SYNTHETIC ALKALI METAL ALUMINO-SILICATES, METHODS AND USES, COMPOSITIONS AND THEIR METHODS OF PREPARATION

Abstract: A family of novel and unique synthetic alkali metal alumino-silicates (SAMS) are produced by the hydrothermal reaction between kaolin clay and alkali metal silicates. The integrated composition of the SAMS products is a unique entity having an overall composition of xM2O:Al2O3:ySiO2:zH2O where x is the number of moles of alkali metal oxide and is an integer from 0.01 to 2.0, M is an alkali metal, y is the number of moles of SiO2 in the unique SAMS composition, and z is the number of moles of bound water and is an integer ranging from 1.0 to 5.0. The composition essentially comprises altered kaolin clay platelets with an integral rim or protuberance of essentially amorphous alkali metal silicate-kaolin reaction product. The unique SAMS compositions are structured materials in which the structure can be controlled, and are therefore useful as functional fillers, as TiO2 extenders, as silica extenders or as reinforcing agents for paper, paint, rubber, plastics and specialty products.

Description: SYNTHETIC ALKALI METAL ALUMINO-SILICATES, METHODS • J , AND USES, COMPOSITIONS AND THEIR METHODS OF PREPARATION CROSS REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of Serial No. 875,120, filed June 17, 1986. FIELD OF THE INVENTION 5 This invention relates to novel and unique synthetic alkali metal aluraino-silicate (SAMS) compositions and, more particularly, to synthetic alkali metal alumino-silicates produced by the hydrothermal reaction of kaolin clays and alkali metal silicates. The.preferred method entails the hydrothermal treatment of an aqueous dispersion of 10 a clay pigment with an alkali metal silicate at molar ratios of alkali metal silicate base (B) to clay (C) of less than 1.0, but SAMS compositions and mixtures of SAMS and zeolites can be formed at B/C ratios greater than 1.0. The SAMS compositions have specific advantages as reinforcing extenders or functional pigments for paper, 15 paints, rubber and polymer systems among i ts many uses. The SλMS compositions are particularly useful in paper filling compositions and in paper coating compositions. BACKGROUND OF THE INTENTIO Alkali metal silicate materials, such as sodium aluminσ- 20 silicates, are well known. Broadly speaking, there are two kinds of alkali metal alu ino silicate materials known in the prior act— he natural and the synthetic alkali metal alumino-silicates. ET Thβ alkali metal alumino-silicates known as natural zeolites are mined products which are crystalline in nature. Synthet¬ ic alkali metal alumino-βilicate products are either amorphous or crystalline reaction products. The crystalline synthetic alkali metal alumino-silicates are also called synthetic zeolites. Various types of amorphous synthetic alkali metal alumino-silicates are known as well as synthetic silicas and alumino-silicates. In order to fully appreciate the present invention it is necessary to draw the appropriate distinctions between the unique compositions of the present invention and the prior art compositions of specific silicas and synthetic silicates referred to in general above. Zeolites The prior art description of the nature of zeolites can be found in the U.S. Patent No. 3,702,886 and is incorporated herein by reference. Both natural and synthetic zeolites can be broadly classi¬ fied as crystalline alkali/alkaline earth metal alumino-silicates having unique properties. Synthetic zeolites are ordered, porous crystalline alumino-silicates having a definite crystalline structure within which there are a large number of small cavities which are interconnected by a number of still smaller channels. The cavities and channels are precisely uniform in size. Since the dimensions of these pores are such as to accept for adsorption molecules of certain SUBSTITUTESHEET di enβions while rejecting those of larger dimensions, these materials have co e to be known as "molecular sieves" and are utilized in a variety of ways to take advantage of these proper fes. Such molecular sieves include a wide variety of positive ion-containing crystalline alumino-silicates, both natural and syn¬ thetic. These alumino-silicates can be described as a rigid three dimensional network of S10, and Λ10, in which the tetrahedra are cross-linked by the sharing of oxygen atoms whereby the ratio of the total aluminum and silicon atoms to oxygen is 1:2. The electrσvalence of the tetrahedra-containing aluminum is balanced by the inclusion in the crystal of a cation, for example, an alkali metal or an alkaline earth metal cation. This can be expressed by formula wherein the ratio of Al to the number of the various cations, such as Ca/2, Sr/2, Na, K, or Li, is equal to unity. One type of cation can be exchang- ed either in entirety or partially by another type of cation utilizin ion exchange techniques in a conventional manner. By means of suc cation excliange, It has been possible to vary the size of the pores I the given aluminσ-silicate by suitable selection of the particula cation. The spaces between the tetrahedra are occupied by molecule of water prior to dehydration. SUBSTITUTESHEET Prior art techniques have resulted in the formation of a great variety of synthetic crystalline alumino-silicates. These alumino-silicates have come to be designated by letter or other convenient symbol, as illustrated by zeolite A (ϋ. S. 2,082,243)j zeolite X (U. S. 2,802,244); zeolite Y (U. S. 3,130,007); zeolite K-G (U. S. 3,054655)} zeolite ZK-5 (U. S. 3,247,195); zeolite Beta (U. S. 3,308,069); and zeolite ZK-4 (U. S. 3,314,752), merely to name a few. Zeolite Identification Zeolites A and X may be distinguished from other zeolites and silicates on the basis of their x-ray powder diffraction patterns and certain physical characteristics. The composition and density are among the characteristics which have been found to be important in identifying these zeolites. The basic formula for all crystalline sodium zeolites may be represented as follows: N a 2 °* A1 2°3-'xSiO :yll 0 In general, a particular crystalline ' zeolite will have values for x and y that fall in a definite range. The value x for a particular zeolite will vary somewhat since the aluminum atoms and the silicon atoms occupy essentially equivalent positions in the lattice. Minor variations in the relative numbers of these atoms does not significantly alter the crystal structure or physical properties o the zeolite. For zeolite A, an average value for x is about 1.85 wit the x value falling within the range 1.85 Hh 0.5. For zeolite X, th x value falls within the range 2.5 + 0.5. SUBSTITUTESHEET Thβ value of y is not necessarily an invariant for all samples of zeolites. This is true because various exchangeable ions are of different size, and, since there is no major change in the crystal lattice dimensions upon ion exchange, the space available in the pores of the zeolite to accommodate .water molecules varies. The average value for y determined for zeolite A is 5.1. For zeolite X it is 6.2. In zeolites synthesized according to the preferred prior art procedure, the ratio of podiumoxide to aluminn should'equal one. But I all the excess sodium present in the mother liquor is not washed out of the precipitated product, analysis may show a ratio greater than one, and if the washing is carried too far, some sodium may be ion ex¬ changed by hydrogen, and the ratio will drop below one. It has been found that due to the ease with which hydrogen exchange takes place, the ratio of zeolite A lies in the range of Sodium oxide „ i n + n ? Alumina * — The ratio of zeolite X lies in the range of Sodium oxide _ n o + n ■» Alumina 0.9 -0.2 Thus the formula for zeolite A may be written as followsI 1.0 + 0.2Ha 2 O!Al 2 O 3 tl.85 + 0.5SiO 2 ,ylt 2 o Thus the formula for zeolite X may be written as'followst 0.9 + 0.2Na 2 ojAl 2 O 3 j2.5 + 0.5Si0 2 ιy|l 2 o y may be any value up to 6 for zeolite A and any value up to 8 fo zeolite X. SUBSTITUTESHEET The pores of zeolites normally contain water. The above formulae represent the chemical analysis of zeolites A and X. When other materials as well as water are in the pores, chemical analysis will show a lower value of? y and the presence of other adβorbates. The presence in the crystal lattice of materials volatile at tempera¬ tures below aboμt 600 degrees Celsius does not significantly alter the usefulness of tjie zeolite as an adsorbent since the pores are usually freed of such materials during activation. Prior Art Patents Synthetic alkali metal silicates, such as sodium alumino-silicates, are generally produced by the reaction of alum with alkali metal silicates. The resulting product usually has a silica to alumina molar ratio of about 11. Amorphous products of. this type are known. For example, amorphous products of this type are sold by the J. M. Huber Corporation under the trademark ZEOLEX. Specific examples of these products, as well as methods of their preparation are dis¬ closed in U.S. Patents Nos. 2,739,073; 2,848,346 and 3,582,379. ' None of these patents teach or even • suggest the synthe¬ sis of the unique compositions of the present invention by the hydrothermal reaction between alkali metal silicate baβes and clay at preferred molar.ratios of silicate base to clay of less than 1.0. Synthetic silicas are also known which are produced by the reaction of sodium silicates and sulfuric acid at temperatures o about 80 degrees C. The products usually have fixed molar ratios. SUBSTITUTESHEET -7- Variouβ products of this type are known In I). S. patents of Satlβh K. Waβon under Noβ. 3,893,840; 4,067,746; 4,122,160 and 4,422,880. Products of this type are sold by J. H. Huber Corporation under the ZEO, ZEOSY , ZEOFREE and ZEODENT trademarks. None of the above mentioned patents teach or even suggest the synthesis of the unique compositions of the present invention by the hydrothermal reaction between alkali metal silicate base (B) and clay (C) at preferred molar ratios of B/C or silicate base to clay of less than 1.0. A comparison of the, Fourier Transform 0 Infrared (FT-IR) spectra of an amorplious synthetic silicate (ZEOLEX 23), an amorphous silica (Hi-Sil 233) and a synthetic alkali metal aluminσ-silicate (SAMS) of the instant invention is shown in Figure 1. Various zeolite products are also known which are produced synthetically by the reaction of sodium aluminate and sodium silicates '5 at temperatures of less than 100 degrees C. This reaction, in gener¬ al, proceeds to form an intermediate gel or amorphous material which then crystallizes. Zeolites of this type are sold commercially under the designations, zeolite A, zeolite X, zeolite Y, as well as others. These zeolites find use as absorbents, ion exchange agents, in 20 catalysis and in other areas. A detailed discussion of this art is provided in U.S. Patents Noβ. 4,443,422 and 4,416,805 and is hereby incorporated herein by reference. None of these patents teach or remotely suggest the synthesis o the unique compositions of the present invention by the hydrotherma 25 reaction between alkali metal silicate base (B) and clay (C) at preferre molar ratios in the batch reaction of BC or silicate base to clay, of les SUBSTITUTESH ET than 1.0. A comparison of the infrared spectra (FT-IR) of zeoliteβ A, X, and Y with a synthetic alkali metal alumino-silicate (SAMS) pre¬ pared by the method described in the instant invention is shown in Figure 2. The reaction of sodium silicate with kaolin clays has been studied under various hydrothermal conditions, as reported by Kurbus, et al, Z^ Anorg. Allg. Chem. , 1977, Volume 429, pages 156-161. These reactions were studied under hydrothermal conditions using essen¬ tially equivalent molar ratios of the kaolin and sodium silicate with the reaction being carried out in an autoclave. The products of the reactions, as identified by x-ray, electron microscope, and infrared methods, showed that sodium silicate . reacta with kaolin to form an alumino-silica gel or a crystallized zeolite mineral analcime of the formula: Na 2 0:Al 2 03:4Si0 2 :2H 2 0. In the reaction, the kaolin dissolves and alpha-quartz simultaneously appears in the product of reaction. Kurbus reference specifically teaches the synthesis of a prior art crystalline zeolite mineral called analcime. This reference does not even remotely suggest the synthesis of the unique composi¬ tions of the present invention. For simplicity, the unique compositions of the instant invention are described as x-ray amorphous materials having attenuated kaolin peaks. The materials will be described in greater detail under the summary of the invention. An FT-IR comparison of analcime with a SAMS composition of the present invention is also given in Figure 2. SUBSTITUTE8-<~- -9- Various reactions of kaolin clays with basic reagents have been studied, including reactions with sodium hydroxide, calcium hydroxide, and the like. U. S. Patents Nos. 3,765,825 and 3,769,383 to Hurst, for 5 example, studied the high temperature, high pressure reaction of slurries of clay with alkali metal hydroxides, such as sodium hydroxides. In this reaction, the kaolinite was decomposed and transformed into alumino-silica materials. None of these patents even remotely suggest about the synthesis of the unique composition of the ■ J ^ Q present invention by the hydrothermal reaction between an alkali metal silicate and kaolin clay at preferred molar ratios of silicate to clay of less than 1.0. Various synthetic amorphous sodium alumino-silicate materials have been produced, as described in U. S. Patent No. 5 4,213,874, by the reaction of sodium silicate and sodium aluminate. This patent does not teach or even suggest the synthesis of the unique composition of the present invention by the hydrothermal reaction between an alkali metal silicate and kaolin clay. In U. S. Patent No. 3,264,130, a hydroxide of barium or 20 calcium is reacted with a siliceous material. This patent does not teach about the hydrothermal reaction between an alkali metal silicate and kaolin clay. An amorphous precipitated sodium alumino-silicate pigment is produced in U. S. Patent No. 3,834,921 by the reaction of sodium 25 silicate and aluminum sulfate. The example of patent 3,834,921 SUBSTITUTE SHEET teaches about the synthesis of an alumino-silicate pigment of the silica to alumina ratio of about 11.5 The product is produced by reaction of aluminum sulfate and sodium silicate. v None of the above mentioned patents teach or remotely suggest about the synthesis of the unique compositions of the present invention by the hydrothermal reaction between alkali metal silicate base (B) and clay (C) at preferred molar ratios of silicate base to clay, or B/C, of less than 1.0. In U.S. Patent No. 4,075,280, zeolite A Is produced by the reaction of a calcined clay with sodium hydroxide. This patent teaches about a new process for the preparation of well known prior art zeolite A of well defined x-ray pattern. Rod-shaped microcrystalline particulatea are produced in U.S. Patent No. 3,837,877 by the reaction of the kaolin clay and an alkali metal hydroxide at molar ratios of hydroxide to clay of at least 2:1. This patent does not even remotely suggest about the synthesis of unique compositions of the instant invention from the hydrothermal reaction between an alkali metal silicate and kaolin clay. In U.S. Patent No. 3,784,392, a method is described for preparing finely divided alumino-silicate pigments from kaolin ' clays by the hydrothermal treatment of kaolin clay dispersions with an alka¬ line earth metal hydroxide, usually calcium hydroxide. The reaction is carried out using a molar ratio of the hydroxide to the kaolin SUBSTITUTESHEET plgment of at least 1:1 at temperatures of 50 to 200 degrees C under hydrothermal conditions. The product produced is an amorphous alumino-silicate pigment having increased brightneββ and having particular utility in coating paper. This patent doe? not even remotely suggest a reaction between an alkali metal silicate and kaolin to produce unique compositions of the present invention. None of the prior art patents teach the synthesis of novel alkali metal alumino-silicate compositions described herein. The products of the present invention are unique and their preparation under the disclosed reaction conditions is truly unexpected. For the sake of brevity, the synthetic alkali metal alumino-silicates of the instant invention are referred to as SAMS throughout the body of thiβ patent. A further background concept necessary to fully appreciate the present invention ia that of "structure." As used herein, in relation to alkali metal alumino-silicatee, the structure concept is as follows: It iβ possible to synthesize alkali metal alumino-silicate or SAMS products with varying structure levels in analogy to the structure definition set forth in U.S. Patent No. 3,893,840 to S. X. ason of J. M. Huber Corporation. Since no universally accepted industrial method for particle size determination of synthetic fillers exists and since it is common practice of filler suppliers to perform the rub-out oil absorption test, ASTH-D.281, on their products, the definition of structure is arbitrarily based on the oil absorption SUBSTITUTE SHEET values rather than the filler particle size. Conforming to the same definition as in use for silica structure, e.g., S. K. tfason, "Cosmet¬ ic Properties and Structure of Fine Particle Synthetic Precipitated Silica," J. Soc. Cosmet. Che . 29, 497-521 (August 1978), the βynthet- ic alkali metal alumino-silicates or SAMS products are called VHS (very high structure) type when the oil absorption values are above 200 ml/lOOg and VLS (very low structure) type when the oil absorption values are below 75 ml/lOOg. The classification of the synthetic alkali metal alumino-silicate or SAMS compositions- based on "atruc- ture" is shown in Table I as it relates to oil absorption. TABLE I DEFINITION: SAMS STRUCTURE VERSUS OIL ABSORPTION Structure Level Oil Absorption (ml/lOOg) VHS (Very High Structure) Above 200 HS (High Structure) 175 - 200 MS (Medium Structure) 125 - 175 LS (Low Structure) 75 - 125 VLS (Very Low Structure) Less than 75 The present invention provides novel synthetic alkali metal alumino-silicate or SAMS compositions and methods for their prepara¬ tion which are unique and unexpected in view of the knowledge of the prior art involving the reaction of clays and alkali ' metal silicates. SUBSTITUTE SHEET SUMMARY OF THE INVENTION The present invention relates to a novel family of unique synthetic compositions hereinafter designated as synthetic alkali metal alumino-silicates or "SAMS" or simply SAMS. The products of the instant invention relate to a novel family of unique synthetic materi¬ als which are shown by transmission electron microscopy (TEM), Fourier Transform-Infrared spectrσscopy (FT-IR), x-ray diffraction (XRD), and electron diffraction (ED) to be unique in composition and morphology and which characteristically contain as a minor portion partially altered kaolin particles which give the characteristic peaks for kaolin seen in the x-ray diffraction patterns of the SAMS composi¬ tions, but which also contain as the major portion a non-diffracting amorphous or microcrystalline reaction product primarily around the edges, but also to some extent over the face of the altered kaolin particle as illustrated by TEM Figures 18 through 23. The TEM Figures 18 to 23 show the SAMS product to be altered kaolin platelets having an integrated rimmed area of amorphous, non-diffracting alkali metal silicate-kaolin reaction product. The integrated composition of the SAMS product is a unique entity having an overall composition of: 2 0:Al 2 0j:yS10 2 :zH 2 0 where x is the number of moles of alkali metal oxide and M is the alka metal, y is the number of moles of S10 2 in the SAMS composition, and z is the number of moles of bound water. SUBSTITUTE SHEET The unique products are further characterized by X-ray diffraction (XRD) as being essentially amorphous and having attenuated kaolin peaks as illustrated by Figures 33, 34, 35 v and 36. The SAMS products are also characterized as having infrared spectra (IR) which differ from the IR spectra of the starting clays, zeolites, and both crystalline and amorphous silicas and silicates. Figure 1 compares the infrared spectrum of a SAMS composition with the spectra of an amorphous synthetic silicate (Zeolex 23) and silica (Hi-Sil 233), and with calcined kaolin clay. Figure 2, likewise, compares the infrared spectrum of a SAMS composition with the spectra of zeolites A, X, Y, and analcime. In both Figures 1 and 2 the infrared spectrum of the SAMS composition is considerably different than the spectra of the other materials. In Figures 3 and 4, the infrared spectra of the SAMS compositions of Example One and Two are compared with their respective starting clays. In both cases, the spectra of the SAMS compositions are considerably different from the spectra of the starting clays, even though the area in the 800-400 wavenumber region is quite similar for both clay and SAMS. The major spectral difference is the 1200-875 wavenumber region where the SAMS compositions exhibit a broader, less detailed Si-0 stretching peak (1200-950 cm "1 ). For simplicity, the SAMS compositions will be described as being essentially multicomponent materials comprising altered kaolin clay platelets integrated with one or more adjacent areas of essentially amorphous alkali metal silicate-kaolin clay reaction product. The preferred unique compositions of the present invention are prepared by the hydrothermal reaction of an alkali metal silicate and clay making sure that the B/C ratio of the batch compositions are SUBSTITUTE SHEET less than 1.0, but by no means limited to values less than 1.0, where B represents the moles of alkali metal silicate and C represents the mole of kaolin clay in a batch composition. While the preferred SAMS compositions are produced at B/C ratios of less than 1.0, unique SAMS products can also be produced at a B/C ratio substantially greater than 1.0 by adjusting the batch composition, pressure, temperature, and reaction time of the hydrothermal reaction. This unique batch composition is heated in a stirred reactor using a steam pressure of 50 psi to 360 psi and preferably between 90 to 150 psi for a reaction time of 15 minutes to four hours and more preferably between 45 minutes to two hours. At the end of the desired reaction period, the reactor is cooled and the unique SAMS product is filtered, washed, dried and milled to the desired degree of fineness. The alkali metal silicate referred to as base in the SAMS reaction has a Si0 to alkali metal oxide ratio of 1-6. When the alkali metal silicate is sodium silicate, the Si0 2 :Na 2 0 ratio is preferably 2.0-3.3, and a preferred sodium form of SAMS composition is produced which can be expressed in terms of mole ratio of the oxides as follows: xNa 2 0:AI2O3:ySi0 2 :zH 2 0 where x is an integer with a value from 0.01 to 2.0, y is an integer with a value greater than 2.0, and z is ■ an integer from 0 to 10 and preferably 0 to 5.0. Correspondingly, when the alkali metal silicate is potassium silicate, the preferred Si0 2 :K 2 0 ratio is 2.8-3.9, and when the alkali metal silicate is lithium silicate, the preferred Si0 2 :Li 2 0 ratio is 4.8-5.6. SUBSTITUTESHEET It is, accordingly, one object of the present invention to provide novel synthetic alkali metal alumino-silicate (SAMS) products or pigments which are useful as reinforcing agents, reinforcing extenders, functional fillers, and/or opacifiers for paper, paints, plastics, and other specialty products. A further object of the invention is to provide a method for the production of novel synthetic alkali metal alumino-silicate products by the reaction of clays and alkali meta.1 silicates under hydrothermal conditions using unique batch composition and controlled reaction time, temperature and pressure conditions. It is a general object of the present invention to produce value added unique compositions from relatively inexpensive kaolin or related materials, which products are controlled structure synthetic alkali metal alumino-silicate products made from mined and refined kaolin. Yet another object of the invention is to produce unique kaolin based compositions of higher brightness and significantly higher opacity than the starting kaolin products. Another objective of the instant invention is to provide unique SAMS compositions of very low abrasion properties when compar¬ ed with calcined clays, and to provide synthetic pigments of superior paper coating properties over calcined clays. Another object of the instant invention is to provide unique synthetic products which can extend expensive functional fillers, extenders, pigments and value added products such as calcined clays, fumed silicas and silica gels. SUBSTITUTESHEET synthetic silicates, synthetic calcium silicates and related compounds. Yet another important and particular object of the invention is to provide unique SAMS compositions of high scattering coefficient and excellent opacifying properties for use in extending the expensive titanium dioxide compositions in such end-use applications as paper, paints, rubber and plastic concentrates. A still further object of the invention is to provide articles of manufacture comprising paper, latex paints, plastics, paint flatting, rubber, dry liquid carrier, defoa ers, antiblocking, " and other products containing, as a reinforcing agent or functional filler or extender, a novel synthetic alkali metal alumino-silicate product produced by the hydrothermal reaction of clays and alkali metal silicates. Other objects and advantages of the present invention will become apparent as the description thereof proceeds. In satisfaction of the foregoing objects and advantages, there is provided by this invention synthetic alkali metal alumino- silicates (SAMS) which comprise altered kaolin clay platelets integrated with one or more adjacent areas of essentially amorphous alkali metal silicate base-kaolin clay reaction product, and which are of the general formula xM^A^C^ySiC^zi^O, wherein x is the number of moles of alkali metal oxide, M is the alkali metal, y is the number of moles of Si0 2 , and z is the number of moles qf bound water. These SUBSTITUTE SHEET products may be characterized as substantially amorphous with attenuated kaolin peaks as characterized by the ptfssent state of the art x-ray diffraction, and yet may be considered micro-crystalline at a future date as the learning curve in the characterization of SAMS type products increases. The present invention provides unique SAMS products which are shown by TEM to be amorphous compositions integrated with altered kaolin platelets. The SAMS products have oil absorption values ranging from 40 to above 200 ml/100g, surface areas ranging from 2 to 300 πr/gr high monovalent cation exchange capacities. of the order of up to 200 milliequivalent/100g and very low abrasion characteristics. Also provided by the present invention is a method for production of these synthetic alkali metal alumino-silicate products which comprises the hydrothermal reaction of a slurry of a clay with an alkali metal silicate wherein the preferred molar ratio of alkali metal silicate base (B) to clay (C) in the starting reaction mixture is less than 1.0, although unique SAMS compositions can be produced at ratios higher than 1.0 under preselected reaction conditions. There is also provided by the present invention compositions comprising paper, paints, plastics, rubber, defoamer, and specialty products, which contain the novel synthetic alkali metal alumino- silicate materials of this invention. SUBSTITUTE SHEET -19- BRIEF DESCRIPTION OF THE DRAWINGS In order to facilitate the understanding of this invention, reference will now be made to the appended drawings. The drawings should not be construed as limiting the invention but are exemplary only. FIO. 1 Shows a comparison of the FT-IR scans of Zeolex 23, an amorphous sodium alumino-silicate, Hi-Sil 233, an amorphous syn¬ thetic silica, Hycal, a calcined kaolin, and the SΛMS composition from Example Two FIG. 2 Shows a comparison of the FT-IR scans of zeolites A, X, Y and analcime with that of the SAMS compo¬ sition from Example Two FIG. 3 Shows a comparison of the FT-IR scans of the SAMS composition from Example One with the starting Omnifil clay FIG.4 Shows a comparison of the FT-IR scans of the SAMS composition from Example Two with the starting Hydragloβs 90 clay FIG. 5 Shows the comparison of the FT-IR scans of Fydxaglosa 90 and SAMS compositions prepared at B/C ratios of 0.5 (Example Two), 1.0 and 2.0 (Example Five, Tetta No. 1 and 2, respectively) FIG. 6 Shows a con εrison of the FT-IR scϊts of the SAMS compositions of Exampl Six prepared from Omnifil clay and different mole rai:io sodium silicate bases using a B/C ratio of 0.5 f'IG. 7 Shows the comparison of the FT-IR scans of the SAMS compositions of Example Nine prepared from HyrJragloβs 90 and 2.5 mole ratio sodium silicate at B/C ratios of 0.75 to 5.0 FIG. 8 Shows the comparison of the FT-IR scans of. the SAMS c ir.jositiona of Example Nine prepared by the reaction of ilydragloss 90 and sodium hydroxide at B/C ratios of 0.75 to 5.0 . FIG. 9 Shows the scanning electron microscope (SEM) photograph of Zeolite A SUBSTITUTE SHEET FIG. 10 Showβ the SEM photograph of zeolite X FIG. 11 Shovrø the SEM photograph of zeolite Y FIG. 12 Shows the SEM photograph of analcime FIG. 13 Shows the SEM photograph of the SAMS composition of Example One FIG. 14 Shows the SEM photograph of the SAMS composition of Example Two FIG. 15 Shόvrs the TEM photograph of prior art amorphous sodium alumino-silicate, Zeolex 23 10 F FIIGG.. 1 166 Shows the TEM photograph of prior art amorphous synthetic silica, Hi-Sil 233 FIG. 17 Shows the TEM photograph of prior art calcined clay, Hycal FIG. 18 Shows the TEM photograph of the SMIS composition 15 of the present invention derived from .Omnifil east Georgia clay at a B/C ratio of 0.75 (Example One) FIG. , 19 Shows the 1EM photograph of SAMS composition of Example One FIG, . 20 Shows the TEM photograph of the SAMS composition 20 of the present invention derived from Hydragloss 90 east Georgia clay at a B/C ratio of 0.5 (Exam¬ ple Two) FIG. 21 Shows the TEM photograph of the SAMS composition of Example Two 25 FIG. 22 Shows the TEM photograph of the SAMS composition of the present invention derived from Hydragloss 90 at a B/C ratio cf 1.0 (Example Five, Test No. 1) FIG. 23 Shows the TEM photograph of the SAMS composition 30 of the present invention derived from Hydragloss 90 at a B/C ratio of 2.0 (Example Five, Test No. 2) FIG. 24 Shows the TEM photograph of the control Omnifil clay 35 FIG. 25 Shows the TEM photograph of the control Hydragloss 90 clay SUBSTITUTE SHEET -21- FIG.26 Is the XRD scan of zeolite A FIG.27 Is the XRD scan of zeolite X FIG.28 Is the XRD scan of zeolite Y FIG.29 Is the XRD scan of analcime 5 FIG.30 Is the XRD scan of Zeolex 23 FIG.31 Is the XRD scan of Hi-Si1233 FIG.32 Is the XRD scan of Hycal FIG. 33 Is the XRD scan of the SAMS composition of Example One showing only attenuated kaolin peaks 0 FIG. 34 Is the XRD scan of the SAMS composition of Example Two showing only attenuated kaolin peaks FIG. 35 Is the XRD scan of the SAMS composition of Example Five, Test 1 showing only attenuated kaolin peaks FIG. 36 Is the XRD scan of the SAMS composition of Example γ c Five, Test 2 showing only attenuated kaolin peaks FIG.37 Is the XRD scan of the starting Omnifil clay FIG.38 Is the XRD scan of the starting Hydragloss 90 clay FIGS. 39A and 39B show the SEM photograph of potassium SAMS compositions of Example Four. Test 2 (Fig. 39A) 20 an Test 4 (Fig. 39B) FIG. 40 shows the SEM photograph of platey SAMS composition derived from Hydraprint clay at a B/C ratio of 0.25 (Example Eleven) FIG. 41 shows the SEM photograph of platey SAMS 25 composition derived from Hydraprint clay at a B/C ratio of 0.75 (Example Thirteen) FIG. 42 shows the SEM photograph of Hydraprint clay used in the preparation of platey SAMS compositio derived from Hydraprint clay at a B/C ratio of 3 0.75 (Example Thirteen) FIG. 43 shows the TEM photograph of l i thium SAMS composition derived from Li thsi l 4 l i thi um silicate and Hydragloss 90 at a B/C ratio of 0.75 (Example Fourteen, Test No. 3) . SUBSTITUTE SHEET - - DESCRIPTION OF PREFERRED EMBODIMENTS The synthetic alkali metal alumino-silicates (SAMS) of the present invention are unique products which are eminently useful as reinforcing agents or functional fillers for paper, paints, plastics, rubber and specialty materials. The preferred products are particularly charac-terized as being rimmed alkali metal alumino- silicate compositions which have increased opacity and structure, and unique morphology when compared with the starting clay material. Further, the brightness of the resul ting product is of ten Q substantially higher than the starting clay and comparable or superior " to various clay materials now used as reinforcing agents or functional fillers for paper, paints, plastics, and the like. It is truly unexpected that the opacity and brightness of the' SAMS compositions would be significantly increased over the starting materials. 5 The alkali metal alumino-silicate products of the present invention also have unexpectedly high oil absorption characteristics, the oil absorption in milliliters of oil per 100 grams of the SAMS product ranging from about 40 to above 200 ml/100g. This is qui te remarkable in that a hydrous clay of very low oil absorption of about 20 30 ml/100g has been transformed into a SAMS product of low to high structure (LS to HS) by the instant invention. For definition of structure, see Table I. In this specification, the SAMS products are defined as structured agglomerates wherein the primary particles comprise altered 25 kaolin clay platelets integrated with one or more adjacent areas of essentially amorphous alkali metal silicate base-kaolin clay reaction product, and wherein the primary particles of said SAMS products have attenuated kaolin clay peaks in x-ray diffraction patterns from kaolin SUBSTITUTE SHEET remnants in the composition, and have the characteristic IR scan shown in Figures 3-6, and which are shown by TEM Figures 18-23 and 43. The morphology and particle size of the structured agglomerates varies depending on the specific reaction conditions and components employed. For example, the agglomerated SAMS products formed by the reaction of alkali metal silicate and a fine particle size clay (like Hydragloss 90) usually have a spheroidal-like morphology, while those from a coarse particle size delaminated clay (like Hydraprint) have a platelet morphology. The products produced from sodium silicate and potassium silicate form rimmed materials having attenuated kaolin peaks, whereas the products produced from lithium silicate form materials having protuberances on the surface and having attenuated kaolin peaks. By the term "rimmed" is meant that the altered primary particles are comprised of a core material having an integral border or outer edge material of different constitution from the core. The lithium silicate products have protuberances rather than rims, the protuberances being integral with the core. The rim areas or protuberances appear to be not only x-ray amorphous but also electron diffraction amorphous, whereas the core appears to have attenuated kaolin peaks on x-ray diffraction. The primary particles are generally in the form of lamella (irregular to pseudo hexagonal shaped plates) . The rim is an outer edge or border which usually substantially encompasses the plate perimeter. The rims and o protuberances generally have an annular width or diameter of 20A to 0 1200A, respectively, as measured from the outer surface of the particle to the beginning of the core area. By the term "amorphous" is meant that the material does not have a characteristic x-ray SUBSTITUTE SHEET diffraction pattern. By the term "attenuated kaolin peaks" is meant that on x-ray diffraction, the material exhibits peaks located in the characteristic position of kaolin, but which are depressed or weakened from the normal peaks found for kaolin in x-ray diffraction. In this specification, the term "functional pigment" means a non-color bearing material which enhances desired properties in other materials and in some cases, reduces costs of the resulting mixture. In the specification the term "hydrothermal" means that the reaction is carried out under aqueous conditions of elevated temperatures and pressures of greater than atmospheric. The preferred temperatures range from 140-250°C The preferred pressure conditions comprise pressures ranging from 50 to 360 psig. The reaction is conducted under conditions of agitation, the speed of agitation depending on the reaction. The specific SAMS products of this invention may be prepared by the following reaction: Alkali metal silicate (B) + kaolin (C) * SAMS The B/C ratio, which is the molar ratio of alkali metal silicate (B) to kaolin clay (C) in the batch composition, determines the variety of SAMS compositions which can be produced by the teachings of the instant invention as can be seen in TEM Figures 18 through 23. A B/C ratio of less than 1.0 is the preferred embodiment of the instant invention. Generally, at B/C ratios higher than 1.0, and especially higher than 5.0 using sodium silicate, zeolites are in some cases produced along with SAMS products, although SAMS of desired morphology and preferred composition can also be produced without the presence of zeolitic species by using special reaction conditions. SUBSTITUTESHEET The preferred raw materials for the preparation of unique SAMS compositions are alkali metal silicate and kaolin clay. Typically, the alkali metal silicate is of the composition: M 2 0:rSi0 2 where M is the alkali metal and r is the number of moles of Si0 2 bound to a mole of alkali metal oxide. When M is sodium, the alkali metal silicates are called sodium silicates and the value of r is the Si0 2 /Na 2 0 mole ratio. Typically, the alkali metal silicates used in the SAMS reaction have an r value of 1.0-6.0; the sodium silicates, the preferred reactants, will have an r value of 1.0-4.0. The kaolin clay used in the SAMS reaction may be represented by the formula Al 2 03:2Si0 2 2H 2 0. In calculation of the B/C ratio, the bound water portion (L0I*13.4%) of the kaolin clay is accounted for in the molecular weight used for kaolin. The molecular weight of pure kaolin is therefore 258. Other ingredients which may be present as impurities, such as Ti0 and Fe 2 0- j , are normally not included in the " clay's MW, but are later accounted for in the % activity assigned to the starting clay material. In this reaction, the alkali metal si licates which may be used are sodium silicate, potassium silicate and lithium silicate. In the reaction of kaolin clay with sodium silicate, there is produced a SAMS product whose primary particles have the characteristic core and rim combination in all cases. In this product, the rimmed area is highly concentrated in silica vs. the core as determined by STEM/EDAX (Scanning Transmission Electron Microscopy/Electron Dispersive Analysis). This type of analysis determines the relative distribution of given elements within a material (i.e., it provides elemental mapping). In addition, this analysis indicates that sodium is SUBSTITUTE SHEET generally well distributed throughout the entire altered particle, both in the core and in the rim. This kind of product is obtained in all ratios of base to clay, except that at high B/C ratios, the likelihood of zeolite formation increases. Therefore, in this invention, when the reaction includes that of kaolin clay with sodium silicate, it is preferred that the B to C ratio be no higher than 5.0, preferably range from 0.1 to 5.0, and more preferably range from 0.25 to 0.9. Further, in B/C ratios of less than 1,' the product has amorphous rims concentrated in silica and contains some residual kaolin. In B/C ratios of greater than 1, the reaction is prone to zeolite formation of the crystalline type, such as the P type and S type zeolite. Also, as the Si0 2 /Na 2 0 ratio decreases in the sodium silicate, there is a tendency for increased zeolite formation in this reaction. Therefore, the preferred Si0 2 /Na 2 0 molar ratio in the sodium silicate is at least 2.0 and preferably is 2.5 to 3.3. The N brand and RU brand of commercially available sodium silicates (obtainable from PQ Corp.) are preferred. In the formation of SAMS products by the reaction of kaolin clay and potassium silicate, the altered primary particles of the resulting SAMS product will exhibit rims in all cases, although the amorphous rims formed in the potassium silicate SAMS product differs from the sodium silicate product in that the rims will be concentrated in both silica and potassium. The acceptable B/C ratios using potassium silicate and kaolin range from 0.10 to 5.0, and more preferably from 0.1 to 0.9, and no substantial zeolite formation will be noted even at molar ratios as high as 5.0. As indicated above, rim alteration occurs during these reactions and the rim material is SUBSTITUTESHEET concentrated in silica and potassium (versus the core material). The morphology of the potassium silicate agglomerates is usually similar to that of the sodium silicate product. However , as the ratio of Si0 2 /K 2 0 increases in the potassium silicate used to react wi th the c kaolin clay, the reactions are prone to producing a product whose agglomerate structure closely resembles a coral-like material. At lower ratios, the material is more similar to that produced from sodium silicate. The preferred Si0 2 2° ratios will range from 2.8 to 3.9 with the commercial potassium silicate products KASI 1, 6 and 42 Q being preferred reactants. The products produced from the lithium silicate and clay comprise a core material having protuberances or raised masses integral with the core. Electron diffraction analysis indicates that these protuberances are totally amorphous, whi le the remaining 5 platelet areas show the typical diffracjtion pattern for kaolinite. Most importantly, it should be noted that the protuberances or raised masses did not form exclusively on the clay platelet edges, but appear in a more or less random fashion about the platelets. Several pseudo- hexagonal clay platelets are still clearly evident in the TEM 2 photographs which indicates great heterogenei y of reaction. Elemental mapping of the Si and Al content within a li thium SAMS material, by STEM/EDAX analysis, has indicated that the alteration product (i.e., the protuberances) is much higher in silicon and deficient in aluminum relative to the unaltered kaolinite regions. 25 Elemental mapping of lithium was not possible because its atomic weight is below the detection limit of the instrument * SUBSTITUTE SHEET The SAMS compositions are produced by the reaction of clays and alkali metal silicates under hydrothermal conditions. The clays which may be used include all kaolin-type clays, including rude, air- floated and water-washed clays, as well as mixtures of clays and equivalent materials. Pure clays, as well as impure clays, may be used. Some of the preferred clays are kaolin clays sold commercially under the trademarks OMNIFIL, HYDRASPERSE, HYDRAPRINT and HYDRAGLOSS. Other mineral sources corresponding to the silica-alumina values present in clays and alkali metal silicates may be used. Sources of alumina such as alumina, sodium aluminate, aluminum hydroxide or other aluminum sources may be used without deviating from the spirit of the instant invention. Silica sources may include synthetic silica, reactive silica, sodium silicate or equivalent materials. The alkali metal silicate can be any of the types of materials known to the art, but preferably sodium silicate, potassium silicate, lithium silicate, or mixtures thereof, or compositions which can react to give equivalent compounds should be used. A critical feature of the invention is the molar ratio developed in the system between the amount of alkali metal silicate and the amount of clay used. It is necessary to control the molar ratio of alkali metal silicate to clay, otherwise a zeolitic crystal¬ line product or mixtures of amorphous and crystalline species will be produced. The products of the present invention are typically rimmed compositions as depicted in TEM Figures 18 through 23. It is preferred that the molar ratio of alkali metal silicate to clay be controlled to produce the desired SAMS product. Further, the reaction of the present invention is carried out in an aqueous system using an aqueous slurry of the clay which is SUBSTITUTESHEET ixed with an aqueous solution of alkali metal silicate. The resulting clay and alkali metal silicate sluπy preferably has a concentration of 1 to 20 weight percent solids, preferably 5 to 15 percent. In a preferred operation of the process, the aqueous slurry of the starting clay material and the alkali metal silicate is formed, the system is closed and heat applied to gradually raise the temperature. In general, the pressure in the system will range from about 50 to 360 psig at temperatures ranging from about 140 to 250 degrees C. A specifically preferred range of conditions is to operate the process at pressures of 100 to 200 psig and temperatures of 164 to 194 degrees C. The temperatures are preferably correlated to the pressure such as that provided by steam. The reaction time is about 0.25 to 4 hours. After completion of the reaction, heat is removed and the mixture is allowed to cool, after which the system is opened, the product separated by filtration or centrifugation, washed with water, and dried. Spray drying is preferred at inlet temperatures of 1000°F (538°C) and outlet temperature of 250°F (121°C). The resulting product may be characterized as having oil absorption values ranging from about 40 to 220 ml/100g. The surface area ranges from about 2 to 300 m /g. More preferably, the product will have an oil absorption value ranging from 80 to 160 ml/100 g and surface areas ranging from 10 to 30 πr/g. Particularly preferred SAMS products are those produced by reaction of delaminated clays with alkali metal silicates. A suitable delaminated clay for reaction with the alkali metal silicate is that delaminated clay sold commercially as Hydraprint by J. M. Huber SUBSTITUTE SHEET Corporation. Hydraprint is a coarse particle size delaminated clay produced by delamination of a cretaceous Middle Georgia Clay. The SAMS product formed by reaction of the alkali metal silicate and delaminated clay has a platelet morphology • which makes the product, referred to herein as a "platey" material, superior for light weight paper coating applications in that it provides excellent sheet smoothness. These platey materials are also especially useful for incorporation into plastics, such as high density polyethylene, since they provide excellent impact strength to the polyethylene. ' EXAMPLES The following examples are presented to illustrate the invention, but it is not considered to be limited thereto. In the examples and throughout the specification, parts are by weight unless - otherwise indicated. EXAMPLE ONE SYNTHESIS OF SAMS FROM OMNIFIL CLAY Water, 1,508 gallons (12,629 pounds) , was added to a 2,500 gallon pressure reactor. To the water was added 101.3 gallons (1,458 pounds) of a 67.7% solids kaol in clay slurry which is sold commercially as Omnifil by the J. M. Huber Corporation. This is a water-refined kaolin clay produced from the East Georgia deposit having the properties shown in Table II. To the clay-water slurry was added 147.2 gallons of a fresh water sodium silicate solution (1,700 pounds) of 34.9% solids having a Siθ 2 tøa 2 0 molar ratio of 2.5. Under these conditions, the final product solids will be approximately 10% and the batch composition will have a base to clay molar ratio of SUBSTITUTE SHEET approximately 0.75. The batch composition for the reaction can be expressed as s Na 2 0: 1.33A1 2 0 3 : 5.21Si0 2 :278H2θ and has an H/N (moles water/moles Na 2 0) ratio of 278, a S N (moles Si0 2 /moles Na 2 0) ratio of 5.2 and a S/A (moles Si0 2 /moles A1 2 0 3 ) ratio of 3.9. The hatch waa heated to a reaction preββure of 120 psig and a tempeiβiure of 172 degrees C. The fixture was allowed to react for one hour under continuouβ agitation. t the end of the one-hθϊ;f rctction time, the mixture waa vented into a drop tank and the result¬ ing mixture was then filtered, washed and spray dried. The product of Example One was evaluated and characterized by various test methods. The physical properties of the resulting synthetic alkali metal alumi o- silicate composition, .or SAMS, reprβ- renting the present invention are listed in Table II. The properties of the starting Omnifil clay control are also listed Jn Table II for comparative purposes. TABLE II SttTHESIS OF SAMS FROM OMNIFIL CLAY SAMS from Omnifil Chemical Analysis, X Omnifil Clay Clay Control : Ti 2 1.43 2.12 Fe 2 0 3 0.81 1.11 sιo 2 52.82 44.33 Al 2 o 3 24.32 .37.60 Na 2 0 7.35 0.03 SUBSTITUTE SHEET (Table II Coitfc.) Physical Properties: Loss on Ignition, X 10.90 13.40 Pore Volume, cc/g (Mercury Intrusion) 3.10 1.10 Surface Area, m.2/g 19.8 20.0 pit (at 20% Solids) 10.8 6.5 Oil Absorption, ml/lOOg 136 37 Valley Abrasion, (mg of wire loss) 8.7 10.5 Cation Exchange Capacity, meq/lOOg NH. » κ+ 186 2-3 meq/lOOg Ca*S Mg +Z 45 1-2 Brightness, X 86.1 82.0 Sedigraph Particle Size, X: +10 microna 0.5 1.8 -1- 5 microns 3.0 4.0 - 2 microns 58.5 89.0 - 1 micron 34.0 82.9 - 0.5 micron 15.0 68.1 EXAMPLE TWO SYNTHESIS OF SAMS FROM HYDRAGLOSS 90 CLAY A second reaction was conducted in which 1,500 gallons (12,562 pounds) of water was used with 110 gallons (1,613 pounds) of a 70.IX solids kaolin clay slurry sold commercially as Hydragloss 90 by J. M. Huber Corporation having the properties shown in Table III. To the clay-water slurry was added 112.4 gallons of a fresh water sodium silicate solution (1,298 pounds) of 34.9X solidβ having a Si0 2 /Na 2 0 SUBSTITUTESHEET molar ratio of 2.5. Under these conditions, the final product β olid β will be approximately 10% and the batch composition will have a base to clay molar ratio of approximately 0.50. The bat^ch composition for the reaction can be expressed as 0.76Na 2 O:1.52Al 2 O 3 :4.94SiO 2 i278H 2 O and has an H/N of 366, an S/N of 6.5 and an S/A of 3.25. The batch was heated to a reaction pressure of 120 psig and a temperature of 172 degrees C. The mixture was allowed to react for one hour under continuous agitation. At the end' of the one-hour reaction time, the mixture was vented into a drop tank and the result¬ ing mixture was then filtered, washed, and spray dried. The product of Example Two was subjected to various tests. Set forth hereinafter in Table III are the physical properties of the resulting synthetic alkali metal alumlnorsilicate composition, or SAMS, representing the present invention and the kaolin clay control from which the SAMS composition was prepared. SUBSTITUTESHEET Physical Properties: Lose on Ignition, X 10.71 13.86 Pore Volume, cc/g (Mercury Intrusion) 3.56 0.86 Surface Area, m 2 /g 21.5 22.0 pH (at 20% solids) 11.2 6.8 Oil Absorption, ml/lOpga 156 43 Valley Abrasion, ((mggβs ooff wwiirree llooββββ)) 6 6..88 7.5 Cation Exchange Capacity: meq/lOOg - Nir4, K* 183 2-3 meq/lOOg - Ca +<4 , Mg +Z 48 1-2 Brightneββ, % 92.6 91.0 Sedigraph Particle Size, %: +10 microns 0.0 0.0 + 5 microns 0.0 0.0 - 2 microns 61.0 98.0 - 1 micron 37.0 96.1 - 0.5 micron 18.0 84.7 The following procedures were used for characterizing the data listed in Tables II and III. Chemical analyses (% Ti0 2 , X Fe 2 0 3 , % Si0 2 , % A1 2 0 3 ) were determined by x-ray fluorescence. The sodium content (Na»0) of the final product was determined by atomic absorption. Ignition loss was determined by pre-drying the SAMS product to a constant weight at 110 degrees C, heating to 925 degrees C for one hour and cooling. Calculations of ignition loss were made as follows: Ignition Lose - (Weight of ignited sample) 6 ( Weight of dried sample ) SUBSTITUTE S HEET -35- Thβ pH was measured using a standard pH meter on a 20% solids (by weight) mixture of the product with water. The specific surface area was determined by the nitrogen absorption method described by Brunauer, Emett, and Teller (BET) in the "Journal of the American Chemical Society," Volume 60, page 309, published in 1938. A single point surface area determination was made on the SAMS compositions using outgaβsing conditions of three hours at 300 degrees C. The oil absorptions of the beginning and end products from Examples One and Two were determined by the oil rub-out method. This method is based on a principle of mixing linseed oil with the produc by rubbing with a spatula on a smooth surface until a stiff putty-lik paste is formed which does not break or separate. By measuring th quantity of,oil required to give a paste mixture which will curl wha spread " out, one can calculate the oil absorption value of th product—a value which represents the volume of oil required per uni weight of product to saturate the product sorptive capacity. Calcula tion of oil absorption value was done as follows: ... .. ... _ ( ml oil absorbed ) „ .__ n Oil Absorption - ,—j—r-r—= -j— . x 100 0 v (weight of product, g) ■ ml oil/lOOg product Cation exchange capacity was determined by adding t products (0.25g- eighed to O.lmg) to tarred, screw-cap, 15-ml centr fuge tubes. The samples were centrifugally washed three times wi 5 10-ml of a 0.5M solution of the saturating cation. The samples we subsequently washed five times with a 0.05M solution of the saturati cation. Following the fifth washing and decantation of t SUBSTITUTE SHEET βupernatant solution, the tubes were capped and weighed. This weight, less the sample weight, represents the amount of excess 0.05M_ saturat¬ ing solution. The occluded (soluble) and exchangeable cations were then displaced by washing three times with a 0.5M_ solution of a displacing cation, collecting the washings in 100 ml volumetric flasks. The amount of the saturating cation was determined by atomic absorption spectroscopy with the exception of ammonium (Nil ) which was determined by potentiometric titration. The net amount of ex¬ changeable cations was calculated by subtracting the amount of soiu- hie, occluded cations (wet weight times 0.05M) from the total analyzed amount. Brightness measurements were performed by the standard TAPPI (Technical Association of Pulp and Paper Industry) procedure T-534 pm-76, published in 1976. J Particle size was determined using a Sedigraph 5000 ET Particle Size Analyzer from Micro eritics Instrument Corporation, Norcross, Georgia. This instrument uses a sedimentation technique which measureβ the particle size distribution as a modification of Stokes Law. The procedure is described in "Instrumen 0 Manual-Sedigraph 5000 ET Particle Size Analyzer," published May 3, 1983. The Fourier Transform-Infrared spectroscopy (FT-IR), trans mission electron microscopy (TEM), scanning electron microscopy (SE and x-ray diffraction (XRD) scans were determined using standar 5techniques. SUBSTITUTE SHEET - - From the above data, it will be seen that the process of the invention yields new products having novel combiπationβ of physical and chemical properties. A β shown in Tables II and III, the synthetic alkali metal alumino-silicates of the present invention prepared from the commer¬ cial kaolin clays exhibit substantial improvements in cation exchange capacity, oil absorption and brightness. This is quite astonishing in that a hydrous clay product of relative worth haβ been converted into a synthetic product of greatly added value by the -relatively simple procedure of the present invention. Of particular interest is the significant improvement in oil absorption which indicates that a higher structure product haβ been formed aβ a result of this inven¬ tion. The infrared spectra of the SAMS compositions of Examples One and Two are compared with the infrared spectra of their respective base clays in Figures 3 and 4, respectively. Aβ anyone skilled in infrared spectroscopy can see, the IR spectra of SAMS compositions are considerably different from those of their respective base clays, especially in the 1200-875 wavenumber (cm " *) absorption region. The 0 Si-0 stretching band between 1200 and 950 wavenumbers iβ much broader and less well defined for the SAMS than for the control clays, indi¬ cating that the compositions contain considerable amorphous material. SUBSTITUTESHEET In addition, the aluminum O-H vibration band between 950 and 875 wavenumbers are essentially identical for the SAMS compositionβ and their baβe clays, with the SAMS composition showing only a slight decrease in peak intensity. In Figure 1, the FT-IR scan of the SAMS composition of Example Two iβ compared with the FT-IR scans of an amorphous synthetic silicate (Zeolex 23), a calcined kaolin (Hycal) and an amorphous synthetic silica (Hi-Sil 233). The spectrum of the SAMS composition is similar to those of Zeolex 23, Hycal, and Hl-Sil in the 1200-950 wavenumber Si-0 stretching region but iβ considerably different in the 950-400 wavenumber region. Only the SAMS composition haβ the aluminum 0-H vibration band between 950 and 875 wavenumbers. In Figure 2 the FT-IR spectrum of * the SAMS composition of Example Two is compared with the spectra of zeolites A, X, Y and analcime. The spectrum of the SAMS composition differs from th spectra of the crystalline zeolites across the entire IR spectrum. The Si-0 band (1200-950 cm "1 ) for the zeolites is very sharp, indicat ing good crystallinity, while that of the SAMS is broad. Again, onl the SΛMS spectrum shows the aluminum O-i! vibration band. Based on the infrared spectra, it must be concluded that th SAMS compositions of the instant invention are unique entities tha differ significantly from the starting clays as well aβ from crystal line and amorphous zeolites, synthetic silicates and synthetic silica of prior art. SUBSTITUTE SHEET The unique characteristics of the synthetic alkali metal alumino-silicates (SAMS) of the instant invention can also be seen by comparing the SEM photographs of the SAMS compoβitionβ of Example One and Two (Figureβ 13 and 14, respectively) with those of prior art zeoliteβ A, X, Y and analcime (Figures 9, 10, 11 and 12, respective¬ ly). The SEM photographs show the prior art zeoliteβ to be large, well crystallized materials, while the SAMS compoβitionβ appear to be structured agglomerates composed of small flat platelets. The TEM photographβ of the SAMS compositionβ of Example One and Two, prepared by following the preferred teachings of the instant invention (B/C less than 1.0), and the photographβ of SAMS compoβi¬ tionβ prepared at B/C ratioβ equal to and greater than 1.0 can be seen in Figures 18 through 23, respectively, and show the SAMS to be unique in composition and morphology. The TEM photographs . (Figureβ 18-23) show the SAMS compositions to contain remnants of altered clay platelets having an integrated rimmed area of alkali metal silicate-kaolin reaction product. The rimmed area can be shown by electron diffraction (ED) to be amorphous and non-diffracting. The SAMS compositionβ shown in Figures 18-23, are unique and considerably different In appearance than the starting Omnifil and Hydragloss 90 clay (Figures 24 and 25, respectively), as well aβ the prior art silicates, silicaβ, and calcine4 clays shown in Figures 15-17. ■ OBSTITUTESHEET When comparing the x-ray diffraction patterns of the SAMS compositions of Examples One, Two and Five (Figureβ 33-36) with the XRD patterns of the starting clays (Figures 37 and 38), only attenuat¬ ed kaolin peaks from the kaolin remnants can be observed. The XRD patterns of the SΛMS compositions are also obviously different than the XRD patterns of the prior art zeolites, silicates, silicas, and calcined clay shown in Figures 26-32. END-USE APPLICATIONS The novel SΛMS products of the present invention were evaluated in a variety of end-use application compositions. Truly remarkable performance of SAMS products are documented below. 1. PAPER COATING COMPOSITIONS The SAMS product of Example Two derived from Hydragloss 90, clay was evaluated in a typical paper coating composition and evalua- tion data are shown In Table IV. A coating is applied to a paper substrate primarily to improve printing quality, although improvements in optical properties such as brightness or sheet gloss may also be obtained. The SΛMS product made from Hydragloss 90 in Example Two was included at low 0 levels in coating compositions and compared with a composition using only a commercial grade of delaminated kaolin clay (Hydraprint), and a composition containing the delaminated clay and a w level of a commercially available, ' high brightness, low abrasion calcined clay (Hycal), in an application for lightweight publication grade paper. SUBSTITUTESHEET The end-use of this particular paper and its coating formulation waβ in the art of printing by the rotogravure method. Coatings were applied to a commercially produced paper substrate^ at a coat weight typical to the grade using the Keegan Laboratory Blade Coater. Following supercalendering, coated sheets were tested for optical properties in accordance with the following TAPPI (Technical Associa¬ tion of Pulp and Paper Industry) standards: T-452: Brightnesβ of Pulp, Paper and Paperboard T-480f Specular Gloss of Paper and Paperboard at 75 degrees Rotogravure printablllty waβ determined using the Diamond National Print Smoσthnesa Tester. The procedure followed iβ to coat, calender and print paper samples by the rotogravure method with a series of lines composed of dots. The dots are the result of printing cells engraved on the rotogravure printing cylinder, each of identical diameter and depth. The number of dots which do not transfer to the sheet iβ determined, with the greater number of miββing dote being Interpreted aβ poorer rotogravure printablllty. As noted from Table IV, when used at one-half the loading level of calcined clay, the product of the current invention unexpect- edly produced a sheet of equivalent rotogravure printablllty, and clearly superior to that where only delaminated clay waβ used. Thus, one part of the product of the current invention can replace two parts of calcined clay resulting in βubβtantial cost savings for those SUBSTITUTE SHEET skilled in the art of paper coating. Furthermore, when used at an equal loading level with the expensive calcined clay, the SAMS product of this invention yielded a sheet of comparable optical properties, and clearly superior rotogravure printablllty. TABLE IV PAPER COATING COMPOSITIONS CONTAINING SAMS 90% 90% 95% Hydraprint Hydraprint Hydraprint 10% 10% ' 5% 100% Calcined SAMS from SAMS from Hydraprint Clay Example Two Example Two Brightness, % 68.2 69.2 69.0 68.7 75 Degree Glosβ, % 43.7 45.0 45.5 * 44.0 Missing Dots/Sheet* 31 22 15 23 *Diamond National smoothness test 2. FINE PAPER FILLER COMPOSITIONS Pigments are used as fillers in paper sheets for many reasons, among which are the improvement of optical properties such as brightness and opacity. The most efficient pigment for this purpose i fl titanium dioxide; however, its price is prohibitive for its sole use in this application. A class of pigments, known aβ titanium dioxide extenders, are less expensive, but still quite costly. When used in combination with titanium dioxide, these pigments allow for reduced titanium dioxide use while maintaining optical properties. SUBSTITUTE SHEE Two pigments from thlβ group which are quite effective are calcined kaolin clay and amorphous sodium silico-aluminate (Hydrex) pigments. The SΛMS product made from Hydragloss 90 in Example Two waβ substitut¬ ed directly for the titanium dioxide extender pigments, calcined clay (Hycal) and sodium silico-aluminate (Hydrex), in a filler furnish containing 50% No. 2 grade clay (Hydraβperse), 17% titanium dioxide (DuPont LW), and 33% extender pigment. Handsheets were formed using the British Standard Handsheet Mould, weighed to assure uniform basis weight, and tested according to the prescribed TAPPI standards: T-425: Opacity of Paper T-452: Brlghtnesβ of Pulp, Paper, and Paperboard Additionally, the scattering and absorbance coefficients (S and K, respectively) were determined using the Kubelka-Munk equation. The value K/S was then determined, and presented as the scattering efficiency. Greater efficiency is noted as the K/S value approaches zero. The comparative evaluation data of SAMS and other extender pigments used in the paper filler composition is given in Table V. It will be noted from Table V that the product of the current invention compares favorably to the expensive extender pig- ments in all parameters at each filler loading level. This iβ quite surprising in that the SAMS products of the present invention can be a match for the most expensive extender pigments normally used by the paper industry. SUBSTITUTE SHEET - TABLE V FINE PAPER FILLER COMPOSITIONS CONTAINING SAMS Light Scattering Bright¬ Efficiency, Filler, ness, Opacity, K/S X X X X 10-2 Unfilled Control 0 82.5 71.8 1.87 50% No. 2 Clay 2 84.3 74.4 1.46 0 17% Titanium Dioxide 4 85.4 78.5 1.25 33% Calcined Clay (Hycal) 8 86.0 81.2 1.14 50% No. 2 Clay 2 84.8 73.9 1.36 17% Titanium Dioxide 4 85.5 78.2 1.23 33% Hydrex 8 86.2 81.6 1.10 15 50% No. 2 Clay 2 85.0 75.2 1.32 17% Titanium Dioxide 4 85.4 78.1 1.25 33% SAMS from Example Two 8 86.0 81.5 1.14 3. NEWSPRINT PAPER COMPOSITIONS CONTAINING SAMS Another function of fillers in uncoated paper is to retard 20 the amount of ink which penetrates the sheet, causing discoloration to the other side of the paper. This problem, frequently referred to aβ "print show-through" or "print through," is generally encountered in newspaper printing. Improvement in this property is of more concern as quality standards for newsprint and similar grades continue to 25 tighten. SUBSTITUTESHEET The SAMS products made from Omnifil and Hydragloss 90 clayβ in Examples One and Two are compared with their respective starting materials, to a commercial grade of high brightness, low abrasion calcined kaolin clay (Anailex), and to a high brightness sodium βilico- aluminate (Zeolex 23P) in their ability to reduce show-through. Handβheets were prepared from commercial newsprint pulp using a Noble and Wood sheet machine, and tested in accordance with the following TAPPI standards: T-410: Basis Weight of Paper and Paperboard T-425? Opacity of Paper T-452; Brightness of Pulp, Paper and Paperboard Additionally, printing teβtβ were performed at standard condltionβ of temperature and humidity on a Universed No. 1 Vandercook Proof Press using a standard newsprint ink and a printing plate mounted type high. The plate was designed for printing a solid area 4 inches by 4-1/4 inches. Prints were made with 4 mile impreββion by press bed adjustment, and the ink pickup determined by weighing each sheet before and after printing. Variations in printing and ink pickup necessitated printing each ash level at three ink levels, and obtaining printing valueβ at exactly 2.0 g/m ink pickup graphically. Printed βheets were conditioned overnight at 73 degreeβ and 50% relative humidity prior to evaluation by a brightness teete at 457 n on the side oppoβite the printing surface. Show-through wa determined in accordance with Larocque'β equation: Show Through , (lOO-Reflectance (Printed)) 6 ( Reflectance (Unprinted) ) Λ luυ Comparativβ data on the newβprint evaluation of SAMS an other expenβive extender pigments are given in Table VI. TAB LE VI NEWSPRINT EVALUATION OF SAMS AND OTHER EXTENDER PIGMENTS TAPPI Show-' Through Filler Basis <** Filler Level, Weight, Bright¬ Opacity, e2g/m Z Reduction, Pigment % f/reaa ness, % % Ink, X % Unfilled None 3P.6 52.9 85.1 *q. β - Omnifil (Control) 2 3.0.3 52.9 85,J 12.6 (16.7) 4 30.4 60.0 85,5 H.7 (8.3) Hydragloss 90 2 30.5 59.4 85.1 13.1 (21.3) (Control) 4 30.1 60.6 85.4 12.8 (18.5) Ansilex 2 29.8 60.5 85.6 10.8 0 (Calcined Clay) ' 4 30.1 62.0 87.4 9,1 15.7 Zeolex 23P 2 30.4 60.2 85.5 9.1 15.7 (Sodium Silico- 4 30.4 61.3 86.5 6.4 40.7 Aluminate) SAMS from 2 30.3 59.9 86.3 9.6 U.I Example One 4 30.7 61.9 88.0 7.0 . 35.2 SAMS from 2 30.3 60.5 86.4 8.7 19.4 Example Two 4 30.6 62.0 88.5 6.8 37.0 SUBSTITUTE SHEET It it seen in Table VI that the SAMS product from Example Two performs as well aβ the calcined clay and βupβrior to the other pigments in brightness improvement, and Jβ alβo the superior pigment in opacity improvement. The SΛMS product from Example One la βurprlβ- lug in its performance aβ well. Its opacity is βecond only to the product made from Example Two, exceeding both of the other higher brightness pigments, Anβllex and Zeolex 23. Concerning show-through,- it can be noted from Table VI that the use of the starting hydrous clay materials (Omnifil and Hydragloss 90) actually result in more show-through then observed with the unfilled sample. T e use of calcined clay, while Improving show-through modestly βt 4% filler loading, leaves the sheet unchanged from unfilled at the 2% fille level. When the products of the current Invention are substitute directly at the 2% filler level for the Zeolex 23 pigment, tha pigment being the product of choice for this purpose in commercia applications, the results were indeed surprising. The SΛMS produc from Example Two actually surpasseβ the Zeolex 23 pigment, while tha made in Example One lβ only slightly deficient. Although the product of the current invention are slightly less efficient than the Zeole 23 at the higher loading level, they are clearly βupβrior to the β tarting inexpensive clay controlβ and to the expensive calcined cla Furthermore, due to the high cost of the Zeolex 23 pigment, it can ea β ily shown that the coβt per unit of strike-through reduction f the products of the present Invention iβ much more favorable then th SUBSTITUTESHEET of the Zeolex 23. Thuβ, if used at quantities sufficient for equal strike-through reduction, the products of the current invention would f provide significant coβt savings in this application. 4. LATEX PAINT COMPOSITIONS CONTAINING SAMS In the past, functional extender pigments were primarily used in paint as adulterantβ to replace more expensive prime pigments and binders; thereby resulting in a lower coβt paint formulation. However, with the advent of new and improved functional extender pigmentβ, the use of these pigments has grown. They are now incorpo- rated into the paint formulations to improve optical properties such aβ whiteness, hiding power/contrast ratio, and tinting strength. In this regard, the SΛMS product made from Hydragloss 90 in Example Two waβ compared with the kaolin clay from which the SλMS composition waβ prepared and leading commercial pigmentβ used as functional extendera in latex-based paints. Whiteness (directional reflectance, Y-value) and contrast ratio were determined by making drawdowns of the paints containing control clay (Hydragloss 90), the SAMS product from Example Two made from Hydragloss 90, a commercial extender pigment (Ili-Sil 422), and calcined clay (Huber 90C), on opacity charts having a simple combina¬ tion of black and white areas large enough for reflectance measure ments. Such charts are supplied by the Leneta Company, Ho-Ho-Kua, Ne Jersey. .Directional reflectance, Y values, are determined using SUBSTITUTESHEET -49- Gardner XL-20 Triβtimulus Colorimeter on the dried paint films over both the black and white areas of the chartβ. Whiteness iβ reported as the Y value determined over the white area. Contrast ratio iβ determined by dividing the Y values over black areas by the Y valueβ over the white areas of the charts and iβ a meaaure of the relative opacity of the paint. Relative tint βtrength waβ determined by blending IX, by weight, of a lamp black colorant to each paint, making drawdowns on the opacity chartβ and then determining Y valueβ of the dried paint filmβ over the white areaβ of the charta. Relative tint βtrength iβ reported aβ thlβ Y value. Comparative paint performance results of unique SAMS prod¬ ucts and other expensive extender pigmentβ are contained in Table VII. TABLE VII LATEX PAINT EVALUATION OF SΛMS AND OTHER PIGMENTS • Whiteness (Directional Relative Reflectance, Contrast Tint Pigment Y-Value, %) Ratio Strength, % Hydragloββ 90, Control 87.9 .944 38.8 SΛMS from Example Two 88.8 .958 41.0 Hi-Sil 422 88.7 .947 40.8 Huber 90C 88.6 .949 40.5 Regarding Table VII, it will be noted that the control clay Hydragloββ 90 and the commercial products, Hi-Sil 422 (fine particle hydrated β lica pigment), and Huber 90C (high brlghtneββ, low abrasion calcined clay) are compared with the Hydragloββ 90 product of Example SUBSTITUTESHEET Two with respect to whiteness, contrast ratio and tint βtrength. The variouβ pigmentβ were evaluated in a typical high pigment volume concentration, interior, flat, vinyl acrylic paint. Pigmentation of the paint conaiβted of 17.6% rutile titanium dioxide, 19.6% atandard calcined clay, 58.8% coarse particle-size calcium carbonate, and 4.0% of the evaluated pigment. It will be noted from Table VII that the SAMS product of this invention produces significant improvements over the kaolin clay from which the product of this invention waβ prepared in whiteness, contrast ratio and relative tint strength. Even more unexpectedly, the product of this invention gave an enhanced contrast ratio and superior tint βtrength to the more costly functional extend¬ er, Hi-Sil 422. Additionally, aa can be seen from Table VII SAMS products of the present invention exhibit the best whiteneββ, contrast ratio (or hiding power) and tint strength when compared with expensive commer¬ cial extender pigments. It is truly remarkable how the inexpensive starting clay haβ been converted into a functional product SAMS by the teachings of the present invention. 5. NATSYN 2200 RUBBER COMPOSITIONS CONTAINING SAMS Fillers are added to rubber compounds to provide reinforce¬ ment or act aβ a diluent. Small particle substances are considered to reinforce rubber if they give to the vulcanizate high abrasion resis¬ tance, high tear and tensile strength, and some increase in stiffness. The most important characteristic required of a reinforcement agent is SUBSTITUTESHEET a fine particle size. Among non-black fillerβ, the beet modulus and tenβile βtrength are produced by precipitated silica (Hi-Sll), fol¬ lowed by synthetic sodium silico-aluminate (Zeolex). Fine particle size filler β that are approximately spherical in shape, such ββ many silicaβ, give better tear reβistance and abrasion resistance to rubber than do needle-shaped or plate-like particles. SAMS from Examples One and Two were evaluated in rubber compositions and their performance compared with the more expensive fine particle precipitated, hydrated amorphous silica product, Hi-Sil 233. The rubbers which can be employed in the invention include both natural and synthetic rubbers. Exemplary of suitable synthetic » rubbers are βtyreπe-butadiene, butyl rubber, nltrile rubber, neσprene rubber, polybutadiene, polyiβoprene, ethylene prσpylene, acrylic, fluorocarbon rubbers, polysulfide rubbers, and silicone rubbers. Mixtures of copolymers of the above synthetic rubbers can be employed alone or in combination with natural rubber. The most preferred rubbers are natural rubber, polyisoprene, nltrile rubber, β tyrene-butadiene, and ixtureβ thereof. The SAMS product made from Hydragloββ 90 in Example Two waβ evaluated againβt a fine particle precipitated, hydrated amorphous β ilica product (Hi-Sil 233) in a non-black βynthetic polyisoprene (Natβyn 2200) rubber formulation. SUBSTITUTE SHEET Thβ SAMS and βilica products were used at a 38-40 part level per 100 parts rubber * The filler products were compered with respect to modulus and tensile strength (ASTM D1456), heat buildup (rectangu¬ lar block oscillating horizontally between two weights), compression set (ΛSTH 395—ability of rubber compounds to retain elastic proper¬ ties after prolonged action of compressive stresses), and tear βtrength (ASTM 624). Evaluation reβultβ of the reinforcing properties of SAMS and a commercial expensive synthetic silica, Hi-Sil 233, are listed in Table VIII. TABLE VIII NATSYN RUBBER REINFORCING PROPERTIES OF SAMS SAMS from Hi-Sil 233 Example Two 300% Modulus, psi* 460 630 Tenβile Strength, psi* 2,850 2,870 Heat Buildup, Degrees F 267 136 Tear Strength, ppi 140 155 Compression Set, % 41.6 23.2 *10 Minute cure It will be noted from the Table VIII that the SAMS product of thiβ invention iβ βuperior to the amorphouβ silica product in modulus, compression set, and heat buildup, where the βilica product haβ twice the heat buildup when compared with SAMS productβ of the present invention. It iβ truly remarkable that the inexpensive clay ha β been converted into a unique functional SAMS composition. Tills SUBSTITUTE SHEET uniqua property of low IIBU (heat buildup) cauβeβ the product to have particular utility for use in tireβ, hoses, and belts where lower heat generation from friction will substantially prolong the longevity of these products. In thiβ regard, the synthetic alkali metal alumlno-βillcateβ of thiβ invention can also be used gainfully In elaβtomerlc applications where exposure to high temperatures can cause severe deterioration of standard elastσmeric systems. The tire industry haβ been looking for a reinforcing filler which will provide low heat buildup in rubber formulations. As data clearly show in Table VIII, the heat buildup Imparted by SΛMS of the present invention iβ almoβt one-half that of the commercial expensive β ilica, Hi-8il 233. The control structure of the unique SΛHS con osi- tionβ is reβponβible for providing excellent rubber reinforcing propertieβ. 6. GIANT TIRE RUBBER COMPOSITIONS CONTAINING SAMS The SΛMS products made from Omnifil and Hydragloss 90 in Example One and Two were evaluated against a fine particle, precipi¬ tated, hydrated amorphouβ βilica product (Hi-Sll 233) in an -t off-th β -road giant tire tread natural rubber formulation containing N220 carbon black. The SAMS and silica products were used at β 15 part level and the N220 carbon black at a 40 part level per 100 parts i of rubber. SUBSTITUTESHEET Thβ filler products were compared with respect to modulus, tenβile βtrength, tear βtrength, heat buildup, and a flex fatigue failure teβt (ASTM D1052—Rose flexing machine that allows a pierced rubber specimen to bend freely over a rod through an angle of 90 degrees for the number of cycles required for specimen failure). It will be noted from the teβt results of Table IX that the SΛMS products of thiβ invention from Omnifil and Hydragloss 90 are equal or superior to the high-priced amorphouβ silica product in modulus, tenβile strength, tear βtrength, heat buildup, and flex fatigue. Of particu- lar interest is the startling increase in flex fatigue property which should be very important in elastomeric systems in which a great deal of. bending and stretching stresses are involved, such aβ shock sup¬ pressors, hoses and tubing, bushings, etc. By examining the evaluation data in Table IX, if can be clearly seen that the unique SAMS products provide excellent fle fatigue protection to rubber compositions when compared with th expensive commercial βilica products, Hi-Sil 233. It is quite remarkable that the inexpensive clay product have been converted to more useful value-added aterialβ called SAM by t e teachings of the inβtant invention. Hie performance propertie of SAMS in rubber compositions are unique and quite unexpected. I appears that the novel SAMS compositionβ of the present invention ar controlled structures in nature and provide optimum filler-polym Interaction in rubber compositionβ. TABUS IX GIANT TIRE RUBBER REINFORCING PROPERTIES OF SAMS SAMS From Hi-Sil 233 Exa olβ One Example Two 300% Modulus, psi* 1,360 1,490 1,500 Tenβile Strenigth, pel* 3,700 3,780 3,870 Tear Strength , ppi 605 575 625 Heat Buildup, Degrees F 278 267 260 Flex Fatigue, (Cycleβ 471 835 666 To Failure X 1000) *90 Hinuteβ Cure 7. COLOR CONCENTRATE PLASTICS COMPOSITIONS Pigments, fillers and extenders are mixed with plastics ' reβinβ to produce color concentrateβ. Titanium dioxide and colored pigments are widely used to produce pigmented plastics concentrateβ. A study was undertaken in which a 50% TiO, concentrate waβ produced in high density polyethylene (HOPE) reβin. Thiβ concentrate was called the control concentrate. The SλMS product from Example Two waβ used to extend Ti0 2 „f the control concentrate by replacing 10 and 20% by weight of the TiO, with SΛMS. The following plastic compositions were used to produce the various concentrateβ. Ingredients Control Concentrate A Concentrate B HDPK 50 50 50 R-10 (T10-) 50 45 40 SAMS (fro - 5 10 Example Two) SUBSTITUTESHEET The control and concentrates A and B containing 5% and 10% SΛMS were compounded in the 3# Farrel Banbury. Each sample wa β then granulated, extruded and pressed out for testing. The optical proper¬ ties of the various concentrates were then evaluated. The opacity and brightness of the control and SΛMS contain¬ ing concentrateβ are listed in Table X. This study suggests that SΛMS of the instant invention can be used in color concentrates without loss in opacity and brightness. Data are listed in Table X. TABLE X PLASTIC COLOR CONCENTRATES CONTAINING SAMS Elrepho Brightness, Opacity, Concentrate % % Ti0 2 - Control 89. 1 0.980 Concentrate A (w/SΛMS) 91.8 0.985 Concentrate B (w/SAMS) 91.4 0.990 8. DEFOAMER COMPOSITIONS Defoamer compositions are used to suppress foam formation in the paper, paint, food and many specialty industries. Defoamer compositions were prepared by using the following formulations: SUBSTITUTESHEET Ingredients Parts (by weight) Dow 3011 Λntlfσam Chemical 4. ,0 Ammonium Carbonate 1 , ,0 Mineral Oil 200, .0 11090 or SAMS 10 .0 (from Example Two) The mineral oil called for in the above formulation waβ weighed out and placed in a stainless steel cup. Control clay or SAMS from Example Two waβ hand-mixed with the mineral oil. This mixture waβ diβperβed on a llockmeyer mixer for five minutes at 2300 rp speed. The antifoam chemical was then added, followed by ammonium carbonate. The whole composition was mixed for an additional three minutes. The contents of the stainless steel cup were transferred into a 500 ml flask and heated at 80 degreeβ C until the foaming βtopped. The temperature waβ then increased to 105 degreeβ C and the composition maintained at this temperature for two' hours. Ihβ flask wa β removed from the hotplate and after cooling, the contents were transferred to a one-half pint can for storage. At thiβ point the defoamer composition iβ ready for evaluation. The defoamer composition was checked for foam suppression properties. One liter of black kraft liquor (15% βolidβ) waβ poured into a 2500 ml burette which waβ hooked up to a gravity feed circulat¬ ing pump flowing at the rate of five liters per minute. While the black liquor was at rest, 0.)2g (or two drops) of the defoamer composition waβ added to the burette. Tiie pump and a stop watch were simultaneously started to record the tine it takes the SUBSTITUTE SHEET foam height to reach six inches from starting point of liquor at rest. A defoamer composition which suppresses the foam from reaching a six-inch height for the longest time is considered the best defoamer compound. Defoamer efficiency data are given in Table XI. TABLE XI DEFOAMER COMPOSITIONS Defoamer Compositions Six-Inch Suppression Time Compound w/HG-90 - Control 27 seconds Compound w/SAMS 233 seconds (from Example Two) From data in Table XI, it is clear that SAMS makes an excellent defoamer when compared with the starting clay. In fact, the defoaming efficiency of SAMS from Example Two iβ about 762% better than the Hydragloss 90 control. It is truly remarkable that the present invention haβ converted the Hydragloss 90 clay into a valued ' added SAMS product of unique efficiency for use in defoamer composi¬ tions. SUBSTITUTESHEET 9. DRY-UP LIQUID/CARRIER COMPOSITIONS Liquids., active substrateβ and rubber chemicals are dried up on fine particle carriers. The dry, free flowing powders are produced by adding the powder to the liquid while mixing in a llobart mixer until a dry, free-flowing powder iβ produced. From the weight of the liquid carried on a carrier solids, one can calculate the carrying capacity of the carrier powder. The SAMS product from Example Two waβ compared with the control clay (Hydragloss 90) in terms of the carrying capacity of mineral oil and Flexon (Exxon) processing oil. These liquids were converted to dry, free-flowing powders with the carrying capacity expressed as the percent by weight of liquid (% active) present. The carrying capacity data is given in Table XII. TABLE XII CARRYING CAPACITY OF SAMS Liquid; Mineral Oil Carrier Powder % Active Control Clay 10 SAMS from Example Two 58 Liquid: Flexon Oil Carrier Powder % Active Control Clay 10 SAMS from Example Two 60 Fron data in Table XII, it can be readily seen that JAMS of the instant Invention haβ excellent carrying capacity when pared with the clay control. It is quite remarkable that clay us been converted into the functional carrier SΛMS by the teachings of the instant invention . 10. PAINT COATING COMPOSITIONS In order to provide protection and to produce a pleasing appearance, a variety of surfaces, such as wood, metal fabric, paper, or plastics, are coated with clear flatting compositions containing dispersed or suspended particles of a flatting agent which reduces the gloss or sheen of the coating and the coated substrate, preferably without substantially reducing the transparency of the flat coating. For example, wood finishes which serve to protect the surface against abrasion and stain,' yet do ot conceal the beauty of the grain, are made to simulate desirable hand-rubbed finishes by incorporating flatting agents therein which normally are dispersed fine particles of such materials as silicas. The best effects are obtained with silicas of uniform particle size down to the submicron range. Small size and uniformity are necessary to achieve a smooth coating without white - specks or without a graying effect which would detract from the appearance of the coating. For paint flatting application, 10 grams of SAMS from Example Two of the instant invention waβ mixed with 350 grams of nitrocellulose lacquer (conforming to Military specification MlL-L-10287A-amendment 2, Type II, of issue 27, Aug. 1959), and mixed SUBSTITUTESHEET for three minutes uβing the low speed setting of the Hamilton Bββeh 130 mlxmaβter. The lacquer containing dispersed SAHS ores tested for ilegmβn fineness of grind. The lacquer containing dispersed SΛMS from Example Two waa evaluated for paint flatting properties. A drawdown was made on Carrara glass uβing a 13* wire coatings application rod. The Carrara glass drawdowns were allowed to dry for 45 minutes under duet-free conditions. Uβing the above method, drawdowns were also made by using a control synthetic βilica normally used in thiβ application. Uβing the Gardner multi-angle gloββ meter, the gloss and sheen valueβ of the various drawdowns were measured βt 60 degreeβ and 85 degreeβ, respectively. These valueβ were compared with measured valueβ obtained when a control βilica waβ dispersed in the lacquer. SAHS of the present invention result in cleaner Hegman grinds and exhibit better clarity when dispersed in the lacquer. Flatting data listed in Table XIII suggests that the novel SAMS of the present invention exhibit lower gloss and sheen valueβ than the control silicas. Lower gloss and sheen valueβ are preferred and advantageous for paint flatting applications. SUBST IT UTE S HEET TABL8 XIII FAINT FLATTING EVALUATION 60 Degree 85 Degree Flatting Agent Gloss Sheen SΛMS (Example One) 10 21 SAMS (Example Two) 8 16 Control Silica 15 A5 (Zeothix 95) A close examination of the data in Table XIII clearly shows the SΛMS compoβitionβ of the inβtant Invention aβ having superior flatting propertieβ compared with the synthetic βilica control, it is quite remarkable that clay haβ been converted into a value added functional product by the teachingβ of the inβtant invention. 11. DEIERCENI COMPOSITIONS Typical home laundry detergentβ are generally formulated aβ a 50-60Z solids slurry and spray dried to give the familiar powdered products. A typical ome laundry detergent consists of the following ingredientst Ingredient Percent, by weight., Sodium Tripσlyphosphate 12-50 Surface Active Agents 10-20 Liquid Sodium Silicate 5-8 Soil Redepσsition Agents 0.5-1.5 Fluorescent Dyes 0.05-1 Hater 2-12 Sodium Sulfate Balance SUBSTITUTESHEET Surface active agentβ mainly consist of anionic linear alkyl benzene βulfonate (LAS) and non-ionic alcohol based ethσxylateβ (AEO). A surfactant iβ needed in the detergent to extend the functional performance of the detergent builder. Non-ionic surfactants are added at a level of 4-6% (typical non-ionic surfactants currently being used are Shell's Neodol 25-7 and 45-11) baaed on the weight of other ingredients of the detergent compositions. The resulting slurry is sptay dried. Non-ionic surfsctants contain small fractions of short-chain molecules called "light ends." During the spray drying step, the "light ends" do not incorporate into the finished detergent bead and go out of the dryer exhaust and result in a white cloud referred to aβ "plume." Detergent producers are anxious to cut down this "plume" and several mechanical advances have been made to scrub the stack gases but the scrubbing process iβ not 100X effective. Also, the equipment required to clean the stack gases is very expensive. He have found an inexpensive solution to the problem in which SAMS of the present invention can be used to convert the liquid non-ionic surfactants to dry, free-flowing particulates so that SUBSTITUTESHEET dried-up surfactant can be post added to the βpray dried detergent formulation. Thuβ, SAMS compositions of the instant invention are useful for drying-up non-ionic surfactants in the ^ree-flowing form. Thus, SAMS can be used in the detergent compositionβ to solve an air pollution problem called "pluming." Neodol 25-9 surfactant (manufactured by Shell Chemical Company) was dried-up on SAMS from Examples One and Two. The maximum amount of Neodol that can be dried up is listed in Table XIV. TABLE XIV DRYING-UP NEODOL 25-9 ON SAMS PRODUCTS Flow Time % Active Carrier (seconds) Surfactant SAMS (Example One) • 18 51.2 SAMS (Example Two) 15 55.9 Clay Control • 86 10.0 From data in Table XIV above, it ia clear that SAHS composi¬ tions of Examples One and Two exhibit superior flow propertieβ and drying capacity when compared with the corresponding control clay used in Example Two. Thus, the method of drying up non-ionic βurfactantβ results in superior free flowing surfactant powders. These surfactant powders can be efficiently used by post-adding to detergent compositions. Thuβ, SAMS of the instant invention are useful in detergent composi tions and these SAMS pigments impart superior properties which help i solving an important air pollution problem. SUBSTITUTESHEET -65- 12. PLASTIC FILM ANTIBLOCK COMPOSITIONS Low density polyethylene (LDPE) and polypropylene (PP) film have a tendency to stick together. This phenomenon iβ called "biock- Ing." SAMS pigments of the instant invention were evaluated to determine if SAMS could be used as antiblocking agents in LDPE, PP and other plastics films. Approximately 1300 gram batches of LDPE and SAMS compoβi¬ tionβ from Examples One and Two, as well aβ the control clay from Example Two, were compounded In the Mo. 3 Banbury. Each sample was then granulated and extruded through the one and one-half inch Davis Standard Extruder using a 20/100/60 mesh screen pack. Each sample extruded contained 90% LDPE Gulf Resin 5200 and 10Z of either the SΛMS composition from Example One and Two, or the control clay from Example Two. Press-outβ from each concentrate were made from each sample to determine the quality and dispersion of each material. Film waβ then produced on the one-inch Killion extruder. All film samples were produced on the same machine on the same day at a constant rpm, identical temperature profile, and constant film thickness. Q Film samples were heated after 24 hours of film aging to let the antiblock additive migrate to the surface of the film. The blocking force, coefficient of friction (COF) and percent haze were determined on each film sample. These results are summarized in Table XV. SUBSTITUTESHEET TABLE XV ANTIBLOCK COMPOSITION (FILM THICKNESS; 2 HILS) Blocking Compound Antiblock Agent Force, gm- COF, g X Haze Gulf Reβin 5200 None 76 0.6 11 Gulf Resin 5200 HG-90 Clay 74 0.5 12 Gulf Resin 5200 SΛMS from Example One 38 0.5 10 Gulf Resin 5200 SΛMS from Example Two 45 0.4 9 Data in Table XV clearly show that SΛMS have better antiblocking properties than the starting resin and the clay control. Also, the COF and the haze properties of the film containing SAMS are definitely superior to the film containing the clay control. SYNTHESIS OF SAMS AS A FUNCTION OF B/C RATIO Except as expressly noted below the procedures of Example One and Two were followed using laboratory reactors of two-liter, one-gallon or two-gallon capacity in carrying out the examples below which are otherwise abbreviated to focus on the variables changed. Experimentation was performed on a laboratory scale. SUBST IT UTESHEET EXAMPLE THREE A reaction in accordance with Example Two was carried out at 135 psi, for one hour of reaction time using Hydragloss 90 and a 2.5 mole ratio sodium silicate to illustrate the novelty of the invention over a wide range base to clay ratios. Conditions and results are shown below in Table XVI. TABLE XVI SAMS SYNTHESIS AS A FUNCTION OF B RATIO Monovalent Base to Oil Cation Exchange Clay Ratio Absorption, Capaci y, B/C ml/100 g meq 100 g Clay Control 30 2 .20 89 72 .35 127 123 .50 164 170 .70 124 189 .90 122 186 This clearly points to the fact that a wide variety of SAMS compositions of high oil absorption and high ion exchange capacity, when compared with control clay, can be prepared by the teachings of the present invention. EXAMPLE FOUR To illustrate the present invention in regard to the use of different alkali metal si licates, reactions of potassium si licates (Kasil 42 and Kasil 1, respectively) with Hydragloss 90 clay were conducted at 120 psig over 1.5 hours using 10% solids. Reactions conducted at B/C ratios ranging from 0.25 to 5.0 yielded the results set forth in Table XVII. TAILS XVTI SAHS sτ« iChaal* fraa Pacaaalaa Stllαaca Sc«rc: las I/C OtX laaaraclea 1ST S.Λ.. ?MH* « ^ l.cio ■ • 1/I00t a'/t uc-fO (βaacra n 43 22.0 C«*ll 42 0.23 Mi 27.1 « * ) 0.30 170 22.2 0.73 1(4 It.3 I.00 1 at U.3 1.30 132 13.2 1.00 1*1 11.7 CO 3.00 1*2 10. * c 03 K * •aall 1 0.23 139 29.9 0.30 l»7 2a. • CO 0.73 170 21.9 H «• 1.00 170 l».7 1.30 133 11.4 3.00 lit ».J H C I •The St0t/Kι0 aα β ratio coaaoalclααa at ctta «c»rcta» alllcacaa »•(>: m - Kaall *2 - 2.β CO Kaall I • l.i X Sllleacaa are caaaardally available tie* FQ Cαraacaclaa. m The data in Table XVII clearly shows that potassium s i lica tes can a lso be used in the syn thes is of unique SAMS compositions. A unique characteristic of SΛMS products prepared from potassium silicates is the absence of zeolite formation even at B/C ratios as high as 5.0. At high B/C ratios (i.e., B/C >1) , the potassium silicate/clay reactions were found to always yield completely amorphous materials rather than any zeolite. Under similar reaction conditions, sodium silicate/clay reactions typically produce zeoli te (see Example Nine for comparison) . Another interesting feature of potassium SΛMS products, is an observed change in thei r morphology as the Si0 2 2 mole ratio of the potassium silicate used for reaction is increased from 2.8 to 3.9. SEM photographs comparing the potassium SAMS prepared from Kasil 42 and Kasi l 1, both at B/C ratio of 0.5, are shown in Figure 39. Λ change in the agglomerate morphology of the products, from generally spheroidal to coral-like, is apparent when Kasil 1 rather than Kasil 42 was used. EXAMPLE FIVE In accordance with the teachings of this invention. Example Five shows the formation of SAMS compositions at B/C ratios of 1.0 to 2.0, using alkali metal silicate bases of different Si0 2 /Na 2 0 molar ratios. To exemplify this aspect of the invention, a Hydragloss 90 clay was reacted with 2.5 and 3.3 mole ratio«sodium silicate at approximately 100 psi for one hour at 10% solids. The results are set forth in Table XVIII. SUBSTITUTE SHEET -70- TABLE XVIII SYNTHESIS OF SΛMS AT HIGH B/C BATCH COMPOSITIONS r Base to Cation Clay Oil Surface Exchange Bright¬ " 5 Teβt Ratio Absorption, Area, Capacity, ness No. (B/C) ml/100 g Structure m 1% meg/lOOg X Hydragloββ 90 Control 30 VLS 20 2-3 91.0 1* 1 162 HS 24 141 91.7 2* 2 . 193 HS 19 191 93.0 10 3** 1 187 HS 16 159 92.6 4** 2 115 LS 11 136 91.2 *2.5 Silicate Hole Ratio (S10./Na 7 0) **3.3 Silicate Hole Ratio (Si0 2 /Na 2 0) Data in Table XVIII clearly show the formation of SA 15 compoβitionβ at B/C ratios equal to and greater than 1.0 using alka metal silicate bases of different S10 2 / a 2 0. olar ratios. The SΛM compositions had oil absorption valueβ which would correspond materials having from low (LS) to high (HS) structure. TEM Figures and 23 also show the same unique SΛMS composition and morphology 20 SΛMS compositionβ prepared at B/C ratios of 0.5 and 0.75 (Figures through 21). Figure 5 shows a comparison of the FT-IR spectra Hydragloss 90 control clay, SΛMS from Example Two prepared at a B/C 0.5, and SΛMS from Example Five prepared at a * B/C of 1.0 and 2.0. 25 sodium silicate having an S10,/Na 2 n mole ratio of 2.5 was used In SAMS synthesis. The only difference observed in the IR spectra of SAMS compositionβ occurred in the 1200-950 wavenumber region in SUBSTITUTESHEET Si-0 stretching peak. As the B/C of the SAHS composition increased the peak became broader and less detailed. Thiβ would indicate an increase in £he amount of amorphous material present in the SAHS compositions. The TEHS and FT-IR spectra clearly show that the unique SAMS compositions can be formed at B/C ratios of one and greater. To further demonstrate the functionality feature of the variety of SAHS compositions prepared at different B/C ratios, the products from Tests 1 through 4 were evaluated as functional extenders in a typical paint formulation similar to that described earlier.. In Table XIX the products from Tests 1 through 4 were compared in con¬ trast ratio with Zeolex 80, Hydragloss 90 and Satintone 5, a commer¬ cial, high brightness calcined clay. TABLE XIX , PAINT PROPERTIES OF SAMS VERSUS B/C OF BATCH COMPOSITION Silicate Contrast Test No. B/C Hole Ratio Structure Ratio 1 1 2.5 HS .977 2 2 2.5 IIS .978 3 1 3.3 HS .975 4 2 3.3 LS .970 Satintone 5 «. VCS .975 Hydragloss 90 - VLS .976 Zeolex 80 - LS. .973 SUBSTITUTE SHEET Aβ noted in Table XIX, the SAHS compositions having mediu to high structure produced excellent contrast ratio valueβ whic equalled or surpassed values for commercially available calcined clay or silicas in paint propertieβ. r EXAMPLE SIX To illustrate the present invention in regard to the use o silicates comprised of various S10 2 /Ha 2 0 ratios, a reaction of Omnifi and various silicates at a pressure of 120 psi for one hour of reac tion time at 10Z solids yields the results set forth in Table XX. TABLE XX SYNTHESIS OF SAHS AS A FUNCTION OF SILICATE HOLE RATIO Silicate . Monovalent Hole Cation Base to Ratio Oil Exchange w Surface Bright- Test Clay Ratio (S10 2 / Absorption, Capacity, Area, neββ, St :ru No. (B/C) Na.n) ml/lOOg meq/100g a 2 /g X ttur '* 1 .50 3.33 161 4J5 24 83.5 HS 2 .75 3.33 167 149 2P 85.8 HS 3 .50 2.50 156 143 25 85.5 HS 4 .75 2.50 148 175 21 85.9 H 5 .50 1.00 123 148 28 84.0 L 6* ,75 1.00 83 2 6 28 85.1 L Omnifil (Control) - 37 2-3 20 82.P V *XRD pattern showed presence of zeolitic material SUBSTITUTE SHEET As can be seen from the data in Table XX, SAMS compositions having low to medium structure were formed under the preferred v conditions of B/C less than 1.0 using alkali metal silicate bases of varying Si0 2 NA 0 molar ratios. Low structured SΛMS compositions were prepared in Tests No. 5 and 6 using sodium metasilicate. The XRD pattern of Test 6 showed the presence of a zeoli ic material. Figure 6 shows a comparison of the infrared spectra of the SΛMS compositions of Example Six prepared at a B/C ratio of 0.5 using the different molar ratio sodium silicates. The IR spectra of the SΛMS prepared from the 2.5 and 3.3 mole ratio silicate are essentially identical and closely resemble the IR pattern of the SAMS compositions of Example One, Two and Five (Figures 3, 4 and 5). The IR spectrum of the SAMS ' prepared with meta silicate more closely resembles that of the 'starting clay (Figure 3), reflecting the lower silicate content of the starting reaction mixture. This is especially true in the 1200-950 wavenumber Si-O stretching region. It must be concluded, based on the physical and analytical data, that unique SΛMS compositions similar to those produced in Example One and Two were formed by reacting cla with sodium silicates of Si0 2 /Na 2 0 molar ratios of 1.0 to 3.3 at B/ ratios less than 1.0. SUBSTITUTESHEET EXΛHPLE SEVEN To illustrate the effectiveness of the present invention on a clay pigment produced from another locale, a delaminated Central Georgia clay (Hydraprint) having the propertieβ shown in Table XXI waβ employed for a three-hour reaction time at 120 psi mid 10% solids, u β i 3.33 mole ratio sodium silicate. Results of the reactions are shown in Table XXI. TABLE XXI SYNTHESIS OF SΛMS FROM CENTRAL GEORGIA CLAY Base to Oil Surface Clay Ratio Absorption Area, (B/C) ml/lOOg m g Structure Hydraprint (Control) 49 13 VLS 0.25 153 19 HS 0.50 |79 H HS 0.75 • m 14 H3 The oil absorption data shown in Table XXI would sugges that unique SAHS compositions of medium to high structure can b produced by the reaction of a relatively coarse particle size, lo surface area clay such aβ Hydraprint with an alkali metal silicat base. SUBSTITUTE SHEET EXAMPLE EIGHT To llluβtrate the importance of controlling reaction time and pressure/temperature in the SΛMS synthesis, a series of SAHS reactions was conducted in wliich pressure and reaction time were varied between 100-150 psi and one to three hours, respectively. Results of the tests are shown in Table XXII. The reactions were conducted at 101 solids using a Hydraprint, middle Georgia delaminated clay, and a B/C ratio of 0.8. A 3.3 mole ratio sodium silicate was used in the tests. TABLE XXII SYNTHESIS OF SAMS AS A FUNCTION OF REACTION, PRESSURE AND TIME Pre 100 1 89.2 134 SAHS 13 2 90,0 135 SAMS 11 3 90,3 145 SAHS 11 120 1 89.9 131 SAHS 11 2 90.6 133 SAHS 11 3 91.1 157 SAMS + 112 Trace Z** 135 1 90.3 137 SAHS 9 2 91.2 156 SAHS + 33 Trace Z 3 91.3 16P1 SAHS +Z 91 (Table XXII Cont. ) 150 1 90.6 144 SAHS 10 ? 91.5 158 SAHS + 49 Trace Z , 3 .s ISO SAHS + Z 124 Hydraprint 87. 4? 14 (Control) * Corresponding temperatures can be found in steam table ** Zeolite The above tests illustrate the wide variety of SAHS compoβi- tionβ that can be produced by reacting clay and alkali metal silicate. Brightness, oil absorption and surface area of the resulting SAHS compositions can be changed by varying reaction time and steam pres sure (temperature). The data show that if the presence of zeoliti material in the SAHS composition is undesirable, it can be eliminate by reducing reaction pressure and/or time. EXAMPLE NINE To illustrate the uniqueness of the clay-sodium silicat reaction, tests were conducted in which Jlydraglosβ 90 east Georgi clay was reacted with both a 2.5 molar sodium silicate and sodiu hydroxide at B/C ratios of 0.75 to 5.0. The reactions were conducte at 10Z βolids at 120 psi for two hours. Results of the tests a given in Table XXIII. TABLE XXIII COMPARISON OF SODIUM SILICATE WITH SODIUM HYDROXIDE AS BASE IN THE SAHS SYNTHESIS x Base to Clay Ratio, Brightness, OA, SA, (B/C) Baβe X ml/lOOg m 2 /g XRD 0.75 Silicate 92.1 147 90 SAHS 1 Silicate 90:9 102 228 SAHS+trace Zeolite 3 Silicate 92.0 90 246 Trace SAHS+Zeolite 5 Silicate 93.5 104 7 Amorphous 0.75 NaOH 81.0 82 20 Hydroxy sodalite* 1 NaOH 74.6 78 15 Hydroxy sodalite* 3 NaOH 83.5 64 17 Hydroxy sodalite 5 NaOH 81.5 60 21 Hydroxy sodalite Hydragloss 90 91.0 43 22.0 *XRD also showed presence of kaolinite. The reaction with sodium hydroxide formed only hydroxy sodalite. In addition, the low brightness, oil absorption and surface area valueβ also show that no SΛMS compositions were formed. In contrast, the sodium silicate reaction produced SΛMS compositionβ having increased brightness, structure (oil absorption) and surface SUBSTITUTESHEET area. The XRD analysis of the silicate reaction products showed the presence of zeolites at B/C ratios of 1.0 and higher. The amorphous character and low surface area of the B/C » 5 silicate reaction indicated the formation of a new phase. Figure 7 compares the spectra of the silicate reaction products in Table XXIII. The spectra show the presence of SAHS but also show the increase in zeolite formation at the higher B/C ratios as the Si-0 stretching peak (1200-950 wavenumber) becomes sharper and the peaks typical of kaolin located between 800 and 400 wavenumbers disappear. Figure 8, likewise, compares the IR spectra of the sodiu hydroxide reaction products. The Si-0 stretching peak (1200-95 wavenumbers) is sharper, indicating the formation of a crystallin phase (hydroxy sodalite), and the loss of peaks in the 800-40 wavenumber region is observed at lower B/C ratios than for the sili cate reaction. SUBSTITUTESHEET EXAMPLE TEN Nylon Plastic Compositions Containing SAMS Fillers are added to plastics to provide reinforcement or to act as an inexpensive diluent wi thout resulting loss of physical properties. The SAMS product of Example 2 was evaluated as a reinforcing filler in amorphous Nylon 66 at loadings of 5, 10 and 20% respectively. The physical properties of these filled compositions were then compared to those of an unfilled Nylon plastic to assess the reinforcing potential of SΛMS. Evaluation results for SΛMS as a filler in amorphous nylon are tabulized below: TABLE XXIV Nylon Reinforcing Properties of ! 3AMS Tensile Modulus, psi 33880 54080 56850 103600 Tensile Yield, pβi 4405 5057 5035 4214 Elσng. § Peak, % 371 324 297 114 Flexural Modulus, psi 47160 54670 64020 88590 Flexural Strength, psi 1933 2226 2491 3191 Izod Impact, ft-lbs/in 11.47 M3 14.12 lβ« 13.59 m 13.40 Gardner Drop t., in/lbs > 160 > 160 > 160 > 16 It should be noted that the filled compositions show marked advantages in their tensile and flexυral modulus values versus the unfilled control. Impact properties were also excellent even at a 20% loading of SAMS. However, advantages in the above physical properties SUBSTITUTE SHEET were not obtained at the expense of any tensile yield or flexural strength. It is remarkable that the conversion of §n inexpensive clay into a SAMS results in such a unique functional filler for nylon. EXAMPLE ELEVEN Conduit Pipe Composition Containing Sams To further illustrate the plastic reinforcement properties of SAMS, the SAMS of Example One was evaluated as a filler in a conduit pipe composition which utilizes a high-density polyethylene base resin (Phillips C-568). In this particular application, the SΛMS of Example One was surface modified with a standard, commercial-grade azido silane coupling agent (Hercules AZ-CUP MC) at a 0.75% treatment level. The modified SAMS was then incorporated into the HDPE resin at "a 25% loading level. A silane modification was made as known in clay technology by adding the azido silane in its pure form in up to 10% liquid involving dilution of the si lane wi th methylene chloride or ethanol followed by low shear solid-liquid mixing with the SΛMS using a device such as a Sigma Blade Mixer. The physical properties of the SΛMS/HDPE composite were then compared to those of an unfilled HDPE control. Integral Corporation's (of Dallas, Texas) criteria for their conduit compounds include good process iblity, high tensile and stiffness properties and a minimum Izod Impact of 2.7 ft-lbs/in. Test results on 1 5/8 inch O.D. pipe produced from each composition are tabulized below. SUBSTITUTE SHEET TABLE XXV Reinforcing Properties of Modified SAMS* in a Conduit Pipe Composition HDPE Control HDPE with SAMS/AZ-CUP (Phillips C-568) At 25% Loading Tensile Modulus, psi 157800 223500 Tensile Yield, psi 5407 5269 Elong. @ Peak, % 11.57 12.41 Flexural Modulus, psi 105600 224100 Flexural Strength, psi 3393 5015 Izod Impact, ft-lbs/in 13.66 15.72 *SAMS of Example One surface modified with Hercules azido silane (AZ - CUP MC) at 0.75% treatment level. The test data clearly show that the SAMS/HDPE composition satisfies all the physical property criteria needed by Integral Corporation in their conduit applications. Versus the unfilled HDPE control, one will note that modified SAMS addition provides notable improvements in the tensile and flexural modulus, flexural strength and izod impact properties. ' It is therefore obvious that SAMS serves as a highly functional filler in this plastic system. EXAMPLE TWELVE In accordance with the teachings of this invention, SAMS products were evaluated as reinforcing fillers for high-density polyethylene at a 25% loading. The SAMS products for this filler application were prepared from a coarse particle size. Middle Georgia delaminated clay (i.e., Hydraprint) in combination with a 3.3 mole ratio sodium silicate used at B/C ratios of 0.25, 0.50 and 0.75 respectively in accordance with the procedure of Example 8. SAMS products were produced from the above batch compositions by reaction at 120 psig for one hour at 10% solids. The agglomerate products were in the form of platelets. The reinforcement properties of these platey SAMS in HDPE were compared to those of hydrous delaminted clays. The results are set forth in the table below. SUBSTITUTE SHEET TABLE XXVI Reinforcing Properties of SAMS in Allied HDPE 7-731, 25% Loadings Filled HDPE Compositions at 25% Filler Loadings HDPE HP- "Platelet" SAMS Products" Control Clay 0.25 B/C 0.50 B/C 0.75 B/C The test data clearly indicates that platey SAMS products, when used as fillers for HDPE, provide physical properties essentially equivalent to those provided by hydrous clays, except with respect to Izod Impact which was improved. The platey SAMS provided notable advantages in Izod Impact, particularly as their B/C ratio increased from 0.25 to 0.75. It is truly unexpected that the conversion of a delaminated clay into a platey SAMS product of high B/C should produce a unique functional filler for HDPE. An increase in impact strength from approximately 5 up to 12 ft-lbs/in is considered very significant. EXAMPLE THIRTEEN Platey SAMS products of B/C ratios of 0.25, 0.50 and 0.75, respectively, prepared as in Example Twelve, were evaluated as coating pigments for paper that was used in a printing application by the rotogravure method. All pigment coatings were applied to the paper substrate at a coat weight of 5.0 #/R using a Keegan laboratory blade coater. Following supercalendering, coated sheets were tested for sheet smoothness and for various optical properties (including • brightness, opacity and printed gloss) in accordance with standard TAPPI test methods. Test coating compositions containing platey SAMS were prepared by simply replacing 5% of the standard, commercial-grade of delaminated clay (Hydraprint) with the desired SAMS product. Coating compositions containing 100% Hydraprint, and 90% Hydraprint 10% calcined clay (Hycal) for their pigment portions were also prepared and evaluated as comparative controls. The rotogravure printing results are tabulized below. SUBS TI TUTESHEET ♦' TABLE XXVTI Sheet Properties for SAMS Paper Coating Compositions ^ (Rotogravure Printing) 90% HP-Clay 95% HP-Clay + 5% Platey SAMS Product 100% + 10% Calcined SAMS of SAMS of SAMS of HP-Claγ Clay 0.25 B C 0.50 B/C 0.75 BC Brightness, % 70.0 72.6 71.1 70.7 70.6 0» c Opacity, % 85.2 86.8 86.1 85.7 85.9 03 CO H Printed Gloss, % 60.8 56.1 59.9 56.7 57.1 H Missing Dots/Sheet** 48 40 27 28 24 C * Coating Parameters were as follows: ω Base Stock = 24 #/R St. Regis Offset (wire side) x Application » Keegan Trailing Blade Coater Ϊ Coat Weight = 5.0 #/R m Calender Conditions =■ Supercalendered using 800 PLI H at 150°F and 2 Nips ** Diamond National Smoothness Test The observed sheet properties indicate that the replacement of only 5% delaminated clay with platey SAMS results in several notable performance improvements. Versus a straight delaminated clay composition, 5% of a platey SAMS significantly improved brightness, opacity and sheet smoothness. Although platey SΛMS at 5% replacement did not provide quite the level of sheet brightness and opacity provided by the 10% calcined clay, the printed gloss and sheet smoothness properties provided by platey SAMS were far superior. Consequently, in those printing applications where printed gloss and sheet smoothness are of utmost importance, platey SΛMS will out perform calcined clay used at double the concentration level. The above test data also clearly indicate that platey SAMS products of low B/C ratio (i.e., about 0.25) are preferred coating pigments on the basis of their overall performance properties. The platey morphology of the sodium SΛMS products prepared from delaminated clay (i.e., Hydraprint) is clearly-seen in their SEM photographs presented in Figures 40-41. Λ comparative SEM photograph of the starting Hydraprint clay is shown in Figure 42. The above photographs suggest that SAMS prepared from Hydraprint largely maintain the flat, platey structure inherent in the delaminated clay. The unique physical properties exhibited by such platey SAMS are therefore a consequence of the observed rim alteration material. The degree of rim alteration (i.e., the rim width) can be easily varied on platey SAMS depending on the specific synthesis conditions employed. Comparison of the platey SAMS prepared at B/C ratios of 0.25 and 0.75 (Figure 40 versus Figure 41) shows that increased rim alteration occurs at the higher B/C ratio. The physical properties of these two SAMS therefore differ significantly, as shown below: SUBSTITUTE SHEET TABLE XXVIII Comparison of Properties for Two Platey SAMS of .Different § ? Platev SAMS Product* SAMS of SAMS Of 0.25 B/C 0.75 B/C Brightness, % 89.7 90.9 Oil Absorption, ml/100 g 97 117 BET Surface Area, m 2 g 15.7 9.3 Na 2 ° Content, % 3.75 6.93 10 LOI (@ 1000°C), % 11.45 8.97 Kaolin Content (XRD) , % 55.2 18.1 Rim Alteration thin thick *Platey SAMS prepared in accordance with reactions described in Example Twelve. 15 Platey SAMS are not as structured as agglomerates of SΛMS of Examples One and Two. The apparent reluctance of large, delaminated clay platelets to agglomerate upon hydrothermal alteration further lends itself to platey SΛMS formation. Given the flat, platey structure of SΛMS prepared from Hydraprint, it is not surprising that 20 these products impart excellent sheet smoothness and printed gloss when used as paper coating pigments. EXAMPLE FOURTEEN This example further illustrates the present invention with regard to the use of lithium silicates as an appropriate alkali metal 25 si licate base for producing SAMS products. Reactions between a lithium silicate (Lithsil 4) and Hydragloss 90 clay were thereby SUBSTITUTE SHEET conducted at 120 psig for 1.5 hours at 10% reaction solids using B/C ratios of 0.25, 0.50 and 0.75 respectively. Results from these lithium silicate/clay reactions are set forth in the table below. TABLE XXVIX SAMS Synthesis from Lithium Silicate Selected Hydragloss 90 Li - SAMS Products Properties (Clay Contrc 0.25 B/C 0.50 B C 0.75 B C Oil Absorption, mL 100 g 43 81 92 97 BET Surface Area, m g 22 28 22 25 Brightness, % 91.0 88.9 90.1 91.2 Specific Gravity g inl 2.60 2.53 2.50 2.45 LOI (@ løøflAc) , % 13.86 12.17 11.61 11.11 Li 2 0 Content, % 0.0 0.89 1.26 1.47 ♦ The lithiun silicate employed had a 4.8 Si0 2 /Li 2 0 mole ratio c iposition (Lithsil 4 of Lithiun Corporation) The above data clearly shows that a lithium silicate can be used in the synthesis of unique SΛMS compositions. Examination of the li thium SAMS compositions by TEM and STEM/EDAX methods revealed that an alteration product was indeed produced as a consequence of the lithium silicate/clay reaction. The TEM photograph of the 0.75 B/C product (Figure 43) clearly shows the presence of some dark, blobby masses or protuberances on the kaolinite platelets. Electron diffraction analysis indicates that these protuberances or blobby masses are totally amorphous, while the remaining platelet areas show the typical diffraction pattern for kaolinite. Most importantly, one should note that the blobby masses or protuberances did not form exclusively on the clay platelet edges. but appear in a more or less random fashion about the platelets. Several pseudo-hexagonal clay platelets are still clearly evident in the TEM photograph which indicates great heterogenei y of reaction. Elemental mapping of the Si and Al content within a lithium SAMS material, by STEM/EDAX analysis, has indicated that the alteration product (i.e., the blobby masses) is much higher in silicon and deficient in aluminum relative to the unaltered kaolinite regions. Elemental mapping of lithium was not possible because its atomic weight is below the detection limit of the instrument. S U H H A R Ϊ As suggested by the above examples, the materials of the present invention may be used as effective pigment (titanium dioxide) extenders in paint and paper applications, as functional fi llers or reinforcing agents- in plastics and elastomers, as a catalyst support and carr ier in ca talyst prepara tion, as a th ixotrope , as a conditioning and free flow agent, and in defoamer composi tions. Because of their low abrasion characteristics, the materials of the present invention may be used to fill Xerox and electrostatic copier papers. Products of the present invention can also be used in a variety of specialty applications and as an opacifier, a diazo paper filler, a flatting agent, in silicone rubbers and other applications. In addition, the SΛMS compositions, tecause of their unique physical and chemical properties, may be used in certain catalytic applications if they are first exchanged with hydrogen, ammonium or other suitable cation, i.e., either as a separate particle or intimately mixed with the components of a hydrocarbon conversion SUBSTITUTE SHEET catalyβt. Moreover, the wide variation one can achieve in surface area, pore volume, Siθ 2 /Λl 2 θ ratio, and ion exchange capacity (solution or gaβ phase) suggest tlielr πfγillcatlon for emission control catalysts and in metal scavenging, and in the clean-up of residue materials and/or resid-type feeds to fluid catalytic cracking units in particular. In the preferred embodiment of the Invention, x is an integer of 0.01 to 2.0, y is an Integer of at least 2.0 and preferably 2.0 to 20.0 and z is an integer of 1.0 to 5.0. The terms Hydraprint, Hydragloss, Huber 90C, Omnifil, Hydrasperse, Hycal, Zeolex 23, Hydrex, Zeolex, Zeolex 23P, Zeo, Zeosyl, Zeofree and Zeodent used herein are trademarks of the J. M. Huber Corporation. Hi-Sil is a registered trademark of PPG and Λnsilex is a registered trademark of Engelhard Corporation. Although a specific preferred embodiment of the present invention has been described in the detailed description above, the description is not intended to limit the invention to the particular forms or embodiments disclosed herein, lire present disclosure is to be recognized as illustrative rather than restrictive. It will further be obvious to those skilled in the art that the invention is not so limited. The invention is declared to cover all changes and modi ications of the specific examples of the invention herein . -t disclosed for purposes of illustration, which do not consti tute departures from the spirit and scope of tiie Invention. SUBSTITUTE SHEET

Claims: What la Clahned la 1. An alkali metal alumino-silicate having a composition in terms of mole ratio of oxides as follows* x j OtΛ^O j t S^szl^O wherein x is the number of moles of alkali metal oxide, M is an alkali metal, y is the number of moles of Slθ 2 associated with the compositionβ, and z iβ tiie number of moles of bound water, wiierein the primary particles of said alkal i metal alumino-silicate comprise altered kaolin clay platelets integrated wi th an adjacent area of essentially amorphous alkali metal silicate base-kaolin clay reaction product. 2. An alkali metal alumino-silicate (SΛMS) composition according to claim 1 which has the morphology of integral rimmed particles as depicted in TEH Figures 18-23. 3. An alkali metal alumino-silicate comprising altered kaolin clay platelets integrated with one or ore adjacent areas of essentially amorphous alkali metal silicate-base kaolin clay reaction product (SAMS) having a composition in terms of mole ratio of oxides 5 aβ followst xH^Of A1 2 0 3 1 ySiθ 2 1 zH j O where H lβ sodium or potassium, x Is the number of moles of sodium oxide or potassium oxide and iβ an integer of 0.01 to 2.0, y iβ the SUBSTITUTE SHEET number of moles of Si0 2 in the SAMS composition and is an integer greater than 2.0, and z is the number of moles of bound water and is an integer of 1.0 to 5.0; wherein the primary particles of said alkali metal alumino-silicate products have attenuated kaolin peaks in x-ray diffraction patterns from the kaolin remnants in the compositions, and have the characteristic physical features shown by TEM Figures 18-23 and 43. 4. An alkali metal alumino-silicate (SAMS) composition according to claim 3, where the alkali metal silicate is sodium silicate, and the SAMS product has a rimmed structure concentrated in silica. 5. An alkali metal alumino-silicate (SAMS) composition according to claim 3 where the alkali metal silicate is potassium silicate and the SAMS product haβ a rimmed structure concentrated in silica and potassium. 6. An alkali metal alumino-silicate (SAMS) composition according to claim 3 wherein the alkali metal silicate is lithium silicate and the SAMS product comprises a platelet area with amorphous protuberances thereon. 7. An alkali metal alumino-silicate (SAMS) composition according to claim 3 wherein the composition also contains at least a trace of a zeolite composition. 8. A composition according to claim 1, wherein the SAMS compositions have a controlled structure, an oil absorption value having a range of about 40 to 220 ml/løøg, and a surface area of about 2 to 300 πι 2 /g. SUBSTITUTE SHEET 9. A composition according to claim 3, wherein the unique SAMS compositions have an oil absorption range of about 80 to 160 ml/100g and a surface area range of 10 to 30 rrr/g. 10. A method for the production of unique SAMS compositions which comprises reacting kaolin clay (C) with an alkali metal silicate base (B) in B/C molar ratios of 0.25 to 5.0 in an aqueous reaction batch composition under hydrothermal conditions of elevated pressure and temperature. 11. A method for the production of unique SAMS compositions according to claim 10 which comprises reacting kaolin clay (Q with an alkali metal silicate base (B) in B/C molar ratios of less than 0. 12. A method for the production of unique SAMS compositions according to claim 10 which comprises reacting kaolin clay (C) with an alkali metal silicate base (B) in B/C molar ratios of 1.0 to 5.0. 13. A method for the production of unique SAMS compositions according to claim 11 wherein the B/C molar ratio range is 0.1 to 0.9. 14. A method according to claim 10, wherein the hydrothermal conditions for carrying out the reaction comprise a closed system under steam pressures ranging from 50 psig to 360 to psig, with a corresponding temperature range of 140 degrees C to 250 degrees C and for a reaction time ranging from 0.25 to four hours. SUBSTITUTE SHEET 15. A method according to claim 14 wherein the alkali metal silicate base is sodium silicate and the clay and sodium silicate are reacted as an aqueous slurry ranging from 1 to 20 weight percent solids. 16. A method according to claim 14 wherein the alkali metal silicate base is potassium silicate and the clay and potassium silicate are reacted as an aqueous slurry ranging from 1 to 20 weight percent solids. 17. A method according to claim 14 wherein the alkali metal si licate base is lithium si licate and the clay and li thium sil icate are reacted as an aqueous slurry ranging from 1 to 20 weight percent solids. 18. A method according to claim 14 wherein the clay is a delaminated kaolin clay and the SΛMS product is in the form of platelets. 19. As an article of manufacture, a paper containing the SΛMS composition of claim 1. 20. An article of manufacture according to claim 19 containing the SAMS composition as a functional- filler. 2 An article of manufacture according to claim 19 containing the SAMS composition as a coating pigment. SUBSTITUTE SHEET 22. An article of manufacture according to claim 20 wherein the SΛMS filler is contained in fine paper. 23. An article of manufacture according to claim 20 wherein the SΛMS filler is contained in newsprint. 24. As an article of manufacture, a latex paint composition containing as a pigment opacifier, the SΛMS composition of claim 1. 25. λβ an article of manufacture, a rubber formulation containing aβ a reinforcing filler, tiie SΛMS composition of claim 1. 26. As an article of manufacture, a plastics color-concentrate composition containing as at least a portion of the filler, the SΛMS composition of claim 1. , 27. As an article of manufacture, a defoamer composition containing as a functional filler, the SΛMS composition of claim 1. 28. As an article of manufacture, a dry-up liquid/carrier composition containing as a functional carrier, the SΛMS composition of claim 1. 29. Aβ an article of manufacture, a paint coating composition containing aβ a flatting agent, the SΛMS composition of claim 1. SUBSTITUTESHEET 30. As an article of manufacture, a detergent composition containing as a dry-up liquid/carrier for surfactants, the SAMS composition of claim 1. 31. As an article of manufacture, a plastic film composition containing as a functional antiblocking filler, the SAMS composition of claim 1. 32. As an article of manufacture, a catalyst composition having as the catalyst support, the SAMS composition of claim 1 in which the alkali metal cation has been exchanged with hydrogen, ammonium, or other suitable cation and having the desired properties of high surface area, cation exchange capacity and pore volume. 33. As an article of manufacture, a plastic composition containing as a reinforcing filler, the SAMS composition of claim 1. 34. An article of manufacture according to claim 34 wherein the plastic is a polya ide. 35. As an article of manufacture a polyethylene conduit pipe containing as a reinforcing filler, the SAMS composition of claim 1 which has been reacted with a silane. SUBSTITUTE SHEET

Inventors: WASON SATISH K, WASON, SATISH, K.
Applicants: HUBER CORP J M, J.M. HUBER CORPORATION
Application year: 1987
Main classification: C01B33
IPC codes: C08K3, C09C1, C09D5, C09D7, C11D3, D21H17, D21H19