- •Preface to the Second Edition
- •Preface to the First Edition
- •ACKNOWLEDGEMENTS
- •Contents
- •1.1 EXERCISES, QUESTIONS, AND PROBLEMS
- •2.1 INTRODUCTION
- •2.2 CORROSION BY LIQUIDS
- •2.2.1 Introduction
- •2.2.2 Crystalline Materials
- •Attack by Molten Glasses
- •Attack by Molten Salts
- •Electrochemical Corrosion
- •Attack by Molten Metals
- •Attack by Aqueous Media
- •2.2.3 Glasses
- •Bulk Glasses
- •Fiber Glass
- •Bioactive Glass
- •2.3 CORROSION BY GAS
- •2.3.1 Crystalline Materials
- •2.3.2 Vacuum
- •2.3.3 Glasses
- •2.4 CORROSION BY SOLID
- •2.5 SURFACE EFFECTS
- •2.5.1 Surface Charge
- •2.5.2 Porosity and Surface Area
- •2.5.3 Surface Energy
- •2.6 ACID/BASE EFFECTS
- •2.7 THERMODYNAMICS
- •2.7.1 Mathematical Representation
- •2.7.2 Graphical Representation
- •2.8 KINETICS
- •2.9 DIFFUSION
- •2.10 SUMMARY OF IMPORTANT CONCEPTS
- •2.11 ADDITIONAL RELATED READING
- •2.12 EXERCISES, QUESTIONS, AND PROBLEMS
- •REFERENCES
- •3.1 INTRODUCTION
- •3.2 LABORATORY TEST VS. FIELD TRIALS
- •3.3 SAMPLE SELECTION AND PREPARATION
- •3.4 SELECTION OF TEST CONDITIONS
- •3.5 CHARACTERIZATION METHODS
- •3.5.1 Microstructure and Phase Analysis
- •Visual Observation
- •Optical Microscopy
- •X-ray Diffractometry
- •Transmission Electron Microscopy
- •3.5.2 Chemical Analysis
- •Bulk Analysis
- •Surface Analysis
- •3.5.3 Physical Property Measurement
- •Gravimetry and Density
- •Porosity-Surface Area
- •Mechanical Property Tests
- •3.6 DATA REDUCTION
- •3.7 ADDITIONAL RELATED READING
- •3.8 EXERCISES, QUESTIONS, AND PROBLEMS
- •REFERENCES
- •4.1 INTRODUCTION
- •4.2 ASTM STANDARDS
- •4.2.16 Permeability of Refractories, C-577
- •4.2.26 Lead and Cadmium Extracted from Glazed Ceramic Surfaces, C-738
- •4.3 NONSTANDARD TESTS
- •4.4 ADDITIONAL RELATED READING
- •4.5 EXERCISES, QUESTIONS, AND PROBLEMS
- •REFERENCES
- •5.1 ATTACK BY LIQUIDS
- •5.1.1 Attack by Glasses
- •Alumina-Containing Materials
- •Zircon
- •Zirconia
- •Carbides and Nitrides
- •5.1.2 Attack by Aqueous Solutions
- •Alumina
- •Silica and Silicates
- •Concrete, Cement, Limestone, Marble, and Clay
- •Zirconia-Containing Materials
- •Superconductors
- •Titanates and Titania
- •Transition Metal Oxides
- •Carbides and Nitrides
- •5.1.3 Attack by Molten Salts
- •Oxides
- •Carbides and Nitrides
- •Superconductors
- •5.1.4 Attack by Molten Metals
- •5.2 ATTACK BY GASES
- •5.2.1 Oxides
- •Alumina
- •Alumino-Silicatcs
- •Magnesia-Containing Materials
- •Zirconia
- •5.2.2 Nitrides and Carbides
- •Silicon Nitride
- •Other Nitrides
- •Silicon Carbide
- •Other Carbides
- •5.2.3 Borides
- •5.2.4 Silicides
- •5.2.5 Superconductors
- •5.3 ATTACK BY SOLIDS
- •5.3.1 Silica
- •5.3.2 Magnesia
- •5.3.3 Superconductors
- •5.3.4 Attack by Metals
- •5.4 ADDITIONAL RELATED READING
- •5.5 EXERCISES, QUESTIONS, AND PROBLEMS
- •REFERENCES
- •6.1 INTRODUCTION
- •6.2 SILICATE GLASSES
- •6.3 BOROSILICATE GLASSES
- •6.4 LEAD-CONTAINING GLASSES
- •6.5 PHOSPHORUS-CONTAINING GLASSES
- •6.6 FLUORIDE GLASSES
- •6.7 CHALCOGENIDE-HALIDE GLASSES
- •6.8 ADDITIONAL RELATED READING
- •6.9 EXERCISES, QUESTIONS, AND PROBLEMS
- •REFERENCES
- •7.1 INTRODUCTION
- •7.2 REINFORCEMENT
- •7.2.1 Fibers
- •7.2.2 Fiber Coatings or Interphases
- •7.2.3 Particulates
- •7.3 CERAMIC MATRIX COMPOSITES
- •7.3.1 Oxide-Matrix Composites
- •Al2O3-Matrix Composites
- •Other Oxide-Matrix Composites
- •7.3.2 Nonoxide-Matrix Composites
- •Si3N4 Matrix Composites
- •SiC-Matrix Composites
- •Carbon-Carbon Composites
- •Other Nonoxide Matrix Composites
- •7.4 METAL MATRIX COMPOSITES
- •7.5 POLYMER MATRIX COMPOSITES
- •7.6 ADDITIONAL RELATED READINGS
- •7.7 EXERCISES, QUESTIONS, AND PROBLEMS
- •REFERENCES
- •8.1 INTRODUCTION
- •8.2 MECHANISMS
- •8.2.1 Crystalline Materials
- •8.2.2 Glassy Materials
- •8.3 DEGRADATION OF SPECIFIC MATERIALS
- •8.3.1 Degradation by Oxidation
- •Carbides and Nitrides
- •Oxynitrides
- •8.3.2 Degradation by Moisture
- •8.3.3 Degradation by Other Atmospheres
- •Carbides and Nitrides
- •Zirconia-Containing Materials
- •8.3.4 Degradation by Molten Salts
- •Carbides and Nitrides
- •Zirconia-Containing Materials
- •8.3.5 Degradation by Molten Metals
- •8.3.6 Degradation by Aqueous Solutions
- •Bioactive Materials
- •Nitrides
- •Glassy Materials
- •8.4 ADDITIONAL RELATED READING
- •8.5 EXERCISES, QUESTIONS, AND PROBLEMS
- •REFERENCES
- •9.1 INTRODUCTION
- •9.2 CRYSTALLINE MATERIALS—OXIDES
- •9.2.1 Property Optimization
- •9.2.2 External Methods of Improvement
- •9.3 CRYSTALLINE MATERIALS—NONOXIDES
- •9.3.1 Property Improvement
- •9.3.2 External Methods of Improvement
- •9.4 GLASSY MATERIALS
- •9.4.1 Property Optimization
- •9.4.2 External Methods of Improvement
- •REFERENCES
- •Glossary
- •Epilog
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Chapter 6 |
It is interesting that these glasses exhibited minimal corrosion from atmospheric moisture, even when exposed to 100% RH at 80°C for up to one week. Gbogi et al. [6.90] reported similar results for a ZBL glass exposed to ambient conditions for 30 days, and Robinson and Drexhage [6.91] reported no corrosion for ThF4-containing fluoride glasses up to 200°C.
The time dependency of leaching rates varied with the composition of the heavy metal fluoride additive [6.87]. Compositions containing Zr, Ba, and Th; U, Ba, and Mn; and Sc, Ba, and Y displayed a continuous decrease in corrosion rate with time. Those containing Th, Ba, Mn, and Yb or Th, Ba, Zn, and Yb displayed a minimum. Those containing Pb, K, Ga, Cd, Y, and Al displayed a plateau. Ravaine and Perera also reported a direct relationship between fluoride ion conductivity and corrosion rate. Only the Sc, Ba, and Y composition did not form the outer layer of crystalline precipitates.
Thorium-based glasses containing Zn–Ba–Y–Th, Zn– Ba– Yb–Th, or Zn–Ba–Yb–Th–Na have been reported to be 50– 100 times more resistant to dissolution than the corresponding zirconium-based glasses [6.92].
6.7 CHALCOGENIDE-HALIDE GLASSES
Lin and Ho [6.93] studied the chemical durability of As–S–I glasses exposed to neutral, acidic, and basic solutions. These glasses exhibited excellent resistance to neutral and acidic (pH 2–8) solutions; however, in basic solutions they formed thioarsenites or thioarsenates:
(6.6)
(6.7)
or:
(6.8)
As pH increased from 10 to 14, the rate of attack increased about 400 times. Higher iodine contents lowered the durability.
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For a given iodine content, increased arsenic contents also lowered durability. Plots of weight loss vs. the square root of time were linear, indicative of a diffusion-controlled process. The rate of attack on alkaline solutions increased linearly with temperature. Lin and Ho concluded that the low solubility of these glasses was consistent with the fact that the As-S bond is highly covalent in nature.
6.8 ADDITIONAL RELATED READING
Clark, D.E.; Zoitos, B.K.; Eds. Corrosion of Glass, Ceramics and Ceramic Superconductors; Noyes Publications: Park Ridge, NJ, 1992.
Paul, A. Chemistry of Glasses; Chapman and Hall: New York, 1982;
293pp.
6.9EXERCISES, QUESTIONS, AND PROBLEMS
1.Discuss how pH affects dissolution of silicate glasses including the different mechanisms at low and high pH.
2.Discuss how glass structural variations relate to dissolution and how this is related to composition.
3.What structural factor and what pH relates to the minimum dissolution rate?
4.Describe the surface area/volume ratio of the attacking fluid effects upon dissolution rate.
5.How does a surface treatment of SO2 gas diminish dissolution rates?
6.Why do A12O3 and/or ZrO2 substitutions for SiO2 increase durability?
7.How does the Si/B ratio affect dissolution in borosilicate glasses?
8.Why is the number of nonbridging oxygens important to dissolution?
9.Explain how softening points and/or thermal expansion coefficients may relate to dissolution.
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