Aggregate pigment products made of low-refractive-index raw materials, in which pigmentary, subpigmentary and nonpigmentary components are cemented intrinsically with the aid of in-situ synthesized complex microgels.

1. Field of the Invention
This invention relates to novel aggregate pigment products comprising low-refractive-index pigmentary materials.
More specifically, this invention relates to aggregate pigment products in which particles of single and multiple pigmentary species and other subpigmentary and nonpigmentary components are coflocculated and cemented intrinsically with the aid of in-situ synthesized complex (multicomponent) functional microgels.
2. Discussion of the Relevant Art
White pigments encompass a class of particulate materials which are essentially colorless, insoluble, nontoxic, reasonably nonabrasive, and have dimensions favoring a diffuse reflection, or scattering, of light constituting the visible portion of the electromagnetic spectrum with wavelengths ranging from 420 nm for violet to 660 nm for red.
In accordance with the laws of physical optics, maximum scattering of light occurs when a propagating light wave encounters in its path an obstacle, a pigment particle as the case in point, whose dimensions are equal to one-half of the length of the impinging wave. At equal particle dimensions, pigmentary materials with higher refractive indexes, whose values range from 1.41 for silica to 2.73 for rutile, scatter the light more efficiently than those with lower ones.
The most elementary physical model of light scattering may be considered one in which monochromatic light is diffracted by a single spherical particle. Maximum diffraction of the blue, green and red portions of the light spectrum (additive primary components of light) by spherical particles is obtained when the latter have diameters of about 150 nm, 200 nm and 250 nm, respectively. By integrating the comprehensive spectral response of a single spherical particle scattering polychromatic light, mapped as a function of particle diameter, one can calculate that the maximum light scattering occurs with a particle having a diameter of about 200 nm.
A universally useful physical model of light scattering by pigments must, understandably, be applicable both to any arbitrary pigment shape (virtually all inorganic pigments, other than TiO.sub.2, are nonspherical) as well as to integral end-use formations containing these pigments, such as paper-coating and paint films, filled paper or pigmented plastics. Let us consider, for example, a single, highly anisometric particle of kaolin clay in the form of a hexagonal platelet. The light waves of different lengths impinging upon such a multifaceted platelet are scattered with different intensities depending on how closely the dimensions of a particular facet of this platelet approximate one-half of the length of the impinging light wave. Among the multitude of geometrical facets by which the impinging light may be scattered are, for example, platelet faces (in the x,y plane) or edges and protrusions from platelet surfaces (in z direction). Moreover, the impinging light waves are scattered independently by each of the six triangular tips of the hexagonal platelet, the shorter waves being scattered more efficiently closer to the tips, across shorter distances, while the longer waves are being scattered more efficiently farther from the tips, across longer distances.
The ability to scatter light is a universal property both of particulate and extensive matter. Hence, even an "infinitely" large, most precisely polished mirror also scatters light, though only to a very negligible extent. In general, all light waves, regardless of length, will scatter with different intensities across all physical obstacles encountered in their path, such as individual particles or parts of aggregated matter, grain boundaries, or sites of localized stress concentrations giving rise to elasto-optical effects.
As far as white pigments are concerned, it should be emphasized that the latter represent a pragmatic class of particulate materials, useful in the trade, whose features are defined by a convention. In the very minimum, pigments must consist to a predominant extent of particles whose dimensions uniquely favor the scattering of light, not so much with regard to the performance of individual particles but primarily with regard to the performance of the resultant end-use formations containing these particles. The latter requirement necessitates that pigments additionally possess certain specific features and performance properties, whose scope is not fixed, however, but expands in keeping pace with the scientific and technological advancements in the field of pigments.
Whether a solid particle can be classified as pigmentary depends not only upon raw physical dimensions but also upon the particle's morphology. Hence, monolithic, spherical, virtually perfectly isometric, single-faceted particles of TiO.sub.2, or organic pigments, cease to be pigmentary for all practical purposes when their particle diameters exceed about 1 .mu.m. Overall, the spherical shape is disadvantageous for pigment particles in geometric bodies scatter the light more selectively, hence, less efficiently, than analogous anisometric particles of an equivalent mass. Furthermore, spheres have an inherent tendency to form closely packed structures characterized by a low void volume and poor light-scattering efficacy. A closely packed ensemble of monodisperse spheres has a maximum void volume of only about 26% which, for polydisperse spheres, can fall below 15%, or even 10%.
Multifaceted pigment particles, such as inherently aggregated clusters of elementary, ultrafine (subpigmentary) particles of precipitated silica or metal silicates, on the other hand, can be as large as 10 .mu.m, or even 20 .mu.m, e.s.d. (equivalent spherical diameter) and still be pigment worthy. Regardless of morphological features, however, all ultrafine particulate materials with dimensions finer than 0.1 .mu.m e.s.d. are not pigment worthy, being classified as "subpigmentary." It should be pointed out, though, that inherently fine-particle-size pigment products, such as titanium dioxide or high-glossing kaolin clay, may contain a substantial proportion of subpigmentary particles.
White pigments traditionally have been divided in the art into "primary," having a refractive index of about 2.0 or higher, and "secondary," with a refractive index ranging from approximately 1.4 to 1.65. Following the example of lithopone, introduced on the market around 1875, interspacing of particles of high-refractive-index primary pigments with particles of low-refractive-index secondary ones has become a standing practice in the paper and paint industries. As the first composite pigment ever, obtained by coprecipitating birefringent zinc sulfide (refractive indexes of 2.356 and 2.378), used in proportion of from 30 to 60%, by weight, with barium sulfate (refractive index 1.64), lithopone represents a classical case of a virtually perfect interspacing ("extension") of a primary pigment with a secondary one.
As titanium dioxide (TiO.sub.2) was introduced on the market in 1919, rapidly becoming the dominant high-refractive-index white pigment on the market, it became instantly clear that the most economical performance is obtained when TiO.sub.2 is used in blends with less expensive, low-refractive-index co-pigments. It was also recognized, however, that a great deal of detrimental selective fractionation and flocculation occurs in practical applications involving the use of such loose pigment blends. Various composite pigments were thus developed in which the primary pigments, e.g., titanium dioxide or zinc sulfide (ZnS), were first intimately blended with, and subsequently affixed to, secondary pigments (extenders) to achieve a permanent immobilization of both particulate species relative to each other.
It should be emphasized that the aggregation, as such, was never considered as a goal in itself in making composite pigment products from extraneous primary and secondary pigments as the raw materials. Instead, the primary goal has been to permanently immobilize the particles of primary pigments and extenders relative to each other to prevent a detrimental separation (fractionation) of the pigmentary components according to species and size in the subsequent end-use applications. The second attempted goal was to obtain an optimum spacing between the immobilized TiO.sub.2 particles equal to about one half of an "average" light wavelength with the aid of commercial extender pigments. As is now well understood in the trade, however, the above doctrine was a misconception, the dimensional considerations clearly revealing that a true interspacing of TiO.sub.2 particles with the incomparably coarser particles of the commercial extender pigments is physically impossible.
As is now also well known in the art, a great deal of detrimental (uncontrolled) aggregation of pigment particles, particularly TiO.sub.2, was unavoidable during the synthesis of the prior-art composite pigments under discussion. Since the prevailing doctrines in the art postulate that all TiO.sub.2 particles must be separated from each other by an optimal distance to obtain the highest possible optical-performance efficacy, an aggregation of TiO.sub.2 particles being tantamount to a technological anathema, it is not surprising that the inventors of TiO.sub.2 -based composite pigments have refrained from even mentioning, by name, the aggregation of pigmentary components in all respective patent descriptions known to the applicant.
While the concept of a mutual interspacing of particles of primary and secondary pigments has at least a nominal justification based on the consideration of the well-known laws of physical optics, a purposeful aggregation of low-refractive-index pigments by themselves had never been contemplated in the prior art, to the best of the applicant's knowledge, until after the phenomenon of beneficial in-situ aggregation of pigment fines, discovered by the applicant, was published in 1970. As a matter of fact, the iron-clad doctrine in the pigment science and technology of the prior art has always been that pigments must be optimally deaggregated and dispersed to yield the best optical and other performances.
According to the above-mentioned publication appearing in the Journal of the Technical Association of the Pulp and Paper Industry (TAPPI), Vol. 53, No. 11, November 1970, Pages 2077-2084 ("Performance of Some Commercial Clays in Starch-Containing Paper-Coating Films; Part I. Black Glass Plates as Model Substrates"), preceded by a presentation at the TAPPI Coating Conference held in Houston, Tex., May 3-4, 1970, the light-scattering properties of entire pigment populations can be improved by aggregating in situ pigment fines whose dimensions in a discrete state are too small for efficient light scattering. For example, the light-scattering performance at two different wavelengths (457 nm and 577 nm) for coating formulations prepared from three different clay products in films deposited on optically flat black glass plates as coating substrates was presented graphically as a function of the binder-volume fraction in FIGS. 6 and 7 of the above publication. The slopes of the curves representing the light-scattering coefficients of No. 1 and No. 2 clays as the function of the binder-volume content in the coating ascend initially with the increasing binder-volume fraction and, after reaching the maximum value at a binder-volume fraction corresponding to about 5 parts of starch per 100 parts of clay, by weight, descend as the binder-level is further increased.
This initial increase of light-scattering coefficients is explained in the above publication "...by an aggregation of clay fines effected by the initial addition of binder. The aggregates of ultrafine particles, which are understood here as assemblies of a very few such particles, should scatter the light more effectively than the individual components." The subsequent steady decline of the magnitude of the light-scattering coefficients is explained as follows: "An increase of the binder content of the coating systems beyond the F.sub.bv (binder volume fraction--explanation added by the applicant) value of 0.080 (5 parts starch per 100 parts clay, by weight) appears to cause a further growth of the assemblies of pigment particles, so that the optimum dimensions of the light-scattering sites are exceeded." With the relatively coarse mechanically delaminated clay having only minor proportions of particles smaller than 0.1-0.2 .mu.m, e.s.d., the light-scattering efficacy of the coatings declined from the very first incremental addition of the binder because of the scarcity of ultrafine particles amenable to a beneficial aggregation.
The relatively coarser intrinsic structure of the coating films containing the mechanically delaminated clay, compared to those containing No. 1 and No. 2 clays, was verified with the aid of a new empirical parameter, called "Rho" (after the Greek letter .rho.), defined in the above publication as the ratio of the numerical values of the light-scattering coefficients assessed at 577 nm and 457 nm for the same coating film. With coating films having a relatively fine intrinsic structure, such as binderless coatings or coatings with a low binder-volume fraction, the magnitudes of the corresponding "Rho" parameters are low. As the intrinsic coating structure becomes coarser, as was the case with all coatings discussed in the above publication in which the binder content was continuously increased, the magnitude of "Rho" increases accordingly. Below a certain specific binder-volume concentration (about 5-8%, by weight), the coarsening of the coating structure is beneficial; hence, an increasing Rho value is associated with the increase of the light-scattering coefficients. Above this specific binder-volume concentration, however, the coarsening in question becomes excessive, the increasing Rho value being associated with a decrease of the light-scattering coefficients.
As is evident from the above considerations, the light-scattering efficacy of both high- and low-refractive-index pigments can be significantly improved by a purposeful, in-situ aggregation of pigment fines. The publication by Kaliski (TAPPI Journal, Vol. 53, No. 11, November 1970, Pages 2077-2084) thus provided the scientific foundation for an entirely new pigment technology, opening the way to designing and manufacturing new lines of pigment products with an improved optical performance.
Indeed, the first patent pertaining to the manufacture of an aggregate pigment with improved optical properties, made of a single, low-refractive-index pigmentary raw material, namely, U.S. Pat. No. 4,075,030 ("High Bulking Clay Pigments and Methods for Making the Same"), was issued to Bundy et al. in 1978. According to this patent, a fine-particle-size kaolin clay, also containing 0.1-0.7% platy mica with a diameter below 100 .mu.m (passing through a 150-mesh screen) as an auxiliary material, was treated with ethylenediamine and citric acid and then flocculated with sulfuric acid. After filtration and rinsing, the resultant filter cake was dried at 65.degree. C. The improved optical performance of the resultant pigment product was explained speculatively in terms of incorporation of voids "...to form a high bulking clay." However, the contribution of the "voids" in question to the improved optical performance of the high-bulking pigment product under discussion was not documented by Bundy et al. with any experimental data.
As is readily understood by those skilled in the art, the colloid-chemical action of the above-mentioned reagents leads to the flocculation of the slurry of the clay raw material employed, resulting in the formation of essentially only two types of aggregates: the first type consists of clay fines alone, clustered together by themselves; the second type consists of discrete (individual) clay fines and/or small clusters of such fines attached to the coarser kaolin platelets. However, as is well known to those skilled in the art, the flocculating system employed by Bundy et al. is quite inefficient, necessitating that its action be enhanced with the aid of the coarse mica platelets. That platy mica particles, with diameters of up to 100 .mu.m, do indeed enhance the flocculation of the much finer clay pigment employed in U.S. Pat. No. 4,075,030 (96.4% finer than 2 .mu.m according to the Example I therein) shall be made clear from the considerations to follow.
The enhanced flocculation of small particles in the presence of coarser ones is well known in the art, being first described by V. D. Samygin et al. in the article titled "Mechanism of Mutual Flocculation of Particles Differing in Size" (translated from Kolloidnyi Zhurnal, Vol. 30, No. 4, pp. 581-586, July-August, 1968), dealing with flocculation phenomena in flotation processes. According to the above article, the rate of adhesion of fine particles to coarser ones may be higher by a factor of 10.sup.3 -10.sup.4 than the rate of cohesion between finer particles.
An analysis of the functional aspects of the above-mentioned "high bulking clay pigments" clearly points to the lack of a viable adhesive (cementing) mechanism capable of providing an adequate level of mechanical integrity to the individual pigment aggregates. As a consequence, the aggregates break down under high-shearing conditions encountered routinely during the makedown of pigment slurries or high-speed blade-coating, the enhanced optical-performance efficacy acquired through aggregation being strongly reduced. It is worth noting in the above context that, as documented amply by industrial experience, imparting an adequate mechanical integrity to the aggregate pigments while simultaneously generating in a controlled manner beneficial aggregate pigment structures has never been accomplished satisfactorily in the entire technology of the aggregate pigments of the prior art.
It should also be pointed out that the term "high bulking" is used incorrectly with the aggregate pigment disclosed in U.S. Pat. No. 4,075,030 as well as in other similar disclosures to be discussed hereinafter. Traditionally, the term "bulking" has been applied only to thixotropic pigments , e.g., satin white, which have shear-thinning properties. Hence, satin-white containing coating formulations applied to a web of paper with the aid of a doctor blade become very fluid in the high-shear zone under the blade but set immediately after emerging from that zone. As a consequence, the freshly applied coating films resist the shrinking (compaction) caused by the dewatering process and, at the same coating weight, are thicker (more bulky) than analogous films formed from non-thixotropic coating formulations. In terms of additional benefits, the thixotropic, rapidly setting coating films are mottle-free, the detrimental binder migration being more or less completely eliminated. The common feature of all true bulking (thixotropic) pigments is that their aqueous slurries gel readily and do not settle, or settle only partially, forming very soft, "bulky" sediments.
In contrast, the aqueous slurries of aggregate pigments of the prior art, including slurries of thermally aggregated (by sintering) calcined clays, do not gel, forming instead rock-hard sediments upon settling. Although the latter pigments do indeed provide some limited "bulking" action, they do so solely by virtue of flow hindrance induced by dilatancy rather than by thixotropic setting. Because of this dilatancy, the flow of freshly applied coating films containing the flow-hindering pigments is hampered momentarily so that a thermal setting, induced by drying, can take effect before a major disarrangement of the coating-film structure occurs. However, the latter pigments are not even nearly as effective in preventing the detrimental binder migration as the thixotropic bulking pigments.
Aggregate pigments virtually identical to those of Bundy et al., except for the cementing medium employed, were disclosed in WO 87/00544 to Jones et al. Called "structured kaolin pigments," with the emphasis being placed on structure rather than aggregation, the latter are manufactured in a "dry state" by saturating a fine-particle-size kaolin clay with metal chlorides, e.g., silicon tetrachloride, which are then hydrolyzed in situ and converted into cements bonding the pigment fines to each other and to the coarser clay platelets. The optical-performance efficacy of these pigments, made from fine-particle-size kaolin clay raw materials, is essentially identical to that of analogous pigments disclosed by Bundy et al. Although the mechanical integrity of the structured kaolin pigments made in accordance with WO 87/00544 is higher than that of the pigments disclosed by Bundy et al., the approach used by Jones et al. makes it inherently difficult to generate in situ sufficiently high levels of cement needed for a truly adequate mechanical strength of the resultant pigment aggregates.
As is understood by those skilled in the art, other approaches already employed in synthesizing TiO.sub.2 - or ZnS-containing composite pigments of the prior art are also applicable to synthesizing aggregate pigments made solely of low-refractive-index pigmentary raw materials. One such viable approach, for example, was disclosed in U.S. Pat. No. 2,176,876 to Alessandroni. In accordance with the latter, an anionically dispersed slurry of a low-refractive-index pigmentary raw material is flocculated with the aid of a cationic agent. Although not taken into consideration by Alessandroni, some beneficial in-situ aggregation of pigment fines present in the system is inescapable due to the above-mentioned flocculation.
The inherent difficulty of the above-mentioned approach is, however, that the initial increments of cationic flocculants introduced into the pigment furnish induce an excessive local flocculation of particulate matter, inhibiting a uniform mechanical distribution of the remaining portion of the flocculant throughout the furnish. It is thus impossible to always synthesize an identical pigment product since even moderate differences in raw material properties, such as may be brought about by a mere change of the mining location of a kaolin-clay crude, strongly affect the flocculation kinetics of the furnish, notoriously causing major variations in the end-use properties of the resultant aggregate pigment products.
Other potential approaches applicable to the manufacture of aggregate pigments can be patterned on a modification of the spray-drying or freeze-drying approaches suggested by Fadner in U.S. Pat. No. 3,453,131. The modification in question relies upon adding suitable polymer-emulsion adhesives to pigment furnishes to be submitted to spray-drying or freeze-drying.
As is readily understood by those skilled in the art, the three key processing elements indispensable to a successful synthesis of aggregate pigments of any type, regardless of the method employed, are as follows:
(a) Inducing a statistically uniform spatial distribution of all particulates present in a well-dispersed composite pigment furnish (slurry of pigmentary raw materials), using the best available dispersants and adequate agitation regimes.
(b) Instantly "freezing" the statistically uniform spatial distribution induced in (a), to ensure an equivalent statistically uniform distribution of particulate components in the resultant composite pigment products.
(c) Imparting an adequate mechanical integrity to the resultant pigment aggregates to enable the composite pigment products to withstand the shearing regimes to which they may be exposed in the customary handling and end-use applications.
It should be borne in mind, however, that a truly optimal pigment dispersion, such as is indispensable for generating a statistically uniform spatial distribution of all particulates in the furnish in accordance with requirement (a) can be obtained only with a single monodisperse particulate species. In a slurry of a polydisperse pigment, for example, one can distinguish three classes of particulates which differ considerably with regard to colloidal behavior, namely, the fine fraction encompassing pigment fines with particles smaller than 0.15-0.2 .mu.m e.s.d.; the intermediate fraction encompassing particles with equivalent spherical diameters ranging from about 0.2 .mu.m to about 0.5-0.7 .mu.m; and the remaining "coarse" fraction. Although the commercial slurries of polydisperse pigments (no commercial monodisperse pigments have ever been offered on the market) are commonly referred to in the art as being "optimally" dispersed, in reality each individual size fraction is characterized by an inherently different state of dispersion and thus also by a different dispersion stability and resistance to flocculation.
The overall colloidal picture becomes yet more complicated with pigment dispersions that are both polydisperse and hetero-disperse (consisting of two or more pigment species), such as are used for the synthesis of composite pigments. As is well known in the art, it is fundamentally impossible to obtain an "optimal" dispersion of such composite slurries in that each individual pigment fraction and species has a different optimum dispersant demand, both quantitatively and qualitatively, and a different equilibrium between the dispersant adsorbed on the pigment and dissolved in the carrier medium (water). Hence, even if optimally dispersed slurries of individual pigment species were prepared separately and then blended, a progressive destabilization of the dispersion of the resultant composite slurry would commence immediately. As a consequence, a separation (fractionation) and selective flocculation of the polydisperse and heterodisperse phases according to species and size would immediately set in, starting with the relatively least stable disperse fraction and progressing toward the relatively more stable ones. As a matter of fact, the better the initial dispersion of a composite pigment slurry, the more pronounced become the phenomena of fractionation and selective flocculation when the slow and inefficient flocculation processes of the prior art are employed in the synthesis of composite pigments.
It is thus obvious from the above considerations that composite pigments are considerably more difficult to synthesize than those consisting of a single pigmentary species. For the best possible end results, it is virtually mandatory to first start with optimally dispersed, separately prepared, raw material slurries, blend these slurries within the shortest possible time interval at the highest practical solids, using a vigorous agitation, dilute the resultant pigment furnish to the solids level called for by the synthesis procedure, and then instantly flocculate the furnish to "freeze" the dynamically maintained uniform spatial distribution of all particulates present in the furnish before a detrimental fractionation and selective flocculation of the particulates can set in.
As is readily understood, the cementing (adhesive) medium needed to impart the desirable level of mechanical strength to the resultant pigment aggregates must either be already present in the pigment furnish or be synthesized in situ, regardless of whether the aggregate pigment is synthesized from a single or multiple raw material species.
It should be pointed out in the above context that a successful process scheme for synthesizing aggregate pigments, encompassing all three above-mentioned key elements, was never fully realized in the prior art, as shall become clear from the considerations to follow.
Firstly, while the state of an optimal (for all practical purposes) dispersion is clearly indispensable to attaining a uniform spatial distribution of all particulate components present in a disperse system, the flocculating agents and processes of the prior art are incapable of completely overriding the action of the powerful modern dispersants.
Secondly, because of the detrimental progressive destabilization of composite slurries, the total homogenization of all particulate components in pigment furnishes used for synthesizing composite pigments should be accomplished very rapidly, preferably within an interval shorter than 2-5 minutes. The latter requires, however, that the homogenization be carried out at the highest attainable solids, such as can be handled only with the aid of advanced powerful in-line mixers. Powerful mixers are also indispensable to speedily carry out the dilution of the furnish in that the dispersion stability of diluted slurries deteriorates much faster than that of high-solids ones.
Thirdly, a continuous introduction (metering) of the flocculating agents into the diluted pigment furnish is virtually mandatory. The use of batch processes, such as are commonly employed in the manufacture of pigments in accordance with the prior art, will invariably result in synthesizing non-uniform, non-reproducible inferior end products.
Fourthly, the kinetics of the flocculation process employed must be instantaneous, for all practical purposes. With a non-instantaneous process, of course, the particulates present in the furnish will flocculate sequentially, the least stable fractions being the first ones to be flocculated. Furthermore, the flocculation mechanism must also be indiscriminate, i.e., unaffected by either the physical, chemical or colloidal makeup of the disperse phases present in the furnish. As is rather obvious, a discriminatory flocculation mechanism would invariably lead to a detrimental selective flocculation of the particulates according to species and size. The flocculation must also be complete, manifested by a clear separation of the flocculated phase from a clear supernatant.
As is well known by those skilled in the art, a flocculation process having all the above-mentioned attributes was unknown in the prior art before it was first disclosed in U.S. Pat. No. 5,116,418 issued May 26, 1992 and the co-pending patent application Ser. No. 07/919,831 ("Functional Complex Microgels with Rapid Formation Kinetics"), Filed Jul. 27, 1992 now abandoned, both above applications being incorporated herein by reference.
As is readily understood, the above instantaneous, indiscriminate and complete flocculation process, combined with the intrinsic cementing mechanism, makes it possible to synthesize countless numbers of aggregate pigments from a wide variety of pigmentary, subpigmentary and nonpigmentary raw materials. As a consequence, the novel aggregate pigments of the present invention provide not only an improved optical performance (the primary goal of all analogous aggregate pigment products known in the prior art), but also extend into the hitherto untapped domain of functional pigments. The latter functional pigments are designed to provide a variety of novel material as well as performance properties, such as reduced fiber debonding and increased first-pass retention in paper-filling applications, intrinsic pitch-combating ability, reduced abrasivity, paper-coloring ability, shear-thinning (thixotropy) of coating colors in high-speed coating applications, or affinity to (compatibility with) organic media.
It should be emphasized strongly herein that all composite pigments known in the prior art consisted of high-refractive-index primary pigments, such as TiO.sub.2 or ZnS, in blends with low-refractive-index secondary (extender) pigments, but none was known consisting solely of blends of low-refractive-index particulate components, such as those synthesized in accordance with the present invention. It should be emphasized also that, to the best of the applicant's knowledge, all aggregate pigments of the prior art, regardless of the composition or type, were intended exclusively for the improvement of optical-performance efficacy, aggregate pigments intended for improved or novel functional properties being unknown heretofore.
In accordance with the foregoing and disclosures to follow, it is an object of the present invention to provide compositions for novel aggregate pigment products made of raw materials encompassing solely low-refractive-index inorganic and/or organic pigments, subpigmentary mineral particulates, and non-pigmentary particulate and/or water-soluble materials.
In particular, it is an object of the invention to provide compositions for aggregate pigment products synthesized by the general method disclosed in the previously mentioned U.S. Pat. No. 5,116,418 to.
It is a further object of the invention to provide compositions for aggregate pigment products synthesized from virtually all low-refractive-index pigmentary raw materials applicable to paper making and having a higher optical-performance efficacy and lower abrasivity than the individual materials employed for their synthesis.
It is a yet further object of the invention to provide compositions for aggregate pigment products which, regardless of their predominant kaolin-clay or calcined-clay content, are uniquely suitable for use in the alkaline papermaking process.
It is a still further object of the invention to provide compositions for aggregate pigment products with improved optical-performance efficacy and extra-high bulking properties, synthesized from commercial precipitated pigmentary raw materials deagglomerated mechanically to a subpigmentary particle size, used alone or in blends with pigmentary raw materials and/or other constituents.
It is a yet further object of the invention to provide compositions for aggregate pigment products having intrinsic pitch-combating properties in papermaking furnishes.
It is a yet further object of the invention to provide compositions for aggregate pigment products containing, in addition to pigmentary and/or subpigmentary and other constituents, water-soluble and/or disperse polymer adhesives to reduce fiber debonding in paper-filling applications and improve solvent dissipation in printing.
It is a still further object of the invention to provide compositions for aggregate pigment products for paper-coating applications containing, in addition to pigmentary and/or subpigmentary and other constituents, non-film-forming organic-polymer particulates for improved ink receptivity.
It is a yet further object of the invention to provide compositions for aggregate pigment products for newsprint-filling applications containing, in addition to pigmentary and/or subpigmentary and other constituents, high-surface-area, high-oil-absorption pigmentary raw materials for both improved ink absorbency and immobilization.
It is a yet further object of the invention to provide compositions for extra-high-opacifying aggregate pigment products containing intrinsically dispersed carbon black, thus rendering them particularly suitable for the manufacture of lightweight newsprint and groundwood specialty papers.
It is a still further object of the invention to provide compositions for aggregate pigment products containing intrinsically incorporated color dyes to eliminate the residual yellow hue, inherent to virtually all commercial pigments, and/or render the resultant aggregate pigment products directly applicable to the coloring of paper, paints and the like.
It is a yet further object of the invention to provide compositions for aggregate pigment products containing chemically built-in organic, cationically active compounds with at least two reactive groups in each molecule to impart controlled levels of oleophilic properties to the resultant pigment products, thus rendering them uniquely compatible with, and dispersible in, organic media such as plastics, synthetic fibers and solvent-based lacquers and paints.
It is a yet further object of the invention to provide compositions for aggregate pigment products containing cellulosic and/or synthetic microfibrils to maximize first-pass retention and decrease fiber debonding in paper-filling applications, especially high-ash applications.
A yet further object of the invention is to provide compositions for aggregate pigment products in which the particulate ingredients are coflocculated in a controlled manner into aggregates whose intrinsic structure, as well as spatial distribution of the light-scattering and functional sites, provides an overall performance efficacy of the resultant products that is superior, in terms of the light-scattering efficacy, functional properties and economy of use, to that of the equivalent blends of loose ingredients.
It is also a particularly special object of the invention to provide general principles of qualitative, quantitative and functional formulating of the ingredients of aggregate pigments as well as principles of inducing intrinsic, optically favorable spatial and structural configurations, enabling one to design at will aggregate pigment products suited for the specific needs and preferences of individual customers.

Low-refractive-index aggregate pigments products


An apparatus and a method are disclosed for separating a first fluid from a second fluid wherein the first fluid is lighter than the second fluid and the first fluid is immiscible with the second fluid. A first portion of the first fluid is separated from a mixture containing the first and second fluids in a gravity separator. The remaining mixture flows to a hydrocyclone where a second portion of the first fluid is separated from the remaining mixture. The underflow from the hydrocyclone which includes most of the second fluid and the remaining portion of the first fluid flows to a second gravity separator without substantial pressure reduction to avoid shearing of the droplets of the first fluid. In the second gravity separator a third portion of the first fluid is removed.

Separating oil and water in oil/water mixtures is often desirable. Furthermore, since the implementation of environmental and water-quality regulations, it is often necessary to achieve reduction of oil concentration to less than 50 ppm. There are presently several separation systems available for separating oil from water.
One simple separator system comprises a settling basin in which oil and water separate over time by gravity due to their density differences. The degree of separation is directly related to residence time in the basin.
Another method which is known as floatation uses the buoyancy of gas bubbles rising through the liquid to "float" contaminants, such as oil droplets, to the surface. The gas bubbles may be formed by the bubbling out of dissolved gas that occurs when pressure on the system is reduced or by injecting or dispersing gas into the water by a bubbling device.
Hydrocyclones are known separation devices which use a centrifugal effect to cnhance separation. One design of a hydrocyclone comprises a long, funnel-shaped chamber into which a feed line is tangentially directed. An oil and water mixture under pressure is directed tangentially into the funnel-shaped separation chamber of a hydrocyclone via the feed line whereupon its energy is converted to angular momentum as the mixture swirls around the inside of the chamber. The swirling causes the less dense portion of the mixture (the oil) to move towards the axis of the device while the more dense portion (the water) is urged to the outside.
A typical hydrocyclone has a coaxial overflow outlet in its large end for providing an outlet for less dense phase from the hydrocyclone, and a coaxial underflow outlet, at the opposite end, for providing an outlet for the more dense phase from the hydrocyclone. The pressure difference between the overflow outlet and the underflow outlet, and the inlet flow rate determine the relative volumes of the overflow and underflow streams. Increasing the pressure at either outlet causes the flow through the opposite end to increase.
A predetermined degree of separation for a particular feed is achieved by providing a high enough velocity to create sufficient centrigual force and by setting the relative volumes of the overflow and underflow. The pressure differential between inlet pressure and overflow pressure necessary to achieve sufficient overflow rate in a given hydrocyclone at a given inlet flowrate can be calculated. The pressure at the underflow outlet must be greater than the pressure at the overflow outlet to provide sufficient overflow rate.
It has been demonstrated that the oil droplets that remain in the water underflow of a hydrocyclone are coalesced to droplets having a large size by the action of the hydrocyclone. Because the larger droplets settle out of the water at a higher velocity than the smaller droplets, it is easier to separate in a skim vessel the oil remaining in the hydrocyclone underflow from the water than it is to separate the smaller oil droplets from the water in the inlet stream.
U.S. Pat. No. 5,021,165 discloses a system having separator vessels and a hydrocyclone for separating oil from water that includes a pressure reducing device immediately downstream of the hydrocyclone. The pressure reducing device allows the necessary pressure to be maintained at the underflow outlet while providing a reduction of pressure to vaporize part of the stream to "float" oil droplets in a flotation unit downstream of the hydrocyclone. The passage of the fluid through the pressure reducing device, however, causes shearing of the oil droplets in the water thereby significantly decreasing the efficiency of the flotation unit.
In any mixture of immiscible fluids, because the kinetic energy of the mixture contributes both to dispersion of larger droplets and coalescence of smaller droplets, at any given energy input rate there is a statistically defined maximum droplet size for which the rates of dispersion and coalescence are equal. Maximum droplet size is inversely related to the energy input rate of the system. It is also known that a rapid decrease in pressure results in shear forces on the mixture causing shearing of oil droplets larger than a certain diameter. Hence, to maintain the large droplets developed by coalescence in the hydrocyclone, it is desirable to minimize the pressure drop to which the mixture is subjected.
One disadvantage of the prior art is that the use of pressure reduction to effect flotation causes a decrease in the efficiency of the separation for the reasons stated above. According to the present invention, a mixture comprising at least two immiscible liquids is processed through a system to separate the liquids by avoiding pressure reduction except for the pressure reduction in the hydrocyclone itself. The avoidance of the pressure reduction reduces the difficulties in shearing caused by such reduction in the prior art.
These and other objects and advantages of the present invention will be apparent from the following description.


At least one exemplary embodiment is directed to a sensor for measuring the distance between the sensor and a measuring surface, which includes a light-emitting element and a plurality of light-receiving elements. The light-receiving elements are arranged so that the light axes thereof do not cross one another.

1. Field of the Invention
The present invention relates to an optical sensor that detects the amount of displacement of a detecting object on the basis of a reference characteristic of a surface of the detecting object. More particularly though not exclusively, the present invention relates to an optical sensor installed in a recording apparatus to detect the amount of displacement of a detecting object, to detect the color density, and to determine the type of the detecting object.
2. Description of the Related Art
Inkjet recording apparatuses (hereinafter referred to as recording apparatuses) have been equipped with various sensors corresponding to different purposes in order to meet various needs such as higher image quality, higher precision, and higher user friendliness. Examples of sensors used are a sensor for detecting the width (size) of a recording sheet (recording medium) set in a recording apparatus and the end of the recording sheet, a sensor for measuring the density of a patch (pattern) or an image recorded on the recording sheet, a sensor for detecting the thickness and presence of the recording sheet, and a sensor for determining the type of the recording sheet.
These recording apparatuses generally use optical sensors. Optical sensors include a light-emitting element for emitting light, and a light-receiving element for receiving the light from the light-emitting element. The light-receiving element provides an output in accordance with the amount (intensity) of received light. In particular, a transmissive optical sensor and a reflective optical sensor are frequently used.
In general, a reflective sensor is used to detect the thickness of a recording sheet. In the reflective sensor, a light-emitting element applies light onto a surface of a recording sheet serving as a detecting object to be detected, and a light-receiving element receives light reflected by the recording sheet. The distance between the reflective sensor and the surface of the recording sheet can be measured on the basis of the amount of light received by the light-receiving element. For example, when an optical reflective sensor is mounted on a carriage of the recording apparatus, measurement is performed as follows. First, a recording sheet serving as a detecting object to be detected is moved from a recording-sheet storage unit onto a platen, and the distance between the surface of the recording sheet and the reflective sensor mounted on the carriage is measured by the reflective sensor. In this case, since the distance between the reflective sensor and the platen is set at a value specified in design of the recording apparatus, the thickness of the recording sheet can be detected by calculation on the basis of the measured distance and the specified value.
Japanese Patent Laid-Open No. 05-087526 discusses an optical sensor that detects the thickness of a recording sheet. In this optical sensor, an LED or a semiconductor laser is used as a light-emitting element, and a PSD (position sensitive detector) or a CCD is used as a light-receiving element. In this case, light emitted from the light-emitting element is reflected by a detecting object, and a part of the reflected light is received by the light-receiving element. With this configuration, if the distance between the optical sensor and the detecting object changes, the center of reflected light received by the light-receiving element also changes. When the light-receiving element is a CCD, the amount of light in each pixel can be measured. Therefore, the center of reflected light can be found by detecting the pixel in which the largest amount of light is obtained, and the distance between the optical sensor and the detecting object can be calculated by triangulation. When the light-receiving element is a PSD, the center of reflected light is obtained by calculating two values output from the light-receiving element when the center changes, and the distance between the sensor and the detecting object can be calculated from the obtained position by triangulation.
In a general optical sensor for detecting the width of a recording sheet and ends (a leading end and a trailing end) of the recording sheet, a reflective optical system is constituted by one light-emitting element and one light-receiving element, and the ends of the recording sheet are detected on the basis of changes in intensity (amount) of reflected light. It is checked whether a recording sheet is placed within a detection area of the optical sensor, by using the fact that there is a difference in intensity of reflected light received by the light-receiving element when the light-emitting element applies light onto the surface of the recording sheet and when the light-emitting element applies light onto a portion outside the recording sheet, for example, on a platen or a feeding path. In an inkjet recording apparatus, in which a carriage is scanned in a direction different from the feeding direction of the recording sheet, when the reflective sensor is mounted on the carriage, the widthwise end of the recording sheet can also be detected.
A sensor for measuring the color density of a patch printed on a recording sheet includes three light-emitting elements for emitting red, blue, and green light beams and one light-receiving element, or includes a white light source and a light-receiving element having a color filter. Japanese Patent Laid-Open No. 05-346626 discusses a technique of detecting the color density of a color patch with this sensor. In this technique, reflected light from the color patch is received by the light-receiving element, and the amount of attenuation of reflection intensity from the reference reflection intensity is calculated. In an inkjet recording apparatus in which a carriage is scanned in a direction different from the feeding direction of the recording sheet, when the reflective sensor is mounted on the carriage, the density of a patch recorded at a predetermined position on the recording sheet can be detected.
The above-described known optical sensor for detecting the thickness of the recording sheet includes a light-emitting element such as an LED, and a light-receiving element such as a photodiode. While the optical sensor itself is inexpensive, it cannot check whether the detecting object is shifted closer to or away from a predetermined position. In a reflective optical sensor, a light-receiving element is placed at a position such as to receive the largest possible amount of reflected light from a detecting surface on which light is applied by a light-emitting element, (e.g., FIG. 8B). That is, the light axis of reflected from the detecting surface coincides with the center of the light-receiving element. In this case, the distance between the optical sensor and the detecting surface is referred to as a reference distance, and the detecting surface is referred to as a reference surface.
A sheet having a predetermined reflection characteristic can be used as the reference surface which is the reference for calibration of the optical sensor. When the detecting object is shifted from the reference surface toward the optical sensor, that is, the distance between the detecting object and the optical sensor is shorter than the reference distance, as shown in FIG. 8A, the amount of light reflected by the detecting object and received by the light-receiving element is smaller than when the light is reflected by the reference surface. This is because the light axis of reflected light from the detecting surface does not coincide with the center of the light-receiving element, and a region on the detecting surface in which light is applied from the light-emitting element is not aligned with a light-receiving region of the light-receiving element on the detecting surface. When the detecting object is shifted from the reference surface away from the optical sensor, as shown in FIG. 8C, similarly, the amount of light received by the light-receiving element is reduced.
In FIGS. 8A to 8C, reference numerals 801a-c, and 802a-c denote a light-emitting region of the infrared LED 201, and a light-receiving region of the phototransistor 203. In the above described situation related to what is illustrated in FIG. 8A, the light emitting region 801a and the light receiving region 802a overlapped partially, with a similar amount of overlap for the situation illustrated in FIG. 8C (regions 801c and 802c). In the situation of FIG. 8B, the light emitting region 801b lies completely in the light receiving region 802b.
FIG. 9 is a graph showing changes in the output from the light-receiving element caused when the distance between the optical sensor and the detecting object changes. As shown in FIG. 9, it is difficult for the inexpensive reflective sensor to check whether the detecting object is shifted from the reference surface toward the optical sensor or away from the optical sensor.
In the above-described optical sensor discussed in Japanese Patent Laid-Open No. 05-087526, a PSD or a CCD is used as the light-receiving element. In this case, the distance between the optical sensor and the detecting object can be detected. However, the size of the optical sensor increases, and the cost also increases because of the PSD or the CCD.

Sensor and recording apparatus using the same


A stabilizer for an in situ column drilling apparatus comprises a first and second mounting arms, a first and second stabilizing members, and a first and second stabilizing tabs. The mounting arms are adapted for rotatable coupling to the shaft of column drilling systems. The first and second mounting arms are preferably positioned spaced apart along the shaft near the drilling auger. The mounting arms are coupled together by two stabilizing members at opposite ends of the arms distal the shaft. The stabilizing members are advantageously shaped to fit closely against the wall of the column to prevent changes in the auger's drilling course. The first and second stabilizing tabs are attached to the first and second stabilizing members, respectively. The first and second tabs are mounted to extend radially outward from the shaft and also prevent changes in the auger's drilling course.

1. Field of the Invention
The present invention relates to devices for in situ mixing to produce soil-cement columns. In particular, the present invention relates to a stabilizer for an auger that provides for straight accurate drilling of in situ soil-cement columns even in horizontal directions.
2. Description of Related Art
A method for soil solidification and stabilization is the construction of soil-cement columns. Soil-cement columns are conventionally constructed by mixing soil with a chemical hardener in situ. The need for excavating the soil, mixing the soil with the chemical hardener, and then replacing the mixed soil and hardener in the excavation site is advantageously avoided by using a one step process with special augers and shafts that mix soil and a chemical hardener while the soil remains under ground near its original position. Typically, the auger shaft performs the two functions: (1) rotating to drive the auger and to mix the soil, and (2) providing a path for injection of the chemical hardener during the mixing process. Conventional soil-cement column augers are disclosed in U.S. Pat. Nos. 4,9002,172 issued to Fukuda; 4,909,675 issued to Taki; 5,013,185 issued to Taki and Japanese patent Nos. 1197295 and 1197296.
One continuing problem in constructing soil-cement columns is the ability to form them in accurate inclined and horizontal directions. FIG. 1 illustrates a cross-sectional view of a hillside and a soil-cement column constructed in an inclined direction (perpendicular to the surface). The axis upon which the column was to be formed is shown by the dashed line. As can be seen, the auger is effected by gravity, and as the column is mixed and injected with cement the auger veers from its intended course downward. Similarly shown in FIG. 1B, the problem is more server when constructing a soil cement column in substantially horizontal direction. The column formed in FIG. 1B in nowhere near its intended path at the bottom of the column.
The prior art has attempted to resolve this problem by using rods with greater rigidity and strength to compensate for the forces of gravity and retain the auger on its intended path. To increase the strength off the drilling shaft, its size, in particular the diameter, must be increased. However, one problem with increasing the size of the shaft is there is less area for mixing blades and the efficiency in mixing the soil with a hardening agent decreases. Increasing the size of shaft also increases the volume of the column occupied by the drill which results in more exposed soil being produced. This is a significant problem because it adversely effects the strength of the column being constructed. The less the soil and hardening agent are mixed, the less the strength of the column. Thus, there a need for a system that will provide maximum mixing of soil and hardening agent, and allow columns to be constructed in the horizontal or inclined directions.

Stabilizer for an in situ column drilling apparatus


A battery including a pack housing and a plurality of battery modules accommodated in the pack housing, the pack housing has first and second sides, the first and second sides having openings, and the openings of the first side correspond to respective openings of the second side, the pack housing has a plurality of guide grooves, and each battery module is accommodated into or removed from an inner space of the pack housing through a respective opening by sliding along the guide grooves.

As devices powered by electrochemical energy are being developed, the need for a battery pack having high energy density is increasing.
In particular, in the case of a battery pack for a vehicle, a crash beam is essentially installed in order to endure an impact applied from the outside. However, the space occupied by the crash beam is not small, and the space occupied by the crash beam is not able to be used for other purposes. For this reason, there is inefficiency in terms of space utilization.
Referring to FIG. 1, a conventional battery pack structure to which a crash beam is applied is shown.
As shown in FIG. 1, in the conventional battery pack, a crash beam 2 with a predetermined thickness is disposed between every adjacent battery modules 1, and a battery module 1 is placed between every pair of crash beams.
In this configuration of the battery pack, when the battery module 1 is inserted into each insertion space, the battery module 1 is inserted and fixed in a downward direction. In this case, if the battery module 1 is firmly coupled to a pack housing 3, a lot of time is inevitably taken for the maintenance of the battery module 1.
Moreover, the battery pack of this configuration requires the space occupied by the crash beams 2 disposed between every adjacent battery modules, in addition to the space occupied by the battery module 1, and thus there is a loss in terms of energy density.


A protein comprising an antigen-binding portion formed by two cooperating peptide sequences of FIGS. 3A and 3B of the application. The protein may alternatively comprise an altered antigen-binding portion where at least one of the peptide sequences is an altered sequence, an altered sequence being a sequence of FIG. 3A or 3B in which one or more of an amino acid residue has been added, deleted or replaced by another amino acid residue. The altered antigen-binding portion retains substantially the same antigen-binding specificity as said antigen-binding portion. Also disclosed are apparatus, systems and methods for detecting small assayed molecules in a sample using the protein.

The linear relationship between the change in the oscillation frequency of a piezoelectric crystal and the mass variation on the crystal as a result of binding or absorption phenomena, has been used to advantage in a gravimetric monitoring of antigen-antibody binding. The mathematical relationship between the frequency changes of a piezoelectric crystal, Δf, and mass changes, Δm, on the crystal is given by the following Sauerbrey equation:Δf=−2.3×106fo2·Δm/Awhere fo is the fundamental resonance frequency of the crystal prior to the mass variation and A is the surface area of deposited mass. For example, for a crystal exhibiting a fundamental frequency of 9 MHz and surface area of 1 cm2, a mass-change on the crystal that corresponds to 1×10−9 g, will stimulate a frequency change, Δf, of 6 Hz.
The first analytical use of piezoelectric crystals in relation to antigen-antibody (Ag-Ab) interactions was reported in 1972(1), where a nyebar precoated crystal was further coated via hydrophobic interactions, with bovine serum albumin (BSA) and the association of the BSA-Ab to the crystal was monitored by the frequency changes. Since then, the piezoelectric detection of antigens and antibodies by piezoelectric means or the quartz crystal microbalance (QCM) has been adopted in a series of analytical studies. The progress in this area has been reviewed by Suleiman et al., 1994(2) and Ward et al., 1990(3).
Several patents describe the application of QCM for the analysis of antigens and antibodies. Physical adsorption of antigens to a crystal was used as a means for the detection of antigens by interacting the crystal with a mixture of the analyte antigen and a predetermined amount of Ab(4). The decrease in the antigen concentration was inversely related to the antigen concentration in the sample. In two patents by Rice(5.6), methods for the determination of Abs by QCM were disclosed. The antigen was immobilized on a polymer precoated crystal and the frequency changes as a result of Ab association related to the analyte Ab concentration in the sample. By this method, human IgG against honey bee venom, phospholipase A, and keyhold limpet hemocyanine were analyzed(7). However, non-specific binding to the crystal interfered with the analyses. In a follow-up patent(8), the detection of low molecular weight components by a pre-coated crystal with the anti-Ab and competitive binding assay of the Ab-low molecular weight analyte was described. All of these analyses were performed by treatment of the crystals in solution and subsequent frequency measurements in air. This two-step solution/gas procedure allows improvement of the sensitivity of the resonating QCM, but introduces technical complications and the interference of hydration/dehydration phenomena that are reflected in the frequency parameters.
Piezoelectric immunoassaying in the liquid phase has important technical advantages as it allows stationary and flow analysis of aqueous samples. The method suffers, however, from a basic physical limitation due to substantially lower frequency changes of the crystal as a result of the solution viscosity. QCM immunoassays in solution were reported by Roederer(7) and addressed in a follow-up patent(8). The quartz crystal was modified with glycidoxypropyltrimethoxy silane (GOPS), and the surface-modified crystal was then further modified by anti-human IgG antibody and then applied for the piezoelectric detection of human IgG. The detection limit of the device was determined to be 13 μg·ml−1. A closely related approach was adopted by Muramatsu et al.(9) where the quartz crystals were surface-modified by γ-aminopropyl triethoxy silane and further derivatized by protein A. The surface-modified crystals were then applied for the determination of human IgG in the concentration range 10−6–10−2 mg·ml−1. A related patent disclosed the piezoelectric analysis of thyroxine using a polyamide 6 polymer coating and anti-thyroxine Ab as sensing interface(10).
Piezoelectric analysis of high molecular weight antigens such as microbial cells was addressed using antibody-coated quartz-crystals. C. albicans cells in the concentration range 1×106–5×108 cells·ml−1 were analyzed by an anti-Candida albicans Ab surface(11), E. coli with an anti-E. coli interface(12) and protein A-coated crystals acted as piezoelectric sensing interface for various bacteria including Salmonella, Shigella, Yersinia and E. coli(13). Various schemes allowing efficient use of QCM in assaying analytes in a liquid media have been described in WO 97/04314(14).
QCM techniques were used hitherto only for detection of interaction with substances of relatively high molecular weight, e.g. proteins and other macromolecules. The QCM techniques are generally considered not sufficiently sensitive for detection of substances of a low molecular weight.

Detection of small molecules by use of a piezoelectric sensor

Yissum Research Development Company of the Hebrew University of Jerusalem


The present disclosure provides compositions and methods for enzymatic oil degumming.

With the increasing need for food, cosmetics, and ecologically responsible fuels it is important to optimize the processing of crude oils for high yield and stability. In particular, there is a need for cost effective and efficient methods for removing phospholipids and lecithins, known collectively as "gums", from oil compositions (edible oils, crude oil etc.) to produce a degummed oil product that can be used for consumer products such as food or fuel.
As explained in detail by W. van Nieuwenhuyzen, "Lecithin production and properties" in Journal of the American Oil Chemists' Society (1976) 53: 425-427, lecithin is a complex mixture of phosphatides (such as phosphatidyl choline, phosphatidyl ethanolamine, phosphatidyl inositol and phosphatidic acid), their lyso-compounds, triglycerides, sugars (such as saccharose, raffinose and stachyose), some glycolipids and further minor constituents, wherein lecithin normally contains some 35% by weight triglyceride oil.
Owing to the variety of impurities in a crude oil, a series of chemical and physical methods can be employed to remove undesirable impurities that affect the stability, quality of performance, taste, smell, or color of an oil. More recently, developments were made to use enzymatic degumming.
Enzymatic degumming has several advantages over chemical and physical methods such as lower costs, minimal chemical waste, and higher yields of refined oil.
Francis Turner in chapter 5 "Degumming", book Edible Oil Processing from a Patent Perspective, Albert Dijkstra, Ed. Springer; makes a summary of the state of art since 1990 about the different methods of degumming developed by the principal players in this field. (Chapter 5, "Degumming", p 121-155, A. J. Dijkstra, Edible Oil Processing from a Patent Perspective, Springer Science+Business Media, LLC 2013), this documents is incoporated herein as a reference. Several enzymatic oil degumming technologies have been developed in last years. Some of them are disclosed in patents like: U.S. Pat. Nos. 9,228,211B2, 7,906,307B2, 9,315,764, U.S. Pat. Appl. No. 20120210467; U.S. Pat. Nos. 8,541,211 and 8,241,876.
U.S. Pat. No. 9,228,211B2 discloses a process of water degumming of an edible oil (preferably a crude edible oil) comprising the steps of admixing edible oil (preferably a crude edible oil) and a lipid acyltransferase, under particular conditions. In a particular embodiment, the lipid acyltransferase (LAT) can be used in combination with a phospholipase C enzyme. This patent shows that the best results are reached using the lipid acyltransferase in a concentration of 0.5 TIPU/gr of oil, resulting in a reduction of the gum phase. The patent explains that "the addition of lipid acyltransferase to crude oil catalyses the transfer of fatty acid moiety from phospholipid to sterol, during formation of sterol esters". On a molecular level the amount of sterol is less than ⅓ of the amount of phospholipids in crude soya oil. Because the acyl acceptor sterol is the limiting factor for KLM3′ in crude soya oil, the hydrolysis reaction might occur depending on enzyme dosage and reaction time". So it was found that the addition of more sterol to the crude oil produces more sterol ester, when the oil is treated with lipid acyltransferase KLM3′, and the amount of free fatty acids formed is reduced compared with an oil where no sterol was added. This document shows that enzymatic degumming using LAT (at the recommended dose of 0.1-1 TIPU/g of oil) increases the free fatty acid content of oil. As the acyl acceptor sterol is the limiting factor for LAT in crude soybean oil, the hydrolysis reaction occurs. The alternative of adding 0.25-0.75% sterol is not economically viable and impracticable for an industrial process. Also, in the examples using LAT in combination with PLC the content of diglyceride is reduced compared to the PLC treatment alone.
U.S. Pat. No. 7,696,369 discloses a process for recuperating trigliceride oil from wet gums obtained from water degumming of a vegetable oil, mixing these gums with a phospholipidolytic agent. Such phospholipidolytic agent can be a phospholipase. The patent discloses the use of Novozyme's Lecitase® Ultra (PLA) for wet gums treatment, and describes a process in Example 7 using 250 mg of the enzyme per kg dry gum matter. Not only the amounts of enzyme required for the process are about 100-fold higher than the amount required for a crude oil degumming treatment for an equivalent amount of phospholipids, but also the data provided result from a 5 days long treatment. Therefore, such process could not be used in the crushing industry.
U.S. Pat. No. 9,315,764 discloses methods of processing lipid material such as soapstock, dry gums and wet gums, where enzymes are utilized to catalyze hydrolysis of the lipids materials to recover fatty acids. Examples provided for treatment of wet gums involve the use of 2% Phospholipase A2 in a 20 hrs treatment, reaching 30% oil yield. Such amounts of enzyme and duration of the process are too high to be implemented as a profitable process in the crushing industry.


A tool for engaging a roof includes a peak engagement member for engaging a first surface of the roof, and an operator climbing member including an elongated central body and a plurality of spaced apart step handles mounted on the central body. The operator climbing member is configured for engaging the second surface of the roof and is operatively connected to the peak engagement member.

This disclosure relates generally to tools for use on roofs and, more particularly, to a tool to assist in scaling an inclined roof.
Scaling and inspection of a roof with a steep ridge can be a dangerous task, even for a trained professional. Serious injuries or death may occur as a result of falling while working on or trying to gain access to a rooftop.
Conventional methods used to access steep roofs often involve difficult and time consuming processes. Professionals typically use a personal fall arrest system containing an anchor point, safety line, and harness. The safety line (typically a rope) connects the harness to the anchor point. The set up of the fall arrest system requires climbing up a ladder to get a safety line across one side of the building to another, climbing down the ladder to tie down one end of the safety line, and finally putting on harness gear and climbing back up a ladder. This process must be fully repeated for accessing, inspecting, or repairing the other side of the roof.
Another method for accessing and inspecting steep roofs involves the use of ladder with a roof hook affixed to the ladder. Using the ladder with the roof hook affixed often requires carrying this second ladder up a ladder. Carrying a second ladder while climbing a first ladder increases the difficulty and risks associated with accessing and performing tasks on the roof.
There is a need for an apparatus that can be used by individuals to scale, inspect, and work on steep roofs that is both time-efficient and reduces the risk of injury or death to an individual needing to scale or inspect steep roofs.


A method for finishing a manufactured article by powder painting, comprising the step of applying, on a surface to be decorated of the manufactured article, one decorative layer obtained by means of the transfer by controlled migration of powder particles which originate from a graphic matrix arranged in front of the surface to be decorated and designed to adhere thereto; the transfer and adhesion steps being provided by a first electostatic field which comprises lines of force incident at right angles to the surface to be decorated, the manufactured article acting fully or partly as reference electrode for the first electrostatic field, so as to produce a condition of solid contact between the electrode and the surface to be decorated.

The present invention relates to a method for finishing a manufactured article by powder painting.
Finishing by powder painting is currently widely used in decorating, so as to imitate the grain of a type of wood, metallic profiled elements to be used in particular for door and window parts.
The metallic profiled elements, after being adequately prepared for painting, are subjected to a treatment cycle which provides for the following operating steps: first of all, a first layer of powder paint or primer is deposited on the profiled element; then partial polymerization of the first layer of paint is provided; then a second layer of powder paint, having a different color or shade than the underlying layer, is applied according to a preset graphic configuration; and, final baking is performed to fully polymerize the first and second layers of paint.
The above described painting process, however, has drawbacks which drastically limit the industrial applicability thereof, both in terms of mass-production and of final cost of the finished product. The most critical step of such a treatment cycle is the application of the second layer of paint, i.e., the decorative layer, and this task is often entrusted to the experience and skill of qualified personnel capable of reproducing a particular graphic configuration, such for example an imitation grain, on any metallic or non-metallic substrate, by working manually with the aid of traditional tools such as for example brushes and paintbrushes.
From the above description it is easy to understand that it is not possible to provide an industrial process that includes an operation entirely performed by hand, since this operation constitutes an inevitable and economically unsustainable bottleneck which results in severely slowing the entire production cycle.
Through attempts to convert the process for finishing manufactured articles from a strictly manual to an automated treatment resulted in improvement the speed of the production cycle, they have not been qualitatively successful in terms of resemblance to the original, thus requiring continuous manual intervention by specialized personnel downstream of the treatment cycle.
Examples of powder painting devices are available from the Patent Abstracts of Japan, vol. 008 no. 104 and JP-A-016771 and from U.S. Pat. No. 3,295,440.

Method for finishing a manufactured article by powder painting


The present invention relates to a process of making 2-amino-1,3-propanediol by reacting 1,3-dihyrdroxyacetone dimer with an amine compound.

Amino alcohols are widely used intermediates in the manufacture of radiocontrast agents. 2-Amino-1,3-propanediol (serinol) is used in the production of Iopamidol. There are numerous synthetic routes for the preparation of amino alcohols, many of which have certain drawbacks when evaluated for manufacturing use. Some of the methods include reduction of amino acids or nitro alcohols. One of the simplest routes to 2-amino-1,3-propanediol involves the reductive amination of 1,3-dihydroxyacetone with ammonia. In this process, the solid dihydroxyacetone dimer is first dissolved in anhydrous liquid ammonia at low temperature to form an imine intermediate. Then a catalyst is added and the mixture is pressurized with hydrogen. Typically, the pressure may be as high as 1450 psi. Such high pressure is not desirable in an industrial setting from neither an operational nor from a safety point of view.
A process which would avoid the use of ammonia and high pressure would be advantageous in that it would be a safer process for the large scale production of 2-amino-1,3-propanediol.

Process for production of 2-amino-1,3-propanediol


In an implementation of collect callback, a call-in service establishes a communication link with a caller and initiates a collect callback option for the caller. A switch receives callback data from the call-in service and utilizes the callback data to establish a collect call via a second communication link between the caller and the call-in service.

Some telephone switching systems provide a callback feature that allows a caller to call the switching system, receive a hang-up response tone or some other indication from the system, and have the switching system call back so that the caller can dial a long distance number, yet maintain a cheaper rate through the switching system. Another caller-initiated callback system enables a caller to submit a callback request via the Internet, such as to a call center, and directly from an HTML page. The call center then completes the call to the number provided by the caller. These and other conventional caller-initiated callback systems are convenient and economical for business travelers and vacationers, for example, that travel overseas yet do not want to pay for the high costs, or tariffs, to place a call through a foreign telecommunications system.


An appliance specific laser aiming device for visual spray pattern testing of fire suppression spray nozzles has a hollow cylindrical body with a first end threadably fitted to an adapter that is fitted to the existing spray nozzle. A laser module within the cylindrical body projects a light beam through the interior and out of the lens on the second end. The second end has dial adjustment. A hollow housing with grip removably and rotatably fits to proximal the first end. Rotating the hollow housing positions a chosen nozzle depiction for setting to match specific spray nozzle characteristics wherein one device tests a plurality of nozzles, including those of various manufacturers.

A need to measure exact spray patterns and directions of fire suppression systems used to halt fire or extreme heat is well established. For example, specific sprays are used in restaurant kitchens with such sprays designed to properly cover various appliances, as they are in other industries. One example of such includes 11 exacting nozzle types including: 1. ½N=flow in a fan pattern; 2. 1F=flow in a wide pattern; 3. 1W=flow in a wide pattern; 4. 1N=flow in a narrow pattern; 5. 2W=2 flows in a wide pattern; 6. 230=2 flows in a 30 degree pattern; 7. 245=2 flows in a 45 degree pattern; 8. 260=2 flows in a 60 degree pattern; 9. 290=2 flows in a 90 degree pattern; 10. 2120=2 flows in a 120 degree pattern; and 11. 3N=3 flows in a narrow pattern.
These nozzles are visually quite similar and have various common parts. However, each nozzle tip is designed for quite specific application. It is noted that sprays in use in industries such as the restaurant field require extremely exact placement in order to ensure pattern and directional spray issuance over the various appliances and areas within such environments. Spray testing devices to date have proven inadequate in that the need for a multi-adjustable device to match a plurality of spray nozzles exemplified above to determine both direction and correct spray pattern has not been fulfilled. Single devices for each nozzle have proven impractical and expensive. A device for use with multiple nozzles, with adjustable appliance specificity is needed, wherein one device can be fitted to a variety of nozzles, via adapter, to visually determine direction and spray pattern applicable to each appliance nozzle, nozzles as exemplified by those above.
The present appliance specific laser aiming device removably attaches to an existing fire suppressant nozzle adapter and fulfills this need.


A system is disclosed which facilitates authentication processes with web-enabled wireless devices, including those that do not support the use of cookie files. To facilitate such authentication, a web server analyzes an HTTP request file from a communication device for the presence of security token data. Where none is found, a client is directed to a login page for input of authentication data, such as a user name and password information. Upon proper authentication, the client's communication device is issued a security token using standard HTML—INPUT tags. Thereafter, the web server determines if each additional HTTP request file received from the client includes a security token before responding to the request.

The term "cookie" generally refers to a text-based file generated by a web server and stored on a client's computer for later retrieval when, for example, the client enters a website. A cookie file generally facilitates client navigation within a web site and enable web sites to gather information about users entering the site.
In particular, the cookie file is typically a named piece of data that a web server sends to the client computer, which instructs the client computer to store and send the cookie back to the server each time the client computer transmits a request to that server. The information contained in a cookie file often comprises at least a client ID, which includes a unique number in the form of a name-value pair which assigned to a client upon accessing the web site. The client ID generally includes a name-value pair. For example, a client visiting the website www.goto.com, might receive a cookie file on the client's computer containing a single client ID in the form of a name-value pair as follows:
clientID A9A3BECE0563982D www.goto.com/
Other web sites might store additional information in a cookie file, such as, for example, the cookie generated by www.amazon.com, namely:
session-id-time 954242000 amazon.com/
session-id 002-4135256-7625846 amazon.com/
x-main eKQIfwnxuF7qtmX52x6VWAXh@lh6Uo5H amazon.com/
ubid-main 077-9263437-9645324 amazon.com/
In this example, the information in the cookie file includes a main client ID, an ID for each session, and the time the session began on the client's computer. Cookie data may also contain additional information such as path data, client preference data, geographic information, and/or the like.
Most cookies are also time-sensitive, meaning the cookie is often associated with an expiration date, after which the client computer no longer sends the cookie to the associated server and the client computer removes the cookie from its internal database. Generally, these cookies are classified into two groups, namely a "session-only" cookie which expires automatically when the browser shuts down, and a "persistent" cookie which generally expires at a date and time set by the server.
Web servers may also use cookies to initiate secure sessions. In a secure session transaction, a client visiting a secure web site for the first time is typically queried for client ID and password information. After the client provides the requested information, the information is then compared against a database associated with the server for authentication. Upon valid authentication, a security token is then typically issued to the client. Issuing a security token usually occurs by sending to the client's browser a cookie file with the security token information contained therein. A copy of this cookie information is then sent back to the web server that issued the cookie upon each new web page acquisition, or "clickthrough," request made by the client within that particular web site. During the secure session, the cookie file is generally configured to expire when the client terminates the browser session, either by logging out of the web site or by closing out the browser.
The server can also utilize the cookie information for session tracking purposes. Sessions often include grouping individual and seemingly unrelated HTTP requests together to identify a particular client's session, as if the requests came across a single persistent connection between the server and the client. Of course, such connections are not persistent, as HTTP is really a connect-and-release protocol wherein a client makes a cormection to the server, sends a request, waits far a response, and then disconnects. This allows the server to service many more clients than would otherwise be possible if all the clients kept their connections open. However, it also means that a session may not be defined by a single persistent connection. Accordingly, many web sites track a user's session by accessing special information within a cookie file, such as a session ID, or even a security token, to maintain a database which logs the various cookie file submissions from a particular client within a given period of time to define a particular session.
Recently, there has been tremendous growth in the utilization of wireless devices, such as cell phones and personal data assistants (PDAs), with web-browsing capabilities. However, these devices usually pose significant challenges to web site operations, particularly in systems seeking to conduct secure sessions, session tracking, and other functionality typically associated with cookie files. Most wireless devices do not support the use of cookie files for various reasons, most notably is memory limitations on the wireless device. Cookie files tend to be very large, sometimes up to approximately 32 kb, and websites typically serve numerous cookie files within a single session. However, wireless devices typically do not have sufficient memory to handle these types of files, making such memory intensive interfaces problematic.
Various methods have been attempted to circumvent this problem. One method requests device-specific information associated with a wireless or handheld device and maps this device information onto a proxy database associated with a server for that device. For example, this information may be mapped onto a gateway between a client and the device. However, protocols for obtaining such information is often device specific such that a server is not always able to determine how to obtain this type of information from a particular device. Moreover, such methods often leave artifacts of device-specific information on third-party servers that are susceptible to cloning. Finally, some gateways do not store all types of cookies files. For example, some gateways permit the storage of only persistent cookie files, while excluding session cookies.
Another method, commonly referred to as "URL rewriting," essentially eneodes the necessary information onto a URL generated by the server. For example, where a server would normally return a standard URL as follows:                www48.amerieanexpress.com/en/intl?request_type=wl_CardsListHandler&Face=Ja_JP_IMODEa URL rewriting enabled Server might retain the following URL instead:        www48.americanexpress.com/en/intl?requst_type=wl_CardsListHandler &Face=ja—JP_IMODE&sessionid=f0bd52f63fbbf8b3dfdd3abb65e04cle
In accordance with this method, information that would normally be stored in a cookie is added to the URL string instead. When a request is received from the client, the server looks for this special session information in lieu of a cookie. Here, however, the length of such URL strings tend to become very long, and often surpasses the management capability of many wireless devices. For example, many wireless devices enable a URL capacity of approximately 100 characters or less, whereas many enhanced URL strings may comprise 100 characters or more.
In a related method, secure links are established using URLs where server communication with a client is conducted using secure socket layers (SSL). In this example, the SSL would be placed between the gateway and the server. In another example, unique identification data or session data may be added in a header of an HTTP request. However, this approach is also problematic in that client ID and password data are typically inputted through a Popup logon box, and many wireless devices are not compatible with this type interface.
Accordingly, systems and methods are therefore needed in order to overcome these and other limitations of the prior art.

Device independent authentication system and method

American Express Travel Related Services Company, Inc.


A glass antenna device for a vehicle includes a glass sheet to be fitted to a window opening of a vehicle, which has a first antenna conductor for a low receiving frequency band and a second antenna conductor for a high receiving frequency band arranged thereon; a first coil connected between the first antenna conductor and the second antenna conductor, the first coil having an inductance value which exhibits low impedance in at least the low receiving frequency band; wherein the first coil cooperates with a first other element to generate first resonance so that the first resonance has a resonant frequency existing in a lower frequency band region than the high receiving frequency band.

1. Field of the Invention
The present invention relates to a glass antenna device for vehicles which is suitable for a receiving set on a vehicle, and which is used for receiving signals in radio broadcast, TV broadcast, telephone communication and satellite communication or the like.
2. Discussion of Background
There has been known a glass antenna device (a first conventional glass antenna device) which, as shown in FIG. 28, includes a glass sheet 31 for an automobile rear window, an electric heating type defogger 33 arranged on the glass sheet and having heater strips 32 and bus bars for supplying power to the heater strips 32, an antenna conductor 136 which is capacitively coupled to the defogger 33 in proximity thereto so as to make transmission of a direct current therebetween and to prevent transmission of a high frequency current therebetween, and a choke coil 139 connected between the bus bars and a d.c. power source 10 for the defogger 33.
In the first conventional glass antenna device, the choke coil 139 is inserted between the bus bars and the d.c. power source 10 to increase impedance of the choke coil 139 in a high frequency band region such as a broadcast frequency region, thereby allowing a direct current to flow from the d.c. power source 10 to the defogger 33 and preventing currents in the broadcast frequency band region from flowing.
By this arrangements the choke coil 139 can isolate the defogger 33 from a vehicle body ground in terms of high frequencies, and prevent high frequency received current induced in the defogger 33 from flowing to the vehicle body ground, thereby transmitting the high frequency received current to a receiving set 20 in their entireties.
As a conventional glass antenna device (not shown) other than the one shown in FIG. 28, there has been a glass antenna device (a second conventional glass antenna device) wherein an antenna conductor for an AM broadcast frequency band (hereinbelow, referred to as the AM band) and an antenna conductor for an FM broadcast frequency band (hereinbelow, referred to as the FM band) are separately arranged in a glass sheet for an automobile window in order to improve receiving sensitivity. The second conventional glass antenna devices create a problem in that the antenna conductors occupy large areas to deteriorate a visual field.
In the first conventional glass antenna device, a decrease in inductance due to magnetic saturation has to be avoided in order to interrupt a high frequency current because a high direct current for the defogger 33 flows in the choke coil 139 at tens of amp. As a result, adoption of a special winding structure is normally required.
Since the inductance of the choke coil 139 is normally as large as 0.6-1 mH, and since the value of a d.c. resistance is required to decrease to minimize power loss, the winding of the choke coil 139 has to use a coil having a large diameter.
As explained, when the defogger 33 is used as an antenna to ensure good receiving sensitivity, the provision of the choke coil which has a large structure and which is large-sized and heavy, and measures to avoid receiving sensitivity in the FM band are required, creating problems in that the entire structure of the glass antenna device is complicated and productivity is low.
As to the second conventional glass antenna device, since, in receiving AM broadcast, the antenna conductor for the AM band is used without utilizing the antenna conductor for the FM band, receiving efficiency is low. It has been desired to develop a glass antenna device which can use both antenna conductors to improve receiving sensitivity and receive radio waves efficiently.


An intermediate-pressure turbine is divided into a high-temperature, high-pressure side high-temperature, intermediate-pressure turbine section 11a and a low-temperature, low-pressure side low-temperature, intermediate-pressure turbine section 11b, the component members of the high-temperature, intermediate-pressure turbine section 11a are formed of austenitic heat-resistant steels or Ni-based alloys, and the high-temperature, intermediate-pressure turbine section 11a is operated by steam having a temperature of 650° C. or more. Other turbines are mainly formed of ferritic heat-resistant steels. Thus, a steam turbine power plant having high thermal efficiency and being economical can be provided.

1. Field of the Invention
The present invention relates to a steam turbine-power plant provided with a high-temperature steam turbine, and more particularly to a steam turbine power plant provided with a steam turbine which has individual components comprised of suitable heat-resistant materials.
2. Description of the Related Art
Conventionally, because the individual components configuring thermal power generation facilities are used under steam conditions including generally a steam temperature of 600° C. or less, ferritic heat-resistant steels having outstanding productivity and economical efficiency have been used for main members such as a turbine rotor, a turbine blade and the like which are exposed to high temperatures (see Japanese Patent Publication No. SHO 60-54385, and Japanese Patent Laid-Open Applications No. HEI 2 -149649, No. HEI 6-306550 and No. HEI 8-3697).
In recent years, the thermal power generation facilities are positively made to be more efficient with environmental conservation as a background, and a steam turbine is operated using high-temperature steam having a temperature of about 600° C. Such a turbine has quite a few parts which cannot meet the required properties because of the various properties of the ferritic heat-resistant steels used. Therefore, austenitic heat-resistant steels and the like more excelling in high-temperature properties are used.
But, there were problems that the use of the austenitic heat-resistant steels increased the facility cost, and a thermal stress tended to occur at a time of change in load when the plant was activated or stopped because the austenitic heat-resistant steels had low thermal conductivity as compared with the ferritic heat-resistant steels and also had a high coefficient of linear expansion.
Therefore, it is proposed to configure a steam turbine generating system by restrictively using the austenitic heat-resistant steels for a steam turbine using steam having a temperature of 650° C. or more in comparison with a steam turbine using steam having a temperature of about 600° C. (see Japanese Patent Laid-Open Applications No. HEI 7-247806 and No. 2000-282808, and Japanese Patent No. 3095745). For such a steam turbine generating system, the austenitic heat-resistant steels having outstanding high-temperature properties are mainly used for a high-pressure turbine.
In the above-described steam turbine generating system, the high-pressure turbine is frequently set to have a pressure about four to six times higher than that of an intermediate-pressure turbine, so that the casing configuring the high-pressure turbine, a main steam pipe for guiding steam to the high-pressure turbine, boiler component members and the like are formed thick so to resist a high pressure.
But, the use of the thick austenitic heat-resistant steels increases the facility cost. Besides, the austenitic heat-resistant steels might generate an excessively high thermal stress at a time of change in load when the plant is activated or stopped because it has low thermal conductivity and a high coefficient of linear expansion. Therefore, it is necessary to suppress a load change rate to a low level at the time of activating or stopping the plant, and there are problems that operating characteristics are degraded considerably and the like in comparison with an ordinary steam generating plant.