text:
|Publication number
|Publication type
|Application number
|Publication date
|May 8, 1990
|Filing date
|May 18, 1988
|Priority date
|May 18, 1988
|Fee status
|Also published as
|Publication number
|Eric H. Urruti
|Original Assignee
|Corning Incorporated
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (4), Referenced by (12), Classifications (15), Legal Events (4)
|External Links: USPTO, USPTO Assignment, Espacenet
The present invention relates generally to coating compositions suitable for coating glass and glass products. More particularly, the invention relates to radiation-curable acrylate coating compositions for glass optical fibers.
A relatively recent innovation in the field of telecommunications is the development of glass optical fibers. These fibers, when properly protected by suitable coatings and cabling, have the capability of carrying large amounts of information over long distances with very low signal attenuation.
As is well known, however, protective coatings must be applied to these glass telecommunications fibers at the time of manufacture, both to preserve the inherent strength of the fibers and to protect them from certain types of bending which can induce signal loss in telecommunication cables. More specifically, the coatings applied to the fibers must enable them to resist short radius bending (so-called microbending) which can arise when the coated or cabled fiber is subjected to physical stress and/or changes in temperature in use.
In combination, these requirements dictate that the coating applied to the optical fiber have both substantial toughness and yet be soft enough to distribute transverse strain applied to the fiber. A wide variety of organic coating materials designed to meet these needs have been proposed for use as optical fiber coatings, including but not being limited to silicone polymers, silicone oils, lacquers, and urethane and/or acrylate polymers.
An additional requirement for optical fiber coating materials derives from the fact that very high optical fiber drawing speeds are now being employed in the industry for reasons of manufacturing efficiency. For economic production, therefore, a glass coating material is needed which can be rapidly applied to and cured on the surface of the optical fiber. Currently, the preferred coating materials for rapid optic fiber production are radiation-curable coating formulations which can be very rapidly cured without the need for solvent volatilization or heating, simply by exposing the fibers coated with the uncured resin coating material to intense radiation.
Among the radiation-curable coating formulations presently used for the application of protective coatings to glass optical fibers are radiation curable acrylate materials. These are typically ultraviolet-curable oligomers or polymers, available in liquid form, which exhibit good softness over a very broad temperature range, good tensile strength and toughness, and rapid UV curing characteristics.
Preferred examples of these UV-curable acrylate compositions are reported in published European patent applications EP 0204160 and EP 0204161. The compositions therein described, loosely termed UV-curable polyurethane acrylates in the art, are based on resins more specifically designated in these applications as acrylate-terminated polyurethane, polyurea, or polyurethane/polyurea oligomers.
It is of course important that the resin formulations selected for application to these optical fibers maintain properties over an extended period of time. Thus the coatings should not exhibit significant changes in properties, and especially in their elastic properties, with prolonged exposure to ambient temperature variations and other environmental conditions. Many of the older optical fiber coating materials exhibited substantial variations in properties when exposed to environmental changes, these variations being attributable to the chemical structure, purity, and/or the degree of cure of the coatings. To counteract these effects, it has been conventional to employ various additives such as antioxidants, UV-stabilizers, and antihydrolysis agents which help to stabilize the cured coatings against changes in composition and structure.
The type of additive employed of course depends upon the coating system being modified. Thus it is not readily predictable whether an additive having demonstrated effectiveness in one resin system will exhibit helpful or harmful effects when employed in a different resin system. In the case of polyurethane acrylates such as presently utilized for optical fibers, additives such as hindered piperidine derivatives have been used in the past. See, for example, "Weathering of UV Cured Coatings," L. R. Gatechair, UV Curing: Science and Technology, S. P. Pappas, Ed., Vol. 2, Chapter 7 (1985). However, other additives have not been used because of concerns about their effects on the cured and uncured resins. For example, it is known that antioxidant additives can interfere with the free radical curing process relied upon for the rapid curing of these resins.
When adding stabilizing constituents to UV-curable resin formulations for use as optical fiber coatings, several key properties of the resins must remain substantially unaffected. The additives must not reduce the curing speed of the resin used to apply the coating, must not undesirably affect the shelf life of the uncured resin formulation, and must not affect the short or long term elastic properties of the cured coating.
Presently available resins of the kind described in the aforementioned published European patent applications, some of which are currently used to provide high-elasticity, low-modulus, primary protective coatings on optical fibers, generally exhibit all of the required properties of rapid cure, low elastic modulus, and high toughness. However, it has recently been determined that at least some of these formulations do not exhibit the requisite thermal stability. Thus sample materials of these types have recently been evaluated which exhibit readily observable deterioration on brief exposure to elevated temperatures.
While the precise mechanism giving rise to the thermal instability observed in these coatings has no been identified, it has been observed that significant weight loss in the radiation-cured resins can be observed at heating temperatures as low as 85� C., with substantial losses occurring after even a relatively brief exposure to temperatures as low as 130� C. Moreover there is reason to believe that thermal degradation also occurs, although more slowly, at even lower temperatures such as may be encountered by optical fibers in actual use. This is deemed unacceptable since gas or liquid by-products of the degradation reaction could potentially cause fiber attenuation problems, as the result of unpredictable stress generation by these by-products when trapped in optical cables.
It is a principal object of the present invention to provide a solution to the problem of cured coating thermal instability in polyurethane and/or polyurea acrylate coatings of the presently used type above described.
It is a further object of the invention to provide stabilized polyurethane or polyurea coatings which, after curing, do not exhibit the rapid thermal degradation of the known coatings of this type.
Other objects and advantages of the invention will become apparent from the following description thereof.
One suspected mode of deterioration which could account for the instability of polyurethane and polyurea acrylate resins of the known type above described is oxidative depolymerization. Hence, interaction of the cured resin coatings with oxygen at elevated temperatures could cause the formation and volatilization from the cured resin of monomeric species or volatile organic compounds.
Investigations designed to test this hypothesis, however, have indicated that the postulated depolymerization reactions, if indeed they occur, can occur in the absence of oxygen and in fact will proceed rapidly in an inert atmosphere such as argon. Hence differential scanning calorimetry tests indicate an exothermic reaction at 90�-100� C. in argon for at least one commercial coating of the described type. This suggests that an important thermally induced mode of degradation for these coatings does not depend on the presence of large amounts of excess oxygen.
In accordance with the invention, a combination of additives has been identified which exhibits a high degree of effectiveness in stabilizing the cured resins against heat-induced depolymerization and/or other degradation reactions without unacceptable side effects. That combination is a combination comprising a hindered piperidine derivative and a hindered phenol derivative.
Hindered derivatives of this type have previously been used as antioxidants in polybutadiene systems. Thus M. G. Chan et al., in "The Stabilization of UV Curable Coatings for Optical Fibers," 4th International Conference on Plastics in Telecommunications, The Plastics and Rubber Institute, 14/1-14/9 (1986) disclose that these derivatives have shown beneficial effects in oxidative environments to retard polybutadiene resin oxidation.
Surprisingly, the identified combination of phenol and piperidine derivatives has now been found to be highly effective in reducing heat-induced depolymerization and/or other degradation reactions in the polyurethane acrylate systems of current commercial interest without unduly retarding the cure rate of these systems. This effectiveness is demonstrated over a relatively broad range of temperatures and at relatively low derivative concentrations. Further, thermogravimetric analyses (TGA) of compositions comprising these stabilizers show clear evidence that the reactions leading to coating weight loss can be significantly retarded in inert gas as well as under oxidizing conditions. Hence it is expected that thermally induced weight losses can be effectively eliminated with this combination of stabilizers at anticipated use temperatures in the cabled optical fiber environment.
The present invention therefore includes a method for stabilizing UV-curable polyurethane acrylate, polyurea acrylate, and polyurethane/polyurea acrylate resins against post-curing thermal decomposition, that method comprising the step of adding to the resins the above-described combination of stabilizers. The stabilizer combination will consist essentially of both a hindered piperidine derivative and a hindered phenol derivative, the combination being added in a concentration at least effective to reduce the thermal decomposition rate, i.e., the rate of thermally induced weight loss, exhibited by the cured resin.
The invention further comprises an improvement in a composition for a UV-curable polyurethane acrylate, polyurea acrylate, or polyurethane/polyurea resin of the known type, that improvement comprising the addition to the resin of a combination of stabilizers which comprises a hindered piperidine derivative and a hindered phenol derivative. The stabilizers are added in concentrations which, in combination, are at least effective to reduce the thermal decomposition rate of the cured resin.
UV-curable urethane-acrylate coating compositions suitable for stabilization in accordance with the invention include the known compositions described in European patent applications EP 0204160 and EP 0204161, these compositions comprising polyacrylate-terminated or acrylate-terminated linear polyurethane, polyurea, or polyurethane/polyurea oligomers as the principal components. By polyurethane/polyurea oligomers or resins is meant, for the purpose of the present description, a resin or oligomer comprising both urethane and urea groups in the molecule, such materials and the synthesis thereof being fully described in the referenced patent applications. By principal components is meant that one or a combination of these oligomers makes up at least about 50% by weight of the coating composition.
It has been demonstrated that compositions of this type can be modified with the described additives without incurring unacceptable increases in curing time, and without undesirably altering the elastic properties of the cured coatings. Further, the shelf life of uncured resins of this type which comprise the stabilizer combination, and the cosmetic properties of the coatings provided therefrom, remain substantially unaffected.
The invention may be further understood by reference to the drawings wherein:
FIG. 1 is a graph reporting weight losses for stabilized and unstabilized samples of cured polyurethane acrylate coating resins as a function of temperature;
FIG. 2 is a graph plotting long term weight loss at selected elevated temperatures for a stabilized cured polyurethane acrylate coating resin provided in accordance with the invention;
FIG. 3 is a graph plotting delay time to the onset of rapid thermal decomposition at several selected heating temperatures for a stabilized cured polyurethane acrylate coating resin provided in accordance with the invention, and
FIG. 4 is a graph plotting weight loss at an elevated temperature (190� C.) for a cured polyurethane acrylate coating resin before and after stabilization in accordance with the invention.
A number of tests have been employed in the prior art for the purpose of evaluating the stability of plastic resins over time. In the present work, however, thermal aging has been found to be the most effective method for evaluating the characteristics of cured urethane-acrylate coatings which exhibit the depolymerization behavior above described.
Thermal testing of these resins may be carried out in two distinctly different ways. The first approach involves determining weight loss as a function of temperature while heating a cured resin sample. The second approach is to heat the sample for a prolonged period at some fixed elevated temperature, continuously determining sample weight loss as a function of time.
Heating resin samples at constant temperatures for prolonged periods is considered more representative of actual aging conditions in cabled fibers, but aging at the projected upper use temperatures of cabled fibers, which temperatures are typically below 100� C., is not practical because of the very low rates of heat degradation at these temperatures. Therefore accelerated aging at temperatures somewhat above the projected upper use temperatures of the coating is used to develop information from which projections of the stability of the coatings at use temperatures can be made. Accelerated aging also aids in understanding the mechanisms by which deterioration occurs in these coating materials.
As previously noted, it has been established that the reactions causing rapid weight loss in the known UV-curable urethane acrylates occur even under inert atmospheres such as argon, i.e., in the total absence of free oxygen. Referring to FIG. 1 of the drawing, this effect is demonstrated by Curve A which plots the weight loss of an unstabilized cured sample of a polyurethane acrylate resin as the sample is heated in a flowing argon atmosphere over the temperature range 50�-350�0 C. As is evident from a study of FIG. 1, the unstabilized resin exhibits rapid weight loss commencing at about 130� C., with weight loss exceeding 20% at 300� C.
Curve B in FIG. 1 of the drawing demonstrates the behavior of a stabilized cured polyurethane acrylate coating provided in accordance with the invention on similar heating. In contrast to the behavior of the unstabilized coating, the stabilized urethane-acrylate resin plotted in FIG. 1 exhibits very little weight loss at temperatures below 300� C. in argon.
The significant difference between Curves A and B shows the unexpected effectiveness of the selected stabilizer combination in retarding the undesired depolymerization reactions observed on heating these coatings. Such behavior is particularly important in view of the fact that the optical cable environment, like that of the test environment, generally contains little or no free oxygen.
FIG. 2 of the drawing shows the results of thermogravimetric analyses (TGA) of a stabilized cured polyurethane acrylate coating material provided in accordance with the invention. The data shown are curves plotting sample weight over time, and were generated by TGA tests conducted on small samples of cured resin, wherein each of the samples was heated in air at a selected elevated decomposition temperature for a prolonged period. The elevated temperature for each test is indicated adjacent the curve corresponding thereto.
Characteristic features of TGA curves exhibited by these stabilized resin coatings and shown in FIG. 2 are a small but rapid weight loss (approximately 2%) on initial heating, due to the volatilization of low molecular weight unreacted materials such as monomers, photoinitiators, or water. This initial weight loss is followed by a more gradual weight loss over a relatively long time interval, the duration of which depends on both resin composition and the heating temperature. Thereafter, and even at the lower test temperatures, the samples exhibit a very rapid weight loss, quickly exceeding 10% of sample weight, which is clearly indicative of a substantial deterioration of the cured polymer.
The relatively long interval of gradual weight loss shown in FIG. 2 and occurring between the initial and final rapid weight losses of the samples is referred to as the induction time for the material. At any given heating temperature, this time interval is found to depend on the presence or absence of certain stabilizers, and on the composition and concentration of any such stabilizers present. Although the stabilized composition analyzed in FIG. 2 demonstrates near-zero induction times at 180� C. and above, the induction time at 140� C. approaches 280 hours. In contrast, the induction time for an unstabilized resin such as reported in FIG. 1 of the application is only on the order of about an hour at 140� C. As is evident from these figures, composition modifications which increase the induction time for the resin at a given temperature effectively decrease the overall rate of thermal decomposition exhibited by the cured resin at that temperature.
From data such as reported in FIG. 2 it is possible to determine the reaction or decomposition rate of a particular composition as a function of temperature, and from that function to predict the induction time for the composition at some selected lower temperature, e.g. the projected maximum use temperature for the material. FIG. 3 of the drawing is an Arrhenius plot of induction time versus temperature for a stabilized polyurethane-acrylate resin provided in accordance with the invention. In the Figure, the vertical axis indicates the induction time (t) in units of ln [1/t], while the horizontal axis indicates the test temperature (T) in units [1/T] or T in degrees Kelvin. The plot includes data at four heating temperatures, those temperatures actually lying in the range of 140�-180� C. and being shown in the field of the graph. The measured induction times ranged from approximately 1 hour at 180� C. to approximately 280 hours at 140� C.
Extrapolation of the plot of FIG. 3 to the projected maximum continuous use temperature of 85� C. for this particular coating suggests an induction time on the order of 100 years. While this result must be viewed cautiously in view of the fact that a synergistic combination of stabilizers is being used, it is apparent that a substantial safety margin against thermal decomposition of the coating has been provided.
As previously noted, an important concern associated with the use of additives to these UV-curable coating systems is that of cure speed inhibition due to the presence of the stabilizers. Additives of the antioxidant type have the potential for interfering with the free radical oxidation process involved in the curing of these resins. Nevertheless, while some slight increases in curing time are noted in the stabilized coatings provided in accordance with the invention, the increases are not of sufficient magnitude (below 15%) to be of concern. Further, the key properties of the cured resins, including the glass transition temperatures thereof, remain substantially unaffected.
Finally, an evaluation of the optical and other properties of the stabilized resins important in optical fiber coating applications indicate no major problems arising from the use of the disclosed stabilizers. No detectable difference in optical performance is seen between optical fibers coated with stabilized formulations and those coated with formulations comprising no stabilizing additives.
A slight increase in coating adherence to the glass fiber surface is observed in the stabilized coatings, with a slight increase in water absorption also being noted. However neither effect is of sufficient magnitude to significantly affect the utility of the coatings for optical fiber use, and in fact the stabilized formulations exhibited better resistance to cosmetic changes such as color and transparency variations during subsequent storage under ambient conditions.
Among the polyurethane acrylate coating compositions which can be stabilized in accordance with the invention are compositions wherein the major component, comprising 50% or more by weight of the composition, is a linear acrylate-terminated polyurethane, polyurea, or polyurethane/polyurea oligomer. These may be oligomers wherein the acrylate terminal groups are provided by a monohydric polyacrylate capping component, or by more conventional acrylate capping component such as 2-hydroxyethyl acrylate.
As is known, the polyurethane/polyurea oligomers are conventionally provided by reacting an aliphatic diisocyanate with a dihydric or diamino polyether or polyester, preferably a polyoxyalkalene glycol such as a polyethylene glycol. The oligomer typically comprises 4-10 urethane or urea groups, and may be of high molecular weight, e.g., 2000-8000. However, lower molecular weight oligomers, having molecular weights in the 500-2000 range, may also be used.
The coating composition will typically also comprise, in addition to the oligomer component, a lower molecular weight liquid acrylate-functional component and, optionally, a reactive diluent. The liquid acrylate-functional component is added to the acrylate-terminated polyurethane, polyurea, or polyurethane/polyurea oligomer component in order to provide the liquidity needed to apply the coating composition with liquid coating equipment. The reactive diluent is typically an acrylate monomer and, if present, is added to increase the curing speed of the composition.
Suitable acrylate-functional liquids are monoacrylate monomers and linear aliphatic diacrylates. The latter compounds may be low molecular weight polyalkylene (e.g., polypropylene or polyethylene) glycol diacrylates, a specific example of such a compound being tripropylene glycol diacrylate. The reactive polyacrylate diluent may be a triacrylate monomer, an example of such a compound being glyceryl propoxy triacrylate.
Many other polyurethane/polyurea acrylate coating compositions are described in published European patent applications Nos. EP 0204160 and EP 0204161, and those applications are expressly incorporated herein by reference for a further description of alternative acrylate compositions. As noted in these applications, the polyacrylate-terminated polyurethane, polyurea, or polyurethane/polyurea oligomers used in these formulations to impart the necessary low temperature softness are oligomers which have molecular weights in the range of about 2000 to about 8000.
These oligomers typically comprise from 4 to 10 urethane groups per molecule, with the urethane groups being wholly or partially replaceable by urea groups if needed to provide better cured resin strength. The urea groups, if present, may include from about 2 to about 6 urea groups per molecule.
The end-capping components or moieties used as terminal groups on these oligomer molecules are preferably monohydric polyacrylates, an example of such an acrylate being pentaerythritol triacrylate. These capping polyacrylates are bonded to the oligomers by means of diisocyanate linking molecules interposed between each of the terminating polyacrylate capping moieties and the opposing ends of the oligomer chains. This diisocyanate linking is conventional for UV-curable polyurethane acrylate formulations of the known type. The diisocyanates may be of relatively low molecular weight, or they can preferably be selected from among the longer chain diisocyanates such as 1,12-dodecyl diisocyanate.
Diisocyanate species are also typically employed in the synthesis of the polyurea and polyurethane oligomers, the diisocyanates described in the patents typically comprising at least 6 carbon atoms separating the two diisocyanate groups. Thus these oligomers are generally built up or formed by a reaction of the diisocyanates with dihydric or diamino polyethers or polyesters, the latter comprising alkylene groups of from 1-16 carbon atoms and molecular weights in the range of 500-4000. Examples of particularly preferred polyethers for this purpose are polyoxyalkylene glycols having molecular weights in the range of about 1000-3000.
The low glass transition monomers preferably included in the coating compositions of EP 0204160 to render them liquid at room temperature are acrylate monomers which can be cured by exposure to ultraviolet light. Examples of such compounds are ethoxyethyl ethoxyethyl acrylate, phenoxyethyl acrylate, butoxyethyl acrylate and the like, with ethoxyethyl acrylate being preferred. These acrylate monomers liquefy the coating compositions without unduly reducing the softness of the cured resins at low temperatures.
As is-well known, these polyurethane, polyurea, or polyurethane/polyurea acrylate coating formulations generally also comprise conventional photoinitiators, such as the known ketonic photoinitiating additives, these being present in amounts sufficient to provide rapid ultraviolet curing.
As previously noted, hindered phenol derivatives and hindered piperidine derivatives have been employed as antioxidants for butadiene-based UV-cure resins, and a variety of these derivatives are known. Hindered phenol derivatives have been described by Chen et al. and suitable derivatives of this type for use in the invention may include, for example, octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, tetrakis(methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate))4, and thiodiethylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate).
Hindered piperidine derivatives, also sometimes referred to as hindered amine light stabilizers, are also known, some of these materials being described by Chen et al., supra. One family of compounds which may suitably be employed in combination with the above described hindered phenol derivatives in accordance with the invention includes the bis(2,2,6,6-tetramethyl-4-piperidyl) sebacates, a specific example of this family being bis(2,2,6,6-tetramethyl-4-piperidyl) decanedioate.
Concentrations of these derivatives which are effective to usefully increase the induction time or time to rapid degradation of urethane-acrylate coatings in accordance with the invention will depend on the exact acrylate formulation selected for use. However, in the preferred formulations, concentrations of phenol derivatives in the range of about 0.2-1.0% in combination with piperidine derivative concentrations of about 0.2-1.0% will normally be preferred. Most preferably, the combination of stabilizers will be added to the coating formulation in proportion providing a total derivative concentration of at least about 0.5% by weight. Lesser concentrations of these additives are found to be insufficient to produce a useful stabilizing effect in these acrylate resin compositions, while greater concentrations risk undue increases in cure time and/or increasing degrees of instability in the uncured resin systems.
The invention may be further understood by reference to the following example.
A liquid coating composition suitable for apply as a UV-curable protective coating to a glass optical fiber is provided using a base resin consisting of a polyurethane diacrylate oligomer. This resin is a polyethylene glycolbased diacrylate having a molecular weight of about 508, and is commercially available as Sartomer 344resin from the Sartomer Company of West Chester, Pa., USA.
The liquid coating composition is prepared by combining 70 parts by weight of the diacrylate oligomer with 22 parts by weight of a liquid diacrylate effective to reduce the viscosity or the composition, 5 parts by weight of a reactive diluent, and 3 parts by weight of a photoinitiator. The liquid diacrylate included for viscosity control is a tripropylene glycol diacrylate having a molecular weight of about 300 and being commercially obtainable as Sartomer 306 resin from the Sartomer Company. The reactive diluent is a triacrylate monomer identified as glyceryl propoxy Lriacrylate and being commercially obtainable as Sartomer 9020 monomer from the Sartomer Company. The photoinitiaor is a ketonic photoinitiator identified as 2-methyl-l-(4-(methylthio)phenyl)-2-(4-morpholinyl)-1-propanone, this compound being commercially obtainable as Irgacure 907 photoinitiator from the Ciba-Geigy Corporation of Hawthorne, N.Y., USA.
The foregoing components are combined with thorough mixing to provide a liquid optical fiber coating composition, and then the liquid composition is divided into two portions and one of the two portions is chemically stabilized against thermal decomposition. This stabilization is achieved by the addition to the composition of a combination of a hindered phenol derivative and a hindered piperidine derivative.
The hindered phenol derivative employed is thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),commercially available as Irganox 1035 antioxidant from the Ciba-Geigy ,Corporation. The hindered piperidine derivative employed is a bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, this derivative being commercially obtainable as TinUVin 292 hindered amine light stabilizer from the Ciba-Geigy Corporation. The additions are in proportions providing weight concentrations of 0.5% of the phenol derivative and 0.5% of the piperidine derivative in the stabilized composition.
Each of the stabilized and unstabilized compositions thus prepared is applied as a thin coating to a number of glass test substrates, and the coatings are cured by exposure to 3.5 J/cm2 of ultraviolet radiation from a Fusion Systems D bulb. No significant difference in curing speed between the two compositions is noted, and the cured coatings are flexible yet sufficiently tough to provide an effective protective layer on the glass surface.
Samples of the cured coatings thus provided are next subjected to isothermal heating at 190� C. in air to determine stability against thermal decomposition. Results of this test are illustrated in FIG. 4 of the drawing, wherein curve A plots weight loss as a function of temperature for the composition free of the stabilizer combination, and curve B plots weight loss at the same temperature for the stabilized composition.
As is evident from these curves, the unstabilized composition (curve A) exhibits rapid and continuous weight loss over the entire testing interval at this temperature. In contrast, the stabilized composition (curve B) exhibits significantly higher stability as indicated by the prolonged period of gradual weight loss (induction time following the initial small loss of volatile components. The induction time for the stabilized composition or this Example is approximately 650 minutes at 190� C., or approximately equal to the induction time of the stabilized composition of FIGS. 1-3 at 160� C. Thus a substantial improvement in thermal stability without an objectionable attendant increase in curing time is achieved.
Of course the foregoing example is merely illustrative of stabilized formulations and methods for their stabilization which may be carried out within the scope of the present invention, and numerous variations and modifications of these specific procedures and composition may be resorted to within the limitations of the appended claims.
|Cited Patent
|Filing date
|Publication date
|Aug 4, 1975
|Oct 4, 1977
|Phillips Petroleum Company
|Stabilization of olefin polymers
|Mar 7, 1984
|Nov 26, 1985
|E. I. Du Pont De Nemours And Company
|Acrylic polyurethane coating composition
|May 8, 1985
|Aug 26, 1986
|Desoto, Inc.
|Polyacrylated oligomers in ultraviolet curable optical fiber coatings
|May 8, 1985
|Sep 2, 1986
|Desoto, Inc.
|Ultraviolet curable buffer coatings for optical glass fiber based on long chain oxyalkylene diamines
|Citing Patent
|Filing date
|Publication date
|Sep 30, 1993
|Mar 28, 1995
|At&T Bell Laboratories
|Optical fiber apparatus
|Sep 26, 1996
|Jun 30, 1998
|Lucent Technologies Inc.
|Method for the manufacture of optical gratings
|Sep 22, 1997
|Nov 2, 1999
|Dsm N.V.
|Radiation-curable compositions having fast cure speed and good adhesion to glass
|May 12, 2000
|Feb 26, 2002
|Dsm N.V.
|Process for preparing uniformly consistent radiation-curable compositions
|Jun 30, 2000
|Jun 25, 2002
|Corning Incorporated
|Use of inhibitor in optical fiber reel covers
|Dec 22, 2000
|Aug 5, 2003
|Corning Incorporated
|Optical fiber coating compositions
|Aug 11, 2006
|Dec 29, 2009
|Canon Kabushiki Kaisha
|Method of manufacturing ink jet recording head
|Sep 26, 2005
|Jan 19, 2006
|Canon Kabushiki Kaisha
|Ink jet recording ink, ink jet recording method, ink cartridge, and ink jet recording apparatus
|Aug 11, 2006
|Mar 15, 2007
|Canon Kabushiki Kaisha
|Method of manufacturing ink jet recording head
|Sep 21, 1994
|Apr 5, 1995
|AT&T Corp.
|Optical cable
|Jun 21, 2011
|Jan 5, 2012
|Dsm Ip Assets B.V.
|D1479 stable liquid bap photoinitiator and its use in radiation curable compositions
|Jun 21, 2011
|Jan 26, 2012
|Dsm Ip Assets B.V.
|D1492 liquid bapo photoinitiator and its use in radiation curable compositions
|U.S. Classification
|524/102, 524/291, 524/284, 522/97
|International Classification
|Cooperative Classification
|European Classification
|May 18, 1988
Owner name: CORNING GLASS WORKS, CORNING, NEW YORK, A CORP. OF
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:URRUTI, ERIC H.;REEL/FRAME:004912/0420
Effective date: 19880513
Owner name: CORNING GLASS WORKS,NEW YORK
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:URRUTI, ERIC H.;REEL/FRAME:004912/0420
Effective date: 19880513
|Oct 22, 1993
|Fee payment
Year of fee payment: 4
|Sep 29, 1997
|Fee payment
Year of fee payment: 8
|Sep 28, 2001
|Fee payment
Year of fee payment: 12


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I have a few videos up to 4 GB in size on an SD card. I am able to watch them and I think this proves they are intact.
But whenever I try to copy file larger than perhaps 1.5 GB, the operations dies after about 2 minutes saying it cannot read the source even though it was making good progress. I've had the same issue copying over USB from my camera directly.
Is there some blind timeout on copying a single file here? How can I tweak or bypass it?
In other words, how can I copy a large file that may need a few minutes from an SD card or USB to the hard drive?


text:
Dan D.
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text:
Pentax K-7
|I own it
|I want it
|I had it
The K-7 is Pentax's latest enthusiast/semi-pro grade DSLR. It the first Pentax DSLR to have a magnesium-alloy body making it smaller than the K20D it replaces, while still offering reassuring build quality. The body is weather sealed (though not weather proof) and features a 920,000 dot LCD and 100% viewfinder and the ability to shoot 720p HD movies. Like the models before it, the K-7 has image stabilization built into the body, stabilizing all lenses. It offers the high level of exterior control you'd expect on a camera at this level and its operation can be customized to a high degree.
|Body type
|Mid-size SLR
|Max resolution
|4672 x 3104
|Effective pixels
|15 megapixels
|Sensor size
|APS-C (23.4 x 15.6 mm)
|Sensor type
|Auto, 100, 200, 400, 800, 1600, 3200, (6400 with boost)
|Lens mount
|Pentax KAF2
|Focal length mult.
|Articulated LCD
|Screen size
|Screen dots
|Max shutter speed
|1/8000 sec
|Motion JPEG
|Storage types
|USB 2.0 (480 Mbit/sec)
|Weight (inc. batteries)
|750 g (1.65 lb / 26.46 oz)
|131 x 97 x 73 mm (5.16 x 3.82 x 2.87″)
Semi-pro spec for mid-range money makes the K-7 an incredibly attractive option for the serious photographer wanting something a little less mainstream without compromising performance. Solid as a tank and feature packed--yet surprisingly compact--the K-7's only real weak spot is its high ISO performance.
Good for: Anyone wanting a semi pro camera that won't make a hole in your pocket or weigh you down too much.
Not so good for: Low light work, movie makers
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|Jürgen Schmidt <jogischm...@googlemail.com>
|Re: [CODE]: changed about box
|Thu, 01 Mar 2012 16:32:50 GMT
On 3/1/12 5:24 PM, Ariel Constenla-Haile wrote: > Hi Jürgen, > > On Wed, Feb 29, 2012 at 04:10:43PM +0100, Jürgen Schmidt wrote: >> On 2/29/12 3:32 PM, Jürgen Schmidt wrote: >>> Hi, >>> >>> i have changed the about dialog box a little bit and would like to get >>> your feedback. >>> >>> I added a new key in the version.ini/versionrc >>> >>> Revision=<svn_revison_number> >>> >>> But after some experimenting I don't use this key right now but left it >>> in the version file for further references to the underlying revision. >>> >>> I changed the value of buildid in the version file to >>> >>> e.g. versionrc >>> ### >>> buildid=340dev1 (Revision:1294675) >>> # instead of >>> buildid=340dev1(Build:9586) >>> ### >>> >> >> I learned from Oliver that the space is not good. The "buildid" from >> the version file is used to generate the<meta-generator> entry in >> the ODF docs. >> >> Example: >> <meta:generator>OpenOffice.org/3.4$Unix >> OpenOffice.org_project/340dev1$Rev-1294675</meta:generator >> >> That means the space have to be removed and probably more work is >> necessary. >> >> Maybe I should switch back to my experiment with the "Revision" key >> and adapt the code for the about box. >> >> I will keep you informed ... > > In my tries I've found that the easiest way to change this is in sub > replace_setup_variables solenv/bin/modules/installer/scriptitems.pm#789 > > See > > my $buildidstring = $localbuild . $localminor . "(Build:". $installer::globals::buildid . ")"; > > This is where the buildid in versionrc|.ini is generated. > You can try to get the revision from svn, if not possible, then from > git, if not possible, default to the above code. yep, I have played with this code and added the part for the revision number to become part of the version file. > > (I have some working code, but didn't have time to test it other than in > git). just checked in some code a few minutes ago. As a result of some further investigation I thought it might be a good idea to keep the buildid for now and increase it for every public build. Means dev snapshots, RC, release. I added the revision number in the About box independent of the used --with-build-version switch because I think it can be a useful info. And I also reduced the font size for the build info to make the productname + version more dominant here. As I mentioned earlier more changes for the next release. And no I wasn't able to figure out how to make the build info copyable :-( Juergen > > > Regards
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Apollo 11
Content Marketing Put a Man on the Moon, What Can it Do For You?
NASA not only put the first man on the moon, but pioneered the use of brand journalism, product placement, and real-time storytelling with the epitome of transparency and authenticity. Here's what you can learn from marketing the moon.
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Pope Francis on Saturday said Catholics should not be afraid of renewing "old and flimsy structures" in the Catholic Church and urged future priests and nuns to buy "humble" cars and respect their vows of poverty.
"In Christian life and in Church life too there are old and flimsy structures. We need to renew them," the pope said in his homily at a private mass for Swiss Guards, Vatican radio reported on its website.
"We should not be afraid of allowing the flimsy structures that imprison us to fall down," he said.
"The Church has always allowed itself to be renewed... That is how the Church has developed, leaving it to the Holy Spirit to renew these structures. We should not be afraid of this," the pope was quoted as saying.
The pope later on Saturday addressed thousands of cheering trainee priests and nuns from around the world at a special audience in the Vatican in which he urged them to remember their vows of poverty.
"I feel bad when I see a priest or a nun with the latest car model. This cannot be!" he told them.
"Maybe you need a car to move around for work but get one that is more humble. If you like the nice one, just think how many children die of hunger," he said.
"Wealth does a lot of harm. We priests and nuns need to be coherent about our poverty," he said.
"I would like a more missionary Church, not so tranquil. A beautiful Church that moves forward".
Francis, a moderate conservative elected by a conclave of cardinals in March, is planning a major overhaul of the Vatican bank and bureaucracy and has previously said he would like a "poor Church for the poor".
He has launched an investigation into the Vatican bank and has ordered a group of top cardinals to propose ways of reforming the Vatican administration at a meeting planned for October.
The Vatican bank, the Institute for Works of Religion, is at the centre of an Italian money-laundering probe but the Vatican has made efforts in recent years to bring it into line with international rules.
A series of leaks of confidential Vatican documents by then pope Benedict XVI's butler last year exposed allegations of corruption and mismanagement in the Roman Curia, the central administration of the Church.


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Thora Birch
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Age: 34, born 11 March 1982
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Description: From Monkey Trouble (1994) to Americká krása (1999)-- that's Hollywood "Hocus Pocus"! Thora Birch was born on Thursday (as in Thor's Day) March 11, 1982. Her father, Jack Birch, and mom, Carol Connors (both parents are producers and performers of adult films), named her after the Norse God Thor ("Thora" being the feminine), the God of Thunder; she has a younger brother named Bolt Birch. Thora appeared in one of the "classic" California raisin commercials in 1986 (at age 4), and later did other commercials. At age 6, Thora appeared in Purple People Eater (1988) and won a Youth in Film Award for her ... (more)
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B&H Photo celebrates release of iPhone and iPad apps with exclusive MacBook dealsApple power reseller B&H Photo is celebrating the release of its first iPhone and iPad apps by offering AppleInsider readers exclusive pricing on a half dozen MacBook Air and MacBook Pro models.
The free apps (AppStore: iPhone and iPad) aim to deliver all the speed and flexibility of shopping B&H's vast product catalog on a traditional computer, but from an iPhone or iPad in the palm of your hand.
The apps showcase products in a clean and bright user interface with full-screen high-resolution photos, quick links to PDF-based guides and user manuals, professional reviews, a powerful product search, and clearly marked rebate and promotional offers, as well as real-time product availability feedback.
To celebrate the launch and help spread the word, B&H is offering AppleInsider readers exclusive pricing on the following MacBook Air and MacBook Pro models. The MacBook Air prices are for the notebook only, while the last three MacBook Pros are bundled and priced with 3-years of AppleCare extended warranty protection. These last three bundles knock 50% off AppleCare in addition to the savings on the MacBook Pro.
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Prize Details
[Image credit: Jodie Wells | Zealous Search | 2014 | oil on canvas | 105 x 105 cm ]
The Sunshine Coast Art Prize 2016 offers a major prize of $25,000 cash plus a residency at Montville Country Cabins. The winning work is added to the Sunshine Coast Art Collection. A non-acquisitive Highly Commended $5,000 prize sponsored by the Proost-De Deyne family and People's Choice $2,500 prize are also on offer. The award is open to any Australian resident.
Major Prize – $25,000 cash
Sponsored by Audi Centre Sunshine Coast and Sunshine Coast Council, plus artist studio residency sponsored by Montville Country Cabins
Highly Commended Prize – $5000 cash
Sponsored by Proost-De Deyne Family
People's Choice Prize – $2500 cash
Sponsored by Caloundra Chamber of Commerce
Key dates
- Entries open: Monday 1 February
- Entries close: Friday 15 April
- Finalists announced: mid-May
- Exhibition dates: Thursday 18 August to Sunday 2 October
- Official Opening and winners announced: Thursday 1 September
- Exhibition venue: Caloundra Regional Gallery


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Read an Excerpt
MinnesotaThe Prairie Blossoms with Love in Four Complete Novels
By JoAnn A. Grote
BARBOUR PUBLISHINGCopyright © 2003 JoAnn A. Grote
All right reserved.
Chapter One
They're not going to chase me away!" Laurina Dalen stood alone on the edge of the bluff, silhouetted against the vast pearl gray sky of early morning, and flung her declaration into the air with bright determination. "For fourteen years I've waited to return to this beautiful wild prairie, and I'm not going to let some grasshoppers chase me away now."
Her brown cotton skirt billowed out behind her in the wind that rose with the sun each day on the prairie. The deep brown of the wool shawl clutched about her to ward off the chill in the morning air was drab beneath the rich chestnut curls cascading about her slender shoulders.
But Laurina's mind wasn't on the cold nor on the wind that playfully tugged at her hair. Her thoughts followed the gaze of her large brown eyes to the covered wagons in the cottonwood grove of the village below.
The bellows of oxen, the voices of men shouting orders, and the creak of wagon wheels were carried up the bluff by the wind and sounded loud to Laurina compared to the usual silence of the plateau. Beneath the waving, empty branches of the cottonwoods, men scurried about loading last minute supplies, and women hugged friends and neighbors farewell. The stripped branches, more typical of the branches in December than the last week in July, were a grim reminder of the grasshoppers that were forcing these people from the fertile lands of western Minnesota.
The voracious green creatures were gone now. They had left over a week ago in one large, dark cloud. But they were still chasing away her friends-the strong, vital people she had come to know this past year. The wagons were heading farther west, some to the goldfields of the Black Hills, some beyond to the Pacific. The people would find new lands, build new homes, dream new dreams.
But Laurina's dream was here in Chippewa City. In spite of the grasshoppers, the drought, and the hailstorm that had combined to wreak havoc with the crops, she had never been so gloriously happy. Just living with her father again after fourteen years was cause enough for joy.
And there was Matthew-Matthew Strong, the only doctor in Chippewa County.
"Thank You, Lord. Thank You that Matthew isn't leaving," she breathed softly. Her smile deepened as she pictured his hair that shimmered like soft gold when the sun shown on it, his wide face with its lively eyes the blue of Minnesota's lakes on a sunny summer day, and his cheeks that were always ruddy from the sun and wind.
She hadn't seen him for five days, but it wasn't uncommon for Matthew Strong to spend days out on the prairie of southwestern Minnesota visiting patients. His office was here in Chippewa City, but he felt such a responsibility for the scattered settlers that he visited the more distant settlements at least once every few weeks.
Laurina knew that Matthew tried to see as many patients as possible on each trip so the hours he spent bouncing across the lonely prairie on a hard buggy seat would not be wasted. The prairie grapevine, still amazing to Lamina after her many years in the East, preceded him as he came near their homesteads. As she looked out over the valley, Laurina smiled to herself. What was it about Matthew that caught her heart when she had been immune to the young men who had courted her back east? Was it his sense of responsibility, his dedication to helping people, that kept him here on the prairies of western Minnesota where his patients often couldn't afford to pay for his services?
Or was it the way Matthew rejoiced in just living? Despite the heavy responsibilities he carried on his broad shoulders, he had the most joyous spirit of any man she knew. Perhaps, above all else, it was his love of life that drew her to him. When she was with him, she felt like a carefree schoolgirl rather than an aging spinster of twenty.
How she loved him! But Matthew, the only man who filled her waking and sleeping hours with dreams of a future together, had never spoken of love or marriage, had never kissed her. Instead of flirting with her, he normally spent any time they were together teasing her. Sometimes when the teasing in his voice and eyes turned to tenderness, she let herself hope he might return her love. A thousand times she had imagined being swept into his muscular arms, his voice husky with emotion as he confessed his love for her, his eyes-
"Morning, Miss Boston."
Laurina jumped as the voice that had been playing in her mind spoke from behind her, and she whirled around to look up at the young giant. If he only knew what she, a minister's daughter, had been thinking, he wouldn't call her by that proper nickname! As usual his flashing smile and sparkling blue eyes caused her heart to skip a beat. She tripped over her simple words of greeting.
"M-Matthew! I mean, Dr. Strong. I-I didn't hear you come up."
Matthew pushed the broad-brimmed black hat back on his head, exposing his blond hair to the morning's rays, and warmly smiled down at her. "Thought the 'hoppers stripped the prairie of flowers, but I can see now I was wrong."
Confused but pleased at his words, Laurina lowered her lashes over flushed cheeks. She hugged her shawl more closely about her shoulders in an effort to muffle the beat of her runaway heart. Unsuccessfully, she struggled to think of an appropriate answer.
"Not going down to say good-bye to anyone, Boston?"
She brushed back tendrils of coppery hair the wind was whipping into her face and shook her head. "No, I've said my good-byes."
She turned back to the scene in the valley-it was easier to keep her thoughts together when she wasn't trying to meet those captivating eyes. Such a thing to worry about when our friends are leaving their homes, she reprimanded herself silently as she watched the bustling people below. "I feel sorry for them, Dr. Strong. It must be hard to leave. They all had so many dreams when they came here."
"They'll make new dreams, Boston. They're a tough lot, for the most part."
"Father is down there. Some of the people asked if he'd pray with them before they left. I thought ...," she hesitated, then continued with a rush, "I thought I'd pray for them from up here. Somehow, it seemed appropriate, as though the blessing would float down and settle over the tops of the wagons." She glanced up at him. "I guess that seems silly."
The blue eyes she loved looked down at her. "Doesn't sound silly to me. Expect they can use those prayers. Mind if I join you?"
Laurina stared at him in surprise as he bowed his head. They had never prayed together before.
They stood next to each other, etched against the slowly bluing sky, as Matthew brought their request before God. "Lord, we lift our departing friends before Thee. We ask that Thou keep them safe as they journey and supply their daily needs. Guide each family to the place Thou hast reserved for them alone and refresh their spirits with hope. We leave them in Thy arms, Lord. Amen."
"Amen," Laurina repeated softly. We haven't even touched, yet I've never felt so close to him.
"The wagons look like loaf after loaf of frosted bread, don't they?" she said, breaking the comfortable silence.
"Might wish we had some bread here before the winter's up, frosted or not. Looks as though only one field in the county survived the 'hoppers. Won't be half enough flour to go around this winter." His tone was matter-of-fact, with no hint of bitterness.
As she contemplated his comment, Laurina's fingers played idly with the edge of her shawl. Last year the grasshoppers had turned their ravenous appetites on the waving fields of wheat in Chippewa County and approximately half the crops had been lost. This year was far worse-even the gardens of Chippewa City had been invaded. There were no vegetables to be had anywhere, at any cost.
The people who remained spoke of a brighter future. Laurina was fiercely proud of the way they held to their hope in the midst of poverty, in the face of the stagnation of the young community. She was glad to be one of them.
She lifted her pointed chin a trifle, and determination glinted in her usually soft eyes. "Well, a few green pests aren't going to chase me away!"
Matthew's laugh rang out on the morning breeze. "A few green pests? You know, you make a pretty good prairie woman for a lady from Boston."
Laurina drew herself up to her full five feet, squared her shoulders, and looked up indignantly at him. "I was living on the Minnesota prairie long before you."
"Until you were six years old. Hardly counts as pioneering," he chided playfully.
"You can't look down your nose at me too much, Dr. Strong. After all, since no one lived here ten years ago, everyone in Chippewa City is a transplant. Some of them even come from Boston."
"Ah, yes," he agreed amiably, disciplining the smile on his lips though not succeeding with the laughter in his eyes. "But there's a mighty difference in the transplanting of a farmer or a blacksmith and the transplanting of a proper Boston maiden. Yet, I admit I'm fairly impressed with your progress." As he looked at her, he rocked back on the heels of his dusty boots, lifted his eyebrows, and tilted his head.
Was that a hint of admiration she saw lurking behind the laughter in his eyes? "I'm going to pretend you meant that as a compliment and change the subject." She turned her back on him primly and looked out over the valley again as he chuckled.
Below them, simple log and frame buildings straggled bravely alongside the dusty main street at the bottom of the bluff. Her eyes roamed past the river that bordered the town and the stripped cottonwood grove with its band of wagons to the far bluff and beyond where the prairie resumed its unending flat expanse.
"I'm glad Father's cabin is built up here where the view goes on forever, rather than down in the valley. It seems impossible that there will ever be more buildings up here on the bluff, what with so many people leaving."
"But the town fathers have plans for this village, Boston. It's not going to stay trapped down there forever." Matthew swung around, taking in the plateau behind them with the sweep of his arms. "They don't see just a one-room schoolhouse and a half-dozen log homes up here like there are now. They see rows and rows of tall, fine houses, with churches there, and there, and there." His broad index finger stabbed the air. "And maybe over there a university, a large brick university standing solid and majestic against the prairie winds. With a library beside it, filled with the knowledge and literature of the world. And trees, trees everywhere-elms and oaks and maples and cottonwoods-stretching their limbs out over wide streets, sheltering fine carriages pulled by matched mares." With a wink and a grin, he looked over his shoulder at her. "Carriages filled with beautiful women." He rested his hands on his slender hips, his eyes shining over the barren plateau. "It's going to be a fine town, Boston."
Laurina smiled at his enthusiasm. "I can almost see it growing before my eyes when you talk about it like that." This is what I love most about him, she thought. The eager way he approaches life.
"It's the most up-and-coming town on the prairie, Boston. Even the St. Paul Pioneer Press says so."
"Those statements were made before the grasshoppers came, Dr. Strong."
He brushed her argument aside with a wave of his hand. "The 'hoppers are gone now, and the most reliable reports say they won't be back next year."
"The people are leaving, also," she reminded gently, nodding toward the crowd bustling about the wagons in the valley below, "and not only the farmers. The probate judge has already left, and one of the owners of the mill And now the sheriff, the tinsmith, and the farm implement salesman are leaving."
"Merchants from the East and immigrant farmers poured into the area before the 'hoppers came, and they will again, you'll see."
Before she arrived last year, Laurina thought the destruction of the crops affected only the farmers. She hadn't realized that the entire economy of a new town on the edge of the frontier was dependent on the farmers for survival. Chippewa City was less than ten years old and hadn't the capital to withstand the economic blow dealt by the grasshoppers.
Wind-tangled curls brushed her shoulders as she shook her head. "You are an eternal optimist."
His beautiful smile flashed. "So are you, or weren't you just telling me a few minutes ago that the 'hoppers weren't going to chase you out?"
"Well ..." A grin tugged at the comers of her mouth, and she bent her head, studying the ground to hide the laughter in her eyes.
"So here we are, two optimists in the middle of a county entirely destroyed by 'hoppers. And what's wrong with that?" He shrugged his broad shoulders. "Remember the verse your father preached on Last Sunday?"
Laurina stared at him in surprise. First he prayed with her, and now he was talking about Scripture?
"You remember, Boston, the verses from Joel 2," he urged.
"I remember, it's just-" She swallowed her astonishment. "I remember. `And I will restore to you the years that the locust hath eaten, the cankerworm, and the caterpiller, and the palmerworm, my great army which I sent among you. And ye shall eat in plenty, and be satisfied, and praise the name of the Lord your God, that hath dealt wondrously with you: and my people shall never be ashamed.'"
Matthew nodded emphatically. "That's the one. `I will restore to you the years that the locust hath eaten.' I believe that. Besides, looking on the dark side of things never solved any problems. Sure never built any dries! And Chippewa City will be a fine city one day, Boston. You'll see."
I can see a lot of things I haven't seen before, Lamina thought, and I like what I see. "If everyone else did leave this town, I declare you'd build it yourself, Dr. Strong."
"Wouldn't have to build it all by myself, Boston, since you're determined to stay put." The look he gave her sent chills scurrying all the way down to her toes.
Laurina's gaze seemed glued to his. She tried to swallow the lump growing in her throat. Unsuccessful in the attempt, she forced her voice past the maddening obstruction. "S-sounds like building that town you described is more your vision than it is the town fathers'."
"That's only a piece of my vision." Matthew turned back to the broad, empty plateau, his hands on his hips, a distant look gentling his face. "I want a hospital here, Boston. A place where people can come when they're sick, instead of lying in dirty sod huts and cold log cabins scattered across the prairie where I can't reach them in the middle of a blizzard."
Excerpted from Minnesota by JoAnn A. Grote Copyright © 2003 by JoAnn A. Grote
Excerpted by permission. All rights reserved. No part of this excerpt may be reproduced or reprinted without permission in writing from the publisher.


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Hendersonville, NCUSA
Hometown: Hendersonville
January 25, 2009
1. From my friend Jacqueline Corbett... 2. I started Asheville's Rawfood Meetup in November 2006 3. Support in making healthier choices and hanging out with the best folks in the mountains. 4. Monthly birthday celebrations...? 5. Kale chips
I'm looking forward to being with you guys again.
Meetup members, Log in
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Chapter 3 - Milla
Edit Page Last Edit: 2 years 10 months ago
Chapter 3 is where the game's story really begins to unravel and focus will shift more towards the main plot. A short chapter overall with relatively few sub-events to complete. Check down below for our guide through the third chapter of Tales of Xillia told from the perspective of Milla Maxwell.
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So, I have a spider that crawls pages, harvesting data for each item it encounters. If the item has no options, it simply sends the item down the pipeline. If there are options, it assembles a list of option lists, and sends a request for each unique combination of options (returns as HTML snippet, so I treat it like XML). For each option combo, it extracts the price for the item and sends that down the pipe. Only, it doesn't.
Here's some code:
#spider code above here that does all the normal stuff,
#plus gets and organize all options. Then this:
for optLists in uberList:
queryString = '?func=Options¤tOption=1&Modal=False&AddUniqueID=False&sku=' + sku + '&option1=' + optLists[0] + '&option2=' + optLists[1] + '&option3=' + optLists[2]
reqURL = urljoin(baseAjaxURL, queryString)
req = Request(url=reqURL,
meta = {'item' : item},
self.log('simplified item: ' + reqURL, level=log.DEBUG)
yield req
And the callback function:
def parse_ajax(self, response):
print 'parsing ajax'
xxs = XmlXPathSelector(response)
item = response.meta['item']
item['price'] = xxs.select("normalize-space(substring-before(substring-after(.//skuMainPrice/text(), 'ppPrice:'),'/span'))").extract()[0]
print 'parse_ajax price: ', item['price']
return item
The for loop in the first method fires correctly, once for each set of options. The Request throws an error if the callback is to a nonexistent method (which is good), but the print statements in the callback method never fire, nor is the item propagated down the pipeline.
Any advice on what I'm doing wrong or how to do it right would be appreciated.


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Welcome to the 2016 Season of P10 Select Fantasy Racing.(last rev date: 7/21/16 11:20 am CST)
All Entry Lists are now ready!!
* Point system for Cup, Xfinity and Trucks series will be adjusted to the new format NASCAR announced for 2016
Dirt Track Racing at Eldora!Kurtiskraft earns her seventh career victory in the P10 Trucks series.
Xfinity in New HampshireKEKE races to victory lane in the P10 Xfinity series with a top score of 779.
New Hampshire 301bryce1897 earns 1st career Cup series victory in New Hampshire.
BTS in New Hampshire Sees Multiple WinnersKyle Busch was the selection of the day as 7 players tied for the top spot in New Hampshire.
GRE Gets Win in Week 19 Elite.GRE earns his third career victory in the Elite series race at New Hampshire.
P10 Qualify Washed Out by Rain at Kentucky.


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Why Hire Utah Bike Law?
You probably need to make a decision about hiring a motorcycle lawyer because you have been in a crash. You also have probably looked at other motorcycle lawyer websites and thought we all offer the same thing – "we will fight hard for you" – "we are the best" – "we… fill in the blank – bla-bla-bla." How are you supposed to make a decision?
Well… we are different…
First of all…
I am the owner of Utah Bike Law and I am the motorcycle accident attorney who handles your case. This is not so in the large personal injury firms where your case will probably be assigned to an associate or junior attorney. This means I have a vested interest in doing the best possible job I can for you – why – because Utah Bike Law is my firm and I care deeply about the outcome of your case.
I have been a motorcycle rider for over 30 years. I ride my motorcycle to work almost every day. I love riding my motorcycle. So what, you might ask. Well, I think it takes a motorcycle accident attorney who actually rides a motorcycle to appreciate – I mean really appreciate – how the crash happened. If you are not a motorcycle rider you can not understand, really understand, how the crash happened. This means I can make strong arguments in your behalf to get the best value for your case.
I am a registered nurse. This is important because, as a registered nurse, I can read your medical records and make sense of them and then use that knowledge to convince the insurance companies to pay fair value for your injuries from your motorcycle crash.
You need an accident attorney who is skilled at taking cases to trial. This is important because insurance companies know the attorneys who will, and will not, take cases to trial. The insurance companies often pay more on claims when represented by an attorney who is ready, willing and able to go to trial if necessary. We go to trial if necessary, however most cases settle short of trial. Having said that, the insurance companies will only pay top dollar if they know you will go to trial when necessary.
Contact George at Utah Bike Law
OK – we will stop blowing our own horn. If you need help or just some simple straight answers about your accident case, contact us and we will be happy to help you out – however we can. By the way – if you are in a crash and need immediate help call and leave a message – the message goes directly to my cell phone and I will get back to you ASAP!
I welcome you to follow us on Facebook and/or Twitter – let's all watch out for each other out there!


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8 Chains North is a small family-owned and -operated farm winery located in the town of Waterford in picturesque Loudoun County, Virginia. Our business began in 2006 when our original vineyard, Furnace Mountain, was planted by father and son on the bluffs of the Potomac River. We believe that the best wines begin in the vineyard, and invite you to enjoy a glass or bottle with us.
July 24: Music & Wine on Rt. 9
Join us today from 2:00–5:00 for live music from "Panhandle Dan." Dan Cronin is one of those musicians who can play it all—Rock, Folk, a little Bluegrass. His laid-back style is sure to entertain (and would make a great pairing with our 2015 Sauvignon Blanc). Come "wine down" your weekend at 8 Chains North.
Vineyard Weddings
Recently engaged? If you and your beloved are looking for a special place to hold your wedding, 8 Chains North just might be the perfect venue for you. With ceremony space overlooking the vineyard, our beautiful and intimate Compass Rose Banquet Room for your reception, and some of Loudoun County's best wines, you and your guests will enjoy an authentic winery experience you'll remember for many anniversaries to come. Take a look at some of the gorgeous photos and get more information. >>
Be Part of the Chain Gang
If you love our wines, we invite you to become a member of our wine club—affectionately known as the Chain Gang. Chain Gang members enjoy special benefits and events, as well as wine crafted exclusively for them. 20% discount on quarterly wine purchases, 20% discount on all wine purchased at the Tasting Room, free tastings for members and one guest each, and more. Join Now!
Photo by Jennifer Godbold Photography.


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Orange County Rescue Mission, Inc.
Rating: 5 stars 2 2 reviews
One Hope Drive Tustin CA 92782 USA
The Orange County Rescue Mission desires to bring help and hope to the homeless and needy of Orange County California. Our Vision is to minister the love of Jesus Christ to the least, the last and the lost of Orange County through the provision of assistance in the areas of guidance, counseling, education, job training, shelter, food, clothing, and health care.
Geographic areas served:
Orange County and Inland Empire, CA
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1 person found this review helpful
the most hopeful & promising missions facility i have ever seen.
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I've personally experienced the results of this organization in...
i had a conversation with a grateful and changed resident, who told me of his rescued life and that of his family, and understood this conversatioon for be somewhat of a divine appointment for me... something i really needed to see, and god arranged just the right person for me to hear it from.
If I had to make changes to this organization, I would...
have other drop off locations for donations all around orange county


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I notice if I make a HTML form and use it as a submit form it automatically uses the title as meta info. Example if I post then copy and past that posts title into the Google search if unique it will pull up the post in the search results. I can't get this to do the same using a Gravity form for some reason. Is there something I'm missing in the theme or a setting in the form? Maybe a merge tag in the title field, like "embedded url" or and such?
I do have this in my header.php not sure if it applies
<?php if (is_single() || is_page() || is_archive()) { wp_title('',true); } else { bloginfo('description'); } ?> — <?php bloginfo('name'); ?>
Please help


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This Sweet-Smelling Perfume Is A Bug Spray In Disguise
Listen, we hate mosquitoes as much as the next girl, but we're also not so keen on smelling like nose-burning chemicals every time we apply our bug spray. Obviously this is a total #firstworldproblem, but for those of us who spend the majority of our time outdoors, we're getting a little sick of being constantly enveloped in an unpleasant funk. Is it too much to ask that we have some options that are a little less, shall we say, pungent?
Apparently not, thanks to Harvard business grad Melissa Fensterstock and her husband. They've founded a new, functional fragrance brand called Aromaflage, and their debut product is a chemical-free, DEET-free perfume that claims to keep the bugs at bay. While many natural scents do have bug-repelling properties, sadly, geranium, tea tree oil, and the like — while lovely non-chemical alternatives — are not the most pleasant aromas to douse oneself in. Aromaflage solves that problem by using essential oils that are a little gentler on the olfactive senses.
The secret behind its bug-be-gone powers is vanillin, a crystalline compound found in vanilla beans that has been proven to be highly effective at repelling mosquitoes. It also has vanilla, cedarwood, and exotic orange, which gives the perfume a warm, sweet aroma.
Our one concern with the scent is how effectively it keeps the bugs from swarming if you use it like a perfume. We don't normally drown ourselves in fragrance — just a few delicate spritzes — and we wonder if that little bit will do it, or if we'll need to cover our exposed skin like we do with traditional bug spray. We've packed this in our weekend bag, so fingers crossed — if we come back on Monday scratching and itching, we'll be sure to let you know.
Aromaflage Botanical Fragrance & Insect Repellant, $65, available at Aromaflage.
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From Our Editors
Guaranteed to be in good hands for your personal eye care. There's no better place than Ultimo Eyewear in Huntingdon Valley! Ultimo Eyewear has a wide selection of hard and soft lenses, as well as stylish designer glasses.
Walk-ins are more than welcome. This vision center is waiting for you now. Your beauty services can be paid for with a major credit card at this establishment. Ultimo Eyewear's customers can park in a neighboring lot just seconds away. Commute by bike to Ultimo Eyewear and find easy bike parking. At Ultimo Eyewear, you can be sure the expert staff will see you through to better vision.


text:
The Gym is really nice and the attendants are helpful.
the place is clean and a good place to relax.
It is also well equipped and in a good environment
Own or manage this property? Claim your listing for free to respond to reviews, update your profile and much more.


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Who should I choose; daughter's father or friend?
This is little hard to explain so please bear with me. My daughters father broke up with me two months before I had her but then got back together with me after few months. But...
Started by Alisha on 09/18/2010 in Moms Doin' It Alone
Last update on 09/24/2010 by Michala


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It seems that, every time I search for my ancestors bearing this surname, there is a different spelling *sigh*. Sometimes it is used as a middle name on a death certificate, where it didn't appear on the birth certificate. It makes searching for a brickwall ancestor very frustrating. But when it comes to the surname's religion...
Johanna YATES (or YEATES or YEATS) was born in 1808 in Chudleigh (my ggg grandmother). Or it might have been Colridge. Or Coldridge (even the town can't make up its mind how to spell its name!). Her mother, Sarah, was unmarried at the time of the birth - and has vanished ever since, so maybe she married another man and I haven't discovered her new surname. It will probably be something unusual, like JONES in Wales *genealogical cringe*... Sarah was christened in 1780 like many of my ancestors, as an Independent. Later members of the family were described as Congregationalist. From Wikipedia:
"In English church history, Independents advocated local congregational control of religious and church matters, without any wider geographical hierarchy, either ecclesiastical or political. Independents reached particular prominence between 1642 and 1660, in the period of the English Civil War and of the Commonwealth and Protectorate, wherein the Parliamentary Army became the champion of Independent religious views against the Anglicanism or the Catholicism of Royalists and the Presbyterianism favoured by Parliament itself.
The Independents advocated freedom of religion for non-Catholics and the complete separation of church and state. During the First Civil War, an alliance between supporters of the "War Party" led by John Pym and moderate MPs brought the Independent faction to prominence in Parliament. The Independents favoured confrontation with the King and an outright military victory rather than the negotiated settlement sought by the Presbyterians of the "Peace Party". The Independents actively supported the military alliance with Scotland in 1644 and the re-organisation of the armed forces that resulted in the formation of the New Model Army in 1645. After Pride's Purge, the so-called Rump Parliament of around fifty Independent MPs sanctioned the trial and execution of King Charles in January 1649 and the creation of the republican English Commonwealth."
Johanna married into the MURCH family, who had been Protestant Dissenters for well over a hundred years. In fact, looking into the religions of these families is proving to be almost as interesting as finding them was in the first place.
In 1972, three-quarters of the Congregationalist church merged with the Presbyterian church to form the United Reformed church. About 600 Congregationalist churches, however, continued to be Independent. Or independent. It would be interesting to find out if Chudleigh/Colridge/Coldridge is one of them.
Saturday, 11 September 2010
Surname Saturday: Yates or Yeats or Yeates
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Oct 29
Oct 23
The Sweets will play our final show with Pete at the Kennedy School Gymnasium on Thursday, October 23rd from 7pm - 9pm. The show is free and all-ages. Don't miss this opportunity to see the last show with the six original members of the Sweets!
Oct 17
Join us at the lovely Charbonneau Country Club for some old jazz and a "sweet" ice cream sundae buffet bar! This is a BYOB event.
Jul 23
This concert is part of the Portland Parks Summer Free for All series. Pack a picnic dinner, bring a blanket or chairs and spend time with family and friends!
Jul 4
Join us for a day of community activities, veteran recognition and FIREWORKS at Lewis & Clark Festival Park! The Sweets play from 1pm - 2:30pm.
Bio: The Stolen Sweets formed in 2005 with the intention of reviving the songs of 1930s sister act, The Boswell Sisters. Comprised of vocalists Jen Bernard, Lara Michell and Erin Sutherland, guitarists Pete Krebs and David Langenes (both of whom sing) and double bass player Keith Brush, The Sweets' re...See Full Bio


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Results 11 — 20
3D Animation Mascot
sarahandcee — Virtual
May 10 2016
CCCX media is a media company from Boston, Massachusetts who are working on several projects. We are currently working on branding our online clothing store and we would like our brands mascot to be a…
Application Deadline: Available Year-round
Animation Content creator
Repair Baadshah — Virtual
March 09 2016
Repair Baadshah is an aspiring startup in the ecommerce domain.Visit www.repairbaadshah.com for additional details.
Application Deadline: Available Year-round
CrispTalks — Virtual
June 28 2016
CrispTalks provides awesome affordable animated videos to startups, entrepreneurs & trainers. It offers end-to-end video designing services starting from script writing, voice over recording to delive…
Application Deadline: 8/15/2016
Motion Graphics / Animation
Studio Center — Virginia Beach, VA
January 22 2016
The Nation's Fastest Growing Production Company is looking for Superstar Interns to work in our Virginia Beach office! We are looking to educate and have interested students contribute to the Motion G…
Application Deadline: Available Year-round
2D ARTIST INTERNS at TutoTOONS (Work from Anywhere in the World)
TutoTOONS — Virtual
July 22 2016
Are you passionate about drawing? Would you like to create your own mobile games? About Us TutoTOONS is an international start��up, providing a free drag and drop mobile game builder. We help artists …
Application Deadline: Available Year-round
Lyfe Problems - Animation
Lyfe Problems — Virtual
September 14 2014
Lyfe Problems is looking for Animation majors who can effectively come up with designs for article content. Animation majors can also write content about animation as well. Work load would not require…
Application Deadline: Available Year-round
Animation/Graphic Design Intern
The Rise Network — Virtual
April 04 2016
The Rise Network has an internship opportunity for a creative and imaginative animation/graphic design intern who is interested in setting the pace and leading the pack in multi-media and entertainmen…
Application Deadline: Available Year-round
Animation Intern - Adobe Flash
Elliot Tailor — Boston, MA
September 30 2015
Elliot Tailor is a full service tailoring company. We sell high end business clothing, assist with sewing and alterations to create the best fit. In business for almost half a century, we have an old …
Application Deadline: Available Year-round
Animation Specialist (Unpaid Internship, Great Opportunity To Learn)
Bavanimation — Brooklyn, NY
May 25 2016
Bavanimation is a start-up animation company looking for individuals who are interested in the animation field/business. If you've ever had dreams of starting your own cartoon series, or just want to …
Application Deadline: Available Year-round
Animation and Motion Graphics Internship Opportunity
New Company — Brooklyn, NY
June 18 2015
Tambour USA is a supplier architectural products in the USA. Based in New York City specializing in architectural interiors including projects for hotels, super structures, office buildings, retail sp…
Application Deadline: Available Year-round