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Benefits of Utilizing Nepheline Syenite in Porcelain Tile

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Benefits of Utilizing Nepheline Syenite in Porcelain Tile 1 BENEFITS OF UTILIZING NEPHELINE SYENITE IN PORCELAIN TILE AND SANITARYWARE Anais do 48º Congresso Brasileiro de Cerâmica Proceedings of the 48th Annual Meeting of the Brazilian Ceramic Society 28 de junho a 1º de julho de 2004 – Curitiba-PR SCOTT E. BARTON UNIMIN CORPORATION 500 WILSON PIKE CIRCLE, SUITE 127 BRENTWOOD, TENNESSEE 37027 USA EXECUTIVE SUMMARY Nepheline syenite is a commercially prepared, rare feldspathoid-rich rock product that contributes both potassium and sodium oxides to the ceramic formulation. It has been used in both North America and Europe for the production of porcelain tile and sanitaryware for many years. It is the unique mineralogy and high levels of alkalis of nepheline syenite that justify its use in ceramics. These characteristics promote lower firing temperatures that can enhance productivity and lower production costs. Depending on location, the use of nepheline syenite can lower raw material cost by allowing more silica to be used in the formulation. Additionally, the process control found in most nepheline syenite operations offers a controlled level of Fe2O3 that can help to improve fired color. The goal of this study is to illustrate the practical benefits of using nepheline syenite for the vitrification in a ceramic body formulation. Keywords: nepheline syenite, porcelain, tile, feldspar, sanitaryware INTRODUCTION As the porcelain tile and sanitaryware industries continue to globalize, manufacturers must continually improve the control and quality of their raw materials to effectively compete on the global scale. To do so, many manufacturers must look not only at domestic materials but also at external sources for these important requirements of quality and consistency. Nepheline syenite is one such product that is utilized on a global basis due to these requirements. Used both in ceramic bodies and glazes, nepheline syenite can both reduce vitrification temperature and allow for increased usage of more economic raw materials. More importantly, nepheline syenite can enhance productivity and quality in most ceramic applications. This paper will introduce nepheline syenite as a raw material and investigate its uses and benefits in porcelain tile formulation. Comments will also be made on its effect in other ceramic systems such as sanitaryware. 2 BACKGROUND ON NEPHELINEAnais do 48º SYENITECongresso Brasileiro de Cerâmica Proceedings of the 48th Annual Meeting of the Brazilian Ceramic Society GEOLOGY 28 de junho a 1º de julho de 2004 – Curitiba-PR Nepheline syenite is an igneous rock, formed in a silica-deficient environment that is somewhat similar in appearance to granite. It is typically found as an irregularly shaped intrusion or in ring structures. The texture of the mineral is granitic and normally medium to coarse grained. Typically the most commercially viable deposits are found in intrusive structures with good liberation from contaminants such as biotite, hornblende and magnetite. Most noncommercial nepheline syenite deposits are gray or dark in color and have high iron levels that severely limit their potential in industrial applications. Those deposits associated with ring structures are especially difficult to beneficiate due to the extensive mixture of contaminant minerals. A few special ore reserves exist in Nephton and Blue Mountain, in Ontario, Canada, and on the island of Stjernøy in Norway where the ore is unusually light or near white in color. A third such deposit is located about 40 kilometers from Rio de Janeiro in the municipality of Duque de Caxias. Commercially, the Nephton/Blue Mountain deposit is an open pit operation owned and operated by Unimin Canada Ltd. The primary market for the Canadian material is the U.S. and Canada with ever increasing offshore usage due to industrial globalization. The Stjernøy deposit, owned and operated by North Cape Minerals AS, is both an underground and open-pit operation located on the island of Stjernøy in the Norwegian Arctic1. Primary distribution for the Stjernøy materials is in Western Europe with the majority of product used in ceramic and glass applications. MINERALOGY Nepheline syenite is typically composed of three primary minerals: the albite form of feldspar, the microcline form of feldspar, and nepheline. The Norwegian and Brazilian deposits also contain what can be classified as perthitic feldspar, meaning a combination of sodium and potassium feldspar that began crystallization in solution but upon cooling became incompatible, forming sodium and potassium-rich lamellae. The percentages of each vary depending on the deposit location. The typical ceramic grade nepheline syenite will be composed of 20 to 30% nepheline. CHEMISTRY Nepheline syenite is anhydrous sodium potassium aluminosilicate. The typical chemical formulas for the components of nepheline syenite are: albite (Na2O•Al2O3•6SiO2), microcline (K2O•Al2O3•6SiO2), and nepheline (3Na2O•1K2O•4Al2O3•8SiO2). While “pure” nepheline has a theoretical chemistry of (Na2O•Al2O3•2SiO2), it is normally found 3 to have a 1:3 substitution of potassium into the matrix. Table 1 gives the calculated chemical composition of nepheline compared to that of microcline and albite, the two Anais do 48º Congresso Brasileiro de Cerâmica th most common formsProceedings of feldspar. of the 48 (Note Annual Meetingthat SiO of the2 Braziliancontained Ceramic in Society albite, microcline, and 28 de junho a 1º de julho de 2004 – Curitiba-PR nepheline is not “free-silica”, because the silicon and oxygen are combined with Al as well as Na/K.) It is the nepheline component of nepheline syenite that separates its performance from feldspathic minerals. This component boosts the concentration of alumina and alkali oxide levels higher than that found in typical feldspar sources. Table I. Calculated Chemistries of Nepheline Syenite Components Oxides Nepheline Albite Microcline (Na3, K) AlSiO4 NaAlSi3O8 KAlSi3O8 Alumina 34.9% 19.4% 18.3% Silica 41.1% 68.7% 64.8% Soda 15.9% 11.8% Potash 8.1% 16.9% Physical Properties Nepheline syenite is a moderately hard feldspathoid mineral assemblage that is deficient in silica. As an igneous rock, nepheline syenite was formed from molten magma material from deep within the earth’s crust. Unlike the igneous rock granite, which contains crystalline silica (SiO2), nepheline syenite was formed in nature only when the molten material was deficient in that chemical combination. This deficiency in silica means that the cooling molten material did not form crystals of quartz or other forms of crystalline silica, but instead only formed the components of nepheline syenite. The Mohs hardness of the rock is about 6. It possesses a fairly low index of refraction, in the range of 1.50 to 1.53. Table II. Typical properties of nepheline Syenite Particle Shape angular to nodular Specific Gravity g/cc 2.56-2.61 Mohs Hardness 6.0 Refractive Index 1.51-1.53 Figure 1. SEM photomicrograph of nepheline syenite grains at 5,000x. 4 MATERIALS AND METHODS Anais do 48º Congresso Brasileiro de Cerâmica The first step of this Proceedingsproject was of the to 48 thselect Annual Meetingthe raw of the materials Brazilian Ceramic for comparisonSociety and prepare 28 de junho a 1º de julho de 2004 – Curitiba-PR the formulations. The goal of the project was to illustrate the benefits of utilizing nepheline syenite in porcelain tile formulations. Three (3) nepheline syenite products were identified from the three (3) main sources: Canada, Norway, and Brazil. Two (2) feldspar products were identified from the Brazilian tile market: F1 and F2. All of the fluxes were obtained in granular form, approximately –30 / +200 mesh. Additional materials necessary for the testing were ball clay and ground silica. Respectively Unimin Premier BL AF and Unimin Cerasil 200 were utilized. These materials were obtained in 200-mesh form. Each of the fluxes were ground to 2% +/- 0.5% retained on 200 mesh in 5 liter capacity laboratory jar mills. After each material was milled, chemical and physical analyses were made for use in preparing the theoretical formulations. Those analyses can be found below in Table III. Table III. Results of chemical and physical analysis of fluxes after milling Norway Canada Brazil F1 F2 Residue (%) (+) 200 mesh 1.97% 2.26% 2.11% 1.63% 1.55% (+) 325 mesh 19.03% 18.96% 20.79% 17.58% 18.24% (-) 325 mesh 79.00% 78.78% 77.11% 80.79% 80.20% Total Grinding Time 390 min 420 min 286 min 260 min 290 min SSA 1.10 1.09 1.23 1.32 1.69 PSA 20m 59.0 57.4 53.9 57.5 56.6 (-100 mesh) 10m 40.4 40.0 33.5 38.5 35.0 5m 24.1 23.8 18.9 21.9 20.9 2m 8.9 8.0 6.5 7.9 8.9 1m 2.9 2.9 2.5 3.6 4.4 0.5 m <0.1 <0.1 0.2 1.2 1.2 Chemistry (by XRF) SiO2 56.45 61.09 62.62 69.32 77.83 Al2O3 24.50 23.74 22.36 17.20 12.09 Fe2O3 0.11 0.08 0.10 0.17 0.29 TiO2 0.06 0.01 0.02 0.02 0.08 MgO 0.03 0.03 0.01 0.02 1.14 CaO 1.06 0.24 0.64 0.19 0.96 K2O 8.96 4.90 6.22 7.40 4.52 Na2O 7.89 10.51 8.53 4.27 4.63 Total Alkali 16.85 15.41 14.75 11.67 9.15 LOI 0.95 <0.05 <0.05 1.42 <0.05 Using these analyses, formulations were prepared in two (2) phases. The 1st Phase used a set formula based on 45% ball clay, 10% silica, and 45% flux. This formula was based on porcelain tile formulations actually used in the Brazilian ceramic industry. The 2nd Phase controlled the theoretical chemistry of the formulation by varying the flux and 5 silica levels, while holding the ball clay concentration constant.
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