COLOURED GLASSES. Woldemar A. Weyl. Professor and Head of the Department of Mineral Technology Pennsylvania State University

Transcription

1 COLOURED GLASSES BY Woldemar A. Weyl Professor and Head of the Department of Mineral Technology Pennsylvania State University Published by Society of Glass Technology Don Valley House Savile Street East Sheffield S10 5BT

2 CONTENTS FOREWOED BY PROFESSOR W. E. S. TüRNER.. V AUTHOR'S PREFACE vii PART I. THE CONSTITUTION OF COLOURED GLASSES. 1AP. I. THE ORIGIN OF COLOUR IN INORGANIC SUBSTANCES 3 Inorganic Chromophores The Influence of Solvation on Colour.. 9 The Influence of Adsorption The Influence of Temperature on Colour.. 15 II. THE CONSTITUTION OF GLASS General Review of the Problem Ions as the Building Units of Glasses.. 22 The Principles Governing the Ionic Structure of Crystals and Glasses The Atomic Structure of Silica Glass.. 28 The Atomic Structure of Binary and Ternary Silicate Glasses The Atomic Structure of Boric Oxide-Containing Glasses The Atomic Structure of Phosphate Glasses. 35 The R61e of A , BeO, ZnO, PbO and Ti0 2 in Glasses III. THE CONSTITUTION OF GLASS The Replacement of Oxygen by other Elements 44 Sulphur and Selenium as Substitutes for Oxygen 44 Halogen Ions as Substitutes for Oxygen.. 46 IV. THE TERMS ACIDITY AND BASICITY IN RELATION TO MODERN THEORY OF STRUCTURE.. 52 V. THE CLASSIFICATION OF GLASSES ACCORDING TO THEIR CHROMOPHORES Coloured Glasses with One Colouring Ion.. 59 Coloured Glasses with Chromophore Groups Consisting of Two Ions Coloured Glasses with Chromophore Groups Consisting of Three Ions VI. THE CONSTITUTION OF GLASS AS REVEALED BY COLOUR AND FLUORESCENCE INDICATORS. 64 The Determination of the State of Oxidation of a Glass by the Indicator Method 65 xi

3 XU CHAP. The Determination of the Acidity and Basicity of a Glass by the Indicator Method.. 66 The Determination of the Co-ordination Number of an Ion Indicators for the General Electric Perturbation of an Ion Fluorescence Indicators PART II. THE COLOURS OF GLASSES PRODUCED BY VARIOUS COLOURING IONS. VII. THE COLOUBS PBODUCBD BY IRON The Influence of the Iron Content on the Technology of a Glass General Discussion on Absorption, Transmission and Colour A. The Spectral Absorption of Iron Compounds in Aqueous Solutions and Glasses B. The Blue Colour in Iron-containing Glasses 95 VIII. IX. C. Colourless Iron Complexes in Glasses The Equilibrium between Di- and Tri-valent Iron in Glasses.... A. The Influence of Temperature and Time B. The Influence of the Iron Concentration C. The Influence of the Composition of the Glass D. The Influence of Oxidising and Reducing Agents.... THE COLOURS PRODUCED BY MANGANESE Introduction.... The Nature of the Manganese Colour Reactions During the Melting of Manganese Glasses... The Melting of Manganese Glasses. THE COLOTTRS PRODUCED BY CHROMIUM 132 Introduction The Colour of Chromium Compounds The Nature of the Chromium Colour in Glasses The Melting of Chromium Glasses. Chromium Pink..... X. THE COLOURS PRODUCED BY VANADIUM The Chemistry of Vanadium Compounds Vanadium in Glass.... XI. THE COLOURS PBODUCED BY COPPER

4 CHAP. XII. XIII. XIV. XV. XVI. The Chemistry of Copper The Colour of Cupric Ions in Solutions and Glasses The Reduction of Cupric to Cuprous Ions i; Aqueous Solutions and Glasses. The Properties of Copper Glasses. THE COLOUBS PEODUCED BY COBALT The Colour of Cobalt in Crystals and Solutions Cobalt Pigments..... Cobalt Glasses..... Influence of Temperature on the Colour of Cobalt Glasses..... Cobalt Glasses as Pyrosols The Melting of Cobalt Glasses Influence of Infra-Red Absorption on the Melting and Working Properties of Glasses THE COLOUBS PEODUCED BY NICKEL The Colour of Nickel in Glasses, Crystals and Solution THE COLOUBS PEODUCED BY UEANIUM The Chemistry of Uranium Compounds. Uranium in Glass..... THE COLOUBS PEODUCED BY TITANIUM, TUNGSTEN AND MOLYBDENUM.... I. Titanium..... II. Tungsten and Molybdenum THE COLOUBS PEODUCED BY THE OXIDES OF THE RABE-EABTHS ELEMENTS. The Absorption Spectra of Neodymium and Praseodymium..... Glasses Containing Neodymium and Praseo dymium Some Applications of Neodymium Glasses Cerium-Containing Glasses PART III. THE COLOURS OF GLASSES PRODUCED BY THE NON- METALLIC ELEMENTS : SULPHUR, SELENIUM, TEL- LURIUM, PHOSPHORUS AND CERTAIN OF THEIR COMPOUNDS. XVII. THE COLOUBS PEODUCED BY SULPHUB AND ITS COMPOUNDS Historical Review of the So-called Carbon-Amber Glasses 237 Xlll

5 xiv CHAP. XVIII. The Constitution and Colour of Polysulphide Glasses 242 The Melting of Carbon-Amber (Sulphur) Glasses 252 The Blue Sulphur Glasses Glasses Containing the Sulphides of Heavy Metals 260 Equilibria between Sulphides and Silicates. 261 The Striking of Colour in Sulphide Glasses. 265 The Melting of Sulphide Glasses Special Sulphide Colours in Glasses The Melting of Cadmium Sulphide Glasses. 274 Antimony Ruby Glasses Miscellaneous other Sulphides in Glasses GLASSES COLOÜRED BY SELENIUM AND SELENIDES 282 Elementary Selenium The Nature of Selenium Pink Reactions during the Melting of Selenium Glasses 287 The Melting of Selenium Pink Glasses Conclusions on the Use of Selenium in Glassmaking Glasses Coloüred by Polyselenides Iron Selenide Glasses Selenium Ruby Glasses and the Nature of the Colour 308 The Melting of Selenium Ruby Glasses..313 Selenium Black Glasses XIX. GLASSES COLOÜRED BY TELLURIUM AND BY PHOSPHORUS I. Tellurium 324 II. Phosphorus 325 PART IV. THE COLOURS PRODUCED BY METAL ATOMS. XX. FUNDAMENTALS CONCERNING THE RELATIONSHIP BETWEEN METALS AND GLASSES The Formation of Metal Atoms in Glasses The Solubility of Metals and the Formation of Pyrosols The Influence of Some Constituents on the Solubility of Metals in Fused Salts and Glasses The Röle of Tin Oxide in the Formation of Ruby Glasses The Röle of Stannous Chloride in the Formation of Silver Mirrors XXI. THE CRYSTALLISATION OF METALS FROM THE GLASS MELT 352 The Mobility and Diffusion Speed of Metal Atoms in Glasses

6 CHAP. XV Nacleus Formation and Crystal Growth The Theory of Coagulation. von Smoluchowski's Equation XXII. THE ABSORPTION OF LIGHT BY METALS Fundamentals Concerning the Absorption of Light by Metals 366 The Scattering of Light 369 The Effect of the Näture of the Dispersed Phase on the Absorption of Light by Colloidal Metals 371 The Effect of Shape and Internal Structure. 375 XXIII. GOLD IN GOLD-RUBY GLASSES Historical 380 The Nature of the Ruby Colour The Melting of Gold-Ruby Glasses The Striking of Gold-Ruby Glasses The Basic Types of Gold Dispersion in Glasses. 391 XXIV. SILVER IN GLASSES The Chemistry of Silver Glasses The Melting of Silver Glasses The Colour of Silver Glasses XXV. THE SILVER-STAINING OF GLASSES The Fundamentals of the Staining of Glasses by Cementation The Effect of the Glass Composition on the Silver Stain 418 XXVI. COPPER IN COPPER-RUBY GLÄSSES (HEMATINONE AND COPPER AVENTURINE) The Nature of the Red Colour Produced by Copper The Work of P. Ebell 423 The Melting of Copper-Ruby Glasses The Röle of the Tin in Copper-Ruby Glasses. 427 The Röle of the Copper in Copper-Ruby Glasses 428 The Striking of Copper-Ruby Glasses XXVII. THE COPPER STAINING OF GLASSES PART V. THE FLUORESCENCE, THERMOLUMINESCENCE AND THE SOLARISATION OF GLASS. XXVIII. THE GENERAL THEORY OF FLUORESCENCE IN GLASSES

7 XVI CHAF. PACUS Pseudo-Fluorescence The Fundamentals of Fluorescence The Excitation Process The Lifetime of the Excited State Influence of the Type of Binding of the Atoms. 447 The Quenching of Fluorescence The Classification of Fluorescent Glasses XXIX. FLUORESCENT GLASSES 453 Glasses Containing Crystalline Fluorescence Centres Glasses Containing Energy-Isolated Atoms or Molecules Glasses Containing Fluorescent Ions The Uses of Fluorescent Glasses XXX. THERMOLUMINESCENCE 495 XXXI. THE SOLARISATION OF GLASSES Fluorescence and Photosensitivity The History of Studies on Solarisation The Explanation of Solarisation The Control of Solarisation The Regeneration of Solarised Glasses The Solarisation Equilibrium Helpful Models for the Study of Solarisation in Glasses XXXII. PRACTICAL APPLICATIONS OF PHOTOSENSITIVE GLASSES AUTHOR INDEX SUBJECT INDEX NOTE ON TEMPERATURE SCALES. All temperatures recorded in the Monograph are on the Centigrade scale unless otherwise stated.