Clays, Nanoclays, and Montmorillonite Minerals

FAHEEM UDDIN The recent introduction of nanoclays as llers or additives in polymers for various desired eects is a subject of an increased interest for research and development to establish various applications. An increased consumption is indicated by the wider applications of clay nanocomposites approaching to almost one-quarter (24 pct) in 2005 of the total nanocomposites used. However, an interesting concern, along with the studies addressing how nanoclays change the behavior of polymeric materials, is to discover what are clays, nanoclays and montmorillonite minerals. The various structures of montmorillonite available in nature and their modication for application are discussed. An attempt is made to review the origin of using clays when nanotechnology did not exist, coupled with the eects of montmorillonite-based nanoclays on commercially known polymers. DOI: 10.1007/s11661-008-9603-5 The Minerals, Metals & Materials Society and ASM International 2008

I.

INTRODUCTION

NANOPARTICLES used as llers or additives in polymers for various desired eects are receiving an increased interest for research and development. Various types of nanoparticles, including nanocarbon, carbon nanotubes, nanoclays, and metal oxides, are currently used to modify the polymer performance. The viable interest in the use of nanoclays for the modication of polymeric material for numerous applications may be indicated from the increased commercial interest,[1] and consumption of clay nanocomposites that was almost one-quarter (24 pct) in 2005 of the total nanocomposite consumed.[2] Moreover, the nanoclay composites are estimated to raise their market share to 44 pct by 2011. Apart from the studies addressing how nanoclays and montmorillonite change the behavior of polymeric material, an interesting concern is to know what these nanoclays and clays consist of. The purpose of this study is to discover clay minerals with particulars reference to nanoclays and montmorillonite minerals.
II. DEVELOPMENT IN CLAY STUDIES

The essential nanoclay raw material is montmorillonite.[3] Nanoclay technology is a recent development; however, the science of clay has existed since prehistoric times. Ceramists have used nanoparticles since antiquity;[4] however, nanotechnology is the knowingly scientic utilization of nanoparticles. The use of kaoline is dated to the 3rd century BC in China. China clay, a traditional name of kaoline, is a mixture of minerals generally containing kaolinite, quartz, mica, feldspar,
FAHEEM UDDIN, Associate Professor and Chairman, Textile Department, is with the School of Science and Technology, University of Management and Technology, Johar Town, Lahore, 54700, Pakistan. Contact e-mail: faheem@umt.edu.pk; dfudfuca@yahoo.ca Manuscript submitted October 1, 2007. Article published online September 24, 2008
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illite, and montmorillonite.[5] Raw kaoline collected from a deposit in Swat, Pakistan, was found to contain disordered kaolinite, paragonite clinocblorey epidote, disordered calcian albite, quartz, calcite, montmorillonite, and halloysite.[6] From prehistoric times, the use of clay is known in architecture, industry, and agriculture. Production of sun-dried or red bricks for building construction still follow the procedures that can be traced back to several centuries. Clay-based products, including tiles for wall and oor, ceramics, earthenware, and pipes for drainage, were all used by men for ages. An interesting behavior of clay is its ability to swell and to mold in water, and to retain the shape of the container when dry. This characteristic behavior had been used in the formation of several traditional clay products. The concept of using nanoparticles llers came with nanotechnology traced in a talk by Richard Feyman on December, 29, 1959, at the annual meeting of American Physical Society (California Institute of Technology, Pasadena, CA). Nanotechnology was then perceived as the design, characterization, production, and application of structures, devices, and systems by controlling the shape and size of material particles on a nanometer scale.[4] Clay belongs to a wider group of minerals; however, in chemistry, all clay minerals may simply be described as hydrous silicates. In terms of their natural locations, clay minerals can be divided into two classes: residual clay and transported clay (or sedimentary clay).[6] Residual clays are produced from the surface weathering of rock or shale (a dark ne-grained sedimentary rock composed of layers of compressed clay, silt, or mud) through various means, and they are generally found in the place of origin. Residual clays could be produced by the chemical decomposition of rocks, i.e., granite containing silica and alumina; by the solution of rocks, i.e., limestone; and by the disintegration and solution of shale. The transported clay, the second type, is removed from the original deposit through erosion and deposited to a distant place.
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A common characteristic of clay minerals is their negrained natural structure with sheetlike geometry. The sheet-structured hydrous silicates are generally referred to as phyllosilicates.[710] Individual natural clay particles are smaller than 0.004 mm in diameter; these can ranged from 0.002 to 0.001 mm in diameter for quartz, mica, feldspar, iron, and aluminum oxides.[11] Colloidalclay particles are ner (<0.001 mm in diameter) and are found in layered silicates. Clay minerals may be divided into four major groups, (Table I) mainly in terms of the variation in the layered structure. These include the kaolinite group, the montmorillonite/smectite group, the illite group, and the chlorite group. The kaolinite group has three members, including kaolinite, dickite, and nacrite, each with a formula of Al2Si2O5(OH)4. The same formula indicates that the members of this group are polymorphs, meaning that they have same formula but diering structures. Each member is composed of silicate sheets (Si2O5) bonded to aluminum oxide/hydroxide layers (Al2(OH)4); the two types of layers are tightly bonded. These clays are used as llers in ceramics, paint, rubber, paper, and plastics. Montmorillonite, talc, pyrophyllite, saponite, and nontronite are a few members of the larger smectiteclay group. The general formula for the chemical structure of this group is (Ca,Na,H)(Al,Mg,Fe,Zn)2 (Si,Al)4O10(OH)2XH2O. The important dierence among the members of this group is seen in the chemical characteristics. The layer structure contains silicate layers, sandwiching an aluminum oxide/hydroxide layer (Al2(OH)4). These are used as llers in paints, rubbers, as plasticizer in molding sands, in drilling muds, and as electrical, heat, and acid-resistant porcelain. One of the members, talc, has traditional presence in facial powder. The illite group is represented by the mineral, illite, the only common clay type. The general formula is (K,H)Al2(Si,Al)4O10(OH)2XH2O. It is an important rock-forming mineral and a main component of shales. The structure of this group is similar to the montmorillonite group with silicate layers sandwiching an aluminum oxide/hydroxide layer in the same stacking
Table I. Solution 1 2 Group Name kaolinite Member Minerals

sequence. Mineral illite is used as ller in some drilling mud, and it is a common constituent in shales. The chlorite group is relatively large and not necessarily considered as clays; therefore, it is placed as a separate group in phyllosillicate. Amesite, chamosite, cookeite, and daphnite are some members of this group; however, they are dierent in formulas and structures. These clays do not possess a general formula.

III.

STRUCTURE OF CLAY PARTICLES

Relative to the known practice of assessing the material performance from chemical behavior, the physical characteristics of clays are more important in dening various groups of clays. Clay particles can absorb or lose water in response to simple humiditycontent changes in the surrounding environment; when water is absorbed, it lls the spaces between the stacked silicates layers.[12] The specic gravity of any type of clay is, therefore, highly variable, resulting from the loss or gain of water. Most of the known clay types are rarely found separately in nature and are usually mixed with other types of microscopic crystals, including carbonates, feldspars, micas, and quartz. The structure of clay particles is perceived in layers; each layer is composed of two types of structural sheets: octahedral and tetrahedral. The tetrahedral sheet is composed of silicon-oxygen tetrahedra linked to neighboring tetrahedra by sharing three corners, resulting in a hexagonal network.[8] The remaining fourth corner of each tetrahedron forms a part to adjacent octahedral sheet. The octahedral sheet is usually composed of aluminum or magnesium in six-fold coordination with oxygen from the tetrahedral sheet and with hydroxyl. The two sheets together form a layer, and several layers may be joined in a clay crystallite by interlayer cations, Vander Waals force, electrostatic force, or by hydrogen bonding. Theoretical formula and structure, as produced by Nanocor, are shown in Figure 1.[13] The elementary structural units are silica tetrahedron and aluminum octahedral. The cation-Si+4 is fourfold

Major Groups of Clay Minerals General Formula Remarks members are polymorphs (composed of the same formula and different structure) X indicates varying level of water in mineral type

kaolinite, dickite, nacrite Al2Si2O5 (OH)4

3 4

(Ca,Na,H)(Al,Mg,Fe,Zn)2 montmorill-onite montmorillonite, or smectite pyrophyllite, talc, (Si,Al)4O10(OH)2-XH2O vermiculite, sauconite, saponite, nontronite illite illite (K,H)Al2 (Si,Al)4 O10(OH)2-XH2O X indicates varying level of water in mineral type (i) (Mg,Fe)4Al4Si2O10(OH)8 chlorite (i) amesite, each member mineral has separate (ii) chamosite, formula; this group has relatively (ii) (Fe,Mg)3 Fe3 AlSi3O10(OH)8 (iii) cookeite, larger member minerals and is (iii) LiAl5 Si3O10 (OH) 8 (iv) nimite etc. sometimes considered as a separate (iv) (Ni,Mg,Fe,Al)6AlSi3O10(OH) 8 group, not as part of clays

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Fig. 1Theoretical formula and structure of montmorillonite (courtesy: Nanocor Inc., IL, used with permission).

and possesses tetrahedral coordination with oxygen, while the cation, Al+3, occurs in sixfold or octahedral coordination. The variety of clay minerals can be described by the arrangement of tetrahedral and octahedral sheets, i.e., 1:1 clay mineral would have one tetrahedral and one octahedral sheet per clay layer; 2:1 clay mineral would contain two tetrahedral sheets and one octahedral sheet sandwiched between the two tetrahedral sheets (montmorillonite is an example of a clay mineral having 2:1 sheet-structure); and 2:1:1 clay minerals are composed of an octahedral sheet adjacent to a 2:1 layer.[14] Therefore, the structure of clay minerals can be described in terms of arrangement of tetrahedral and octahedral sheets. The sheet structure for the layers of various clay minerals with the possible charge is shown in Table II.[15] The presence of charge in tertrahedral and octahedral sheets inuences the layered structure. Isomorphous substitution in clay mineral mainly results in the charge development. Isomorphous substitution is the replacement of an element with another element in mineral crystal without modifying its chemical structure. For example, Al3+ can replace Si+4 in tetrahedral coordination, and replacement of Al3+ is possible by Mg2+, Fe2+, and Fe3+ in octahedral coordination.
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Table II. Solution 1. 2. 3. 4. 5.

Sheet Structure for the Layers of Clay Minerals[15] Clay Mineral Group kaolinite montmorillonite or smectite illite vermiculite chlorite Layer Type 1:1 2:1 2:1 2:1 2:1:1 Layer Charge <0.01 0.5 to 1.2 1.4 to 2.0 1.2 to 1.8 variable

IV.

CATION EXCHANGE CAPACITY

Clay and organic matters provide the characteristic property of soil called cation exchange capacity (CEC). It is the capacity of soil to hold cations (generally Al3+, Ca2+, Mg2+, Mn2+, Zn2+, Cu2+, Fe2+, Na+, K+, and H+)[16] and is described as the quantity of positively charged ions held by the negatively charged surface of clay minerals. It can be expressed as centimol positive charge per Kg of soil or milliequivalent (meq) of positive charge per 100 g of soil. Each particle of clay silicate is composed of sheets. Pure silica oxide (quartz) has no charge. However, in general, most of the clay minerals tend to have a negative charge resulting from the substitution of silica
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cation (Si4+) by aluminum cation (Al3+) in the claysheet structure. This phenomenon (referred to as isomorphous substitution) produces the capacity in clay sheets to hold positive charges. Several types of clay minerals are present in soils with varying levels of CEC. For example, kaolinite clay found in most Carolina soils has a CEC of 5 meq/100 g, while smectite and vermiculite have in excess of 100 meq/100 g. However, smectite and vermiculite are found only in limited amount in some Carolina soils.[17] Traditionally, the use of CEC can be seen in the measure of soil fertility, plant nutrient retention capacity (K+, Ca2+, Mg2+, and NH+), and preventing cation 4 contamination in ground water.[18] More recently, the development of nanoclays through the modication in clay sheet structure is producing additives for polymers. However, research is needed to explore the inuence of CEC in the functional performance of nanoclay additives. It is possible to know the amount of various cations present in a given mass of soil if the CEC values are available. When the CEC of a cation present is equal to 1 meq/100 g of soil, the possible amount of various cations in one acre soil (Carolina) to a depth of 6 in. are shown in Table III.[17]

V.

ELECTRICAL CONDUCTIVITY

Fine-grained particles of clay result in an increased surface area per unit volume or per unit mass where signicant cations can be adsorbed. Clay minerals are porous materials. The electrical conductivity (mS/m) of a porous material is the combination of electrical conductivities of the matrix material and the pore uid.[19] The pore uid may be air, water, or saline water. When pore uid is of low conductivity, i.e., air or water, the bulk conductivity of clay mineral is contributed to by the matrix material. However, where pore uid has higher conductivity, i.e., saline water, and the porosity level is signicant (40 to 50 pct), then the bulk conductivity is mainly the contribution of the pore uid. In this later case, there would be slight dierence in the conductivities of sand and clay. The movement of electrons in bulk soil is indicated as a complex phenomenon.[20] It can be through pore uid, along the exchangeable ions of soil minerals, including clays. The electrical conductivity of soil is a function of several factors, including soil water (density, structure,
Table III. Amount of Cation Present in One Acre Soil to a Depth of 6 Inches, Where CEC is 1 meq/100 g[17] Solution 1 2 3 4 5 6 Cation Al3+ Ca2+ H+ Mg2+ K+ Na+ Atomic Mass of Element 27 40 1 24 39 23 Cation Mass in Pounds per Acre 180 400 20 2 780 460

and potential), soil content (clays, organic matters, and electrolytes) and their structure (aggregation and exchangeable ions), and the mineral phase conductivity. However, evaluating the soil electrical conductivity under the inuence of such factors is an area where little research has been done. An approach that had been successfully utilized in measuring the soil conductivity is the use of sensor electromagnetic devices. Ground conductivities can be measured using the appropriate instrument, depending upon the soil depth. Such instruments may be represented as EM 38, EM 31, EM 34, and the GEM 2.[11] Using the EM series, EM 38, EM 31 and EM 34, the soil conductivities can be measured to a maximum ground depth of 1.5, 6, and 60 m, respectively. The increasing clay content in soil was found to enhance the measured value of conductivity. In general, a linear relationship was observed when soil conductivity was assessed against clay content, using an EM 38 in a survey conducted in Denmark. For example, at 15 pct clay content, the soil conductivity was 10 mS/m and reached 15 mS/m at 20 pct clay content. Signicant contribution of clay saline water in the soil conductivity can be realized from the spread of soil contents and measuring individual conductivity (Table IV).[21] Higher content of clay minerals with a 2:1 sheet structure results in an increased bulk electrical conductivity for nonsaline soils.[22] This eect was attributed to the exchangeable cations or proton transfer from the dissociation of interlayer water content. A reduced level of interlayer water contents in K-saturated clays resulted in the lowest electrical conductivity. Because the clay content, pore uid, clay type, saline water, and water saturation inuence the soil conductivity, the assessment of electrical conductivity of reservoir rock may be used to estimate these factors.[23] However, the modeling of electrical conductivity of a heterogeneous porous medium is complicated by the variation in the distribution of solid and uid phases. Smaller particle size (0.002 to 0.001 mm in diameter) of clay minerals results in signicantly higher surface area per unit volume, where a large number of cations can be adsorbed. These adsorbed cations impart a signicant level of electrical conductivity in clay minerals.[11] The distribution of electrical ions around clay pores is called membrane polarization. Under the inuence of
Table IV. Measured Range of Electrical Conductivities of Soil Fractions[21] Electrical Conductivity, Resistivity, mS/m ohm m 0.1 to 1 1 to 5 5 to 25 12.5 to 25 1000 to 10,000 200 to 1000 80 to 200 40 to 80

Solution 1 2 3 4 5 6

Soil Fraction sand, gravel silty sand loam (sand + silt + clay) silt (fine-grained sediment) clay saline soil

25 to 100 10 to 40 100 to 200 5 to 10

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a DC potential across the clay pore, the negative ions are oriented to one end of the pore, and this polarization resists the current ow. Electrical conductivity and membrane polarization are the function of clay content, and these are used in soil studies to determine the clay fraction.

VI.

THERMAL BARRIER PROPERTIES

Thermal barrier properties of clay minerals have been used in heat-resistant and ame-retardant applications. Recent introduction of nanoclays is extensively used and investigated in nanoclay-polymer composites exhibiting increased thermal stability and ame retardancy. The variation in the expansion of metals, polymers, and ceramics has been noted under the inuence of heat. In general, the order of thermal-expansion magnitude in these materials can be described by the following relationship: polymer > metal > ceramic This order can be indicated through the values of the linear thermal-expansion coecient, which are in the range of 20 to 100 ppm/C, 3 to 20 ppm/C, and 3 to 5 ppm/C for polymers, metals, and ceramics, respectively.[24] Higher thermal stability of clay mineral is the characteristic that allows its use as ller in producing polymers with low thermal expansion. However, it has been indicated that the enhancement in polymer thermal stability is inuenced by the aspect ratio. Preferably, an aspect ratio of greater than 100 was required. The increased aspect ratio and low cost possible with nanoclays were important reasons to consider them for nanoclay-polymer nanocomposites. Extensive studies are currently addressing the evaluation of nanoclays to develop commercially viable polymer composite with enhanced thermal-barrier properties. The sheets present in montmorillonite are composed of a 2:1 structure. The sheets in the crystal plane have a negative charge and hydroxyl groups linked to aluminum or magnesium. The electrostatic force is primarily the force of attraction between the sheets; however, it is breakable. Therefore, the clay nanoparticle can be intercalated or exfoliated. Where clay crystal is used as nanoparticle, it can be referred to as intercalated clay, and when the single of clay is the constituent unit, it is referred to as exfoliated. The interaction between nanoclay particles and polymer matrix signicantly depends upon the hydroxyl groups and charges present in the nanoclay particles. Reduction in thermal-expansion coecient of polymers was indicated where nanoclays were used as additives. Linear thermal-expansion coecients of nanoclay-polymer composites can be in the range of 30 to 40 ppm/C. Possibly the dierence in imparting the enhanced desired eects in the polymer properties, using exfoliated clay and intercalated clay as ller, can be appreciated in terms of the strength properties and thermal
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stability (as assessed by the reduction in the thermalexpansion coecient) of polymer. Polyethylene oxide (PEO)-clay (polyvinyl pyrolidone (PVP)) nanocomposites, using intercalated clay with an aspect ratio of approximately 20 (based on calculated clay-crystal size), was studied. Signicant reduction in the linear thermal-expansion coecient and improvement in the heat-distortion temperature were observed with the added clay content. However, the data indicated a critical clay loading when these thermal-barrier properties were changed abruptly. Signicant reduction in the thermal-expansion coecient and enhancement in the heat- distortion temperature were observed in PEO-clay (PVP) nanocomposite lm. For example, at a clay loading of 12 vol pct, the thermal-expansion coecient of PEO-clay (PVP) nanocomposite was reduced to 12.2 ppm/C, which was signicantly smaller relative to the value of 51.7 ppm/C achieved for the PEO-PVP polymer. The heat-distortion temperature was improved to 200 C from 65 C. It was noted that virgin PEO crystals were found to melt upon heating above 70 C; however, PEO-clay (PVP) lm retained its integrity up to 200 C. Importantly, the nanocomposite lm was signicantly transparent, staying at a transmission of 80 pct.

VII. MONTMORILLONITE CLAY MINERALS Bentonite is an important source of montmorillonite in nature. It is a rock formed from highly colloidal and plastic clays mainly composed of montmorillonite.[5] Bentonite particles are indistinguishable from kaolinclay minerals viewed under scanning electron microscope (SEM); however, the main dierence indicated is thickness. Sodium or potassium salts of bentonite exfoliate into thin plates that could be 1 nm in thickness, theoretically.[25] In addition to montmonillonite, bentonite may contain crystalline quartz, cristobalite, and feldspar. In general, the clay minerals based on bentonite may exhibit the properties of thixotropic-gel formation with water, high water absorption, and high cation-exchange capacity. These properties could be varied in clay minerals depending upon the nature of interstitial water, and exchangeable cations in the interlayer space. Montmorillonite was discovered in 1847 in Montmorillon in the Vienne prefecture of France. However, the presence of clay minerals has a natural origin; therefore, they occur around the world with variation in nature and composition. Because man has used clay minerals since antiquity, the discovery in a particular region is mainly an indication of presence. For example, the use of montmorillonite for medicinal purposes may have occurred in over 200 cultures, including the ancient Egyptians, pre-Aztec Amargosians, natives of Mexico, South Americans, and North Americans.[10] Bentonite, which mainly contains montmorillonite, was discovered in approximately 1890 in the United States, and the name, bentonite, is associated with the name of an American geologist from the former Fort Benton in the Rock Creek area of eastern Wyoming.
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However, there has been some ambiguity in the use of the terms clay and bentonite and what they described.[5] An important behavior of clay mineral is the ionic substitution in the sheet structure, resulting in useful modications. Ions, i.e., Fe3+ and Al3+, are small enough to enter the tetrahedral coordination with oxygen and substitute Si4+. Similarly, cations, i.e., Mg2+, Fe2+, Fe3+, Li1+, Ni2+, and Cu2+ can be substituted for Al3+ in the octahedral sheet.[8] Largesized cations, i.e., K+, Na+, and Cs+, can be located between the layers and, therefore, are referred to as interlayer cations. Anionic substitution is also possible, and the hydroxyl ion (OH-) can be substituted by F-. Chemical composition, ionic substitution, layer structure, and particle size of natural clay minerals have important roles in creating a variety of minerals with specic characteristics. However, sheet structure was used to classify the clay minerals, and chemical composition was used for nomenclature. Traditionally, geological/civil-engineering applications of clays and silica have used particle size. The diameter of a particle or grain, called particle size, had been used to identify the main type of clay minerals. However, such classication is purely on physical assessment and describes a broad category. An example is the Wentworth scale, which describes the grain-size range to dene classes for granular material. The modied Wentworth scale is a Krumbein phi (u) scale based on a logarithmic relation, which is used to nd particle diameter in the following form:[26] D D o 2u where u is the Krumbein phi scale, D is the diameter of particle in millimeters, and Do is the diameter of a 1-mm particle. The Krumbein phi scale permits the naming of granular material on the basis of the size range in millimeters. The size range for clay minerals using this scale is smaller than 3.90625 lm. The essential nanoclay raw material is montmorillonite, a 2:1 sheet-layered smectite clay mineral with platey structure.[3] Chemically, it can be described as hydrated sodium calcium aluminum magnesium silicate hydroxide, (NaCa)0.33(AlMg)2(Si4O10)(OH)2nH2O.[10] Particle size, surface area, and aspect ratio are highly important characteristics desired in nanoclays. The length and breadth of the particles can range from 1.5 lm to a few tenths of a micron.[27] The third dimension of a particle has been described in the literature as thickness, width, or diameter; however, diameter seems more appropriate. The diameter of a particle is exceptionally smaller relative to its length, measuring to only one-billionth of a meter (1 nm). Therefore, an extremely high average aspect ratio of (length to diameter ratio) 200 to 500 is possible. A small amount of nanoclay exhibits a high surface area; i.e., a nanoclay product is known with a surface area in excess of 750 m2/g,[28] which is an approximate equivalent to the area occupied by nine soccer elds.[29] Nanosized particles may approach the scale of resin molecules. When a nanoclay is surface modied, a close
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encounter is possible between nanoclay particles and resin molecules, resulting in a constrained region at the particle surface,[27] which immobilizes a portion of the resin matrix. The overall eect with several nanoclay particles is the creation of a cumulative percent of constrained polymer. An example is seen in a nylon polymer where the constrained region may exceed 60 pct of the total matrix. The swelling response of montmorillonite, and the corresponding development of swelling pressure when swelling is restrained, is a result of complex montmorillonite-water interactions between particles and within the particle itself. The clay-water interactions on the swelling of montmorillonite were studied.[30] The simultaneous measurement of swelling and swelling pressure was conducted using a cell developed by the author. Undisturbed clay samples at a dened swelling (0 to 75 pct) were removed from the cell and analyzed using SEM, Fourier transform infrared (FTIR), microattenuated total reectance (ATR), and spectroscopic studies. Study revealed that the silicate (Si-O) stretching region (1150 to 950 cm-1) showed signicant changes with variation in swelling and orientation. It was found that the reduced particle size with increased swelling was related to the increased misorientation of the clay platelets. The rearrangement of clay platelets was observed as a direct result of the breakdown of the clay particles with increased hydration. In the study of clay minerals from extraction to natural deposits to their application as a functional ller in polymeric material, through the development of nanoclays, the subject requires the interdisciplinary approaches involving geotechnical engineering, geoenvironmental engineering, material science, industrial engineering, coordination chemistry, medical science, and polymer science and engineering. For the past several centuries, clays have been used for a variety of applications. Therefore, with the recent introduction of montomorillonite clay as a functional ller in thermoplastic and thermoset polymers, the clay minerals, or montmorillonite, have been studied for various applications and performance including the use as a catalyst in organic synthesis,[31] as a food additive for health and stamina,[32] for antibacterial activity against tooth and gum decay,[33] for the assessment of frictional and sliding behavior,[34] for the study of mineralogical attributes,[6] and as a sorbent for nonionic, anionic, and cationic dyes.[35] More recently the interest and volume in the investigation of the use of clay minerals, particularly montmorillonite clays, have signicantly increased. The research has concentrated on the development of nanoclays through modications in physical and chemical structures and on the study of the eects of nanoclays on the thermal-mechanical properties of polymers.[3643] Montmorilionte derived from bentonite may contain sodium or calcium. Sodium montmorillonite is the main fraction in bentonite in combination with 10 to 20 pct of various minerals, including feldspar, calcite, silica, and gypsum.[44] The use of sodium montmorillonite is
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known in plaster, oil-well drilling mud, cat litter, matches, cement tiles, lubricating grease, paints, dynamite, paper, shoe polish, concrete, cleaning and bleaching agents, etc. Calcium montmorillonite, the second type, contains minerals useful for the production of enzymes in living organisms. Its advantageous eects were investigated, and it was demonstrated that calcium montmorillonite exhibited growth enhancement in cattle. An exposure to a hydrothermal environment may increase the exchange properties of calcium montmorillonite for small-sized trace elements. The existence of major montmorillorite deposits were indicated at ve places: the Himalayas in China, the Urals in Pakistan, the Caucasus in Georgia and Russia, the Andes in Peru and Ecuador, and the Wasatch mountains in Utah.[44] It is interesting to note the association of the deposits of montmorillonite at these places with their location at high attitudes and that the people living in such areas were found to live for approximately 120 or even 140 years.[32,44] The possible reason primarily perceived for longevity is the inhabitance at high attitudes was that the soil contains abundant amounts of montmorillonite deposits produced from volcanic ashes and ancient oceanic sediment. The agricultural crops produced in these areas taste better, grow faster, and are more resistant to diseases. Essential trace minerals present in montmorillonite enhance the enzyme production in all living organisms. The people living in areas not rich in montmorillonite clay are relatively lacking in longevity. It was pointed out based on studies by U.S. Department of Agriculture that there is a relationship between human malnutrition and depletion of trace elements in the soil. People have to eat 75 bowls of spinach in order to get an equivalent amount of iron provided by one bowl in 1948. Consequently, malnutrition was found in 57 pct of U.S. citizens over the age of 65. Clay is indicated to absorb dietary toxins, bacterial toxins, and metabolic toxins to resist nausea, vomiting, and diarrhea. Montmorillonite-based products are indicated to work immediately on the digestive channel and bind the toxic substances, resulting ultimately in their removal from the body through the stool.[45] Use of montmorillonite by astronauts in the NASA space program was noted for its highly absorptive calcium content. Moreover, during the Balkan war of 1910, the use of clay was found to reduce the mortality rate caused by diarrhea among soldiers from 60 pct to a signicantly low level of 3 pct. Clay was also realized as an invaluable medicine to resist a cholera epidemic in 1919 that swept through China. Montmorillonite is hydrophilic like most other clay minerals. It swells with the absorption of water, which greatly increases its volume. Water penetrates the interlayer molecular spaces, and the variation in the level of swelling is possible in various grades. Montmorillonite typically exhibits a gradual dehydration and phase change to a stronger nonexpendable clay, illite, under increasing temperature and pressure. These two clay minerals coexist as a mix-layer phase at
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intermediate states. The temperature and pressure at which the transition begins depends on various factors, i.e., original composition of montmorillonite, chemistry of available uids, porosity, and geological environment.[34] The interlayer cations are exchangeable, and the amount of expansion as a result of water absorption largely depends upon the type of exchangeable cation. When sodium is present as the predominant exchangeable cation, the increase in montmorillonite volume is several times the original amount. This characteristic had been made sodium montmorillonite a major constituent in nonexplosive agents for splitting rock with reduced waste. Various chemical formulas known for montmorillonite are the result of its modiable structure. Moreover, the cation substitution creates a charge imbalance that allows the chemical composition to vary. The exact theoretical formula is never seen in nature;[13] therefore, it is also shown without the structural substitution as (OH)4Si8AL4O20nH2O.[46] However, the occurrence in nature in any form consists of water molecules. Montmorillonite discovered at Montmorillon, France, had the following chemical formula: (Ca0.14Na0.02)P=0.16 (A1.66Mg0.36Fe0.04)P=2.08(Si3.90Al0.10)P=4.00O10(OH)2 1.02H2O. The constituent oxide fractions for this montmorillonite are shown in Table V.[47] The oxide composition shows that it was predominantly calcium montmorillonite discovered at Montmorillon, with dominant fractions of SiO2 and Al2O3, where SiO2 was slightly more than the 50 pct of total oxides. Details concerning the physical features, i.e., crystallography, optical properties,[47,48] cell data, X-ray powder pattern, and polymorphism[45] are known. The important physical properties are summarized in Table VI.[48,49] The best eld indicators are softness, color, water, soapy feel, and expansion with water absorption. Commercially available nanoclays with over 98 pct montmorillonite have variable colors, which are the result of substitution of interlayer cations by iron, titanium, and manganese within the lattice structure and depend upon the level of substitution and valence state of cations.[13] Because the metals have central coordination positions in the layer structure, they cannot be economically removed.

Table V. Constituent Oxide Fractions of Montmorillonite (Montmorillon, France)[47] Solution 1 2 3 4 5 6 7 8 9 Constituent Oxide SiO2 Al2O3 Fe2O3 MgO CaO Na2O K2O H2O+ H2Ototal Percentage 51.14 19.76 0.83 3.22 1.62 0.11 0.04 7.99 14.18 99.52

METALLURGICAL AND MATERIALS TRANSACTIONS A

Table VI. Solution 1 2 3 4 5 6 Property Name color cleavage fracture hardness density crystal system

Physical Properties of Montmorillonite[48,49] Observation Remarks pink with yellow or green tints also exists perfect in one direction. claylike fracture Talc-Gypsum average 2.35 tiny scaly crystals, lamellar microcrystalline aggregates, compact[47] crystals expand to several times the original volume on water absorption[49] crystals are translucent and masses are opaque[49]

white, gray white, yellow, brownish yellow, greenish yellow perfect uneven to lamellar 1.5 to 2.0 2.0 to 2.7 monoclinic

7 8 9 10

luster streak luminescence transparency

dull white none translucent

Central metal ions, Al3+ and Si4+, in the crystal lattice can be substituted for lower-valence ions, i.e., iron, resulting in a charge imbalance on at surfaces of each platelet.[13] The negative-charge imbalance can be neutralized by the adsorption of hydratable cations, usually sodium and calcium. Adsorbed cations can further be replaced by other hydratable cations, including organic cations. Cation-exchange capacity (assessed in milliequivalents of substitution per 100 grams of mineral) indicates the level of potential substitution. Organic-cation substitution can be used in producing organophilic montmorillonite nanoclay. Natural or unmodied nanoclays are dicult to disperse in polymers;[3] therefore, montmorillonite are surface modied to become organophilic. Intercalant is an organic or semiorganic chemical capable of entering the montmorillonite clay gallery (space between parallel platelets layers) and bonding to the surface. Hydrophilic montmorillonite clay is made organophilic through the process of compatibilization (intercalation). Organophilic montmorillonite is dispersible in polymer-resin matrices. It is the source of producing polymer nanocomposites. It has been used to achieve ame-retardant eects in terms of mainly reduced peak-heat release rates for several thermoplastic polymers, including polystyrene, polyamide-6, polypropylene, polyethylene, ethylene-vinyl acetate, polyamide-12, polymethylmethacrylate,[50] acrylonitrile-butadiene-styrene (ABS) using two types of ABS with dierent acrylonitrile content,[51] styrene-butadiene rubber,[52] and wood-ber/plastic composites using ASTM D635.[53] However, dierent mechanisms are operating during the pyrolysis. Possibly nanoclay may change the decomposition products depending upon the polymer. It may produce cross linking and ultimately catalysis to carbonaceous-char formation.[50] Inclusion of functionalized nanoclays into polymers to improve ame retardancy is also reviewed as an important recent advancement in polymer ammability.[54] Clay migration to the surface of polymer/montmorillointe nanocomposites over the range of temperatures 200 C to 400 C was indicated by X-ray diraction and ATR-FTIR assessment under isothermal conditions.
METALLURGICAL AND MATERIALS TRANSACTIONS A

Mechanisms, decomposition of organic layered silicates, and clay-migration aspects were studied.[55] Thermal degradation of polymers is indicated by the initiation of bubbling products below the heated polymer surface and increases with the supply of more degradation products from the surrounding molten plastic. Nanoclays reduce the polymer ammability and thermal decomposition by retarding the bubbling process. Nanoclay particles form a continuous protective solid layer on the burning-polymer surface that reduces the polymer ammability. The movement of nanoclay particles induced by bubbles was observed in the studies on the gasication of a polyamide-6 nanocomposite.[56] However, ame retardancy and thermal modication are only some eects investigated using nanoclays; organophilic montmorillonite has also been studied for improving the mechanical and barrier properties of polymers.[3643,57,58] The level of intercalation and exfoliation of nanoclays are some important characteristics in inuencing the performance of nanocomposites; however, these require more research to establish the obtainable improvement in polymers. Ethylene-vinyl acetate copolymer and methylmethacrylate/poly (methyl methacrylate) mixtures for montmorillonite and organically modied montmorillonite were studied, respectively,[59,60] for this purpose. A small amount of nanopoarticles, generally 5 to 7 pct, may produce a sucient improvement in strength and thermal stability relative to a 20 to 30 pct amount of conventional inorganic llers (glass ber, mineral ber, etc.).[61] Nanoclays may be used alone or in combination with traditional ame retardants to achieve synergistic eects. Anionic clays, as an alternative to most common cationic clays, were found to exhibit improved ame retardancy.[62] Organic layered silicates have an eective improvement on the structure and ammability behavior of polymer/montmorillonite nanocomposite. Organic layered silicates begin to decompose above 200 C; therefore, the nanocomposite structure is gradually destroyed even prior to the pyrolysis and decomposition.[55]
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The data on the decomposition of polymer/organic layered silicate composite, including rates and energies of activation on the temperature range of 200 C to 400 C were presented. An interesting aspect of montmorillonite clay, leading to its application as a catalyst, is its structure that oers Bronsted and Lewis acid catalytic sites.[31] The exchangeability of interlayer cations helps in altering the acidic nature by using ion-exchange procedures. In organic chemistry, montmorillonite and its modied types, referred to as montmorillonite-K-10 (produced by the calcinations of montmorillonite), were found as ecient catalysts. Cation exchange produces more eective montmorillonite types, including Fe+ montmorillonite and clayfen. A variety of organic reagents have been synthesized using montmorillonite types (cation substituted) as a catalyst. These include a-aryl b-hydroxycyclic amines, silanols, methyl cinamates, carboxylic acid (synthesized with 100-fold reduction of reaction time under microwave irradiation and ecofriendly conditions), and the production of multisubstituted imidazopyridines, imidazo pyrazines, and imidazo pyrimidines under microwave irradiation in solvent-free conditions. The capacity in modifying the structural composition of montmorillonite, its processing, and surface treatment may be indicated by the achievement of 40[52] patents issued to one commercial organization.[63] Possibly, the primarily development in these patents involves the creation of various types of nanoclays (predominantly montmorillonite-based products) or surface-treatment procedures.

VIII.

ENVIRONMENTAL CONCERNS

The extraction, development, and application of montmorillonite, like several other products, are also experiencing concerns addressing its ecofriendly nature and safety. Information on occupational exposure to bentonite dust in mines, processing plants, and user safety are limited.[5] A varying amount of silica is present in bentonite and kaolin clays; however, there are no reported cases of marked diuse/nodular pulmonarytissue brotic reaction to montmorillonite containing no free silica. Bentonite, which has montmorillonite as a major fraction, and kaoline have not shown local or systematic adverse eects in cosmetics. However, they have shown low toxicity toward aquatic organisms. Possibly two important characteristics that should be assessed for ecofriendly and safety concerns when using montmorillonite are primarily based on the particle size and chemical composition. The increased concerns in the toxicity of airborne ne (0.1 to 2.5 lm) and ultrane (<0.1 lm) particles have received interest for studies. Epidermological studies revealed an increase in morbidity, and mortality was associated with the rise in airborne particles, particularly in the ultrane-size range. The decreasing potencies of quartz, kaolinite, and montmorillonite to cause lung damage were related to their known relative active surface areas and surface chemistry.
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The size of the particle is only one aspect; for any particle, its structure and composition and its known interaction with living organs must be established to ascertain the eect in a particular situation. Natural-clay particles are smaller than 0.004 mm in diameter; however, manufactured nanoclay particles are in the ultrane-size range and have shown toxic properties.[4] These nanoparticles can enter the human body, reaching vital organs through blood circulation. The possibility therefore exists for tissue damage. However, the toxicity and health- risk concerns are indicated for nanosized particles, and they exclude the bulk materials or polymer products where they are incorporated. Therefore, there is a clear partition line in risk assessment for the two types of products, each having dierent requirements. Montmorillonite, in the form of a voluminous product, has been used eectively as medicine[32] for open wounds and for stomach or intestinal distress. Calcium montmorillonite has also been referred to as living clay, because it contains minerals capable of improving enzyme production in living organisms.[32,33,64] The use of montmorillonite toothpaste is claimed to help absorb bacteria from teeth and gums, reducing tooth and gum decay by up to 90 pct.[33] Tooth decay aects over onefourth of children in the United States aged two to ve and half of those aged 12 to 15. Two things that would possibly require further assessment are the eects of various montmorillonite types and the change that occurs in the nanometer size range. Because the properties of nanosized particles are dierent from the bulk material of the same composition, any safety risk or environmental hazard found in one form would not be valid in other forms of montmorillonite. Size eects of particles require to undergo the assessment work and processing through levels of regulations. The framework of the new European chemical policy, registration, evaluation, and authorization of chemicals (REACH), does not include the nanosize-particle eect.[4] With the increasing production and application of nanoclay particles, the concerns of assessing their ecofriendly nature and safety risks will lead to the possible introduction of new regulations. However, it is important to note that there are several standards practiced, mainly in industrialized regions that have addressed more or less the health and safety risks at work places. Therefore, it is unlikely that nanotechnology would be eliminated in the future,[29] and the consumption of nanoclays as llers or additives in polymers for several applications.

IX.

CONCLUSIONS

Clay minerals have long been used in several applications, ranging from industrial materials to consumption in health-related products. More recently, the introduction of nanoclays as llers or additives in polymers for various desired eects has been of enormous interest for research and development studies. An increased consumption is indicated by clay nanocomposites approaching almost one-quarter (24 pct) in 2005
METALLURGICAL AND MATERIALS TRANSACTIONS A

of the total nanocomposites used. However, an interesting concern, along with the studies addressing how nanoclays change the behavior of polymeric materials, is to discover more about clays, nanoclays, and montmorillonite minerals. An appreciation of montmorillonite and nanoclays is useful in exploring their applications in nanocomposites.

ACKNOWLEDGMENTS The author thanks the staff of the textile department and the Rector, University of Management and Technology (Lahore, Pakistan), as well as Nanocor, Inc., for permission to use the picture.

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61. S. Lao, W. Ho, K. Ngyuen, J. Cheng, J.H. Koo, L. Pilato, and G. Wissler: 37th ISTC Conf., Seattle, WA, Oct. 31Nov. 3, 2005. 62. M. Zammarano: in Flame Retardant Polymer Nanocomposites, A.B. Morgan and C.A. Wilkie, eds., Published Online (Apr. 9, 2007), John Wiley & Sons, Inc., New York, NY.

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METALLURGICAL AND MATERIALS TRANSACTIONS A