text:
|Publication number
|Publication type
|Application number
|Publication date
|Apr 29, 1997
|Filing date
|Jun 30, 1995
|Priority date
|Jun 30, 1995
|Fee status
|Also published as
|Publication number
|Ellen S. Forbus, Paul R. Suitch, Thomas Dombrowski
|Original Assignee
|Engelhard Corporation
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (17), Referenced by (56), Classifications (25), Legal Events (6)
|External Links: USPTO, USPTO Assignment, Espacenet
This invention relates to calcined, low abrasion, high brightness calcined kaolin clay pigments, their manufacture from selected soft kaolin crudes and the use thereof in the manufacture of paper products.
One of the seminal developments in the industrial minerals field was the discovery that calcination of a particular type of poorly crystallized, ultrafine tertiary kaolin clay, known in the art as "hard" kaolin, resulted in bright, e.g., 93.5% GE brightness, pigments having desirable low abrasion and outstanding potential to provide opacity to filled and coated paper products. Reference is made to U.S. Pat. No. 3,586,523, Fanselow et al (1971). Products made in accordance with the teachings of this patent by the assignee and its licensees have accounted for a substantial proportion of the sales of high performance industrial minerals in the United States and abroad. Aside from possessing a unique combination of high brightness, low abrasion and opacification potential, the processing was remarkably economical because of the unique morphology as well as inherently fine particle size and desirable particle size distribution of the kaolin in the crude. In such crudes, colored impurities, in particular iron-contaminated titania particles, concentrate in the coarse fraction of the crude. Thus, conventional degritting and fractionation to recover calciner feed yield a fine fraction of hydrous kaolin with a lower content of colored titania than the crude. As a result of these factors, the yield of calcined kaolin product was high, e.g., roughly about 50% based on the weight of degritted crude or about 40% by weight of the particles finer than 1 micron in the degritted crude.
Unlike the hard Georgia Tertiary kaolins that are poorly crystallized and have an average particle size of about 0.3 microns, (equivalent spherical diameter or e.s.d.), the soft kaolins that are present in even greater abundance in Georgia, U.S.A. and throughout the world are composed of much larger, well crystallized kaolin particles having an average particle size of approximately 0.6 microns, e.s.d., roughly twice that of the hard kaolins. Fractionation of a soft clay to isolate the fine size fraction of the crude having generally the same average particle size and particle size distribution of a typical degritted hard kaolin would represent only about a 15% yield (or 85% loss) of degritted kaolin. Thus, assuming that calcination of such a fine fraction of a degritted soft kaolin would result in a bright, low abrasion opacifying pigment, at least comparable in all significant performance characteristics to calcined pigments prepared from hard clay, the processing would not be economically viable.
It is well known in the industry that the brightness of uncalcined and calcined kaolin pigments is adversely affected by the presence of colored impurities, notably titaniferous and ferruginous impurities. It has long been the practice to remove these impurities to various extents by physical or physical-chemical means, such as froth flotation, selective flocculation, magnetic purification, bleaching and combinations thereof. It is also known that calcination generally increases brightness of a hydrous kaolin when the clay is "fully" calcined, i.e., calcined to undergo the characteristic exotherm, and may decrease in brightness when the clay is calcined under less severe conditions, i.e., to so-called "metakaolin" state. Thus, 90% brightness (fully) calcined pigments can be produced readily from hard crudes by degritting, fractionation, bleaching and calcination; 93% brightness pigments can be obtained from the same crudes by adding one or more steps to remove colored impurities, especially titaniferous matter. The Fanselow et al patent (supra) discloses 95% brightness calcined kaolin pigments.
Attempts were recently made to produce calcined pigments having much higher brightness from the hard kaolin crudes that are readily processed to provide 93+% brightness calcined kaolin pigments. To the best of our knowledge, there is at present no means to produce calcined kaolin pigments having a 95+% brightness merely by decreasing the content of colored impurities in the hard kaolin by conventional means such as flotation.
On the other hand, there are reports in the patent literature dating back to the early '60's of the recovery of calcined kaolin pigments having 96% brightness and higher from certain Georgia kaolins crudes. These crudes are obviously of the soft type as evidenced by information about particle size and particle size distribution in the patents. Reference is made to the following:
U.S. Pat. No. 3,058,671 (1962) Billue
U.S. Pat. No. 3,343,973 (1967) Billue
U.S. Pat. No. 3,171,718 (1965) Gunn, et al
Billue allegedly discovered that media grinding of the coarse fraction of kaolins resulted in "fracture-induced" brightness and found that the enhanced brightness was carried over when the fractured kaolin was fully calcined. Specifically, Billue isolated from a naturally occurring crude a coarse fraction that contained not more than 35% by weight of particles finer than 2 microns, i.e., a coarse fraction of crude containing at least 65% by weight of particles larger than 2 microns. In Example II (both patents), a coarse fraction of kaolin was "fractured" to produce a fractured clay having an initial brightness of 89.1%. This hydrous kaolin was calcined to produce a product having a brightness of 96.3% (col.7). However, data in the patent reveal that the portion of the clay that was fractured (the 86% minus 2 micron cut) represented a meager 28.8% by weight of the crude. Thus, while calcined brightness was very high, the process depended upon the removal of minus 2 micron fines before grinding and would be commercially useless unless the higher brightness would compensate for the high cost associated with low yield. Billue did not report the abrasion value or provide information about the opacification potential of his 96.3% brightness calcined clay. Gunn et al teach media grinding of coarse filler clay in the production of calcined kaolin pigments made by mechanical delamination of a coarse hydrous filler clay fraction. Disclosed is a product having a GE brightness value of 95% and "low" abrasion as obtained by a specific modification of a Valley Abrasion test. The clay was delaminated gently to separate kaolin booklets (as contrasted with severe grinding to break particles after delaminating the clay). In an example, delaminated kaolin having a GE brightness of 92.1% was calcined to a GE brightness of about 96%. Gunn et al do not report data such as to permit calculation of yield, however, the teaching of Billue (supra) provide guidance and suggest yield would be low.
The Gunn et al patent also clearly teaches that the finest fraction of the kaolin has the highest content of TiO2 impurity (Example 9). In other words, in this type of kaolin, colored impurities concentrate in the fine end. This is well known to clay mineralogist and the clay industry. It is noted that Gunn et al did not disclose calcining the fine fraction. However, based on the disclosure as to the concentration of colored impurities in the fine end of soft kaolins, one would avoid the presence of excessive fines if seeking brightness from a purified kaolin obtained from a soft kaolin crude. This is consistent with the specific disclosure in the Gunn et al patent of ultrahigh brightness calcined pigments made by processing the coarse fraction of a crude after the removal of fines.
In U.S. Pat. No. 5,137,574, Suitch et al, a high opacifying pigment is produced by calcining one or more high titania content kaolin fractions which are separated from a whole crude by size classification, froth flotation, magnetic separation or the like. In embodiments of the invention, a grinding step is practiced before calcination. The grinding step is said to be necessary in order to reduce the particle size by virtue of the use of a titania enriched product. The calcined product has a brightness in the range of about 70 to 82% and the titania content in greater than 2%. The low brightness product is supplied under the registered trademark OPACITEX. Production of such a pigment by selection of a low brightness kaolin crude is described in U.S. Pat. No. 5,371,051, Pope et al.
McConnell et al, U.S. Pat. No. 4,381,948, now commonly assigned, discloses a process for producing high brightness, low abrasion calcined kaolin pigments having exceptionally high light scattering (superior opacification), a GE brightness of at least 93% and low abrasion (Valley Test Method) when used as a paper filler. Processing involves use of a crude clay containing not more than 0.5% glass forming oxides, not more than 1.5% Fe2 O3 and more than 2% TiO2 and separating a very fine particle size fraction from such crude, i.e., a fraction that is 100% by weight finer than 1 micron, followed by conventional steps of drying, pulverizing, calcining and repulverizing. In all illustrative examples, a hard kaolin crude was processed. The highest brightness disclosed was 94.3%. The patent also teaches that soft Georgia kaolin crudes (identified as crudes that are 50-60% finer than 2 microns) can be used. However, the inventors caution that in such case the particular crude should contain sufficient 1 micron particles to enable "worthwhile recoveries". Teachings sufficient to suggest, much less to enable, the achievement of worthwhile recoveries are not presented in making the disclosure as to the usefulness of soft kaolins.
Moreover, patentees did not deal with the problem inherent in the use of a very fine fraction when using soft kaolin because of the concentration of colored impurities, especially colored titania, in the finest fraction of soft kaolins.
An early patent in the art, U.S. Pat. No. 3,014,836, Proctor, discloses that the particle size of a calcined kaolin product depends on the particle size of the uncalcined kaolin feed and that the feed should be free from abrasive impurities to produce low abrasion, calcined clay. The highest GE brightness value was 93%.
U.S. Pat. No. 3,519,453, Morris et al, mechanically delaminate booklets of a coarse kaolin and calcine to metakaolin conditions in an effort to obtain low abrasion; GE brightness was below 90%. Slepetys et al, U.S. Pat. No. 5,393,340, commonly assigned, severely grind booklets in a coarse kaolin fraction so as to obtain a ground material, the particles of which are substantially all finer than 1 micron as a result of grinding. Patentees then calcine to metakaolin to obtain ultralow Einlehner abrasion; brightness was about 90%. Thus, ultrahigh brightness calcined kaolin, 95-96% and above, has been reported as has calcined kaolins characterized by low abrasion (by various methods including the now obsolete Valley method), high opacification or combinations thereof. Prior to this invention, however, brightness values above 95% have been achieved only by processing fractionated soft kaolin crude by steps that resulted in economically unattractive yields and do not inherently provide calcined kaolin pigments that also possess sufficiently high light scatter for paper use combined with the extremely low abrasion values now demanded by the paper industry. On the other hand, high yields have obtained when using hard crudes but 96% brightness products were not produced. Grinding and/or delamination prior to calcination have been advocated with kaolin but not in a process that results in pigments brighter than 95% at high yields, for example a recovery in excess of 45%, based on the weight of particles finer than 1 micron in the crude.
We have invented a simple method for processing kaolin clay that results in a calcined pigment having both low abrasion, ultrahigh GE brightness (at least 95.0%, preferably at least 95.5%, most preferably at least 96.0%), and high light scatter, using a novel combination of steps that results in remarkably high yields of the calcined product.
Our method features the selection of a degritted soft kaolin crude that contains from about 50 to 60% by weight of particles finer than 2 microns or, preferably, a fraction of degritted soft kaolin crude that is from about 60 to 85% by weight finer than 2 microns, the crude or crude fraction possessing the following combination of properties: iron content (as Fe2 O3) below 0.80%, preferably below 0.60 wt. %, and most preferably below 0.45 wt. %, and TiO2 below about 1.80 wt. %, preferably below 0.75 wt. % and most preferably below about 0.50 wt. %. The minus 2 micron component of the degritted material contains less than a total of 2.0% preferably, less than 1.0%, and most preferably less than 1.0% of any of the following impurities: mica, quartz, cristobalite (or other forms of silica), or smectite (montmorillonite) minerals; less than about 1% by weight of the selected degritted crude or crude fraction is composed of particles larger than 325 mesh (U.S. Sieve).
Unless the TiO2 content of selected crude or crude fraction is below 1%, it must then be purified by physical or physical/chemical means, preferably by froth flotation, high intensity magnetic separation (HIMS), selective flocculation or combinations thereof, to remove discrete particles of TiO2 and in some cases, discrete iron minerals. The pure (or purified clay) must then be agitated in the presence of water with a particulate grinding media such as, for example, glass beads, sand, alumina or zirconia beads, to increase the 2 micron content by at least 20%, preferably 25 to 30%, in the case of a degritted crude or at least 10%, and preferably from about 15 to 20% in the case of fractionated crude, and to result in a ground material that is at least about 75%, preferably 80 to 87%, finer than 1 micron. Thus, an intermediate ground product that contains a substantial weight percentage of particles finer than 1 micron is generated as a result of grinding. The particles finer than 1 micron in the ground kaolin also include those particles in the previously pure or purified kaolin that were present in the naturally occurring clay. A pulp of the ground clay is then fractionated to remove particles larger than 2 microns, e.g., to remove at least 95%, preferably 100% by weight, of the particles larger than 2 microns, while minimizing the removal of particles finer than 1 micron. The resulting fine particles size fraction is then treated by conventional series of steps, i.e., optional bleaching, drying, pulverization, calcination and repulverization.
In one embodiment of the invention (using degritted but unfractionated coarse soft kaolin), the process comprises the following steps;
a) providing a degritted soft kaolin crude that is from 50-65% by weight finer than 2 microns, e.s.d. and contains substantially all the minus 1 micron particles present in the degritted naturally occurring clay, the degritted crude containing from 0 to 1.8% by weight TiO2 and 0 to 0.8% by weight Fe2 O3 based on the dry weight the degritted crude, and having low levels of mica, quartz or other silica minerals and montmorillonite minerals;
b) removing colored impurities by selective flocculation, froth flotation or combinations thereof to reduce the titania content thereof to a level below 1% if the titania content exceeds 1% in step (a);
c) agitating the degritted kaolin clay in the presence of water with particulate grinding media until the particle size is from 85-92% by weight finer than 2 microns;
d) removing sufficient particles larger than 2 micron from the product of step (c) by sedimentation or centrifugation to produce a product that is about 95-100% by weight finer than 2 micron and about 88-92% finer than 1 micron and to provide calcined feed that is at least 40% by weight of the clay from step (a); preferably bleaching the fractionated clay;
e) spray drying the recovered product of step (d) pulverizing, fully calcining and repulverizing in conventional manner and;
f) recovering the calcined product having a GE brightness of at least 95%, and Einlehner abrasion below 25 and a white color. (L value greater than 98)
In preferred embodiment, the improved process for producing an ultra high brightness, low abrasion kaolin clay pigment from a soft kaolin crude comprises:
a) selecting a soft kaolin clay crude that contains less than a total of 1% by weight quartz or other crystalline silica minerals, mica, and smectite minerals in the minus 2 micron fraction thereof, the crude containing less than 0.8% Fe2 O3 and less than 1.8% TiO2 after removal of grit in step (b),
b) removing grit from said crude,
c) fractionating the resulting, degritted crude and recovering a fine size fraction thereof that is from 60 to 85% by weight, preferably about 76% to 82%, e.g., about 80% by weight, finer than 2 microns, e.s.d.,
d) subjecting the resulting fraction from step (c) to flotation, selective flocculation or combination thereof to remove colored impurities and recovering a beneficiated fraction of clay that contains from 0-0.8% TiO2 and from 0-0.8% Fe2 O3,
e) agitating the beneficiated fraction of kaolin with particulate grinding media until from 95-100% by weight is finer than 2 microns, e.s.d.,
f) removing sufficient particles larger than 2 micron e.s.d. from the product of step (e) to result in calciner feed that is about 90-95% finer than 1 micron, e.s.d., and represents at least 50% by weight of the degritted crude from step (b); optionally bleaching,
g) spray drying the recovered product of step (f);
h) pulverizing, fully calcining and repulverizing the product of step (g) in conventional manner and;
i) recovering the calcined product having a GE brightness of at least 95%, an Einlehner abrasion below 25 and a white color--(L value of at least 98).
The latter embodiment of the process is preferred because it permits a significantly greater recovery of clay suitable as calciner feed. This improved recovery results from the fact that more of the minus 1 micron particles generated during grinding are recovered when operating with feed that is fractionated to remove some plus 2 micron particles prior to grinding. The removal of the coarse fraction prior to delamination improves the yields and economics of the grinding step.
Calcined kaolin pigments of the invention have a G.E. brightness of at least 95% (typically 95.5-96.8%), an Einlehner abrasion below 27, preferably below 22 mg, typically 19 to 21, and light scatter as determined by the known black glass test procedure of at least 0.2 m2 /g usually 0.312 to 0.317 m2 /g. The pigments have a white color, with a more blue shade than commercial 93 brightness calcined kaolins produced from hard crudes. Typical color values are: L*=97.44, a*-0.58 and b*-2.84. Particle size is typically 97-100% minus 5 microns, 84-88% minus 2 microns and 55-65% minus 1 micron.
The interaggregate pore volume is from 0.9 to 1.4 cc/g at a pore radius of 2000 to 4000 Angstrom units, preferably 1.0 to 1.3 cc/g, at a radius of 2500 to 3500 Angstrom units, as measured by Mercury Porosimetry.
Calcined kaolin pigments of the invention are useful in coating and filling a variety of paper and paperboard products. The pigments are also useful as extender pigments in paints, plastic and rubber. Presently preferred best modes of use is as a filler for uncoated specialty papers such as premium/specialty printing paper and recycled fiber containing printing papers. In such use, the pigments are a cost effective alternative to hydrated alumina and precipitated silicates.
It is well known in the art that when kaolin clay is calcined, it undergoes a series of characteristic changes, detectable by differential thermal analysis (DTA). At about 840�-1200� F. (450�-650� C.), the clay undergoes a strongly endothermic dehydration reaction resulting in the conversion to material known as metakaolin. The metakaolin state is conveniently ascertained by acid solubility testing because the alumina in the clay is virtually completely soluble in strong mineral acid. Typically, about 45% by weight of metakaolin is soluble in hydrochloric acid of 18% strength. In contrast, solubility in hydrochloric acid of the alumina component in hydrated kaolin is very limited. Furthermore, when kaolin is calcined beyond the endotherm at higher temperatures it undergoes a characteristic exothermic reaction, resulting in phase transformation manifested by markedly reduced alumina solubility. Upon further calcination, mullite is crystallized. Formation of mullite is avoided in practice of this invention because mullite is abrasive.
Calcined kaolin pigments have been used for several decades in a number of industrial applications such as paper coating, paper filling, paints, plastics, etc. In these applications they impart to the finished products a number of desirable properties: brightness, opacity, hiding power, strength (in plastics), friction (in paper). Paper coating and filling applications require almost exclusively fine fully calcined kaolin pigments such as the 93% brightness ANSILEX 93� pigment manufactured by Engelhard Corporation. See, for example, U.S. Pat. No. 3,586,523, Fanselow et al, which describes the production of such pigments from ultrafine Tertiary "hard" ultrafine kaolins. Because of high brightness and light scattering properties of these fine fully calcined kaolin pigments, their primary function in paper applications is to provide opacity and brightness, often as a replacement for much costlier titanium dioxide pigments, which can also be used to enhance these functional properties.
Although these fully calcined kaolin pigments obtained by calcining ultrafine hard kaolins are less abrasive than other calcined kaolin pigments, they are relatively abrasive when compared with available noncalcined kaolin pigments. For example, the conventional so-called "low abrasion" calcined kaolin pigments, such as the pigment supplied under the registered trademark ANSILEX 93, typically have an Einlehner abrasion value of about 20 mg. The Einlehner abrasion test is now practiced widely by the industry and has replaced the older Valley test. In practical terms, high abrasion translates into increased wear of bronze web forming screens (wires) on paper making machines, dulling of paper slitter knives, wear of printing plates when they come in contact with coated paper containing fine calcined pigments in the coating formulation, and, in general, wear of any surface that comes in contact with these pigments. Paper makers are becoming increasingly demanding in their need for lower abrasion.
Brightness of calcined kaolin pigments is very strongly influenced by discoloring contaminants. The two most important ones in kaolin pigment technology are iron and titanium oxides. Typically, fully calcined kaolin pigments which are produced from fine hard Middle Georgia Tertiary kaolin crudes, such as those mentioned in U.S. Pat. No. 3,586,523, carry iron and titanium contamination of about 0.90-1.1% Fe2 O3 and 1.0-1.8% TiO2, respectively. While the role of colored impurities in the brightness of calcined kaolin pigments is recognized, prior to this invention those skilled in the art were not successful using this knowledge alone to introduce to the market calcined kaolin pigments with ultrahigh brightness (e.g., 96 GE % brightness or above), in combination with low abrasion and good opacification potential.
This invention uses grinding of coarse kaolin booklets as opposed to delamination to achieve valuable fully calcined kaolin pigments. The terms "delamination" and "grinding", as used herein, are distinguishable. Soft clay deposits contain naturally separated platy kaolin particles as well as "booklets", which comprise stacks of kaolin platelets. These stacks are concentrated in the plus 2 micron portion of soft kaolin crudes. See, for example, the Morris et al. patent, supra and U.S. Pat. No. 3,743,190, Whitley. To accomplish "delamination" of these booklets, comminution of kaolin is carried out under carefully controlled conditions of intensity. The intent of delamination is to provide impact energy which is just sufficient to cleave apart the kaolin platelets comprising the booklets without further fracturing these platelets. The resulting delaminated particles are highly crystalline. The intent in grinding as practiced in the present invention is to achieve a desired degree of comminution with the generation of the highest yield of particles in the desired (finer) particle size range i.e., 1 micron and finer. The difference is most readily apparent by comparing the generation of particles finer than 2 microns (as determined by conventional sedimentation techniques). In delamination, the increase in the content of particles finer than 2 microns particles is generally minimal. In grinding, at least grinding of the type contemplated in practice of this invention, the increase in the content of particles finer than 2 microns is significant. It is typically slightly less than 30% by weight when operating with a degritted crude (full fraction) and about 15 to 20% by weight when operating with a No. 2 fraction (80% by weight finer than 2 microns). Some media grinding operations, for example, the glass microballoon media grinding described in U.S. Pat. No. 3,743,190 (supra) actually effects delamination although the term "grinding" is used. This is suggested by the text of the patent.
It is well known to kaolin pigment technologists that the amount of iron and titanium oxides in soft Middle Georgia clays decreases significantly as the particle size of the clay increases. See also the Gunn et al patent (supra). In other words, these impurities concentrate in the fine particle size fractions of soft clays during fractionation. While our process utilizes substantially all of fine particles (e.g., minus 1 micron particles in the naturally occurring soft clay) most of the fine particles used as calciner feed in our process have been typically generated by grinding coarser kaolin products which have a lower content of colored impurities than the naturally occurring minus 1 micron fraction of the crude. Thus, we must grind degritted crude or a fraction of degritted crude that is low in iron, e.g., less than 0.6% by weight, in order to assure low iron in the recovered calciner feed. Preferably, the degritted crude or fraction used as grinder feed in our process is beneficiated by froth flotation or the like to further remove the undesirable titanium and iron before grinding. Titanium is especially responsive to removal by physical/chemical processing such as froth flotation.
The clay is media milled to grind the kaolin particles to a point where a significant proportion thereof constitutes a suitable size for the production of fine calcined pigments after minimal removal of oversize by fractionation. All particle size values referred to herein are determined by sedimentation using a SEDIGRAPH� 5100 particle size analyzer. Typically, the kaolin charge is ground to at least approximately 85% by weight finer than 2 microns and preferably to at least 90% by weight finer than 2 microns and then separated by gravity or centrifugal sedimentation into a fraction which is typically approximately 85% to approximately 95% by weight finer than 1 micron. The accuracy of measurements at 1 micron and 2 micron is �2%. Thus, a fraction reported to be 95% finer than 1 micron could be from 93-97% finer than 1 micron. By using a prefractionated clay as feed to the grinding equipment, as opposed to a degritted but unfractionated feed, improved recovery of particles finer than 2 micron is achieved in the classification step following grinding. The fine ground fraction is recovered, washed, dispersed, spray dried, pulverized, calcined and pulverized again. If necessary, high intensity magnetic separation, flotation or other beneficiation techniques can be applied to the clay advantageously after grinding, when some internally lodged impurities are exposed by the grinding.
A suitable kaolin feed is obtained by purifying an unfractionated but degritted soft kaolin crude (about 50-60% by weight finer than 2 microns) by froth flotation to remove colored impurities, e.g., by the procedure described in U.S. Pat. No. 4,492,628, Young et al (the teachings of which are incorporated herein by cross reference). This procedure is referred to in the clay industry as TREP.
Flotation processes such as ULTRAFLOTATION, e.g., U.S. Pat. No. 2,990,958, which operate with prefractionated feed (as opposed to whole, unfractionated feed useful in TREP) is recommended. The teachings of this patent are incorporated herein by cross reference. In adapting ULTRAFLOTATION to the present invention, the degritted crude clay is fractionated into a typical No. 2 coating clay fraction, e.g., a fraction that is about 80% by weight finer than 2 microns. The fraction remaining after removal of the coating fraction can be used elsewhere in a kaolin refining plant.
High intensity magnetic separators (HIMS units) can be used with floated as well as unfloated feed clay to remove paramagnetic colored impurities, preferably before grinding.
The ultrafine hard kaolin used to manufacture ANSILEX 93 and similar calcined kaolin pigments supplied by other kaolin producers is not suitable as the sole source of kaolin in practice of the invention. The fine particle fraction (about 90% by weight finer than 1 micron) derived from this ultrafine kaolin will not result in a pigment of desired brightness upon calcination to using presently available kaolin beneficiation technology. Brightness of about 93-94% is typically obtained. However, such pigments may have the desired low Einlehner abrasion. Similarly, grinding of fully calcined high brightness pigments (i.e., post grinding of previously calcined kaolin pigments) will not yield a fine calcined kaolin pigment displaying a unique combination of high brightness and low abrasion with excellent performance in paper filing and coating.
Grinding is carried out with particulate hard grinding media, and is preferably conducted in the presence of water. This type of operation is conventionally referred to as "wet grinding". The clay feed is preferably placed in the form of an aqueous slip that is sufficiently fluid to be pumped and transported through the grinding equipment. Typically, the clay solids during grinding is from 20-25% by weight.
Usually a clay dispersant is employed to provide a slip of such solids that has useful fluidity in the grinding equipment. Preferred dispersant is ammonium polyacrylate, but sodium polyacrylate or other organic dispersants employed in kaolin pigment processing can also be used. The amount of dispersant used is typically 0.05% to 0.10% based on the weight of clay. An excess of dispersant beyond that needed for good dispersion may be added at the beginning of the milling period (or in the grinder feed, if continuous operation is used) to allow for the newly developed surface area during the grinding operation.
The grinding media should be a dense hard particulate material which does not discolor the clay charge or leave objectionable residues in the ground clay. Density of the grinding media is preferably at least 2.4. A preferred medium is glass beads (such as 20-40 mesh). Examples of other milling media are alumina, zircon, small ceramic balls, coarse sand, plastic cylinders, beads, or pellets of nylon, styrene-divinyl benzene copolymer, polyethylene or other plastic. Grinding should take place in equipment which is not degraded by the grinding media since this may result in staining of the ground clay charge.
Most preferably, the milling media is minus 20 plus 50 mesh (US sieve) glass beads. Generally, the volume of beads to clay slurry varies between 20-70%, most preferably between 35% and 50%. The clay feed to the process should typically be controlled between 20% to 50% solids; however, optimum processing conditions are often achieved between 35 and 45% solids.
A suitable vessel used for the process contains vertical baffles and typically has a height to diameter ratio greater than 1.0 and optimally 1.5 to 2.0. Such a vessel is equipped with an agitation system containing multiple agitator elements attached to a vertical shaft. The number and spacing of the agitators must be optimized for the specific process conditions in order to impart the necessary combined shear and percussive and frictional energy input necessary to overcome the Van der Waals forces holding individual platelets in a stacked array. Energy input required for delamination will vary due to differences between crudes, process conditions, and equipment; typically, requiring 10 to 50 horsepower hour per ton of clay charged to the delaminators.
Conventional pre and post processing steps such as flotation, selective flocculation, magnet separation, floc/filtration, bleaching and spray drying may be employed.
In the following examples, delamination was performed in a standard stirred tank delaminator using glass beads at solids content between 20 and 30%. The bead content of the delaminators was 45-50%. Delamination was performed in a batch system for 30-60 minutes. A slurry of delaminated kaolin pigments was bleached with a hydrosulfite bleach to meet a brightness specification and flocced with sulfuric acid (target pH 3.5) and alum (at 6 lbs/ton of dry clay) for filtration. Filtration in the following examples was performed using pan filters. The filtercake was washed and re-dispersed using a blend of soda ash and polyacrylate (C-211) as a dispersant. This was followed by spray drying.
Grinding time will depend on the specific mechanical details of the grinding unit (bead size, specific gravity, charge, clay solids, intensity of agitation, etc.) and the coarseness of the clay feed. Typically grinding time is 20-60 minutes in the laboratory impeller driver unit. In a commercial unit, the average retention time is about 40-60 minutes.
The slip of fine particle size ground clay is passed through a centrifuge to remove particles larger than 2 microns and then optionally further purified by magnetic separation and brightened by a bleach such as sodium hydrosulfite (dithionite). The clay is then filtered and washed. The filter cake is dispersed preferably with ammonium polyacrylate before spray drying. Prior to conversion to fully calcined kaolin, the ground clay must be pulverized. Commercial vertical and horizontal rotary calciners can be used to produce conventional low abrasion calcined kaolin pigments. Operation is controlled to avoid calcining at sufficiently high temperatures to form mullite. Suitable calcination temperatures are in the range of 1950� to 2100� F. (1065�-1150� C.).
In the examples, samples were calcined in open refractory trays in a muffle furnace at temperatures of 1065�-1150� C. for 52 min. The trays were rotated 180� after 30 minutes.
After calcination, the material is pulverized. In the laboratory-scale examples, this was done in a single pass through a MICROPULVERIZER� mill equipped with a 0.020" round hole screen. In commercial operation, this could be accomplished in a HURRICANE� mill.
The following examples are given for illustrative purposes.
The following test procedures were employed to obtain values reported herein. The disclosures in the cited patents are incorporated herein by cross-reference.
G.E. brightness--TAPPI T646 om--86
Black Glass Scatter--U.S. Pat. No. 4,738,726 col.11, lines 34-52
Particle size--Sedimentation using Sedigraph� 5100 particle size analyzer--Values reported as microns (equivalent spherical diameter)
Hunter "L" "a" and "b" values were measured using the equipment and procedures described in U.S. Pat. No. 5,011,534, Young, col. 8, 1. 45-66.
In the Einlehner Abrasion test, the weight loss of a wire disc contacted by a rotary abrader and test material is used a relative measure of the abrasiveness of the test material. Details of the procedures and equipment used to obtain values reported in this application are described in U.S. Pat. No. 5,393,340 (supra).
This example illustrates the presently preferred embodiment of the invention involving the steps of extensive wet grinding of a No. 2 fraction of a flotation beneficiated kaolin clay followed by controlled removal of plus 2 microns particles from the ground clay to achieve a high purity ultrafine particle size kaolin suitable as calciner feed to produce 96% brightness calcined kaolin. In a control test representing a method for producing high brightness calcined clay, outside the scope of the invention a portion of the same flotation beneficiated clay was fractionated to about the same particle size distribution and used a calciner feed without intermediate grinding and fractionation steps. The example demonstrates both the improvement in product yield and product quality achieved by practice of the process of the invention.
In these tests, the crude was a soft coarse white kaolin crude from Middle Georgia. The crude was of the type known to provide a No. 2 coating fraction responsive to the froth flotation beneficiated process known in the art as ULTRAFLOTATION.
The crude was degritted in conventional manner in a dragbox using a 40% solids slurry of crude. The overflow was passed to a product tank. The degritted crude in the product tank was 60.4% by weight finer than 2 microns and contained 1.78% (wt.) TiO2 and 0.36% (wt.) Fe2 O3. Brightness was 80.1%. Grit content (+325 mesh, US Sieve) was 0.949%. The degritted crude was dispersed with sodium silicate and fractionated in conventional manner in a centrifuge to a typical No. 2 kaolin cut, i.e., 99.3% finer than 10 microns, 94.2% finer than 5 microns, 76.2% finer than 2 microns and 60.8% finer than 1 micron. The fractionated dispersed feed was then processed by ULTRAFLOTATION to reduce the TiO2 level in conventional manner using a fatty/rosin acid collector, calcite "carrier" and an alum-silicate hydrosol dispersant at pH 8.1. The purified kaolin recovered as the underflow product had an unbleached brightness of 86.3% and contained 0.47% TiO2 and 0.44 Fe2 O3. The flotation treatment removed some of the coarse particles; consequently, the relative proportion of fines increased. Thus, about 1/3 of the TiO2 was removed by flotation but Fe2 O3 concentration increased because removal of coarse particles resulted in concentration of fines which were richer in iron. The combined recovery from the degritting step and the flotation was 60.7% by weight.
In accordance with this invention, a 10 gallon sample of the flotation purified fractionated kaolin was placed in a delaminator with 0.5#/ton of C-211 sodium polyacrylate dispersant and 50% bead volume of 0.75 mm glass beads for one hour. The particle size of the kaolin discharged from the delaminator was 95.9% finer than 2 microns and 86.8% finer than 1 micron. Since the feed to the delaminator was about 76.2% finer than 2 microns and 60.8% finer than 1 micron, approximately 20% by weight of additional particles finer than 2 microns were generated as a result of the grinding treatment; approximately 26% by weight of additional minus 1 micron clay was generated during the grinding step.
To convert the flotation beneficiated ground kaolin into suitable calciner feed, this intermediate product was fractionated in a laboratory centrifuge under conditions selected to remove substantially all of the particles larger than 2 microns while maximizing the recovery of particles finer than 1 micron for use as calciner feed. The resulting fine fraction (calciner feed) was 97.1% finer than 2 microns and 88% by weight finer than 1 micron. This fine fraction was recovered at 21.1% solids. The coarse (discard) fraction was 71.0% minus 2 micron and 41.9% finer than 1 micron. From these data, it was calculated that the recovery of the minus 1 micron particles in the fractionation step was 95.5%. The total calculated recovery of calciner feed was 57.9% based on the 60.7% weight recovery of clay after degritting and flotation.
The recovered fine fraction was bleached in a conventional manner (flocculation with sulfuric acid to pH 3.0 and bleaching with 6#/ton sodium hydrosulfite). The slurry of bleached kaolin was filtered and rinsed with water using about one part by weight water to one part by weight clay. The filter cake was dispersed by adding 5#/ton sodium polyacrylate at pH 6.2 and spray dried in a conventional manner. The brightness of the spray dried kaolin was 90.7%.
For purposes of comparison, a portion of same flotation beneficiated fractionated kaolin used in carrying out the process of the invention (supra) was fractionated in a laboratory centrifuge to a particle size distribution substantially the same as that of the calciner feed described above, i.e., 97.9% minus 2 microns and 88.8% minus 1 micron. The coarse fraction was 38.9% finer than 2 microns and 14.9% finer than 1 micron. In this test, the flotation beneficiated clay was not subjected to a grinding step before or after flotation. Thus, all of the minus 2 micron and all of the minus 1 micron particles in the calciner feed originated in the kaolin crude whereas in the process of the invention, most of the minus 1 micron particles and a substantial proportion of the minus 2 micron particles were produced during grinding.
The recovery for the fractionation step was calculated to be 62%. The total recovery based on a 60.7% recovery of clay after degritting and flotation was only 37.6%.
This product was then bleached, filtered and rinsed as described above and redispersed to pH 6.3 with 5.5 #/ton of the same polyacrylate dispersant and spray dried.
Table I is a summary of properties of the calciner feeds obtained by the control process and the process of the invention.
All spray dried samples were pulverized by 3 passes through a MIKROPULVERIZER� mill with a 0.020 inch screen. Pulverized products were calcined in open trays in a muffle furnace at 2000� F. for 52 minutes and repulverized in the same pulverizing mill with the same screen.
In Table II, properties of the calcined products are compared.
Data in Table II show that the control process for making calcined clay from a coarse floated clay resulted in a 96.1% brightness, and a 294 black glass scatter value. These values are acceptable to a papermaker, but this method resulted in a relatively highly abrasive clay, (26.1 mg Einlehner). Such an abrasion value is unacceptable to many papermakers. Furthermore, the clay producer would normally not use this method because it gives a poor yield, 29.3% compared to a 52.3% yield commonly attained by using a hard kaolin to obtain a 93 brightness calcined kaolin.
The surprising benefits that were realized as a result of the process of the invention are that the process of the invention increases the yield to 45.2% and resulted in an Einlehner abrasion which was 20% lower. The 45.2% yield makes the product acceptable to the clay producer. This process produces a calcined clay that has a high brightness (96.1%) and acceptable scatter (283) which when combined with the low Einlehner abrasion of approximately 20 mg loss produces a product that is valued by paper customers. Obtaining the high brightness, low Einlehner, acceptable scatter and high yield are the key factors that make this a viable commercial process.
TABLE I__________________________________________________________________________EFFECT OF PROCESSING ON PROPERTIES OF CALCINED FEEDWT % RECOVERY, BASED ON PSD OF FEED, MICRONS DEGRITTED Fe2 O3 TiO2 0.3 0.5 1 2PROCESS FRACTION CRUDE WT % WT. % WT. % FINER THAN__________________________________________________________________________Control 62 37.6 0.282 0.481 38.8 63.7 88.9 97.9Invention 95.5 60.7 0.207 0.468 33.6 62.1 88.8 97.1__________________________________________________________________________
TABLE II__________________________________________________________________________COMPARISON OF PROPERTIES OF CALCINED KAOLIN PIGMENTS POROSITY BLACK Pore Vol ABRASION GLASS cc/g/Pore PSD OF PRODUCT, MICRONSGE BRIGHTNESS EINLEHNER SCATTER Radius 0.5 0.75 1 2PROCESS % % m2 /g Angstrom WT. % FINER THAN__________________________________________________________________________Control 96.1 26.1 294 0.975/3000 6.3 -- 49.7 84.4Invention 96.1 18 283 0.998/3500 4.3 -- 38.2 68__________________________________________________________________________
Another possible way to manufacture a high brightness, low abrasion, good light scattering calcined pigment would be to use a commercially available, extremely high purity halloysite (a species of kaolin minerals). A commercial sample of such material having a brightness of 88%, Fe2 O3 content of 0.31% and a TiO2 content of 0.12% was obtained. This material was pulverized three times through a 0.39 inch screen and calcined at 1950� F. for various periods of time in a muffle furnace. After calcination, the material was pulverized (two passes) through a 0.039 inch screen. Based on the inability of produce products with low abrasion in previous testing with clay of this origin, samples were pulverized three passes through the 0.039 inch screen when carrying out the Einlehner test. Also, the pulverized material was slurried to 15% solids and then screened through a 100 mesh screen before testing for Einlehner abrasion. Calcined pigments having 96+% GE brightness were obtained at calcination time 20 minutes or more, but the black glass scatter ranged from only 182-204 (too low to be effective); Einlehner abrasions values ranged from 37.2 to 41.5 mg loss. Clays from these samples do not have the light scattering capacity and are too abrasive to be sold in most segments of the paper markets.
Thus, merely calcining a high brightness, high purity kaolin mineral that is low in iron and low in titania may result in a high brightness calcined pigment but does not necessarily result in desired opacification and low abrasion.
Tests were carried out to determine the results of calcining flotation beneficiated, ultrafine fractions of kaolin clay without a grinding step. The ultrafine fractions, subjected to the calcination treatment, had a particle size distribution similar to the fine fractions processed in the McConnell et al patent. These fractions were obtained from fine particle size fractions of kaolin previously purified to remove colored impurities by TREP or by ULTRAFLOTATION. In the case of kaolin purified by TREP, all of the kaolin was from a soft Georgia kaolin crude. In the case of kaolin purified by ULTRAFLOTATION, the feed was a mixture of soft and hard kaolins.
In both tests, a 90% <2 micron fraction of flotation purified kaolin, obtained as a dispersed low solids slip, was cut to 90-95% <0.5 micron using a Merco nozzle bowl centrifuge.
Samples of the ultrafine clay were flocculated with sulfuric acid and bleached with 10#/t of sodium hydrosulfite.
The bleached pulps were filtered and washed with water (1:1 by weight). The filter cakes were redispersed with sodium polyacrylate dispersant, spray dried, pulverized and calcined as in Example 1.
The feeds were as follows: TREP--0.41 wt % Fe2 O3, 0.64 wt % TiO2 and particle size distribution of 91% <2 micron, 75% <1 micron and 51% <0.5 micron Ultraflotation--0.70 wt. % Fe2 O3, 0.70 wt. % TiO2 and particle size distribution of 90% <2 micron, 79% <1 micron and 61% <0.5 micron.
The results are summarized in Tables III and IV.
TABLE III__________________________________________________________________________Effect of Processing and Feed on Properties of Calcined Feed Wt % Recovery Based on PSD of Feed (Microns) Based on Degritted % Fe2 O3 % TiO2 0.3 0.5 1 2Feed Frac. Crude wt. wt. Wt. % Finer Than__________________________________________________________________________TREP 29.8 12.1 0.42 0.7 62.2 89.3 98.5 99.5Ultraflotation 95.2 26.2 0.74 0.54 79.9 93.5 97.2 98.4__________________________________________________________________________
TABLE IV__________________________________________________________________________Comparison of Properties of Calcined Kaolin Pigments Einlehner Black Porosity PSD of Product (Microns) Brt. Abrasion, Glass Pore Vol/ 0.5 0.7 1 2Feed % mg Scatter Pore Radius Wt. % Finer Than__________________________________________________________________________TREP 96.9 26.7 344 1.33/2700 19.3 51.6 79.4 95.9Ultraflotation 95.2 19.1 307 1.22/2199 22.4 49.7 70 87__________________________________________________________________________
Data in Table IV show that the calcined ultrafine, flotation beneficiated clay made by the TREP process had high brightness but higher abrasion than desired. The ULTRAFLOTATION process resulted in a calcined product having brightness below 95.5% but with low abrasion. However, in both cases, yields were poor. See data in Table III.
This example demonstrates that equivalent products can be obtained by processing of full fraction of floated feed or fractioned floated kaolin made from the same feed. The processing was essentially the same as the one described in detail in Example 1. The feed had been beneficiated by the TREP process. The full fraction product had an initial impurity content of 0.44% Fe2 O3 and 0.46% TiO2 ; particle size distribution was 61.3% <2 micron, 48.9% <1 micron, 32.1% <0.5 micron, and 18.9% <0.3 micron. The product obtained by centrifuging the full fraction in a Bird centrifuge had an impurity content of 0.5% Fe2 O3 and 0.5% TiO2 ; particle size distribution of 80.9% <2 micron, 65% <1 micron, 54,8% <0.7 micron and 43.9% <0.5 micron. Results are summarized in Tables V and VI.
TABLE V__________________________________________________________________________Effect of Processing and Feed on Properties of Calcined Feed Wt % Recovery Based on PSD of Feed (Microns) Based on Degritted % Fe2 O3 % TiO2 0.3 0.5 1 2Feed Frac. Crude wt. wt. Wt. % Finer Than__________________________________________________________________________Full Frac. 66.4 49.8 0.46 0.47 40.8 67.7 91.8 98.8Bird Frac. 89.4 45.8 0.5 0.57 36.4 62.1 89.4 98.7__________________________________________________________________________
TABLE VI__________________________________________________________________________Comparison of Properties of Calcined Kaolin Pigments Einlehner Porosity PSD of Product (Microns) Abrasion, Pore volume/ 0.5 0.7 1 2Feed Brt. mg. Pore radius Wt. % Finer Than__________________________________________________________________________Full Frac. 96.5 20.7 1.19/3000 11.2 34.8 65.3 93Bird Frac. 96.5 21.5 1.23/3100 10.1 33.9 64.9 93.8__________________________________________________________________________
Using pigments of the invention as a furnish constituent in the manufacture of uncoated specialty printing papers, products can meet or even exceed brightness demand and can substantially reduce the cost of raw materials by replacing some of the pulp fiber in the furnish. Recycled specialty papers, at least comparable in quality to paper produced from virgin fibers, can be manufactured. A less expensive grade of recycled pulp can be used to achieve the same sheet brightness achieved using 93% brightness calcined kaolin. There is essentially no difference in opacity between the commercial Ansilex 93 pigment and a 96% brightness pigment of the invention. However, since opacity is a function of light absorption and scatter, one would expect the pigment of the invention to have higher scatter (due to its greater porosity e.g., by approximately 0.100 cc/g and lower absorption due to higher brightness. The effects of the factors tend to cancel each other out in paper; thus, paper sheets filled with the 96% brightness pigment of the invention would have higher brightness with equivalent opacity as compared to sheets filled with 93 brightness calcined kaolin.
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|Use of high-absorption-capacity precipitated silica for the production of a colorant by means of impregnation with an inorganic pigment, the colorant thus obtained and the application thereof in the colouring of ceramic materials
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|Jul 7, 2004
|Apr 27, 2006
|Sharad Mathur
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|Apr 27, 2006
|Howard Goodman
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|Jan 2, 2014
|Outotec Oyj
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|Mar 9, 2006
|Engelhard Corp
|Ultrafine hydrous kaolin pigments, methods of making the pigments, and methods of using the pigments in gloss paint formulations
|U.S. Classification
|106/484, 501/145, 241/22, 162/181.1, 162/181.8, 241/29, 241/23, 241/24.1, 428/537.5, 106/486, 209/162
|International Classification
|Cooperative Classification
|European Classification
|Aug 28, 1995
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Ross Erla Jane Ross, died February 23, 2013 in the Venice Regional Hospital, Venice, Florida, after a long illness. Jane was born in Allegheny County, Pennsylvania on June 1, 1925 and was 87 when she died. After graduating from Carnegie Mellon College she was a stewardess for American Airlines for five years where she met and married Lenard Klasmeier, American's chief pilot. They had two daughters, Carol and Janice. After leaving the Airlines she taught school in Valley Stream, New York for 21 years. Lenard died in 1997. Later, Jane reunited with her high school sweetheart, Ken Ross of Grove City, Ohio. Ken had lost his wife Helen in 1999. They had one daughter, Joy. Ken and Jane were married on May 7, 2002 and moved to Englewood, Florida where they remained till Jane's death. Friends may visit Thursday, March 21, 2013 from 5-8 p.m. at THE SPENCE-MILLER FUNERAL HOME, 2697 Columbus Street, Grove City, where funeral will be held 10 a.m. Friday. Interment Grove City Cemetery. Funeral Home, 2697 Columbus Street, Grove City, Ohio.
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Attractions open at 7:00pm
Park closes about an hour after the box office closes.
$25-$44 --Prices vary by date and options. See our website for more information.
We accept cash, debit and credit cards on-site
For Groups of 15 or more, please contact our Sales Team:
414-224-9283 or email email@example.com for special group pricing.
The Rock Sports Complex
7900 Crystal Ridge Rd
Franklin WI 53132
42.920120 / -88.015300
October 9
Join APA for our 2nd annual Trunk or Treat! This is a FREE, safe trick or treat event that is open to the community. Local businesses will be hosting the trunks. Friday, October 2 - Oak Creek location Friday, October 9 - Franklin location *both events are from 5-7pm Come ...
October 30 - October 31
You feel a shiver down your spine as your ghoulish guide approaches. He leads your group toward the cabin in the woods. What happened in that cabin? There are hints along the pathway and as you move forward, you are certain someone is watching, following, stalking you. If you survive ...
October 2 - October 31
FEATURED 8mi
Rated #1 in Milwaukee, we are Wisconsin's only TRULY haunted house and are in the 2nd story of a building built in the late 1800's in Milwaukee's Historic District. Come experience what a REAL Haunted House is. You'll be blown away by the detailed sets and actors coming from all ...


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Tiger Woods
Tiger Woods News
News on Tiger Woods continually updated from thousands of sources around the net.
Waste Management Open raised record $9 million for Arizona charities
22 hrs ago | The Arizona Republic | Comment?
International issue: How to make peanut butter and jelly
Thursday | The New Zealand Herald | Comment?
MomentumIS Everybody Happy?
Thursday | American Reporter | Comment?
Tiger Woods likely done as contender in golf majors, Nick Faldo says
Wednesday | Sporting News | Comment?
Lee Westwood looking up
Wednesday Oct 7 | Sky Sports | Comment?
Nicklaus says Spieth versus Day 'may happen'
Tuesday Oct 6 | The Peninsula | Comment?
American Terrorism: Plain and Simple
terrorism 1,266
Iran Nuclear Agreement: Black Mark or Gold Star for Obama?
policy 1,547
What 41 Female Celebs REALLY Weigh
Thailand's Janewattananond signs with ISM group
Tuesday Oct 6 | Golfweek | Comment?
Tiger Woods to attend, but not play Bridgestone America's Golf Cup
Tuesday Oct 6 | Golfweek | Comment?
Karma wins again: Steelers kicker Josh Scobee mocks Tiger Woods and no
Monday Oct 5 | Golf World | Comment?
Man stands on a boulder wedged 3,245 feet above a fjord and bounces a ball on a wedge
Monday Oct 5 | Golf World | Comment?
Bryson DeChambeau weighing decision to leave SMU men's golf team
Monday Oct 5 | Golfweek | Comment?
EditorialJOIN the Boycott Against Tiger Woods' Ex-Sponsors
Sunday Oct 4 | American Reporter | Comment?
2015 Was One of the Greatest Years the Pga Tour Has Ever Seen
Sunday Oct 4 | Pro Golf Now | Comment?
Men's Golf Set to Play in Fossum MemorialThe UC men's golf team plays ...
Saturday Oct 3 | Cincinnati Bearcats | Comment?
Tristan Thompson rejects Cavs' offer
Friday Oct 2 | SFGate | Comment?
Did Justin Thomas get robbed for the PGA Tour Rookie of the Year Award?
Friday Oct 2 | Golf World | Comment?
Jordan Spieth wins PGA Tour player of the year
Friday Oct 2 | WZVN-TV Fort Myers | Comment?
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Usher and Nicki Minaj Team Up for 'She Came to Give It to You'
While Usher chose to get seductive on 'Good Kisser,' he goes for the fun and flirty approach with his new song, 'She Came to Give It to You.'
While Usher chose to get seductive on 'Good Kisser,' he goes for the fun and flirty approach with his new song, 'She Came to Give It to You.'
Chris Brown is just weeks out of jail, and already he is diving headfirst back into the music -- first, with his killer performance of 'Loyal' last night at the 2014 BET Awards, and now, with his new song 'New Flame,' featuring Usher and Rick Ross.
Usher's upcoming album is definitely anticipated. The 2014 BET Awards reminded viewers of that very fact. The singer has a pretty good track record when it comes to hits.
Chris Brown offers a preview of his new song, 'New Flame' featuring Usher and Rick Ross.
Usher has released a statement in regards to Justin Bieber's recently leaked videos showing a young Justin using racist language. The R&B star defends Bieber and labels him "not a racist."
Usher has opened up about mentoring Justin Bieber amidst his many troubles in the new issue of NYLON Guys magazine.
Usher performs a sexy rendition of his latest single, 'Good Kisser,' on 'The Voice.'
Chart-topping superstars Usher, Kendrick Lamar, Ariana Grande and others rocked the stage at the 2014 iHeart Music Awards in Los Angeles on Thursday (May 1).
A new Michael Jackson song, titled 'Love Never Felt So Good,' made its debut last night (May 1) and the King of Pop got a little help his modern contemporaries. Usher danced along to the song as a snippet was played at the iHeartRadio Music Awards. Meanwhile, the track was officially released to iTunes late last night, with Justin Timberlake lending his voice to help modernize the archived MJ song.


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John F. Lyons Sr.November 14,2013John F. Lyons Sr.
BENNINGTON John F. Lyons Sr., 84, died Tuesday, Nov. 12, 2013, at his residence.
Funeral arrangements are pending at the Mahar and Son Funeral Home in Bennington.
A complete obituary will be published in a future edition of the Rutland Herald.MORE IN Obituaries
Myrtle A. Greene
WELLS — Myrtle A. Greene, 99, died Oct. Full Story
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SOUTH LONDONDERRY, VT — Marvin W. Full Story
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WYE MOUNTAIN, Ark. Full Story
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Osphena is produced in the USA and has its own website that offers no other products, except this one. The manufacturer is badly-known and not really trustworthy. Osphena is a prescription oral pill that purposes to treat painful intercourse, a phenomenon which results from changes in the female vagina due to menopause... read more
Male decreased libido can affect a man in more ways than one. It is a known fact that men who suffer from a low sex drive also have some serious health issues. While initially most physicians diagnosed this problem to be a completely psychological one, today the opinion is very different... read more
Contemporary women live very busy lives. They make careers, bring up children, spend time with their husbands, do the housework, take care of their aging parents, and much more. All this leaves little time for taking care of themselves, proper nutrition and rest... read more
Are you looking to enhance your sex life? If so, you may want to consider eating foods for sexual enhancement. By eating certain foods, you may see an increase in your sexual drive and ability to become and remain aroused during sexual activity... read more
A libido booster works very well for those who find their desire to have sex dwindling rather rapidly. While it is normal to not want sex all the time, those who find that they seem to be shying away from sex a little too often, need to get their libido levels checked... read more
Most women face menopause at the age of 51, however, the exact time when this phenomenon takes place varies significantly from person to person, just as the intensity of menopausal symptoms does... read more
Perhaps the biggest myth about menopause is that it's the beginning of the end. That may have been true in the sixth century, when the average age of menopause coincided with or often surpassed life expectancy, but today women are living longer and healthier lives than ever before... read more


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Numerical Aspects of the Implementation of Artificial Boundary Conditions for Laminar Fluid-Structure Interactions
C. Boeckle[1], P. Wittwer[1]
[1]University of Geneva, Geneva, Switzerland
We discuss the implementation of artificial boundary conditions for stationary Navier-Stokes flows past bodies in the half-plane, for a range of low Reynolds numbers. When truncating the half-plane to a finite domain for numerical purposes, artificial boundaries appear. We present an explicit Dirichlet condition for the velocity at these boundaries in terms of an asymptotic expansion for the ...
Electromagnetic Field Computations for Saturated Porous Media
S. Cambon[1], I. Bogdanov[1]
[1]CHLOE, Bâtiment UFR Sciences et Techniques, Pau Cedex, France
Non-conventional hydrocarbon resources become more and more challenging object for energy producing companies throughout the world. Being already known and long-explored method, the electromagnetically (EM) assisted recovery constitutes a promising idea of technology for deposits of such a kind. COMSOL has been used recently for modeling the thermal multiphase flow through porous media in the ...
Can Oscillatory Convection Accelerate Signal Propagation in Simple Epithelium?
M. Nebyla[1], M. Pribyl[1]
[1]Institute of Chemical Technology, Prague, Department of Chemical Engineering, Prague, Czech Republic
We introduce a mathematical model of signal transmission in simple epithelial layers. The mathematical model consists of reaction-transport equations for extracellular ligands, cellular receptors, ligand-receptor complexes and a ligand releasing protease. We consider diffusion and nonstationary convective transport of protein ligands in the extracellular space. The study was carried out using ...
Development of Magnetic Field Components for the Polarisation Option of the Neutron Spectrometer FOCUS
L. Holitzner[1], U. Filges[1], J.P. Embs[2], T. Fennell[2], T. Panzner[1]
[1]Laboratory for Developments and Methods, Paul Scherrer Institut, Villigen, Switzerland
[3]Laboratory for Neutron Scattering, Paul Scherrer Institut, Villigen, Switzerland
We show a new, favourable space-saving method to host a neutron polarizer in the iron-containing monochromator shielding of a time-of-flight spectrometer for cold neutrons. In this poster you can learn e.g., how to create a robust, homogeneous, rectangular magnetic field (here realized by permanent magnet queues inside an iron tube). The time-of-flight spectrometer FOCUS at the spallation ...
Quantitative Analysis Design of MEMS Based Micropreconcentrator for Cancer Diagnosis
Sang-Seok LEE[1]
[1] Tottori University, Tottori, Tottori, Japan
We have proposed a high performance MEMS based microstructure array of micropreconcentrator (microPC) for breath diagnosis of cancer biomarkers. Our microPC has been designed based on quantitative analysis results, which gives explicit evaluation criteria for determination of microstructure array performance. We will present the quantitative analysis results performed by COMSOL Multiphysics ...
Determining Degradation in Solid Oxide Fuel Cells Electrode Materials Using COMSOL Multiphyics® Software - new
G. Cui[1], Z. Chen[1], F. Tariq[1], V. Yufit[1], N. Brandon[1]
[1]Imperial College London, London, UK
Solid Oxide Fuel Cells (SOFCs) are one of the most attractive technologies for meeting our future energy demands. They promise the efficient conversion of chemical to electrical energy and are a growing area of both academic and industrial interests. Typical electrode-supported SOFCs consist of three key components, two porous functional electrode layers (anode and cathode) and one dense ...
Sensitivity Analysis for High Temperature Proton Exchange Membrane Fuel Cell - new
A. Lele[1], N. Lodha[1], R. Srivastava[1], U. Bipinlal[1], A. Pandey[2], A. Paul[3]
[1]CSIR - National Chemical Laboratory, Pune, Maharashtra, India
[2]Reliance Industries Ltd., Reliance Technology Group, Navi Mumbai, Maharashtra, India
[3]CSIR - Central Electrochemical Research Institute, Chennai, Tamil Nadu, India
A Proton Exchange Membrane Fuel Cell (PEMFC) is an electrochemical device, which converts a part of heat from the formation of water into electricity. Each cell has a Membrane-Electrode Assembly (MEA) which is placed between two electrically conducting plates having gas flow channels. An MEA is made of a solid proton-conducting electrolyte sandwiched between two electrodes (anode and cathode). ...
Variation of the Frost Boundary below Road and Railway Embankments in Permafrost Regions in Response to Solar Irradiation and Winds
N.I. Kömle[1] and W. Feng[2]
[1]Space Research Institute, Austrian Academy of Sciences, Graz, Austria
[2]State Key Laboratory of Frozen Soil Engineering, Cold and Arid Regions Environmental and Engineering Research Institute, Lanzhou, China
We present COMSOL solutions for a coupled gas flow and heat transfer problem, which occurs particularly when traffic pathways are constructed in high altitude and arctic regions, where the underground is frozen soil. To avoid melting of the frozen ground (which usually leads to mechanical instability) one has to find suitable measures to keep the subsurface soil and the embankment suitably cool. ...
Modeling of Drying of Cellular Ceramic Structures: Coupled Electromagnetic and Multiphase Porous Media Model
A. Dhall[1], G. Peng[2], G. Squier[2], M. Geremew[3], L. Bogaczyk[2], J. George[3], W.A. Wood[3], and A.K. Datta[1]
[1]Biological and Environmental Engineering, Cornell University, Ithaca, New York, USA
[2]Manufacturing Technology & Engineering, Corning Inc., Sullivan Park, Corning, New York, USA
[3]Corporate Research, Corning Inc., Sullivan Park, Corning, New York, USA
Cellular ceramic substrates are extensively used for pollution control systems in vehicles. The manufacturing process of them can involve microwave drying. In this study, we describe the development of a modeling framework for the microwave drying process of these substrates. The transport model is implemented in COMSOL 3.5a using 4 PDEs: 1) Convection-Conduction for temperature, 2) Convection ...
Control of Rolling Direction for Released Strained Wrinkled Nanomembrane
P. Cendula[1], S. Kiravittaya[1], J. Gabel[1], and O.G. Schmidt[1]
[1]Institute for Integrative Nanosciences, Dresden, Germany
Strained wrinkled and flat nanomembranes have different bending properties when they are released from the underlying substrate. This is caused by increased bending rigidity of the wrinkled film in one direction. We provide theoretical and numerical analysis of the directional rolling of wrinkled films, which is important for positioning rolled-up tubes on the short mesa edge during fabrication.


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United States & Canada Customers: Call 1-800-813-6897
Available 24 hours a day, 7 days a week.
International Customers: Call 1-512-837-4810
Available 24 hours a day, 7 days a week. English language only.
The unique Cutter & Buck Men's Big & Tall Cocona CB DryTec Luxe Shorts feature an attractive textured herringbone pattern. But more importantly, they are created from proprietary Cocona technology, so they wick away moisture and create evaporative cooling so you stay drier, cooler, and more comfortable all day.
Additional features:
Online Shipping Information
Golfsmith.com offers simple, flat-rate shipping to destinations in the continguous U.S. via FedEx.
Our policy is to strive for the best possible combination of price and service for your shipment.
In order to better serve our guests, we will occassionally offer discounted shipping promotions. Any shipping discounts will be applied in your shopping cart.
"Overnight" shipments will arrive the next business day (excluding weekends and holidays) after departing Golfsmith. "2-Day Air" shipments arrive in two business days after departing Golfsmith. On-time delivery for both methods is guaranteed by FedEx. Shipping delays may occur during busy Holidays or in the spring -- we will do our best to accommodate last minute and expedited orders placed during these times.
Most orders are shipped within 48 hours of online placement. Orders must be placed by 9am (CST) Monday-Friday in order to be eligible for that day's "Overnight" or "2-Day Air" shipments. Orders for residential delivery placed on Sunday or Monday will not be shipped until Tuesday and orders for business delivery placed on weekends will not ship until Monday, so please take this into consideration when specifying expedited shipping requests.
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Men's Big & Tall Gabardine Microfiber Shorts
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Men's Big & Tall Gabardine Microfiber Shorts$84.99
Pro V1 Logo Overrun Golf Balls$35.99
Men's Golflayer Longsleeve T-Shirt$39.99
Men's HyperFlex Golf Shoes - White/Grey/Blue (FJ#51022)$159.99
Men's ClimaChill 3-Stripes Deboss Short Sleeve Polo


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Methane is a potent greenhouse gas that, pound for pound, traps more than 80 times as much heat on our planet than carbon dioxide does. It is leaked or intentionally vented and flared by the oil and gas industry with virtually no oversight. If this rogue practice is not addressed, it stands to derail our efforts to mitigate climate change.
Recently, EPA introduced the first-ever methane pollution standards for new and modified oil and gas facilities. This landmark proposal will blunt the growth of methane and smog-forming pollution produced by the industry. The new standards, when finalized, will help to safeguard public health and put the United States closer to meeting the Administration's goal of reducing oil and gas methane emissions by 40 to 45 percent by 2025. Take action today to support these standards.


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After a World Cup light rail project forced them to relocate, residents continue to fight for fair compensation and housing.
The Koch brothers and utility giants are bankrolling a ballot initiative to block the development of home solar, protecting the utilities' continuing oligopoly on energy generation.
Julie R Butler grew up near Littleton, Colorado, gained a BA in philosophy values and social policy from the University of Colorado at Boulder, and went on to live a nomadic lifestyle of travel throughout North and Central America. She now lives with her husband in South America, where she is working as a writer and editor. Her blog, Connectively Speaking, is an expansive exploration of the progressive philosophy of connectivity.


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The Honors College Family Weekend Open House
October 3, 2015
James C. Kirkpatrick Library, Suite 1450
10:00 a.m. – 11:30 a.m.
Light refreshments will be served
Join us at The Honors College Open House as UCM hosts UCM students' family members for a weekend of events.
Developing an Honors Project
October 5, 2015
Wood 105
3:30 p.m. - 4:00 p.m., Browse completed projects
4:00 p.m. - 5:00 p.m., Discussion
An array of completed honors projects will be on display and honors students can learn more about this exciting part of their educational experience.
Honors Early Enrollment
October 19, 2015
Honors College members should remove any holds on their accounts and plan to meet with their college academic advisor a few weeks before this date so they are ready to enroll for Spring 2016 classes.
Homecoming 2015
October 24, 2015
Mulitpurpose Building Parking Lot
Parade Begins at 9:00 a.m.
Participate in the festivities of the week and join Dean Lewandowski with your fellow honors students in the parade.
The Honors College Lecture Series
October 28, 2015
James C. Kirkpatrick Library, Performance Corner
3:00 p.m. – 4:00 p.m.
Event is free and open to the public
Light refreshments will be served
Join us for Honors College Faculty Fellow, Dr. Ashley Wellman's presentation on victim advocacy.
Mackenzie Harding Gains Business Experience in the Netherlands
Mackenzie Harding, a junior in The Honors College, gained a worldly perspective through a study abroad program supported by the UCM Foundation Honors College Fund and The Honors College Study Abroad Travel Grant. ... More »
A Prudent College Path
The value of an Honors College education was recently highlighted in the New York Times. ... More »
Dr. Ashley Wellman, 2015-2016 Honors College Faculty Fellow, Partners with Five Victim Advocacy Agencies
Honors College Faculty Fellow, Dr. Ashley Wellman, created partnerships with five victim advocacy agencies as part of her "Victim Advocacy" Honors Colloquim class. ... More »
Shayne Fisk and Miranda Maher Prepare for Global Vision 2015 Summer Experience
The two-week experience allows students to experience the culture of another country. ... More »
UCM on Target to Meet Study Abroad Goals by 2019
University of Central Missouri has reached the half-way mark toward its Generation to Study Abroad goal. ... More »
Alix Calon and Tyler Carpenter are Learning to a Greater Degree
Alix Calon and Tyler Carpenter are profiled on UCM's Feature Stories under the heading, "Students Create Tactile 3D Map of Campus for Blind Student". ... More »
Fulbright Competition Nominees
Kaitlin Becker and Tera Swearngin receive an endorsement from UCM for the Fulbright Competition. ... More »
The Honors College 2015-2016 T-shirt Design Winner
The winner of the 2015 Honors College T-shirt design competition is Alix Calon, a junior Design & Drafting Technology major and Honors College student at UCM. ... More »
Dr. Katie Jacobs, 2014-2015 Honors College Faculty Fellow, Named Faculty Mentor of the Year
Honors College Faculty Fellow, Dr. Katie Jacobs, is the 2015 recipient of the Undergraduate Research and Creative Project Faculty Mentor Award. ... More »
Dr. Katie Jacobs, 2014-2015 Honors College Faculty Fellow, Cultivates Learning to a Greater Degree
Honors College Faculty Fellow, Dr. Katie Jacobs, is profiled on UCM's Feature Stories under the heading, "Course Challenges Student Perspectives, Empowers Those in Need". ... More »
Jennifer Carson Receives Learning to a Greater Degree Award
Our Coordinator of Undergraduate Research and External Scholarships, Dr. Jennifer Carson, is profiled on UCM's Feature Stories under the heading, "Jennifer Carson Receives Learning to a Greater Degree Award for Commitment to Criminal Justice, The Honors College". ... More »
UCM Endorses Two for Truman Scholarship
Congratulations to April Roller and David Rogers on receiving the UCM endorsement for the Truman Scholarship.
UCM Criminal Justice Team Claims 13th Regional Championship
Honors students; MacKenzie Carreon, Ryan Kanoy, Tyler O'Neal, and Stacia Pottorff contribute to the CJ Team's success. ... More »
Alex Fleischman wins a Silver Award in the Fifth Annual State Farm® Marketing and Sales Competition
Alex Fleischman, a senior in The Honors College, earned honors in the fifth annual State Farm® Marketing and Sales Competition at UCM. ... More »
Nicole Valenzuela Participates in Global Vision Experience Panel
Nicole Valenzuela, a senior in The Honors College, shares her experiences in India as one of four participants in UCM's Global Vision Service Learning Program during the summer of 2014. ... More »
Lucas Woodling is Learning to a Greater Degree
Lucas Woodling, a sophomore in The Honors College, is profiled on UCM's Feature Stories under the heading, "Future English as a Second Language Teacher Gains Worldly Perspective". ... More »
Ashley Garrard Cultivated a Worldly Perspective Through High Impact Study Abroad Programming
Ashley Garrard, a sophomore in The Honors College, is profiled in the second edition of the Hanze Summer School newsletter under the heading, "Ashley Garrard, DBIE student from the University of Central Missouri, USA". ... More »
Elizabeth Wood Named Student Member of UCM Board of Governors
Missouri Gov. Jay Nixon has announced the appointment of Elizabeth Wood, Adrian, as a student representative of the University of Central Missouri Board of Governors for a term ending Dec. 31, 2016. .... More »


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The latest Intel® Core™ processors deliver maximized performance and stunning visuals
Why choose? Get the best of both worlds with a razor-thin laptop and ultra-fast tablet in one. Easily switch back and forth from productive tasks to immersive entertainment in a flash.
With Intel smartphones you'll experience fast web browsing, super-responsive apps, and effortless multi-tasking. Your smartphone will keep up with your every move, and you'll have the remarkable pictures and HD-quality video to show your friends and family.
With a touch-screen interface and a portable size, the tablet combines entertainment, social networking, and productivity in one neat package. It's personal. It's flexible. You'll take your tablet around the house, around town, or even to the office because it connects the way you live, play, and work.
Enjoy a sleek, clutter free design with full touch capabilities combined with style and high performance. Whether you're watching HD videos, playing interactive games, or editing and sharing photos, experience the smooth, seamless, and robust features comprising the All-in-One PC.
Features support visual communication, gaming, home video, interactive learning, and meal planning.
Intel meets a family's multiple performance needs with a portable All-in-One desktop solution.
Intel delivers speed, an HD web cam, touch screen, and more with an All-in-One desktop PC solution.
See a preview of Disney's Tomorrowland and learn about the benefits of a portable Lenovo All-in-One.


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Select Local Merchants
Angels FeetRead MoreIf a name like Angels Feet wasn't enough to let a customer know this business's focus, one step inside would do the trick. Long rows of cushy massage chairs draped in clean linens line the long studio, each paired with a matching ottoman just waiting to cradle a foot or two. Therapists lead each newly arrived customer to one of these chairs, where they welcome feet to soak in a salt-water solution as they massage the guest's scalp, neck, shoulders, and arms. After a dousing of lotion, the therapist begins the foot-reflexology massage, which seeks to quell stress and ease pain by targeting areas of the feet believed to correspond to organs in the body. Finally, they wrap feet in steamed towels and give ankles and legs an invigorating stretch. When the session concludes, customers refresh themselves and help purge toxins from their systems with a cold beverage and a nap on a giant magnet.1048 W. Golf Rd.Hoffman Estates, IL US
Asha Salon & Spa - Multiple LocationsRead MoreAt Asha SalonSpa, aestheticians and massage therapists combine forces to ensure the whole-body well-being of clients. Spa services such as facials, microdermabrasions, and prenatal care coddle the corpus from head to toe, beginning with a neck pillow and cup of tea. At the salon, makeup and nail services revitalize faces and fingers, and hair treatments such as cuts and color rely on Aveda's natural line of products. Asha also offers several massages, including deep-tissue, couples, and chakra-balancing modalities, allowing patrons to unwind without setting off their clockwork motors.601 N Martingale Rd.Schaumburg, IL US
Hand & Stone - ChicagoRead MoreAs a physical therapist with his own private practice, Hand & Stone founder and chief operating officer John Marco made sure that he kept abreast of the rapidly growing health and wellness industry. After a period of careful research and planning, John decided to create a spa based around convenience and affordability—Hand & Stone Massage and Facial Spa. Since its launch, Hand & Stone has expanded to more than 20 states and four planets. The spa's core concept is to offer massage, facial, and hair-removal services performed by licensed, certified, or registered professionals and offered at convenient times, seven days a week. Each location adheres to a traditional spa aesthetic with soft lighting, heated treatment tables, and plush linens.1215 Golf Rd.Rolling Meadows, IL US
The Pink Nail SpaRead MoreFlower murals and rose-colored walls draw guests into The Pink Nail & Spa like honeybees into a garden; cushy leather seats await them, as inviting as lush flowers. Guests plop comfortably into the chairs during manicures, pedicures, and waxing services. Creative Spa manicures and pedicures condition skin with elixirs infused with citrus oils, antioxidants, and vitamin E. Nail technicians also pamper the hands and feet with relaxing soaks and moisturizing treatments. During regular spa mani-pedis, the techs knead palms and soles and slough off expired skin with gentle exfoliation tools. Clients can also opt to pamper their whole bodies with more than a half-dozen types of massage therapy, including Swedish and deep-tissue treatments that melt pain, tension, and subcutaneous cheddar wheels.1014 West Rand RoadArlington Heights, IL US
Spa VargasRead MoreThe staff at Spa Vargas Wellness pampers bodies and minds with luxurious spa services that deploy the spa's own line of naturally sourced products. Moving to their new location, the team at the Pheasant Run Resort outfits clients with cozy robes and slippers before inviting them to relax in an aromatherapy waiting room, which is more fragrant than a dessert buffet at Strawberry Shortcake's house. Nimble hands can exfoliate skin with a sea-salt or mud scrub, and the spacious Moroccan-style Vichy shower rejuvenates skin during hydrotherapy treatments. The calm-inducing crew passes on kneading know-how to up-and-coming massage therapists and play-doh sculptors at Spa Vargas University.250 West Schick RoadBloomingdale, IL US
Avalon Salon & Day SpaRead MoreFrom skin treatments to massages, Deer Park's Avalon Salon and Day Spa is a luxury day spa that offers a wide variety of services. Cleanse, exfoliate and moisturize your skin with a variety of skin care treatments, such as a body wrap, microdermabrasion, and a steam bath. Increase mobility and improve posture with a full body massage from this spa. The alternative services offered at this spa are one-of-a-kind and extremely beneficial. Spice up your toenails and fingernails with a specialized nail treatment. For on-trend and creative hair care services, head on over to this spa. This spa prefers to take care of its clients by appointment only. Call to set up one today. The prices may be on the higher end, but your spa experience will be off the charts. Avalon Salon and Day Spa is more than willing to accept your major credit card as a form of payment for your beauty services. Drivers can take advantage of the parking lot near Avalon Salon and Day Spa and save time on hunting for a parking spot. If you need to work out some kinks in your body, give Avalon Salon and Day Spa a call and schedule an appointment.20530 North Rand RoadDeer Park, IL US


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Get the latest reviews and recommendations from our team of noted local art, theater and film critics.Watch online →
Classical WETA 90.9 FM showcases notable new (or newly reissued) CDs each week. Hear selections from the CD on-air throughout the week, and check online to learn more about the artist and the music.Learn more →
This WETA TV 26 production explores the history, mission and daily operations of Arlington National Cemetery, the final resting place for more than 400,000 Americans. This revered place honors the dead and brings great meaning to the living.Watch now →
Surprises await Thomas and his friends as they dig up their most daring adventure yet!When to watch on WETA Kids →
Luis Araya immigrated to Arlington, Virginia from Bolivia in 1966, when very few Latinos lived in the county. He reflects on the changes he has seen over the years and the influence of Latinos in Arlington today.Watch now →
WETA's mission is to produce and broadcast programs of intellectual integrity and cultural merit that recognize viewers' and listeners' intelligence, curiosity and interest in the world around them.Learn more →