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Publication number | US6169160 B1 |
Publication type | Grant |
Application number | US 09/225,888 |
Publication date | Jan 2, 2001 |
Filing date | Jan 4, 1999 |
Priority date | Sep 26, 1996 |
Fee status | Lapsed |
Also published as | WO2000041188A2 |
Publication number | 09225888, 225888, US 6169160 B1, US 6169160B1, US-B1-6169160, US6169160 B1, US6169160B1 |
Inventors | Richard C. MacQueen, Marc Jackson, Mark S. Pavlin |
Original Assignee | Union Camp Corporation |
Export Citation | BiBTeX, EndNote, RefMan |
Patent Citations (71), Non-Patent Citations (2), Referenced by (16), Classifications (53), Legal Events (8) | |
External Links: USPTO, USPTO Assignment, Espacenet | |
This application is a continuation-in-part of U.S. Patent application Ser. No. 09/074,070 filed May 6, 1999, now U.S. Pat. No. 5,998,570, U.S. patent application Ser. No. 08/939,034, filed Sep. 26, 1996, now U.S. Pat. No. 6,111,055 and U.S. patent application Ser. No. 08/734,523 filed Oct. 18, 1996, now U.S. Pat. No. 5,783,657.
This invention generally relates to protecting moisture and/or corrosion sensitive substrates from moisture and/or corrosion, to articles that contain a moisture and/or corrosion sensitive component as well as a protectant composition; and to compositions that may be used to protect substrates from moisture and/or corrosion.
Transmission cables (e.g., service or power wires/cables) as well as telecommunication devices (e.g., fiber optic cables, telephone cables, terminal blocks, junctions and connections) are often exposed to harsh environmental conditions. Yet, both are required to maintain uninterrupted mechanical and electrical characteristics despite the surrounding environmental conditions. In the past, transmission cables were strung above ground between poles, and occasionally, placed under water. Increasingly, these cables are being buried beneath the ground for aesthetic reasons and to protect them from extremes of temperature, rain, snow, ice, high winds, falling tree limbs and the like. However, even when placed underground, these cables are subject to many environmental stresses including mechanical shock during back filling, moisture, the possibility of water immersion, attack from rodents and exposure to salt and other corrosive materials.
Transmission cables typically contain either a bundle of individually insulated copper wires, or a bundle of fiber optic cables. The copper wires, in particular, are protected by an inner metal shield, which covers the bundle of wires, and an outer sheath made from plastic or other insulating material. Likewise, a communication cable is generally constructed of an outer plastic jacket and an inner metal core wrap with an annular space therebetween. See, e.g., U.S. Pat. No. 3,745,321 to Eager, Jr. et al. The core wrap enwraps a plurality of twisted insulated conductors with a filler material, such as petroleum, wax, or other hydrocarbons, located between the conductors. The filler material typically functions as an insulator.
Even though wires and cables are normally well protected, if the protective outer sheath is cut or otherwise broken, water can seep into the wire or cable. Whenever moisture is present in the interior of a cable or wire, it tends, over a period of time, to migrate or flow longitudinally into connections at the splice closures, terminals, or the like. In the special case of optical fibers, passage of the water to connection points or terminals and associated equipment can not only result in damage to such equipment, especially to any metal parts thereof, but can cause problems at low temperature or freezing environments due to fiber microbending. This is particularly true when an immersed wire is cut.
In an inadequately unprotected device, corrosion of the contacts or short circuits caused by moisture or other outside elements will eventually interrupt service. Replacement or repair of the cables, whether strung along the ground or buried, can be particularly difficult and/or expensive, and the interruption of service may be particularly irritating to the customer. Because of this, much attention has focused on the protection of these cables from both physical damage and from chemical attack. As a result, various techniques have been disclosed to prevent or restrict migration of moisture along cable internal passages.
In one such technique, cable passages may be filled by a pressurized gas. Upon an escape of gas through a ruptured cable jacket, an alarm provides notice of cable damage. However, the gas does not prevent the flow of water into and along the cable internal passages before the repair is effected.
U.S. Pat. Nos. 4,867,526, 5,082,719 and 5,163,115 disclose a super-absorbent polymer or tape which is impregnated with a superabsorbent material for preventing water migration through cables. It has been found that, for a number of reasons, the production and/or installation of these materials is often impractical and/or uneconomical.
Silicone grease lubricant, elastomeric seals, or mastic sealing strips have been used in an attempt to seal out moisture. While these sealants offer some protection, moisture can often seep into the enclosure and cause a short circuit, which will interrupt telecommunications service, particularly when the terminal block is buried underground.
It is also known that insulating materials, such as mineral oil, protect the conductor from moisture and corrosive materials. Such insulating materials, however, drip when the cable is being serviced (i.e., cut). To overcome this "dripping" problem, various gelling agents are know to be added to the insulator, to thereby provide a gelled, non-dripping protectant composition.
The requirements imposed on gelled protectant compositions for transmission cables and telecommunication devices are numerous. A gelled protectant composition must remain stable throughout the temperature range of use of the cable or device, which is typically from about −40� to +70� C. If the maximum working temperature of the gelled protectant composition is not at least as high as about +70� C., then during operation of the cable or device, the insulating material may be subjected to a temperature sufficient to reduce its viscosity to the point that it runs out of the enclosure, exposing the component to moisture and/or other environmental conditions that may induce corrosion. In addition, the gelled protectant composition must be sufficiently fluid over the temperature range experienced during installation, for the composition to completely fill the enclosure without the risk of breaking or over-stressing the components.
A gelled protectant composition should also be sufficiently cohesive to ensure that compression of the enclosure will not result in the formation of voids in either the interior or on the surface of the composition. Also, the gelled protectant composition should be soft enough to allow such compression without subjecting the protected components to any significant strain, and yet be resistant to flow under gravitational forces as well as the hydrostatic pressures likely to be applied to the protected components if the end of a service wire is exposed in a flooded manhole. Moreover, the gelling agent must not chemically attack the components of the service wire or the enclosure of the terminal block.
Due to the relatively long lengths of cable that are typically installed, certain cable components are made from inexpensive plastic components such as polypropylene in an attempt to reduce the cost of the cable as well as obtain multiple supply sources for such components. This presents a problem to the supplier of protectant compositions in that many such compositions are not compatible with materials such as polypropylene and can cause deterioration of those materials.
Hydrophobic fumed silica has been used as a gelling agent, particularly for fiber optic cables, however, hydrophobic fumed silica is expensive and relatively large amounts of fumed silica must be used to provide useful gels. Use of hydrophobic fumed silicas, moreover, can cause the resulting gels to be abrasive.
A need therefore exists for suitable protectant compositions to be used in transmission cables and telecommunication devices. More specifically, there exists a need for gelled cable filling) compositions having improved properties against moisture and corrosive materials, and which avoid the abrasiveness of silica-based gel formulations. The gelled compositions should be compatible with the insulating material, the cable wire and the cable components. The present invention fulfills these needs and further provides related advantages.
In one aspect, the present invention provides an article that includes a moisture-sensitive or corrosion-sensitive substrate in contact with a protectant composition. The protectant composition includes a polyamide gelling agent and a gelled solvent. The protectant composition is preferably shear thinning and/or non-dripping at the operating temperature of the protected article, and/or thermally stable at temperatures up to 50� C. for at least one week.
In a related aspect, the invention provides a m ethod of protecting a moisture-sensitive or corrosion-sensitive substrate against moisture or corrosion. The method includes contacting a substrate with a protectant composition. The protectant composition includes a polyamide gelling agent and a gelled solvent.
In a related aspect, the invention provides a protective composition that includes a polyamide gelling agent and a gelled solvent. The composition preferably further includes a bleed inhibitor.
In a related aspect, the invention provides a method of preparing a protectant composition. The method includes the steps of dissolving a polyamide gelling agent in a solvent at an elevated temperature in excess of 35� C.; combining a bleed inhibitor with the polyamide gelling agent; and cooling the resulting composition to a cooled temperature less than 35� C.
These and other aspects of the present invention will become evident upon reference to the following detailed description and attached drawings. In addition, various references are identified below and are incorporated by reference in their entirety.
The reader's understanding of this invention will be enhanced by reference to the following detailed description taken in combination with the attached Figures, wherein
FIG. 1 represents the relationship between the dropping point of a protectant composition and the composition of the protectant composition, in terms of the relative amounts of polyamide gelling agent and mineral oil in the composition.
FIG. 2 represents the relationship between the shear stress of a protectant composition and the shear rate under which the determination of shear stress was made, for a protectant composition having 3 wt % polyamide.
FIG. 3 represents the dielectric strengths of five compositions, where the gelling agent is present in the composition at a concentration of either 0 wt %, 20 wt % or 50 wt %, and the gelling agent is either a high or low molecular weight polyamide gelling agent.
The present invention provides compositions that may be used to protect moisture-sensitive and/or corrosion-sensitive substrates from moisture and/or environmental factors that cause, or contribute to the corrosion of a substrate. The present invention fuirther provides articles that include a moisture-sensitive and/or corrosion-sensitive substrate in combination with a protectant composition therefor, and methods of protecting moisture-sensitive and/or corrosion-sensitive substrates with a protectant composition.
Moisture-sensitive and/or corrosion-sensitive substrates (hereinafter, "substrates") which may be protected according to the present invention generally include materials having performance properties that may be detrimentally effected by contact with moisture (i.e., water), and/or may undergo corrosion upon contact with corrosive environmental conditions. The present invention provides compositions, termed protectant compositions, that may be contacted with a substrate in order to shield or otherwise protect the substrate from contact with moisture and/or other corrosive conditions. The protectant composition therefore provides a barrier between the substrate and conditions, e.g., moisture, in the environment that may corrode the substrate or otherwise harm the performance properties of the substrate.
Exemplary substrates that may be protected according to the present invention are found within transmission cables and telecommunication devices. Telecommunication cables generally contain some kind of moisture-sensitive or corrosion-sensitive conductor, such as a fiber optic cable or a metal wire, where copper wire is an exemplary metal wire. Telecommunication cables having fiber optics are also referred to as data communication cables. Telecommunication devices generally include terminal blocks, connections and junctions. Transmission cables are also referred to as power cables, and generally conduct, or transmit, electricity or other energy source. Transmission cables typically include a copper wire within a sheath. Each of these materials may be harmed by exposure to moisture, and/or may undergo corrosion upon contact with harmful environmental factors, and accordingly are substrates which may be protected according to the present methods and with the present compositions.
The protectant composition of the present invention includes a solvent and a gelling agent for the solvent. Upon combination, the gelling agent and the solvent form a gel, (i.e., gelling agent and gelled solvent) where upon contact with a substrate, the gel affords protection to the substrate from harmfal environmental factors.
The gelling agent is a polyamide. In a preferred embodiment, the polyamide has a structure that results from the incorporation therein of dimer acid or a reactive equivalent thereof. The following U.S. Patents describe relatively high molecular weight polyamides that may be used as the gelling agent of the present protectant composition:
U.S. Pat. No. 3,645,705 to Miller et al., where the polyamide is derived from the reaction of dimerized linoleic acid with di- or polyamines and has a molecular weight (number or weight average) in the range of 6,000 to 9,000 and a softening point in the range of 48� C. to 185� C., and is capable of producing a gel structure in oil when the solubility of the polyamide in the oil is exceeded.
U.S. Pat. No. 3,819,342 to Gunderman et al., where a thermoplastic polyamide resin is the reaction products of dimerized linoleic acid with di- or polyamines, and these resins have an average molecular weight of between 2,000 and 10,000, and are described in greater detail in U.S. Pat. Nos. 2,379,413 and 2,450,940.
U.S. Pat. No. 3,615,289 to Robert Felton, disclosing solid polyamide resins that are the condensation product of an aliphatic dicarboxylic acid and a diamine, where the polyamides have a molecular weight within the range of from about 2,000 to about 10,000, and are of the type generally set forth in U.S. Pat. No. 2,450,940.
The polyamide gelling agent may be a relatively low molecular weight polyamide, of the type described in U.S. Pat. No. 5,783,657 to Pavlin and MacQueen and denoted therein as an Ester-Terminated PolyAmide (ETPA). ETPA comprises molecules of the formula (1), wherein n, R1, R2 and R3 are defined below.
Thus, in one embodiment, the present invention is directed to gelled protectant compositions formed, in part, of an ester-terminated polyamide of the formula (1) wherein n designates a number of repeating units such that ester groups constitute from about 10% to 50% of the total of the ester and amide groups; R1 at each occurrence is independently selected from C1-42hydrocarbon groups; R2 at each occurrence is independently selected from C2-42hydrocarbon groups; R3 at each occurrence is independently selected from an organic group containing at least two carbon atoms in addition to hydrogen atoms, and optionally containing one or more oxygen and nitrogen atoms; and R3a at each occurrence is independently selected from hydrogen, C1-10alkyl and a direct bond to R3 or another R3a such that the N atom to which R3 and R3a are both bonded is part of a heterocyclic structure defined in part by R3a—N—R3. U.S. Pat. No. 5,783,657 discloses various embodiments which are preferred therein, and which, in one embodiment of the present invention, are also preferred for preparing polyamide gelling agents in the protectant compositions described herein.
Preferably, the ETPA molecules are of relatively low molecular weight, so that n is preferably 1 to about 10, and more preferably is 1 to about 5. Because the ETPA molecules have such a low molecular weight, they could equally well be referred to as ester-terminated oligoamides. In any event, viewed another way, the ester groups constitute about 10% to about 50%, preferably about 15% to about 40%, and more preferably about 20% to about 35% of the total of the ester and amide groups.
The ETPA may be in combination with some molecules wherein n=0. However, such molecules, termed "diesters" because they do not contain any amide groups, are preferably present in minor amount since they are unable to gel hydrocarbons or ester solvents.
The diacid portion of the ETPA, i.e., the R2 group, is preferably from dimer acid. However, some of the dimer acid may be substituted with shorter-chain diacid(s). Thus, the ETPA may be prepared with a mixture of dimer acid and "co-diacid", where the term co-diacid refers to any diacid of the formula HOOC—R2—COOH (where R2 is defined above) excluding polymerized fatty acid. An exemplary co-diacid is a so-called "linear" diacid of the formula HOOC—R2—COOH wherein R2 is a linear C4-12 hydrocarbon group, and more preferably is a linear C6-8 hydrocarbon group. Linear diacids suitable for the present invention include 1,6-hexanedioic acid (adipic acid), 1,7-heptanedioic acid (pimelic acid), 1,8-octanedioic acid (suberic acid), 1,9-nonanedioic acid (azelaic acid), 1,10-decanedioic acid (sebacic acid), 1,11-undecanedoic acid, 1,12-dodecanedioic acid (1,10-decanedicarboxylic acid), 1,13-tridecanedioic acid (brassylic acid) and 1,14-tetradecanedioic acid (1,12-dodecanedicarboxylic acid).
In one embodiment, in formula (1), n designates a number of repeating units such that ester groups constitute from 10% to 50% of the total of the ester and amide groups; R1 at each occurrence is independently selected from an alkyl or alkenyl group containing at least 4 carbon atoms; R2 at each occurrence is independently selected from a C4-42 hydrocarbon group with the proviso that at least 50% of the R2 groups have 30-42 carbon atoms; R3 at each occurrence is independently selected from an organic group containing at least two carbon atoms in addition to hydrogen atoms, and optionally containing one or more oxygen and nitrogen atoms; and R3a at each occurrence is independently selected from hydrogen, C1-10 alkyl and a direct bond to R3 or another R3a such that the N atom to which R3 and R3a are both bonded is part of a heterocyclic structure defined in part by R3a—N—R3, such that at least 50% of the R3a groups are hydrogen.
In preparing an ETPA gelling agent, the equivalents of carboxylic acid are substantially equal to the combined equivalents of hydroxyl contributed by monoalcohol and amine contributed by diamine. In other words, if the reaction mixture used to form an ETPA gelling agent has "x" equivalents of carboxylic acid, "y" equivalents of amine and "z" equivalents of hydroxyl, then 0.9≦{x/(y+z)}≦1.1, and preferably {x/(y+z)} is substantially 1.0. Under these conditions, substantially all of the carboxylic acid groups will react with substantially all of the hydroxyl and amine groups, so that the final product contains very little unreacted carboxylic acid, hydroxyl or amine groups. In other words, each of the acid and amine numbers of the gelling agent is preferably less than about 25, is more preferably less than about 15, and is still more preferably less than about 10, and is yet still more preferably less than about 5.
When co-diacid is employed to prepare an ETPA gelling agent, the co-diacid preferably contributes no more than about 50% of the equivalents of carboxylic acid present in the reaction mixture. Stated another way, the co-diacid contributes from 0-50 equivalent percent of the acid equivalents in the reaction mixture. Preferably, the co-diacid contributes 0-30 equivalent percent, and more preferably contributes 0-10 equivalent percent of the acid equivalents in the reaction mixture.
In order to prepare the ETPA gelling agent, it is important to control the relative equivalents of hydroxyl and amine used in the gelling agent-forming reaction. Thus, hydroxyl groups contribute about 10-70% of the total equivalents of hydroxyl and amine employed to prepare the gelling agent. Stated another way, 0.1≦{z/(y+z)}≦0.7, where y and z have been defined above. In a preferred embodiment, 0.2≦{z/(y+z)}≦0.5, while in a further preferred embodiment, 0.25≦{z/(y+z)}≦0.4.
A suitable low molecular weight polyamide gelling agent may be prepared by a method that includes reacting x equivalents of carboxylic acid from diacid or a reactive equivalent thereof, y equivalents of amine from diamine and z equivalents of hydroxyl from monoalcohol or a reactive equivalent thereof, where monoalcohol is substantially the only monofunctional reactant used to form the polyamide, and wherein each of x, y and z is greater than 0, where these terms have been previously defined in U.S. Pat. No. 5,783,657.
Another suitable gelling agent is a tertiary amide-terminated polyamide, or ATPA, wherein the terminal amide groups are formed from secondary amines. ATPA comprises molecules of the formula (2) wherein n, R2, R3 and R4 are defined below:
Thus, the invention is directed to gels formed, in part, of an amide-terminated polyamide of the formula (2) wherein n designates a number of repeating units such that tertiary terminal amide groups constitute from about 10% to about 50% of the total of the amide groups; R2 at each occurrence is independently selected from C2-42hydrocarbon groups; R3 at each occurrence is independently selected from an organic group containing at least two carbon atoms in addition to hydrogen atoms, and optionally containing one or more oxygen and nitrogen atoms; R3a at each occurrence is independently selected from hydrogen, C1-10alkyl and a direct bond to R3 or another R3a such that the N atom to which R3 and R3a are both bonded is part of a heterocyclic structure defined in part by R3a—N—R3; and R4 at each occurrence is independently selected from C1-22 hydrocarbon groups.
As may be seen from formula (2), the ATPA gelling agents have tertiary terminal amide groups, i.e., —N(R4)R4 groups at both ends of a series of (non-terminal) amide groups, i.e., —N(R3a)C(═O)— groups (which may equally well be written as —C(═O)N(R3a)— groups). The letter "n" designates the number of repeating units present in a molecule of ATPA, and is an integer greater than 0. According to the invention, n may be 1, in which case the ATPA contains equal numbers of terminal amide and non-terminal amide groups, i.e., the terminal amide groups constitute 50% of the total of the amide groups in the ATPA molecule. The preferred ATPA gelling agents are of relatively low molecular weight, so that a is preferably 1 to about 10, and more preferably is 1 to about 5.
Because the ATPA molecules have such a low molecular weight, they could equally well be referred to as tertiary amide-terminated oligoamides. In any event, viewed another way, the terminal amide groups constitute about 10% to about 50%, preferably about 15% to about 40%, and more preferably about 20% to about 35% of the total of the amide groups. A preferred ATPA resin includes a mixture of ATPA molecules of formula (2) having various n values. The ATPA resin has a weight average molecular weight of less than about 10,000, and typically less than about 5,000, when measured by gel permeation chromatography (GPC) using polystyrene calibration standards.
In one embodiment, the R4 group in formula (2) is an alkyl or alkenyl group which contains at least 1, typically at least 4, and preferably more than 4 carbon atoms, e.g., 8, 10, 12, 14, 16, 18, 20, 22 carbon atoms. Alkyl groups are preferred, however alkenyl groups having 1-3, and preferably 1 site of unsaturation are also suitable. The upper range for the number of carbon atoms in the R4 group is not particularly critical, however preferably the R4 group has less than or equal to about 22 carbon atoms. R4 groups having about 16-22 carbon atoms are highly preferred. Linear R4 groups are preferred in one embodiment of the invention. The identity of R4 at any occurrence is independent of the identity of R4 at any other occurrence.
The R2 group in formula (2) is preferably a hydrocarbon containing 4 to 42 carbon atoms. A preferred R2 group contains 30-42 carbon atoms (i.e., is a C30-42 group), and at least 50% of the R2 groups in an ATPA gelling agent preferably have 30-42 carbon atoms. Such R2 groups are readily introduced into an ATPA when the gelling agent is prepared from polymerized fatty acid, also known as dimer acid. Polymerized fatty acid is typically a mixture of structures, where individual dimer acids may be saturated, unsaturated, cyclic, acyclic, etc. Thus, a detailed characterization of the structure of the R2 groups is not readily available. However, good discussions of fatty acid polymerization may be found in, e.g., U.S. Pat. No. No. 3,157,681 and Naval Stores—Production, Chemistry and Utilization, D. F. Zinkel and J. Russel (eds.), Pulp. Chem. Assoc. Inc., 1989, Chapter 23.
While the preferred ATPA gelling agents contain at least 50% C30-42 groups as the R2 group, more preferably the total of the R2 groups consist of at least 75% C30-42 groups, and still more preferably consist of at least 90% C30-42 groups. ATPA gelling agents of formula (2) wherein R2 is entirely C30-42 are preferred gelling agents of the invention.
However, ATPA gelling agents may also contain R2 groups having less than 30 carbon atoms. For example, an ATPA gelling agent may contain one or more R2 groups having about 2 to 19, preferably about 4 to 12, and more preferably about 4 to 8 carbon atoms. The carbon atoms may be arranged in a linear, branched or cyclic fashion, and unsaturation may be present between any two carbon atoms. Thus, R2 may be aliphatic or aromatic. When present, these lower carbon-number R2 groups are preferably formed entirely of carbon and hydrogen, i.e., are hydrocarbon groups. Such lower carbon-number R2 groups preferably constitute less than 50% of the R2 groups; however, when present, constitute about 1% to about 50%, and preferably about 5% to about 35% of the total of the R2 groups. The identity of R2 at each occurrence is independent of the identity of R2 at any other occurrence.
The —N(R3a)—R—N(R3a)— group in formula (2) links two carbonyl (C═O) groups. In a preferred embodiment of the invention, all of the R3a groups in an ATPA gelling agent are hydrogen, so that R3 alone joins the two nitrogen atoms shown in the formula —N(R3a)—R3—N(R3a)—. In this case, the R3 group contains at least two carbon atoms, and optionally oxygen and/or nitrogen atoms, in addition to any hydrogen atoms that are necessary to complete otherwise unfilled valencies of the carbon, oxygen and nitrogen atoms. In a preferred embodiment, R3 is a hydrocarbon group, having 2 to about 36 carbon atoms, preferably having 2 to about 12 carbon atoms, and more preferably having 2 to about 8 carbon atoms. These carbon atoms may be arranged in a linear, branched or cyclic fashion, and unsaturation may be present between any two of the carbon atoms. Thus, R3 may contain aliphatic or aromatic structures. The identities of R3 and R3a at each occurrence are independent of their identities at any other occurrence.
The R3 groups may contain oxygen and/or nitrogen in addition to carbon and hydrogen atoms. A typical oxygen atom-containing R3 group is a polyalkylene oxide, i.e., a group having alternating alkylene groups and oxygen atoms. Indeed, the oxygenation in a R3 group is preferably present as an ether group. Representative polyalkylene oxides include, without limitation, polyethylene oxide, polypropylene oxide and copolymers (either random, alternating or block) of ethylene oxide and propylene oxide. Such oxygenated R3 groups are readily introduced into an ATPA molecule of the invention through use of JEFFAMINE™ diamines (Huntsman Chemical Inc., Houston, Tex.; http://www.huntsman.com). These materials are available in a wide range of molecular weights. While some of the R3 groups may contain oxygen (at least about 1%), preferably a minor number (less than 50%) of the R3 groups contain oxygen, and more preferably less than about 20% of the R3 groups contain oxygen. The presence of oxygen-containing R3 groups tends to lower the softening point of the ATPA.
When present, the nitrogen atoms in an R3 group are preferably present as secondary or tertiary amines. A typical nitrogen atom-containing R3 group having secondary amine groups is a polyalkylene amine, i.e., a group containing alternating alkylene groups and amine groups, which is sometimes referred to as a polyalkylene polyamine. The alkylene group is preferably a lower alkylene group, e.g., methylene, ethylene, (i.e., —CH2CH2—), propylene etc. A typical polyalkylene amine may be represented by the formula —NH—(CH2CH2NH)mCH2CH2—NH— wherein m is an integer from 1 to about 5.
However, the nitrogen atoms in the nitrogen-containing R3 group may alternatively (or additionally) be present as tertiary nitrogen atoms, e.g., they may be
present in a heterocycle of the formula:
wherein RC is a C1-3 alkyl group.
In the above-described nitrogen atom-containing R3 groups, R3a was hydrogen. However, R3a is not limited to hydrogen. In fact, R3a may be a C1-10 alkyl group, preferably a C1-5 alkyl group, and more preferably a C1-3 alkyl group. In addition, R3 and R3a, or two R3a groups, may together form a heterocyclic structure, e.g., a piperazine structure such as
. In this case, the two R3a groups may be seen as joining together to form an ethylene bridge between the two nitrogen atoms, while R3 is also an ethylene bridge.
Compounds having the formula HN(R3a)—R3—NH(R3a), which are referred to herein as "diamine" are a preferred reactant to prepare ATPA and thereby introduce R3 and R3a groups into ATPA. These diamines are commercially available from many sources, including Aldrich (Milwaukee, Wisc.) and Huntsman Chemical (Houstan, Tex.).
R4 groups may be incorporated into ATPA by including secondary amine of the formula NH(R4)(R4) among the ATPA-forming reactants. Such secondary amines are available from many commercial sources, for example, Akzo Nobel Chemicals, Surface Chemistry (Chicago, Ill.; http//www.akzonobelusa.com) and Aldrich (Milwaukee, Wisc.; http://www.aldrich.sial.com). Such secondary amines may be referred to herein as "monoamine" in order to distinguish them from "diamine", which is the other amine-containing reactant that is preferably used to prepare ATPA.
The ATPA gelling agent typically includes a mixture of ATPA molecules of formula (2) in addition to, for example, by-products that are formed during the ATPA-forming reaction. While the ATPA molecules of formula (2) may be purified from such by-products using, e.g., chromatography or distillation, the by-products are typically either minimal in amount or impart desirable properties to the gelling agent, and thus need not be separated from the molecules of formula (2) in order for a suitable ATPA gelling agent to be formed.
As described herein, amines (monoamine and diamine) and carboxylic acids are preferred starting materials to form the ATPA gelling agents of the invention. These starting materials are preferably reacted together with a stoichiometry, and under reaction conditions, such that the acid number of the resulting gelling agent is less than 25, preferably less than 15, and more preferably less than 10, while the amine number is preferably less than 10, more preferably less than 5, and still more preferably less than 1. The softening point of the gelling agent is preferably greater than room temperature, more preferably is about 50� C. to about 150� C., and still more preferably is about 80� C. to about 130� C.
It is important to control the stoichiometry of the reactants in order to prepare an ATPA gelling agent according to the invention. In the following discussion regarding reactant stoichiometry, the terms "equivalent(s)" and "equivalent percent" will be used, and are intended to have their standard meanings as employed in the art. However, for additional clarity, it is noted that equivalents refer to the number of reactive groups present in a molar quantity of a molecule, such that a mole of a dicarboxylic acid (e.g., sebacic acid) has two equivalents of carboxylic acid, while a mole of monoamine has one equivalent of amine. Furthermore, it is emphasized that the diacid has only two reactive groups (both carboxylic acids), the monoamine has only one reactive group (an amine group, and more specifically, a secondary amine group) and the diamine has only two reactive groups (preferably both primary amines), and these are preferably, although not necessarily, the only reactive materials present in the reaction mixture.
When co-diacid is employed to prepare an ATPA gelling agent, the co-diacid preferably contributes no more than about 50% of the equivalents of carboxylic acid present in the reaction mixture. Stated another way, the co-diacid contributes from 0-50 equivalent percent of the acid equivalents in the reaction mixture. Preferably, the co-diacid contributes 0-30 equivalent percent, and more preferably contributes 0-10 equivalent percent of the acid equivalents in the reaction mixture.
The stoichiometry of the reactants will have a significant impact on the composition of the ATPA gelling agents. For example, ATPA gelling agents made with increasing amounts of monoamine will tend to have lower (number and weight) average molecular weights. In other words, as more monofunctional reactant is used, the number of amide pairs in an average molecule of formula (2) will decrease. On the other hand, as less monoamine is used, the average molecular weight of the molecules in the ATPA gelling agent will increase. In general, increasing the average molecular weight of the ATPA component will tend to increase the melting point and melt viscosity of the gelling agent, which tends to provide a firmer gel when the gelling agent is combined with a low polarity liquid or other solvent.
In order to prepare an ATPA gelling agent, the above-described reactants (diacid, monoamine and diamine or reactive equivalents thereof) may be combined in any order. Preferably, the reactants are simply mixed together and heated for a time and at a temperature sufficient to achieve essentially complete reaction, to thereby form the ATPA gelling agent. During formation of the ATPA gelling agent, the diacid and diamine groups will alternate to form what may be termed an alternating copolymer. The ATPA is not a block copolymer. The terms "complete reaction" and "reaction equilibrium" as used herein have essentially the same meaning, which is that further heating of the product gelling agent does not result in any appreciable change in the performance characteristics of the product gelling agent, where the most relevant performance characteristic is the ability of the product gelling agent to form a clear, firm gel upon being combined with a solvent.
Thus, the ATPA gelling agent may be formed in a one-step procedure, wherein all of the diacid (including co-diacid), monoamine and diamine are combined and then heated to about 180-250� C. for a few hours, typically 2-8 hours. Longer reaction times are typically needed at lower reaction temperatures. Since one or more of the reactants may be a solid at room temperature, it may be convenient to combine each of the ingredients at a slightly elevated temperature, and then form a homogeneous mixture prior to heating the reaction mixture to a temperature sufficient to cause reaction between the diacid, monoamine and diamine. Alternatively, although less preferably, two of the reactants may be combined and reacted together, and then the third reactant is added followed by further heating until the desired product is obtained. Reaction progress may be conveniently monitored by periodically measuring the acid and/or amine number of the product mixture.
As one example, the diacid may be reacted with the diamine so as to form polyamide, and then this intermediate polyamide may be reacted with monoamine to form tertiary amide-terminated dimer acid-based polyamide. Or, the diacid may be reacted with the monoamine to thereby form diamide, and this diamide may be reacted with diamine to thereby form tertiary amide-terminated dimer acid-based polyamide. Because the components of the product gelling agent are preferably in reaction equilibrium (due to transamidation), the order in which the reactants are combined typically does not impact on the properties of the gelling agent.
Any catalyst that may accelerate amide formation between carboxylic acid and amine groups may be present in the reaction mixture described above. Thus, mineral acid such as phosphoric acid, or tin salts such as dibutyltin oxide, may be present during the reaction. In addition, it is preferred to remove water from the reaction mixture as it is formed upon amide formation. This is preferably accomplished by maintaining a vacuum on the reacting mixture, or by passing a gentle flow of an inert gas (e.g., nitrogen through the reaction mixture).
The protectant composition contains, at a minimum, a solvent in addition to a gelling agent. The gelled solvent may be a liquid or solid at room temperature, but is preferably a liquid. As used herein, the term solvent includes any substance which is a liquid at a temperature between 10-60� C., and which forms a gel upon being combined with a polyamide gelling agent. As used herein, the term solvent will be used to encompass oils and other fluids which may be gelled, and is not otherwise limited. Examples of solvents that are solid at room temperature include fatty acids and fatty alcohols, such as myristic acid (flash point >159� C.) and myristyl alcohol (flash point (>143� C.).
A preferred solvent is a low polarity liquid, while a preferred low polarity liquid is a hydrocarbon, and preferred hydrocarbons are oils, such as mineral oils. Mineral oils useful in the invention include, but are not limited to transformer oil, spindle oil, cable insulating oil and machine oil. In one embodiment, the mineral oil is food grade mineral oil. Examples of suitable, commercially available mineral oils include SONNEBORN™ and CARNATIONM white oils from Witco Corp. (Greenwich, Ct.); ISOPAR™ K and ISOPAR™ H from Exxon Corp. (Houston, Tex.); and DRAKEOLTm and PENETECKT white mineral oils from Penreco (Karns City, Pa.). These oils are preferably liquids at room temperature.
Other hydrocarbon solvents that may be used in the invention are relatively low molecular weight hydrocarbons including linear saturated hydrocarbons such a tetradecane, hexadecane, octadecane, etc. Cyclic hydrocarbons such as decahydronaphthalene (DECALIN™), fuel grade hydrocarbons, branched chain hydrocarbons such as PERMETHYL™ from Permethyl Corp. and ISOPAR™ from Exxon Corp. (Houston, Tex.); and hydrocarbon mixtures such as product PD-23T from Witco Corp. (Greenwich, Conn.) may also be used in preparing gels of the invention. Such hydrocarbons, particularly saturated hydrocarbon oils, are a preferred solvent for preparing a gel of the invention. The hydrocarbon solvent may be aliphatic (as described above) or aromatic. Suitable aromatic solvents include toluene and xylene.
Another class of suitable solvents is esters, and particularly esters of fatty acids. Such esters may be monofunctional esters (i.e., have a single ester moiety) or may be polyfunctional (i.e., have more than one ester group). Suitable esters include, but are not limited to, the reaction products of C1-24 monoalcohols with C1-22 monocarboxylic acids, where the carbon atoms of both the monoalcohol and monocarboxylic acids may be arranged in a linear, branched and/or cyclic fashion, and unsaturation may optionally be present between carbon atoms. Preferably, the ester has at least about 18 carbon atoms. Examples include, but are not limited to, fatty acid esters such as isopropyl isostearate, n-propyl myristate, isopropyl myristate, n-propyl palmitate, isopropyl palmitate, hexacosanyl palmitate, octacosanyl palmitate, triacontanyl palmitate, dotriacontanyl palmitate, tetratriacontanyl palmitate, hexacosanyl stearate, octacosanyl stearate, and triacontanyl stearate. Other suitable esters include glycerol and propylene glycol esters of fatty acids, including the so-called polyglycerol fatty acid esters and triglycerides.
Preferably, the solvent is a low-polarity liquid as described above, and more preferably the solvent is a liquid hydrocarbon. The liquid may contain more than one component, e.g., hydrocarbon as well as ester-containing material. In the mixture, the gellant (e.g., ETPA) typically contributes 10-95%, and the solvent typically contributes 5-90% of the combined weight of the gellant and the solvent. Preferably, the gellant is combined with the solvent such that the weight percent of gellant in the gellant+solvent mixture is about 5-50%, and preferably is about 10-45%. Such gels may be transparent, translucent or opaque, depending on the precise identities of the gellant and solvent, as well as the concentration of gellant in the mixture. Generally, the appearance of the gelled protectant composition is unimportant when it is used within the interior of a cable.
In one embodiment, the protectant composition further includes a bleed inhibitor. The bleed inhibitor serves to reduce, or eliminate, any syneresis that may otherwise occur in the protectant compositions. U.S. Pat. No. 4,701,061 discloses bleed inhibitors that may be incorporated into the present protectant compositions. Thus, the bleed inhibitor may be one or more of a polyurethane elastomer, polyester elastomer, butadiene acrylonitrile copolymer, polyacrylate, acrylate copolymer and rubber block copolymer. In one embodiment, the bleed inhibitor is fumed silica.
In order to prepare a gel from a solvent and gelling agent, the two components are mixed together and heated until homogeneous. A temperature within the range of about 80-150� C. is typically sufficient to allow the gelling agent to completely dissolve in the solvent. A lower temperature may be used if a homogenous solution can be prepared at the lower temperature. Upon cooling, the mixture formns the gelled protectant composition of the invention. The bleed inhibitor, and any other optional components, are preferably added to the molten composition, and are dispersed and/or dissolved to provide a homogeneous composition prior to cooling of the molten composition.
The protectant composition should meet three important criteria in order to be advantageously used as a cable filing composition for fiber optic cables. Those criteria are non-dripping behavior at temperatures up to about 80� C., shear thinning behavior, and heat stability at 50� C. for at least one week. The non-dripping behavior is desirable in order that the protectant composition does not flow out of the cable in the event the cable is cut or spliced. The non-dripping behavior should be exhibited at temperatures up to, and including, the working temperature of the cable, which is typically less than about 80� C. The temperature at which the protectant composition starts to drip will be referred to herein as the dripping temperature.
In general, the dripping temperature of a protectant composition will increase as the softening point of the polyamide gellant increases. Increases in the softening point of a polyamide gellant may generally be achieved by incorporating short-chain diacids into the polyamide reactant formulation, where short-chain diacids have about 2-12 carbon atoms including two carboxylic acid groups. Sebacic and azelaic acid are two exemplary short-chain diacids. Increases in dripping temperature may also be achieved by incorporating greater proportions of the polyamide gelling agent in the protectant composition. The dripping temperature of a protectant composition can be measured in the laboratory, to a close approximation, by determining the dropping point of the protectant composition, where dropping points may be measured using a Mettler FP 900 dropping point apparatus available from Mettler-Toledo International, Inc. (CH-8606 Greifensee, Switzerland; http://www.mt.com). Preferred protectant compositions of the present invention have dripping temperatures in excess of 80� C., more preferably in excess of 90� C., 100� C., 110� C., 120� C. or 130� C.
Shear thinning behavior is desirable in a protectant composition so that the composition does not put mechanical stress on the fiber optic portion of the cable, when the composition is being pumped into the cable. Whether a protectant composition has shear thinning properties can be determined by measuring the viscosity of the composition as a function of shear rate. Instruments that can make these measurements are well known in the art. One such instrument is the Rheometrics Dynamic Analyzer Model 70 (Rheometric Scientific, Inc.; Piscataway, N.J.), however other instruments capable of performing Dynamic Mechanical Analysis may also be employed. Preferred protectant compositions of the present invention display shear thinning behavior at 25� C.
Moisture and/or corrosion-sensitive substrates in a cable may be exposed to elevated temperature for extended periods of time. It is therefore desirable that the protectant composition retain its protective properties under these conditions. Whether a protectant composition is stable at 50� C. can be determined by measuring relevant properties of the protectant composition before and after exposure to 50� C., where the exposure time is typically at least one week. Solvents commonly employed in cable filling compositions, such as hydrocarbons and esters, are stable at 50� C. Accordingly, whether the protectant composition will be stable is largely a function of the stability of the gelling agent. Whether a gelling agent is thermally stable may be determined by measuring its molecular weight before and after exposure to the relevant elevated temperature.
Molecular weight measurements are readily made by dissolving a sample of the gelling agent in a suitable solvent, and then using gel permeation chromatography (GPC) to measure the molecular weight of the gelling agent. Polystyrene standards may be used to calibrate the GPC instrument. Typically, the molecular weight of the gelling agent is much larger than the molecular weight of the solvent, and accordingly a sample of the heated protectant composition may be characterized by GPC, and thereby any changes in the molecular weight of the gelling agent are readily determined. Preferred gelling agents of the present invention are stable, in terms of their molecular weight, at 50� C.
When the protectant composition is used as a cable filling composition for copper or other metal wire-containing cables, it is desirable that the protectant composition have a dielectric strength that is approximately equal to, or somewhat greater than, the dielectric strength of the ungelled solvent used in the protectant composition. Dielectric strength may be measured according to standard procedures known to one of ordinary skill in the art. See, e.g., ASTM D 149 (American Society for Testing and Materials, West Conshohocken, Pa.; http://www.astm.org). The dielectric strength of the protectant composition that incorporates polyamide gelling agent is preferably at least about 50% of the dielectric strength of the same composition absent the polyamide gelling agent.
Thus, the present invention provides a method of protecting a moisture-sensitive or corrosion-sensitive substrate against moisture or corrosion, wherein the substrate is contacted with a protectant composition as described above, containing, at a minimum, a polyamide gelling agent and a gelled solvent. The "contacting" preferably covers all of the substrate from which it is desired to exclude moisture and/or corrosion causing agents. In order to contact the substrate, the protectant composition may be warmed to a fluid composition, and then poured onto, or sprayed onto, or brushed onto, or otherwise applied to the substrate. Alternatively, the substrate may be dipped into the fluid protectant composition.
The protectant composition preferably exhibits shear thinning behavior. Thus, upon stirring, the protectant composition will assume a lower viscosity. This lower viscosity forrn of the composition may conveniently be applied to a substrate using any of spraying, brushing, dipping, etc. When the protectant composition will be disposed between a moisture and/or corrosion sensitive component of a cable, and the sheath of the cable, the protectant composition may be extruded into the interstitial space of the cable. The extrusion process itself may cause the viscosity of the protectant composition to be sufficiently low that the protectant composition will flow into the cable. Alternatively, the protectant composition may be warmed to enhance its fluid character.
The protectant composition preferably does not contain any chemically reactive groups, so that the composition is essentially inert. Chemically reactive groups include carboxylic acid and amine groups. Accordingly, the acid and amine numbers for the polyamide gelling agents are both preferably low, that is less than 10, and more preferably less than about 1. Preferably, the polyamide gelling agent does not contain any appreciable free amine or free carboxylic acid.
Thus, in a preferred embodiment of the invention, the protectant composition is used as a cable filling composition, or a component of a cable filling composition. The following publications disclose various cables that may be filled by the compositions of the present invention and/or set forth various additives that may be included in the cable filling compositions of the present invention, and/or various techniques by which a cable may be filled by the cable filling compositions of the present invention: U.S. Pat. Nos. 5,402,516; 5,358,664; 5,348,669; 5,243,675; 5,187,763; 4,870,117; 4,666,968; 4,190,570; 4,105,619; European Patent Application No. 0 735 395 A2and 0 037 611 A1.
The following examples are offered by way of illustration and not by way of limitation.
Five ester-terminated polyamides (labeled ETPA A, B, C, D, and E) were prepared having the compositions set forth in Table 1. In Table 1, under the column "Composition (eq %)", each of ETPAs A through E is characterized by two lines, where the top lines refers to the acids that were used to prepare the ETPA, and the lower line refers to the diamine and monoalcohol that were used to prepare the ETPA. The percentages values in this column are based on the total of the acid equivalents (top line) and the total of the amine and hydroxyl equivalents (lower line) used in preparing the ETPA, where the reactants were combined such that the acid equivalents equaled the total of the amine and alcohol equivalents. In Table 1, viscosity values were measured when the sample was at 160� C.
In Table 1, ALFOL™ 18 is stearyl alcohol from CONDEA Vista Company (Houston, Tex.; http://www.condea.com); EDA is an abbreviation for ethylene diamine, from Aldrich (Milwaukee, Wisc.; http:I/www.aldrich.sial.com); EMPOL™ 1008 is hydrogenated second pass dimer acid from Henkel Corporation, Emery Oleochemicals Division (Cincinnati, Ohio; http://www.henkelcorp.com); EPAL™ 1618 is a mixture of C16-C18 alcohols from Amoco Corporation, Amoco Chemicals Division (Lisle, Ill.; http://www.amocochem.com); DRAKEOL™ 7 is a mineral oil from Penreco, a division of Pennzoil Products Company (Karns City, Pa.; http://www.chemexpo.com/show/exhibitorhall/penreco/chemindex.cfm); UNIDYME™ 18 is unhydrognated first pass dimer acid from Union Camp Corporation, Chemical Products Division (Jacksonville, FL; http://www.unioncamp.com).
Composition (eq %)
10% sebacic acid;
10% sebacic acid;
10% sebacic acid;
12% sebacic acid;
ETPA D was prepared with EMPOL™ dimer acid as the only acid-containing reactant (and using a 61.3/34.5 EDA/ALFOL™ stearyl alcohol ratio), and had a softening point of 83.9� C. In order to increase the softening point of the ETPA, and thereby increase the working temperature of a gel prepared therefrom, a portion of the dimer acid was replace with sebacic acid. The result is shown with ETPA E, which has a softening point of 135.6� C. when sebacic acid contributes 12% of the total acid equivalents.
The softening point of a gelled protectant composition can also be increased by incorporating greater amounts of the gelling agent (e.g., ETPA) in the composition. The effect of gellant concentration on the softening point of the gelled protectant composition is shown in FIG. 1, for various concentrations of ETPA A in DRAKEOL™ 7 mineral oil. Softening points as reported in Table 1 were measured using a Mettler FP 900 dropping point apparatus (Mettler-Toledo International, Inc.; CH-8606 Greifensee, Switzerland; http://www.mt.com) operated using a 2.8 mm diameter cup without a lead weight, and a heating rate of 1.5� C./min.
Thus, as shown in FIG. 1, the softening point ranges from about 88� C. at 3-5 wt % (weight percent) ETPA, to over 120� C. at 30 wt % ETPA, in mineral oil. At ETPA concentrations above about 25%, the gelled composition was clear and hard, while below about 25 wt % ETPA, the compositions were translucent or opaque, somewhat soft gels. FIG. 1 shows that at 30 wt % ETPA, the dropping point of the gelled composition was nearly the same as the softening point of the neat ETPA. This data suggests that an ETPA-based gelled protectant composition, which should not drip at 80� C. or below, could be prepared from ETPA A at an ETPA A concentration of 3 wt % or greater.
Since the 3% gelled protectant composition prepared from ETPA A and DRAKEOL™ 7 mineral oil was a soft gel compared to the very rigid composition that resulted when ETPA A was at 30 wt % solids, the shear thinning behavior of the 3 wt % composition was determined at 25� C. as shown in FIG. 2. Shear thinning is defined as a decrease in viscosity as a function of increasing shear rate. Measurements shown in FIG. 2 were made using Dynamic Mechanical Analysis (DMA). The data indicates that as the shear rate was increased, the viscosity of the gel decreased, and when the shear rate was decreased the viscosity increased. This type of non-Newtonian viscosity behavior indicates shear thinning behavior.
To determine the high-temperature stability of the ETPA-based protectant compositions, the molecular weights of two ETPA gellants (ETPA D and ETPA E, from Table 1), were measured before and after exposure to 50� C. for 48 hours. The results are shown in Table 2, and demonstrate that ETPA gellants are stable at 50� C. for at least 48 hours. Molecular weight (MW) measurements were performed using gel permeation chromatography, and polystyrene standards.
48 h @ 50� C.
48 h @ 50� C.
Attempts were also made to determine the dropping point, shear thinning behavior, and heat stability of mineral oil thickened with famed silica, but dispersion (activation) of the fumed silica in the mineral oil required very high shear. In contrast, polyamide gelling agents are easily combined with solvents to provide a gelled protectant composition, without recourse to expensive high shear mixers.
Two ETPAs were prepared, from the reactants listed in Table 3. Since ETPA F contains less monofunctional reactant (i.e., less stearyl alcohol) than ETPA G, ETPA F will have a higher molecular weight than ETPA G.
Dimer Acid
Stearyl Alcohol
76.4 wt %
17.7 wt %
5.9 wt %
71.9 wt %
23.3 wt %
4.8 wt %
The dielectric strengths of five compositions were determined according to ASTM D, using DF-100 alkyl benzene dielectric (Shrieve Chemical, the Woodlands, Tx.; http://www.shrieve.com) as the solvent, with the results shown in FIG. 3. As shown in FIG. 3, the solvent itself had a dielectric of 350 volts/mil (see 0% ETPA), while a combination of the solvent and an ETPA (at each of 20 wt % and 50 wt % ETPA solids, and using both of ETPA F and ETPA G) provided compositions with dielectric strengths which, within experimental error, were approximately the same as the non-gelled solvent. Accordingly, the presence of the ETPA gellant does not significantly impair the dielectric strength of the solvent.
Several ATPAs (labeled ATPA A, B, and C) were made from the reactants, and relative amounts thereof, as set forth in Table 4. In Table 4, "DTA" is an abbreviation for ditallow amine, "SA" is an abbreviation for stearyl amine, and PD-23 is a petroleum distillate, all of which are available from Witco Corporation (Greenwich, Conn.; http://www.witco.com). Selected properties for the ATPAs are also set forth in Table 4, including acid number, amine number, softening point ("S.P.") and the appearance when combined at 20 wt % solids in PD-23 petroleum distillate ("Appearance").
In preparing ATPAs, a 60/40 EDA/DTA equivalent ratio results in a material that forms a clear, hard gel in PD 23 distillate (at 20% solids). Increasing this ratio to 75/25 (see ATPA B) and 80/20 (see ATPA C) decreases the ATPAs solubility in PD-23 distillate, resulting in opaque, hard gels.
Composition (eq. %)
hard gel
hard gel
hard gel
As a comparative example, a polyamide at the same diamine/mono-amine ratio (60/40) as used in ATPA A of Example 3 was prepared to determine if termination with a primary mono-amine would result in polyamide that gelled hydrocarbons. The composition, and certain properties of this polyamide, are set forth in Table 5. This material, "Comp. D" was not compatible with PD 23 hydrocarbon solvent.
Composition (eq. %)
two phases
All publications and patent applications mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually incorporated by reference.
It will be appreciated by those skilled in the art that changes could be made to the embodiments described above without departing from the broad inventive concept thereof. It is understood, therefore, that this invention is not limited to the particular embodiments disclosed, but is intended to cover modifications within the spirit and scope of the present invention as defined by the appended claims.
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US7253362 * | Jun 7, 2006 | Aug 7, 2007 | 3M Innovative Properties Company | Closure with wrapped cable |
US7304242 | Jun 7, 2006 | Dec 4, 2007 | 3M Innovative Properties Company | Shrinkable closure |
US7304244 | Jun 7, 2006 | Dec 4, 2007 | 3M Innovative Properties Company | Method of making closure housing for sealing |
US7307219 * | Jun 7, 2006 | Dec 11, 2007 | 3M Innovative Properties Company | Closure housing for sealing |
US7531748 | Jun 7, 2006 | May 12, 2009 | 3M Innovative Properties Company | Sealing apparatus |
US20040265497 * | Jul 21, 2004 | Dec 30, 2004 | Great Canadian Shield Corporation | Protection of electrical power systems |
US20050079143 * | Oct 10, 2003 | Apr 14, 2005 | Alison Betz | Polyamide stick dispensing product and method of use |
US20050180725 * | Feb 11, 2005 | Aug 18, 2005 | Carlson John R. | Coupled building wire having a surface with reduced coefficient of friction |
US20050180726 * | Feb 11, 2005 | Aug 18, 2005 | Carlson John R. | Coupled building wire with lubricant coating |
US20070284131 * | Jun 7, 2006 | Dec 13, 2007 | 3M Innovative Properties Company | Closure housing for sealing |
US20070284132 * | Jun 7, 2006 | Dec 13, 2007 | 3M Innovative Properties Company | Method of making closure housing for sealing |
US20070284146 * | Jun 7, 2006 | Dec 13, 2007 | 3M Innovative Properties Company | Shrinkable closure |
US20080000684 * | Jun 7, 2006 | Jan 3, 2008 | 3M Innovative Properties Company | Sealing apparatus |
US20080217044 * | Dec 31, 2007 | Sep 11, 2008 | Southwire Company | Coupled building wire assembly |
U.S. Classification | 528/310, 523/173, 528/292, 528/339.3, 174/19, 524/600, 528/322, 528/324, 528/345, 528/332, 528/397, 385/84, 174/76, 528/326, 385/66, 528/272, 528/288, 524/606, 439/275, 174/77.00R, 385/100 |
International Classification | H01B7/285, A61Q13/00, C11C5/00, A61Q17/02, A61K8/88, C08G69/34, A61Q17/04, C08G73/06, C08G73/02, C08G69/44, A61Q17/00, A61Q19/00, H01B3/30, B01J13/00 |
Cooperative Classification | C08G73/0273, C08G69/44, B01J13/0065, C08G73/0206, C08G69/34, C08G73/0633, C11C5/002, H01B7/285, H01B3/305 |
European Classification | H01B7/285, C08G69/44, C11C5/00B, B01J13/00D6, C08G73/02A, C08G69/34, C08G73/02Q, C08G73/06E2, H01B3/30C2 |
Date | Code | Event | Description |
Jan 4, 1999 | AS | Assignment | Owner name: UNION CAMP CORPORATION, NEW JERSEY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MACQUEEN, RICHARD C.;JACKSON, MARC;PAVLIN, MARK S.;REEL/FRAME:009704/0500;SIGNING DATES FROM 19981210 TO 19981220 |
Mar 19, 2001 | AS | Assignment | Owner name: ARIZONA CHEMICAL COMPANY, FLORIDA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:INTERNATIONAL PAPER COMPANYU;REEL/FRAME:011627/0543 Effective date: 20010124 Owner name: INTERNATIONAL PAPER COMPANY, NEW YORK Free format text: MERGER;ASSIGNOR:UNION CAMP CORPORATION;REEL/FRAME:011627/0547 Effective date: 19990430 |
Oct 16, 2001 | CC | Certificate of correction | |
May 15, 2002 | AS | Assignment | Owner name: ARIZONA CHEMICAL COMPANY, FLORIDA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:INTERNATIONAL PAPER COMPANY;REEL/FRAME:012852/0878 Effective date: 20020424 |
May 23, 2002 | AS | Assignment | Owner name: INTERNATIONAL PAPER CO., NEW YORK Free format text: MERGER;ASSIGNOR:UNION CAMP CORPORATION;REEL/FRAME:012884/0689 Effective date: 19990430 |
Jul 21, 2004 | REMI | Maintenance fee reminder mailed | |
Jan 3, 2005 | LAPS | Lapse for failure to pay maintenance fees | |
Mar 1, 2005 | FP | Expired due to failure to pay maintenance fee | Effective date: 20050102 |


text:
Prices, specials, features and availability subject to change.
Contact for details
Located right in the middle of it all, we are just minutes from from Route 2 and the Lake County Captains Stadium. The Great Lakes mall in Mentor and a downtown Cleveland are only a short drive away.
Manor Park Apartments also has convenient access to local shopping, dining, entertainment and public transportation in Eastlake and Willoughby. There is always something to do even if you would prefer to just stay home. We have a beautiful courtyard with grills and tables available to all of our tenants and during the summer you even get to see the fireworks from the baseball stadium.
We currently have three floor plans coming available to rent:
Our junior one bedroom is 425 sq. ft. and rents for $615.00 per month.
Next is our deluxe one bedroom suite with 480 sq. ft. and rents for $635.00 per month.
Let's not leave out our 2 bedroom suite! Measuring 680 sq. ft., this suite rents for $715.00 per month.
Each floor of our 7 buildings comes equipped with washer, dryer and a utility sink, as well as, extra storage lockers. Our office is open seven days a week and we provide after hours emergency maintenance.
We are a pet friendly property. Accepting both cats and dogs (with breed and weight restrictions), we look forwards to welcoming the furry part of your family too!
Come make Manor Park Apartments your new home today!
Lease Terms: 6 and 12 months.
Security Deposit: $299.00
*** Heat/Water/Sewer & Trash pickup included.***
Pet Policy: Cats and Small dogs under 30lbs with some breed restrictions
Pets Accepted. Cats Allowed. Dogs Allowed. Call for service animal policy.
172 units
Monday-Friday: 9:00am-6:00pm
Saturday: 10:00am-6:00pm
Sunday: 12:00pm-5:00pm
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The American Concrete Institute is offering a series of seminars this year to focus on the newly-released ACI 318-14, Building Code Requirements for Structural Concrete and Commentary. Sign up and earn CEUs. More
The Concrete Cares of Nebraska 2014 Kickoff Event is one of many similar events planned across the nation. More
Ceramic tile and stone installation systems manufacturer Laticrete International Inc. (Booth S11327) continues expanding into the restoration and decorative markets with the acquisition of L&M Construction Chemicals Inc. (Booth S10348). More
Editor Bill Palmer comments on the concrete industry and the recent ACI convention. More
The contractor has assembled a top-notch team of employees and fleet of equipment. More
This Nebraska contractor has made flat floors its specialty. More
The American Road & Transportation Builders Association Transportation Development Foundation (ARTBA-TDF) presented national awards to four individuals who have demonstrated extraordinary leadership and dedication to innovation in the transportation construction field, as well as the promotion of women leaders within the industry. More
SCC is increasing in use and this article provides some tips for achieving success. More
Attendees can earn Continuing Education Units (CEUs) by participating in any of five seminars to be offered this spring. More


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The town of Wytheville is located in Wythe County in the Blue Ridge Highlands region of Virginia. It's beautiful landscape includes lush forests, an abundance of water, fields, rolling hills and surrounding mountains.
Visitors can enjoy a leisurely walk through history and see some of the oldest and most interesting structures in Wytheville. This self-guided tour begins in downtown at the Thomas J. Boyd and Haller-Gibboney Rock House Museums and leads you to more than 50 sites.
For outdoors enthusiasts, the 5,609 acres that comprise the Beartown Wilderness are some of the most remote in the Jefferson National Forest.
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$60.00 per person


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MD Anderson Events
Advances in Oncology Institutional Grand Rounds
Quality of Supportive Cancer Care in Texas and the U.S.: Initial Results from the CERCIT Study
Session Chair: Linda Elting, DRPH, Professor and Chief
Adherence to National Guidelines for Granulocyte Growth Factor use Among Elderly Cancer Patients Receiving Chemotherapy
Linda Elting, DRPH, Professor and Chief
Cardiac Monitoring in Elderly Traztuzumab-treated Patients
Mariana Chavez-MacGregor, MD, Assistant Professor
Breast Medical Oncology
Quality of Bone Health Care in Patients with Cancer
Maria Suarez-Almazor, MD, PhD, Professor
General Internal Medicine
150 lunches provided on a first-come, first-served basis.
Separate Faculty and Clinical Fellows table.
Available as web videos via the Special Medical Education Programs Institutional Grand Rounds intranet page
The video links are available for viewing 3-5 days after recording for 60 days.Date: 10/5/12, 12pm to 1pm
Time: 10/5/12, 12pm to 1pm
Location: Hickey Auditorium, Main Building, Floor 11 (R11.1400)
Format: Grand Rounds
CME: AMA PRA Category 1, 1.0 credit
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text:
Stochastic Optimization of Reservoir Systems Operations
by Dapei Wang, Univ of Toronto, Toronto, Ont, Canada,Barry J. Adams, Univ of Toronto, Toronto, Ont, Canada,
Document Type: Proceeding Paper
Part of: Water Power '87
Abstract: This paper addresses the stochastic optimization of real-time monthly operations of multi-reservoir systems by Dynamic Programming. A two-stage optimization framework that consists of a real-time model followed by a steady-state model is proposed for describing the operations problems. Effective optimization procedures are proposed for both the steady-state model and the real-time model. A case study of the Manitoba Hydro System, Manitoba, Canada, is implemented to demonstrate the applications of the optimization approaches presented.
Subject Headings: Optimization models | Reservoirs | Stochastic processes | Mathematical models | Model analysis | Steady states | Computer models | Computer programming | North America | Canada | Manitoba
Services: Buy this book/Buy this article
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Penny's Other Life, CHAPTER 2
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Yes, I have been working in cinema since my 17. I had a long path from assistant director to independent filmmaker.
I was working as first assistant director, executive producer, script supervisor. And this year I produced my own film. So there are a lot of things I am interested in.
Good day, Last summer I made a film "The Wanderer". It was first shown on the Festival L'evenart in Paris. This year I have another project. I would like to meet different people from our industry to share experience and to make new friends.
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Planning a party in East Greenwich and need a DJ? Searching for the perfect party Disc Jockey in East Greenwich, NY?
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Rock of the Marne
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Rock of the Marne Product Description
Rock of the Marne covers both the final attack of the German army in July 1918, and the Allied counteroffensive that produced the battle known to Americans as the Second Battle of the Marne. The Germans believed they could launch an offensive on both sides of Reims, which would pinch out an Allied salient and draw in Allied reserves, and thus possibly produce a breakout across the Marne leading to the final drive to Paris. Despite gaining their bridgehead across the Marne, the Germans did not expect the fierce resistance offered by the Allies including the American 3rd infantry division-which earned its honorific name "Rock of the Marne" for its steadfast defense.
An even bigger surprise awaited the Germans, however, when the Allies attacked them with crushing power from a wholly unforeseen direction three days later. Refusing at first to relinquish the initiative, the Germans showed why they were masters of defensive warfare in World War 1 as they exacted a fearsome toll in casualties from the attackers including the American 1st and 2nd infantry divisions.
Rock of the Marne shares many of its design features with MMP's earlier game on the 1918 battles - Operation Michael. The Germans' striking power consists of the battle-depleted, but still dangerous, stosstruppen. Trained specifically in infiltration tactics, these hard-core infantry units can find a way to pick apart the toughest Allied defensive position. The Germans also have mobile, and deadly, machine-gun units that will wreak havoc on unwary attacking Allied units. The Allies used tanks in record numbers in their initial assault, and these are shown in the game, as well as the six big American divisions that participated including the famous 1st Infantry Div, The Big Red One, the 42nd Infantry Div, the Rainbow Division, as well at the 3rd.
The air game has been significantly expanded in Rock of Marne as both sides deploy their air assets to bomb bridges, and strafe infantry. Finally, both the Allied and the German player must learn to operate within their constraints and opportunities of the WWI command and control environment, which means you may not automatically get to attack with all the units you had planned!
Rock of the Marne is part of the Standard Combat Series.
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Discover and discuss the manliest content on the Web
If a wise man has an argument with a fool, the fool only rages and laughs, and there is no quiet. - Proverbs 29:9
1 comment
Robochess 4 years, 5 months ago
Of ourselves he did, because he is in over his head. Obama looked like he didn't care, because he doesn't. Obama doesn't care about people other than himself and his cronies. Biden is just an old avg joe that is trying to fit it, and now trying to get reelected while trying to carry his boss, everybody knows that that is too much pressure for joe.
Sometimes it's easier to laugh away pain and mistakes then to man up and take the blame.


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Music video by Wild Colonials performing Charm. (C) 1996 UMG Recordings, Inc.
Wild Colonials are an American alternative rock band formed in Los Angeles, California in 1992 by Angela McCluskey (vocals), Shark (guitar/vocals/percussion), Paul Cantelon (violin/piano), Scott Roewe (multi-instrumentalist) and Ian Bernard (drums/percussion). After 1993 members included Thaddeus Corea and Jason Payne on drums/percussion and Skip Ward on Bass.
This Can't Be Life is the second album for American Alternative band Wild Colonials, released in 1996
Pick and Click one of the menu tabs above for more artist info.
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What does refundable only on purchase date mean? After we purchase tickets do we email the theater to reserve a date or list several dates? Do we request the seats we want or does the theater just assign them? Thanks.
rose c. asked on Jan 21, 2013
I'm very sorry that we were unable to get to your question! Unfortunately, this deal has ended. Please keep an eye out for similar deals we may offer which could fit your needs.
If you need any further assistance, please reach out to our Customer Service department at email@example.com and we'd be happy to help you.
Christina B. from Groupon replied on Jan 25, 2013


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Cellulite formation in thighs, butts, calves and other parts of the body can bland women's beauty. To get rid of cellulite one must first understand why does it deposit under the skin and then learn about different methods to dissolve it.
What causes cellulite formation
Cellulite is connected with Collagen.When amount of collagen in the skin decreases, cellulite formation increases and vice versa. You might have read or heard about collagen from the celebrities. It is injected in the skin to reverse aging.
Collagen basically is a protein that helps in the formation of connective tissue in the skin, tendons and ligaments. If the collagen is more or less in the tissue then it can become thin and uneven. This can create a lumpy fresh like structures underneath the skin which is usually referred to as cellulite
Before it was considered that cellulite as an older woman problem but young women also have the risk of getting cellulite. The drop in estrogen can weaken the collagen and create cellulite. Eating high amount of processed foods is another cause of cellulite. Hormonal imbalance, stress, birth control pills, excessive calorie intake, fat deposits and pregnancy are other factors that trigger cellulite formation.
How To Get Rid of Cellulite
To get rid of cellulite mainly two changes should happen in the body, one strengthening of connective tissue and other decrease of fat. There are laser treatments that work on reducing cellulite underneath the skin, but following natural methods is the best way to cure or prevent any healthy problem.
Below are some tips that will help you to strengthen your connective tissue
Exercise improves the flow of blood in the connective tissue and strengthens the muscles to give it a strong back bone. By exercising on specific areas one can get rid of cellulite deposits from them.
Creams with Hyaluronic acid, Aloe vera, soy, yeast extract, Vitamin E, A and Proteins can help to increase the collagen levels in the skin. These ingredients are popularly used in the skin tightening creams.
By eating right type of foods that are rich in protein such as nuts, seeds, yogurt, fish, and diary one can increase the amount of collagen in the body. The green foods increase elasticity in the skin and keeps it smooth and connected.
Avoid wearing tight clothes
Tight clothing can restrict proper circulation of blood in the tissues and this can lead to cellulite formation. So if you are having cellulite problems, try to avoid wearing tight jeans, underwear and other tight clothes.
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April 27, 2016
The web provides limitless opportunities for learning, creating, sharing, and exploring the depths of human knowledge. But it is also an unsafe arena where one needs to be equipped with the needed tools and know-how to better stay safe and browse the net securely. As parents and teachers, we need to teach our students about the basics of staying safe online and luckily there are several resources to help you do that. Google Safety Centre is one of the best of them.
Google Safety Centre provides teachers, parents and public users with a plethora of materials, tools and tips to help you manage the security and privacy of your personal data and keep you safe while using the net. Visit this page to learn more about these resources. We have also curated for you this excellent collection of videos created by the folks in Google Safety Center to introduce you to some of the main tips to help you protect your online safety. Check them out and share with your students. Enjoy
1- Think before you share
2- Protect your stuff
3- Know and use your settings
4- Avoid scams
5- Be positive


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Relevant offers
Within a nanometre-scale device, visible light travels infinitely fast - by one measure - a team of physicists and engineers reports.
The gizmo won't lead to instantaneous communication - the famous speed limit of Albert Einstein's theory of relativity remains in force - but it could have a variety of uses, including serving as an element in a type of optical circuitry.
"The demonstration of such a thing is definitely very interesting and possibly useful," said Wenshan Cai, an electrical engineer at the Georgia Institute of Technology in Atlanta, who was not involved in the work.
In empty space, light always travels at 300,000,000 metres per second.
In a material such as glass, it travels slower.The ratio of light's speed in the vacuum to its speed in a material defines the material's "index of refraction," which is typically greater than one.
However, scientists have begun to manipulate the interactions of light and matter to tune the index of refraction in weird ways, such as making it negative, which leads to an unusual bending of light.
Now, Albert Polman, a physicist at the FOM Institute for Atomic and Molecular Physics in Amsterdam; Nader Engheta, an electrical engineer at the University of Pennsylvania; and colleagues have pulled off a particularly odd feat.
They've developed a tiny device in which the index of refraction for visible light is zero - so that light waves of a particular wavelength move infinitely fast.
The device consists of a rectangular bar of insulating silicon dioxide 85 nanometres thick and 2000 nanometres long surrounded by conducing silver, which light generally doesn't penetrate.
The result is a light-conveying chamber called a waveguide.
Researchers fashioned different devices in which the width of the silicon dioxide ranged from 120 to 400 nanometres, as they report in a paper in press at Physical Review Letters.
Light behaves differently in such a waveguide, because the electromagnetic fields must obey certain "boundary conditions" on the sides of the device.
Short-wavelength light bounces back and forth between the ends of the guide, and the peaks and troughs of the counter-propagating light waves overlap to create a pattern of bright and dark bands much like the pressure patterns with a ringing organ pipe. Above a "cutoff" wavelength, light doesn't flow at all.
Right at the cutoff wavelength, things get interesting.
Instead of producing a banded pattern, the whole waveguide lights up.
That means that instead of acting as waves with equally spaced peaks, or "phase fronts," the wave behaves as if its peaks are moving infinitely fast and are everywhere at once.
So the light oscillates in synchrony along the length of the waveguide.
Engheta and company had previously created an index of refraction of zero for longer-wavelength radiation called microwaves.
Repeating the feat for visible light was harder, as the new widget is too small to contain a light source.
Instead, the researchers shot in a beam of electrons to generate light of all wavelengths within the waveguide and measured the light leaking out of it.
The amount of light shining out at a particular wavelength depends on whether the electron beam enters at a point where there should be a dark or a bright spot for that wavelength.
So by scanning the beam along the waveguide and monitoring the output, researchers traced the light pattern at each wavelength.
"It is nanofabrication and characterisation at its best," said Che Ting Chan, a physicist at the Hong Kong University of Science and Technology.
So how does an everywhere-at-once light wave not violate relativity?
Light has two speeds, Engheta explains.
The "phase velocity" describes how fast waves of a given wavelength move, and the "group velocity" describes how fast the light conveys energy or information.
Only the group velocity must stay below the speed of light in a vacuum, Engheta said, and inside the waveguide, it does.
The device could have various uses, Engheta said. Because the light leaking out of the waveguide is all in synch, the waveguide might be bent to form an antenna that emits light wave with sculpted phase fronts, he said.
It might also make a conduit for a hoped-for type of nanoscale optical circuitry, he said.
An array of such waveguides might even make a bulk material with zero index of refraction.
But fabricating that array would be very challenging, Cai said: "In theory it's easy; experimentally it's very hard."
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text:
Number of staff
Key areas of work
Housing and tenancy management; supported housing; estate management; community engagement; housing development; landscaping
Inspection results
Two stars with excellent prospects for improvement
Chief executive
Caroline Titley
Caroline is the former corporate services director at Hyde Housing Association, one of the largest housing groups in the country. She has more than 25 years housing experience, initially in housing management, then in consultancy as a partner and director for DOME. Her consultancy work included research in Liverpool, Hackney and south Humberside. Caroline holds a masters degree from the University of Cambridge and is a gellow of the Chartered Institute of Housing.
Resources director
George McMorran
George is resources director for Bracknell Forest Homes and leads on financing the organisation. He was previously finance director for Metropolitan and Southern Housing Group before becming a consultant and advisor to large housing providers. He is a chartered accountant and holds an MBA from Imperial College London.