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Patent US6586094 - Fiber coated with water blocking material - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsThe present invention relates to a fiber coated with a water blocking material that includes an essentially water free dispersion comprising a superabsorbent polymer and a dispersing medium. The fibers made according to this invention may be used, for example, as fiber reinforcing material used in the...http://www.google.com/patents/US6586094?utm_source=gb-gplus-sharePatent US6586094 - Fiber coated with water blocking materialAdvanced Patent SearchTry the new Google Patents, with machine-classified Google Scholar results, and Japanese and South Korean patents.Publication numberUS6586094 B1Publication typeGrantApplication numberUS 09/443,695Publication dateJul 1, 2003Filing dateNov 19, 1999Priority dateNov 24, 1998Fee statusLapsedAlso published asCA2345318A1, CA2345318C, CN1196141C, CN1276933C, CN1346496A, CN1554679A, DE69937003D1, DE69937003T2, DE69937003T4, EP1133774A2, EP1133774B1, EP1133774B9, US6891003, US20030124350, WO2000031752A2, WO2000031752A3, WO2000031752A9Publication number09443695, 443695, US 6586094 B1, US 6586094B1, US-B1-6586094, US6586094 B1, US6586094B1InventorsSerge Rebouillat, Friedrich V. PfisterOriginal AssigneeE. I. Du Pont De Nemours And CompanyExport CitationBiBTeX, EndNote, RefManPatent Citations (10), Referenced by (36), Classifications (59), Legal Events (6) External Links: USPTO, USPTO Assignment, EspacenetFiber coated with water blocking material
US 6586094 B1Abstract
The present invention relates to a fiber coated with a water blocking material that includes an essentially water free dispersion comprising a superabsorbent polymer and a dispersing medium. The fibers made according to this invention may be used, for example, as fiber reinforcing material used in the manufacture of cables, and in particular in yarns for fiber optical cables that use optical light wave guides for optical communication transmissions.
What is claimed is: 1. A fiber coated with a water blocking material that includes an essentially water free dispersion comprising a superabsorbent polymer and a wetting agent and an oil,
wherein the superabsorbent polymer is present in an amount of from 0.5 to 10 weight percent on the weight of the uncoated fiber, wherein the superabsorbent polymer is in the form of particles having a particle size below 100 microns, wherein the wetting agent is a superwetting agent having a surface tension below 30 millinewtons per meter, and wherein the oil has a kinematic viscosity of 50 to 350 mm2/s at 20 degrees C. 2. The fiber of claim 1 wherein the dispersion contains less than two weight percent water.
3. The fiber of claim 1 wherein the superabsorbent polymer is a partially or totally neutralized, partially or totally crosslinked poly(acrylic acid) derivative; a partially or totally crosslinked poly(sodium or potassium acrylamide-2-methyl-propane sulfonate) derivative; a partially or totally crosslinked poly(chloro-trimethylaminoethyl-acrylate) derivative; a partially or totally crosslinked poly(acrylamide) derivative; mixtures thereof; or copolymers thereof.
4. The fiber of claim 1, wherein the superabsorbent polymer is present in an amount of from 0.1 to 5 weight percent based upon the weight of the uncoated fiber.
5. The fiber of claim 1, wherein the superabsorbent polymer is in the form of particles having a particle size below 20 microns.
6. The fiber of claim 1, wherein the superabsorbent polymer is in the form of particles having a particle size below 5 microns.
7. The fiber of claim 1, wherein the superwetting agent is selected from the group consisting of trimethylsilane, a polyethylene oxide-modified trimethylsilane, trisiloxane, a polyethylene oxide-modified trisiloxane, polydimethylsiloxane, a polyethylene oxide-modified polydimethylsiloxane, and polyether modified siloxane.
8. The fiber of claim 1, wherein the fiber is a glass fiber, an aramid fiber, or blends thereof.
9. The fiber of claim 1, wherein the fiber includes poly(p-phenylene terephthalamide).
10. A yarn comprising a plurality of the fibers of claim 1.
11. A fibrous material comprising a plurality of the fibers according to claim 1.
12. A fiber optical cable comprising glass fiber wave guides, said guides surrounded with a yarn comprising a fiber according to claim 1.
13. The fiber of claim 1 wherein the oil has a kinetic viscosity of 50 to 350 square mm at 20 degrees C.
14. The fiber of claim 1 wherein the oil is thermally resistant losing less than 5 weight percent when exposed to heating of 150 degrees C. for 2 hours.
15. The fiber of claim 1 wherein the oil is thermally resistant losing less than 15 weight percent when exposed to heating at 230 degrees C. for 2 hours.
16. A method for coating a fiber with a water blocking material comprising the steps of providing a fiber and applying to the surface of the fiber an essentially water free dispersion comprising a superabsorbent polymer and a wetting agent and an oil,
wherein the superabsorbent polymer is present in an amount of from 0.5 to 10 weight percent on the weight of the uncoated fiber, wherein the superabsorbent polymer is in the form of particles having a particle size below 100 microns, wherein the wetting agent is a superwetting agent having a surface tension below 30 millinewtons per meter, and wherein the oil has a kinematic viscosity of 50 to 350 mm2/s at 20 degrees C. 17. The method of claim 16, comprising providing a dispersion which includes 0.5 to 70 weight percent superabsorbent polymer.
This application is based on Provisional Application Ser. No. 60/109,719 filed Nov. 24, 1998 now abaondoned.
The present invention relates to the use of a water blocking material in the form of a surface coation on a fiber. The substrate may be used in a fiber optic cable to prevent water ingression into the cable.
Many processes for the treatment of substrates with water blocking materials are known. In particular fibers, fibrous materials or yams are impregnated with water blocking materials in certain applications where water is undesirable.
For example, water blocking materials are used in fiber optic cables to prevent ingression and propagation of water in the cable. Fiber optic cables are normally made by surrounding wave guides with reinforcing fibers that prevent elongation of the cable, and those reinforcing fibers are then encased in plastic. If water enters the fiber optic cable, it migrates inside the cable, usually longitudinally by capillary action, until the water contacts the sensitive wave guides and ultimately optical network connection boxes. The wave guides are made of glass, and when contacted by water become dull. The efficiency of the signal transmission through the wave guide drops until the wave guides can no longer transmit a signal. When that happens, the damaged portion of the cable must be located and then replaced. Since these fiber optic cables may be buried underground or may be placed along the bottom of large bodies of water, the location and replacement of the damaged sections of the cable can be time consuming and expensive.
As a result of these problems, there have been developed numerous methods to protect the fiber optic cable from water ingression. One method has been to coat the surrounding reinforcing fibers with a water blocking material so that if water should leak through the plastic casing, that water will be absorbed by the water blocking material on the reinforcing fibers to prevent damage to the wave guides.
There are processes in which the treatment of fibers is carried out with water blocking material as an aqueous dispersion such as in EP-A-0 351 100. One disadvantage of this process is that the viscosity of these aqueous dispersions is very high.
In EP-A-0 666 243, a method is disclosed in which glass fiber bundles are treated with a dispersion of a water absorbing material in an oil, wherein poly(sodium acrylate) is the water absorbing medium. In the same way derivatives of polyacrylic acid are disclosed in WO93/18223 as super-absorbing materials. In both cases, the water blocking materials are used in water-in-oil emulsions for the treatment of substrates, with the super-absorbing materials being contained in the aqueous phase. These emulsions are, however, complicated to manufacture and require the use of emulsifying agents.
In general, conventional water blocking materials are based on cross linked polyacrylics and/or cross linked polyacrylates, such as water-in-oil emulsions. These types of water blocking materials all contain water and oil, and when the material is applied to a fiber or yam some of the water and oil must be removed. The removal of water and oil is an additional processing step that is energy intensive, limits productivity and is an environmental burden.
What is needed, therefore, is a water blocking agent that is effective and is easy to apply to fibers.
None of the known water blocking materials, when applied to a substrate, completely meet the following four criteria defined as ideal industry standards and related manufacturing requirements:
First, the substrate coated with the superabsorbent polymer must be easily processable when used in manufacturing, for example, optical cables. This means that the reinforcing superabsorbent coated substrate must have good frictional properties and a low tendency to generate deposits when spiraled or braided around a core optical fiber. Conventional superabsorbent polymers used for the coating of substrates are known to be prone to deposits due mostly to the high stiffness of the film formed or their relatively large particle sizes, that is, above 40 microns.
Secondly, the residual water present in substrates coated with conventional superabsorbent polymers causes blistering, for example, during the extrusion of the outer layer jacket of an optical cable. Therefore, such coated substrate must be as dry as possible to avoid this blistering problem. For example, water in oil emulsions of superabsorbent polymers contain a substantial proportion of water (up to ⅓) which may cause blistering when substrates having high loadings of the superabsorbent polymers are extruded above certain temperatures and thus be detrimental to the overall quality of the cable.
Thirdly, the substrate coated with the superabsorbent polymer must withstand temperatures encountered during thermal processing, such as the extrusion process mentioned above. It is known in the art that most superabsorbent polymers do not tolerate temperature cycling and therefore lose their ability to absorb water. The detrimental chemical mechanism is generally associated with the formation of inter-chain anhydrides which does not constitute a good entrapping network for the “ingressing” water.
Fourthly, most aerial or liaison cables (sometimes referred to as riser cables) which connect aerial/underground cables to building networks, are exposed to freezing conditions in most regions where they are used. Therefore it is essential that the cable in general and the coated substrate in particular be resistant to freezing conditions. The formation of ice within the cable structure does not only affect the dimensional stability of the system but also may cause internal damage related to the reduced flexibility associated with a microbending crushing effect. Therefore, the strength of the coated substrate in the cable is very important and therefore its dryness is absolutely essential. Unfortunately a large number of known superabsorbent polymers not only contain water but also are not resistant to freezing conditions.
In view of the above, an object of the present invention is to provide a substrate coated with a water blocking material which meets the four criteria discussed above. Such substrate is highly processable, essentially water free and temperature tolerant, that is resistant to freezing and temperature cycling.
The present invention relates to a fiber coated with a water blocking material that includes an essentially water free dispersion comprising a superabsorbent polymer and a dispersing medium. The fibers made according to this invention may be used, for example, as fiber reinforcing material in the manufacture of cables, and in particular in yarns for fiber optical cables that use optical wave guides for communication transmissions.
The present invention relates to a fiber coated with water blocking material that includes an essentially water free dispersion comprising a superabsorbent polymer and a dispersing medium. The water blocking material of the present invention is easily applied to the surface of fibers, has a good water blocking action, and does not impair the mechanical characteristics of the fiber. The fibers are usually used in the form of multifilament yarns or fibrous materials such as nonwoven or other textile structures.
As used herein, the term “essentially water free” means that no free water is present in the dispersion except for water in a bound form that occurs naturally in the superabsorbent polymer or dispersing medium. Practically speaking, such water is present usually in an amount of less than two weight percent of the total weight of the dispersion.
Superabsorbent polymers useful in the invention can be a crosslinked, partially neutralized polyacrylic acid (see U.S. Pat. No. 4,654,039), a crosslinked, partially neutralized starch acrylic acid graft polymer (U.S. Pat. No. 4,076,663), a crosslinked, partially neutralized copolymer of isobutylene and maleic anhydride (U.S. Pat. No. 4,389,513), a superabsorbent polymer saponification product of vinyl acetate-acrylic acid copolymer (U.S. Pat. No. 4,324,748), a hydrolyzate of acrylamide polymer or acrylamide copolymer (U.S. Pat. No. 3,959,569), a hydrolyzate of an acrylonitrile copolymer (U.S. Pat. No. 3,935,099), mixtures thereof, or copolymers thereof. The teachings of the above patents are hereby incorporated by reference.
More specifically, examples of a superabsorbent polymer suitable for use in the dispersion of the invention include a partially or totally neutralized, partially or totally crosslinked poly(acrylic acid) derivative (PACA); a partially or totally crosslinked poly(sodium or potassium acrylamide-2-methyl-propane sulfonate) derivative (PAMPS); a partially or totally crosslinked poly(chloro-trimethylaminoethyl-acrylate) derivative (PCTA); a partially or totally crosslinked poly(acrylamide) derivative (PAAD); mixtures thereof; or copolymers thereof.
Examples of PACA include Sanwet® IM 3900 available from Hoechst AG, Aqua Keep® available from Atochem, and Dry Tech® available from Dow Chemical.
The superabsorbent polymer should be present on the coated fiber in an amount of from 0.05 to 10.0 weight percent based upon the weight of the uncoated fiber. A range of 0.1 to 5.0 weight percent is preferred because below 0.1 weight percent the water blocking effect may be insufficient in certain uses and above 5.0 weight percent the processability of the yarn can become more difficult because of deposit formation, for example. While it is possible to use higher loadings of the superabsorbent polymer, such higher loadings are not practical. If the fiber includes a sizing agent that is added prior to treatment of the fiber with the superabsorbent polymer dispersion, then the values for the percentage by weight refer to the dry weight of the untreated fiber without the sizing agent.
The superabsorbent polymer has a particle size less than 100 microns, preferably less than 20 microns, and more preferably less than 5 microns.
Superabsorbent polymers having particle sizes of 100 microns or greater may be used, but have problems of lumping or aggregate formation. These problems may be overcome by reducing the particle size of the superabsorbent polymer and dispersing the superabsorbent polymer in a dispersing medium.
The typical particle size of a commercial PACA, such as Aqua Keep® SHP10, is provided below:
From 500 to 800 microns
From 225 to 500 microns
From 100 to 225 microns
This table shows that commercial PACA includes polymer particles having a particle size much greater than that preferred for use in the present invention. Normally, such superabsorbent polymers are used to coat hygiene products which require polymers having a comparatively large particle size.
Therefore, another aspect of the present invention is to modify superabsorbent polymers so that such polymers have a particle size below 100 microns, preferably below 20 microns and more preferably below 5 microns.
There are four general methods for obtaining a superabsorbent polymer having a particle size less than 100 microns.
First, one can take superabsorbent polymers, such as the commercially available polymers mentioned above, and separate out the undesirable large particles by screening. The main drawback using this technique is that it has a very low and variable yield.
Therefore, the other three methods are preferred to prepare or obtain a superabsorbent polymer having an optimum particle size below 100 microns, preferably below 20 microns and more preferably below 5 microns. It is preferred that the particle size of the superabsorbent polymer is equal to or less than the diameter of the fiber to be coated.
One method is dry grinding of the superabsorbent polymer prior to dispersing the superabsorbent polymer in the dispersing medium. Particle size as low as 5 microns can be produced using the Condux® CGS air jet grinder from Condux® Maschinenbau GmbH & Co.
Another method is wet grinding of the superabsorbent polymer performed at high intensity, that is, grinding which takes place at greater than 12 000 RPM, such as by using the Megatron® MT 5000 micronizer from Kinematica AG, after the superabsorbent polymer has been dispersed into the dispersing medium.
Still another method is to make the superabsorbent polymer having a particle size less than 100 microns during the polymerization of the superabsorbent polymer from its monomeric ingredients. In this process, the superabsorbent polymer is prepared by providing a monomer of the superabsorbent polymers described above, partially or totally neutralizing the monomer, adding a catalyst and a crosslinking agent, raising the temperature of the monomer to initiate the polymerization of the monomer, maintaining the temperature during the polymerization, and evaporating the water to produce a polymer powder, all the while providing a shearing rate of at least 10,000 revolutions per minute during the entire process to produce a polymer having a particle size below 100 microns.
In another embodiment, before the polymerization step, the mixture of the totally or partially neutralized monomer, crosslinking agent and catalyst can be added to a reactor containing a hydrocarbon solvent to prepare an inverse suspension polymerization. The hydrocarbon solvent should be present in an amount 2 to 3 times the weight of the monomer, crosslinking agent and catalyst. The hydrocarbon solvent may be a C6, C7, or C8 alkane or an aromatic material. A preferred aromatic solvent is toluene. In the evaporation step, the solvent as well as the water should be removed.
In a preferred embodiment, a superwetting agent (SWA) can be added during the polymerization step by blending the SWA in the solvent in an amount from 0.05 to 10%, preferably 0.5% based on the weight of the solvent and SWA only. The SWA and solvent are added to the monomer solution, preferably in a weight ratio of SWA and solvent to the aqueous monomeric solution of from 1:1 to 3:1. The solvent and the water are removed by distillation at the end of the polymerization. The distillation temperature is adjusted depending on the solvent used, depending whether vacuum is available and depending whether azeotropic distillation can be performed. Typically a water-cyclohexane mixture can be removed at 80 to 90 C. under vacuum. It is also possible to add the SWA without solvent directly in the monomeric solution since the surfactant effect of the SWA is also observed in aqueous medium.
As used herein, the term “SWA” means a superwetting agent having surface tension below 30 millinewtons per meter (mN/m). Preferably, the SWA has a surface tension below 25 mN/m. Such SWAs are disclosed, for example, in Polymeric Materials Encyclopedia, Volume 10, Silicone Polymers, CRC Press 1996. This surface tension is lower than usual surfactants based on organic oils which are in the range of 30 to 35 mN/m.
Examples of SWAs include:
1. trimethylsilane;
2. a polyethylene oxide (PEO)-modified trimethylsilane, that is, a trimethylsilane branched with a polyether containing sequences of ethylene oxide propylene oxide (EO/PO), such as Tegopren® 5840 supplied by Th. Goldschmidt AG;
3. trisiloxane
4. a polyethylene oxide (PEO)-modified trisiloxane, that is, a trisiloxane branched with a polyether containing sequences of ethylene oxide propylene oxide (EO/PO), such as Tegopren® 5878 available from Th. Goldschmidt AG;
5. polydimethylsiloxane (PDMS)
6. a polyethylene oxide (PEO)-modified polydimethylsiloxane, that is, a polydimethylsiloxane branched with a polyether containing sequences of ethylene oxide propylene oxide (EO/PO), such as Tegopren® 7008 available from Th. Goldschmidt AG;
7. polyether modified siloxane such as the Tegopren® 5845 available from Th. Goldschmidt AG;
The advantage to using an SWA in polymerization is that a superabsorbent polymer having a relatively smaller particle size is obtained, that is, a superabsorbent polymer having a particle size below 5 microns, with a high percentage of particles below 1 micron. The smaller the particle size of the superabsorbent polymer, the faster that polymer will absorb water, and the lower the loading of the polymer on the fiber needs to be because of the improved distribution of the smaller particles inside the fiber.
The dispersing medium may be an oil, a superwetting agent, a blend of an oil and a superwetting agent, a finish oil composition, glycol, or mixtures thereof.
The oils which may be used in a superabsorbent polymer-oil dispersion include mineral oils, vegetable oils, and fully synthetic oils. Such oils should have a low viscosity, that is a kinematic viscosity of 50 to 350 mm2/s at 20° C., preferably 80 to 200 mm2/s at 20° C. Further, such oils should be thermally resistant, that is, losing either less than 5 weight percent when exposed to heating at 150° C. for 2 hours, or less than 15 weight percent when exposed to heating at 230° C. for 2 hours.
Examples of oils which may be used are those disclosed in U.S. Pat. Nos. 5,139,873 and 5,270,113. For example, U.S. Pat. No. 5,270,113 discloses a finish oil composition that includes 30-70% by weight of an esteroil lubricant composed of an alcohol and a carboxylic acid, 20-50% by weight of an emulsifying system composed of unstaturated ethoxylated fatty acids or alcohols or ethoxylated alkylamines, 5-15% of an antistatic agent, 0.2-2% of a corrosion inhibitor, and optionally other additives. In order for the oil to have the heat resistance described above, it is preferred that the esteroil is an aromatic derivative and the antistatic agent includes a derivative of a sulfonate and/or a phosphate. These oils may also include hydrophobic active ingredients such as ketene dimers as disclosed in U.S. Pat. No. 5,275,625.
For oils that include an emulsifying system, that emulsifying system may be replaced by an SWA as described above. In that case, the SWA, which does not include any solvent or water, is present in an amount of 0.05 to 50 percent by weight of the oil composition.
These oils advantageously contribute to the water blocking action of the superabsorbent polymer by allowing water to diffuse more easily between and among the superabsorbent polymer particles. Other advantages of these oils are that they enhance the processability of the coated fiber and they provide antistatic protection to the fiber.
If the dispersing medium is an oil that does not already include an SWA, then the oil dispersing medium may include an SWA. The SWA may be any of those described above, and is typically used in amounts of from 0.05 to 95, preferably 10 to 50, most preferably 30 weight percent based on the total weight of the SWA and oil only.
The SWA in an SWA-containing dispersing medium brings certain advantages to the water blocking material of this invention. The SWA enhances the hydrophilic-lipophilic balance of the superabsorbent polymer, dispersing medium and fiber to obtain a more homogeneous and faster dynamic wetting of the multifilament fiber surface which results in a homogeneous coating that allows a lower loading of superabsorbent polymer to obtain a desired water blocking effect. Further, this homogeneity and faster dynamic wetting allow the on-line application of the water blocking material to a fiber.
Alternatively, the dispersing medium may also be a water-free SWA alone.
If the dispersing medium includes glycol, the glycol may be ethylene glycol or propylene glycol or any other derivative of glycol. Further, the glycol may include an ethylene propylene oxide emulsifying agent. The glycol may advantageously contribute to the protection of the optical cable against freezing.
The dispersing medium may also include other antifreeze compositions such as dimethyl sulfoxide, potassium or sodium salts, or mixtures thereof. The amount of antifreeze composition may be easily evaluated knowing that 1.5 grams of glycol are required to lower the freezing point of 1 gram of water to −40° C.
After the superabsorbent polymer dispersion is applied to the fiber, the dispersing medium remains on the fiber. As stated above, the inventive water blocking material is essentially water free, which makes the material simpler to apply and simpler to use than water-in-oil based water blocking materials that require water and oil to be removed as one step in applying the acrylic water blocking material to a fiber.
As used herein, the term “fiber” includes fibers composed of organic and inorganic materials. As organic fibers one may use natural and synthetic fibers. Examples for natural organic fibers are cellulose fibers, wool fibers, silk fibers. Examples for synthetic organic fibers are rayon fibers, fibers of regenerated cellulose, aliphatic and aromatic polyamides, polyesters, polyolefines, polyacrylonitriles, polyvinyl chlorides, polyvinyl alcohols, and the like. Examples for inorganic fibers are glass fibers, carbon fibers, metal fibers, ceramic fibers, mineral fibers, boron fibers and the like. Preferred fibers include glass fibers, aramid fibers, nylon fibers, polyester fibers, such as fibers of poly(ethylene terephtalate) and polymethacrylates, and cellulose fibers including ones of regenerated cellulose.
Prior to being coated with the dispersion, it is preferred to dry the fiber so that it is bone dry to protect against blistering during the extrusion of the outer jacket of the cable and to protect against freezing when the cable is exposed to low temperatures. For the same reason, it is preferred that the superabsorbent polymer be bone dry prior to being dispersed in the dispersing medium.
For use in fiber optic cables, the fibers should have a specific breaking strength of 2.65 to 33.5 cN/dtex (3 to 38 g/den) and a specific modulus of 8.83 to 2297 cN/dtex (10 to 2500 g/den).
Aramid fibers are fibers of polymers that are partially, preponderantly or exclusively composed of aromatic rings, which are connected through carbamide bridges or optionally, in addition also through other bridging structures. The structure of such aramids may be elucidated by the following general formula of repeating units:
(—NH-A1-NH—CO-A2-CO)n
wherein A1 and A2 are the same or different and signify aromatic and/or polyaromatic and/or heteroaromatic rings, that may also be substituted. Typically A1 and A2 may independently from each other be selected from 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 4,4′-biphenylene, 2,6-naphthylene, 1,5-naphthylene, 1,4-naphthylene, phenoxyphenyl-4,4′-diylen, phenoxyphenyl-3,4′-diylen, 2,5-pyridylene and 2,6-quinolylene which may or may not be substituted by one or more substituents which may comprise halogen, C1-C4-alkyl, phenyl, carboalkoxyl, C1-C4-alkoxyl, acyloxy, nitro, dialkylamino, thioalkyl, carboxyl and sulfonyl. The —CONH— group may also be replaced by a carbonyl-hydrazide (—CONHNH—) group, azo- or azoxy-group.
Further useful polyamides are disclosed in U.S. Pat. No. 4,670,343 wherein the aramid is a copolyamide in which preferably at least 80% by mole of the total A1 and A2 are 1,4-phenylene and phenoxyphenyl-3,4′-diylene which may or may not be subsituted and the content of phenoxyphenyl-3,4′-diylene is 10% to 40% by mole.
Fibers derived from wholly aromatic polyamides are preferred.
Examples of aramids are poly-m-phenylene-isophthalamide and poly-p-phenylene-terephthalamide.
Additional suitable aromatic polyamides are of the following structure
(—NH-Ar1-X-Ar2-NH—CO—Ar1-X-Ar2-CO—)n
in which X represents O, S, SO2, NR, N2, CR2, CO.
R represents H, C1-C4-alkyl and Ar1 and Ar2 which may be same or different are selected from 1,2-phenylene, 1,3-phenylene and 1,4-phenylene and in which at least one hydrogen atom may be substituted with halogen and/or C1-C4-alkyl.
Additives may be used with the aramid and, in fact, it has been found that up to as much as 10% by weight, of other polymeric materials may be blended with the aramid or that copolymers may be used having as much as 10% of other diamine substituted for the diamine of the aramid or as much as 10% of other diacid chloride substituted for the diacid chloride of the aramid.
It is also possible to use fibers comprising mixtures of the above materials including hybrid fibers. Furthermore, two-component fibers may also be used in accordance with the invention, in which the core consists of a different material from the skin.
The fibers of the invention may be round, flat or may have another cross-sectional shape or they may be hollow fibers. Further, the term “fiber” includes endless fibers (filaments) and short fibrous structures, microfibers and multi-filaments. Further, the fibers may be made into yarns of short fibrous structures, which are spun, as well as yarns of endless fibers. The fibers may be used to make fibrous materials in woven, knitted or nonwoven form such as including fleeces, wadding, and felt.
The fibers coated with the water blocking material of this invention have an excellent water blocking effect because the superabsorbent polymer applied to the fiber swells when contacted with water and thus prevents further penetration of the water along the fibers. The mechanical characteristics of the fiber are not impaired by the superabsorbent polymer deposited on it. Since a good water blocking action is already achieved with small quantities of superabsorbent polymer on the surface of the fiber, the weight and volume of the fiber do not substantially increase so that the coated fibers may be used in the same applications as uncoated fibers with similar processability characteristics.
The fibers made according to this invention may be used, for example, as fiber reinforcing material used in the manufacture of cables, and in particular of fiber optical cables that use optical light wave guides for optical communication transmissions. In fiber optic cables, multi-filaments of glass, aramids or other strength members are used as tensile load relief fibers or as reinforcing fibers. However, the fibers of the invention are not limited to these uses and may be used in any application where it is desired to absorb water in order to hinder the propagation of the water.
The dispersion of the superabsorbent polymer in the dispersing medium contains from 0.1 to 70% by weight of superabsorbent polymer, preferably from 20 to 40%, based upon the total weight of dispersing medium and superabsorbent polymer only. If the dispersing medium includes an SWA, then relatively lower amounts of the superabsorbent polymer are needed to obtain a desired water blocking effect. Higher loadings of the superabsorbent polymer may be used, but become impractical because the stability of the dispersion decreases. The quantity of the superabsorbent polymer used in the dispersion to coat the fiber is selected from the indicated range above based upon the viscosity of the dispersing medium so as to provide a uniform coating of the dispersion on the surface of the fiber. This is especially important when the fiber is in the form of a yarn, multi-filament or fibrous material, because when the water blocking material is applied to these materials it is desired to obtain the best penetration into the yam or bundles of yarn in order to coat as many fibers as possible.
The dispersion may be made simply by adding the superabsorbent polymer in powder form into the dispersing medium while stirring the dispersing medium at a rate that insures a uniform distribution of the superabsorbent polymer into the dispersing medium. If an impregnating bath is used to coat the fiber by passing the fiber through the bath, then the dispersion is continuously held in motion, for example by stirring.
The size of the fibers for many applications, such as for use in fiber optic cables, is in the range of from 10 to 15 microns, and therefore the superabsorbent polymer particles should have a particle size below 100 microns, preferably below 20 microns, and more preferably below 5 microns.
The dispersion may be applied to the fiber by any conventional coating process, for example by roll coating with or without doctor blade, spray coating, immersion coating, a serpentine system, or using a finish application (e.g. metering system), or using any other known coating devices. If desired the dispersion may be applied in a multi step process in which the fiber is coated several times with the dispersion. Ultrasonic systems may also be used in order to enhance the uniformity or penetration of the dispersion. With fibers, it is preferred to use an immersion coating method in which the oil dispersion is present in an impregnating bath and the fibers to be treated are passed through the bath. However, at higher coating speeds a metering applicator may be preferred. With fibrous materials of two-dimensional form, other processes such as spray coating may be used in addition to immersion coating.
The coating speed may be adjusted between 0.1 and 1200 m/min depending on the selected process. A process in which the dispersing medium, such as the oil, is not removed, has the additional advantage of significantly increasing the coating speed, and thus the productivity, since one can coat the fiber at high speeds without being limited by the residence time required to evaporate the dispersing medium. Typical speeds are 60 m/min for the fiber treatment other than during the spinning process, and 800 m/min for the coating speed during the manufacturing of the fiber.
Polymeric fibers are known to absorb moisture. Therefore it is preferred to precondition the fiber in order to feed a bone dry fiber to the coating process. This may easily be achieved by conventional fiber drying techniques, or advantageously during the spinning of the fiber.
The temperature of the dispersion may be selected in order to enhance the fiber penetration and coverage uniformity and is only limited by the temperature resistance of the dispersion components. Nonetheless a range of 10 to 100C. is preferred, with a range of from 35 to 75C. being more preferred.
This Example is directed to a method for producing a superabsorbent polymer which has a particle size of below 100 microns from a monomer.
A Megatron® MT5000 reactor was fitted with a device to introduce solids as well as liquids, said reactor having a high intensity micronizer cell rotating at 16000 RPM, a system for purging with inert gas, a series of temperature probes and a heating and cooling device consisting of a jacket in which a heat transfer fluid is circulated at a targeted precise temperature. This reactor was used to polymerize a monomer yielding a superabsorbent polymer having particle sizes below 100 microns.
The micronizer was set at a rotation speed of 16000 RPM, and a given amount of aqueous solution containing about 80% by weight of hydroquinone stabilized acrylic acid was quantitatively neutralized with a sodium or potassium hydroxide solution at 20%. This was done in a way that the temperature in the micronizer did not exceed 35C.
Once the temperature was stabilized, 2.8% by weight relative to the amount of acrylic acid, of an aqueous solution of sodium persulfate at 2% was added to the reactor. The sodium persulfate solution acted as a catalyst in the polymerization. This solution can be substituted by any similar catalyst known in the art for use in related reactions. While the temperature was carefully maintained at 30° C., 0.5% by weight of ethylene glycol diglycidyl ether, relative to the amount of acrylic acid, was added to the reactor. The ethylene glycol diglycidyl ether acted as a crosslinking agent in the polymerization of the acrylic acid, but can be substituted by any similar crosslinking agent known in the art that is at least a bifunctional covalent crosslinking agent or ionic crosslinking agents such as aluminum sodium sulfate. The temperature was raised at 40° C. and maintained for a stabilization period of 15 minutes while nitrogen was purged through the reactor.
After this 15 minute period the temperature of the liquid in the reactor was raised to 70° C. to allow the polymerization to start. The contents of the reactor was maintained carefully at this temperature for about 30 minutes which is sufficient to obtain quantitative polymerization of the neutralized acrylic acid. The rotational micronizer speed of 16000 RPM was maintained throughout the polymerization. The temperature was then raised to 125° C. to remove the water phase by evaporation. This separation can also be done by mechanical means such as ultrafiltration or centrifugation.
After complete evaporation of the water a superabsorbent polymer was obtained in the form of very fine particle size well distributed below 20 microns. After suitable purification the superabsorbent polymer powder can be used to prepare the dispersion of the invention. The process described here can be easily adapted to polymerize particles of other superabsorbent polymers of the invention to sizes of below 100 microns. The typical particle size distribution was as follows:
50% of the particles were below 8 microns;
10% of the particles were below 3 microns;
90% of the particles were below 12 microns.
The particle size was measured using a Mastersizer® Micron from Malvern Instruments Ltd. U.K. suitable for the analysis of particle size ranging from 0.3 to 300 microns either in dry or wet media.
A finish free yarn of para-aramid fibers (Kevlar® type 49, 1580 dtex), comprising poly-para-phenylene diamine terephthalamide was treated with a dispersion of 35% (by weight) superabsorbent polymer as prepared according to Example 1 in a finish oil as disclosed in U.S. Pat. No. 5,270,113 which included 30-70% by weight of an esteroil lubricant composed of an alcohol and a carboxylic acid, 20-50% by weight of an emulsifying system composed of unstaturated ethoxylated fatty acids or alcohols or ethoxylated alkylamines, 5-15% of an antistatic agent, and 0.2-2% of a corrosion inhibitor. The main component of finish oil was an esteroil lubricant synthesized from an alcohol and a carboxylic acid, and had suitable hydrophilic properties to allow rapid spreading of water among superabsorbent polymer particles thereby enhancing the water blocking effect of the superabsorbent polymer. The yarn was coated with a dispersion which yielded a coating on the yarn which had an amount of 2.5% superabsorbent polymer and 4.5% oil, based on the dry weight of the uncoated yarn.
The so obtained para-aramid yarn, coated with the mentioned dispersion, was tested for its water blocking property in the column test described below.
The Column Test Procedure
The water blocking action of the yarn of this Example was determined using the through-flow test. In this test the inner cylindrical space of a section of glass tube open on both ends was filled with a bundle of the yarn, such that the longitudinal axis of the yarn bundle was substantially parallel with the longitudinal axis of the cylindrical space in which the bundle was positioned. The tube filled with the yarn was cut through in a direction perpendicular to its longitudinal axis in two places, such that a cylinder-shaped test tube of a length of 50 mm was formed such that the ends of the yarn bundle present in the thus obtained test tube approximately coincided with the test tube ends. Next, one of the ends of the test tube was connected with the contents of a vessel of water and subjected to the pressure of a head of water of a particular height. The time required to wet the entire yarn bundle in the test tube is referred to as the through-flow time. This time is a measure of the water blocking action of the yarn. The through-flow time was taken to be the time which passes after the application of water pressure to one end of the test tube and prior to the first drop appearing at the other (free) end.
Test tube, inner diameter
Test tube, outer diameter
Length of test tube
50 mm Number of yarns in test
1 per test tube
Height of liquid head
100 cm Testing liquid
The number of yarns in the test tube was chosen such that the bundle formed from them will fully fill the inner cylindrical space of the test tube. For a yam linear density of dtex 1580 this number was found to be 100, giving an overall linear density for the yam bundle of dtex 158 000. A yarn coated according to this Example passed the column test. Effective water blocking activity was still maintained after 3 weeks when the test was ended.
Aqua Keep® SHP10 polymer was dry ground twice in a Condux® CGS air jet grinder from Condux® Maschinenbau GmbH & Co, and the polymer had the following particle size:
50% of the particles were below 9 microns;
10% of the particles were below 4 microns;
90% of the particles were below 15 microns.
This ground polymer was used to make dispersions as in Example 2 with varying amounts of superabsorbent polymer and the finish oil of Example 2. Yams of dtex 1580 were coated according to Example 2 with the loadings as set forth below.
Wt. % SAP*
column test time
*= superabsorbent polymer As indicated above, the yarns from each of Examples 3, 4 and 5 passed the column test and effective water blocking activity was still maintained after 3 weeks when the test was ended.
A dispersion was made as in Example 2 using Aqua Keep® SHP10 polymer (not ground) and the finish oil in that Example. The dispersion was wet ground for 30 minutes at 12,000 RPM using the Megatron® MT 5000 micronizer from Kinematica AG. The temperature in the micronizer was maintained at 15° C.
The polymer in the dispersion had the following particle size:
50% of the particles were below 12 microns;
10% of the particles were below 5 microns;
90% of the particles were below 19.5 microns.
Yarns were coated as in Example 2 using dispersions having varying amounts of superabsorbent polymer and finish oil as set forth below.
*= superabsorbent polymer As indicated above, the yarns from each of Examples 6, 7 and 8 passed the column test and effective water blocking activity was still maintained after 3 weeks when the test was ended.
A Kevlar® 49 finish free yarn, 1580 dtex, was treated as in Example 2 with about 1 weight percent finish oil without the superabsorbent polymer. The finish oil was the same as used in Example 2. The water blocking performance of the yarn was measured in a water column test device as in Example 2, using the same amount of yarn, and after 2 minutes the yarn did not block the water but let it run through the column.
A Kevlar® 49 finish free yam was treated as in Comparative Example 9 except that the yarn was coated with about 5 weight percent finish oil. The water blocking performance of the yarn was measured in a water column test device as in Example 2, using the same amount of yarn, and after 2 minutes the yarn did not block the water but let it run through the column.
A superabsorbent polymer was made as in Example 1, except that a superwetting agent (SWA)-solvent solution was added to the aqueous monomeric solution prior to initiating the polymerization while maintaining the micronizer cell rotating speed at 16000 RPM.
A SWA-solvent solution was prepared by adding 0.5 weight percent of Tegopren® 5845 silicone wetting agent to 99.5 weight percent of cyclohexane. The dissolved oxygen had been removed from the cyclohexane using nitrogen purging before being added to the SWA.
The polymerization of the monomer was performed as in Example 1, and the cyclohexane and water were then removed from the polymer by vacuum distillation at 80-90C. The particle size distribution of the polymer was as follows:
10% of the particles were below 0.3 microns;
50% of the particles were below 0.8 microns; and
90% of the particles were below 3 microns.
A finish free yarn of bone dry para-aramid fibers (Kevlar® type 49, 1580 dtex) was treated as in Example 2 except that the superabsorbent polymer used was that prepared according to Example 11. A yarn coated according to this Example passed the column test. Effective water blocking activity was still maintained after 3 weeks when the test was ended.
Yarns were treated with a superabsorbent polymer as follows. A superabsorbent polymer was prepared according to Examples 3-5. The ground superabsorbent polymer was added to a dispersion medium of a water-free finish oil as in Example 2 and a superwetting agent of Tegopren® 5845 in varying amounts. In Examples 13 and 14, the proportion of components was 30 weight percent superabsorbent polymer, 50 weight percent of water-free finish oil, and 20 weight percent of Tegopren® 5845.
Yarns were coated according to Example 2 with the loadings as set forth below.
and SWA
Wt. % SAP
As indicated above, the yarns from Examples 13 and 14 passed the column test and effective water blocking activity was still maintained after 3 weeks when the test was ended.
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS4837077Jun 23, 1986Jun 6, 1989IntisselHydroexpansible composite material, the preparation thereof and a composition for its implementation as well as the uses thereofUS5389442 *Nov 25, 1992Feb 14, 1995At&T Corp.Water blocking strength membersUS5635569Aug 9, 1995Jun 3, 1997Bayer AktiengesellschaftSuperabsorbent polymers from cross-linked polyacrylonitrile emulsionsEP0188959A1Dec 20, 1985Jul 30, 1986IntisselComposite hydroexpansible material, its manufacture and composition for the latter, as well as its usesEP0666243A1Feb 7, 1995Aug 9, 1995Roblon A/SGlassfibre bundle, and method and apparatus for its manufactureEP0779389A2Oct 17, 1991Jun 18, 1997Akzo Nobel N.V.Superabsorbent-coated aramid yarnWO1993018223A1Mar 12, 1993Sep 16, 1993Akzo Nobel N.V.Process for treating a substrate with a superabsorbent materialWO1996040849A1Jun 6, 1996Dec 19, 1996Lee County Mosquito Control DistrictLubricant compositions and methodsWO1997008579A1Aug 20, 1996Mar 6, 1997Owens CorningWater blocking optical cable reinforcementWO1998054395A1May 21, 1998Dec 3, 1998E.I. Du Pont De Nemours And CompanyFiber coated with water blocking material* Cited by examinerReferenced byCiting PatentFiling datePublication dateApplicantTitleUS7177507Jun 7, 2004Feb 13, 2007Corning Cable Systems, LlcOptical tube assembly having a dry insert and methods of making the sameUS7236670Sep 12, 2005Jun 26, 2007Corning Cable Systems, Llc.Optical tube assembly having a dry insert and methods of making the sameUS7254302 *May 18, 2004Aug 7, 2007Corning Cable Systems, Llc.Optical tube assembly having a dry insert and methods of making the sameUS7277615Feb 10, 2006Oct 2, 2007Corning Cable Systems, Llc.Fiber optic cable having a dry insert and methods of making the sameUS7336873Sep 12, 2003Feb 26, 2008Corning Cable Systems, Llc.Optical tube assembly having a dry insert and methods of making the sameUS7349607Jun 18, 2002Mar 25, 2008Corning Cable Systems Technology IncorporatedOptical transmission elementUS7471861Oct 31, 2007Dec 30, 2008Corning Cable Systems LlcOptical transmission elementUS7471862Dec 21, 2006Dec 30, 2008Corning Cable Systems, LlcDry fiber optic cables and assembliesUS7664354Nov 16, 2006Feb 16, 2010NexansSystem and method for loose tube tight buffer indoor/outdoor optical fiber cableUS7693375Mar 9, 2009Apr 6, 2010Corning Cable Systems LlcFiber optic cable having a dry insertUS7747117Nov 13, 2007Jun 29, 2010Corning Cable Systems LlcOptical tube assembly having a dry insert and methods of making the sameUS7751666Nov 18, 2008Jul 6, 2010Corning Cable Systems LlcOptical tube assembly having a dry insert and methods of making the sameUS7787727Sep 3, 2009Aug 31, 2010Corning Cable Systems LlcDry fiber optic cables and assembliesUS8722137 *Dec 16, 2008May 13, 2014Hitachi Metals, Ltd.Hydrated water-absorption polymer containing resin composition, porous body and insulated wire using same, method of making the wire and coaxial cableUS9477057Apr 2, 2014Oct 25, 2016Corning Optical Communications LLCFiber optic cables and assembliesUS9482837Jul 26, 2010Nov 1, 2016Corning Cable Systems LlcDry fiber optic cables and assembliesUS9494755May 5, 2014Nov 15, 2016Corning Optical Communications LLCFiber optic cable assemblyUS20010049344 *Feb 9, 2001Dec 6, 2001Lee County Mosquito Control DistrictLubricant compositions and methodsUS20040120663 *Sep 12, 2003Jun 24, 2004Lail Jason C.Optical tube assembly having a dry insert and methods of making the sameUS20040156603 *Jun 18, 2002Aug 12, 2004Reiner SchneiderOptical transmisson elementUS20040208462 *May 18, 2004Oct 21, 2004Parsons Alan T.Optical tube assembly having a dry insert and methods of making the sameUS20040223707 *Jun 7, 2004Nov 11, 2004Parsons Alan T.Optical tube assembly having a dry insert and methods of making the sameUS20060002668 *Sep 12, 2005Jan 5, 2006Lail Jason COptical tube assembly having a dry insert and methods of making the sameUS20060165355 *Feb 10, 2006Jul 27, 2006Greenwood Jody LFiber optic cable having a dry insert and methods of making the sameUS20060237285 *Apr 21, 2005Oct 26, 2006Desanto Anthony JDiverter for a conveyorUS20070098339 *Dec 21, 2006May 3, 2007Bringuier Anne GDry fiber optic cables and assembliesUS20080031580 *Nov 16, 2006Feb 7, 2008David KellerSystem and method for loose tube tight buffer indoor/outdoor optical fiber cableUS20080080821 *Oct 31, 2007Apr 3, 2008Reiner SchneiderOptical transmission elementUS20090067791 *Nov 13, 2007Mar 12, 2009Greenwood Jody LOptical tube assembly having a dry insert and methods of making the sameUS20090074363 *Nov 18, 2008Mar 19, 2009Parsons Alan TOptical Tube Assembly Having a Dry Insert and Methods of Making the SameUS20090190887 *Mar 9, 2009Jul 30, 2009Freeland Riley SFiber Optic Cable Having a Dry InsertUS20090190890 *Nov 28, 2006Jul 30, 2009Freeland Riley SFiber optic cable having a dry insert and methods of making the sameUS20090220817 *Dec 16, 2008Sep 3, 2009Hitachi Cable, Ltd.Hydrated water-absorption polymer containing resin composition, porous body and insulated wire using same, method of making the wire and coaxial cableUS20110079416 *Feb 25, 2010Apr 7, 2011Hitachi Cable, Ltd.Hydrous water absorbent polymer-dispersed ultraviolet curable resin composition, porous substance, and insulated wire cable using the sameCN103246030A *Apr 28, 2013Aug 14, 2013江苏七宝光电集团有限公司Optical cable paste spraying device and processing technique thereofCN103246030B *Apr 28, 2013Dec 7, 2016江苏七宝光电集团有限公司光缆缆膏的喷涂装置及其加工工艺* Cited by examinerClassifications U.S. Classification428/372, 428/373, 428/395, 428/375, 385/102, 385/104International ClassificationD06M15/00, G02B, H01B, C03C, G02B6/44, D06M, D06M23/08, D06M15/647, H01B7/282, H01B7/288, C03C25/10, D06M15/03, D06M101/00, D06M13/513, D06M101/36, C03C25/26, D06M15/267, D06M15/285, D06M23/10, D06M15/643, D06M13/507, D06M15/263, H01B11/00, H01B7/28Cooperative ClassificationY10T428/2929, Y10T428/2969, Y10T428/2927, Y10T428/2913, Y10T428/2933, Y10S526/902, Y10S526/922, G02B6/4494, D06M23/10, D06M13/507, D06M15/285, C03C25/26, H01B7/288, D06M15/643, D06M15/263, D06M23/08, D06M13/513, D06M15/647European ClassificationG02B6/44C11, D06M15/647, D06M13/507, D06M15/643, H01B7/288, D06M23/10, D06M13/513, D06M15/263, D06M15/285, D06M23/08, C03C25/26Legal EventsDateCodeEventDescriptionJun 25, 2002ASAssignmentOwner name: E.I DU PONT DE NEMOURS AND COMPANY, DELAWAREFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:REBOUILLAT, SERGE;PFISTER, FRIEDRICH V.;REEL/FRAME:012826/0288Effective date: 20000127Dec 8, 2006FPAYFee paymentYear of fee payment: 4Dec 3, 2010FPAYFee paymentYear of fee payment: 8Feb 6, 2015REMIMaintenance fee reminder mailedJul 1, 2015LAPSLapse for failure to pay maintenance feesAug 18, 2015FPExpired due to failure to pay maintenance feeEffective date: 20150701RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services

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Business Associate Jobs, Employment in Cherry Point, NC
Business Associate jobs in Cherry Point, NC
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Inside Slant: Oregon State vs. UCLA - Oregon State - Scout
Inside Slant: Oregon State vs. UCLAThe Sports Exchange09/21/2011YES, OREGON STATE HAS settled on a quarterback, with redshirt freshman Sean Mannion getting the nod from the Beaver coaching staff. The question now becomes, who's going to step up to help him get the OSU offense going?The sure addition for the tilt with the Bruins (TV: Prime Ticket/Fox College Sports; 12:30 p.m.) is senior tight end Joe Halahuni, held out of the first two games as he recovered from spring shoulder surgery. Another likely addition for the offense is senior flanker James Rodgers, who has been out since last season with a severe knee injury. "If we can get this thing rolling a little bit with those guys making plays, we'll be a lot better," OSU coach Mike Riley said of their return. Unlikely to be ready to play is freshman running back Malcolm Agnew, still hobbled by a strained hamstring suffered in practice two weeks ago. And definitely out is left guard Josh Andrews, who suffered a knee injury against Wisconsin that likely puts him on the shelf for a month. Grant Enger takes his place. At least the Beavers had a bye to work around all the questions, and to better prepare Mannion for his first start after he played extensively as a reserve in the first two games. The "first start" talk is somewhat misleading. Mannion has essentially played the last six of the Beavs' eight quarters this season, including virtually the entire game at Wisconsin. "He's had some game experience, and I think he's handled himself very well," Riley said. "Now what we're looking for is continued growth. He does not seem to be phased by the situation he's in at all. He doesn't appear to be overwhelmed by any of this." SERIES HISTORY: UCLA leads 40-15-4, with a 17-14 win last year. SCOUTING THE OFFENSE: The Beavers should have more options offensively, with the return of TE Joe Halahuni and the likely presence of WR James Rodgers, both for the first time this season. That should help the passing game in the first start for redshirt freshman QB Sean Mannion. The bigger issue is likely to be whether the Beavers can effectively run the football to keep a balance to the play calling. With Agnew likely out, that task would fall to Jordan Jenkins and Terron Ward. Sophomore Jovan Stevenson is expected to also be used. SCOUTING THE DEFENSE: With the biggest defensive lineman, Castro Masaniai, sitting out the game in his delayed suspension, it will be a challenge for the Beavers to hold off the UCLA running game. That was the major issue last season in a loss, and with the usual questions about UCLA's passing game, holding up against the run will be crucial for the OSU defense. Kevin Frahm and Andrew Seumalo are the d-tackle starters. STRATEGY AND PERSONNEL, THIS WEEK'S GAME: UCLA at Oregon State, Sept. 17, 12:30 p.m. -- The conference opener for two teams that could use a lift after the Beavers lost their first two games and the Bruins went 1-2 in non-conference games. Any hopes of a bowl game and winning record all but require a win in this game for either team. THE QUESTION: Can the Beavers measure up in a physical matchup with the Bruins on both sides of the football? Both the offensive and defensive lines of OSU will be tested by UCLA's size up front. PLAYERS TO WATCH: H-Back Joe Halahuni -- In his first game this season, he figures to be a prime target. In Halahuni's place, Colby Prince had six receptions in the first two games, but only for a total of 34 yards. Halahuni gives OSU more of a threat for deep passes down the middle and is more of a challenge to tackle once he has the football. S Anthony Watkins -- Cited for his much improved play against Wisconsin, when he was in on seven tackles, the junior figures to be busy helping against the UCLA running game as well as pass defense. LB D.J. Welch -- He missed the first two games while recovering from an elbow injury but will become the 10th true freshman to play this season. He's expected to be a contributor on up to all four of the return or coverage teams as well as a primary backup with the defensive unit. ROSTER REPORT
--Reserve TE Connor Hamlett will be available, with his scheduled one-game suspension again put off until later in the season.
--Even on the eve of fall term classes beginning next week, the Beavers are still awaiting a final determination on the eligibility status of DT Dominic Glover. The senior has been practicing but hasn't played in the first two games while awaiting a determination on summer class grades.
--OSU will have two more first-time starters against the Bruins in Mannion and Enger. That will bring to 15 the number of OSU players who already this season have made their first collegiate start. --The Beavers have lost six of their past seven conference openers. But they haven't gone 0-3 to open a season since the 1996 season, which ended with a 2-9 record and led to the firing of Jerry Pettibone as the head coach. Share on Facebook Share on TwitterTrending on ScoutPac-12 Hoops: Season PreviewBeavs in the NFL: Week 7McMaryion readies for start against CougsHow do the Beavers stop the Cougars?Clardy's Corner: Pac-12 MidtermsShare & EmbedHow do the Beavers stop the Cougars? Full StoryBeaverBlitz Top StoriesPre-visit: Mo Unutoa breaks down Oregon StateBig offensive tackle Mo Unutoa will be flying to Oregon State Thursday night from his home in Kauai to check out all that the Beavers have to offer. He fills us in on his…by Adam NicholsonBeaverBlitz4:20 PMHow do the Beavers stop the Cougars?How do the Beavers plan to stop the Air Raid Cougar attack? BeaverBlitz checks in with defensive coordinator Kevin Clune and players Phillip Napoleon and Xavier Crawford to get…by Brian RathboneBeaverBlitz1:49 PM4-star Cole excited for visitRelationships are key in recruiting and life. Coach Andersen's relationships run deep and it the main reason 4-star safety Brian Cole will be visiting Corvallis this weekend. Hear…by Adam NicholsonBeaverBlitz12:13 PMBeaverBlitz Mid-season AwardsTime to take a look at the MVP's for the Beavers midway through the season.by Raju WoodwardBeaverBlitz8:22 AMBeavs in the NFL: Week 7BeaverBlitz is keeping tabs of the former Beavers in the NFL with our weekly run down.by John NewbyBeaverBlitz7:54 AMMcMaryion readies for start against CougsQuarterback Marcus McMaryion is back on the practice field and working to improve before the Beavers host Washington State on Saturday.by Brian RathboneBeaverBlitzYesterday at 4:42 PMFollowing the Future: Week 10BeaverBlitz.com will touch base with the 2017 & 2018 commits weekly to hear how they did during the week. Keep tabs with our popular Following the Future weekly feature.by Adam NicholsonBeaverBlitzYesterday at 8:49 AMThree-Star DB talks Pac-12 commitmentLos Angeles (Calif.) Cathedral defensive back Jeffrey Manning committed to Oregon State on Monday and said there were several reasons why he chose the Beavers.by Greg BigginsScout FootballMonday at 7:36 PMVideo: Coach Andersen Monday PresserCoach Andersen met with the press on Monday to discuss the Beavers next opponent in Washington State.by Angie MachadoBeaverBlitzMonday at 7:27 PMUpgrade now and enjoy a year of SIWe continue to look for ways to add value to your BeaverBlitz membership and are excited to announce a great benefit for our new annual subscribers.by Angie MachadoBeaverBlitzThursday at 5:07 PMPac-12 Hoops: Season PreviewPac-12 basketball is almost here. Campus Insiders' Jordan Cornette gets fans ready for the 2016-2017 season by predicting which team will win the conference, who will be the player…by StaffScout CBK2:06 PMLoad More

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text:
Re: [Nms-cgi-support] WWWBoard Errors
From: Webmeister Beinbrech <webmaster@me...> - 2005-07-24 21:27:54
I put the original wwwboard.pl back in the cgi-bin since its errors were
with syntax. You had asked that I send you a copy of the configuration
section of the script and I did. Did you find a typo?
Today, I used a perl script tester of the wwwboard.pl and have come up
> String found where operator expected at (eval 6) line 405, near "'''
> => "'"
> (Missing operator before ' => "'?)
> String found where operator expected at (eval 6) line 819, at end of line
> (Might be a runaway multi-line "" string starting on line 405)
> (Missing operator before ",
> Global symbol "self" requires explicit package name at (eval 6) line 405.
> Global symbol "string" requires explicit package name at (eval 6) line
> 405.
> panic: restartop syntax error at (eval 6) line 405, near "''' => "'"
I do not know how to page down to line 405 of the script to copy for you
the apparent error in the syntax of the script there. I will assure you
that I did not make any changes other than in the configuration section
If it helps to assure you that the Perl installation of the server isn't
corrupt, the wwwadmin.pl script works flawlessly as well as the other
perl scripts in the cgi-bin.
[Nms-cgi-support] Application Error -- Guestbook
From: <kealaz@st...> - 2005-07-24 19:49:44
Angel (kealaz@...) on Sunday, July 24, 2005 at 19:49:36
description: Hello, I have been using your guest book at my website http://www.bayareascrappers.com for about 5 months now.  It has been working fine.  We occasionally get spammed, and I go into the guestbook-admin and delete those entries before anyone notices.  I get emailed anytime an entry is made to our guestbook, so I am able to do that.  Today I received an email from one of my friends telling me there was a ton of SPAMs on our guestbook.  I did not get any emails letting me know that any entries had been made.  When I went to the guestbook, sure enough there was a lot (over 20) spams.  I deleted them, and then tried to figure out why I didn't get the emails, and in testing the guestbook, I got an Application Error.
close sendmail pipe failed, mailprog=[/usr/sbin/sendmail] at guestbook.pl line 666.
This is the only text on the page after I hit the submit button from /addguest.html  The interesting thing is, although I get this error, the entry is still made to the guestbook, if I go back to guestbook.html and hit refresh.
This script has been working for so long with no problems, I can't imagine what could have changed.  I went to my ISP to verify that the $mailprog info that I have in my script is correct $mailprog = '/usr/sbin/sendmail'; and I'm pretty sure it is.... however, while signed in to the ISP, I received an announcement about port changes.  I have copied it here for your reference.  I do not really understand what it means, and I'm hoping you can help me figure out how it affects my website/guestbook and why it is not working properly now with this change.
As our mail servers are being migrated, port 24 will be closed as an STMP option. We've had port 587 open since August 2004 and that is our official alternative SMTP port. Our support documentation already reflects this change.
If you're currently using port 24, you should switch over to port 587.
Port 25 will continue to work if your ISP allows it.
[Nms-cgi-support] =?windows-1251?B?zeUg8uXw/+ny5SDi8OXs5e3oIS1hbmdlbEBmZW1lbmluby5jb20g?=
From: <blair@he...> - 2005-07-24 18:02:05
[Nms-cgi-support] Need some help with formmail
From: <jamie@fo...> - 2005-07-24 16:39:00
Jamie  Milne (jamie@...) on Sunday, July 24, 2005 at 16:38:56
I've been using the nms formmailer script and I have been unable to get 3 functions working.
1.  required - nothing happens, if the field is not filled in, the user can still submit
2.  email  -  I have a text box called email in my form, but when filled out it just returns the email
address in the form, it does not mask the sender's email as such.
3.  realname  -  I have a text box called realname in my form, but when filled out it just returns the
name in the form, it does not mask the sender's name as such.
All other function work fine.
From: Mail Delivery Service <postmaster@bl...> - 2005-07-24 13:54:22
hana.jezek@...; Failed; 5.2.2 (mailbox full)
Remote MTA mssazhb-int.msg.bluewin.ch: SMTP diagnostic: 552 RCPT TO:<hana.jezek@...> Mailbox disk quota exceeded
[Nms-cgi-support] =?windows-1251?B?3fLuIPDl4Ov87e4hLXNpZGhhcnRhQG5vdGltZXhpY28uY29tIA==?=
From: <michael@fr...> - 2005-07-24 13:34:23
[Nms-cgi-support] dir for lib formmail_modules-3.14m1
From: ludo <ludo@de...> - 2005-07-24 11:06:01
Ref: You will also need to have the Perl modules under the lib/ directory in
this distribution installed on the machine where FormMail.pl is to run.
The directory structure under lib/ must be preserved.  For example, if
you choose to install the modules under /usr/local/nms on the web
server then you should end up with a file heirarchy that looks like:
I installed this dir in cgi-bin next to FormMail.pl
But I wonder why no reference needs to be set in FormMail.pl
Of course it does not work, that is why I ask the question.
I did install formmail_compat-3.14c1 first to get the basics right and that
worked. I use the same setting now in formmail_modules-3.14m1
[Nms-cgi-support] =?iso-8859-1?B?TkVFRCBKT0IhPyBCRVNUIE9QT1JUVU5JVFkhIFNPTElEIFNBTEFSSUVTIQ==?=
From: Julia Stort <anharmonic@et...> - 2005-07-24 09:16:37
Re: [Nms-cgi-support] Possible to send photos with from?
From: Dave Cross <dave@da...> - 2005-07-24 07:35:37
On Sun, Jul 24, 2005 at 07:14:15AM +0000, Ahsan wrote:
> Ahsan (badnews_3@...) on Sunday, July 24, 2005 at 07:07:39
> description: Hi,=20
> I want user to my side to attach photos with their submissions. Is it
> possible for to use this script to accept attachments with the emails?
> If not could you please guide me in the right direction!=20
You don't say which of our programs you are using.
Our Formmail program doesn't allow file uploads, but our TFMail program
[Nms-cgi-support] Possible to send photos with from?
From: <badnews_3@ya...> - 2005-07-24 07:07:47
Ahsan (badnews_3@...) on Sunday, July 24, 2005 at 07:07:39
I want user to my side to attach photos with their submissions. Is it possible for to use this script to accept attachments with the emails?
If not could you please guide me in the right direction!
[Nms-cgi-support] =?windows-1251?B?cmlja+7yIP3q8e/l8PLu4iE=?=
From: <ben@ex...> - 2005-07-24 02:18:49

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Rollerblade Inline & Roller Skating Equipment for sale | eBay
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text:
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Tiffany Style Classic Hanging Lamp
http://www.overstock.com/Home-Garden/Warehouse-of-Tiffany-Classic-Hanging-Lamp/6542271/product.html?recommendation_id=dd603a73-e0c0-485e-ab9a-8c9eb04cc383&rcmndsrc=2&atcError=1
Submit Cancel Can this simply be plugged into the wall or is a ceiling mount necessary?
tory2012 on Jan 1, 2013
does this lamp use more than one 60 watt bulb? says there are 3 chains for the switch but requires only i - 60 watt bulb?
Submit Cancel This lamp uses more than one light bulb, it uses three 60-watt light bulbs.

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