MEIHODOLOGY FOR mvssrmnon OF INTERNAL *9 . COATING IN WATER MAINS Thesis for the Degree of M. S. MICHIGAN STATE UNIVERSITY JOHN C. O’MAUA 1972 ’\\W\\\\W\\K\$\\W§\§\1\X\w\l -- 7 ____ “a 3,1293 01 _ L I B R A R y j hfiiC‘lIgan State E University. ABSTRACT METHODOLOGY FOR INVESTIGATION OF INTERNAL COATING IN WATER MAINS BY John C. O'Malia The purpose of this thesis is to develop a methodology in which to review any type of internal coating in a water main. It brings together an overview of the various scattered data and techniques into focus on several specific samples and conditions. A review of the literature reveals that various identification techniques have been used in identifying various internal coatings (protective and non-protective). The thrust of the methodology is to coordinate a multi-investigation as regards the identification of coat- ings or compounds. This investigation involved the use of chemical testing, X-ray diffraction and use of the petrographic microscope. The coatings for testing were for both the Calcite (Calcium ion bearing) or iron bearing compounds. The use of the three methods on the two coating systems did reveal that the combined tri-effort can be John C. O'Malia very informative, accurate and reinforcing. That is, that the strong feature of any one method compensates for any drawback that another method may have. The method that allows the quickest and most accurate identification of any coating or compound is the use of X—ray diffraction. The initial use of the X-ray method then allows effective and efficient use of the chemical and petrographic microscope methods. The Visual aids to illustrate the laboratory techniques as regards each methodology will be most helpful in refining the physical parameters that are involved in the protective coating mechanism on the internal surface of a water main. METHODOLOGY FOR INVESTIGATION OF INTERNAL COATING IN WATER MAINS BY John C. O'Malia A THESIS Submitted to Michigan State University in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE Department of Civil and Sanitary Engineering 1972 DEDICATION This thesis is dedicated to my family. ii AC KN OWLE DGMENT S The author wishes to express his sincere appre- ciation to: Dr. Robert F. McCauley for his able guidance advice and encouragement without which this thesis would not have been possible; to the Division of Engineering Research for the financial support to make this thesis possible. In addition deep appreciation is acknowledged to my wife Beverly who provided encouragement and typed the rough draft. DEDICATION / TABLE OF CONTENTS ACKNOWLEDGMENTS. . . . . . . . . . . . . LIST OF FIGURES. . . . . . . . . . . . . Chapter I. INTRODUCTION . . . . . . . . . . . II. LITERATURE REVIEW . . . . . . . . . The Theory of Corrosion . . . . . . Parameters Used in Developing a Pro- tective Calcium Carbonate Coating. . The Role of Oxygen in Protective Coatings . . . . . . . . . . The Role of Velocity in Protective Coatings . . . . . . . . Protective Coating Using Polyphosphates. The Investigation of Protective Coatings . . . . . . . . . . III. THEORETICAL CONSIDERATIONS . . . . . . Introduction. . . . . . . . Two Typical Corrosion Cells. . . . . Formation Chemistry . . . . . . . X-ray Diffraction to Identify Internal Coatings in Water Mains . . . . . Optical Crystallography . . . . . . IV. EXPERIMENTAL TEST APPARATUS AND MATERIAL. . Chemical Testing . . X-ray Diffraction . . Petrographic Microscope Test Specimens . . . iv Page ii iii vi 12 20 20 21 22 29 34 52 52 52 53 54 Chapter Page V. EXPERIMENTAL PROCEDURE. . . . . . . . 60 Introduction. . . . . . . . . . 60 Visual Inspection . . . . . . . . 60 Evaluation of Coatings or Compounds Using Chemical Identification . . . 62 Evaluation of Coatings or Compounds Using X-ray Identification . . . . 65 Evaluation of Coatings or Compounds Using the Petrographic Microscope for Identification. . . . . . . 70 VI. DATA. I O O O O O O I O O O O O 82 Remarks on Data Format and Notation . . 82 Protective Coatings . . . . . . . 84 Iron Compounds and Coatings. . . . . 92 VII. DISCUSSION OF RESULTS . . . . . . . . 164 General . . . . . . . . . . . 164 Protective Coatings . . . . . . . 164 Iron Compounds and Coatings. . . . . 171 VIII. CONCLUSIONS . . . . . . . . . . . 191 IX. RECOMMENDATIONS . . . . . . . . . . 196 BIBLIOGRAPHY. . . . . . . . . . . . . . 200 APPENDICES . . . . . . . . . . . . . . 204 A. Data for Non-Opaque Minerals. . . . . . 206 B. Calcium (Ca) and Iron (Fe) Percentages in Various Compounds . . . . . . . . . 207 C. X-ray Diffraction Data. . . . . . . . 208 D. Some Calculations of "d" Spacing for Calcite (CaCO3 or CaO-C02) Using Bragg's Equation . 211 E. Data on Minerals for Use of Petrographic Microscope. . . . . . . . . . . . 214 F. Crystal Group Data . . . . . . . . . 221 LIST OF FIGURES Figure Page 1. Tuberculation . . . . . . . . . . . 21 2. Calcite Coating. . . . . . . . . . . 22 3. Special Types of Planar Nets . . . . . . 30 4. Lattice Plane . . . . . . . . . . . 31 5. Diffraction of x-Rays. . . . . . . . . 33 6. Petrographic Microsc0pe . . . . . . . . 36 7. Plane-polarized Electromagnetic Wave. . . . 37 8. Plane-polarized Electromagnetic Wave. . . . 38 9. Passage of Light through a Microscope Containing Polarizing Filters . . . . . 39 10. Upper & Lower Filter . . . . . . . . . 41 ll. Becke Line Method . . . . . . . . . . 47 12. Half or Oblique Illumination . . . . . . 49 13. Half or Oblique Illumination in Plan. . . . 50 14. 1" Cast Iron Water Pipe Nipple with Corrosion Blister (M = 4x) . . . . . . . . . 58 15. Chemical Testing Equipment . . . . . . . 64 16. Petrographic Microslope . . . . . . . . 72 17. Data Sheet . . . . . . . . . . . . 81 18. Calcite: l-A. . . . . . . . . . . . 86 19. Protective Coating: 1-B. . . . . . . . 88 20. Cast Iron: l-C. . . . . . . . . . . 90 21. Calcite l-A-I . . . . . . . . . . . 93 vi Figure Page 22. Calcite 1-A-II . . . . . . . . . . . 95 23. Calcite l-A-III. . . . . . . . . . . 97 24. calCite l-A-IV o o o o o o o o o o o 99 25. Calcite 1-A-V . . . . . . . . . . . 101 26. Protective Coating l-B-I. . . . . . . . 103 27. Protective Coating 1-B-II . . . . . . . 105 28. Fe 0 (Pure). . . . . . . . . . . . 109 2 3 29. Fe203 (Pure) @ 1 Hr. - 500°C . . . . . . 111 30. Fe203 (Pure) plus nH20 . . . . . . . . 113 31. Fe203 (Pure) plus nHZO @ 1 Hr. - 500°C . . . 115 32. Fe0. Fe203 or Fe304 . . . . . . . . . 118 33' Feo' Fe203 or Fe304 @ 1 Hr. - 500°C. . . . 120 34. No "d" Spacing as the Material Tested was Amorphous (without crystal structure) . . 122 35. No "d" Spacing as the Material Tested was Amorphous (without crystal structure) . . 124 36. No "d" Spacing as the Material Tested was Amorphous (without crystal structure) . . 126 37. FeCO3 @ 1 Hr. - 500°C. . . . . . . . . 128 38. FeCO3 @ 1 Hr. - 500°C. . . . . . . . . 130 39. FeCO3 @ 1 Hr. - 500°C. . . . . . . . . 132 40. Corrosion Sample - Top . . . . . . . . 134 41. Corrosion Sample - Bottom . . . . . . . 136 42. Corrosion Sample - TOp 1 Hr. - 500°C. . . . 138 43. Corrosion Sample - Bottom 1 Hr. - 500°C. . . 140 44. Hematite - Fe 0 , Reagent Grade, Index Oil - 2.00, M - 246x . . . . . . . . . 144 45. Magnetite - FeO. Fe203 . . . . . . . . 146 vii Figure Page 46. Siderite - FeCO (Formation) Index Oil - 2.00, M - 243x . . . . . . . . . . 148 47. Siderite - FeCO (Formation) Becke Line Index 011 - 3.0, M - 240x . . . . . . 150 48. Siderite - FeCO3 . . . . . . . . . . 152 49. Siderite - FeCO3 o o o o o o o o o o 154 50. Corrosion Sample - Pipe Nipple Taken from Top. 156 51. Corrosion Sample - Pipe Nipple Taken from Bottom. . . . . . . . . . . . . 158 52. Corrosion Sample - Pipe Nipple Taken from Top. 160 53. Corrosion Sample - Pipe Nipple Taken from Bottom. . . . . . . . . . . . . 162 54. Calcite . . . . . . . . . . . . . 225 55. Aragonite. . . . . . . . . . . . . 225 56. Apatite . . . . . . . . . . . . . 226 57. Vivianite. . . . . . . . . . . . . 226 58. Ankerite . . . . . . . . . . . . . 227 59. Hematite . . . . . . . . . . . . . 227 60. Magnetite. . . . . . . . . . . . . 228 61. Siderite . . . . . . . . . . . . . 228 62. Goethite . . . . . . . . . . . . . 229 63. Lepidocrocite . . . . . . . . . . . 320 viii CHAPTER I INTRODUCTION It was reliably estimated a little over 13 years ago that the replacement cost of all water distributions systems in the United States was ten billion dollars (1). In addition, it was estimated that 60% of all water works capital is in the water distribution system. The internal area of a water distribution system for a population of 25,000 has been estimated to be 17 acres or 740,000 square feet (2). These staggering statistics point to a need to maintain a water distribution system in near perfect shape. Technology will surely lead to development of corrosion resistant pipe. However, we are presently installing pipe that can corrode and deteriorate and must maintain thousands of miles of installed pipe that is deteriorating. In partial answer to reducing or eliminating cor- rosion in the water distribution system several "protec- 'tive coatings" have evolved and experienced much labora- tory refinement. Calcium carbonate (calcite) is one ;protective coating that has proved beneficial over many years. In the past fourteen years, the refinement of the calcite protective coating--through water chemistry—-has evolved to a workable anti-corrosion mechanism that has field application. Refinements of the coating process have, however, related to the mechanism of deposition and not to the coating formation and/or composition. It has been the object of this thesis to develop a methodology for investigating the corrosion products, calcite protective coating and iron compounds that are a result of the protective coating mechanism or are caused by corrosion before, during or after the coating process. To accomplish the investigation reported here, water chemistry, X-ray defraction and Optical crystal- lography were used on various Calcite and iron compound formations or coatings. The development of an orderly investigation or methodology to correlate the unknown to the known has advantages not only for identifying coating composition and structure, but for refinement of the coating process. CHAPTER II LITERATURE REVIEW In 1903, M. Whitney (3) first stated the electro- chemical theory of corrosion. In the ensuing years his thesis has been used, refined and reused to predict this natural phenomena. Many techniques for water main corro- sion control, some successful and others with limited success, have been tried over the years and include; (a) pH adjustment, (b) deareation for removing oxygen and carbon dioxide, (c) silicate feed, (d) poly and glassy phosphates, (e) mechanically applied inert internal pipe coatings, (f) biological growth control using chlori- nation, and (g) a balanced control of pH-alkalinity- calcium carbonate. The presence of calcium carbonate in most domestic ‘water supplies makes this compound a logical choice as a corrosion inhibitor. Calcium carbonate appears in nature in three forms. The one most common and stable at standard temperature and pressure is Calcite. The other tn“) (Aragonite and Vaterite) are either unstable at :atandard temperature and pressure or readily alter to Calcite. The Theory of Corrosion The corrosion process can be quite complex. Cor- rosion is an electrochemical balance between the anode and cathode areas and generally is described with the following reaction: anode: Fe° (metal) + Fe++ + 2e_ (1) cathode: 2H + 2e + 2H+ (2) Secondary reactions that occur in the aqueous 2H + 1/202 + H20 (3) Fe++ +-20H' + Fe(0H)2 (4) 4Fe (0H)2 + 02 + 4H20 2Fe203 (5) The corrosion cell is an electrolytic cell in which metal is removed from the anode (negative) during the passage of a direct current between the cathodic (positive) area and the anodic area. The cathode area is usually adjacent to, and larger than, the anodic area. A review of equations 2, 3 and 4 indicate that both oxygen and pH play important roles in the rate of «corrosion. Many authors (14, 25, 31 and 34) have stated that dissolved oxygen is the most important mechanism of renmwing hydrogen from the cathode and increasing the :rate of corrosion. Also, corrosion of iron in aqueous solutions has been found to be under cathodic control if the pH is less than 11. Therefore, some workers have postulated that if a metal is under cathodic control, the corrosion rate may be slowed by removing oxygen, by cover- ing cathodic areas with protective coatings to reduce contact with oxygen or by altering the reactions of cor— rosion. Control of corrosion is a control of equation 2 and/or 3. Parameters Used in Developing a Protective Calcium Carbonate Coating The early recognition that calcium carbonate may form an internal protective coating for inhibiting cor- rosion were empirical. Baylis (15), as reported by Evans (14), in 1926 recommended that an aggressive water be treated with just sufficient alkali to cause it to develop calcium carbonate slowly on pipe interiors. Once the pipe had a continuous calcium carbonate layer, he recommended that alkali be added in such an amount that it would cease to deposit, but not dissolve the film. In 1932, Tillman and others (5) developed a prac- tical and useful test to determine the degree of water super- or under-saturation with calcium carbonate. This .initial refinement or "marbel test" did provide control .and.predicted the tendency toward scale formation or dissolution. Four years later, another more important test or index was developed--the "saturation index" by Langelier (6). The "Saturation index," based on physical chemistry principles, provided an indication of the duration of the chemical equilibrium driving force. A positive index indicated a tendency for the water to be scale forming and scale solution was association with a negative index. A discussion by Moore (7) described how a water might be adjusted by addition of lime and/or sodium carbonate to yield a positive scale forming indes. The Langelier "saturation index" provided a new refinement (8, 9) by considering temperature effects on the pH of the water. Progress also resulted from the work of Larson and Buswell (10) who computed the effect of temperature and salinity on ionization constants. Ryznar (11) proposed an empirical "stability index" with the View of estimating the degree of scaling to be expected from a water with a specific alkalinity, calcium and hydrogen ion correlation. Dye (12) suggested that the concentration of calcium carbonate in excess of the solubility product constant be called the "momentary excess" of calcium carbonate. The "momentary excess“ is that concentration ___ UI/(AL/ 1T 1T 0 \\ / '\ 7' 2 \ \ / \ / \ o ‘o’ \o/ // \\ /’ \ / \ It 1L + / \JL/ \\IL/ T \ /T\ /‘r\ 0 b a A a A A T 17 fl %* 90° I 0 120° 0 (F <> A; 0- / 7 / .e—I It JIGURE 3 -SPECIAL TYPES OF PLANAR NETS 31 Lattice Although the net does describe the two dimension aspect of the crystal, the crystal lattice identifies the crystal in three dimensions as on array of identical points. This array of points has an ordered arrangement such that all points fall on straight rows and are repeated at regular intervals along the row. Every pair then forms a lattice net-plane in which a unit parallelogram is repeated by translation throughout the net. The symmetry displayed by some lattices require that certain nonparallel sets of lattice planes be identical in spacing. Therefore, crystal faces develOping parallel to these equivalent sets of lattice planes will be symmetrically equivalent and appear at regular intervals and this then constitutes crystal form. A typical lattice plane is as shown in Figure 4. Figure 4 shows that a lattice plane passes FIGURE 4 - LATTICE PLANE 32 through NM' N'M in "a" where the P Pole is normal to the NM' N'M plane. In "b" of Figure 4 the Pele is normal to the page. However, R and Q are both normal to the arranged lattice. This illustrates the stacking at equal distance of lattice planes. The crystal classes are listed at six. They are based primarily on symmetry although the names of the six systems are derived from the Special dimensional properties of the lattices required by the symmetry. The length of the three lattice rows and the angles of the unit all serve to define a given lattice. These three lattice rows become the axes of reference for crystals. The crystal systems are then; Triclinic, Mono- clinic, Orthorhombic, Hexagonal, Tetragonal and Isometric. The axis layout and crystal system as pertains to the minerals under investigation are as found in Appendix B. Bragg's Law (42) X-rays are produced when high Speed electrons strike the atoms of any substance. An X-ray tube con- tains a heated element which provides a constant source of electrons that are directed at a metal target. The tube is an evacuated glass chamber fitted with a fila- Inent, a water cooled metal target and with several xvindows. The target is grounded and a rectified high 'voltage current is supplied to the filament. 33 The X-rays are emitted from the target in three wavelengths K0, K02 < KBl’ The intensity of K0 is double K02 and several times KBl' Because three X—ray intensity lines occur it is necessary to filter out the less intense x—ray line KBl’ X-ray Diffraction Theory In crystals the planes of atoms are arranged parallel to one another at a regular repeat spacing, form- ing a crystal lattice. Figure 5 depicts a vertical sec- tion through a crystal lattice. REFLECTED WA INCIDENT WAVE FRONTS VE FRONTS nxc GY+YH - adsina one -o—-o—--o---o—-o-—o---o---o-—-o-—-o- FIGURE 5 -DIFFRACTION OF X-RAYS_ Each point row P—P', Q-Q' or R-R' in Figure 5 are equally spaced lattice crystal plans. It is shown that each single lattice plane may produce a diffracted X-ray Jbeam incident at any angle. The X-ray beam is measured 34 in Angstron A units. For a regular stacking of such planes to produce a diffracted beam the rays diffracted from the planes must reinforce one another. Thus, a dif- fracted beam results when the path difference between reflections from adjacent identical planes are equal to a whole number of wavelengths of the X-ray in use. The path difference AXD and BYE is GYH or by geometry GY + YH = 2d sin 0 (11) The diffracted beam will follow the direction XD or YE if A = 2d sin 8 (12) where d is the lattice Spacing in A and A the wavelength in A. This relationship is termed Bragg's Law. Therefore Bragg's Law is A = 2d sin 0 (12). (See Appendix D and E for X-ray, lattice spacing and sample calculations.) Optical Crystallography Introduction The theory of optical crystallography includes several facets; light source, microscope, index oils and crystal index investigation. Each facet is important in itself and collectively they represent a large portion of Optical crystallography. The overall concept is 35 to identify crystals by identifying the respective refrac- tive indexes. Polarizing (Petrographic) Microscope The polarizing (Petrographic) microsc0pe is a very important tool in crystal investigation. The micro- scope is constructed for the specific measurement of refractive indexes while observing crystal structure. Figure 6 shows the general cross section of the Petro- graphic microscope. Items that can be changed or interchanged are the lower fixed lenses of the condenser, objective lenses and the upper lenses. Items that can be hand adjusted are the revolving stage, the mirror to focus light, coarse and fine focus adjustment. It is possible to incline stage if required. may. Light is a form of radiant energy. Modern theory accepts the combined approach of electromagnetic-wave and particle concept and recognizes them as not neces- sarily contradictory but as complementary (45). Figure 7 illustrates a plane polarized electromagnetic wave. Figure 7 shows an electric and magnetic vector oscillating in a perpendicular plane reaching maximum and minimum magnitudes. This wave is said to be plane ‘8 -L‘hu: 'I 36 FOCUSING EYE LENS EYEPIECE COARSE FOCUSING *r, FIELD LENS ADJU \ STMENT - AMICI -BERTRAND FINE ADJUSTMENTX ' . f an « v POLARIZER—UPPER I COM PENSATING LENS COMPENSATING LENS OBJECTIVE LENSES SWING OUT UPPER LENSES OF CONDENSER 1 LOWER FIXED LENSES . . _,. OF CONDENSER . ‘ UPPER IRIS '- . DIAPHRAGM POLARIZER - LOWER LOWER IRIS DIAPHRAGM STAGE MIRROR BASE Figure 6: Petrographic Microscope 37 II 9‘“ / ; MAGNETICS VECTOR ”\‘ELECTRIC VECTOR FIGURE 7- PLANE-POLARIZED ELECTROMAGNETIC WAVE polarized. In crystallograph work the emphasis is on the electric vector because this vector is the most important as regards optical phenomena. The electric wave aSpect is as described by the following equation: t = ‘7:- (13) frequency in cycles per second velocity of propogation of energy waves in vacuum (186,000 miles/sec) a wave length in Angstrom units A where: t >’G H H The visible light range is near a one micron wave 15 length and 10 frequency in cycles per second. Light of lig vac tha lea‘ in I leng not in t‘ re5pe light the alte or O ”N I: I 38 a particular wave length is described as monochromatic light. If light is traveling in a vacuum and a glass plate suspended so that the light passes through the vacuum and glass the velocity in the glass plate is less than in the vacuum. However, the same number of waves leave the glass plate as enter and accordingly, a change in the velocity must be accompanied by a change in wave length while the frequency remains a constant that does not change with any medium. An example of what can occur in two substances that are isotropic and anisotropic respectfully (do not alter the light ray and do alter the light ray) is shown in Figure 8. N o 0' 75:; o“ A FIGURE 8 - PLANE - POLARIZED ELECTROMAGNETIC WAVE NDTE: A IN AN ISOTROPIC MEDIUM 9 IN AN ANISOTROPIC MEDIUM As the light wave direction is altered as in B the altered wave does not move perpendicular along O'N' or O"N" but along O“R‘ and O"R". 39 Passing of Light Through the Microscope Light is passed through a microscope as illustrated in Figure 9. RETINA EYE LENS HUYGENS OCULAR 04/ \\‘\ i (I, OBJECTIVE ”We ‘1 LENSES I, i OBJECT ON S‘TAGE CONDENSING l: ‘. LENSES . I, — IRIS DIAPHRAGM ‘. ; POLARIZING FILTER (LOWER) 6- _________________ .4, / REVERSED VIRTUAL IMAGE LIGHT FIGURES - PASSAGE OF LIGHT THROUGH A MICROSCOPE CONTAINING POLARIZING FILTERS Scattered light enters the polarizing filter (lower) (termed the lower filter) and the ray direction is 4O resolved into one wave front. That is the lower filter only allows light through a directional slit. The light then passes through the condensing lenses to focus on the stage that contains an isotropic material (passes light without a wave front change). The light then enters the objective lens where a refocus is accomplished through the polarizing filter (upper) (termed the upper filter) and toward the ocular. The upper filter is rotated 90° from the lower filter and will not allow light to pass because the light ray is 90° out-of-phase. However, if an anisotropic material is on the stage, light will be omitted when the ray rotation is altered off 90° from the lower filter. Assuming then that light does pass the upper filter the light ray is refracted again, enters the eye and is focused on the eye retina where reversed enlarged image is seen by the observer. Upper and Lower Filters To illustrate how the upper and lower filters operate Figure 10 is included. When the lower filter is inserted the light is passed in PP' direction only. However, when the upper filter is inserted the light path is A-A' turned at 90° from light path direction PP'. Therefore no light is passed to the ocular or the viewer's eye. 41 UPPER FILTER NO LIGHT TRANSMITTED] CRYSTAL LOWER FILTER FIGURE IO-UPPER BI LOWER FILTER Magnification The magnification of the petrographic microscope is based on the power or magnification of the objective lense and the ocular. The magnifying power of a micro- scope is obtained by multiplying the magnifying power of the objective lenses times that of the ocular. It is important to note that both the objective lense and ocular can be changed to adjust the microscope to the needs of the work involved. For each particular microscope barrel or tube length only certain objective lenses or ocular are designed for insertion. 42 Index of Liquids To determine the index of the crystals a refer- ence must be established. A reference liquid is selected for crystal inmersion so that the solid can be contained in the liquid phase for microscope viewing. Index Oils A complete set of index oils for measuring crystal index can be obtained commercially (46) and the index oils come in sets that cover a specific range. The index is a unitless ratio of light in air to a substance. The range of liquids can vary from as high as 0.2 to as low as 0.002 units in a set. The variations may be above and below the actual index that is required. These limitations can be overcome by oil mixing in any ratio to yield the correct numerical index. The oil can be used with confi- dence and are stable over long periods of time. If an index oil set provides step increments of 0.002 and has been calibrated to 0.002 then accuracy of 1 0.0005 is possible. Temperature Each oil set is referenced to 25°C temperature. It is not usually possible to conduct microscopic studies at 25°C, and it is necessary to correct the index oil to the investigation temperature. The temperature coefficient is on the label of the index oil and is multiplied by the 43 difference between 25°C and the working temperature. If the working temperature is lower than 25°C then the pro- duct is added to the index oil numerial value. The reverse is true if the working temperature is higher. Therefore + dn . . — —E = temperature coeff1c1ent x (AT) (14) When $2.: + T < 25°C or when §2-= - 25°C > T dt Where AT = Temperature difference (T < 25°C > T) T = Working temperature. Crystal Refractive Index The determination of the correct or exact crystal under investigation depends largely upon identifying corresponding refractive indexes. To accomplish this, several approaches have been developed. The refractive index is a unitless ratio of light in air to a substance. A discussion of several techniques is useful. Emmersion To investigate a crystal to determine optical properties the crystal must be emmersed in a known index oil. This is done by putting a drop of a known oil on a watch glass and sprinkling a minute quantity of 44 comminuted crystal into the oil. It is possible to then put another watch glass over the index oil drOp without interference. The top watch glass Spreads the oil crystal phase out and allows for neat viewing. It is also possible to emmerse the objective lense into the oil and thereby view the crystal in close proximity. Crystal Group The crystals are broken down into two groups, uniaxial and biaxial. Each group will be discussed separately. However, the mineral system is as discussed in Appendix F. Uniaxial The uniaxial group as discussed by (42, 43, 45, 46) is a group with only two axes (see Appendix F) or two refractive indexes. The indexes are designated Nw (ordinary ray) and Ne (extraordinary ray). When a beam of ordinary light with equal vibrations in every direc- tion passes into an anisotropic crystal it is broken into two rays vibrating at right angles to each other in planes representing the different refractive index direc- tions. These rays are said to be polarized. A uniaxial crystal is said to be either positive or negative. A positive uniaxial crystal is one for ‘which the Nw ray is smaller than the NE ray and for a :negative crystal the opposite is true. 45 Biaxial The biaxial group has three distinct axes or three refractive indexes. These are designated: Na (alpha or lowest), NB (Beta, intermediate), and NY (gamma, highest) indexes. As monochromatic light is passed through the C or main optic axes of the biaxial crystal, this ray is the NB (Beta) and has only one index. Like the uniaxial crystal the biaxial crystal has a positive or negative sign. For the positive biaxial crystal N is closer to Na’ for the negative crystal NB 8 is nearer to NY Extinction To first investigate a refractive index a posi- tion of extension is necessary. The thin section crystal is first viewed with only the lower filter. The crystal is selected that appears to lie in a flat plane with very little distortion. The upper filter is then placed and the stage rotated until the crystal under investigation shows gray, white or black in any position of rotation. The extinction is then a lower filter polarizing the light ray. The crystal axis is oriented parallel to the microscope base to allow the polarized light to pass parallel to the axis without any distortion. The polarized light, although passed by the crystal, cannot pass through the upper filter because the upper filter 46 is at a 90° rotation to the lower filter. This condition is the extinction position of a crystal and a refractive index check can be made. Crystal Refractive Index Determination There are two methods commonly used to determine crystal refractive indexes. These methods are: (l) Becke line and (2) half or oblique illumination. The refractive index should only be attempted on crystals that show extinction. The two methods to determine extinction are as follows. Lower Filter When viewing crystals in thin section and when the lower filter (polarizer) is in place, as is always the case, a crystal shows extinction or darkens if the light ray passed by the lower filter is vibrating parallel or along one of the optic axes. This can apply for uniaxial or biaxial crystals. Lower and Upper Filter The insertion of the upper filter to View a well illuminated crystal may produce darkness or distinction. This can happen for either of the two crystal groups. This indicates that the light is passing parallel to (one of three axes. The only way to check a refractive index is when the light is parallel to an axes. 47 Therefore, when extinction occurs a crystal index check can be undertaken. Becke line methodrmThis method is based on the crystal immersion in a refractive oil and generally the two substances (crystal and oil) having difference refractive indices (45, 46). If the two materials (crystal and oil) do have different indices then a line will form around the crystal. As the barrel is raising this line appears to move in toward the crystal center or outside the crystal outline. However, if the crystal and oil have the same index value then the crystal outline, as the barrel is raised, does not move in or out. The illustration of Figure 11 is descriptive in terms of graphic display. FIGURE II - BECKE LINE METHOD NOTES N - HIGHER INDEX — OIL n - LOWER INDEX — CRYSTAL 48 The depicted Figure 11 is based on the fact that when light rays from below encounter the higher index oil and strike the lower crystal medium the rays are deflected. Also as the rays pass through the crystal (lower index) and strike the oil (higher index) the light is refracted into the higher oil index medium. However, part of light rays 1 and 2 are reflected. It is important to note that as light rays 1 and 2 are refracted and light rays 3 and 4 reflected they enforce one another. When the microscope barrel is raised, very slightly, the edge of the crystal line appears to move outward giving the appearance that the crystal is getting larger. Conversely, if the crystal had a higher index than the oil and the microscope barrel is raised the crystal edge line outline appears to move in toward the crystal as if the crystal was getting smaller. The edge or line is termed the Becke line and can move in or out depending if the crystal has a higher or lower index value than the oil. Half or oblique illumination method.--The half or oblique illumination method (45, 46) is determined by xxzflected or refracted light. This method uses only half time field of illumination so the light enters the crystal- cxtl phase at a definite angle from the directed incoming litflrt. As the light enters the crystal it is either reflected or refracted and as the light enters the oil at 49 the crystal-oil interface it is also reflected or refracted, depending on whether the oil or crystal has the higher index. As the light is reflected to enforce other light rays the light intensity at the crystal-oil interface appears dark. However if the light rays are deflected at the crystal-oil interface, this edge of the crystal portion then appears as a lighted area. Both Figure 12 and 13 illustrate the effect that takes place when using the half or oblique illumination method. The half illumination of the microscope stage is accomplished by partially blocking the entering light by decentering the lower iris diaphram. FIGURE l2 - HALF OR OBLIQUE ILLUMINATION NOTE: A. INDEX OF FRAGMENT LOWER THAN THAT OF SURROUNDING MEDIUM 8. INDEX OF FRAGMENT HIGHER THAN THAT OF SURROUNDING MEDIUM 50 OIL TO HIGH OIL TO LOW FIGURE I3 - HALF OR OBLIQUE ILLUMINATION IN PLAN NOTE: A. FIELD HALF-DARKENED. INDEX OF FRAGMENTS LOWER THAN THAT OF IMMERSION MEDIUM. 8. FIELD HALF-DARKENED AT ACCESSORY SLOT. INDEX OF FRAGMENTS HIGHER THAN THAT OF IMMERSION MEDIUM. C. ENTIRE FIELD ILLUMINATED. Birefringence The birefringence of a crystal is the numerical difference between the maximum and minimum indices of refraction. The birefringence are those colors as viewed when both the upper and lower filters are in place. Birefringence can also be as effected by crystal thick- ness and orientation. Two exact crystals with different thiCkness and orientation do in fact show different .interference colors or birefringence. Thus the need to select, in all cases, a thin section of a specific crystal. The larger the index separation, the higher the birefringence. For uniaxial crystals the difference is between the Na: and Ne rays. For biaxial crystals the I.“ sI 11 is Sa la 51 difference between the longest and smallest of the three indices is the birefringence. Birefringence as Viewed with both filters and the stage rotating will reveal a kaleidsc0pe effect of chang- ing colors. Relief When a crystal is at extension and one index ray is under investigation it is possible to quickly view the same crystal in 90° rotation to check the relief. A large relief at 90° rotation is an indication of the index separation. The greater the relief the wider the indices are apart. Very small relief is an indication then that the indices are close together. Pleochrism Certain nonopaque crystals absorb light dif- ferently in different directions of vibration. The Viewing for pleochrism should be with the upper filter removed. For some crystals, in one optic direction light Inay be absorbed more than when the stage is turned 90°. Pleochrism may be described as for Goethite: clear yellow to brown brown yellow orange yellow where x Y 2 although many crystals do Show pleochrism some do not. CHAPTER IV EXPERIMENTAL TEST APPARATUS AND MATERIAL Chemical Testing The chemical testing approach was conducted by using Standard Methods, 12th edition. The ions or radi- cals tested for were: Ferrous Fe(II), Ferric Fe(III), Calcium Ca(II), Silica SiO2 and Carbonate CO3 radical. The equipment consisted of Corning Glassware and the following: Balance--2 arm Pan Balance, Model #750-0 Serial No. M-12652 as manufactured by Voland and Sons, Inc. pH meter-~Model 76004 Expandometer as manufactured by Beckman Co. Analysis-~Hellige Aqua analyzer Photoelectric Colormeter including pre-calibrated concentration charts. .Model 950-A Serial No. 137 as manufactured by Hellige Inc. X-ray Diffraction The X-ray investigation of the various minerals and crystal structures were as performed by the Norelco X-ray’Efiffractometer (Range 12045-60 cycles or 12048-50 cycles) wide range Goniometer (Range 12099+ 60 cycles or .12048-50 cycles) Electronic Circuit panel manufactured by 52 53 Phillips Electronics Inc., Instrument Division, Mt. Vernon, New York. The unit is assembled in a two part module. The scanner, with X-ray gun, and receiver is in one module and the instrumentation plus paper strip recorder is in the second module. Petrographic Microscope To use the Petrographic Microscope on crystal identification several items of auxilliary equipment are necessary. The equipment, including the microscope, is as follows: Microscope--Mode1 624681 biocular polarographic microscope as manufactured by Leitz-Wetzlar in Germany. Light-—Model 651, 60 cycle 115V with 5, 6 or 7.5 volt adjustment to include varying intensity (1-10) with adjustable focus. Manufactured by American Optical Company. Standard Index Oils--Two sets of standard index oils were used to include one of intermediate range-- 1.4-1.8 in range increments of .015 and a second of a higher index with a range of 1.8—2.0 in variations of 0.02 units. The index oil refractive index is a unitless value in that it is the ratio of the speed of light in air to the speed of light in a particular substance. In this case the index liquid. The oils were as manufactured by Cargille Laboratories, New Jersey. 54 Camera—-To illustrate the various techniques and to present visual crystal review photographs of pertinent views were recorded. The camera was a Nikon F, No. 158755 with an "f" setting of 1.4 and focus length of 5.8 cm or 58 mm. Also equipped with Bellow attachment as manu- factured by Nippon Kogaku, Japan. The camera was mounted above the microscope on a ring stand that could rotate over or away from the microscope focus. Pedistal and Mortar--Used to comminute the samples to a fineness of 100 mesh or less. Glass Plates--The glass plates are 3/4" x 2" x 1/32". The sample plus the index oil are placed on a glass plate in a small area and a cover glass is then placed over the sample and oil to secure the sample for viewing. Test Specimens Reagent Grade Chemical Calcium Carbonate-Calcite-- CaCO3 or CaO-CO2 Contained the following mineral percentages: SO4 - .01%, Na - .01%, Fe - .001%, and magnesium - .01%. H ' -— ematite Fe293 Contained the following minerals: SO - .20% CN4 - .005% Zn - .005% 55 with a molecular weight of 159.70 as manufactured by General Chemical Division. Magnetite--Fe3g4 or FeO(Fe293L or Fe(Fe294) or Fe(Fezg4L As obtained from the inside of a fire Kiln where iron had been fired. The material formed on the inside wall is magnetite. The physical properties that identify magnetite are the magnetic property and the black color. Siderite--FeCO3 It is impossible to purchase FeCO3 commercially or chemically due to the instability of the compound. To obtain the FeCO3 compound 2 grams of Ferrous Sulfate FeSO4 were added to 50 ml. of demineralized water. Also, 2 grams of Sodium Carbonate Na2C03 were added to 50 ml of demineralized water. Both the Ferrous Sulfate and Sodium Carbonate have large solubility and all the material was in solution. The two solutions were mixed to form Siderite FeCO3. Siderite has a low solubility (.0065 grams/100 ml.) and the precipitate is FeCO3. The precipitate was "Green"‘ with an oatmeal texture. This precipitate was filtered through a Buchner funnel using 45 micron filter paper. .As vacuum was applied to the receiving flask the green filtered material immediately turned Brownish—Black, as reported in the literature (14, 44). The Ferrous Fe (II) ion in the carbonate structure quickly oxidized to 56 Ferric Fe(III) state. The oxidized formation is the con- 2 + 2 Fe203 - nH20'+ 2C02 The immediate product is Limonite (ngg3- nHzg) with no version of 2FeCO3 + 30 T. crystal structure. As will be discussed and illustrated later the oxidized form of FeCO is in fact Limonite. 3 This conversion of Siderite to Limonite was an immediate reaction and the long term oxidation of Limonite to Goethite did not take place at standard temperature or pressure. Also, the product was removed to a dessicator for drying. This removal did break the chemical reaction chain in that no new corrosion products were added to the system and altered corrosion products were not carried away. L1mon1te--Fe293 - nHzg Limonite was the oxidized product of Ferrous Carbonate FeCOB. Calcite Protective Coatings-- Laboratory Formation In past work (29, 39, 40), the prediction of the Calcite coating and the formation evaluation were performed on cast iron strips that were 1" x 3" x 1/16" in size coated on the back to eliminate corrosion. The coating face was machine ground and then inserted into a static or dynamic testing program to receive a Calcite formation for testing. Several samples from work by Woodruff (40) were still available for scientific review. The cast iron 57 test speciman had a dull gray Calcite coating or reported as a Calcite. The physical-chemical environment under which coatings were develOped on the cast iron test speci- man was as follows: Run Time - 2 Hrs. Water Velocity - 7.6 fps. Water Temperature - 14°C pH - 9.43 Alkalinity - 430 ppm as CaCO Calcium - 224 ppm as CaCO Carbonate - 93 ppm as CaCO3 Total Dissolved Solids - 451 ppm K's x 1010 - 126 *M.E. - .92 ppm as CaCO3 **D.F.I. - 165 *Momentary Excess **Driving Force Index These cast iron test Specimens were selected because the macroinspection of the coating indicated a Calcite coating, and because the cast iron test speciman could be placed into the X-ray equipment and yield ready results without transfer of the Calcite material from the cast iron test Speciman to a glass plate. Cast Iron Test Speciman It is essential that an X-ray of the cast iron Inaterial be conducted to review the background effect of the cast iron speciman on the Calcite coating X-ray. 58 Iron Formations or Corrosion Products on a Cast Iron Pipe Surface Several cast iron water pipes were available to allow an actual corrosion blister investigation. A 1" cast iron water pipe was extracted from a corrosion environment from the Fairmont, Minnesota Municipal Water System. The blister was intact and the entire pipe sec- tion was cut in half and a 4" long piece was stored in a dessicator until testing time. Figure 14 shows a photo- graph (M = 4x) of the half pipe and removed blister. The blister took the shape of a shoe print with the heel at top. ._.__ _ 1._ /_ j, Figure l4.--l" Cast Iron Water Pipe Nipple with Corrosion Blister (M 4x). 59 The blister top was removed and comminuted into 100 mesh size. The center or bottom material was scraped loose from the cast iron and also comminuted for sample preparation. From the photograph the layer separation can be viewed-~especially at the top (or heel) where the scale depth differential produces a shadow. It is estimated that the corrosion product scale depth was 1/32". be a sepe are calc the tics ofC DecE Cons Char and metho In the CHAPTER V EXPERIMENTAL PROCEDURE Introduction In previous and following chapters it is or will be apparent that discussion of the various compounds is separated into two distinct categories. These categories are those coatings or compounds that (1) contain the calcium Ca(II) or (2) contain iron (Fe II or III) ion as the common constituent. This was done in consideration of the fact that each category has similar characteris- tics and natural groupings. In the following discussion of procedure the lack of category identification will be evident. This was necessary to eliminate duplication of discussion and for conservation of space. Although each category has unique characteristics the overall format procedure for known and unknown investigations is similar and in some cases identical. Visual Inspection The intent of this research is to provide a methodology on testing internal coating in water mains. In the past the determination of a coating was by visual 6O 61 inspection, which is of real value. Visual inspection is the place to start an investigation of any protective coating or formation regardless of whether the coating contains calcium or iron as the common ion. The trained scientific eye can "get a handle" on the nature of the unknown coating and make valuable first-judgments by visual inspection. Color Materials that contain the calcium Ca(II) ion, and may be Calcite, appear white, gray or colorless and may, in fact, reflect the color of there surroundings when still attached to metal. Compounds that contain a trace if iron impart a color trace to the crystal. As the iron concentration percentage increases in a crystal or compound a gray to brown to black color will be noted. As iron Fe(II) is oxidized to Fe(III) the color changes from brown to black, as for Magnetite. Hematite, however, is blood red and the iron phase is Fe(III). Therefore, a thorough knowl- edge of the calcium and iron compounds found in protec— tive coatings is necessary (see Appendix A). Hardness The tighter and more stable the crystal lattice the harder is the compound. Hardness is based on numeri- cal values of the Mohr Scale between 1-10 with 10 being 62 diamond. Numerical values are assigned to each compound. The thumbnail test on a coating is a good test of relative hardness because the thumbnail can scratch a surface with a 5.0 or less hardness. Most of the compounds investi- gated in this report have a 5.0 or less hardness. Hardness is a quick aid to general compound classification and of specific value to coatings studied here (see Appendix A). Acid Test Many compounds will dissolve in acid, some in hot acid and others in a specific acid. Coatings may or may not effervesce on contact with acid. This visual test in general allows some decisions (see Appendix A). Magnetism A quick determination of Magnetite is a check for magnetism. The other 10 compounds considered here do not exhibit this tendency (see Appendix A). Evaluation of Coatings or Compounds Using Chemical Identification After the usual inspection of the known or unknown coating the chemical testing approach will be narrowed as to what general category is under investigation. Sample Preparation The sample amount should be sufficient to conduct three complete tests for a weighted average. The calcium 63 and iron test requires acid for dissolution and in the case of Magnetite the dissolution will require two-three days depending on how the comminution is handled. There- fore, chemical testing results may require several days away. The time frame of chemical testing must be con- sidered. Equipment Calibration Results are as good as the equipment calibration and the scientific handling. The first consideration is a mechanical approach where the second consideration is familiarity and technique. At first, equipment calibra- tion should be conducted each two-three days to note the sensitivity of the equipment. Once equipment sensi- tivity has been observed calibration can then be as needed. The calibration of any equipment should be from known standards. The known standards are used to develop standardization curves for the equipment used in testing. See Figure 15 for equipment display. Testing Format The testing format is basically one of uniformity. That is, each test should be standard and identical to Others of a series. Consistency relates to technique and to the reagents being used. Although not normally considered at a reagent, demineralized water should be 64 Figure 15.--Chemical Testing Equipment. checked periodically for purity. Erratic data may be a function of deterioration of the laboratory demineralized water quality. Testing is conducted to gather data and the data gathered must be recorded in an orderly manner. Recording is a function of data usage and the worker must, before beginning his work, decide his objective. Once the data arrangement is selected a data form can be devised to assist in data collection. 65 The chemical test and results presented here were conducted as prescribed in Standard Methods, 12th edition, published by the American Public Health Association. Evaluation of Coatings or Compounds Using X-ray Identification When use of x-ray equipment is employed the format for testing is the same for both the calcium or iron based compounds. However, the radiation and filter selection is important. Some types of radiation cannot be used for iron detection-~specifically, copper cannot be used. It is therefore necessary to select radiation and filters that yield usable results. Sample Preparation Known Reagents or Compounds The use of X-ray equipment to test unknown com- pounds should be preceded by the testing of known com- pounds to observe characteristics or "thumb-present" patterns that in turn reflect the crystal habit and lattice. A glass test plate is used for testing of a known dry dessicated reagent grade compound or mineral. Glass is excellent for this purpose because it has no crystal structure (it is amorphous) and results in zero loackground interference). The glass test plate can be 1" x 2" x 1/16". In.the center of the plate a small rectangular area 66 1/2" wide x 1" long should be marked off. The enclosed area is considered the target area. A clear grease, of a type used to lubricate glass on glass surfaces, or silicone base as manufactured by Dow Chemical is used as an adhesive. The known test material is sprinkled on the greaSe to a depth and surface uniformity of 1/64". This loose sprinkled material then should be compressed by placing another piece of glass over the tOp and press- ing down. The top glass may or may not be removed and if left in place allows the prepared sample to be handled without fear of disruption. This sample should be used as a standard and retained in a dessicator for future reference. Cast Iron Test Specimen The time saved by using a cast iron test specimen that has received a protective coating is appreciable. The cast iron test specimen can be extracted from the test cell, dried, dessicated and made ready for testing in a matter of hours. This time saving is two fold: (1) the coating, whether calcium or iron based, does not have to be disturbed for removal and (2) the plate size is compatible for X—ray use. It is important that the cast iron X-ray pattern be known to check for background interference and when the pattern is known the X-ray data can be reviewed 67 accordingly. Should a corrosion blister form on the cast iron test plate, however, removal of the blister is necessary. The removal should be accomplished in layers because (27) the corrosion blister develops in layers that are, at best, difficult to define. An interface is present because the Fe(II) is being oxidized to Fe(III) and a change of state is observed as the blister enlarges. The most valuable feature of cast iron specimens is the manner in which they can be removed from the test cell at random, be X-rayed for a protective coating or corrosion products and then reinserted into the test cell for further observation. Removal of the cast iron test specimen for x-rays do not alter or change the crystal structure or lattice nor destroy the integrity of the protective coating. Magnetite Magnetite forms in layers in an iron furnace. The layers can be striped off in sheets. An iron sheet 1/8" thick makes an excellent sample for X-ray testing. The sheet should be dessicated and then tested after being reduced in size to 1" x 3" x 1/64" thick. Equipment Calibration Calibration of the X—ray equipment is always necessary and must be done as per manufacturers recom- :mendation. Once the equipment is calibrated the standards 68 used as controls should be tested and these standards should be retained as a baseline. During the testing program the standard should be tested from time to time to check calibration of the equipment. An identical X-ray pattern for a control standard is a positive indi- cation that the equipment is still in calibration. As X-ray patterns are recorded for known com- pounds it is important to record the base level of intensity. Some materials may record zero diffraction intensity while others exhibit a baseline intensity of 30 or 40 percent. The measurement is based on the observed diffraction angles and on the diffraction intensity peaks. It is necessary that the technique used in test- ing the various compounds be consistent. Selection of the radiation and the filter equipment is important because calibration of equipment and test sample obser- vations require a standard technique and use of the proper radiation and filter. The X-ray equipment has one very important control termed the Rate Meter. This meter alters both the X-ray emission in conjunction with the filter material and also adjusts the receiver to coordinate physical aspects so as to yield Specific results. This rate meter can be adjusted to vary or alter results to meet specific conditions. The X—ray experimental data, included in 69 the following section, was set at l6-l-l, meaning that all X—ray patterns are a result of constant rate meter control and the results can be compared with a valid data base. Testing Format Before any unknown coatings or compounds are tested the standards must be first tested to establish a thumbprint with which to review all subsequent data. Broad Range Any known or unknown should first be tested across the complete 28 range of 0-180°. This will dis- play all diffraction angles and illustrate the diffrac- tion intensities. §elective Range Upon completion of the Broad Range testing those diffraction intensities that exhibit the five highest values should be retested to redefine both the defraction angles (20) and intensities in that specific range. This is the X—ray range for future testing. Only the three largest diffraction intensities eare required to specifically identify a mineral or com- pound . 70 Data Evaluation Data is the key to identification. The recorder speed is slow and the diffraction intensity peaks can be recorded by the ink pen and the diffraction angle (28) can be noted. The Bragg equation (10) can then be employed for known radiation wave legnth (A). As the data is printed the "d" lattice spacing can be calculated,and a search undertaken for comparing the data to the knowns can be implemented at once. Preliminary identification of unknown test coatings or compounds is possible immed- iately. Evaluation of Coatings or Comppunds Using the Petrographic Microscope for Identification Sample-Preparation Each mineral or compound should be comminuted to 100 mesh. This comminution crushes any large masses to a finely divided powder which is easy to View in thin section. It is not necessary to use a sample amount greater than 1.0 milligram, only a toothpick amount is used for each respective slide preparation. Once comminuted, the sample should be placed in a salt cup and marked with a grease pencil--as to data and amount and composition of iron. This cup should always be stored in a dessicator. 71 The preparation of the glass slide is accomplished by placing a drop of oil in the center of the glass slide and then adding to the oil the amount of material that can be perched on the thin end of a wood toothpick. A glass slide of identical size is then placed over the oil and sample,and the slides should then be squeezed together. It is wise to mark the index oil, date and material if known on the slide. As the index of the material is checked it is advisable to make notations, on the glass slide, for future observations as required. Also, it is most helpful if the area being viewed is circled in red and the crystal orientation under investigation be recorded on the data sheet. This technique also allows for future observations. Equipment Calibration The calibration of a petrographic microscope is one of familiarization. It is important first to select the magnification that is to be used in the work. This is accomplished by multiplying the ocular power by the objective lense power. The higher the magnification the smaller the field of vision. The arrangement of light source and microscope mirror is important and must be arranged to allow the operator to work freely around the microscope. Also, the intensity of the light should be selected for eye comfort in viewing. Figure 16 illustrates the micro- scope, light source and oil index set arrangement. 72 Figure l6.--Petrographic Microslope. The operator of the microscope should become com— pletely familiar with all the working parts of the petro- graphic microscope-—especially the ocular, upper and lower filters, objective lense, etc. The most significant calibration, in the identi- fication of minerals by use of the petrographic micro- scope, is the index oils. This calibration is difficult 73 to identify, and it is important that new, fresh cali- brated oils be purchased at the start of any project. The index oils contain many organic materials that age and affect calibration. Testing Format General View Once the sample has been prepared and is ready for investigation it is advisable to view the entire slide for crystal layout, thickness and habit with only the lower filter in place. Many compounds exhibit a physical tendency that is a clue to the mineral or compound identification. A general view of the slide, for instance, provides back- ground to pick out the crystal for color identification. Very small crystals may be ideal to work with, but can be too small. The larger crystals show up very distinctly, but may illustrate excessive thickness and exhibit birefringence. It is therefore advisable to select a crystal of intermediate size that apperas to lie hori- zontal (one axis) to the stage. Oil Range If after visual inspection the mineral or com- pound falls into a category the general refractive index group can then be estimated. This works well for the calcium or iron compounds. Calcium compounds have a 74 refractive index of less than 2.0 units, whereas the iron compounds have a refractive index near 2.0 units or above with the exception of Siderite which is 1.613 to 1.855 units. If the index is less than two (2.0) units and with brown to black color, the unknown is probably Siderite. If the general group cannot be estimated, it is best to then try an intermediate oil to start. Thin Section A review of crystals in thin section using the lower filter can often shed light on the crystal type. It is best to look for general color arrangement for crystal comparison and to view for extension of a par- ticular axis. Crossed Filters To convert from thin section to crossed filters the upper filter is added. The crossed filters allow the operator to look for extinction and birefringence. Extinction can be seen as two phenomenon. The first is total extinction when the crystal appears grey, white or black regardless of the stage rotation. Secondly, when viewing high birefringence the stage can be rotated to allow viewing of an extinction index. A rotation of 90° from this extinction index shows another extinction index of the crystal if it is in the uniaxial categories. 75 Crystal Groups As has been discussed, crystals fall into two distinct categories: uniaxial and biaxial. The uniaxial group have only two index axes whereas the biaxial group have three axes. The following information allows a quick check on crystal group identification. Uniaxial Group 1. Insert upper filter. 2. Check for extinction (the crystal will appear grey, white or black regardless of crystal rotation). 3. Identify the index axes with upper filter removed. 4. This axis will be omega without ray. 5. Once nw has been determined insert the upper filter and select a crystal that shows high birefringence. Then use upper filter--turning the crystal to extinction and checking the index. Always be sure that the index is not the nw ray; if the index is not the nw ray, it muSt then be the Epsilon nE ray. 6. When the ne ray is Viewed check the index to see if the index is larger or lower than nw. 7. If nw > n€—-Negative crystal if nE > nw-—Positive crystal. Biaxial Group In the biaxial group there are three axes and therefore three index of refractions. By definition the three indexes are Alpha a (the lowest), Beta 8 (the 76 intermediate) and Gamma Y (the highest). The following procedure is necessary to define a biaxial crystal. 1. Observe, under crossed filters, a section that is grey (no birefringence) in any rotation. 2. Determine the index by removing the upper ‘filter. The index is Beta 8 or the inter- mediate index of refraction. 3. With both filters in place observe crystals by rotating the stage for those which Show the highest birefringence; determine the index using only the lower filter. 4. These two other indexes will be alpha 0 or gamma y. 5. A mineral or crystal will be termed "posi- tive" or "negative" when: Alpha a is closer to Beta 8 = Positive Gamma y is closer to Beta 8 = Negative. Determination of Index of Refraction Although the procedure is very similar the determination of the index for each group will be dis- cussed separately as Uniaxial and Biaxial. Uniaxial 1. If the crystal is unknown select a 1.50 index oil. 2. Insert both filters and select a "check"' crystal with no birefringence at any rotation. The crystal will appear isotropic and the axis and index will be parallel to the microscope barrel at any stage rotation. 77 3. Determine the index of the crystal by use of the Becke line or the half or oblique illumination method, with only the lower filter in. The Becke Line Method is accomplished by raising the microscope barrel to unfocus the crystal fragment slightly. If the Becke line moves out away from the crystal the oil is higher than the index of refraction of the omega ray or nw (isotropic at any rotation). If the Becke line moves in toward the crystal center and the crystal center appears to brighten then the crystal index is higher than the oil (see Figure 11). Depending on results, it is necessary to make another slide mount and again utilize the Becke Line Pro- cedure to narrow the crystal nw index. Before a new mount is made it is wise to check the Becke Line findings by using the half or oblique illumination method. This is accomplished by a refocus of the crystal to cut off half of the light entering the crystal. To this end, insert a plate below the stage in a slot especially designed for this purpose. If the crystal shows a dark shadow toward the dark half, the oil refractive index is lower than the crystal (see Figure 13). If the opposite is true the oil is higher than the crystal. Now is the proper time to make a new slide mount using another index oil. 4. Continue to make slide mounts until the n U) ray has been determined. 78 5. Using the slide with an index oil of the nw, insert the upper filter and select a crystal with large birefringence. Remove the upper filter and turn the crystal to an extinction angle. New check to determine whether the index of refraction is identical to the nw or higher or lower than the n If the refraction index w“ is identical, the extinction is for the nw ray; if above or below the slide oil nw value the extinction position is the Epsilon n8 ray. If the n6 is lower than nw select another mount with a lower oil and if higher select a higher oil. When the oil and index are identical rotate the crystal 90° to View the ne extinction position. 6. Pursue the n8 ray identification by making new mounts with different oils and using the Becke Line or half oblique illumination methods. 7. When nE has been determined the unknown crystal can be identified by the uniaxial group sign (positive or negative), nw ray and n8 ray index of refrac- tions. Biaxial 1. If the crystal is unknown, mount in an oil of intermediate range such as 1.5 units. 2. The Orthorhombic, Monoclinic and Triclinic mineral systems have three indices of refraction. 79 3. Of the three axes, the Beta 8 will show extinc— tion (grey) when viewed under crossed filters. This section should be selected and the index determined using the Becke Line or half-oblique illumination methods (as per description 3 under Uniaxial, p. 77). Several mounts must be made for exact index determination. 4. Remount a sample in an index 011 lower than for Beta 8. View the new mount using crossed filters. Select a crystal with the greatest birefringence and determine the index. The fact that a lower oil than Beta 8 is being used automatically means that the alpha a ray index is being investigated. In this determination it is important that for the observed index, no other crystal has a lower index than alpha a. 5. Select an index oil that is higher than the oil used to determine the Beta 8 ray index. This index of refraction is termed the gamma Y index and is larger than Beta 8. Follow the procedure as above in step 4 but no other crystal may have a larger index than gamma 7. 6. Once the three Biaxial indices have been determined then the unknown crystal can be identified by the group (biaxial) sign (positive or negative) beta 8, alpha 0, and gamma Y indexes of refraction. Data The collection of data for the Petrographic microscope when identifying crystals requires a careful 80 recording of the oil used and the manner in which the Becke Line or illumination methods reacted. Also record each new oil selection when it is necessary to select a higher or lower index oil. The data shown in Figure 17 is a typical "trackdown" record for crystal identification. 81 DATA SHEET FOR REFRACTIVE INDEX DETERMINATION Date: Sample: Temperature: -dn +dt Index* Index Oil Becke Line Half-Oblique Oil (+,-) Temp. Method Illumination Ref Temp. Change Method * The refractive index is a unitless ratio of the Speed of light in air to a substance. Figure 17 - Data Sheet. CHAPTER VI DATA Remarks on Data Format and Notation The data format isolates the minerals under investi- gation into two groupings. The first grouping is the Protective Coatings group that contain the Calcium Ca(II) ion as the common crystal or agent. The second group Iron Compounds and Coatings contains the iron Fe(II or III) ion as the common crystal or agent. The Protective Coatings include the following minerals: Calcite, Aragonite, Apatite, Vivianite and Ankerite. The Iron Compounds and Coatings group contain the following minerals: Hematite, Magnetite, Siderite, Limonite, Goethite, and Lepidocrocite. The data consists of the following categories: (a) Chemistry, (b) X-ray, and (c) use of the Petrographic Microscope. The Chemistry data is from the investigation of the two principal common ions to the coatings group, mainly the Calcium Ca(II) and Iron Fe(II and III). The X—ray data includes the investigation of the various known and unknown minerals in both coating groups by comparison of known lattice crystal patterns. The Petrographic Microscope data includes the verbal description of the minerals and, as a supplement, photographs were taken of selected minerals to illustrate detection techniques. 82 83 The following notations are used for data display: Chemical; X-ray; Petrographic Microscope. 1, 2 ... are used for mineral group identification with an a, b, or c array. l-A, l-B ... are individual mineral identification breakdown within a grouping. l—A-I, 2-A-II ... are used to identify the data included in the Petrographic Microscope Section. the I, II ... designate the respective photographic and visual descriptions. Because the same I, II ... are also used to identify the photograph and descriptive work, the words "photo" and "description" are written immediately below the number-letter-number data designation. The valance of an ion always follows the ion notation with (I), (II), (III), etc. The letter notations used are as follows: d = Lattice distance spacing in Angstrom units. = Angstrom units. Light source setting for microscope from 1-10. 3 L“ 3’0 II = Magnification of microscope. For instance 6x10-60 times magnification of camera (4) and total magnification is 240x. "f" - Camera appature setting. T = Camera time setting. T.S. = Crystal view in thin section using only the bottom polarizing filter. C.F. = Crystal view in thin section using the bottom and top polarizing filters. 84 Bire = Birefringence. Rhomb = Rhombohedral crystal. Appendix material has been referenced for the data as follows: Chemical Appendix A - Data for nonopaque minerals. Appendix B - Calcium (Ca) and Iron (Fe) percentages in various compounds. X-ray Appendix C - X-ray diffraction data. Appendix D - Some calculations of "d" spacings for calcite (CaCO3 or CaO.C02) using Bragg's equation. Petrographic Microscope Appendix E - Data on minerals for use of petro- graphic microscope. Appendix F - Crystal group data. Protective Coatings These are minerals that contain calcium Ca(II) as a common ion. The discussion of the protective coating- laboratory formations can be found on page 85 Chemical 1. Calcite (CaCO3L l-A l-B Calcite (CaCO3) Protective Coating Reagent grade Laboratory Formation 39.6 % as Ca(II) 37.8% as Ca(II) 39.5 % as Ca(II) 38.0% as Ca(II) 38.0% as Ca(II) Average 39.55% as Ca(II) Average 37.9% as Ca(II) X-ray l. Calcite (CaCO3L 1-A (See Figure 18) l-B (See Figure 19) Calcite (CaCO3) Protective Coating Reagent Grade Laboratory Formation l-C (See Figure 20) Cast Iron Petrographic Microsc0pe l. Calcite (CaCO3L (See Figures 21—27) l-A l-B Calcite (CaCO3) *Protective Coating Reagent Grade Laboratory Formation * In complete petrographic microscope testing of the referenced sample, the identification of the No - 1.658 and Ne - 1.486 index rays were tested and confirmed on three distinct and different samples. From this, it can be concluded that the referenced sample is a Calcite (CaCO3) formation. 86 coflumflcmu m.nH m.mH hm.H om.H mm.m ov.m QOHH COMH mh.mv Hm.hq anus.“ nose ow coflumflcmu HOQQOO mo mm.H ov.m couH mm.nv w.ha mo.m Nw.m couH Nv.mv ...-m." mN.N ww.N COMH mo.mm hw.m HH.m couH mm.mm .wmh. H oflumu mcflommm c cmuomuuou .1 o.m mm.m mm.m couH on.Hm o.ooe m.e eeo.m em.m me.m ee.e couH couH mo.a~ He.em .«IH ”eneofimo mpflchDcH w «@IMD pmwomuuoo «Iv 0 coflpmflpmm om we mesmem P! . 1 cl ...-'5 (ivoco .02 Pic-.9 “I Hwomponm I ma musmflm I II ..I. III I .. u . I A L. ' IlIIIIIIIIIIIIII .‘IIIIII .IIIII coin—III. II II.I|. AI 4 .I« III AIII I. . u . 0N II .. 9T .. n 0m. m n .. . . . . . III! III I.. . - IIIOJJII. . I.- - .- I II- -I.I4.I. II-I---II..III. .- ..- I. - , . . ... ,. .. x4 I.- .H . .-....I .- ....- .. g. -‘ 4...-... II-..-¢T.-.IIII III-I-IZIII- -. . . .. . ......- 44 .-.-I7- . ..uo . II.I.I.I _ . we I... .. 15-47.44,.- .. a. . I II II . t I.- III I. II II.|.IJ If-I I...I.|I.‘|IJ.IIII.‘. II. .-.. . .l? I IIILILIIII 4 . _ . . . I . 44 . 4 4.. ... . I I. . .H .. II I. I. .I-I .II I - 'I I III ..... I I. .IIIIIIIIIIIIL o 4 .5- I L. ..I 4. - 8 . .. . 4 s. ...... . ..-._ . -..-.... - .I p .l ." ... . . I a . L ... a .n . . 3. . I LIM . I. . 4.14.1... . . .~. _ .0 ImI .I. I . . .III. .I v A . I r . loam U . -.I... . .4... 3.. ..4. 4... . ... IIIIIIII. I. II I .I III. III! I|II_LIIIIJ|III.II JII.IIIIIIII I L. I“? a . . _I u .- . u . ...“Ll . l ”I m 4.... - . . _.. ....24 I. 9 III..I-II.IIIIIIIIII-|IIL . I. . In I . .IIIIIIIII. . . _ . .. 4 4 --. .. -...4 ..4.....:I 8 II. I . ..I .. HIII u .. . ... . t o . I . ol- I-I .. III ... .. .-. . . .4 .I ..-. H ...4. -fi- .. III-IIJII (III. III IIIIIIII .- II. III ‘IIILI- IIII. .III‘I Illl .IIIIIII-l I a “ IIIIIII I‘lll 4 4 ..4 . . . - -..-4-..... I . 4. . .w .I . .-..I .. 45.-4 .. .. 4- ” . . . III . I-.. . _.4 ..I .. 4 . . w .....n” .1 IIII I4... H I. .I On. . W I.- I . .- 4 -|.. I.._. . . ... . . .. .I. 4 m. I . ..I -. I" . I .4 I. | .. 4 . ...-l. I ”I. LI. II . by . I .II.Iu . I - I . ..rli . . .I. I .I . I I I— I0 . II I IIIIII l III-II II 1| I§ p 4w i “LI“ ltlu {I11 1.... 4.. Illl-l'mlblhl.” _ .. . I .l. I. I 4..: II I I . I .- 4.... .-:-HI... -44.. 4 . .... -- . I. u .4 .II 4 . . ...... I “I ... . .- . I!!! I. ”I .~ . Ir . . .. IL ... .. I . I . U. .4 . . .. .. - I. ..I... ..Im. I. -. . . - . 44-1.. . .- 4. .-. ...” II I III ' II lill| IIII IOIOII..| 10.! IIIIII'ILIII IIIIII III I'll IIIIIIIII J L- 1' I . 1.111! I .. . I . I I'd III. 4. .I I _ .... . .. .I D...- . .- I .m I I .Ifik. I.- _ — .w . .- . . . .. i . I .. I. ~. O. .u. I u .I I I . I . . . . 4 .... In“. I» .4. ..- .. I . . .... . .. .I. - “a “I ... V ...II I.rII .. I4."- I....“ .. . I ”Ir . .1“- .p I I .. ... .. . -. . . - 4...-ff -4. 44.4.9.4 g..- - I. . I. I . I .A. 19. I. I . II. T. oI. . I . II... . a .ILI. I I. III I . .-. . . .-- I III II. . _ F . L I J . H. I. 4. LI .r. JII 4. . . . . .- H. .. .. ..... 4. .. ...--..I. I 4...-1...“...4-M .. .; .. ”- .. .mJ .... .. I 4 ...r-.. .M . -. W. .- . 2. . .. .- I... .. ...i .. . _. . .. . In. .. ... . 4h . . .... .. I _ . . . I-I ...I It. I I 2, . _ . u II I- .s. ...r.... I .. .. ... I . . a. I _ 4 . 4 L I. D. . . Tl‘ .JJM .. .. . .. .n . . ... I .. .. . - ”q;- . . I.l ... ...-...... ...... - I". . ...I.I-. ...I. a I I . .I .a .I— ... . ... u. . ..I..... .H .. .IIII... I . I _. I. I.. ... . . . "I. . .m .— I. . . .III l..u I .. -..“! ...- “26.—Pry 0.1“.” ..:-0dr. 4.5.. . . . I”. I 4. I. ... .. . ...-4 .. . . .. I ..I.-., 1 .II.IFllIL.I|IFI|Idu‘P.-d .0 11.. .1! I .. ...-IIIIIIH «I L II Ill—[III ll; '1' LII.IIIII|LIIIIIIIIIIIQIJIO U III“. b .lllludllla.'| IILJIIIP‘.‘ --.. . -. . 0.1404.an . .o .. . . ...-I... ..I. - 34.... .. ...- ...-4i .- . ... .... ..m .... 4. II I . “I. ... ... . III. .I . ... .. . .I.II.r Al. . IL. .4._. .r..~. ..-. .. t... .L HI. m . I2... 1.. I . I MI ... I ‘ . on. . . . I I . .. . . I '1 I... I. .II . I .5 II . . .0. .7.. . .Q.. It.) ... ..l. . I.... v”. . . 1‘fi‘....lunl¢ I. . Ii I I.‘ drava‘ J .~ u. ... n. o u . . I 1 _I—.. .u. r!” ...I.. bo.l._ .. .I l. . u . . I ImJ . a.” n u i! .L — Ftp . . I... .. . I? _ III— . . 4- — - . LI: d 1 Ir 4. Id» . . 4 I II- 1 . I . .. . n . .II- n ...H . . .I .I. .u A I. . . . ...l .c .l ._ . . .- I .. I“. .1I..IIII...O. . .. a. . . "In...II.I I .“I .44 0...? . .. 5-2L 3.. Ir . . . 8... .4 . - -. .. I -.---.. .-:. . .. -. _ ...-...; iAw ‘#V 11. .I (m? IL».’. 0 mkm.u.muh . I ..I. . . t 1.. — 0 $43... I+~ '1. n. “.5.|HrI“..I ..H.. “In. .. 4.. I I . ALI”! A. II... I. .1... I.. .- nut .1 .. . I—II. .I..r I... . .&c I. . . . I. ..II I | 01.. ...-III .I . . . ....I ...I. v . ...I . In I! .I «o B L‘. I III .IIIDIII .. 0!-.. 0!!!! .... ... -.I II! .I Iil'l III p Ill-1| 1. .I— .!{.II livinuil. III-[IT‘S .- .II...J.4I-I.I.1. \- . ”- mll . . I . . _ .. II)... .. -.I-_. . I. 4.... . .. .. I. ... .4 J... . ..:-... 4 II.- 1 I — - I «I . ...“ . I I I. u .01. Q! II . n .. In In WI... . . .I A l I. I A I . Q . .....2. a ..H .-.m ....4. .4.. .... ...H “.... ..r“...L:I . _- . 4 4 4 w. ... .. .4. .-.... b.- .. -- I.“ . -. 4.4.“ . . “.4... .. ..-“..I.w. .4 IuELII—II.LIP .IL. .. urv1.» . . I» P (III. 4.. 8—.IIIII 4 III. -«.w. . _ . «.- E. .In I r L -L. I . 90 "-' ' xiv-'41:. .mumwcmpm may mm cmm: ma :mo :ofiuMvau GOMH mm uomuuoo on www: oz «« .hmHIX mnemmn Um>oEwH mm3 ucflmm may .mUounoo no umsu uoc vac .wuowmuwnu Ucm ucflmm m nufl3 wwumoo mm3 mwfimxomn mumam umwu may mcflumoo mnu mcfluso .owms mmz wuwam umme COHH ummu may Mo mwflmxomn mne .muoumnonma may CH omEMOM mmz mcfiumoo w>Huowuonm may scans :0 wumam coufl wEMm mph :— o.mm o.mm m.mm .ooa wuflmcmucH w I I I I IIme Umuowuuoo mm.m mm.m mm.m mn.m «Io O COHH couH COHH COHH coflumflwmm mb.mv mh.nv om.vv mm.mm mm «.UIH ”couH ummu I om musmflm 91 I. 1" 10111 11.1.!!- .14!!! all 4151! ...I . . _ . ...... 121.41... .1. LI I .1. I . I . .4 . ... I . 4 .. .4. .1. . AI... .. 1 1. 4 .. . . . . 4 ..4 .. . ... _ 4...... . T 70..” .I . .. _ ... _ :1 ...4..-4__;._454.. ......f. 4 .4. .4. I . I I I . . . . . . . u 4 . . 4.. .. . N . 4. .. . . .... ...44..... . . . . ..4 n4 _ _;_4_. .. 44.4....._... 6%....4. .. .3. I .I I . . . . . . . . . _ . . . . . I u. .— u... u - ... . .h. m._m_ ..t. _. ~ . . _ _4”__ .b __ "u 4_ u .. . . . .. *4. ~.~.°. ~»_.m ... .... u ..I I In. _ IF .I. ..rII.n_. . 1» L ... .. 1...»; 4- H 4 r . r L L —. I» PIC. . . .. I.. 1411 o u‘ 1 11 . I41 I . 4 I I d .1 1H 4 I I I . .rJ'H I l.I..I. I... a - u. I .4. (..III IHI ..II'H'IOh ‘1 #1 .I .l. ~10 I u tit _I *1 II.I.V I .1 «.11.? .I O m 141.*c.f III 1%.!“ III; I~I1IIII1R “4| r1b1. II . T1II9H1~11¢IA Ifivldl .JIMNII «I‘IOIFIIA «In -I n «I. YI4 . III. I. u u . u . II I IIIII. III II.+I-II .III In. IHrI I..I.IfI.flI1.. pII 014 III. +J “III-I1 I» II. m1 .1.1 ..111 IIO. ICIIql. o . I4. JJJI 1.... I . - IL ‘11. rql1tI TI I 7|. « will .4... II; I 0+ ~I1 woLI—III I” I. 1 .I IAIh II.I - .I.I AI'J I ..I III I I I I I IdIII II ..t a u I... q.- . ..I.I I 1 I. DI 14.3 II . l .o I . .HOII . ..S. I.) I—1 v III-LJI1I— .ITHI. .7 IA- .0 I.. ...-oHI—IIN II J rLII ..JII. ”I. JI.II 115’ IflII I.. If]. I I flu!”- .I "It III III I.: I .. . I I mIoI1 I IL. I I -I —I III . 3... I111. (I 14 VI 17) .1 II I .1 .I... I I .11. I. I I... II ... I. A u. . .4 “I 1 4|. - I..-w. II II IT. . I I..”. I ' I. I-4 1: .I . III . 1- 1W P IN n Lhmrhn up I . LIIp—n u “I u . F 1 I11. I . 14 . . . ._ L1 14. .MLII . h . 9 “I . 1N IHII. L? I" 4ban . p .F o > 01. .I I . I. I IIHJ II. Ib1v 1.1a IMIIIIIIQI . I I II II-oI II. I. .. 1-..... — II .I..I.Io . - I II II I IQIOI I1 I.II.. I.I I. I..-III; *4 II .II 4.. II I..-I ..IIJ . 17th.}... L .I.... .II;I¢.u.I.. «I... .4 ..l-IIIII.III I.I III I. I I I. I 470 II I I 1 I o I alien.’ I 41 LII I ”111. III-IIIIII. I. 1 1. .1 1c I1ILI5II¢I I I11 1' l o . a .1 a I I 4 ol [VI-4 to I.. .JII I 1tl IIII-Il I I.. I .I... I.I It I. 0T If... I I I .VII-Iva-II. . .1 If F» I.LI+I . II I II I III,- II— .I. I. qIIIIoI.I II.- III .I It. I .. I. _ ..I .I 1.1 I.. II LI II II III IFIJIII 4: I4]; III. I .II IIJI 1.1 III 4 ..I++~+II+ ...II. I 7.7.6147; I.. II... ._ -I.IL I.. .« "Ir-1. IL 1.4-I --I .I..- -I -II .I- -. II. I. ....-.NLI41ILI l {...-I .-. l . . LI- .4 I- 7 . I NI. ..II.. I H4 4 II I- I... I..”...SJI I4 4...-”TINA. IIDI. +II4 .. ...II. .I 4. . .I4 I I I M . I . 1 .. . I. I 4 I . A I. 11 I 4 4 a 1 . . A <1. .4 . . . II-IINII.0II<5IIJ II II II AI... .5 LII! III—II.IIITIJII *4: I JI-IIo I. Uw‘ ..I ... ...J I .h III.I.¢:.I IqIn w I.. . a. II fI‘INIr. II .AIrIII*I1 rGAIL Ir Ll I.I . I . II_1I.+I. WWI-”IIIIILI. IIJI~IIM ..I.I I .I II1IHIIII . . ..II NI—. _I1I I..L IIIIIII+DIQIL I1? .I II ....II I I. I ..II .IOIIM . 45... IT IPA-I .111 +2 YIWLI .I .I HI-IIIW. .- I.' III. I .I . .rI LI JI II III; I”. I III-... I III I I. ... I II. I I47. I III ..LIII .I .Ir-II ..II I.. .LIJI:III II .I .II 1 ..Ir. It IIIIIIIO. .l .I In. .I .-.I II-ILIO oT-JIIIIIIIJJIOIII. IIII-. . .I. JIII..I-..III. .II .~II. .. I .. ... .4 II ~I..Y I4 I III IL...I|. . . .ItIIt Iwr I I I I II . I I II PPI ...I .. I». ..Ir .II- ..I.- I. n 4.II.. III III I. - .I II. II I I.--..I- r I II I -. I . I I. - ..II . ...I ..III ..I. l. ..I.I I r. . - I ...-II.- I . I .- Li ..I .. .-. ...III .I .. ...-I . .I i... ...-...: . . III .I .T .. lI-I . I. I I W. 4 ..I .4 m1 . 7.. .HI ”...-I; 1.. . . .l..III-II- -IIII- _ 1. . I .4 w LIL 4 I . I .4 fi I. 4 11B III. I 41... . . 1 . . n . U 4 _ I 1— ‘ I n 4 11 ‘ . ‘ ‘4 II II I a I o I III 0 It . I I I I ..I I I I LI. I I GITIJ I I . a n.- “In. . 1 III LITII I I I.I i I I I I. YIIHIJIIlI III! a I ..IioIé-WII1-II II .A.* . ..I. I.. . 1911.81 ‘W-ITJI 014v I.. L.&I1II.I.I + I." III I '11 01*.-. u o I H l- IIId I I . I. I”: I.. o I.I «1 I47 I . I u a. IN . . c .4 h. 1" JIHII T.. . w IL. I” w ‘1. ... I II I. I. III—III I .4! II 1 c .- IkiMI I.I« TII”|..“ LIh . .I a ...-I.. IIIII 1.5.1.! .I. I I . Pwlll. III‘ . rl r" I I.. II Io-IIIIbI I .IIII III .4- I... I... II I I n I II In. I _ . ...44I I . . . I .II ...II ... I .4. ~. .I.. .III II . II. - .4 ....L-.. IJIT .1. ..I .I. .. IwLJA-TIII. H-f IIMWMIWImIdili-III III-1.1 . I.. . ... HM q1IOII IPHI III-I III- ItI .- I’IPC?I .I II. Inhlul-InIIO .1 IN. I I I: *1 I II b. T11.LI . II . III I“...I¢1 MI I I ‘JII . 14 4 .¢.I1I ”I o 0 PI. II I .. II I .I*.-.I.II.LY III . I.. I . ..I. INII‘ F.I 1.1”. .III I. I Ibi. . ..IV ..IJI In J I d a 1 I 1‘ I1. . . 4 .11 x. 4 4 . . 11 1 I 4 . 4. I1....- I.- I .IMIJ- 1 PIL-l u ..‘I “III. INIIIL I rIoI IhIII-II II.A *IIIII .h n Al-IJJI IL I II I ..IM 1 I.“ .JII 1:1”: I «I . Id . IIHI 0. LT III. 4H I P1~.I . ... NITH-m . 4 .uIiAI-41.6+o II. I -. IL. . - r. I - IF. I “I I II... In... . II I. I I a I. I I.. .I .IIIII . .1I. ._ I .I I I 4 I.. Iqo. I... . .1 .MIT 74 I I... II I I ...... . ... *I . II. I. III-.- II- I. .4-IIII.IL.. I. 1 .- IuII I I— I u- ..... I I. I}. L. I .t4 "I I III? n II ..I. I. .I a I1 . I I I I. I“..IIII.._...I. +- .4II I II . I L - I.. 4 III I” .. . . ......l ..HII. a. #4 . III-N I...;II.I‘III.I-. WI: 1...! ..I I . I I 4..-.-.... .1: -. I..-... I1..I..I In. I I 4 .-.-L. -. ..I.III4 -.-.h-pI .1... - .- .1. - -- ..- 4- 4 .. .I .. I..- T..-.... .IIIII . . . I I .I 1.. ...I I .I4 . .... .II. . 4 . - I. .. . L . . .1 .11. I . . WIW III. d-I— ..IA .OI .I.HII II «J4 I II. II I I0 4L I ... I..!dIIo. It. “I I“. JI . I I a . — I . 1 4 II . I. I. I . I I .MI I. fi .4 _ I I41 I 0 I - III 'I ‘III . I I I..-JIII4I I.. v . ..I.I-I . I 1I I .1. “I. I~. ‘ I .1. .I w 1.. 4| Y I.. II. II III I a .1. ..I.IJI III I I I III III -I. I ..I. .I .I III IIII III ..I.I?UII ...-.-. 4“. I IwII. .I—IH‘. ."I III..« - .III...I “II—.... I%- run. 4 I a. .II. I .I .4 I lII4.+..-I-...I4I +1 I\. ~ . . . . . k . a N . . _ .L . . . a. I III in I 1 I. I. III .. .I .vWII II I I u. IflHI.II m1; .I. I I. I. .. II1.—.I I- 1 .1- ? .. II.I.I1I4I. IIQ I II .. . .. 1 . I . .qlrh an I . -. . +7. . . . I ' I.. I - t. in” I.. o I II I prLI I“. I I I u 81 . - VF I )I . .L 1. . I ..1 It I" I -I- .I 1-" ...I... .III .I I I-“ . 1.»: I If- - ¢ . II»! -II. III.- .II.I I.. . II .LI. . I? III-4- II.- n-..-.. ..1 III. .I «Iv-4 III. ..I.II I . .. hr IF . . ... .1»! II . I . I. . ‘ 4. I ‘14 U . I -N-.-.I. ..-..1. f-.. -...I .41-.......-.-.IHI..... .. -. . .. 1| I I I. I I. IIII I .01. I4 I. s I o IIH.I I V IdIu IL I I C I I 1| . I II . ILvl I I IIHI m1 IIIWI.» III ILI I. II 5 Id” I I I I ulbIIHII . I.- . In? I v.1 1b I1 MI. III-MIA L W I I‘m. rI. - -.-... ..I.- - .. .11.-- II...I.I.I...H- ”I. .. - .24..“ -I I u.- - .IJNIID “..dIII AI—Im I.. . . .OI .. -.»71uL\.L. II. I FII nIuwl.. I.T.t .II I. “II 15.-I- .“ Id "I\I d ... .4 I TITI- III O.l‘.w. III1 L I In n . .I ITV- I ...? . II ”1 ...--.- .y IpflqI ..I. I.- ..FI I.. - I 1 1 * I 1 q- | + I I L .1 5'4.- . J ’- + '4 I .. LL”; 1 44,-?“ I. . I .I. .. d4,.-.—1.. .- I . ...-.... I 19.-.... 1 I . J 11 I 1 II b I I IIIII - III a a I .IIIMuI I I I I . .m . . o L L g I . . . . I.. ... . I I.. I I“ - 4 .. .I ..... .... . .~ . 4 .. ...4.. . I . .. .. 4.. . _ . . . 1.4I In. .I .. ...-u... . 1...! 44 J I. . . .. .-.-.. VII .4 - -. -. 4.. 24; 4...-- .m- -1- 444- 1.1..-452-441 - 4 .4.I....4.9-.-I-.....II.-....-.--.4--.I... ..I.I.-- .... - ..I- — ... *I .4 III I... J . I.M.III .‘II . u 4fiI .IoIHIIII If I. .. I..I .» w..q.\1 I IldI-IflIII?“ I I III-“I IIwII-I. .I ...I..-» T .... ., 4. .- . I4 -... .. I-.-L .. .44. .- -. II. -- h“...- .IT. 4 -1414. I. 1.4.-- . I I. .I. W...- . -.- 4 . 1 11. - ...IHIIIT; ...-.4. .. I 4.1. I ..-. I.- .. 2.1-19.1 .- .II. I.--4U- ..I . fin . - ... I .41- I u A . I L - I. . .Ir-IILIIII I 41. .17 I I “I . I» . . II. -- I o I... . Iu-«LI a II III. II . I_I . . LIII . I; I « ... IrLIII. -T.II ...- fo .I. I _ IoIIvI I ~ II . I III .16.. III ..II 4. h II T I'L- II . +4 I II . III ..I.I l. .I III Ifil. II ...\”| I 4 + v.- . I a .I. II Infa. VIII AI LIIIOI 1 I I II I 4 I I I I. 1 r .. .I’b I «II VI 1 1.1 4 . L. p 3 t1 b . .. 1%. .Iw I I. ..I In I I.“ I .II 14.-.4...- ”Iwa 11.1.1.4 4 I. I L .1 . H .. I. flu II.. ...-M”- .. I“. I I. . I In. I I .I. r1. I II - . u I T . . I I I 4 ‘ III-4 .| .I.wl4 I . I .III-.II Ina. . I T II I. - II II II . III I In .—-. 4 o . I % II I ..I I. . I ... pl 418 ‘11-‘14 II ...4 o I IA I..» m .I II! I IIIIoJ II I 1 III. .. I I L .I.hII I 0| I 1.1- 0.I IbI III. . c . I 1. I141 . . I. .I .. I L In I I H 2; n 1m“. 0 III 1. .1 I1LWO ..u .I a] V «IN I II I I“. l. I.— .I .4 . . - I I. I . I. I . I I 4|. I . II I I... 4.1T!- II III ..... . I . I -.I. . I. .- . . I - .I: I . I I- . I. I . III -- .I I.- II - .. - I .. I I I I. I - .n. I—- 4.... -4 I 1 r. I ... +714 I 1I.+- -.TILLw4-.\...I.I-‘ . .H: -1-- In... . II I 3...... I] .. I.. I -— . 0. I .II IL...II.‘| - I . I —.~' bi“ . 4. . II... I 1.. . .. . . 4 . . .. . . .. ..IM - ......4.... .J........ ...-.... T -....I%-. ....-- ..4-._..w....4.I.-.-.4-.I-I-...-..H.H.... ...-.-...fiwI ...- .14 I..-«H.443. I : I . I - I . ...I‘ .u I . . I .. I. I . I I .I . I a I ”H — I h L ,1. .7.—I '. n-trL-‘ ..:I . 2 ol I: II II I .1 A“ I I v... I 1 r—‘uT 1 .— I I -.--L. I F—-- .& O t. I ., 5..., vv L- -..- I O ..l I 1——4_.L'_ -I 'f 'I par L I 1 I I" w I I I -1 r I 1. J I I; I Q I I Hol- I I 0‘ * '6 L I I I“- 92 Legend: C.F. = Crossed polarizing filters. T.S. = Thin section. L = Light. M = Magnification of microscope and camera. "f" = Camera appature setting. T = Camera time setting. bire Birefringence. Iron Compounds and Coatings Those minerals contain Fe(II) or Fe(III) as a common ion. It is possible that Fe(II) can be in an oxidization state to Fe(III). l. Hematite (Fe293l Reagent Grade l—A F8203 (Pure) 69.7 % as 70.4 % as 69.7 % as 70.4 % as Average 70.05% as l-C Fe203 (Pure) + water Chemical iii F8203 (Pure) @ 1 Hr. - 500°C F8(III) 70.2 % as Fe(III) Fe(III) 71.0 % as Fe(III) Fe(III) 70.6 % as Fe(III) Fe(III) Fe(III) Average 70.60% as Fe(III) 1:2. Fe203 (Pure) + water @ 1 Hr. - 500°C 93 Figure 21 - Calcite l-A-I. CaCO (Pure), Index 011 -1.55, m -3240 x. l-A-I Photo--l-A-I Description: Focus calcite crystal in E-ray position: 1 - 5.0; "f" - 5.6; T - 60; M - 240x. T.S. - perfect Rhomb colorless crystal. C.F. - shows slight blue and orange bire due to crystal thickness. ‘5 95 Figure 22 - Calcite l-A-II. CaCO (Pure), Index Oil -1.55, m - 340x. l-A-II Photo--l-A-II Description: (See Description l-A-l). This photograph illustrated the effect of crystal index identification using the Becke Line Method. Oil - 1.55; Ne = 1.486. The microscope barrel is raised and in that the oil is higher than the Ne. The Becke Line moves out into the higher oil--the crystal appears to enlarge. 97 Figure 23 - Calcite l-A—III. CaCO (Pure), Index Oil - 1.55, M 2 Ox. l-A-III Photo--l-A-III Description: Rotation of 90° of crystal in Figure 21 and 22 focus of crystal to observe O-ray. Notice crystal appears darker at edges. L = 5.0; "f" - 2.8; T - 250; M = 240x. 99 Figure 24 - Calcite l-A-IV. CaCO3 (Pure), Index Oil - 1.55, M - 240x. TV__..- l—A-IV Photo--l-A-IV Description: (See Description 1—A-III). Oil is 1.55 and * Nw - 1.658. The Becke Line Method shows that the lines move in toward the crysta1--the crystal edge actually darkens. This indi- cated the O-ray is larger than the oil index. it " \ 101 Figure 25 - Calcite l-A-V. CaCO3 (Pure), Index Oil - 1.55, M - 240x. 1-A-V Photo--1-A-V Description: *See Description l-A-III). The Half or Oblique Method is employed. Oil is 1.55 and O-ray 1.658. Darkening one-half of the light source the crystal shows dark toward the dark and light toward the light. The illustration that the crystal index is higher than oil. 103 Figure 26 - Protective Coating l-B-I. Laboratory Formation Index Oil - 1.55, M — 240x. l—B-I Photo--l-B-I Description: Focus on Rhomb crystal that has the appearance of Calcite. The entire sample appeared as Calcite except that the individual crystals were Smaller and some nonopaque material was present. This position allows observation of the O-ray, No - 1.658 with; L=5; "f" - 2.8; T - 250; M - 240x; index Oil - 1.55. T.S. - small perfect Rhomb that are colorless, with some blue and orange appearing. However, some massing of crystal structure to form vitreous mass. C.F. — black is black with bire colors from the large masses. 105 Figure 27 - Protective Coating 1—B-II. Laboratory Formation Index Oil - 1.55, M - 240x. 1-B-II Photo--1-B-II Description: (See Description l-B-I). The illustration here is that in observing the O-ray the Becke Line Method is used. Notice the black riSes on the crystal when the microscope barrel is raised. Also, observe the "light" Spot in the center of the crystal--this phenomena occurs sometimes in conjunction with a Becke Line illustrating that the crystal fragment is higher than the oil index. '1 I'l‘lIlf“!j‘ll’1:|ll"lillilll‘ll‘{111[ 107 67.0% as Fe(III) 70.0 % as Fe(III) 66.0% as Fe(III) 71.5 % as Fe(III) 66.0% as Fe(III) 71.6 % as Fe(III) *Average 66.6% as Fe(III) Average 71.03% as Fe(III) 2. Magnetite (FeO.Fe7O3) or 53394 or Fe (Fe294: 2-A 2-B FeO.Fe203 FeO.Fe203 1 Hr. - 500°C 73.6 % as Fe (total) 72.0 % as Fe (total 72.3 % as Fe (total) 71.84% as Fe (total 70.2 % as Fe (total) 70.54% as Fe (total) Average 72.03% as Fe (total Average 71.46% as Fe (total 3. Siderite or Ferrous Carbonate- FeCO3 (formationgfrom mIXIng Ferrous Sulfate and Sodium Carbonate) 3-A 3-B FeCO3 (Formation) FeCO3 (Formation) 1 Hr. - 500°C 52.5 % as Fe (total) 61.8% as Fe (total) 55.5 % as Fe (total) 62.4% as Fe (total) 56.2 % as Fe (total) 61.5% as Fe (total) 55.7 % as Fe (total) 63.0% as Fe (total) 53.5 % as Fe (total) 61.7% as Fe (total) 54.2 % as Fe (total) 61.1% as Fe (total) 52.2 % as Fe (total) 60.3% as Fe (total) Average 54.25% as Fe (total) Average 61.7% as Fe (total) * The sample had a moisture content of 5.33% as water. The water was added to the sample then filtered through .45 micron filter paper and disiccated before testing. 108 4. Corrosion Sample-Pipe Nipple; The sample was removed from the nipple in layers--top to bottom and will be discussed in that sequence. 4-A 4-B tOp bottom 63.0% as Fe (total) 57.0% as Fe (total) 64.0% as Fe (total) 59.5% as Fe (total) 65.0% as Fe (total) 57.0% as Fe (total) 64.0% as Fe (total) 59.5% as Fe (total) 65.2% as Fe (total) 58.8% as Fe (total) 59.5% as Fe (total) Average 64.2% as Fe (total) Average 58.2% as Fe (total) 4—C 4-D top bottom @ 1 Hr. - 500°C 1 Hr. - 500° C 67.0% as Fe (total 60.0% as Fe (total) 67.0% as Fe (total) 60.5% as Fe (total) 66.2% as Fe (total) 59.8% as Fe (total) Average 66.7% as Fe (total Average 60.1% as Fe (total X-ray l. Hematite (Fe223l Reagent Grade l—A (See Figure 28) l-B (See Figure 29) F8203 F8203 (Pure) (Pure) @ 1 Hr. - 500°C l-C (See Figure 30) 1-D (See Figure 31) Fe203 Fe203 (Pure) (Pure) plus nHZO plus nH?O @ 1 Hr. - 500°C 109 NH.N couH Hm.vm om.m couH Hm.mv o.mN o.Hh o.ooa b.nm mummmmowz uoz wb.m wH.m nm.m Hw.v couH couH couH couH mo.av w.mm vm.mm mm.vm .Amusmv 0 mm muwmcmch w «to oopomnuou «-6 O cofiumflemm om mm musmflm a; 4.. (is... g 4...: 8. an; . «..:: .0: 2.5.0 . «3 (ital—1...! *1: I. 5 .8103 ..I- 580 . 4 _ . J . L I ‘IlrllI' IJI . .~ 4 n19 . |I . I . I IILIII.I|.I.I9.9IH.IIILI‘4III.I. hIIIIIII999I.II9 IILIII 9' . . I‘M“. . I. . «I....IMIJI (fr . l .l... H .11 "Ir II.. .911. . ‘4“ 3.44.. LI I. III—.1915». I0 J1. .9 .II . I. . I . .. I . . fi . .94. rII +4: I I..: L OICIOIOLIEIHI ILIII J I II . n I. .9 III . 9 II AIL I c . I, 4| . I. .l.. .III..I.eI 4 I n 4 I .dl».a.4un rIla...ILI04.IvI9 .IOIII...I Ill.» 1 I ..IRI4L 44. Tulor .9919. l o 4 ... .. I a IIIV In . I u- III .. ... I . 91.4.4.4I TILINLM.IIII.J.0I»LL9IIIHJJ. . I | ...: n 1 .. . u - . I > L > 4 .-.... -. .I ..--I .I ...II.-.I¢T . . Jr... LI 9...... . I..-.. I.. .. ..I . .I n .I ... III..” L . I. ..- n... ... v ...m... .III I . I mI I. .. .I IN... I -|.I.- HI...» ...-I...1I. -. -.I ..I-I I. .I..I4 .. . . I. .I . . 1-... . .. .5. I 4'- ”'7"??? _. . . ..I . , . . .419 1 . 4 "4.414“. #7... .+..I..II4 .4wI -.:. .1J43: I. Nigel?“ 2.1.1 ..uT1II....I1 I I..-5...... I....LI.‘ I.I.. III . . . I... . .n .. . . . A I. w .A. I.9 -.IL‘IV u Ilr. _ I IrIlIl I- .II IILII. I-.- I. 9I . . .. u. . . ..”I H I. . 9w . ..... ......IA . ...... . . . u .o I v. IIJ.I4I. 11 Jib — . . II IIIIo.. .. 4|. 0 L. .. II . . ...v ... _ I.II4.v I..: A III AI.HII‘JII ....I . .I 9 It“; .0 9.4 .?.I.m ‘II.I ...I.- N -A.4v ... IDII‘ ... I w .. ... I u L; 4 ..-». . . -.., J4 .. .......I....._ 4....-.4 9-71.... -.-..- 44...-..1IM 1.4.... I? . .....- . ......D I...-- p“ .. 4‘... o . 4 Jwtt. _. I”. I" II. I .m. H; . ..“H. . . 4. 4 . .. .Ih . I .. . . .. I... . .I .. .'.v c. I ht »1 I..... I I.. III . . .n I. .4. l. . I.. u..» .. ...4 . .Ik..4 \l. IOIIIH. b I I u . o I l“ u I o. o 4 . 4 - . . I I.....,_....II..I:II. . III, I. -..- - . .. ...; . ...... ...... .... . .... 4.. I ... ... 4 -...II. .. .. . . . ._ . .4 4 . ... 4 .4. 4. , ,. . . I .I I. 4 ..I. . u. . h . I ‘I ...“ p I . .L’ . 1 &1 L I]. <.Hr W n VIII-9. B L .. ...‘I I1! II 4. .1.|Infi . . .—. .7 .*.. .... -. ._ . . I . - .. I -... ...-.. 4I... ..-.r .. .. .. -.. ..:. ; _-_..-;-... o I . . I I. 4 . . .. . P n. 4* . .4 . I... r! I . llulal IllIIOIIII9II I .‘IIIII uLIIII'LII I 9L|9 r9 99.9 I l IL.9.| I09 I9 I IIII.I 9’. 4 I I "I . . I . 9.... . . . . ... . n _ .I I 4 A. I .H 4- ._ .4I . .4 I4. 4. “ ... I I . . . I .I i. . . m .I .u I . .3. H . " ‘IIFI. nu . — 4M .. .4. .II— . 4w. I. .. . I“ . .- -.. I. .lIIIcoIIIIIIIIII. . 2 I.. 4 . . I _ .-.... .- .... 4...-.- ._ 41L. 4.. .I. ... . .4 I4 4.. 4. . 4.. .4 .... fl...II...F .1 $I4114! .w c h I ... . I . .v ..n 94 4 .. 4 H II . . . _ ... ....u ...II. I“). I .IO..II.L 4.I.I . . . I . . . . .. i .w I . l . I. J I» . .9 I. .. ... IIIWI lihlIwhl .IPII I. 9' LI II9 .III I I.I I.94I'II I I | I IL I. III M .II II II.LI III .. .4. IJII..HHI9JI .III I . I.I.I9.I. . PAH.” .a—u ”IIWI. "..II I I a ”.WLI ”LII” 41.”. .P... . s . 1 I . . 4.? 4 IL.... .4 I. 4.. . 4. I . . .. . H tarp . h ..I r. ..1 Ian»- ..IAI. .IL slbL . I .u ..IF. . . .. . .. 4 ..9 .I I4 4..... ......II —._. .4... . .4... H. 4.._H4P.». -.4..4~r IL.LT4~. I n . a . M ... m . ml .L.. .I b I ... . . .I .44. ...»I. . I p . . . J 1'» .x b. . I. It. I .. . 4.. h I . I r . .I o II II». ..I I. IPI [..III a PI 1.1 4 IIIIIIIIIIOTIIIIIIJIIIIIJIII. - .. .... .- .411; . 4.. . n 4. . I4. --- .4 --MTI..fiI_II_.-.-.U. JHI- ...?FF 1 4.2... . 1...... I... _ \J .. . . ... . . T.. .-. - ... .. 4.... i l . .....Z I .141 .....L .4. . . .117.-. ......1... -l....LIZII _- . r . _ . n. z u .....-M; c....... r._. __ .:. _.. . z 4... p...t-un.dt.u.xuq.rn r... ;_;.I...... .. ..l ..»H .v . . l .. ;r.z.- .12: :._IL.II4 h; .ugt -J; -... _ .I ..t ...... I. ..II w..I. ;-..w«é “Ll....lll..IIII I III IT- II I- LI .L. '93. ..I-Iqu L TI I 91+J III I .. IILITIIIIIIJIHJ; 1.9...rl. II . 4| . 4 4. _44 .. . ...a. . 4 .II. I J LII. I 4. IL I 7. III. w.‘ I. — .....H". q. . ... {AI J ..I.. .-r . r.— ..4 .r. ... .‘.:¢ . . . T .44 ..4. .4 i 4%... . .. .... . _ .4 ._ .4 .. .4 ....4... 4 4 . . L. .. Tr -.....r.II". .444 -14... I..4I.LIH.. Hi: .14.... . _. u .u I — oo . u _ . u 4 L .. ..1. . . .I . I .. . . I. - _ h . . I _ 4 VII." .... .Iil. ...II I I I. I II — ~ .. .4 . I .. v — I. I I .I o l I r I. I .14IO . 4 \ .fi 1- 4 w . . . .. _ .. IL. ...4...u4. . I -4 H4. . 4 4. . I .I. y I 4 ..-”..4.9I H..:... 4-..“) . I.I . I. .lthLIr. )4. ..J. .. I u m J. . . I a I . -lnslIIIIIIITIIIIIJII I. .III. |I. LII.I4. _ . 4 4.. u .I 4.99 . IrI.I..I. .l.. . 1 II ..I. .4... . 1.4 - I..W1.I .4 ..4.. I1. 4.-. 3.4.4.4-. .. 474.4,”..I 1.-..-. I—“ 44.9.4 ..v _ In! . . . .4 . . . ..r. 4 .. 4 ... .Iu. .. . 4. . . .. . .. -4. .. I _I o. 7-4.-. . .rwj *4D-I.¢.. ..u..I.J : _. . .4 .. .. . . . .. . . ... .~ ... I .. .. .1 4 . . . 4.. ..... . I o- .III..rI ...... . L” d... 4 .. . I4. . .‘ . _ . . .. _ .4 . .. . . . . . II . 7&9 II. _ . I..- FIII. p. . ..... .9 1.4+.v.-+.IJ.TIH IuIII . . «W. ..:). . o s I .. . . . .5 u 4 -. h. _|.4. .. . ._ ..... . I..» I 4 .. .w....... ...u o J.. . .o II_IIIIIJI|¢.IPII..4IIIIrI.I )J )r.. I .>l 4W4? WAI- . . .‘ m1] . .. I 999. «I. . .III I9 .I . . .9III9 I'll.’ .T b . 1w In » II In . ..I $ 4 . “ll 9.91lul9l. .I . IL. ..I . ... In . .I.“ t . II. . .uJ.‘ .A I.. IJI.II I..II¢I4 1 99I9I..IIII.I>I.II.II.W. ||.6v|“9Vl.IIII It'dkg—lard é.” . I 4 “n-0I. . .~ . .H . .... . 4 '.L . 5.. .4 . .. .a . . .... .M.Ia—4I— In. . I I pr. . .. . .l.. ~I4Y 4. 14. w c. u 4+44IH1 _ J. .414"4.1+.990| . In”! LIBIIH49..AI .. .. II‘ .... . .. . .... ... . . .m ..h . . _ A . .. . .uv... T... .I..I..4..... . . 4 .... 4. . 4+.)JH \ .a ....LI .a. H ...... .l..: -oII.. 1...... ..444. ....m.n.h.._.JvI. . .11-». . .41T I..4.. .« INHIQ. a...I.I«II.I_ ..I.I. - . .b (“4 I- . I W .9” . . I..-”Jab“ ‘oluo. . .... .I.. 1“ .Un 4.. v“ ..I.. . ._ u “.l....HA .II4II .. . ... . .\ an .4 .. . .. .mw...n31” . .. .w I..nv-+I4J. ....l. I.. “4“ I III - In 9.1 ...UIH Pqp. .Mla . __ ... .I .I. ..nmadflAG .... .. W . . . . . . . . . . . . {p u . . ---- .- -I IL- I.- -I J I....-QN. I -.IJIdI. . - . . . T . In... . . 4 4 ...... ._ ... ..-IIh LIL .-M I lll NH.N COHH Hm.vm om.m couH Ho.mv o.mm o.Hh o.ooa h.hm mummmmomz uoz mh.m va.m hm.m Hw.¢ COHH couH COHH couH mo.Hv m.mm vm.mm mm.vm m m .Uooom I .Hm H ® 4mnsm4 0 mm muflmcwucH w 4I© meomuuou ¢IU O coflumflwmm om am mnsmflm 2 l l iLiL! ...‘ol...>‘ ”I. 113 HH.N COHH mm.vm mm.m COHH 0.0m o.mN N.vh 0.00H w.mm anammmomz uoz vh.m no.m vm.m mm.w GOHH COHH COHH couH ov.Hv oh.mm on.mm mw.vm N m N .0 ma msam Amusmv 0 mm muflmcmucH w MIG Umuomuuou <1U 0 coaumflwmm om om wusmflm ‘i ii i" . I." ..I.I il.’ll'||". ..- . 4-3.1. - .l.. . x . .113: ....»i :1 ...I- I. 1 -l 2| 1 . ..A . u ‘ v a .’F u > ,. . w. .. .5. H11 u . I]. 4‘ n .u ..L ., g a . L . . . h I-- nlJu!‘ I 'I. IIJII: nllnllll -.I.I. .l. . .I :Illll’llsu II‘ II III. II: I'll qt 1: I ‘II “T L . 'fll III...|..|.I..|.. . . .5 n. s O 5 “III 1 -..IIIDI l4- lllllra.°lll.l . I Y. J . .o . s . I . 9 .. .. b . 3 I'll! a . _ . _ . _ . _ m .. E Ilsa!!! i i _ {I -.l . _ . w _ , I I ---: 14.1.14! [-.: --.».-. ; In Ir- i- - i . u * . .. , ~ . . . » .uil I.....Illulv'lt- .lilu_l .l.. I . . ‘ a. . ... . LI u, . ._ . ‘ _ . ééllwljllur--.‘ 2.8 ..... .l..! in- F . M “ I'll L. . . . .. . . . . u ‘ . ., HELEN, $43.2 . ,7 n . _ . . . ‘ . . . ‘I .l.. I III -II‘I\ ill] ll||1-|u‘|h|nl|u . -, ll... Illnl I E II. .I I I I ll II -II III u;|-]|n|| IIIII . p L O I»: I Ill 1 . . ... . . 04.9. .Mo a 1. . fl .. . . . _ U . V ; a, n . - . . V ... ” _ . . . .. 'J'l'tl uguli‘lllonllug allillcllullllllglllllllnllln IIII'QIIIIIIIII. iillll ..:III. _ ”Fl 4. + ,' I? 1|. . .. . . . . . . ...- .. . _ . . . . . . . H . .. . . _ m . . . ,. . . ¢ . . . _ . ; ‘ .. _ _ .I‘IIIIII'... L. in? II. .I . . Lb? . .: Ill-II. ‘. . .. h . . , . n . n ' . . . M . . . . g u o . m _. . . 1| .. 0 II I . II. nlv || l ln|l|m| Int I II" .III ' -l! ‘tl I III. II .I II 1 ' II I» l. l| III. 0. . 1|..1Ilu II I. . 1|". 'l' | ‘Il . I III I l I." In I u . ‘ 4 . . . o . H o .. 8- . .. . DI . “L H 9.. . . lllllll'lll' 'l’ I: l‘Il I‘llin 5" '4 L 4” IA } Ill" - . “ luv \pl. Ill“! tll-‘ m a ..I . fl . . u . — . h . . . l . . .. . . . n n ._ - - .. - x n .. x In I I x I x - .. I“! I -l..: Illllai-ll..-l. -l-.]LIu:--.. : I1 l!::|..-.--.l ll I.....I- . _ . :P r by Lt a an ”jib..- l 115 m.m¢ m.vv H.mN n.mm o.ooa m.Hq anammmowz uoz HH.N mN.N mn.N ma.m mm.m om.v couH conH couH couH couH couH m.vm w.mv om.Hv o.mm mm.mm m.vN . . N m m N oooom I mm H w o m: mnH Amusmv 0 mm muflwcmucH w MIG Uwuowunov «.w 0 soapmflomm ®N Hm musmflm 116 9.310-; .. ii ...-..I.I. .l..-0.": infill-I A . J .. - a I 4 . .II AI . I. m J 4 - J 4| J u . 1 I «I. .1 IIIJ . .. a ..q AJ « _I a. . _ . . . . ( w H. . _ a H a . ,. . . w . _ n _ 0N. h . _ H . . QW _ _ . _ . ’ p I I I ~ ’I. . I >1 . r II. #_ I I III ’ I» I. .4 I . ...- III I... .... .m M . . . . .I. . .I. ..I. ... . I. . ... . -. I. .J. I .III. III-".- ..I" .... I. - . IM..u.IH .. h . ... _ .. . .. “ I.-.. .. H ...; . .I.“ .H.. .. I ....H.. . ..hH.-I.u..--..: .. -.. m .-.... .. .. . .... .. . a o I. .I .l.. I . n . w. I. Iw . 0.. _ «HI Iml . I; . . . v. . I .. « L I . ... “I . .g . .c . — u u III I I III II..I- I. I H. I. . H ..I I...I..I. I . I...- I +I.«II n it ..LII..+I.. . M I III I .. ..... I. .. I. ..I .. . . : ..III...-..I.II.._I.I.I.II..I.II+IIII- I ..:.I!-..IIII.Im-I ..III I..-”.IIIIII .II III 0 I‘. I. v ll. I n .It. I . u I“ .‘II .IW I”. I. . .. I h . g. a. . u I ... .. I I n l I . ... ...! .....t. 0. 0| CI . l D I..-I I a. I. II . II "I. o I ”I L-II - I w. . ...I . .. I . .JI . ..I .. . . I. . .I .II.. . I. I. . .1 . I . . . .I . ..I.-I-. HII I . I w J m .. .. I H -- I..“.IIII~ . k .\ I, I.. 4 . . ..IIpI . “..I. ..- .. . . .. . - .- .bp .. I. HIII. ..I I _ I ..I. J— .I 7.4 J ..I-II... _ A. I411 .1. u I . m I . I“. J I.. ..I . .. .I . .-.: .. - . ...... , . . I . .. . I . . I” 4. I . .II.... II“ .I I f. ..I.I-.LL .. .. m .- - .. I. . .- , “I... I _ I F I . .- . I _ n I . h VIII-..I I. I III. r .. . a ,. J .l.l.lJ;II! I I..-II .-....III I..II- II..II.IIWI. III-.II I... .. I. II I I I I. II... IIJIIILIIIJUIIIIJIII. II III-III I IIII'A 0 I .- ul . _ -.. n. .. I. . on .I v, . I . ”In LEI-.... r . 2;}... ... w _ . . .... w _ . .- I* I . I 69 _ III . . lfi . I ......II.. ,2. . - ZI _ .. .. . - ..-..2. . 2. ...I I é. . . o . ~ . . . o ..I... - -I; I: ..I..- r.-- .... . o . . 1|: mIJuI b ~ . ~ .y. . . .I . Infil... h . a ”‘1. I s I.-- ... . - .... I . n, -- i..- -- . I I. f. I, 18 II .. m . . III-0°! J. I I» OI . o 1,.._.. d: L .... {I L. .5 \ I .. . o I. I .. ... . . .9“ o . .I. .I .717 II U... . I . I . . . I... I .. .... .. .. .. ......IIH. .. .. . w -.m .3 . . . . . . l J I- II .IIIIIII-Il..lI.II II II I. III .II. lL.IIIII..IIIIr _ IIqIIIIII. ..IIIIII III. IIIII.-IIIIII.I.I III I.II|I. .I -Vwa-IT I. . .. .... ._ . I d.4 I II . II --a-3-.v. . I.. dpfi puol I I ’1" II. I I I’- [534? 1’- I I I J, “:1"; .I...--.I+I.4 m MU ..Iranvwm. .U..d*I_. APCMT . u .I . _ . *1 . . _ .- 4.-. L.I .-I I . .. . .I-... IH.I..I.III I1-.I...--.I..|I. I...-..I.I ...I.III-....I... I . .. .. . . .- . ”WWII-...? -.. .-.. ... “10.. wry-fig I... 4- ...-.. ....H... H. .. .. . .Iw . . . a . r . . . OII'IIIT IWIIIIII lllllllll I|1r|I I I IIIIIPIIIIIII l 0 fl . H a I. .. — H0 a u II* I. III .I . _ - . _ I . .I I . I. I I . I “I . I._.. I... . . ... . I “..I“. LI.“ .L I I . d -I..~ ...-I I l I I 1 D. .IVI _ “I L . .L. *4. Fl J I . . i .. . .. m. . .. I 4* .I I ._ . I Y I. . II. a . I II I . . o _ I I . I .. I. 1 . ...II_ ...... .Ifl _. I. *h .- I . I. -w I. .. .L. . .nI... I. . u . , . I . .. .I . . D. II III . ..I. I . - II - g .. .II I...-.+. ... . w... . .. n .... I I. ...... a .r I . .u. ..I L I .. .I r ILl I II J — L1} 4 . L '4‘ A III. II. .II., .I. . “I. t I s w I. o I.. ~ . .a. I II I . .I- II a I I I. I .I.+II ¢ . . ~ .. II I l I. . .I ».I. I I .a — III - .I I1 I. I I .IIJI.+I H - I . . I . I I I . . . r I .u n l I. I I s I I! . II I . 9’ I II I r .pgnlfl .. . H L _ — r H 5;. _r .. LP . F . h m g! h .. K 1‘ 1‘ I‘IJI 1‘ 117 Magnetite (FeO. Fe293) or Fqud or Fe(FeZQ4L 2-A (See Figure 32) 2-B (See Figure 33) FeO. Fe203 or Fe3O4 FeO. Fe203 or Fe3O4 @ 1 Hr. - 500°C Siderite or Ferrous Carbonate- FeCO3 (formation from mixing Ferrous Sulfate and Sodium Carbonate) 3-A-I (See Figure 34) _ 3-B-I (See Figure 37) FeCO3 (Formation FeCO3 (Formation) at 1 Hr. - 500°C 3-A-II (See Figure 35) 3-B-II (See Figure 38) FeCO3 (Formation) FeCO3 (Formation) at 1 Hr. - 500°C 3-A-III (See Figure 36) 3—B-III (See Figure fin _ o FeCO3 1 Hr. 500 C Corrosion Sample-Pipe Nipple; The sample was removed from the nipple in layers--top to bottom and will be discussed in that manner. 2:5 (See Figure 40) 3:33; (See Figure 41) Corrosion Sample - Top Corrosion Sample - Bottom 4-C (See Figure 42) 4-D (See Figure 43) Corrosion Sample - Top Corrosion Sample - Bottom @ 1 Hr. - 500°C @ 1 Hr. - 500°C 118 .OOH ¢.Nm o.mm mummmmomz uoz mw.m 0H.m mH.m couH :OMH :OHH .vOmmh HO mONmm .me v . "V mwflmcmucH L d mIm U Umuommuou «IS 0 coflumflcmm mm mm musmfim 1LL9 3...: ‘§?...;I I. :31': 53--T; Ii ii, .Ig'l. . 111I_ i 1)1. I I 11.1 .- _ u 1 I .. _ .. . _ 1.. .- .. . I _ .I: J I. J. .4” .4 ..11. . . . . . . . . u . . .. 1 . H . . . u I . _.. ..ow . _. In .... ...om ..: . om. . . 0Q.” .. H . h . .0 ..N I. . . . m” 0 ... m . q . . u c . u . a . . . . u . . . I . . . . I . .I—. b. k bl . . 4 6 _ . L. I III 0 r . I1. 00 I J. ‘.I.V1q1- .14 I I I I|WIIun -. . I I .. . .... ._ .J .- I”; I......... .I.- . . ..u...III.h..III..II.-...I... -... . L .. ..I..... _ U . . I " t I I I . l u 'I II- I I . II . g . ... I . I.-,f I I II I . . IIII| .J I. s .I . . I. J — .. u o. I . .I -.I ..I . ._ - . u. .11.. . .... . ..I .. 9.1 -I-.. .. .-.. ... .. I ...... M. K1... J . I J .IIIII. II 1|.III I—1. . I. .ioil .- I'IIILIII I . I. 1.11 . I I I u d a I. .II.1J. II . I . III. .I II J . I.‘ I I I I I. d o I. U I .411 I.l| I '3, I. II.II~II II I . I. I ”J I I ILI IF] I II I. — . I* ~ I. o I L I .II . I... .II.. I.- IAIN-I“..- _. -II.--. .I. -. ..:..I. ._ L. I. . . ... .111. II ..-...II. . .I..--...... I “..I; . . H . .I .- I... .. .I l . II .. .. I.. ..I .. . u .L .I. I m- I .I -I... I” .II..|I .-.IIIIMIJ. .u. ._ I. I.....I -I... .I.-..I-.-I...I.I.I. .-. 1.. I ..II .I.II ..I ’n. I. I. wI . I .I, I . I. 4 II I. .. I’HanIb . . 1.... I I“ .10 I . II» . I II 1 . . .. 1 ‘1I .1 ...1 . .. . 1 I ... I..... . .1 ..I- . ILII.N.IIII. I . . .I.- -...- H. I I. I. ..I” -I.. . —. Jo.-. In In. ..H .... - --.. . .- .... -. ..- .I . ..I.. I. . -..-.1 .I .. - II IL ...- .II.-Iii“ I .II- I. ..I.-”-..- .II. .I II . ”I. II ..., ...v... I. II I IIL-Iw. . ...q.....-o..II. .III w. .l........IHIHWIIMIIILIIIIII-I. “HUM-III..-I ... r. ILr. 1.4 .III .I II. .- h . I.. .....I. a u .I.- III. 1 w . . ... . .I ..H . .Ir 1 L1. . I I _ I I a II. . . 3. 11.1.1. 14111 -l..|..” 4.. . J - . J. ,u 1.41. I 4 - I . I..-- I.. 17 I . .. .. ...II .L I... ..I. I..-..I“ ... .-I - I... U. . .. . ...: .. ..:... ... . . .I-.-“ w: U_- - ...” ......F........t..;....... .. .. I I . I . M . I... .. . . I . . .. .r . I III .I II. . . ...l ... II II. I I I1”. . I I I I.. .1! ”-.I. .. 2:14 I I - I I. h. n I VIII u. ..I“. _, W ... I.. I #. . . .. $02.3. .I. -. i. .. «L1... I.” I :I, . I 11 -I. I H ..... . Ion .. .. ... : - .- I.. - . - I ..-.I I-.. I; -I.-.-I- . I ... .. “I. ...... I... .-I... .... ,. ..- . I . . .. n . .. I.. .... . .I ..I.. u I. -I. . I........M.. .....- _ .. I H II I . I . .. . n I ... ..m..II wI I..... .III ..I I I4 I 1.. a I»..- .I.... 0.? .wIIII. ..mJLIIII ..I . . .. I» a $1.114.II1 4 1 . A . I 11111 .4 ...-..- 3. .I .....I I. . . .I A. ...........“II._I...I.4..I....H_. -I...-...... ..I. -.U ...“ .... ..-..LI I... -.., ...-IR 111 m. 1. ... . ..I. . . .. .. . ..I. .- “. ... -IIrIIII ”I ..I.I.-- .. ..I.I I a . I . . u I .II.. ..I..... I I I III .:I. I .I... II. IuI. . ..I. u . u U .L 1 JI 111.4 'T" .13 NA) .. .I .1 .. 21 I II‘ fl . . . I. . . . I - u - I .I . I ..... I I“! .I I .IIII .. . I! I . ..I I .. I . -. I. . .1 3 1 . L I; I I 1. m 1. .I I00. .. ... .II.... M . H .II.. .. . n .. 1 II .I I . Iv .0 I“ . I . .I H I K I. .M “.1 . II .... . Ir. . I. . IV“... a . ll 4 1mq.1 ...I .I‘III I.. I .1.- .I.. .. I . . .I ... II . a . ..I I I..- .u I . . . .. . . .- I I. . . . I .. . 1 II. 1 . m . -. . .II. In 1 H .. I .111 1-.I-..I..I1I1. 11.211 .III.I..II.I I- 1|11.+-IIL1II...I.1 . P .1 I. . T ._I_1 11L. I LII . II 11 -.I1 . . 1I M IIIII .I III..I.I .1 -.III1I I..... . I . I 4, I1. I I I I I I . «I I.. I . In . IAJ. ” A . .u.. I. .. .. ...-..I . “I! a . n I .— .. ~ um u . I v... I I. I 4 .1. I. . . ._ ... I w”. I . . . I... .. .H. n. l. I... . . I-II I. .H .I.~ I . .II I I I. I. . I II I . . II . I .— . I II . _ —I . I I I a .II- * I IN... I I I I . . I u . u l .. I I .. . I- . . . . I . . . I. . I .. I . I .I I . . .. . . I .3. . I. .. .. I III . L . U DD I II . 1. m 1 — I.. I. . .. I . I. .N 1.1!. .I...--.IIIWw — I.... ..um. . .. ...a . m . I. I.1 _ ..I. a . — . . H .. .q I. ..I I .I...”... ".I..- .... . I . . . I I . ”I . I . .. . _ . .. . . I. . I1 I. . . .II I .. u I a I . a — _ . .. T I. . . .. . . .II. .I .11. 14.. M II I . II ”I. II.I.L .- .. u I . . I ..I .. I 1.1 .. .I u . I - _ I - I I. . . ..I . . ..1. . I. .. J. I n — 4 1r D I . h AIIfi. III IIhIII 1 -.I I u'! I I II I Illl‘1 III II'II |I If l1lhll II I'll I lllilll'l I‘ll.-- I. .III Y'l'll II- -I‘ '9' I‘I‘ IIIII.:I"- I. u I I n" (I I III ~ I 1l1 I I I ; Ill I a I c I I o. T . s . ol I. I ”I I . 1 7 ~ II.|I. I- I _. 1 n .I . III. | .. I. I. II . .MI . -. I. . I . I. I IHII I I [m .w c. . - I I ..v. I“ I m — ' I ‘ t u u n u . .& m 4 I I I I I . I.I. . .III. I ..I 4 I .II* . o. u I n ..L I II II”: .1-21 .IL I I. . I I I I L w. . . . . . . . I I . . . . .. . . I .. I.. I . . . ._I I. . I . . In HI. . I ..--I. I m II“ . I I I. _ I _ In I I I. #4. ” ~ . In H u I . . . :1» . I .q 1 :1 I. I .I1. . . I 11. . .. . . I. .‘I1 4.! m. I I . .II r~ .I. I . I I— . I.. a I u .T . I v .o _ . . u mfl . . I . I r. . II. I I ..I&, .II I ..I.. .III I . a m I . n I . . . .. ... I . . II. a. _ _ . . . .I . I I 1I 1 11 u I II. III . n . . . ... . . ,k. ... . . ... 1.. I. . I I . I . . I . ... II II . 9 II I I I . . I.. _. I . . I . I. I I I .I . . “.III I . .I I . . I . . . 111... IIII1II .IIII 1_II1II..I1.I1I 1.1 I.. I1II.1 . 1.1.11... 114:1..1 . . I. I. L.1- 11.. I IIIIHIIIIJI. 11....I .1I-II...I-:.II.-II.1.II. I- I1- . - I. . . ... I..I. .... .I.... t... I”: . .. I. . I.. m. . ... . .. I . u . . . . . I” .. . . . I . . .1 ... . on. . I ..... c . I . z i I NM . In, I .I .- _ I —I ...-I q I I b. . 1.— I c. ..I. N . ..III . I I.. I I! I . Id . I I u - 8 .III. I . 1 1 n a m . 4 . u. H I .II.11 .w I ..I I II II I I n I 11 I u . n I w . n . . .:. ...I-.II. . . . I . . ... . -....r. .. H. I .-. ._ .. .. . . n I .. . I . . r . I. u. n . ~ ” # a. . . . ..I . I—u. . II. 9” .I m . . I H I 11 I o . . I .I I . _ . ..I . I.. II . .I II? I . I . . I I.. tl‘l 0. PI). Il‘LlIla'i'Iol I II‘.II1|I‘. . I I'JI"III‘I‘II,I II I!“ I..! -I ‘I'll|'|'|l"l...ll’ II'C. I . J I! I q I I I. . OJMIWO 1.“. "..I-III -. - . . I. ... . Im- . i. .I z .n I . _o I I”..I .. ._ ,. . ..r f . : . .. . . fl . . .. --..-- I _ ..I m . ..., . .... ...- n. __ n. . . ... . . I I . I .... I II I . h I . u. u . . II I .I I I'- h . I . _ . . I I. B I I? 1 . . - . .1 L F I11 LP. I.. v w . 11 . 1. I 1 .AH . 111'! 1 .. . Gil. 4.. u I I I .I I I ..I . . . .. II N\ I . . I I I - . H. I q . .. . I .l .. _ I . . I I I I... . . I_ 4..! a . o .m .. v. ..I... . I .—.. I II . I. IIIIII n. . . .. . . .. . . l . . . .. I- . . ._ . I. f ..... .. T n. I..- ..I. T .31....“ . Il- . I . i. ..I . I .- J I I . I . . I. I r I p O a I l 1" '.l 'i'i- .- II | ..I ‘l- I «I II'I I III. III I'll! I1- IQ‘|'I|I l'l" IIII'lr‘I‘I 1 I' II ‘I'I‘ - ‘I-rl ’In" III'II-II'II |-|-IIII.I "I Cll 0': “I’ll ‘ . I. III--III.' I.'I.II I -.Al'- - I. I.’ III-Jkl'UII lo I'. A . l I u I . I w... I O — I I .‘ I N . . . . . . H . h .I II . .. . . a . . . .l. L. I— u u . I . . . I.. . I u H . I- a ..uvI I w m I I.. u . .. . . I _ H .. . H . . . .. “ ... a . . . . .p. . » .nI. I. [1.1. ILIII I III!- I. I .1 ..I I . r IE» .. I _ F T E I1.1.I II 1. 120 mm.H QOHH mo.mo omIH couH «o.Hm mm.H couH m.mm mINh mo.m couH H.5m m.mh hummmmomz uoz mm.m couH v.mv .Uooom o.ooa o.Hn 9.9m mm.m mo.m mH.m conH COHH COHH o~.NI om.mm Im.mm .um H 9 I0mm... no m mm.m couH m.mm onm .omm muflmamucH w MIC wmuomuuou dIU 0 cofluMmem mm mm musmflm 121 J ..xawvHII'91. «If .00.“. .9. ..:.OJ. I. I .. Mum-IOIK111 1...1.I.|.IL..I1M11I.I. I IIIII I I I I III ..ILI 1.1..-.1117111 I. II. . 122 .Amusuosuum Hmummuo unonpfiBV msozmnofim mmz wmummu Hmflumums mnu mm @cflommm :6: oz 1 «m mnsmflm fan. 123 ii! .3': '1'... '5": . t (u; E 124 .Amusuosuum Hmumhuo usonufl3v msonmuOEm mmB Uwummu Hmfiuwumfi mnu mm mcfiommm :6: oz I mm musmflm " 1.43am. 1111 .J‘X + ‘JL. .111. «I'll. 126 .Awusposuum Hmummno usocuHBV msogmuofim mmz wmummu Hafiuwume mnu mm mcflommm :6: oz 1 mm mmusmflm 127 ‘1'! ii 3"! . 882’s... . ii. .13“... rg': . . .. . 5 5 .. 5. 4.. M an . H . . .. can . . U .111 at . m w _._ . ... 5. H 5 1. . L F .4 I I . . c .H . . . .u c 5 I. . . . . . .. . o N 1 , _ _ . M _ a T m . j... . . . . 1 0 W1 11.. >1 . 5. h . I n . n. . I . . . .5 .I . ... . ....I.... I . . . “I ... .......J. .5 .‘.. . .I.. I‘ .n‘ .. .I. I .l I .II.. _ ‘II ... . 1o . I 3&5 5.1.1...“ 1.. . m1.— Iubl 1. r1 . 5 u I. ... 11”. . . I1 ., . .. . ... . . .n .I . .I 5II. . m. . . .1.. ... . I .I.. I. . I. 9. ....I III .....IIHJIII... . 1.... .11..1II.5.1 I 1.5.I 1.1.1 .1115 1 . I m I . . . I .1- . . . .II .I . .15 .I.... .....I . 5... I.J..IIJ.JI.I..1II. .l..!i...l: .I. T. 1 .. ........ .. .. .1..I.I_I .. .... I... I.- .1 1.51.1... . . Ill... III-111 I II 1" J. 1‘. I . 4 . . 14 I . .5 1110 “W1. .II. I I. ... I... I I. I I. I . 1 . h LII.5 “11*," .u .hh' I — 1L1- n I..- 1 I‘ll 1+ I I I. . I11?“ I . .w. I . I 5 I I . . . . n .I. 151 I .. I r 5 5.. a 5 .1UI 1 l .“1‘ 115 II ..5. I .I.!I I 5 VII 5 II 4 I ”II. . '01. I I I IIIIlL' 1.1 I. I I. I I....III...'+I 1 111. I ...l 1 I.. ... 5 IIJII 5.. .. . . III. I. III. . . I I I. (I .III‘ IIIIFI ..I II IIIJIIII IIII .IIIIIIIL. II. I I I ..I ... . . II 11.. 1 4 . III. . I . ...III .. I. III 1.. o ..I I. .II . . III I I - I1. I I I 1 I ..III . I I I I l. .F a .0 I I .. a 1 . c I I 5 b... I ..ufi' . I 1* III» I.. 1 I . I ...5 _ I III— IIIII I .m...11cu11oh F I +111 151.... . . . . I.G.I... p . ..I .. I . .. H11: 5 I. ......111 nI .....51 I I 5 15.11.... . . .I-..... .15. a . 1w...1..~1...l-2.1Id.uw -11 11. I511. . I... .. . u .I .I. 1 I. . .1... II ._ 511 II ... .15 ... . ... ....5 5 z“ 51 ..I ....I..II... I ..I 1 II I 11ru1. .I I.. 1II.I .111 . II I” I 0 OJ. . I I I . I..! I.. I 1 . . .1 II I I . .II.; II.,III II.1II I +- I 5 . I . 10.1I5 III. II. 1.51.151... ... g1+ ..... I 1.11.11 L” I I 1 1I III I?“I.. II 9. I . 1 . . 1. .. 1— I .1 I I L I .I. 1. . I. I .. .I In ,. ..n. I o I” .1.. .1.. 1+ ... I I; 191.....II 1L1JYIII+1151IPuII11sI 1 51. 11 dIIIII 111111r1|11 1111 I1111I'1.I1 I1IIITII I111 111. I 5 .. 11 I L . 151 >1 .111. 111 . “111. I 5 I I 5 I I. .I I . I II . 11“ .I «5.11 I.- 5. II “I I r r I. Hm I I I I I II .l‘III I III 14 £151 .I... _ r a .. . . 5 _ _ . . 11.1.41 a . 1 ...5II I 5 I I. I IJI. .5” I ..I.Ir .1 I 11. 5 ._ .I-.Isl 1. .I I . .Iul. .144 4.11 II I5 1.5. II .. . I ... II I 5 .5 5 l. I 5.1 5 II ‘1 r L5 .rI l . .5 II . {$1. _ I II 11 III I IImlI . . . II 4 III!“ 1L . 1. I .I.. . w .I. I M. I 1 .FII1.III p I 15 .m J. I 15 .I II. $.15! I5. 15 . II. . ....II LI . I I II. 5 1 .PI III a) I 1 ... Iml‘ .E—I ..II 111511111... Ill-1|. 4 I 14 1 I I 1 1. 41111 . 11. . 5 . . .154 A . o . . H . . I. I— 11 II 7” $.15 I... III. _ I I.“ _ I . III5 1 I I I I 5..” .. . .. n .I... . .I 5L1. 1.1 . I I II I IIJIJIHI 11w} IIIIII L I H1 o I c I — J 1 , .I. A u . I . I. 1.. I. 115 I .I ....II 13. I ..I IIIIII. . . .. I. I l. .. I I .1 1. .1. . . .. .. I. . 11 . 11. 1 1-.1.-Ihu1'1. 1.1 I .... 1 .. I.p11 1 . .1 .II.. 1.1 .I....II 5 5 I. .I.I ..I. . 5 ...... .I 5 1 PI._ 5 I. .. . .11 . —..I5F.I I .1 I 1. I. 5. . I '1' . I I. 111 I III 1 IIIIIJIIIIIIII .I1'5 5 _ r . 11 .11.. h u 11L; 1 b-1u.1ll.4 1 1 1. .. 1 . .1 ..11....._1. 1. 1. III I . I . .. . ... .1..- u 1... .L 5.. I . . 1:11-11. ..MIIII 1.1.1.11 11+11 . . .. 1 1 I r I . .w I,“ I 1.1.— , Y‘I IL ..I.I“ I." Iw .I. . . + m I . I.1 r I I I. II11 INI_III.11 11* I. n . 1.. 5 . 11101 I ..II 5 I I 1 1 I. I ». I ...III. I .I. I 1 I II.IIII1 ..I I ..1 1 1 I114 I 11. ‘1 L . . ~11. . , ... .. I- 7.1..- 4.”... 1- _ .2... 1.. 1-1 L11... -1...-1 P1P-- -. 1P 1 5 1" 15 > b 1? 5 1? >1 8 L 51 L 1.1 1. . . - .31. . 1 . 1 ._ 1 . ._ . .1 . .5 .1211 .1 II... HI 1 . .. I .11 ... 1L ... ...1 1 . 1 1.11 I...ILIJII.111111u1111 1 11 . 1, . . . -1 -1 . . _ . 2....-. L.- .. .... .- . 1 .. -.. ..I. - .4 : . .U. - 11.1.1111; . I -1... I 1 I I 14 . 1 I. I «J . . . I _ I . I 1.11.1 . g . 1 .L .I .I . I 5IHH1 1 I1 I 1 .. 111.111 4 II 1111*15 ..11I-11 I11 I . .1. . 1’1111....n. III I I . L I I III 15 . 5 I I a. II. II «.t I 1|.V..1161.III. 1.1111 1111 . . 2 . . II o 1 I «I o I 1 .. J. . 5 I 51 I.., II 15 .I I . I 1% . . I 11 P 4 4. III .1 . 1. 15 1 .LI_ 1.1.1.1 .. L. .1. 1.-...51151511I1 1- .. ..I.- 1.1.. 1. . I . ...... ...I .1 .II. . . ...-1.. . . .1. .LIII.H11MI. 1.110 ..I . 5 .. .. . . . 1 . I . . .. I 1. 1 5 b, 1 P 5 k > L1 3 1. I: J o. 1. M 'l . . .- . I.. . 1 .. ... w .1. . b ._ . II. I .5 I... L 1.9 1 o u I I . 5 . I 1 . I . . 11.11 1.11111.- 111.11-.r11.1..11111 1.1511111511111111 1 ,1 ”1-1- 1. — . 5 I.- . n . .. 1 ._ a. u I.. . _ . I. . 15 n . n 5 . . I1. . . II . .1.I. v 14* D 151 31 5 1 . . I 113 5 1 I I I I I v - - 1A . a 1 M .I .I I . I I- I . . .. . I... . . . 1 . . 5. . _ w . " tauPAIEIId IOdH - . . .. 1 . H .. .. .1 I .. I . I 1 1 . I II 1 . I . . .1 . . _ I .11...1-11.11.-1_11.11 . 013d. . 1.. H. -11- ... - ..I .11 11.1.1 ..--1.1.71.1; .1111. 1.... .1 . II. .. L .I p I 5 u" “a. 1‘21 .. . .1 .III . .51II 5.1 I. I 5 5 . . . ... . . _ . 5 N 1 1 . . ld||dlll u .I 1 1 5. 5 . ..u. . . 1.. -.I .. . J u . . . . A w. . . .. “I... . 1 .. _ . . - . . . 11 ~ 1 . I . . . i .I .1 . . 1 1 . . . 41 T: L 1..» L. . d I .1 . h!- h51 . ’- w 1‘ 1d I 11 11 I . . .. . . .. . . J . MI: 3 p _ I‘l- . 5 u . : . 1 . . d I _ I I. I 1 1 .1.. . L. 5 1 .51 v . I . 11.14.11' .. ....rw 1 ..1 11 .1.- . . . .1.- . . .- I. .1-... . . .. . _ .. 2 . I. 5 _ .11... 11111 112-. .11 1|- 1. . . v . . . . I . .. 1 . . I. 14 I a 5. 1. 1 I 1 ~ . I .. . ¥ . . m - . . 5 I .11 .1 II. n . I A 1-1 5. w! . 1 . . 1 #1 LI . I 1 1 I I 1 1 I I . . .I . . 5 ~ I I I n. .. 1. I I. . O I .I. I 5 . . 5. 55.1 . Pa niI I I. 1 . .14 11. r . I I I I -.I H '1 II .1414 1+1 l‘ I I 11 111.1 11 111111. 111111 11111 11.11 1111 I P 1.1.11 11 1.111 11111 11 11 1.. 111 1 11 1. 1 .r 111 . I . J I 1 1 J I . . . I 1 .1. 4 5 1 . . . 1. . 15 5.. 1. ..I .1 1 «5. 1 1 d1 . 11.1 r . . . 1 ..I-I.- . 1 . 5.. _ . . I. . . . 5. .15 .. .1 1.1. ,III I I . . n 5 I. 11”.. 5.1.1 .I. 5 .11. ....I; . .. I I . - . . i - _ --.._ . . . - ..:. -... . .- -. 1. . -..-7-... - - .. -. .1 . I . . .. . .. 11. . . .1 . I .. 111 I w . I - III 5. I.. 11 .I .. 11 I1 . 1 - I u 1 1 . L1 . L l. w . 5 _ 5 . 5 3.1 .u .. _ . 5 . v I 0 3 4 5. I- 1 .lm . l 1‘ 1 . d i 1‘1 i I. 4 “ ‘ i I 5. . .. g .11 . I m I I . 5 | . I» . H1 . 1 5 . .9 — 1. . 411 I 1“ III . .1111 .IJI. P 11 5 I J- I o 0 ~11 1 1.11. 1. 1T1 1 1 I1.fl.l~ 4 I 4 . ... 1 m I 5 . 1 . .. . I.I I5 . . I! . .1 5 I. ..1 ..I . . «I 1 1111?.514. . .1. 1.5 III» II m n V . . . L 5 o . ..I 5 .. .I 5 . 1 .* . I I .14 II II. 1 1k do .1u1. . I . . . . , 1. . I H 1 I 1 1 11 L .I 15. | ..I 11.1_.II 1.6 I 1 111 I a I I I 1bIl F r. . II 1 1 111111 . --:. .1-- -.1..--1111|11 1111111 I- 1.111. 1.11 1111 II 1 . 1 1 r . 1p1 151. u . . . . n .141 T . 1.5 . I.. .1 1 .1 .H11. 1.. .11 . . .1. 4.1 I I 15. I .. J1.’ 1 1| .1 u-rv I I . . .. -, . 1 5‘55 I I I 1 2 ‘1 1.2 I A: 1.... 1.“.- I. 1 I 1 1 - . . . u u . . 1- . .. I 1 n -. - 1 .w . -. 1,-.. - I -1.1 - .. 1 I I. .1. 11 F . hr' . . 5 1 H1 5 R1 . 4 I _ . _ . . w . . 1111 ‘4‘ 4 . 1 1 q 1 4 A . . . . . . .5 . .. .. _. . 1. . u .. I 5... .1 _. .. .. . 5 _. .. .r: .1 1 H.. .I 5. ”I L ..I.. I I . I4 . .1 o 5 1....11 .. I I I I p 1 .. 1. II 1.. 1 ~41 1 1 III I. 1 I.IIII 1. I 1 IQI . . . . .. . . . ._ -1. 1 . . . . . .1.. .. 1 1 1 .... I . .1 1.215.... . 1 1. ~ -1 .51.. ...... 15 I 1.11 . f . .. I . . I . . III . . I .. .5 I . I I. II . I. . a. 5 . . 5. II .115 II" 11.. .IIIIII 11-111111- - . 11 .1 . ----..--1-1.1 1-1---111111.111111-111- -- 11- L . w -11. . -1--:11. 1 1 . _ 1 1 L .1 I. . _ 5 4 L... I II I I I ...15 ... I . . D I 1 .. II .1 . «I I I. 1 a ..I.. 5I 5 I “.5 . I 5 . 1 1| 5 n 1. 5 I II . . I1 I.. . .. .I‘I1I b I I u . . 5 w 1 H“. I .51. I 5 . I 5 . I.. I. . . I. 1 .1 . 5I I . I 1 . 1 .. . 1 I . . . . ... I . 1 1 I 1.. 1 . . II 5 I .. . . I I 5y _ I 5 % 1 r 1. 1 4;:- >.. 1 _ . L 5 "Err 1» L . .1 . .5 1b . pin. 11- .. I1. I 11 :1 :1 128 NHH.N couH om.wm om.N QOHH m.mv m.mm o.mm o.ooa m.mw mummmwomz uoz wh.m ¢H.m wm.m mm.v COHH nouH cOHH COHH NH.Hv m.mm mv.mm v.vm uooom 1 .um H Q moumm mufimamqu w mIU Umuowumoo £16 0 :oHpmwwmm mm mm musmflm 129 ‘I'Il- 3.3! 0.. is. ..I i 21!! ii... I. ..I.I-II .I.-ital .I.. . 1. . 2 . . .1 .1 . 1 . _ _ . 1 u _ .. ., a u . 1 _1.. .1. .... 17 1.1. .4. 1...... .. _ . 1 d .. ... a 5 . . I. . I 5. . . . 5 . . . . . I 5 . . QIN . ow . ITIII‘ 5 5 ‘ 5 5 5 I . I 5". o 5. a .. . . 5 . 5. . I . ON . . _ 5 5 u 1 I . . 5 5 . 5. 5 m . .. . . . 5. . 5 . 5 5 . . . . . . . . 5. . 5- _ . 5 5 . . . 5 . . . . 5 .5 . . b! J . H 1 . ‘PL 5 1 1 5 L 11” 1. J u. 5 1 0 5 .w L I I . 1 5 . 145 51. m I I . m . . . . .. . . J U I m 1 55 5 ..I m. I .1 5 5.1.1.1 .1115LII .11-.... .I I I 1 a I. . .II 5. . ..I. . . o 5 II Q. I I u I . I1. I 1 - I 5 .5 . .. . 5 .III5' II I. . III M I . . IInII-I II5| 5- .III Ir.ll1lI.4LIIIIII 1.1 I I I. 4II. H II I. I II In 01 a 1 5 .. I v I I. .I .5, I I I I. . I. III. 5 II. . . . 5 5 I.tuu II II A In." «IIJII .III I I I“. 15‘ . I. II 1 L ..1. 11. _ 1 . I 5 .. 1 . .. _ . -, 1 5 -5 I... . 1. I 51 II. ..I.. .II. .II... .1 . .. ...-.5 .114 . 1 4 I 5. ..HI I11 1 11 .II 111 1I1|II1J111I I 14111- II I 1.151 11II+I1 11111 141111511 11 III. 11.1 JI .— d 5. L .L41. 1 u w a 1. 51 1 I. I 5 5I . I b . I“. 514 I. 5 III 151.1 I . .. . III1III.HI 1.1. .1511 I1 1 1. 11.1. .. 1.11.5. J ILI .11.-- 1111.11.1-1109W1Ndffidl-5t-VT 1.11-1.11...- 1 . . A -_ :5 u . . . . . . 1... .1--1.12-1.1... ..1-11. .11-..-..- .-..._. .n. . . o 5. 5 . 1. ~ . - 5 11*" L . . .rl . I 5 II 1 I 1.111! -...III II LI|II I1IIIII1 1‘ II" 1. 111 .1 . III"- Ial 11 1 I 5 I 1 4h .. . 5 . . 5 . 5 . I. 5 . . I I I I .. .. 5 u - . .5 .~ .. 5 .I. 5 .1 . . 15.-5, | 1 I n . 5 I . . . . 11 1 I | -. . . g . L51 . 1 . M 181.51 1. 5 5 III bd- . 1 I . 5a .1 4 .- d 5. 5 1 I 551 5 - I 1 _. .. 1 J‘. .I. . d. - 1 .-- - . .. 1..- . -h. 1 1.1 -.1 _- 1-. 1-. 1. -1 ..1-... - .1.... 1. -- 1.5. _ -51. 11.11 - 11 . . 5- . 5. . I u. 1. 51.-I .I- . I IL... 1 1. - 1111 - . 1 .I.. a. 511.14 1 rI 1.4 I l . 1 . .1 - . 1* I 5, I 5.1 I I . . . I r. o I .1 I I. 51 11 I III! 1.II ....c .I. II... III 1 1511 p 5 II - ..u 11 I V . 4 . . .5 I .11 11 .11-111 . 1-1 1-1 -11-11111.11 ..1-1 .1111 1.1.1 51 I .r P 151 111.1 14 511 1 1 ..1 0 II 5 . - . 5 5‘ 1 I 5 15 U 5 .. . I.-. 51 .I.-.555 111 I 11 .III 111.. II . . I . - 1. 11 «III .15 1.. I I . . 5 5 11 1 1 I 1 . 1 1 111 . II.- I I 11101 I 1 LI I 1 .I 1 .I.? 11.1 .I. 5 . . a . .- ... 4 _ u. -. 41... 1.115115 - -5 1 5 . I1 .15..- . . . - ,. . . 5 5 1 - -1 . 1 -. 11 I . - . . 1. .. 1... 5.1.11.4.“1. 1- 1.1. . I - 1. .- 11 - I. ”- Ll . 8-HT ‘5’: 1 1 I13 1 .. I 1. II” 1 1 4 . .1. 4 4 1. .A ..1 z 5 5 5 I . I 1 I I I .LIII.. IL .5 I. #o I l . III 5 5 I5 1” 41.51. . . .. I V . 4 - . . . 5 -. .. - n I 1 1 I I I I I I 1'1 I 1 1 11 I 1 4 r L L 1'- I! U: I I I 1 l ‘1 ...-.55.}; 1 . ,_ .1 'd I 1.5-1-...»- II -1 I 1 -L 1 . 5 u . 5 ~ - 5 . I. p . 5111II ,IWA I 1 Inl- 1 "1.H51 .bl I 1 . . . I . .. . . I I. -. I I..; 1 I I 1 III 1 I 1.1-. -1 I 5 II. - I .1; II «I a 1I.. I n . I . II I... 1 . . 5 . .. 5 M1. .v .. .. I .. h 1 . ... 1.5.1_r51. . 15 1 .. - 1- 5 .111... 1.1. II. 1 I .I.- I II ... 5 1 I4 I. .1. 5 I- m. -|-.-11h.1. 51 u .. . . . .. .. 1 . I . . 11 . 1 5 . 5 I5 . . . I. . . .. . . 1 I . 1 1 . 1. 1 I I ._.. 1111... III I. III .511. . 1 I . I 1.5 1 - . 1 5.11. I. .I . .El J. . . d. + . 1..- “ t . 1 u .> 1 151.51 1. .E «1 . L1. . . 1.5 1 I ~ . 5. 151 15 I I . 4 a . I . 1 .I u , . 1w . -1- - S. 1w. .. _. . 1.1 ...-.. - .- .. .- .- ...,.:..1...-. ..:-.1.- -- ..1..- .- - 11 . . I . 5 5 . ... 1 ”I.I Ir 1 I .1. + 1 I. 1 I I1 . 1 II.1 I 11 .I . I 1 ..IIII5 IIII... 5 a I - -. 1 I .11-MM . : u . . . : .. .1, . -. 1 1.1 .--11. .11-.. - .1 . J - ..1 1.1.. . .- . I - 11 1. ..I p . 5 5 5 . .1 .. . 51 .51 III- . 1 I I 15:11 11. I.. ...-11 1. f I? 1 I 11 .I . . .. II. IIIL I 5-l I . 111 11111 1 J 5 13.111111 . .1 11 ...-I In - - J . a .5 F . _ . .1. .I.11- . .51 . . 1 . ... . 51 . .1 5 . . J -. . . . . ._ 1 . ..n _. 5 I. .. 5 . ... 1. .. .. LE... .1 I..1. 1115......11 I I... 1 a 5 .. I 11. InI I 1 . . u I 5 .. u h “I I. 5.— . 5 I 1. . ~11. I II 5 . I. .I . 15.1.ILu IIIIIII‘.II .4 l 5 - . I .115 -I 1 5 I.. . 5.1 5 . .u 5 .. . 5 ~1 _ .II M II.+. 5 I . 1 .I.-I.. 5. 1 .51 1 .1 II 116-I I-51 a 5 IL. I .5 .5 ..I 1115I 1 . . ,1 ID a- . _ n _ 5 d . I..... . . _ .... ..1. - . n L. . .- .-I.I. I 1.. ..1.- r5. . ... ... . .-T .- .15 . ..1. -.1 1 51 111. I-III.. 5 . . _ . 5“ .. 1 d I. r m 1.5 . . ... .. .II.-..I.I..I. . ...... 115.1. .I. - . 151-45- ...11 11 1..."-.I 1 . I I I . . II . I . .I . . 5I I . .1 II . I. I. I. H I ~ .11 ...—III... I5.IIIII I..." I. ..I I IIIIPI I. I III I 5 I" ll .9.- I IIIIII I511 11. I11 _ . . . . . . . . _. . . 1 I u .5 . . ..I 5 v5.1. 5 I. I 1.51 .5 5 I. I . 5 1 .1 1515 II I- IIMIII-I.III.I H5 II 11111 . 1 I. .5 II; .ILHIIdI. ... l 1 . I . 5. I . r 1 .I . I . . 1. I . I I. . I I. 1 I I. I . III III? I .II II I I. I II I I u I I I.‘ 1 II . 11 III. - 111-111-111 .1 . 1- . .11 . 1 _ 5 T 1 .. 1 1 r _ . .1.. 5. H15 1 5 I. . r. .1 . 15 I 5 . “11 .W.151. 5 .I 5 1L 1.. ‘- a . 1 I 1.51 1.4.. .I I I. II .IoIJII I ..I.II 4w 1. II 11 JFHI I ..I II. 1 11 1.5 1 1- 1 I 5 . 5 I 51 I. ..I a l I . I I I . 5 5 A I I 5 05;. I I. I. ‘I III. ..fi I 11 I.“ IfiII I 16 II 1. I III ..I 1 IIAfiI, 511.1. 0151 I 1 . 5 I .. .5. I 5.. . .511 .1 L .I 1 II I I I n 5 ....1 151.11 I 5..1HUJ113I..| I151 51 I551! ..I.I..LI 11.. I. L" 151» 1 I . ..I . I . I I .I. III I .I.. III I11 . 1 II I. II? .I. . I ..II 1 . II 5 . g r .... g 00 T 1 ._ 1 1 P .. . 1. 1 . .II.». -. .H. .- 1 .1 u . 1 u - 5. . 1 5. a .. q 5 . . ..I- 15 I5 I 11.5 .1 51 5 _ . .11 5 I . .I 5 4.5.11. . I..11 II .5 ..11 1:1 - 51- .1111: 111 IIIIIII ..h- 5 I 1 1151 I I II I I 1 I 5I 5 r1515IIII. P.11 I III-v.11 I.. “In TI? ‘11. I..I.III I. I III I 1“ I v p I I l I IIJITDI‘III'I II 1 .1 ..I I 5 5 I 15 I . 1 5 v 5. 1 1 I I la I I In I ..5 III .. II... 0 L111 LI I. .II.-I . III I 5 .15 I I. 5. I I.. .5 I5 I I .1. 5 I . I o . LII . I 5| a . . u ..I . 5 . I I III-.11 I. 11. l I1 II vI PI- .-l I I I. I. 11111 1111 I1.11 111111151- .1IJ-.1I1| 1111 1 5 L11 1 11.. 1r 5 1 4 fl 1 1 _ TH.- .. v %HI 1. a“ I 1. I I . .I II I. 5 . . 1M . I I ..1 . ..I a I I III I v I T. 4 I 5 .- II. I II. 5 J .I 5 III I I 5 III. 5 I 5.. I 15 I I .I . .I - . 1 I 1 - a I I 5 I. I 1 . o . . _ I I A I 1 J . I. I 5 II IIIL..”.1I 5 ..I 5 . I I . I5 51 I I I 11.5. I .11 I c .. 1 .5 5 I 5 5 . u I . ..I.I. I I 1 I. . I v I I I 1 4. L I .I. 1.. I III-£15 III. (A .I.” ..I I 5II1. .11 IL.- I II x .15.. .III ..I .5 . .- .. . “‘5... I L . L . 1 ”L I! .-. - . . r 1. - - 1..”- H 1. 5.11 -.:-11 ...-wr-PI. 1 - 2.51:».- L 11.1.... -. 1 .- 130 mummmmomz uoz NH.N om.m couH cOHH om1¢m m1¢v .Uooom m.vm vH.m couH om.mm .mm H @ 0.00H vm1m QOHH ov1mm m 00mm huflmcmucH w ¢1© Umpomumou 41C 0 coflumflwmm mm mm musmfim I..1.-l ‘ 31.-..I.I 3131.51.33 .I.-(..I.I...- ii. xiii-In . 131 3.01.11:qu 40-311.... 1 .. . .- ...1. . i-.. 1 1 _. UUhJK.’ Jung—U51. . , . , . .. .1 . . , . 5 . . 1-...1..1u..mumU-I_;TII..¥-w 11..1.-.1-1-,-.----- .. .. -. . . .- . - _-_. . . . .. .1 . . 1.1-1.11-.- ... . .. $38-$11 . _ . . . ._ . q .. _ _ . .. . -.. .. .-_ .... .w H .. ”-.1. _I a . I I 5.. . . 5 I r .5 .% .. . 5II.«. «.5- 5 .5 I 5 .. I I . 1 . . . . II I .. . . . 5 _. . u- a... 1.13.1.1. . _. . _. _ , . 5 I . 11 1111 1 . 11.1 51 1.1.1.19111-1111 1. 5 I .11 II 1. 11 . _ . . .. . I f N 1 lw- 1 I h . ..I I u II III 1111.11II1- III- I 1| .1! I.11W1L1‘1 1 I11 IIII 15.1111III- JI- 1I III—1'II1 :1 I III 11-1-11 4011I1 I I1.- 1.‘1 I111u111311 I111II. 1 -11I111II . . 5 ~ . I . . I 5 Ir . 51. J 1 . . I. I N .. . .1. u .. .. 1- . ._ 1 . . .. .-.- . . _. .. _ . . I L1 I . . 15 i1- .5. .I. 5 . 1 . I. I . .I . . .I . . _ I .1 .. . . .5 I . “I I 51.. . . 5 . _ . . 1 . . 1 . B . .1 1 . ..1 M.- .q . . ..I. . . . . .. 5 I. .5 1. .. . .11 .. ..1 w H 111. . 5:5. I . . . . I . . . . . I . .I ... u ..I . . . 1 111 . . . 5 . 1 . . . . I.I . I 5 . . I 5 il 1[ 11.1-11.1 .. - . . - ....1 11- 1.1.11 .1. .. .-1-11111. :- . . 5 I . . . .— _ - . h .111 1|I 1.r. 1 1 1 1. .1.- IIWI. 11 ...-111111-. II 11.... -.I.I I11111. . 11.1 .1 I 111111 111111111- 11. 11- .11 115-111 I 1- 11L «1 1 5 . . . _. . . .. . . . .- . J 11111-1 1 :111 _ . . . . . 1. u . . .. .. , . .. . . . 1.!-1:11.11. -1 . . . . . . . . -. . . . .. . . t .5 . .. . .1 .. I .51 Q I I a It!“ . \ 1 . . . .. . .1. 1111. . - .I .1 .I1 1.111.»..1.1.+111*111.111.11I I11..1I11III11111.1. .1.-1.1.1.11 III. 1111.1l.11111.11o.l.11I ..I 11 1.1.111151I .1..I1 1k. . . I .I.W.5I.11k11111 . I . , . . I I . . . . 111.1 £111..I.|1. 14111IT115I|IHI111W 11111Ir111 1(1I 11 1 .I..J1111J1I|J1 1111 . . . . , . _ I . . . . . J 5 11 1111 III' 1 > L1 1 .III . _gh . . I 1 I. . . .. I 1 .. 1 . 11. . . . .1 .00.»--. . . . . r 5 132 NH.N COHH ma.wm o.mm om.m couH mm.mv .HmchHmE wmuwwflmcoo .c3onw pom coo.Hv 1 mm o.h¢ o.ooH o.mm 0.0m o.mm mummmmumz uoz wH.m mm.m hm.m mm.¢ Hm.v COHH COHH COHH QOHH QOHH Nh.mm om.mm mm.mm wm.mm mm.vm m .Uooom I .Hm H @ 00mm huwmcwucH w KIU Umuomnuou mlv O coflpmficmm mm mm 853m ii. if '5'5. 5.3: ..I..-Eco. 1!. (It: . -..—..I}... 5 a I 9 .‘ ...—5‘ _b .I '1- a , o 9111 - 1 . ..1-4. 14 . 1 u h I. 15 .0 .. . 1 . I .. 1 . . .u .. a u. I a 11 .1 . . a .. ..1 .1.1 ..I.. n- -.1 . ... . 1 11. .1. . ... .... u111.1.” .1.. . 1... . 1 ... 1 ......1. ......¢ .. fl .- .- . . . . - . . 1 5.4-" lfiu 1».11 o . II. 11.. 1 0.111.» 1. .1 I.. I 11111 . g . n I . . v . 1 I 1 1. ..1 - .1.-.. _ .. . .. .. .1 .. .....-1... -.-; ..- -_ .. . -. - ..1 1 - . .. . .1... 1. M 1 1.111.111. - 1 -..L... .1 1- . . _ . .. . 1 . 1 1 . —. T1 ...... .1 H w - O _ .1.I. l .14 1... II « a J— 1 .“1 “_1 . .ml Ill .1. 1 .1.11 - . I . u fl. .I. u ‘ 1. .- til I I 11 ..1— 1 I1” 111. . 1h .. .. 1. v . . .. . ..N .. . a . ._ 1 1 1 1 1 .. 1... . a . .- _ .. . .. . ... .1 . 1 .. . 1-- 1 1 . ....1m11w111L . 1.. 1. 1.111.111 1-1 1 .. _. N . .1 . .11. . ...... - . .. _. 1 . w p... .m 1 . u . 1, 1 . J. 1 . Tex... w . -1 . L ; . -. . 1 - . 11.1 .“11..I1.1u1|11h11.11-1“111 q 1. . .. . .... .4 1. 11 1.111111 11 ._ _ _ ; ,. .... 1- ..r. .nu1U—1 H“. 1 n .. .....1. . 1 1.. 1.I 1L .. . ..1—.1. . . . . . . ..I ... ._ . .I.. 1 ... .... ... -. 1. . . .. 1...-..“ . .. ..1. .. . . . a . 11 1 118 1. - .q . . . 11 .1 . . ..o 1. . 1 . . . . 4 h 1 . .1 v. 1..... 1 . 41.19." 0 I .. ”I ..*1.1 4 .1 .- . . .1 — . .m l — u . . 1. 1. . . r .01. 41 ... ..1 . .. 1. .1 I. T. . . v. . . ... m . 1 . 1 ”I - . 1.. u . I . 1 u . - 11111 . . . .. _ 11.1 1-...11111..111 1.1 . - . . , ..1 .. I . 1 zvu141 w. — ... . ..ol 111. it . H1 1. .10 . . _ 11 J I 11. a 1 1 . 111 11 11. 1. 111111 1111. I... u 1.0 . f. 1. 1r. 1. . 1 .. 1.. . 1 m 1 h . .1 1 . 1... o _ o .1. . . I b 1 c . I a . . .I..-“ . 15111 ‘1 o 0| v 1 ... . 1. 11111 .1. 1 . _. . . 1 u . 1 w . m1 1 v u 1. 1 1 1 .- ).1 1T1 — I {I I... 1 o. 10 51 511.. o . ..1. ..1 .1 . h 1 _ _ .1 . L. .I 1 1 “l— .m J ~4II I .- 1 . . 1 I1 . 01 1 1 L1 .. L1 3» .11 . _ . 1. w _ o . . s 1» .1 11 . .1 1 I 1 I“... 1 11... I1 . 1 1. p b B 1. . . L1 1 . fl 1 I 1? ~_.+1. .~ 41.. J 1n . . ..1 a 1 . . o . .. 1. .«1 1 a 4 u . I 11? . ...... .. .1 . .... - .. . . . . . . .. _ .... . 1 . 1 . . H . . . _ . . .. .1” 4 .1.1 1 , , . . ... - .... .1 . . 1.111 1.. 1. . .. I .It 1111 I x . ~ ~.— 1 o . . u . _ . 1 1- 1.1 11111 11.111111111111111 .1 - -1 . 1-. 1 1 . m I 1111.. 1111.111 11 W . . . .1 . J - . . .. .. ..~ . . 1 111 111 111! 11l1 1 1111 1111411 11111 1. 11.. . . .... - . . . 1:. .. ... . .. . -- . . .1 I. . . -l..... 1.. J J 4 1‘ 11 1 ’I P J I ‘1 ..w M . ..~ I—‘ II I . 1. ‘ h 1 O .I. l— U ~ uh. I.. . — l I. A 1.1 .. . 1 . o ....1. . ..I mt 1w .1.. 11¢ 5 l I 1 A .61. ’ Ir H. 1L0 1w-.. In a II _1 . . m u “1 1. on. 1—.1 Q1 ... I 1 . L ' 1' .I I- ’ _ u I' u 1 h '1 I- I. luv. 1 1' l “I a -. 1”» ..I .. 1. . 1.. 1. .1 .“1 .1 - _ 1 1.11... 1 .. 1 11- -1 -l- 11 1 . . .. .11 .. u ... —. _ 1.. 1... . . n . a 1. . a h I. 1 . . .. ., -1... . 1 ... . . - .. .. _ . . 1 . ~ . . a .. 1 ~.. .... 1 . f L _ 1 . ... .. 1 . . . .. 111 1. . . 4 . . BA 1? 1 1 I 1 ...-1o .. 11.1.— . .. CI. .1 .1 . .11. . J .11. A . - - 1 . H . 1. . _ 1 .. . . . _- . . . ‘ I1 1 I o) . .I . . u. u . r . . I n. 1 I . o . . . I . 1. 11 . I h I 1 1 ... .II . . 1 4 «Ii. 11"), 111.110 L 11 1.." 1d ¢ . 1 I." I‘ll. a u 1 u u . _ .4 . 1- .l o o. .1. O n . IIIIIIIII ..I 1 _I. . 1 1h 1 1.11. 11.11. . . . . . u :L. 1" . . . I .. u . . 11 u . . . 1 . r . _. . . ..-. . . .. ... ... . . . ... . . . . 1 . . . _I . I l . I . . . 1 _ 1 . I. 11 1 I . 11 141 . I ..1. 1 1 M 1 1 1 . 1— .. . - . .. A. 1 a . u .. 11 J I1- . +. I. A 1 11 . _ ... 11 g ..1 . . . - . .. . .11 v 1 ~ 1 ..1. . . w . - r . 1 1 .. ... . . . M .. 1.... . 1. I . . , . .. . . ..II-..11..11.11--L- . . .. w ... 1. ..1 . . .. . u . . .. . .. .. . . p . .. . . . .J . ..-...41111111 1 11....11 11111 11 -1111 11111.11 1 11111111. I 11- . .. .. 1 ..1 1 , . . .. .- . _ 1 .1 .. L 1. . . . . . . . *1. . .I. b1 11* ..1—11 . — . A H. I . 1.” . .. | n .11 I.. . J I . . . . a v .. 1. .1 1 I. . . 1 _ L‘D. — > 1 b1 L 1 . JEL. L. 1 F 136 OOH muflmcmuaH w anammwowz uoz U wwuomnuoo hmHIM H div 0 couH u :oflumflwmm vamm H om Eouuom 1 mHmEmm coflmouuou 1 aw wusmfim II; .I.... I. 111.11‘4IrWJ1.I-Ifi 11.01111.-?.|.I14l.‘.4|r .11 :1 . .... ..SJ.. 1..... 111.1... .I’. ...- ...-r. n 1119111? I. 138 _-~ takdcxm. .Hwaflmumfi wmuwwfimcooIIGBOQm uoc ooo.Hv I am o.om o.hm h.mm o.oo~ whammmomz uoz NH.N om.N mH.m hm.m couH :OHH couH nouH om.vm om.mv mm.mm mm.mm .oooom I .mm H 909 I mamfimm COflmonuou .I.! muflmcmucH w MIG Umuomnuoo ¢IU O cowumwwmm om I mw ousmflm 139 '0’! 'I J I J. I J . . _ J. h m J! x _ J: . . I J J . . J I . g I . u - ON . om ._ . III. of . . . . .u u Q“. . .. . . J u ’ r .w J n b J ’ J "DJ. . , J. G .. ..N . . . I I21. .I -.I; a II .I m I ”d - . .. . :I I ‘ II OI .H-II 6.,4— - -- , IJ . . _. I. .u w .m .M I ..I .I ..m. TIR- --..I-...JIIII... - III- I.. J. . . .. .._ . . . p - u I I I..-I-.“ .. I [L .b . J I L. Ll . bJ IQVJIIIIIIIII J :1 . I J ..I . J _ . . . ... . I»... I f . n .. . . ~- _. ... I.. U. ..I .. w H .b. ...IIH. III.I.. I IJ I III I I IIIJ-JI III; II IIWZIIJ..J I - II .I- I III-.II ..I..-IIIJI IJJIIWJJIRMI I - . . J. . . _ . m . _o m J 2 - . J- .2. m .. . . M y .. n -.I. _ m.“ u... .- w GI . .u I- .- J .I. IIaIJIII q . J: ..J h I J 4..» Jill. I I-. .. J . . f -g . “2, . i -._I.. . .n. . . . u .c. .H .. . .. ............ .. .. ... ., -- . . . I. ImII.-II.--..J.;.II- III--II- IJJJ JI.-. I-uJ.LIJ-JuII.I.II . .I ”lg ’ ._ I . II .. .. I 4 .I. g r. . .. .. . . I m s . E . I I. . . O t . _ o I u .IIII I' I||I 'J JJII IJIIJITP I . 0| .l l J .I.Jl I II . I II I! I I II II J 0 III I Jl |I IIIIII .. I l [IIIII IIIIII .IIIIIIIIIIIF IIJ.OIIJIIIIIIJII III II J! I I II J .- 4 I1|JJ J. - . . . u . , . h 9 T . ,P . . . I SIJI' .I.J. - ‘I 4 ‘q T 1 JJ . . n . v .. . I -I- . . . . _ .9. I . ii". .3137.-.- .- HI'... . \KP. . .1. IJ.-II.I-.I... {ObfgpoiINT .1»de II.I. ..J. . IT _ . I. -l.--+I.I.I- . ... .. QIJL Mega . . IIJ. -I-. .I.J. ..-UI.IJ:W.MI. _I.II. Nun-om. WI I-IIIJ....W- .."Ii. JIIJLII --I--I..-... m .. . ”Gum LpIsmmI JSAflQ-aoqw . u. . . .- _ III .. I. “u“? IEJJE III. ._I j. m H. ... . -. . . . H . _ . . . .... I..... IIIII lll....II 'III JIIIJ JII ..Ikll I. . III LII JJIIIIIwI .IIJI..I..IIIIIII. I]. IIILI II IIHJLIIJIII I....IIIIIIFIIIIT J .E» I . I p n . . .r .gPpP I J p 11 w. -" J1 140 NH.N COHH om.vm o.mm o.ooa o.m¢ o.vm muflmcmucH w mummmmomz uoz mlw wwgomnuoo om.m vH.m mm.m om.v MIG COHH COHH COHH GOHH cofluMflwmm on.mv mm.mm mm.mm mv.vm om .Uooom I .mm H Eouuom I mamfimm coflmouuou I mw mnswwm ‘ 583363; 1433...; ..I-...!!! . «33363;: In 141 I J . 4 I II a I J J . ._ .. j .. . . .J . . J a . 1 . I J I . _ _ ._ J . . 5 . T _ _ J. . A . _ __ . . . J . . _ . .3 ... . . .n . _JJIQJIJI. _ ..I. . . II . . _ . WI L W w . % . bl?" J . b J . n J _ _ ’ u I J r I . c - J. I I. I .I - “.I. | . “I H ‘Ifl ¢ . IJ0 . . II L .~ I .. .I. ~II ...-a I — I _ H I I. . u . I . III-“ - I.- I - . . ..-I ... . n . .. ...I- _ , . . . . .II.-.. . .. .IIHH I . . I - .I . - IIIIIII I IIL I . I III IIIIJ I ..I..I+I.II|III... I» II.-. II JII I.II.I. I‘IIIIPIImv .IIIII III I . III — JILI IIII I I... n _ % II I . I . . II . . I .m I I I . I I. . I . .. . I I - , ... 4 .I . . . ... . .- - .. - -I.J.. . L. JIJ- . I ..- .. I. I L . I . u — I . I. . . I I.~ .II II I.. I .I U I . I.. . f m ... .I I It I h It I u . I L‘. » H .A. . . . I ..I . . . .. kl. II .I to I L . Q I .ILI .. I . I . I. I. . . . . . I« u I I . H . . J J J J. I I . J J IJ I J #JJ 1 I .I I I . w " ,JIJII .. I .j . . ..I . .- . . . I (III u. . ..IIII ..I I J 2 L".-. . _ .-Z . - I - I.. U U 7.... _ _. . . u .2... 2.. . I-.u-...:;.- - I.» - .-e {Ir-.I. “-..-.9. II II I . u9. . . I. . L.. I .9 _, er I III I . I-.. .. . I L. in . .. .J .L- II I I III. .I III - 0 III lI-II III A JIIJ J . III % II I III I IIIIIu. J I I 4Y.. . a o . ‘ L. w . T J” “fin. I. . . =. . II I..1. II I I. I. a . h ..I] .H . . . . H I 1 N. . . m .I .I M. II —I 4L. I. .II I. d .S.. d I I I. . .I L. M I. _ .... .... SI . III. I III J . I. lI-v- I . p I I n r L- . I .I Q. I. I ..I.. .... . S... .. E I I a _ .-. I. I .. ,- ”r H l‘g a” Q1 1. a . J . “I . InsllIIII'IIII . ...II ..I.. . -. .... .. .. II II I h.-- I I .u ..I.” . I. B . .5! I .NJII . Q I .I. bIIoIO I VJIJIIIII .r! — . .. ...I .I . m PI I .... .II _ . .. _. . - Er? EFL J _ -. I .I 3» I1 . I I; .I _ I. . .I*. I o. . . I . I. . H II J J . . .. .I - I. l . . o . n . . ,i - . 1' I . I .. ‘ Q . . .I .I . . ... II—J It _. n I H . J . ._ I. I I I .HII. I— o IL? . . p . .. . . .10 O .I .. . ...I. . . . m. . . .. -....- .1.—OI. FGEW Jai¢m ~w dsOU. .I.. . .. I _.._...-f .- -. .. ~ p ... .- 00 J . J . . .5qu I J. I . ... III .. .. ...W I.m..I..“....-.._.... .MIW. HJGAJJ .1-... J I ....a-.... .. .._.- ..I ...-I..” .. . u - - ”- .. I.. I . .. I.. . ..I. J. .. .. I . ... ... ..J I . I .II . JIJIJJILIJIIIJw-HJI .IJI IIIIT... Ir-.. J.. I w .-JII JIIUJIIIII II I- . . “J. IJIIIJJIJMJI I.....HIJI -II. IIII . . I . I.. I o I... . . . . . I. .II . . . L . -... ...I. .... .. .. .-. 4 . . _ .. .. I .-I..... . . . . . _ .. A n . ..:-..:.q -I.; ..I. J a m M .. I -I N. I ... .w m: I . _ 1‘ 1 J b . . .x J J _J _E .. .J.« p k L p E III? III r 142 Petrographic Microscope l. Hematite (FEQQBL Reagent Grade l-A Fe203 (See Figure 44) (Pure) l-C* Fe203 (Pure) plus water of hydration 2. Magnetite (FeO. Fe993) or EEQQA or Fe(Fe294l— Z-A FeO. Fe 0 (See Figure 45) 2 3 (taken from iron furnace) 3. Siderite or Ferrous Carbonate- FeCO3 (formation from mixing Ferrous Sulfate and Sodium Carbonate). 3-A FeCO3 (formation) (See Figures 46 and 47) * l-B* Fe203 (Pure) plus heat 1 Hr. - 500°C “l-D* Fe203 (Pure) plus water and heat 1 Hr. - 500°C 3-B FeCO3 (formation) plus heat 1 Hr. - 500°C (See Figures 48 and 49) No description or photo as the X-ray pattern Figures 29, 30 and 31 were all identical to Fe 0 grade Figure 28. 2 3 reagent 143 Corrosion Sample-Pipe Nipple; The sample was removed from the nipple in layers--top to bottom and will be discussed in that manner. 4-A Top (See Figure 50) 4-C Top 1 Hr. @ 500°C (See Figure 52) 4-B Bottom (See Figure 51) 4-D Bottom 1.0 Hr. @ 500°C (See Figure 53) 144 Figure 44 - Hematite - Fe203, Reagent Grade, Index Oil — 2.00, M - 240x. 1 l-A Photo--l—A Description: Focus on large center mass where L - 7.0; "f" - 5.6; T - 60; M - 240x. The general appearance is an occasional large mass or blob and the remainder is a background of very fine particles. The large mass J appears earthy and compact with little -,J; evidence of crystal structure. However, notice (by arrow) a vitrious crystal right of the large mass. The index oil is 2.00 and the compound appears to have an index higher than the oil. Under C.F. the color is blood red. In T.S. the color is black. 145 - 1 146 Figure 45 - Magnetite — FeO. Fe O 2 3 Taken from Iron Furnace Index Oil - 2.00, M - 240x. 2-A Photo--2-A Description: Focus on center crystal mass group using oil index of 2.00 and L - 7.5; "f" - 5.6; T - 60; M — 240x. The crystal formation was rotated with and without C.F. and the sections were opaque. It is possible on occasion to see some red and blue in the rotation. This may be due to impurities created from firing. Observe (by arrow) the clear vitrious edge on the right. edge of the center crystal group. Generally, the crystals were massive with very few fines. The crystal index appears higher than the oil. Inasmuch as this mineral is difficult to identify by using the microscope, a magnet passed over filings of this material identifies the magnetic character and thus we conclude Magnetite. 147 * t -I*_ ‘ 148 'Figure 46 - Siderite - FeCO3 (Formation) _umfii Index Oil — 2.00, M - 240x. 3-A-I Photo--3-A-I Description: Viewing a sample of Siderite in an index oil of 1.95 using L - 6.0; "f" - 4.0; T - 125; M - 240x. The crystals are large with a few small pieces. The crystal mass observed is as located (by arrow). There are two types of crystals on the glass plate, opaque and clear. Importantly, the Opaque crystals have an index lower than the oil, whereas, the clear crystals have a higher index than the oil. In T.S. the opaque section is orange to orange red. The clear or vitrious sections, however, are orange. In C.F. opaque sections are orange to orange red to brownish. It is not uncommon to find in other samples the large earthy clumps as associated with Hematite. A physical test tried wigh HCl acid--the sample did effervese. 149 150 Figure 47 — Siderite - FeCO3 Formation - Becke Line Index Oil - 2.0, M - 240x 3-A-II Photo--3-A-II Description: (See Description 3uA-I). The crystal viewed is located (by arrow). The section is opaque and the Becke Line has moved out into the oil, indicating that the crystal has a lower index or that the oil has the higher index. A very good Becke. 151 152 Figure 48 - Siderite - FeCO3 Formation - Heat 1 Hr. @ 500°C Index Oil - 2.00, M - 240x 3-B—I Photo--3-B-I Description: Submerged in 2.00 oil with; L-7.0; "f" - 4.0; T - 125; M - 240x and heated for 1.0 Hr. @ 500°C. The sample appeared very much like Hematite (see Figure 44) with large earthy crystals and enormous amounts of fine particle material. In T.S. black mass opaque. In C.F. the large masses are blood red. The oil had a higher index than the crystals. NOTE: These two samples do not resemble each other in appearance at all. The granular characteristic (Figure 49) may be due to the lack of comminution. 153 3):: A . 154 Figure 49 - Siderite - FeCO3 Formation - Heat 1 Hr. @ 500°C Index Oil - 2.00, M - 240x 3-B-II--3-B-II Description: Submerged in 1.95 oil with; L - 5.0; "f" - 5.6; T — 60.0; M - 240x and heated for 1.0 Hr. @ 500°C. The sample contained large particles with very little small crystals. In View the crystal mass is both Opaque and clear. The opaque section has an index lower than the oil, whereas, the clear section has a higher index than the oil. Under C.F. some of the crystals appear yellow to green yellow, others with blood red color. NOTE: These two samples do not resemble each other in appearance at all. The granular characteristic (Figure 49) may be due to the lack of comminution. 155 156 Figure 50 - Corrosion Sample - Pipe Nipple Taken from Top Index Oil - 1.95, M - 240x. 4-A Photo--4-A Description: Sample submerged in index oil 1.95 with; L - 5.0; "f" - 4.0; T - 125 and M - 240x. It can be observed from the figure that there are many Rhombohedral clear crystals (by arrow) in addition to the masses of opaque mineral structure. Under C.F. observation, the opaque sections, if thin enough, are red outside and some are completely red—orange. However, some crystals exhibit varying color to include purple, blue, yellow, and green. In T.S. clear crystals are Rhombohedral shape (as in Calcite) with a vitreous orange mass. In observing the indexes, the clear crystal has a higher index than the oil, whereas, opaque crystals have a lower index than oil. 157 158 Figure 51 - Corrosion Sample - Pipe Nipple Taken from Bottom Index Oil - 1.95, M - 240x 4-B Photo--4-B Description: Sample in 1.95 index oil with; L - 5.0; "f" - 4.0; T - 125 and M - 240x. Again the clear Rhombohedral crystals can be observed. The clear Rhombohedral appear as salt on a. plate in this figure. Under C.F. the opaque section is orange on outside or entire depending on thickness--if thin all orange. Again, there are some greenish-yellow crystals. In T.S. the clear Rhombohedrals are orange to red and the Opaque sections are dark orange to red. 159 160 Figure 52 — Corrosion Sample - Pipe Nipple Taken from Top 1.0 Hr. @ 500°C Index Oil - 1.95, M - 240x 4-C Photo--4-C Description: The index oil is 1.95 with; L - 6.0; "f" - 4.0; T - 125; M — 240x. The clear Rhombohedral crystals are gone and the normal opaque mass (by arrow) and many vitreous masses are visible. The clear crystals have a higher index, whereas the reverse is true for the opaque sections. In T.S. a definite red color appears at the large opaque masses that somewhat resemble Hematite-- especially true in thin section. In thick section a black appearance is evident. As the stage is rotated in T.S., the colors yellow, green and blue appear; disappear, and reappear. 161 t 162 Figure 53 - Corrosion Sample - Pipe Nipple Taken from Bottom 1.0 Hr. @ 500°C Index Oil - 1.95, M - 250x 4-D Photo--4—D Description: The index oil is 1.95 with; L - 6.0; "f" - 4.0; T - 125; M - 240x. The opaque crystals have a lower index than the oil, whereas, the clear crystals have a higher index than the oil. Generally, the Rhombohedrals are absent with mass and vitreous (by arrow) being the bulk for observing. In T.S., most crystals are opaque with some clear vitreous masses. Under C.F. the vitreous mass appears greenish-yellow. 163 CHAPTER VII DISCUSSION OF RESULTS General Discussion of the data will take the following format: the Protective Coatings will be discussed separately as will the Iron Compounds and Coatings (a. Chemical, b. X-ray, and c. Petrographic MicrOSCOpe). A summary will follow coordinating all three test results. Protective Coatings Chemical The data for Calcite (CaCOB) Reagent grade and Protective Coating--laboratory formation relate quite well, 39.55% and 37.9% Ca(II) respectively for the two as compared to the theoretical value of 40% Ca(II) (Appendix B) of pure CaCOB. In any chemical test, the accuracy depends on the technique, reagents, and the interferences as des— cribed by Standard Methods. The limitations of chemical testing when Ca(II) ion is determined relate to other ions such as Carbonate (CO3) or ions in Solid Solution. 164 165 X-ray 1. Calcite (CaCO3L l-A: Reagent Grade The X-ray pattern as illustrated in Figure 18 is very clear and precise. The important measurement is the diffraction angle and intensity. It is important to note the very low background base level of intensity 2.0: %. When comparing the data, Figure 18, with the X-ray data Appendix C and D, the identification is complete. Actually, Appendix D identifies the X-ray pattern with the known X-ray data by the ratio of the two radiations (Copper to Iron). The three principle angles and "d" spacings are: 29.68° - 3.04 > 3.014%; 39.65° - 2.29 > 2.28A; and 43.12° - 2.10 > 2.08A. The X-ray pattern of Calcite (CaCO3) is standard and is used as a match to identify other X-rays. l-B: Protective Coating, Laboratory Formation The Calcite (CaCO3) X-ray pattern was determined and comparison of Figure 19, Protective Coating, to Figure 18 identified Calcite in the coating. It should be noted that the X-ray was conducted on a Calcite formation (CaCO3) as formed on a cast iron test plate and the entire unit (coating and plate) was tested as companions. 166 The results point to a formation of Calcite (CaCO3) when comparing Figures 18 and 19. However, the intensities are generally lower. Conversely, two dif— fraction angles and their intensities are higher or 26 = 31.6° and 47.7°. In addition, a new diffraction angle appears with value of 44.9°. The explanation of the new 26 = 44.9° can be found in Figure 20, Cast Iron X-ray pattern. This angle is approximately 96.0% of the 100.0% intensity value and indicates that the Cast Iron background did exhibit some influence on the X-ray pattern. The Cast Iron test plate with the Protective Coating (expected Calcite (CaCO3) was used because remov- ing the coating might also remove small pieces of Cast Iron which would contaminate the sample. Also, during the coating formation one or several ions may have formed in solid solution to slightly alter the X-ray pattern. It may be concluded that the X-ray pattern of Figure 19 generally fits Figure 18 in angle and inteisity comparisons. l-C: Cast Iron The X-ray pattern of the Cast Iron test plate was made to assist in identifying any diffraction angles that might occur in the testing of specimen l-B Protective Coating, laboratory formation. As discussed above, at least one diffraction angle was identified as showing through the protective coating. 167 The Cast Iron X-ray is used to interpret other X-rays when the coating is formed on Cast Iron and tested as companions. Petrographic Microscope l. Calcite (CaCO3) l-A: Reagent Grade 1:A:£.--From Figure 21, the pure Calcite crystals are rhombohedral in shape. The sizes vary from large to small. The crystal under study as identified by the arrow shows shadow on one side and the edge blends in on the other (this particular crystal is identified to Figure 54, Calcite located in Appendix F). The identified crystal is aligned with one of the Optic axis. The crystal is noted to have all the characteristics of Calcite (CaCO3)-- especially the blue and orange color when viewing with both polarizing filters in place (see Appendix E). l-A-II.--A View of the same crystal as l-A-I except that one axis is parallel to the lower filter axis and a crystal index investigation can be made. The Becke Line Method will be employed. The index Oil is 1.55 and when raising the barrel a very dark outline appears on the crystal edge and has moved out as shown by the arrow of Figure 22. The dark- ness is more apparent on the side, where before the edge 168 was difficult to determine. Darkening at the outer edge indicates that the liquid has a higher index than the crystal in this particular axis alignment. As per Appendix E, the axis in view is the n8 or extraordinary ray axis. The ray n8 is 1.486 < 1.55. l-A-III.--In viewing the crystal in Figure 23, it is apparent that the crystal has been rotated 90°. The crystal takes on a different cast (dark) at the edges than for Figure 21. The darkness is due in part to the crystal depth and also to the large birefringents (0.172) of the crystal (Appendix E). The 90° rotation allows observation of the n - 1.658 from the previous n€ - w i 1.486 ray. l—A-IV.--The observation of Figure 24 immediately reveals that the crystal rotation is as for Figure 23. No ray is now in focus and the Becke Line Method is being used to determine the closeness of the index oil to the nw ray. The oil has an index of 1.55, and the nw ray index is 1.658. Therefore, when the micrOSCOpe barrel is raised--the dark edge outline moves into the crystal-- indicating that the oil has a lower index that the crystal 1.55 < 1.658. Darkness surrounds the sides and leaves only the apparent flat top undarkened. 169 l:§:2,--This sample is identical to the others except the View is as per Figure 23-24. The illustra- tion is for an index determination using the Half or Oblique Method. The oil is 1.55 and the nw ray is being viewed Nm-l.658. The light source to the crystal mounting is one- half blocked and therefore, the half method. The dark side of the stage and the crystal (as per arrow) are dark, and the light side is facing the lighted area of the stage. For this, as for Figures 12 and 13, the crystal index is higher than the Oi1--that is Nw-1.658 < 1.55. l-B: Protective Coating, Laboratory Formation l:§:£.--Figure 26 is of a suspected Calcite crystal. The crystal is a rhombohedral and is difficult to observe even though an arrow is pointing directly toward it. There is one noticeable difference from the reagent grade Calcite; most crystals are generally smaller and less perfect in shape though in some cases, the individual crystals are perfect to observe and to work with. l-B-II.--Figure 27 is of the same crystal observed in Figure 26 and the photograph was taken to observe the Becke Line Method in testing a small, 170 apparent Calcite crystal. As the barrel is raised, the dark moves up into the crystal and a light spot appears in the crystal center. The dark movement into the crystal indicates that the crystal has a larger index than the 1.55 index Oil, and it is suspected that the ray being observed is the Nw-l.658. Summary of Protective Coatings The data for the Calcite (CaCO3) Reagent grade compare quite well for chemical, X-ray with the micro- SCOpe. Comparison of the chemical, X-ray and microscope work of the Protective Coating, laboratory formation, also appear to coincide and the X-ray pattern of the protective coating attached to the Cast Iron plate is valid. Knowledge of the Cast Iron X-ray is of course important in this technique. Differences should be noted, however, when com- paring the Calcite Reagent grade with the Protective Coating. The chemical tests vary slightly, X-ray intensities are either less or (in two cases) greater, and although the crystal structure is always rhombohedral the crystal formation size of the Protective Coating is smaller. From this it is concluded that the formation coating is Calcite, though not in pure form. 171 Iron Compounds and Coatings Chemical It has been reported that the Ferrous Fe(II) oxidized to the Ferric Fe(III) state with time and under prOper conditions. Laboratory testing did not allow natural oxidation of the Fe(II) to (III) and various samples were heated to promote rapid oxidation. The oxidation of the Fe(II) to Fe(III) in some minerals may force an alteration of the crystal structure and mineral type. This oxidation is illustrated in equations 8, 9, and 10 and eSpecially in equations 8 and 10. The con- version of hydrated Magnetite (FeO°FeZO3°nH3O)--Goethite [aFeO(OH)] by rapid oxidation has been reported and, in the interest of time, heating for 1.0 Hr. @ 500°C was selected to promote rapid oxidation. 1. Hematite (Fe293l l-A: Reagent Grade Pure Hematite has an Fe(III) of 70.0% as per Appendix B. The test results average 70.05% Fe(III), which is very good. l-B: Reagent Grade @ 1.0 Hr. - 500°C This check was performed to observe any changes that might occur. The data show that Fe(III) was greater than 70.0%. As noted in Appendix B, the Fe(III) of Hematite is 70.0%. 172 l-C: Reagent Grade Plus Water Water was added to the sample to observe the effect, if any; that is, would the water become bound or water of hydration. The average Fe(III) percentages of 66.6% appear to indicate that some water was chemi- cally bound. The value is 66.6%, and falls between the 62.8% or 57.2% for Fe O with 1 or 2 moles of hydrated 2 3 water (Appendix B). l-D: Reagent Grade Plus Water @ 1 Hr. “ 500°C Sample l-C was heated for 1 Hr. @ 500°C to drive off the bound hydrated water and restore the reagent— grade-plus-water to the original Hematite. Within the chemical testing limits, the Fe(III) average percentage was 71.03%, higher than expected but assuming that the bound water was eliminated, reasonable. 2. Magnetite (Fe394l 2-A and 2-B: Fe3O4 and 1 Hr. - 500°C This sample, as extracted from an iron kiln, was chemically tested to determine Fe(III) both with and twithout heat (1 Hr. @ 500°C). The values for the unheated sample was 72.03%, and with heat was 71.46%. As per is 72.4%. Appendix B, the value of Fe(III) for FeO°Fe O 2 3 173 It is important to note that the Magnetite dis- solved very slowly in the acid solution (hydrochloric), and it is then not surprising that the Fe(III) values are not exactly 72.4%. 3. Siderite (FeCO3) 3-A: Laboratory Formation The laboratory formation exhibited no character- istics of Siderite. Chemical testing revealed that the Fe(total) percentage was higher than that of Appendix B Fe(total) for which FeCO3 + 48.2%. The formation was observed to oxidize immediately from FeCO3 + to Fe203°nH20. The 54.25% Fe(total) places the compound somewhere between Fe203°2H20 - 57.2% or Fe 03°3H20 - 52.5%. 0x1- 2 0 dation from the FeCO3 to the Fe203°nH20 is as predicted. FeCO3 + Fe203°nH20 + Fe203 (9) Siderite Limonite Hematite* From the above, the Siderite oxidized quickly to form Limonite. Limonite is an intermediate step toward Hematite, and the physical appearance of Limonite changed immediately from greenish-gray to brown-yellow. *With water of hydration can be termed Goethite. 174 3-B: Laboratory Formation @ 1 Hr. — 500°C The sample from 3-A was in an oxidized state and heated to force further oxidation. Fe(total) percentage increased from heating to 61.7%. The oxidation level altered the crystal and mineral structure, approaching either Goethite (20) (Appendix B) Fe(III) 62.3%, or Hematite plus water of hydration FeZOB-lHZO Fe(III) of 62.8%. 4. Corrosion Sample The sample was removed from the nipple in layers-- tOp to bottom—-and will be discussed in that manner. 4-A: Pipe Nipple—-Top The sample tested and the percentage recorded 64.2% Fe(total) indicates that the oxidation state is between Hematite (Fe ) and Hematite plus water with 203 Fe(III) of 70.0% and 62.8%, respectively. The top layer of the blister was a green-gray, and a layer effect was apparent. 4-B: Pipe Nipple-—Bottom The bottom layer when removed from the pipe nipple was similar to the top layer in physical appear- ance and color. Testing showed that the (total) Fe was less for the bottom layer. Average percent Iron was 175 58.2% indicating that the oxidation state was between the Fe203-1H20 - 62.8% and Fe203°2H2 These observations were surprising because it O - 57.2% of Appendix B. has been reported (42) that the top layers are of a porous nature and that the oxidation state is predicted as per equation (8); that is, the percentage of iron should increase with depth. -C: Pipe Nipple--Top 1 Hr. - 500°C 4 @ Upon heating, the total iron percentage increased in Sample l-A from 64.2% to 66.7% Fe(total). Some of the water of hydration was driven off, but not all. Hematite (Fe203) has an iron content of 70.0% and Fe203'lHZO is 62.8% Iron. -D: Pipe Nipple--Bottom 1.0 Hr. - 500°C 4 @ This sample from 4-B was heated to drive off water of hydration and Fe(total) increased from 58.2% to 60.1%. This oxidation state approaches Goethite a[FeO(OH)] Fe(total) of 62.3%. Goethite was more prob- able than Lepidocrocite because Goethite is formed by rapid oxidation, and the latter is formed by slow oxi- dation (see equations 8 and 10). The possibility that sample 4-D being Fe203 with hydrated water cannot be ruled out. The range would then be Fe203-3H20 - 52.5% and Fe203'2H20 - 62.8%. 176 X-ray It is important to note that the baseline level of interference for all the iron compounds is higher than the levels for the Calcite coatings. There is no inter- ference with testing or observation, however, so long as an altered baseline is observed. 1. Hematite (FeZQBL l-A: Reagent Grade Hematite was selected as a compound that would serve as a reference for other X-ray comparisons. Hematite (Fe ) was especially apprOpriate because this 203 compound is present in many of the other altered forms and/or oxidation states. In Figure 28, reagent grade Hematite was tested using Iron radiation with a nickel filter. The radia— tion angles are as tabulated below the figure. The three radiation angles (20) with the largest intensities respectively are: 33.34° - 100.0%; 35.8° - 71.0% and 54.21° - 48.4%. Radiation peaks are very sharp and recognizable. Inasmuch as Hematite plays a large role in protective coatings, tests were conducted to observe any changes. l-B: Reagent Grade @ 1.0 Hr. - 500°C Pure Hematite was heated to observe any change and to duplicate rapid oxidation. The result of this 177 testing is shown in Figure 29. Figure 29 is identical to Figure 28, showing Hematite (Fe203) to be a very stable form. l-C: Reagent Grade Plus Water Water was added to Sample l-A to Observe any water of hydration. The sample was mixed, allowed to sit, dissicated and prepared on the glass plate for X-ray testing. Figure 30 is the X-ray pattern. The pattern is identical to Figure 28, Hematite reagent grade (Fe203), and no hydration was experienced. l-D: Reagent Grade Water Added Plus 1.0 Hr. - 500°C Sample l-C was heated and then X-rayed. No change in the X-ray patterns from Figures 28 and 30 was noted, and there was no water of hydration. 2. Magnetite (Fe394l 2-A: Fe3O4 The Magnetite was taken from an iron furnace, and chemical testing showed Fe(total) 72.0% and 71.46% as compared to 72.4% for Appendix B. The X-ray pattern of Figure 32 is for the sample of Magnetite. When compared to Figure 28, the only radiation angle that corresponded was 28 - 35.8° or d = 3.153. 178 2—B: Fe3O4 1 Hr. - 500°C Magnetite is unstable and can be oxidized. A sample of Magnetite was heated for one hour at 500°C and X—rayed. Figure 33 and the table indicates the change that took place after heating. The three 28 angles in Figure 32 were repeated in Figure 33. Angles 35.8° and 42.4° were more intense. However, 26 - 36.3° diminished in intensity. Heating altered the entire crystal structure and six new diffraction angles appeared: 33.3°, 43.40°, 57.10°, 58.90°, 61.04°, and 62.65°. In comparing Figure 28 with Figure 33, the 28 angles that match are 33.34° and 35.64°. This is some improvement over the unheated Magnetite for which one angle only coincided 29 - 35.8°. The oxidized material did not take on the form of Hematite, probably because there was no water of hydration. 3. Siderite (FeCO3) 3-A: Laboratory Formation 3-A—I, II, III.--X-ray pattern for Siderite, Figures 34, 35, and 36 are identical. The formation is amorphous (no crystal structure) and could be only one iron compound, Limonite, not Siderite. As per equation (9), 179 FeCO3 + Fe203°nH20 + Fe203 (9) Siderite Limonite Hematite Siderite is oxidized to form Limonite and the X-ray provides perfect identification. 3-B: Laboratory Formation 1 Hr. - 500°C 3-B—I.--Use of heat to speed the kinetics of oxidation was successful. The Limonite formation (FeCO3 oxidized) plus heat formed Hematite (Fe203) as predicted by equation (9). The formation of Hematite (Fe203) is evident when comparing Figure 37 with Figure 28 Hematite (Fe203) pure reagent grade. The diffraction intensities are not quite as sharp or large but comparison in terms of the diffrac- tion angles (28) is almost perfect. 3—B-II.--Here, the match between Figures 38 and 28 is not perfect. The diffraction angles (28) do not match and in fact; 28 - 24.32° and 28 - 41.09° did not appear. In addition, 28 angles 49.80° and 28 - 54.30° are of very low intensity, barely discernible. It is suspected that the oxidation of the FeCO3 + Fe203-nH20 + Fe203 was not complete; it could well be that the heating period should have been longer. However, the change toward Hematite (Fe203) is evident. 180 3-B-III.--Comparison of Figure 39 to Figure 28 reveals that the pattern generally matches that of Hematite (Fe203) pure reagent grade. The 28 angle - 4l.O° is evident, but barely so. Two new comers have arrived and may be a false background reading or an impurity. Intensities of these new lines are difficult to detect. In spite of imperfections, the compound repre- sents Hematite (Fe203). 4. Corrosion Sample The sample was removed from the nipple in layers-- top to bottom--and will be discussed in that manner. 4-A: Pipe Nipple--TOp Figure 40 reveals that there is only one diffrac- tion angle; 28 - 35.72°. This angle correSponds to 28 - 35.80° in Figure 28. However, it is noteworthy that the angle 35.72° is not the 100% intensity angle of Figure 28 (angle 28 - 33.34°). From Appendix C, Lepidocrocite [y-Feo-(OH)] the 100% intensity and the corresponding 28 angle 34.40° with d - 3.273, generally matches the 100% intensity of Figure 40 with a 28 angle 35.72° where d - 3.16A. The corrosion sample oxidized over a long period of time and the compound X-rayed is organizingtoward 181 the formation of Lepidocrocite [y-FeO'(OH)] as per equations (8) and (10). 4-B: Pipe Nipple--Bottom Samples 4-A and 4-B appear to be identical in X-ray pattern. The 28 angle 35.64° from Figure 41 is only .08° different from the 28 — 35.72° in Figure 40. The conclusions are identical to that for 4-A and the compounds appear to be oxidizing toward the formation of Lepidocrocite [y-FeO'(OH)]. -C: Pipe Nipple--Top 1 Hr. - 500°C 4 @ If the top and bottom corrosion samples are organizing toward Lepidocrocite, heating for 1 Hr. - 500°C should force oxidation toward Hematite (Fe203). In Figure 42, the X-ray pattern is starting to exhibit Hematite (Fe203) tendencies. When comparing to Figure 28 all the 28 angles are observed except 28 — 24.32°. Diffraction intensities and peaks are less sharp and defined than for Figure 28, but the 28 angles are present. The angle in question is 28 - 41.00°, though excitation of this angle is marginal. From this, we may assume that the heated sample was converted to Hematite (Fe203) and not Lepidocrocite. 182 It can be safely presumed that Lepidocrocite did not form inasmuch as the 100% intensity is for a 35.-° angle and the 100% intensity in Figure 42 is 28 - 33.0° range. 4-D: Pipe Nipple--Bottom @ 1 Hr. - 500°C In Figure 43, the X-ray pattern is approaching Hematite (Fe203) and the only angle not in appearance is 29 - 41.09°. For this pattern the 29 - 24.48° did appear over that of Figure 42. It is concluded that the compound X-rayed is exhibiting the near normal pattern of Hematite (Fe203). Petrographic Microscope l. Hematite (FeZQBL l-A: Reagent Grade Figure 44 illustrates the general appearance of (Pure) Hematite (Fe203). The overwhelming color--red-- is an outstanding identification. The random distribu- tion of a vitreous mass--note Figure 44--is important and will be referenced to in later text. Also, it is common to see a "glob" of material, even though the sample has been comminuted. 183 l-B, l-C, and l-D: Reagent Grade (1 Hr. - 500°C; with Plus Water and 1 Hr. - 500°C In the testing of l-B, l-C, and l-D, it was learned from X-ray pattern of these respective samples that each is identical to Hematite (Fe203) reagent grade. The petrographic microscope verified the reagent grade status. Duplication of data has been omitted because Figure 44 is representative of the Sample l-B, l-C, and 1-D. 2. Magnetite (Fe3g4) 2-A: Fe3O4 (taken from kiln) The identification of Magnetite can almost be determined by visual inspection. The material is unique, and the magnetic property is a specific identification. Review of Figure 45 illustrates the crystal mass. Some vitreous material is evident--note arrow. It is difficult to check the crystal index because selection of a prOper crystal is impaired by the fact that the crystal color (Appendix E) is either black or Opaque in nature. A more thorough comminution should assist in crystal viewing and identification. 3. Siderite (FeCO3L 3-A: Laboratory Formation 3-A-I.--It was hOped that the compound Siderite would result because Siderite has been cited in the 184 literature as forming an outer protective coating over other materials. Instead, X-ray and microscopic tests showed the compound had no crystal structure and appeared to be Limonite. Figure 46 shows the lack of real fine crystal material and predominance of large gross crystals. An index check (see arrow) was made because for an opaque compound the index is lower than for the oil. A small percentage of this sample is vitreous and has a higher index than the oil. This compound has a reddish to brownish cast when viewing and the compound appears to be Limonite. 3-A-II.--Figure 47 is from an index check of the Opaque crystals. This figure indicates that as the microscope barrel was raised (slightly out of focus) the Becke Line moved out and away from the crystal as shown by the arrow. Note the light and almost white outer crystal edge. A Becke Line allows a positive confident crystal index oil check. The Oil has a higher index than the compound, suspected to be Limonite. —B: Laboratory Formation 1 3 @ Hr. - 500°C 3-B-I.--Microscope work on the heated Siderite samples showed that two materials may look and appear 185 different but be the same compound or crystal. In com- parins Figure 48 to Figure 44 - Hematite (Fe203) pure, it becomes Obvious that the heated sample is Hematite. The two figures (48 and 44) depict the same material type; that is, the earth compact "blobs" and the blood red color. 3-B-II.--This sample was prepared using the same techniques as of preparation as for the previous sample for Figure 48. Comparison of Figures 48 and 49 shows that in appearance the materials looked dissimilar. However, that is not the case. The materials are simi- lar, but not identical, and the X-ray and microscope work indicate this uniformity. In Figure 37, 38, and 39 (X-ray patterns), it can be seen that the heated sample does not in all cases coincide with the crystal Hematite (Fe203), but is being oxidized toward Hematite (Fe203). This is also true of this sample. There is a very dominant theme of Hematite (Fe203) black opaque crystals with the blood red showing under crossed filters. However, there are also yellow to greenish-yellow crystals in this material and this could be Goethite, suggesting that this material was being oxidized toward Hematite (Fe203). Goethite is suspected because this material is formed under rapid oxidation conditions. 186 4. Corrosion Sample 4-A: Pipe Nipple-~Top Figure 50 illustrates two types of formation. Large masses dominate the sample, but upon close review of the photograph, it is evident that small-clear-fine particles are common. The fine material is rhombohedral in shape and appears to have a higher index than the oil. The opaque crystals have a lower index that the oil. The overriding color of the mass or clear material is the red or orange-red indicating that the compound under investigation is Lepidocrocite [y-FeO°(OH)]. 4-B: Pipe Nipple--Bottom Figure 51 is much the same as Figure 50, a large mass with a great number of fine particles. There are clear rhombohedral crystals, generally very fine. A crystal index of the two types indicated that the clear crystals have a higher index than the oil, whereas, the opaque crystals have a lower crystal index than the oil. The color red is vivid both in the clear and Opaque crystals. It would also seem that this compound, as in 4-A, is Lepidocrocite. 4-C: Pipe Nipple-—Top @ 1 Hr. - 500°C Figure 52 indicates that the sample has changed when compared with 4—A, Figure 50. There are very few 187 fines, although more large vitreous masses (see arrow). The Opaque material is not as large as in 4-A but there are more smaller Opaque pieces. The crystal index of the clear vitreous material is higher than the oil, whereas the reverse is true for the opaque material. The appearance of Figure 52 can be compared with Figure 44 [Hematite (Fe203) reagent grade]. The identification is not perfect, but the trend is apparent. The compound or crystal under investigation has the appearance of Hematite. -D: Pipe Nipple--Bottom 1 Hr. - 500°C 4 @ After heating sample 4-B, the oxidized material has the appearance of Hematite. The red color of the clear and Opaque material is one identifying feature. The comparable appearance between Figure 52 and Figure 44 [Hematite (Fe203) reagent grade] also assists in identi- fying sample 4-D. Comparison of the X-rays of sample 4—A and 4-D indicate that the sample was being oxidized toward Hema- tite. The X-ray figures for 4-C and 4-D are 42 and 43 respectively. 188 Summary of Iron Compounds and Coatings l. Hematite (Fe O Reagent Grade _ 23)— It can be stated that the data as regards test- ing of Fe 03 (Pure) from a chemical, X-ray and micro- 2 scope standpoint correlates very well. One accurate method to correlate data is by use of X-ray diffraction. This procedure positively identified Hematite (Fe203) regardless of added water or rapid oxidation from heat (1 Hr. - 500°C). 2. Magnetite [FeO°Fe29 or {9394 or Fe(Fe294ll The identification of Magnetite can be accomplished by chemical testing if the prOper time and precautions are observed. The X—ray illustrates a perfect thumb print of the crystal, and this is confirmed by the micro- scope, though the dominance of opaque material is some- what limiting. The correlation, however, is solid evidence that the material tested is Magnetite. 3. Siderite or Ferrous CarbonateITFeCO3) (Form- ation From Mixing Ferrous Sulfate and Sodium Carbonate) The complete testing of Siderite (FeCOB) (chemi- cal, X-ray and microsc0pe) illustrates that Siderite was oxidized to form Limonite. Limonite was identified by 189 the chemical percentages, the amorphous structure from X-ray and confirmation of the microscope work, eSpecially the brownish color as described in Appendix E and under Petrographic Microscope, 3-A. The heating of the Siderite (actually Limonite) revealed a change, that is from Limonite toward Hematite. Correlation of this by chemical, X-ray and microscope work is good. X-ray patterns match very well with a few exceptions. However, data from the chemical tests and microscope indicate that oxidation toward Hematite is not complete. The chemical Iron percentage was 61.7 which was less than 70.0%. Also, the microscope work revealed something less than pure Hematite (Fe203). 4. Corrosion Sample-- Pipe Nipple Top The chemical testing of this material revealed an iron percentage of 64.2 which was higher than the suSpected Lepidocrocite. The percentage is somewhere between Fe203-1H20 and Fe203 and X-ray pattern, as compared with Appendix C, revealed Lepidocrocite. Microscopic testing of this compound also identified Lepidocrocite from the blood red color. The X-ray and microsc0pe work identified the unkonwn material which then conformed with chemical testing. 190 Bottom Testing for this unkonwn resulted in about the same results as above. That is, X-ray and microscopic data reinforced for identification even though chemical testing suggested another crystal. The X-ray data as compared with Appendix C and the microscopic data as compared with Appendix E provide sufficient proof that the material was oxidizing toward Lepidocrocite. Top--l Hr. - 500°C and Bottom--l Hr. - 500°C These two substances are grouped together because they are similar materials. The chemical testing data do not conform, 66.7% as compared to 60.1%. The X-ray patterns are quite close and are sufficiently matched to insure that both heated samples are in an oxidation state toward Hematite (Fe203)‘ MicrOSCOpic data reinforce the identification as Hematite. Corrosion samples for top and bottom layers were apparently the same material or the strip removal techniques were not effective. The heated samples are identical and the observation of the oxidation from Lepidocrocite toward Hematite is apparent. Though oxi- dation of the sample is not complete, the appearance and likeness provide sufficient evidence to identify the material as Hematite. CHAPTER VIII CONCLUSIONS The thesis is a format or methodology for the investigation of any internal coatings in water mains. These coatings range from Calcite to any of several iron coatings. Coatings vary widely because each water system is unique in water chemistry. The positive and negative ion balance reveals many types in solution. It should be noted that any trace ion can form in solid solution. In addition, iron released from cor- rosion often forms in solid solution. Therefore, a com- plete water chemistry profile of a water system is important when investigating an internal coating of a water main. 1. The visual observation technique is useful for quick identification. However, the reporting of color, hardness and appearance packing is only one clue in the total identification of a coating. Chemical, X-ray and microscope testing collectively are the real key to correct identification of a coating. 2. The identification of the unknown coating under investigation should start with properly calibrated standard data, eSpecially for Calcite (CaCOB) and 191 192 Hematite (Fe203). Reagent grade materials, or laboratory produced standards, after complete testing for correct- ness, can be used. Standards for chemical tests are as important as the standards used for testing by X-ray and with the microscope. These two latter forms of testing can quickly reveal the nature of an unknown material. The x-ray patterns of Calcite and Hematite, for instance, allow visual comparison with unknown coatings. A quick and accurate method for preliminary checking is to produce an X-ray pattern for comparison with a known X-ray pattern. 3. It is possible to form a protective Calcite coating (CaCO3) formation on a test Cast Iron speciman and to quickly check this coating by X-ray methods. This is called the "companion testing method." The standard X-ray pattern for Cast Iron and the pattern for Reagent grade Calcite (CaCO3) provide a visual X-ray review of a coating for a preliminary check. The "companion testing method" can be used in dynamic testing for Calcite coatings. At designated time intervals, the companion test sample can be dried, dessicated and an X-ray check conducted. The companion may be checked immediately after blot drying; water retained on the sample should not interfere with the X-ray pattern. 193 4. The testing of the Calcite laboratory forma- tion reveals Calcite, but not in pure form. The crystal formations, although rhombohedral in shape, were very much smaller than for reagent grade Calcite. One or more substances in solution in the water system may retard or ‘ alter the formation and reduce crystal size. However, the formation is Calcite and affords a protective coating. 5. It has been reported (14, 21, 22, 24, and 29) that Siderite (Ferrous Carbonate FeCO3) forms a protective coating over a Calcite coating on the water main metal, or over another iron compound. It was necessary to attempt formation of Siderite (FeCO3) in the laboratory because Reagent grade was impossible to obtain. The laboratory formation immediately oxidized to Limonite (amorphous). The X—ray best illustrates this no-crystal structure. It can therefore be concluded that Siderite oxidizes quickly in the presence of oxygen making it very difficult to develop a standard for testing. The oxidation of Siderite to Limonite is in accordance with equation (9) and was expected. The formation of Siderite in a Nitrogen atmOSphere could be used to provide a standard, but kinetics of oxidation after formation in a water system would be helpful. Again, if a water system has some dissolved oxygen, whether this is sufficient to allow oxidation 194 to form Limonite from Siderite is questionable. It seems doubtful that Siderite could be observed in a protective coating! 6. The oxidation of Siderite to form Limonite and the X-ray patterns revealed no crystal structure (amorphous). Testing of Limonite then took another path. From equation (9), Limonite oxidizes to form Hematite (Fe203) and in fact, the X-ray pattern is a close com- parison to Hematite (Fe203), Reagent grade. The simi- larity is not perfect and formation as per equation (9) could be Hematite plus hydrated water or Goethite. The application of heat speeds oxidation. Oxida- tion did take place, but the kinetics under normal con- ditions are not known for formation of Hematite. 7. The investigation of the corrosion formed on the pipe nipple was interesting. The dessicated form had little crystal structure and inasmuch as it was formed slowly, was probably Lepidocrocite. However, to expidite oxidation, heat was applied (1 Hr.-500 C). The x-ray of the heated unknown sample resembled Hematite. It can be concluded that the water of hydra- tion was driven off and the crystal structure changed to form Hematite (Fe203). The X-ray pattern is not perfect, but the general characteristics are apparent. 195 8. Care should be taken in using the microsc0pe for identifying iron bearing compounds. The black or Opaque sections make it difficult to observe the crystal index, but with care and patience, a reliable crystal index can be Obtained. In summary, most of the test data did reveal that a Calcite coating can be formed on a Cast Iron test specimen tested by X-ray. Various forms of Iron were revealed in testing and the oxidation of several com- pounds indicated formation of another crystal structure. No attempt was made to test the capacity of various coatings for inhibiting corrosion. X-ray tests should be the first checks considered for unknown coatings. Once the X-ray check has provided a lead, other testing techniques can follow, including use of the microscope and chemical testing. CHAPTER IX RECOMMENDATIONS The following recommendations are prOposed for refining the methodology of investigation for coatings in water mains. 1. All testing should be conducted on coatings that have been formed in a water system, that is, a formation that has been formed under field conditions. The testing should include the chemical and polarization studies to determine how effective a formation may be for providing a protective coating. 2. Use x-ray as the first check on any unknown compounds or crystals and comparison with the standards will provide good initial direction. 3. PrOper radiation and filter are required for best comparison results. Radiation and filter are sug- gested in Appendix C. 4. When testing for a Specific ion concentra- tion, an atomic absorption machine is recommended. A complete ion check can be conducted to reveal the ions bound in the compound or in solid solution. It is pro- posed that, in addition to Iron and Calcium tests, 196 197 checks for other positive ions such as Magnesium and Phosphorus be made. 5. Use great care in removing the specific layers of coating formation. The peeling or removing of Specific layers will allow the specific investigation of an oxidation layer for the iron compounds. Disturb- ing the layers reveals only one common compound, and does not represent the true nature Of the coating. 6. It is proposed to form a Calcite coating and to then Specifically allow some rusting to take place, causing iron formation to adhere to the Calcite coating. Observe the two in tandum for solid solution or increased protective capacity. Use of atomic absorption may be the only reliable test for the degree of solid solution. 7. More tests on the "companion testing method" to determine the thickness of Calcite (CaCO3) necessary to screen out the Cast Iron radiation pattern. 8. Form Siderite (Ferrous Carbonate FeCO3) in a nitrogen atmosphere to observe the crystal characteri- istics from X-ray and microscope standpoint. This forma- tion can be used for oxidation studies. More importantly, it could permit kinetics study to determine oxidation from the Siderite form to Limonite or beyond. A kinetics study Should be performed under conditions of normal water temperature, normal water pressures and normal chemical quality found in a water main. 198 9. When Limonite is formed observation of the change of crystal structure and the kinetics involved are suggested. The change is reported to form Hematite or, with some water of hydration, Goethite. Again, the formation of a study Should be in a water system near normal as compared to general water conditions in a municipal water distribution system. 10. A formation of Calcite (CaCO3) with several ions in solid solution would reveal much on the protec- tive coating on water mains. The formation of solid solutions could be useful in future interpretation. BIBLIOGRAPHY 199 10. ll. BIBLIOGRAPHY Larsen, Thurston E. "Chemical Control of Corrosion." J. Am. Water Works Association. 58:354, March, 1966. Haney, P. D. "Consulting Engineering Needs." J. Am. Water Works Association. 56:692, June, 1961. Whitney, W. R. "The Corrosion of Iron." J. Am. Chem. Soc. 25:395, 1903. Berry, L. G. and Mason, Brian. Mineralpgy--Concgpts, Descriptions, Determinations. San Francisco and London: W. H. Freeman and Company, 1959. Tillmans, D. Die Chemische Untersuchung Von Wasser. Soale, Ger.: Verlog Von Wilhelm Knapp, 1932. Langelier, W. F. "The Analytical Control of Anti- Corrosion Water Treatment." J. Am. Water Works Assoc. 28:1500, 1936. Moore, E. W. "Calculation of Chemical Dosages Required for the Prevention of Corrosion." J. New Epg, Water Works Assoc. 52:311, 1938. Langelier, W. F. "Effect of Temperature on the pH of Natural Waters." J. Am. Water Works Assoc. 38:179, February, 1946. . "Chemical Equilibria in Water Treatment." J. Am. Water Works Association, 38:169, February, 1946. Larson, T. E. and Buswell, A. M. "Calculation of Calcium Carbonate Saturation Index and Alkalinity Interpretations." J. Am. Water Works Assoc. 34: 1667, 1942. Ryzner, J. W. "A New Index for Determining Amount of Calcium Carbonate Scale Formed by a Water." J. Am. Water Works Assoc. 36:472, 1944. 200 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 201 Dye, J. F. "Correlation of the Two Principle Methods of Calculation the Three Kinds of Alkalinity." J. Am. Water Works Assoc. 50:800, June, 1958. McCauley, R. F. "Use of Polyphosphates for Developing Protective Calcite Coatings." J. Am. Water Workg Assoc. 52:721, June, 1960. Evans, U. R. Mettalic Corrosion, Passivity and Protection. London: Edward Arnold Publ. Co., 1937. Baylis, J. R. Ind. Eng. Chem. 18:370, 1926; 19:777, 1927; 20:1191, 1928. Tillmans, J., Hirsh, P., Weintraud, W. ‘Gas U. 'Wasserfach, 70:900, 1927. Baylis, J. R. J. Am. Water Works Assoc. 15:606, 1926. Schikorr, G., and Zeitseh. "Iron Hydroxides Formed in Rusting." Z. Anorg Chem. (Ger.) 191:322, 1930. Bengough, G. D., Lee, A. R., and Wormwell, F. Proc. Roy. Soc. A:l34, 1931. Girard, A. "A Detailed Study of Formation of the Different Forms of Rust." Unpublished Ph.D. thesis, Tillmans, J., Hirsch, P., and Schilling, K. Koll. Zeitsch, 47:98, 1929. Vernon, W. H. J. Trans Faraday Soc. 31:1693, 1935. Mears, R. B., and Evans, U. R. Trans. Faraday Soc., 31:532, 1935. Baylis, J. R. "Factors Other Than Dissolved Oxygen Influencing the Corrosion of Iron Pipes." Ind. Eng. and Chem., 18:370, 1926. Camp, T. R. "Corrosiveness of Water to Metals." J. New Eng. Water Works Association, 188, June, 1946. Obrecht, M. F. and Pourbaix, M. "Corrosion of Metals in Potable Water Systems." J. Am. Water Works Assoc., 59:977, August, 1967. Pryor, M. J. "Corrosion of Steel in Dilute Solutions of Sodium Salts of Weak Acids." Corrosion-- National Association of Corrosion Engineers, 9:467, December, 1953} 28. 29. 30. 31. 32. 33. 34. 35. 36. 37. 38. 39. 40. 202 Strumm, W. "Calcium Carbonate Deposits." J. Am. Water Works Assoc., 48:310, 1956. McCauley, R. F. and Abdullah, M. O. "Carbonate Deposits for Pipe Protection." J. Am. Water Works Assoc., 50:1419, November, 1958. Endo, H. and Kanazawas. Sci. Rep. Tohoku Univ., 19:427, 1930. Romeo, A. J., Skrinde, R. T., and Eliassen, R. "Effects of Mechanisms of Flow on Corrosion." J. San Eng. Div. Proc. Am. Soc. of Civil Eng., 4 84, July, 1958. Haase, L. W., Zeitsch, L. N. Angew. Chem, 44:992, 1931. Rice, 0., and Hatch, G. B. "Threshold Treatment of Municipal Water Supplies." J. Am. Water Works Assoc., 31:1171, July, 1939. Eliassen, R., and Lamb, J. L., III. "Mechanism of Corrosion Inhibition by Sodium Metaphosphate Glass." J. Am. Water Works Assoc., 46:445, May, 1954. . "Corrosion Control with Metaphosphate Glass." J. New Eng. Water Works Assoc., 44:31, March, 1955. Rosenstein, L. U.S. Patent 2,038,316, 1936; Reissue 20,360, 1937; Reissue 30,754, 1938. Reitemeier, R. and Buehrer, T. "The Inhibiting Action of Minute Amounts of Sodium Hexametaphosphates on the Precipitation of Calcium Carbonate Solutions." J. Physical Chemistry, 44:535, 1940. Larson, T. E. "Evaluation of the Use of Polyphosphates in the Water Industry." J. Am. Water Works Assoc., 49:1581, December, 1957. McCauley, R. F. "Controlled Deposition of Protective Calcite Coatings in Water Mains." J. Am. Water Works Assoc., 52:1386, November, 1960. Woodruff, P. H. "The Development of Protective Calcite Coatings on Iron and the Use of Polarization Measurements to Predict Their Anti-Corrosion Value," Unpublished M.A. thesis, Michigan State University, 1961. 41. 42. 43. 44. 45. 46. 203 Rossum, John R. "Prediction of Pitting Rates in Ferrous Metals from Soil Parameters." J. Am. Water Works Assoc., 303, June 1969. Larsen, Esper S. and Berman, Harry. 'The MicrOSCOpe Determination of Nonopaque Minerals. 2nd Ed. Geological Survey Bulletin 848. washington, D.C.: Department of the Interior, 1964. Berry, L. G., and Mason, Brian. MineralOgy Concepts, Description, Determinations. Saanrancisco: W. H. Freeman and Company, 1959. Singer, Philip C., and Strumm, Werner. "The Solubility of Ferrous Iron in Carbonate-Bearing Waters." J. Am. Water Works Assoc., 198, May, 1970. Wahlstrom, Ernest E. Optical Crystallography. 3d Ed. New York: John Wiley andeOns, Inc.,‘l965. Allen, Roy M. Practical Refractometry--By Means of a MicrOSCOpe. 2nd Ed. Cedar Grove, N.J. R. P. Cargille Laboratories, Inc., 1962. APPENDICES 204 205 mannemshse Boaawk xmmnum «.mlw Hmcowflue m>flummwz mONwm .pflom CH mansaom mum xomam ou wmuw Hmcommxwm Hmflxmecs opeumEmm pfiod ca mansaomnl ee.oenmoomh .ae.emumooms messemstse .ww.mmlmoumu vm.mlw c3oum xumo Hmcomfiua m>Hummwz OUN.OAmm.mEVOMU sufi3 Hmuwcflfi How sumo o.mum Op mmmHHOHou accommxwm HmflxMflcD wuflumxcd .wnan moot ou mans» mcfiumpzom co m.Hum m m was .cmmum we mmmHHOHOU o.m|o Ozam .:wwno m>fiafimom 0 mm. o~m.ome Hum aw mandaom o.mlm ou mmOHHoHoo OflcHHoocoz HmwxMHm wuflcmw>fl> c N s o N N N whm I 00 wan. IO m mum :BOHm Op 00 2.5V EMU .eem.uso .eem.m-m ee.muo msem on romeo meeusmmz moNam .omom mcflmucoo pfiod cw .Hom o.m|m Op mmmHHOHOO Hmcoquom HmeMHcD wueummd Au.cmmoo mufloamuv “mozmu CH pmafion SOSB own mHanmSMGH c3oum ou mcflmpm wam.mm I moomo vm.mlw wsHm Op cmmnw w>Hummmz mou.omu pflom updaflp Ge manwaom vim Op mmmHHOHOU censonuonuuo HMHxMAm muflcommud moo .Omo pwEth wanmflmsmcH czonm Op m woes u moomo mee.~-o spam on sense oomo Ilpfiom :fl mmomm>nmmmm mum on mmeuOHou Hmcommxmm awemecD wufioamo > a a am: u.H.n. m cofiuamomEoo m umEm w >MH>MHO Ho O Ewumwm m . x m camaowmm a 0 anyone: SOHO m can .mmwspnmm Emz Hmumcez a“! «.mamuwcez wsqwmocoz How muma I e xHDzmmm« 206 .vomH .MOHMOUCH mnpxmo ucwauummma .m.D .mvm :Humaasm >m>udm HMOHUOHOOO ..pm cam msqmmocoz mo coflumcHEHmumo Ofimoomouoe: one .muumm .:mfihwm paw ..m memm .cmmumq Eoum cwxme .mamumcflz Omm.mONmm liposuou on emu mmcmuo Hana xmmuum ONm.mONwm Ilpweumu on :80 Hum CH wHQDHOm muflnumow Euom Op pmnwaamummuo Hum Se OHQSHOm NoO.OO pmeumu w :80 .wm- oomo mama cows .womu oomm sou nest .teom sh messeom oaumcmmz AvONmmvwm .vOmmMIpwEHmu on :mu H.¢I0 meneansmse ms.m-o o.e-r pom UOOHm xomHm ou :3oum Ho soHwa xomam 0p :30Hm czoum >muw awesomuw ou ammo Op BOHHOM wmuw mzqmmo .xomam oessosnoseno sensosnoseno msosmuosd Hmcomflue Hmcommxmm OahumEOmH m>flummmz Hafixmflm m>flummmz Hmflxmwm erOHMOmH m>fiummwz Hafixmfics ensemm AmOVOOMIx mufloouoopwqu Amov.ommuo measumoo ONmG.mONmm muflcoefiq moomm meanmeem mONmm.Omm muflumcwmz APPENDIX B CALCIUM (Ca) AND IRON (Fe) PERCENTAGES IN VARIOUS COMPOUNDS Calcite - CaCO 3 Iron Oxide - FeO Hematite - Fe203 plus water - Fe203°1H20 plus water - Fe203°2H20 plus water - Fe203°3H20 Magnetite - FeO°Fe203 Siderite - FeCO3 Ferrous hydroxide - Fe(OH)2 Goethite - d[FeO(OH)] Lepidocrocite — y[FeO(OH)] 207 40% Ca 77.9% 70.0% 62.8% 57.2% 52.5% Fe(II). Fe(III), Fe(III) Fe(III) Fe - Limonite - 2[Fe(OH3)](III) 72.4% 48.2% 62.3% 62.3% 62.3% Fe (Total) or Fe304 Fe(II) Fe(II) Fe(III) Fe(III) APPENDIX C X-RAY DIFFRACTION DATA* The following data is as pertains to the three highest reflection-intensity ratios as per X-ray dif- fraction techniques. Material, Composition "d"°Spacing 28 Angles and Radiation in A units I/Io% in degrees Calcite CaCO3 3.04 100 29.68° Radiation = CuK , o A = 1.5305A 2.29 18 39.65° Nickel Filter 2.10 18 43.12° Aragonite CaCO 3.40 100 * Radigtion = A = 1.98 65 Filter 3.27 52 Apatite 9CaO°3P205 2.82 100 * Ca[Fe2(OH)2, CO3,C12] Radiation = A = 3.45 75 Filter 3.11 75 Vivianite 3FeO P 05°8H2O 6.80 100 * Radiation = A = 2.97 67 Filter 2.91 67 *Data not available. 208 Appendix C.--Cont. 209 Material, Composition "d"°spacing 28 Angles and Radiation in A units I/I°% in Degrees Ankerite CaO'(Mg,Fe)O°2COz * Radiation = CuKa. o l = 1.5405A Nickel Filter Hematite Fe 03 2.69 100 42.20° Ra iation = FeKa, o A = 1.93597A 2.51 80 45.20° Calcite Filter 1.69 80 70.00° Magnetite (FeO°Fe203) or (F8304) 2.53 100 44.80° Radiation = FeKa, o A = 1.93597A 1.48 70 81.60° Calcite Filter 2.97 60 38.00° Siderite FeCO3 2.79 100 40.60° Radiation = FeKa. o A = 1.93597A 1.73 80 68.00° Calcite Filter 3.59 60 31.20° Limonite Fe O3°nHZO Amorphous 0° Ra iation = not A = necessar Amorphous 00 Filter y Amorphous 0° Goethite a—FeO°(OH) 4.18 100 24.73° Radiation = CoKa, o A = 1.7889A 2.44 80 43.00° No Filter 2.69 70 39.47° *Data not available. 210 Appendix C.--Cont. Material, Composition "d"°Spacing 28 Angles and Radiation in A units I/I°% in Degrees Lepidocrocite y—Feo-(OH) 3.27 100 34.40° Radiation = FeKOH o = 1.93597A 7.30 90 15.00° Calcite Filter 2.56 80 44.40° *As compiled from: A. N. Winchel and N. H. Winchel, Elements of Optical Mineralogy (4th ed.; New York: John Wiley & Sons, 1927). Horace Winchel, Optical Properties of Minerals-- A Determinative Table (New York: Academic Press, 1965). Handbook of Chemistry, Physics (36th ed.; New York: Chemical Rubber Pubiishing Company, n.d.). X-Ray Power Data File Set 1-5, ASTM Special Technical Publication 48-JITNew York: American Society for Testing Materials, 1960). X-Rangower Data File Set 1-5, ASTM Special Technical Publication 48-I (New York: American Society for Testing Materials, 1960). APPENDIX D SOME CALCULATIONS OF "d" SPACING FOR CALCITE (CaCO or CaO°C02) 3 USING BRAGG'S EQUATION* A = 2d sin 9 (12) where A = Radiation in Angstron A o d = Lattice spacing in Angstron A 8 = Radiation angle makes with horizontal lattice plane Use: a) Iron radiation where kal = 1.93596 = 1.936A b) Nickel filter w/ 0.021mm thickness Therefore A = 2d sin 6 (12) Select the reflection angle 2 8 = 29.68° from Figure 18. Therefore 2 8 = 29.68° or 8 = 14.84 (sin 14.84° = .256). _ 1.936 _ o d - W’ 3'7“" *As referenced from: L. G. Berry and Brian Mason, Mineralogy Concepts, Description, Determinations (San Francisco and London: W. H. Freeman and Company, 1959). 211 212 AS per Figure 18 the 20 angles, ratio percent intensity and calculated "d" Spacing: 26 Il/IO Calculated "d" spacing 26.71° 6.9% 4.213 29.68°* 100.0% 3.78A* 31.700 5.0%: 3.54% 36.28° 15.0%: 3.11fi 39.65°** 17.6%: 2.68&** 43.42°*** 17.6% 2.62A*** 47.39° 7.5% 2.42% 47.71° 16.3% 2.408 48.75° 17.5% 2.353 However, as per ASTM Data Sheet for calcium carbonate (Calcite) Appendix C the "d" spacing for the lattices yielding the highest reflection ratio is as per astericked above. 28 Il/Io d Ad corrected *29.68° - 100% - 3.04A > 3.014A **39.65° - 18%: - 2.293 > 2.28A ***43.12° - 18%: - 2.10% > 2.08A AThe correction factor is a ratio Of the "d" Spacing as calculated using cgpper radiation Of 1.54A and the iron radiation of 1.935A or iv“!- ‘1- 1.543 = 1.9358 *3.78A x .796 **2.86A x .796 ***2.62A x .796 .796 3.014% O 2.280A O 2.085A 213 APPENDIX E DATA ON MINERALS FOR USE OF PETROGRAPHIC MICROSCOPE* The color of crystal is as viewing without any polarizing filters and isolating one Single crystal. The color of mass is the same as above except that the crystal is in mass. The color of thin section is as viewed with both polarizing filters in place viewing a single crystal. Legend: A Based on various concentrations of ions * Apply only to uniaxial mineral group i Difference between refractive indexes for uniaxial group — when no>n€ mineral considered 0 Difference between nz and n refractive indexes for biaxial group is the refracfive index. *Based on Esper S. Larsen and Harry Berman, The Micro- scope Determination of Nonopaque Minerals, Geological Survey Bulletin 848 (2d. ed.; Washington, D.C.: U.S. Department of the Interior, 1964). L. G. Berry and Brian Mason, Mineralogy Concepts, Description, Determinations (San Francisco and London: W. H. Freeman and Company, 1959). A. N. Winchel and N. H. Winchel, Elements of Optical Mineralogy (2d. and 4th eds.; New York: JOHn Wiley & Sons, 1927). 214 215 Calcite - CaCO3 Group--Uniaxial, Negative System--Hexagonal Trigonal Habit--Rhombohedra1 Color of Crystal--Colorless Color of Mass--Vitreous Color of Thin Section--blue and orange Isotropin--No *Pleochrism—- Refractive Indexes: N0 = w = Ordinary ray = 1.658 NS = E = Extraordinary ray = 1.486 Birefringent Index = .172 Aragonite - CaCO3 Group—-Biaxia1 Negative System--Orthorhombic Habit--Acicular or chisel Shaped Color of Crystal--Colorless Color of Mass--Transparent to translucent *Color of Thin Section-- Isotropic--No *Pleochrism-- Refractive Indexes: nX = a = 1.530 nz = y = 1.685 ny = B = 1.680 gBirefringent Index = -.155 216 Apatite - 9CaO‘3P205Ca[Fe2(OH)2, CO3‘C12] Group—~Uniaxial, Negative System--Hexagonal Habit—-Prismatic AColor of Crysta1--Colorless to Green to Blue to Brown Color of Mass-—Color1ess to Green to Blue to Brown Color of Thin Section--Transparent to opaque Isotropic--No *Pleochrism-- Refractive Indexes: nO = w = Ordinary ray = 1.649 nE = E = Extraordinary ray = 1.644 Birefringent Index = -.005 ViVianite - 3FeO°P205°8H20 Group—-Biaxia1, Positive System-—Monoclinic Habit--Prismatic Color of Crystal--Colorless to green, blue Color of Mass--Black to Opaque Color of Thin Section--Vitreous IsotrOpic--No Pleochrism--Colorless mineral upon powdering x = Dark Blue, y = Colorless, z = Olive green to brownish Refractive Indexes: nX = a = 1.579 nz = Y = 1.633 ny = B = 1.603 Birefringent Index = +.054 l 217 Ankerite - Cao-(Mg,Fe)O°2CO2 Group-—Uniaxial, Negative System-~Hexagonal Trigonal Habit-~Rhombohedra1 AColor of Crystal--Color1ess to Dark Brown Color in Mass--Color1ess to Dark Brown Color of Thin Section--Brown to opaque Isotropic--NO *Pleochrism—- Refractive Indexes: nO = w = Ordinary ray = 1.698 n = E = Extraordinary ray = 1.518 TBirefringent Index = -.18 Hematite - Fe203 Group--Uniaxial, Negative System--Hexagonal Trigonal Habit--Rhombohedra1 Color of Crysta1—-Gray to Black Color of Mass--Deep Red Color of Thin Section—-Opaque except in very thin section which is blood red with x = yellowish red and z = brownish red IsotrOpic--No P1eochrism--Slight to faint Refractive Indexes: nO = w = Ordinary ray = 3.01 ng = s = Extraordinary ray = 2.78 Birefringent Index = -.23 218 Magnetite - FeO°FeZO3 or Fe304 or Fe(FeZO4) Group--Spine1 System-—Isometric Habit--Octahedral Color of Crystal--Black, opaque Color of Mass--Black, Opaque Color of Thin Section--Blue—Black Isotropic--Yes Pleochrism--No Refractive Index n = 2.42 Siderite - FeCO3 Group--Uniaxial Negative System—-Hexagonal Trigonal Habit-~Rhombohedral Color of Crystal--Gray, yellowish gray to greenish gray Color of Mass--Vitreous Color of Thin Section--Translucent to brownish IsotrOpic--No *Pleochrism—- Refractive Indexes: nO = w = Ordinary ray = 1.855 ne = e = Extraordinary ray = 1.613 Birefringent Index = -.232 219 Limonite - Fe203 nHZO Group--Isotr0pic System--Amorphous--No crystal structure Habit--Massive to earthy Color of Crystal—~Yellow Brown-Brown Color of Mass--Yellow, Brown or Brownish Black Color or Thin Section--Translucent yellow (to brownish) Isotropic--Yes Pleochrism--No Refractive Index: n = 2.05+ Birefringent Index = 0.04 203'H2O Group-~Biaxia1, Negative Goethite - a—Feo-(OH) or Fe System--Orthorhombic Habit-~Fiberous Color of Crystal--Yellow to Brown to Black Color of Mass--Brown to Black Color of Thin Section--Gray Isotropic-—No Pleochrism--Variable with x = clear yellow to brown, y = brown yellow, 2 = orange yellow Refractive Indexes: nz = Y = 2.35 ny = B = 2.35 Birefringent Index = -0.140 220 Lepidocrocite - y-FeO°(OH) or Fe203°H20 Group-~Biaxia1, Negative System--Orthorhombic Habit-~Blades Color of Crystal--Blood Red Color of Mass-~Blood Red to Opaque *Color of Thin Section-- IsotrOpic--No Pleochrism-—Strong with x = clear yellow, y = red- orange, 2 = orange—red Refractive Indexes: nX = a = 1.94 nz = Y = 2.51 n = B = 2.21 y _— Birefringent Index = -.57 APPENDIX F CRYSTAL GROUP DATA Since reference has been made to birefringence, in discussing the determination of more than one refrac- tive index, a brief explanation of Optical principles and crystalline structure is included. Minerals and chemicals can all be structurally classed in two groups: amorphous and crystalline. The first, meaning "without form," has no regular molecular structure. Glass is an example of such, as is Limonite. All crystalline substances have definite molecular structure. They can all be classed into six groups or systems which, for simplicity, can be related to their length, breadth, and thickness. These three directions are called crystallographic axes, which are imaginary lines running through the crystal and intersecting at its center. The first, and simplest, group is known as the isometric, or cubic system; all axes are of equal length and cross each other at right angles. The molecular structure is such that no matter what direction light passes through it, its path is the same, as though the crystal were a Sphere. Thus, it has a single refractive 221 222 index (also true of amorphous substances) and light will not be polarized. The second system differs from the cubic in that one crystallographic axis (designated "C" and considered the vertical axis) is either longer or shorter than the other two (designated "A" and "B") which are of equal length and constitute the horizontal axes; all three axes are still at right angles to each other. This is known as the tetragonal system. It can be likened to a cylinder, either longer or shorter than its diameter. The difference in the shape of the crystal reflects the difference in the shape of its molecules. It becomes evident the molecular path offers a different resistance to light crossing the diameter of the cylinder than passing through from top to bottom, i.e., along the vertical or "C" axis. This means that it will possess two refractive indexes, and therefore is uniaxial. These axes are known as nw(omega) and ne (epsilon). The first, w or ordinary ray, corresponds to the index for any ray crossing the diameter of the cylinder, since axes A and B are equal. n6, or extraordinary ray, cor- responds to the index for a ray parallel to the "C" axis. The mineral can be either positive or negative depending on whether the length of the cylinder is longer or shorter than the diameter. 223 The third system is similar to the second except, instead of two equal axes (A and B) at 90° to each other, it has three at 60° forming a hexagonal body instead of a cylindrical one. It is known as the hexagonal (including_trigonal) system. It too has two refractive indexes. Both the tetrahedral and hexagonal systems, while birefringent, are optically uniaxial. The fourth system, orthorhombic, differs from the tetragonal in that the three axes, while at right angles to each other, all have different lengths. Such crystals have three refractive indexes known as na (alpha), nB (beta), and nY (gamma). Instead of a single vertical optical axis parallel to the C crystallographic axis, it has two Optical axes, located symmetrically on each side of one of the three crystallographic axes. The angle which the two Optical axes made with each other varies in different minerals and can amount to anything from near zero to practically 90°. The system is biaxial. The fifth system, monoclinic, differs from the orthorhombic in that the crystallographic axes no longer cross at right angles, but one of the three is rotated to an angle other than 90° to the other two, which are still at right angles to each other. The system is biaxial. 224 Finally, for the triclinic system, all the axes are of different lengths and all three crystallographic axes are at other than right angles to the others. This system is complicated as to the positions of the three Optical axes and is biaxial. It is necessary to display the mineral crystal habit and form of the respective compounds that have been discussed in the text. The following information* is to assist in identification of the various compounds. *As compiled from L. G. Berry and Brian Mason, Mineralogy Concepts, Descriptions, Determinations (San Francisco and London: W. H. Freeman and Company, 1959). 225 FIGURE 54- CALC ITE System--Hexagonal Trigonal Habit--Rhombohedral /\l . F:F1 1 \K FIGURE 55- ARAGONITE System--Orthorhombic Habit--Acicular or chisel shaped 226 +_ ..... I _,_,+ FIGURE 56 -APAT|TE System-~Hexagonal Habit--Prismatic FIGURE 57- VIVIANITE System-—Monoclinic Habit--Prismatic 227 FIGURE 58- ANKERITE System--Hexagonal Trigonal Habit--Rhombohedral FIGURE 59-HEMATITE System--Hexagonal Trigonal Habit--Rhombohedra1 228 FIGURE 60 - MAGNETITE System--Isometric Habit--Octahedral FIGURE 6| - SIDERITE System--Hexagonal Trigonal Habit--Rhombohedral 229 Limonite - Fe203-nH20 System--Amorphous No Crystal Structure (Is sometimes identified with crystalline Goethite) FIGURE 62 -- GOETHITE System--Orthorhombic Habit--Fibrous 230 FIGURE 63- LEPIDOCROCITE System--Orthorhombic Habit--Blades MICHIGRN STRTE UNIV. LIBRRRIES 31293010798340