INVESTIGATION OF THE EFFECT OF LOW-FIRED GROGS ON PROPERTIES OF SOFT-MUD BRICK*

Soft-mud brick were made from various mixtures of Hudson River clay and grog prepared by calcining the clay at 500°, 700°, and 900°C., and rate of drying tests were carried out. The brick were fired to cones 012, 08, and 04, and a special fast fire to cone 08 was also run. The various properties were compared with those of regular mix brick and all-clay brick. Brick made of a mixture of clay with 35% of 900°C. grog had particularly satisfactory properties such as to afford definite advantages as regards faster drying and accelerated firing.     

Kinetics of Cristobalite Formation in Sintered Silica

The kinetics of the cristobalite transformation are reported for sintered silica glass from 1200°C to 1650°C and plotted as a time–temperature–transformation diagram. The 1200°C–1350°C transformation data were fit to the Johnson–Mehl–Avrami–Kolmogorov expression with an time exponent of 3.0 ± 0.6 and an apparent activation energy of 555 ± 24 kJ/mol for the kinetic constant. The temperature of maximum transformation rate was found to fall between 1500°C and 1600°C. Seeding amorphous silica powder with cristobalite resulted in accelerated transformation kinetics. Silica glass powder containing residual quartz had faster transformation kinetics than fully amorphous powder seeded with cristobalite.     

PROGRESS REPORT ON INVESTIGATION OF FIRECLAY BRICK AND THE CLAYS USED IN THEIR PREPARATION1

This is a progress report of an extensive study of fire clays and fireclay brick. It includes the results of a preliminary study of clays representative of those used in the manufacture of refractories throughout the United States. Chemical analyses and a summary of physical tests are given of both fire clays and the brick manufactured from them. The thermal expansion behavior of the fire clays fired at 1400°C and those of the fire brick “as received” from the manufacturer and also after firing at 1400°C, 1500°C, and 1600°C were studied and the materials classified into groups having characteristic thermal expansions. The moduli of elasticity and rupture were determined at 20°C, 550°C, and 1000°C. The resistance of the brick to spalling in a water-quenching test is expressed in an empirical relation correlating the elasticity, strength, coefficient of expansion, and percentage of grog used in compounding the brick batches. Data are presented on individual bricks made by the same manufacturer showing probable reasons for great differences in the number of quenchings required to cause spalling in the water-dip test.     

THERMAL EXPANSION OF SILICA BRICK AND MORTARS1

Thermal expansion from 20 to 950°C and physical data of silica brick from various producing districts in the United States and Europe are presented. The variations in thermal expansion of brick from various parts of kilns are given for plants in the United States. The magnitude of variation of the thermal expansion of silica brick is quite small, the expansion ranging between 1.15% and 1.30% at the highest point of expansion. The expansion of the silica mortars varied between 1.30 to 1.52% depending upon variations in clay, quartzite, and bats. The variations in thermal expansion of silica mortars from various producing plants are also shown. Data on the effect of size of grain, clay content, and P.C.E. on the thermal expansion of mortars are given. An extensive bibliography on thermal expansion of silica brick appears with the paper.     

CONSTITUTION AND THERMAL EXPANSION OF SILICA COKEOVEN BRICK AFTER SERVICE*

Two silica brick which were in service in a coke oven for over ten years have been examined under the petrographic microscope. At the fluc sidc the brick were almost completely converted to cristobalite, next comes a relatively thick layer which is mainly tridymite, and finally near the coke side quartz is found in addition. Measurements on small specimens taken from one of the brick show that the several layers have very different expansions. It is concluded that in cooling a battery of ovens great care should be taken to cool slowly through the temperature range 200 to 300°C.     

On the problem of heat resistance of chamotte refractories

Results of a study of the heat resistance of chamotte refractories as a function of the composition of their binder are presented. The introduction of a refractory particolored clay or clay DN2 rich with alkaline and alkaline-earth oxides into chamotte-kaolin mixtures hampers the formation of cristobalite. The cristobalite effect and the temperature coefficient of linear expansion of the specimens decreases up to a temperature of 600°C, which enhances their heat resistance     

Evaluation of the morphology and pore characteristics of silica refractory using X-ray computed tomography

Silica refractory has excellent high-temperature performance, but its apparent porosity is relatively high. In this work, samples obtained before and after creep testing of silica brick (1550 °C, 50 h), from used silica checker brick (existing only tridymite and amorphous) and from used dome brick (existing only cristobalite and amorphous) were investigated using a three-dimensional structure model based on X-ray computed tomography (CT). The results show that the porosity of silica brick was high but consisted mainly of interconnected pores, with a very small proportion of closed pores (smaller after long-term use). During the use of silica brick, the morphology and phase transformation caused large particles to rupture, and the mineralizer became liquid at high temperature. The broken particles and interconnected pores provided channels for the migration of the liquid in the brick at high temperature. The silica brick presented a homogeneous ceramic structure during long-term operation. Tridymite or cristobalite presented a solid frame leading to an excellent creep performance of the silica brick (the creep rate of the checker brick was ?0.16% at 1550 °C for 50 h). Results were discussed, compared with literature and a model for the transformation of the silica brick from a refractory structure to a homogeneous ceramic structure was established in this paper.     

梅钢焦炉用后硅砖显微结构分析

显微结构分析表明:焦炉炭化室用后硅砖中或多或少存在残余石英,而燃烧室由于温度较高,其硅砖中的石英逐渐经亚稳方石英转变为鳞石英.焦炉用后硅砖的相变过程只限于石英和亚稳方石英的转化,随着石英和亚稳方石英逐渐转变成鳞石英,硅砖结构趋于稳定.炭化室用后硅砖表面出现碳沉积并石墨化,对硅砖起到保护作用,并有利于提高炭化室的热导率.     

Influences of quartz and muscovite on the formation of mullite from kaolinite

A kaolin containing muscovite and quartz (K-SZ) and a pure kaolin (K-SX) with the addition of potassium feldspar, K₂SO₄ and quartz, respectively, were used to investigate the influences of muscovite and quartz on the formation of mullite from kaolinite in the temperature range 1000–1500 °C. In K-SZ formation of mullite began at 1100 °C, and in K-SX at 1000 °C. In K-SZ quartz accelerated the formation of cristobalite and restrained the reaction of mullite and silica. Muscovite in K-SZ acted as a fluxing agent for silica and mullite before 1400 °C and accelerated the formation of cristobalite. The FTIR band at 896.8 cm^− 1 was used to monitor the formation of orthorhombic mullite.     

SPALLING AND LOSS IN COMPRESSIVE STRENGTH OF FIRE BRICK1

A preliminary report of the loss of compressive strength when fireclay brick from the Pacific Northwest were subjected to a series of heat treatments to 1350° and 1250°C. It illustrates some of the variations of heat treatment in the manufacturer's kilns and the differences between the high siliceous type of fire brick and the vitrifying clay type with lower free silica content. It is possible that a satisfactory spalling test may be developed in this direction.     

ELASTIC BEHAVIOR AND CREEP OF REFRACTORY BRICK UNDER TENSILE AND COMPRESSIVE LOADS*

Specimens cut from 9-in, brick of nine brands of firebrick, including two high-alumina, four fire-clay, two siliceous fire-clay, and one silica, were subjected to tensile and compressive creep tests at eleven temperatures from 25° to 950°C., inclusive. The duration of each test was approximately 240 days. Small length changes, independent of stress direction (that is, compressive or tensile), occurred at the lower temperatures. The lowest temperatures at which creep was significant were (a) high-alumina brick, 700° to 850°C.; (b) fire-clay brick, 600° to 700°C.; and (c) siliceous and silica brick, 950°C. Creep results under compressive stress could not be correlated with results under tensile stress. Specimens of different brands, at 950° C. showed greatly different capacities to carry load. Repeated heatings caused growth of silica brick of approximately 0.27%. Moduli of elasticity at room temperature were determined before and after the various heat-treatments and resultant changes were recorded. The changes in moduli were 15% or greater for silica and siliceous brick and 4% or less for the fire-clay brick. The moduli of elasticity at room temperature were approximately 2.7–4.3 × 10⁶ for high-alumina brick, 0.6–1.9 × 10⁶ for fire-clay brick, 0.3–1.7 × 10⁶ for siliceous fire-clay brick, and 0.4 × 10⁶ for silica brick.     

Sealing Glass‐Ceramics with Near‐Linear Thermal Strain,Part II: Sequence of Crystallization and Phase Stability

The sequence of crystallization in a recrystallizable lithium silicate sealing glass‐ceramic Li₂O–SiO₂–Al₂O₃–K₂O–B₂O₃–P₂O₅–ZnO was analyzed by in situ high‐temperature X‐ray diffraction (HTXRD). Glass‐ceramic specimens have been subjected to a two‐stage heat‐treatment schedule, including rapid cooling from sealing temperature to a first hold temperature 650°C, followed by heating to a second hold temperature of 810°C. Notable growth and saturation of Quartz was observed at 650°C (first hold). Cristobalite crystallized at the second hold temperature of 810°C, growing from the residual glass rather than converting from the Quartz. The coexistence of quartz and cristobalite resulted in a glass‐ceramic having a near‐linear thermal strain, as opposed to the highly nonlinear glass‐ceramic where the cristobalite is the dominant silica crystalline phase. HTXRD was also performed to analyze the inversion and phase stability of the two types of fully crystallized glass‐ceramics. While the inversion in cristobalite resembles the character of a first‐order displacive phase transformation, i.e., step changes in lattice parameters and thermal hysteresis in the transition temperature, the inversion in quartz appears more diffuse and occurs over a much broader temperature range. Localized tensile stresses on quartz and possible solid‐solution effects have been attributed to the transition behavior of quartz crystals embedded in the glass‐ceramics.     

THE PRODUCTS OF THE CALCINATION OF FLINT AND CHALCEDONY1

Outline of the Investigation. —This investigation includes the measurement of the following physical properties; specific gravity at 0°, 25° and 98°, the index of refraction, the coefficients of thermal expansion up to 300°, the inversion temperature and volume change on inversion, and the X-ray spectra, the materials studied being quartz, tridymite, cristobalite, silica glass and raw and calcined flint and chalcedony. New Methods —For specific gravity, a special vacuum pycnometer was employed and the immersed powder was later subjected to a pressure of 1000 atmospheres. Resultss .—The numerical data obtained are summarized in Table I and the X-ray spectra are shown in Fig. 10. The specific gravity of calcined chalcedony was raised 2% by fine grinding. Conclusions .—All of the known facts concerning chalcedony are in harmony with the theory that the raw material is colloidal quartz and the calcined material colloidal cristobalite.     

ARTIFICIAL SILLIMANITE AS A REFRACTORY1

Alumina-silica mixtures were prepared by fusing quartz, china clay, fire clay, and alumina in the electric furnace. When alumina is less than 68%, crystalline sillimanite (3Al₂O₃.2SiO₂) with glass is produced. This material is not very resistant to loads at high temperatures because of the early fusion and internal lubricating action of the glass surrounding the crystals. Above 68% alumina, crystalline corundum appears am1 the glass is practically absent. This latter composition is very resistant to high-temperature loads when ail interlocking, recrystallized bond is developed. This material is not affected materially by acid slags, but it cannot resist basic slags. However, the dense structure of a brick of material above 68% Al₂O₃ causes less slagging in a laboratory bath test than silica brick. The laboratory made sillimanite-corundum brick withstood higher temperatures than the best silica, magnesia, chrome, fire clay, or zirconia brick even though the cone of fusion of the former is less than that of MgO, Cr₂O₃ or ZrO₂. More and better service tests with a large number of brick fired in large kilns is needed to follow up this laboratory work.     

Effect of alkali roasting and sulfatization on the extraction of different metal oxides from waste alum sludge

Water treatment plants (WTP) generate a significant amount of sludge as byproducts with environmentally harmful elements. Thus, this work focused on the recycling of alum sludge through the extraction of different metal oxides, i.e., Al₂O₃, Fe₂O₃ and SiO₂, for use in different applications, such as ceramics, cement, and agriculture. The extraction of Al₂O₃, Fe₂O₃, and SiO₂ from alum sludge was performed using sulfatization and roasting to compare which of the two processes could produce the metal oxides of the highest purity. Precipitated powders were calcined at 700°, 900° and 1100 °C. Moreover, the obtained prepared and calcined powders were characterized by studying their phase compositions, microstructure, particle size, and surface area. Results indicated that roasting achieved the highest yield of alumina. Iron oxide was extracted mostly in maghemite form through roasting after calcination at 1100 °C. Further, silica was obtained in cristobalite and quartz phases after calcination at 1100 °C for the samples prepared through sulfatization. However, these phases of silica were combined with albite and obtained after calcination at 1100 °C for the samples prepared through roasting method.     

Pozzolanic reactivity of a calcined interstratified illite/smectite (70/30) clay

Calcined clays can be potential supplementary cementitious materials if effects of heat-treatment on their structure and reactivity are understood. This work reports structural characterization of an interstratified illite/smectite clay, including a quartz impurity, upon heating using ²⁷Al and ²⁹Si MAS NMR spectroscopy and ICP-OES analysis. During dehydroxylation (600–900 °C) the Q³-type SiO₄ sites become disordered and octahedral AlO₆ sites transform into tetrahedral sites, resulting in an amorphous material with substantial pozzolanic properties, as demonstrated by reactivity tests and hydration studies of a Portland cement–calcined clay blend. At higher temperatures (above 950 °C), inert Q⁴-type phases crystallize which radically reduce the reactivity. At optimum calcination temperature (900 °C), the amorphous material contains highly dissolvable elemental species as seen from complementary ICP-OES analysis. The quartz impurity exhibits a unique variation in ²⁹Si spin–lattice relaxation times upon heat-treatment which is ascribed to changes in the concentration of impurity ions in quartz.     

A STUDY OF THE FACTORS INVOLVED IN THE SPALLING OF FIRE CLAY REFRACTORIES WITH SOME NOTES ON THE LOAD AND REHEATING TESTS AND THE EFFECT OF GRIND ON SHRINKAGE1

Of the three factors, elasticity, coefficient of expansion and rate of temperature change, which affect spalling, the former is by far the most important. Only small differences are found between fire clay mixtures of widely varying structure and composition in the rate at which they change in temperature under like conditions of heating. The coefficient of expansion varies directly with the silica content and differences in this respect of large order were found. However, the spalling on the particular mixtures tested varied almost inversely as the coefficient of expansion. This apparent discrepancy is explained on the basis of greater elastic properties of the brick which had high expansions. The elasticity may be varied between wide limits and is sufficiently important as to overbalance the effect of greater expansion. This property is accordingly the one upon which efforts directed toward the development of non-spalling brick should be centered. It was discovered that a plastic deformation could be obtained at as low a temperature as 635°C. This gives the effect of elasticity and undoubtedly has considerable influence on spalling at the higher temperature ranges. Results are given for a number of load tests which show clearly the importance of hard firing. The secondary expansion of brick made from Pennsylvania flint clay is shown to be influenced by the temperature of reheating, as well as its rate. Detailed results showing the effect of grind and firing on the finished size of the brick included in the investigation are also given.     

Effect of Cristobalite on the Strength of Sintered Fused Silica Above and Below the Cristobalite Transformation

Porous fused silica ceramics which had been partially devitrified to cristobalite were stronger at 350°C in the beta‐cristobalite stability range, but weaker at 25°C after the transformation to alpha‐cristobalite. The tensile strength distribution for different cristobalite fractions are compared for three types of specimens. These were beta‐cristobalite samples which had never been transformed to alpha‐cristobalite; room‐temperature samples with alpha‐cristobalite; and samples at 350°C which had retransformed to beta‐cristobalite after prior transformation to alpha‐cristobalite. The alpha‐cristobalite samples displayed 50%–75% the strength of samples tested on beta and the difference in strength was dependent on cristobalite content. Specimens retransformed to beta‐cristobalite had strength similar to virgin specimens. Microcracking associated with the transformation to alpha‐cristobalite contributes to the strength changes but cannot fully explain the impact of the beta–alpha transformation on strength.     

Thermal expansion and Young's modulus evolution of fused silica and crystalline silica-containing materials

Fused silica bricks (FSBs) with exceptional thermal shock resistance are frequently used to repair localized damage in coke ovens and are hold promising candidates for the efficient construction of new coke ovens. To maximize their utilization, the effects of thermal history on the thermal expansion and Young's modulus evolution of FSBs were investigated in comparison to crystalline silica bricks (CSBs). Due to the gradual phase transformation of fused silica into cristobalite, the thermal expansion of FSBs are sensitive to the thermal cycle; both silica materials exhibit an increase in thermal expansion after five cycles at 1200°C, whereas the thermal expansion of CSBs is five times greater than that of FSBs. When the testing temperature is less than 1000°C, Young's modulus of CSBs is more sensitive to the thermal history, which is caused by phase transformation-induced microcracks. This sensitivity reduces when the testing temperature is 1200°C, as microcracks healed by liquid phase as well as the softening of residual glass phase. By contrast, when the testing temperature is 1200°C, Young's modulus of fused silica specimens is sensitive to the thermal history owing to the microcracks caused by the gradual phase transformation of fused silica to cristobalite.     

HIGH TEMPERATURE LOAD AND FUSION TESTS OF FIRE BRICK FROM THE PACIFIC NORTHWEST IN COMPARISON WITH OTHER WELL-KNOWN FIRE BRICK1

Seventeen samples of fire-clay brick from the Pacific Northwest have been tested with twenty-seven other commercial brands of fire clay, silica, magnesia, chromite, zirconia, diaspore, silicon carbide and crystalline alumina, as well as china clay and crystalline sillimanite products made at the University of Washington. The tests show that the fire-clay brick of the Pacific Northwest vary considerably in quality. According to the high temperature load test, the majority of the local brick are among the upper grades, some are to be classed with the best fire-clay brick and one equal to the best diaspore brick. The brick tested is not the best which can be made from Pacific Northwest materials, for the kaolins in eastern Washington and northwestern Idaho give opportunity for the production of an all-kaolin fire brick. A method is suggested for testing super-refractory materials under load at high temperatures similar to the standard load test for fire clay and silica brick except that the temperatures are measured by cones, and are raised until 10% linear deformation of the brick is obtained. The rate of heating and soaking varies with the brick under test, and the principles learned from the cone fusion test are used in the application of heat. A numerical value, expressing the area under the cone-shrinkage curve, affords an easy method for comparing the high temperature load resistance of various refractories. The brick which are best able to resist deformation at high temperatures are composed of crystalline materials which have developed a recrystallized bond of the same composition. These are crystalline silica, silicon carbide, corundum and sillimanite, and they resist deformation at temperatures close to their melting points. Amorphous materials like fire clay, diaspore, bauxite or even the very refractory crystalline materials lie chromite and periclase, which depend on amorphous silicates for a bond or are contaminated with silicate impurities. will fail with the softening of the bond of the amorphous impurities. The cone fusion of the brick as a whole can not be depended upon to indicate the resistance to load at high temperatures.