron pl4ll
`The powdered slag1 used for these tests had the foll6ii
`ing chemical composition:
`'
`
`35.63% Si02
`12.14% Al 20 3
`2.79% MgO
`46.42;{ CaO
`1.77'/r S
`1.47% MnO
`0.29'/i, Fe20 3
`The various additions which were made consisted fl
`1 part of each of the following materials, n.imely NaN01
`ZnO, BaO, CaO, V20:;, CeO,, PbO, Ni,O,u CdO, Mg(l
`SrO, Ti0 2, and Zr0 2 • The glasses resulting from th
`fusions were black with the following exceptions: th
`glass containing NaN03 was brown; the glass with Cd(
`was yellow opaque; the glass with ZnO was water cleat
`Since the effect of zinc oxide on decolorizing the glas
`was so pronounced, some additional exper.iments wet,
`made using this oxide in smaller quantities than th,
`amount of 14 per cent which was used previously. Thi
`series consisted of melts of 5 parts borax + 1 part sll\j
`with additions of 0.02, 0.05, 0.12, 0.25, and 0.50 par
`of ZnO, respectively. The smallest addition was fomti
`to produce a brown glass; the second and third amount:
`produced opaque glasses; 0.25 part of ZnO resulted h
`a clear light yellow glass, while 0.50 part produced ,
`glass with only a faint yellow color.
`It may be con·
`eluded that, for the decolorization of 1 part of slag,
`between 0.5 and 1 part of ZnO is necessary.
`The production of opaque glasses by the addition oj
`0.05 or 0.12 part of ZnO may he explained on the
`assumption that these amounts 'of ZnO (1.6 and 4 pe,r
`cent, respectively) react with the sulfur in the slag to
`form an excess of zinc sulfide. This material forms an
`opaque glass just as was found in the melt containmg
`2 per cent ZnS described in Section II. Further increll$e
`in the ZnO content forms a clear glass, that is, the pre(cid:173)
`cipitate of ZnS dissolves. This assumption was proveQ
`by adding 2 per cent ZnS to a borax glass to form an
`opaque glass and then adding ZnO to this fusion, where·
`upon the precipitate dissolved.
`The above experiences with borax glasses were applied
`to melts of soda-lime-silica glasses of a commercial typl'l
`with the results described in the following account. A
`batch consisting of 61.1 parts sand, 25 parts slag, and
`23.8 parts sodium carbonate forms a glass of the com·
`position 70.0 per cent Si02 , 3.1 per cent Al20 8 , 0.7 per
`cent MgO, 11.6 per cent CaO, 0.37 per cent MnO {or
`equivalent Mn20 3 ), 0.44 per cent S, 13.9 per cent Na20.
`This glass was found to be black. Additions of ZnO
`were made to this batch in the amounts of 1h, 1, 2, and
`4 per cent respectively, and a progressive lightening in
`
`O-I Glass, Inc.
`Exhibit 1021
`Page 009
`
`

`

`ade was produced. However, even 4 per cent addition
`·
`produced a deep amber glass.
`e substitution of soda niter for part of the soda
`Ill the batch should aid in removing part of the sul(cid:173)
`by oxidation. This effect was studied by using the
`batch, 61.1 parts sand, 25 parts slag, 17 .1 parts
`·um carbonate, and 10.7 parts sodium nitrate, the
`d composition (neglecting sulfur} being the same
`,the above. Additions of ZnO were made in the same
`' 0unts as stated above and the colors of the melted
`·asses compared with those produced by the all-car(cid:173)
`nate batch. The results showed that the hatches con(cid:173)
`ing niter were somewhat lighter in shade. However,
`the glasses were amber or black.
`',since the amount of zinc oxide used in commercial
`hatches must be small due to economic considera(cid:173)
`JJS, a series of glasses containing 1 per cent ZnO was
`'ade. Batches containing niter were tried and also niter(cid:173)
`ee hatphes. To these batches additions of a slag were
`· de in amounts from 5 to 25 per cent. The colors
`ttried from amber to nearly black.
`· In order Lo determine the least amount of zinc oxide
`'11ecessary to decolorize a fixed amount of slag in a glass
`batch, a series of m~lts were made using the following
`ioda-lime-silica hatch, namely, 70.7 parts sand, 10.0
`'l'arts slag, 23.8 parts Na2C03, 9.6 parts CaC03 • Vari(cid:173)
`··· , -0US amounts of zinc oxide were added to this batch, pro(cid:173)
`:{-ducing the colored glasses shown in Table I.
`
`AmountZnO
`added to batch
`0
`1
`2
`4
`6
`8
`12
`
`TABLE I
`
`Color of Glass
`Dark amber
`Amber
`Light amber
`Light amber
`Light amber
`Pale yellow-green
`Pale green
`
`The results given in Table I indicate that from 8 to 12
`!Parts of ZnO are necessary to decolorize 10 parts of slag,
`' -0:r roughly 1 part of ZnO for each part of slag.
`
`·•eet of Additions of Arsenle or Aatimony
`\ ,~des on Color of Glasses made from Batehes
`·· •l!Ontalnlng Slag
`, ... The amount of zinc oxide necessary to neutralize the
`.'J;olor caused by the addition of slag might be decreased
`
`>ff part of the sulfur in the slag were removed by some
`
`In order to oxidize part of the sulfur in the
`',µleans.
`, glass hatch, it is advisable to add some material such as
`\.the oxide of arsenic, antimony, or cerium, which will
`·: liberate oxygen at a high temperature. For an experi-
`
`TABLE II
`
`Sand
`61.,1
`
`SI,
`25,
`
`N...CO, NaNO.
`1s.8
`8,.0
`
`.
`
`Asia.
`0
`0.3
`0.6
`0.9
`0
`0.3
`0.6
`0.9
`0
`0.3
`0.6
`0.9
`
`ZnO Color of GI"""
`0 Dark amber
`0 Am!,>er
`0
`Liliht ami.,er
`0
`3
`3
`3
`3 6
`6
`•
`6
`6 Pale yellow-green
`
`TABLE III
`Na.C03 NaNO, CaCO, Asia. ZnO
`18.8
`8.0
`17.9
`0
`0
`I
`a
`"
`"
`"
`2
`3
`4
`5
`0
`1
`2
`3
`4
`5
`
`0.4
`•
`
`~ r 0,4
`
`~
`4
`5
`
`Color
`Sb,().
`0 Darkamber
`"
`Amber
`• Light amber
`Pale yellow-green
`~~n
`: F~tgr~n
`
`J>a.!e yelJ.ow-~n
`
`P,:tle~
`
`mental test of these effects, a 8oda-linie-silica hatch was
`melted with various additions of As 20 8 and ZnO. The
`batches used and the colors produced are listed in
`Table II.
`The results given in Table II show that arsenic oxide
`tends to lighten the amber color. They also confirm the
`decolorizing action of ZnO. However, the amount of slag
`used was too great to be decolorized by the quantities of
`arsenic and zinc which were used. Therefore, a small series
`of melts was made in which the slag was decreased to 1~
`that shown in Table II. The composition of the base
`glass was computed as 71.1 per cent Si02, 0.6 per cent
`A120 3, 0.14 per cent MgO, 12.3 per cent CaO, 0.07 per
`cent MnO (or equivalent Mn 20 3 ), 0.09 per cent S, 13.9
`per cent Na20. The batches are given in Table III.
`Some of the results shown in Table III are illustrated
`in Fig. 1, Glasses A to H. They may be summarized as
`follows, assuming that the pale green tints are due to
`iron.
`a.-The amber color caused by the use of 5 per cent
`slag may be prevented by introducing 4 to 5 per cent
`ZnO in the glass. This action of ZnO may be explained
`on the assumption that these zinc oxide glasses are able
`to hold small quantities of sulfides in solution.
`b.-The use of 0.4 per cent of arsenic oxide destroys
`the amber color, probably by oxidation of sulfur at high
`temperatures.
`c.-Antimony oxide has a similar decolorizing action
`to that of arsenic.
`
`373
`
`- - - - - -~ - -~ - -- ~ -~ - -~ -
`
`O-I Glass, Inc.
`Exhibit 10