text: this corresponds to preparation of the commercial product betagloss ® of the assignee e . c . c . america inc . ( atlanta , ga .). the starting crude material was a blend of crude kaolins , which were derived from northeast georgia , and which were comprised of very fine particle size materials . the ge brightness of the said crude was in the range of 82 to 87 . in all instances in this specification it will be understood that brightness values are obtained according to the standard specification established by tappi procedure t - 646 os - 75 . the crude clays were beneficiated according to the general practice used in kaolinite processing industries . the beneficiated clays were classified by centrifugation to 94 % less than 2 micrometer e . s . d . ( equivalent spherical diameter ). the classified clays were flocculated using 0 . 25 % by weight of aluminum sulfate and adjusting the ph to 3 . 5 with sulfuric acid . the flocculated kaolinites were filtered . the significantly dried ( about 20 % moisture remains ) kaolinites were redispersed with 0 . 25 % by weight of sodium polyacrylate and the ph adjusted to about 7 . 0 . the redispersed kaolinite was spray dried . this method of preparing feed clays is general and may be varied , particularly if so pointed out in specific examples ; the main variations are differences in particle size distribution and the addition of calcium carbonate . the relative sedimentation volume of treated and starting material was measured to determine the extent and nature of aggregation . in the procedure , a nearly 55 % solids slurry of pigment was prepared that contained 0 . 3 milliliter of sodium polyacrylate . this slurry was then spun at 7000 rpm for 45 minutes . the sediment volume was calculated using dry weight of clay , wet weight of clay , and calculating volume of clay using density of dry clay of 2 . 6g / ml . the invention is demonstrated in the following examples which are intended to be illustrative but not limitative . the starting feed clay was prepared from a blend of two fine northeastern crude clays from georgia . the crude clays were refined by common commercial beneficiation methods . the refined clay was classified to 96 % less than 2 micrometer e . s . d . the classified clay was blended with ground calcium carbonate ( carbital -- 90 ) at 3 % weight of dry kaolinite . the blend was spray dried and pulverized using a pulverizer manufactured by mikropul corporation . this clay will be referred to as feed clay - i . 75 g . of substantially dry powder , moisture 0 . 85 %, of feed clay - i was treated with 1 % by weight of tetramethoxysilane , supplied by petrarch chemical co ., with vigorous mixing in a waring blender . once the mixing of powder with liquid was completed , the clay was allowed to mix for an additional 1 . 5 minutes . excess silane and resultant methanol as a by - product were removed by subjecting the clay to vacuum ( nearly 30 torr ). the above process with tetramethoxysilane was repeated once and the final product was allowed to dry at 150 ° c . for fifteen minutes . the particle size distributions of the starting feed clay - i and the final product are illustrated in fig1 . the particle size distribution indicates formation of a structured aggregate with very narrow particle size distribution . handsheets were prepared using the above aggregated clay from bleached sulfite pulp . the sheets were filled at three filler loadings . the reflectivity of the handsheets was measured and converted to light scatter according to a modified kabulka - munk equation . the normalized light scatter of sheets field at 10 % filler loading with this product was 578 cm 2 / g . this is a gain of 60 scatter units from untreated feed clay - i . the intraparticle porosity of the pigment , given as percent wet void volume and determined by the relative sedimentation method ( rsv ) was 57 . 3 %. this is an increase of about 17 percentage units from the feed clay . the increase in wet void volume indicates the formation of aggregate structure and development of the permanent porosity . the process and the chemical used were essentially identical to example 1 , except that the feed was a fine commercial clay , betagloss . the particle size distribution and moisture of this feed clay were 94 % less than 2 micrometer , and 0 . 85 % respectively . the normalized light scatter of a sheet filled with the final aggregated product , at 10 % filler loading , was 562 cm 2 / g . wet void volume of the product determined by rsv was 56 . 4 %, an increase of about 16 % percentage units over the feed clay . the feed clay , aggregating agent and the mixing process were essentially identical to that of example 2 , except that the clay was treated with 0 . 45 % by weight of ammonia gas following each evacuation step . the normalized light scatter of a sheet filled with this pigment , at 10 % filler loading , was 550 cm 2 / g . the wet void volume of the product , determined by rsv , was 56 . 7 %. wet void volume and scatter respectively are about 16 percentage units and 30 scatter units higher than the feed clay . in this example feed clay - ii was prepared by mixing 3 % ground calcium carbonate with previously spray dried and pulverized betagloss followed by drying at 150 ° c . for 15 minutes . the moisture of this feed clay - ii was 0 . 68 % by weight . the aggregating chemical and the treatment process were essentially identical to example 1 . the normalized light scatter of a sheet filled with this pigment at 10 % filler loading was 585 cm 2 / g , which is an increase of about 65 units over the feed clay . wet void volume is about 16 percentage units higher than the feed clay , thus 55 . 9 %. feed clay - ii was treated by the essentially identical method and chemicals described in example 3 . the normalized light scatter of a sheet filled with this pigment at 10 % filler loading was 588 cm 2 / g . there was an about 16 . 1 percentage units increase in wet void volume over the feed clay following the chemical aggregation , thus 56 . 1 %. the feed clay and the process of treatment were essentially identical to the method described in example 2 , except that the aggregating agent was an organo - silicon compound containing ethoxy groups . ( ch 3 ch 2 o ) 4 si . the normalized light scatter of a sheet filled with this pigment at 10 % filler loading was 547 cm 2 / g . the wet void volume of the product by rsv was 54 . 1 %. upon chemical aggregation , wet void volume and light scatter increased by about 14 percentage units and 27 scatter units respectively over the feed clay . the feed clay , aggregating agent , and the treatment process all were essentially identical to the method described in example 6 except that the clay was exposed to 0 . 45 % by weight of ammonia immediately following the evacuation step as described in example 3 . the normalized light scatter of a sheet filled with this pigment at 10 % filler loading was 544 cm 2 / g . the wet void volume determined by rsv of the product was 54 . 9 %. the feed clay and process were essentially identical to the method described in example 4 except that the aggregating chemical was tetraethoxysilane , ( ch 3 ch 2 o ) 4 si . the normalized light scatter of a sheet filled with this pigment at 10 % filler loading was 570 cm 2 / g . the relative sedimentation method showed the product to have 52 . 1 percent wet void volume . the increases in light scatter and wet void volume amount to 50 scatter units and about 12 percentage units over the feed clay , respectively . the process and aggregating chemical were essentially identical to the method described in example 7 except that feed clay - ii was the starting material . the normalized light scatter of a sheet filled with this structured aggregated clay , at 10 % filler loading , was 584 cm 2 / g . in addition , the wet void volume determined by rsv was 54 . 4 %, an increase of about 14 percentage units over the feed clay . the process , aggregating chemical and the feed clay all were essentially identical to the method described in example 1 , except that the moisture content of the feed clay was such that the molar ratio of water to silane was 4 . 69 , which is equivalent to a moisture content of the feed clay of about 1 . 11 % by weight . the relative sedimentation method showed the product to have 57 . 5 percent wet void volume . this product was used to determine coated sheet properties of light weight coated offset grade paper . in the coating formulation , 30 parts of regular coating pigment were replaced with this product . the typical formulation and relevant formulation properties are provided in table 1 . almost all of the coated sheet properties improved by application of this aggregated clay , for example , sheet gloss , print gloss and opacity . these coated sheet properties are illustrated in fig2 through 6 . the properties , i . e . brightness , opacity , gloss , print gloss , and litho print gloss are compared with a common offset control formulation . the feed clay and the process were essentially identical to the method described in example 10 , except that the aggregating chemical was ( ch 3 ch 2 o ) 4 si , tetraethoxysilane . the relative sedimentation method showed the product to have 51 . 9 percent wet void volume , an improvement of nearly 12 percentage units over untreated feed clay . as in example 10 , this pigment was evaluated in a paper coating application . once again , significant improvement of coated sheet properties is observed with this aggregated structure pigment . the essential coated sheet properties , e . g . brightness , opacity , gloss , print gloss , and litho print gloss are illustrated in fig2 to 6 . it is postulated that the hydrolysis , and subsequent polymerization of the hydrolyzed products , of the organo - silicon compound , e . g . silane , would depend on the availability of free moisture . in the presence of excessive moisture it might be possible that the hydrolyzed product would precipitate as an amorphous silica . in this example , the effect of starting feed clay moisture on aggregation is examined . the feed clay , aggregating chemical and process all were identical to that of example 1 , except that the moisture of the feed clay was varied in the range of 1 to 2 % by weight , so that the effective ratios of total water to the amount of silane were in the range of 4 . 56 to 8 . 44 . the light scatter values of the handsheets prepared using respective aggregated clays , at 10 % filler loading , are provided in table 2 . this relationship between moisture and light scatter is graphically illustrated in fig7 . the effective aggregation can be achieved even at a water to silane ratio of 8 . 44 . the preferred range of moisture appears to be between 1 . 0 to 1 . 75 % by weight of dry clay . the feed clay , aggregating chemical and part of the processing were identical to example 12 , the moisture of the feed clay being 1 . 08 % by weight , except that in the process there was a time delay of 10 minutes prior to the repeat chemical treatment . the light scatter of a sheet filled with this product at 10 % filler loading was 582 cm 2 / g . apparently higher residence time is beneficial for developing a more effectively structured aggregate . the starting material was a feed clay - i that contained 3 % ground calcium carbonate , carbital - 90 . the moisture of the feed clay was adjusted to 3 . 29 % by weight . 75 grams of this feed clay was treated with 1 % by weight of tetraethoxysilane , ( ch 3 ch 2 o ) 4 si , by the usual method of mixing , using a commercial waring blender . after addition of the silane , mixing was continued for 1 . 5 minutes . the clay was then subjected to vacuum for about two minutes and the whole process was repeated once . the final product was dried at 150 ° c . for 15 minutes . the wet void volume of the final product , as determined by rsv method , was 51 . 2 %, an increase of about 11 percentage units over the starting feed clay . in this example , moisture of the feed clay - i was adjusted to 2 . 94 % by weight and the clay was treated with 0 . 5 % by weight of tetraethoxysilane , ( ch 3 ch 2 o ) 4 si . the rest of the treatment process was identical to that of example 14 . wet void volume of this product was 46 . 2 %, about 6 percentage units higher than the feed clay . the feed clay , feed clay moisture , aggregating chemical and the treatment process all were identical to those described in example 15 , except that the amount of the aggregating agent was 0 . 25 % by weight of the clay . the wet void volume of this product was 47 . 1 %, an increase of about 7 percentage units over the feed clay . this example demonstrates the relation between the amount of aggregating agent vs . aggregate performance by keeping all other conditions the same . the starting material was a feed clay - i in which the moisture was adjusted to 0 . 95 % by weight . this feed clay was treated separately using 0 . 25 %, 0 . 5 % and 1 . 0 % by weight of tetraethoxysilane , ( ch 3 ch 2 o ) 4 si , according to the process described in example 14 . the normalized light scatter of a sheet filled with these pigments at 10 % filler loadings and percent wet void volumes of these aggregated fillers are provided in table 3 . also , the relation between the amount of aggregating agents vs . wet void volume and light scatter of filled sheets are illustrated in fig8 and 9 respectively . it is evident that the silane enhances these properties . this example further demonstrates the relation between the amount of aggregating agent vs . aggregate performance by keeping all other conditions the same . the starting material was a feed clay - i where the moisture was adjusted close to 1 . 72 % by weight . this feed clay was treated separately using 0 . 25 % and 0 . 5 % by weight of tetraethoxysilane , ( ch 3 ch 2 o ) 4 si according to the process described in example 17 . the normalized light scatter of a sheet filled with these pigments at 10 % filler loadings and percent wet void volumes of these aggregated fillers are provided in table 4 . this example describes use of an aggregation enhancing agent , calcium chloride . in the process , feed clay - i was mixed with 0 . 5 % by weight of dihydrated calcium chloride salt and the feed moisture was adjusted to 1 . 64 % by weight of the clay . the chemical treatment process was identical to that of example 17 . 1 . 0 % by weight of tetraethoxysilane was used . the normalized light scatter of a sheet filled with this pigment at 10 % filler loading was 577 cm 2 / g . the resulting product is more porous as indicated by the substantially higher wet void volume , 61 . 6 % measured by rsv technique . in this example , the effect of amount of aggregation enhancing agent is examined . the feed clay and the chemical treatment were identical to those described in example 19 , except that in a first set , feed clay was separately dosed with 0 . 2 , 0 . 5 and 1 . 0 % by weight of calcium chloride . in each case moisture of the feed clay was adjusted to nearly 1 . 3 % by weight , after mixing feed clay - i with calcium chloride . similarly , in a second set , feed clay was separately dosed with 0 . 05 and 0 . 1 % by weight of calcium chloride except that the moisture of the feed clay was adjusted to 1 . 9 % by weight . each of these clays was treated with 0 . 5 % by weight of tetraethoxysilane . the final products are porous aggregates as seen from wet void volume , measured by rsv technique . the wet void volumes are provided in table 5 . previous examples have demonstrated that the use of tetramethoxysilane produced more efficient aggregates ; however , tetraethoxysilane is more cost effective . thus , to produce efficient , but cost effective aggregates , a combination of tetraethoxy - and tetramethoxy - silane was used in this example . the feed clay was identical to the one described in example 14 . the moisture of the feed clay was adjusted to 0 . 85 % by weight . the chemical treatment process was essentially identical to the method described in example 14 except that the composition of the aggregating agents consisted of 0 . 25 % by weight of tetraethoxysilane and 0 . 05 % by weight tetramethoxysilane . the wet void volume of the final product , determined by rsv technique , was 51 . 4 %. this is an increase of nearly 11 percentage units over the feed clay . the overall amount of chemical required is significantly lower than that required for similar aggregation using either tetraethoxy - or tetramethoxy - silane alone . the starting material for this experiment was a commercial coating clay betagloss . this clay , after initial beneficiation , size classification , filtration and redispersion was diluted to 40 % by weight slurry . this slurry was spray dried and pulverized using a pulverizer produced by mikropul corporation . the particle size distribution of this clay was 94 % less than 2 micrometer e . s . d . the moisture of this clay was adjusted to 0 . 86 % by weight . 75g . of this clay was treated with 0 . 25 % by weight of tetraethoxysilane , ( ch 3 ch 2 o ) 4 si , using a commercial mixer , a waring blender . the wet void volume determined by relative sedimentation method was 57 . 3 %. this is a substantial increase over feed clay wet void volume of 40 %. the feed clay , treatment process , aggregating chemical and amount of the tetraethoxysilane were identical to that in example 22 except that the feed clay was dosed with 0 . 1 % by weight of an aggregation enhancing chemical , calcium chloride , and the moisture of the feed was adjusted to 0 . 98 % by weight . the percent wet void volume of the product was 50 . 4 %, an increase of about 10 percentage units over the feed clay . feet clay - i was equilibrated with moist air to increase moisture of the feed clay from 0 . 85 % to 1 . 5 % by weight of the clay . this clay was treated with 0 . 5 % by weight of tetraethoxysilane , ( ch 3 ch 2 o ) 4 si , under vigorous mixing conditions using a commercial mixer , a waring blender . after the treatment with tetraethoxysilane , mixing was continued for an additional 1 . 5 minutes . this product was dried at 150 ° c . for 15 minutes . wet void volume of this product was 50 . 5 % by weight . the feed clay and chemical were identical to that described in example 24 . this time the feed clay was mixed with 0 . 5 % by weight of an aggregation enhancing agent , calcium chloride and the moisture of the feed clay was adjusted to 1 . 8 % by weight of the clay . 75g . of this clay was treated with 0 . 5 % by weight of tetraethoxysilane , ( ch 3 ch 2 o ) 4 si , in a waring blender . after the addition of the silane , mixing was continued for 1 . 5 minutes . the clay was then subjected to vacuum for about two minutes . the above process with tetraethoxysilane was repeated once . the final product was dried at 150 ° c . for 15 minutes . the wet void volume of the final product was 50 . 1 %, about 10 percentage units higher than the feed clay . a series of experiments was conducted using feed clay - i as a starting material . the moisture of the feed clay was adjusted to 1 . 0 % by weight . three separate portions , 75g each , were treated with 0 . 25 % by weight of tetraethoxysilane , ( ch 3 ch 2 o ) 4 si , according to example 13 , except that the time between each chemical treatment was increased to 15 , 30 and 60 minutes . the normalized light scatter of handsheets filled with these pigments at 10 % loadings is given in table 6 . in addition , the particle porosity measured as wet void volume is included in table 6 . in each case the light scatter and wet void volume improved significantly from the starting material . table 1______________________________________formulations and coatingformulation propertiesformulation pigment a * pigment b ** components control 30 parts 30 parts______________________________________ # 1 clay 75 parts 60 parts 60 partscalcium 25 parts 10 parts 10 partscarbonatelatex 10 parts 10 parts 10 partsstarch 4 parts 4 parts 4 partsnopcote c - 104 0 . 5 part 0 . 5 part 0 . 5 partsunrez 700 m 0 . 12 part 0 . 12 part 0 . 12 partdispex n - 40 0 . 1 part 0 . 1 part 0 . 1 partph 7 . 6 8 . 0 8 . 1 % solids 64 . 1 63 . 9 63 . 8brookfield 880 1080 1040viscosity100 rpm ( cps ) ______________________________________ * prepared by using tetramethoxysilane ** prepared by using tetraethoxysilane table 2______________________________________effect of feed clay moisture onlight scatter of handsheets filled with10 % chemically aggregated kaolinite pigment normalized lightpercent water / silane scatter at 10 % moisture moles / moles filler loading______________________________________2 . 0 8 . 44 5631 . 71 7 . 22 5741 . 08 4 . 56 574______________________________________ table 3______________________________________effect of silane concentration on theproperties of aggregated kaolinitesprepared using tetraethoxysilane normalized molar ratio light scatter percentpercent of water to at 10 % filler wet voidchemical silane loading volume______________________________________ 0 . 25 21 . 96 549 47 . 70 . 5 10 . 98 551 49 . 31 . 0 5 . 48 563 50 . 0______________________________________ table 4______________________________________effect of silane concentration on theproperties of aggregated kaolinitesprepared using tetraethoxysilane normalized molar ratio light scatter percentpercent of water to at 10 % filler wet voidchemical silane loading volume______________________________________0 . 25 39 . 76 562 48 . 90 . 5 20 . 10 564 50 . 2______________________________________ table 5______________________________________effect of calcium chloride on wet voidvolume of chemically aggregated kaolinitesamount of feed claycalcium chloride moisture percent wet (% by weight ) (% by weight ) void volume * ______________________________________ 0 . 05 1 . 9 51 . 10 . 1 1 . 9 51 . 10 . 2 1 . 3 53 . 00 . 5 1 . 3 62 . 51 . 0 1 . 3 62 . 9______________________________________ * the wet void volume of the feed clay was 40 . 2 . table 6______________________________________effect of time delay between chemicaltreatment steps in the aggregation ofkaolinite using 0 . 25 % tetramethoxysilane . normalized lightdelay time scatter at 10 % percent wet ( minutes ) filler loading void volume______________________________________15 542 52 . 230 546 55 . 660 544 52 . 0______________________________________ when used in paper coating applications , the structured kaolin pigments of the invention comprise from about 5 to 60 % and preferably from about 10 to 30 % by weight of the total pigment component of the coating composition . the balance of the pigment can comprise any of the known coating pigments , such as coating grades of kaolines , calcium carbonate , titanium dioxide , plastic pigments , etc . the coating compositions , in addition to the pigment component , include conventional components , such as an adhesive binder , dispersants , and other known additives . while this invention has been particularly set forth in terms of specifics , it is understood in view of this disclosure , that numerous variations upon the invention are now enabled to those skilled in the art , which variations yet reside within the scope of the present teaching . accordingly , the invention is to be broadly construed , and limited only by the scope and spirit of the claims now appended hereto .