The present invention relates to novel aluminosiloxane compounds which have the characteristics to be prepared from waste silicone compounds and to be advantageously used as siloxylating agent for various organic and inorganic materials, processes for preparation thereof, and uses thereof.

The present invention relates to novel aluminosiloxane compounds represented by the following formulae (1) and (2), processes for preparing same and use thereof. Particularly, the compounds of formulae (1) and (2) according to the present invention have the characteristics to be prepared from waste silicone compounds and to be advantageously used as siloxylating agent for various organic and inorganic materials, specifically for materials containing hydroxy group.
in which
R is identical with or different from each other, and represents C1-C6-alkyl or phenyl,
n denotes a number of 6 to 90, and
M represents alkali metal.
Currently used siloxylating agents include silane or siloxane compounds containing reactive hydroxy group(xe2x80x94OH), alkoxy group(xe2x80x94OR), carboxyl group (xe2x80x94OCOR), amine group(xe2x80x94NHR, xe2x80x94NR2), epoxy group
hydrogen(xe2x80x94H), etc at terminal sites of the molecules, and modified silyl compounds wherein silyl groups are bound to the intramolecular side chains.
The novel aluminosiloxane compounds provided by the present invention belong to hetero metallic siloxane series(xe2x89xa1Sixe2x80x94Oxe2x80x94Mxe2x80x94Oxe2x80x94Sixe2x89xa1) wherein a metal atom is placed between two siloxane groups. The aluminosiloxane compounds according to the present invention not only can replace the existing siloxylating, agent, but also exhibit more strong siliconic characteristics through the formation of a long chain wherein at least six(6) dialkyl(or phenyl)siloxyl units
are linked with each other. Particularly, the present compounds are expected to have a highly improved properties in reactivity for siloxylation, etc.
Many researches have been made on aluminosiloxanes. For example, aluminosilsesquioxane prepared from isopropoxyaluminum[(i-PrO)2Al] and trialkoxysilane is disclosed in J. Am. Chem. Soc. 1989, 111, 7288-7289 and Inorg Chem. 1999, 38, 210-211. This aluminosilsesquioxane compound is identical with the compounds of the present invention in that Al atom has a AlO4 configuration, but different therefrom in that Si atom has a RSiO3 configuration. Further, a method for endowing aluminum metal surface with anti-corrosion property and gloss by treating the metal surface with ethoxysilane vapour to form xe2x95x90Alxe2x80x94Oxe2x80x94Sixe2x89xa1 bond on the metal surface(see: Journal of the Electrochemical Society V.143, N.1, 1996); a method for forming xe2x95x90Alxe2x80x94Oxe2x80x94Sixe2x89xa1 structure on aluminum metal surface by treating the metal surface with alkoxysilane through a sol-gel method(see: Colloids and Surfaces A: Physicochem. Eng. Aspects 139, 299-310, 1998); a method for synthesizing phosphine ruthernium(Rh) complex by reacting isopropoxyaluminum with alkoxysilane through a sol-gel method(see: Inorg. Chem. 1997, 36, 862-866 and Chem. Mater. 1998, 10, 217-225); and a method for preparing mullite from aluminum and silicone oxide via aluminosiloxane(see: Chem. Mater, 1996, 8, 2056-2060) are disclosed. However, any of the intermediates or final products disclosed in these prior arts does not have a similar structure or property to the novel aluminosiloxane compound provided by the present invention.
Under the technical background as explained above, the present inventors have studied to develop an effective method for decomposition and recovery of siloxane bond-containing compound such as silicone rubber, silicone oil, etc., which ultimately results in decrease of pollution caused by waste silicone compounds and promotion of silicone chemical industry without any concern about waste. As a result, we filed an application for a novel process for decomposing siloxane bond-containing compound characterized in that secondary and/or tertiary aliphatic alcohols are used as a decomposition facilitator, and if desired, the decomposition product is further sonicated and treated with a terminator. The application has now been granted a patent(see, Korean Patent No 190,752, and U.S. Pat. No. 5,892,087). Specifically, the siloxane bond has the advantage of excellent weatherability whereby it is not aged nor decomposed But, such an advantage rather causes the impossibility of natural decomposition after waste of the siloxane bond-containing compounds, which makes them serious pollutional materials. Therefore, the development of said decomposition or recovery process is considered to have a great importance in the aspect of environmental protection.
The present inventors proceeded with our studies to develop a compound which can be effectively utilized as a siloxylating agent by using a siloxane alkali metal salt represented by the following formula (3), which is obtained through the aforementioned decomposition process, as the starting material. Accordingly, the present inventors have synthesized the compounds of formulae (1) and (2) as above and identified structures and uses thereof, and then completed the present invention:
in which
R is identical with or different from each other, and represents C1-C6-alkyl or phenyl,
Rxe2x80x2 represents hydrogen or C1-C6-alkyl,
M represents alkali metal, and
m denotes a number of 3 to 6.
The present invention will be more specifically explained hereinafter.
One object of the present invention is to provide aluminosiloxane compounds of the following formula (1) or (2):
in which
R is identical with or different from each other, and represents C1-C6-alkyl or phenyl,
n denotes a number of 6 to 90, and
M represents alkali metal.
As can be seen from the above formulae (1) and (2), silicon atoms in the aluminosiloxane compound of the present invention are identified through 29Si-NMR to have the configuration of dialkyl(or phenyl)siloxyl unit
wherein two(2) oxygen atoms and two(2) alkyl(or phenyl) groups are attached to the silicon atom, and aluminum atoms are identified through 27Al-NMR to have the configuration coordinated with four(4) oxygen atoms.
The present compounds characterized by such an unique structure have different molecular weights depending on R, M and n. Further, with the content of M, the compound of formula (1) seems to be associated to form the compound of formula (2). That is, according to G.P.C. molecular weight measurement, the compound of formula (2) having an average molecular weight of 2000 wherein R is methyl, n is 6, and M is natrium(Sample 1 of the following Table 1) may be converted to the compound of formula (1) having an average molecular weight of 1000(Sample 2 of the following Table 1) by the treatment with ammonium chloride(purification=removal of natrium) during which the content of natrium is significantly decreased(1.51%xe2x86x920.55%). Elementary analysis results and n values calculated therefrom for some typical compounds according to the present invention are represented in the following Table 1.
As can be seen from the elementary analysis results of the above Table 1, it has been found that aluminum content is 0.52% and average molecular weight is 5,462(see FIG. 3) in the case of Sample 3(object compound of Example 5) and aluminum content is 0.3% and average molecular weight is 10,948 in the case of Sample 4(object compound of Example 6). If calculated from the elementary analysis results, the n value of Sample 3 is 35 and that of Sample 4 is 65, respectively. Samples 3 and 4 are prepared using different amount of powdered aluminum metal from each other(see Examples 5 and 6). Therefore, it is realized that if the amount of aluminum(starting material) is controlled in the process for preparing the aluminosiloxane compound of the present invention, the n value may be optionally controlled. Upon conducting elementary analyses on the compounds having various molecular weights including the analyses of Table 1, it is identified that 12 to 180 silicon atoms are present for each aluminum atom in the aluminosiloxane compounds of formulae (1) and (2) according to the present invention.
Generally, physico-chemical properties of the aluminosiloxane compound vary depending on the n value. For example, flexibility increases as the n value increases, but if the n value comes close to 90, the compound having such a high n value almost has the state of liquid, which makes the handling thereof difficult(for that reason, the n value is restricted to 90 or less in the present invention). Further, since there is a case requiring high silicone-based properties or a case requiring low silicone-based properties depending on the purpose, it is desirable to prepare an aluminosiloxane compound having a specific n value appropriate for the purpose thereof by considering the correlation between the n value and physico-chemical property.
The aluminosiloxane compounds according to the present invention are soluble in nonpolar organic solvents such as n-hexane, benzene, toluene, tetrahydrofuran, etc. They are stable compounds having, a specific density varying from 0.94 to 0.98, and also stable under atmosphere in the form of gel solid. But, they are not stable in the presence of electron acceptor(H=proton) to be easily dissociated as depicted in the following Reaction Scheme 1.
Therefore, according to the characteristics as described above, it is considered that condensation reaction may be actively carried out between organic or inorganic substance having hydroxy group or epoxy group at terminals, such as for example, thermosetting resin, cellulose, sucrose, epoxy, and the like and the product obtained from Reaction Scheme 1 optionally in the presence of an acid catalyst The condensation reaction is described in Reaction Scheme 2 below.
In the above Reaction Scheme 2, if the compound containing hydroxy group is a hydrocarbon compound and the resulting product has a structure of xe2x89xa1Sixe2x80x94Oxe2x80x94Cxe2x89xa1, this linkage is unstable under atmosphere and thus, may have the problem to be readily dissociated again. However, inside the network structure of thermosetting resins such as phenol, melamine, urea, epoxy resins, or inside the macromolecules such as cellulose, the siloxane group may form a hybrid structure or stable interpenetrating polymer networks(IPN) which is caused by rearrangement from xe2x89xa1Sixe2x80x94Oxe2x80x94Cxe2x89xa1 to siloxane(xe2x89xa1Sixe2x80x94Oxe2x80x94Sixe2x89xa1) bond. Therefore, it is anticipated that compounds of the present invention may be used as a useful siloxylating agent for those thermosetting resins or macromolecules having a network structure. That is, if the aluminosiloxane compound according to the present invention is applied in the final step of preparing those thermosetting resins or macromolecules such as cellulose, the final product may be improved in its physico-chemical properties such as gloss, flexibility, water repellence, heat stability, weatherability, etc.
Further, the aluminosiloxane compound of the present invention may be effectively used as a siloxylating agent for the surface of glass products made from metallic silicate. This is because the aluminosiloxane compound is decomposed in the presence of an acid to have reactive functional groups such as
or
(wherein R is hydrogen or alkyl) at terminals, and the functional groups are readily reacted with HOxe2x80x94Sixe2x89xa1 group on the surface of glass products to form a strong bond.
Therefore, compound of formula (1) or (2) according to the present invention can be used as a superior siloxylating agent for the surface of thermosetting resins, cellulose, epoxy, metallic silicates, pigments made from various metallic oxides and other microorganisms to silanes having the existing functional groups. Therefore, another object of the present invention is to provide such a use. Particularly, when the compound of the present invention is used as a siloxylating agent, each siloxylation is carried out with minimum 6 to maximum 90 dialkyl(or phenyl)siloxyl units
Therefore, materials siloxyated therewith show well established siloxane-based characteristics.
Siloxylation with the aluminosiloxane compounds of the present invention can be carried out in a conventional manner. However, in case of the materials which form a IPN structure during the siloxylation procedure, such as for example epoxy resins, the aluminosiloxane compound according to the present invention is mixed with the epoxy resin in the ratio of 9:1 to 5:5, preferably 8:2 to 7:3 by weight to form a copolymer first and then this copolymer is properly mixed with the epoxy resin to carry out siloxylation procedure.
The desirable amount when used as a siloxylating agent may be easily determined by the person skilled in the art considering the material to be siloxylated, specific structure of the siloxylating agent and the purpose of siloxylation. Generally, the siloxylating agent is used in an amount of 2 to 10% by weight, preferably 2 to 6% by weight with respect to the material to be siloxylated. When the siloxylating agent is not used in the amount as defined above, it may cause some deterioration of physico-chemical properties of the target material or insufficient siloxylation which does not come up to the expectation.
The aluminosiloxane compound of formula (2) according to the present invention can be prepared by a process characterized in that
(i) the siloxane alkali metal salt of formula (3) is reacted with aluminum compound and secondary or tertiary alcohol to produce a hydrophilic compound represented by the following formula (4):
in which
R and Rxe2x80x2 are defined as previously described,
Rxe2x80x3 is identical with or different from each other, and represents Rxe2x80x2 or M, but with at least one of Rxe2x80x3 being different from Rxe2x80x2, and
mxe2x80x2 is identical with or different from each other, and denotes numbers which make the n value in the resulting compound of formula (2) 6 to 90,
(ii) the compound of formula (4) is reacted with hydrohalic acid under a condition of pH 7 to 8 to produce an oil-miscible compound represented by the following formula (5):
in which
R and Rxe2x80x2 are defined as previously described, and
mxe2x80x3 is identical with or different from each other, and denotes numbers which make the n value in the resulting compound of formula (2) 6 to 90, and
(iii) the compound of formula (5) is heated at temperatures ranging from 80 to 220xc2x0 C.
During the procedure of preparing the compound of formula (2) via compounds 4 and 5, the number of siloxyl units(i.e., mxe2x80x2 or mxe2x80x3) is increased due to the successive condensation reactions and the degree of increase may be determined by the amount of aluminum compound introduced. That is, the small amount of aluminum compound leads to a lot of condensation reactions which make the number of siloxyl units and ultimately the n value increase and vice versa. Therefore, it is another object of the present invention to provide such a preparation process.
The above process for preparing the compound of formula (2) may be summarized as the following Reaction Scheme 3.
In Step (i) of the above process for preparing compound(2), the siloxane alkali metal salt of formula (3) includes any alkali metal salts, for example salts with lithium, sodium, potassium, etc., however sodium salt is preferable in view of the easiness of reaction and economy. As the reactant aluminum compound, aluminum metal, or hydroxide, oxide, alkali metal salt, halide, inorganic acid(sulfate, nitrate, etc.) salt of aluminum, such as for example, Al, Al(OH)3, Al2O3, AlCl3, AlO2Na may be used. Among them, aluminum metal is most preferable in view of the easiness of reaction and economy. Aluminum compound is used in an amount to make the Si/Al mole ratio in the resulting compound of formula (2) or (1) 12 to 180. As stated above, the n value of the final compound of formula (2) or (1) varies according to the amount of aluminum compound used. Reaction is carried out under room temperature or warming. Reaction temperature may be different according to the kind of aluminum compound used. For example, room temperature is preferred when aluminum metal is used, and some warming is required when aluminum chloride is used. Alcohol compound participated in the reaction should be secondary or tertiary alcohols, and isopropyl alcohol or t-butyl alcohol is particularly preferable. The resulting compound of formula (4) thus obtained by the reaction as explained above is hydrophilic.
In Step (ii), the compound of formula (4) is reacted with hydrohalic acid under a condition of pH 7 to 8 to produce the compound of formula (5). As the hydrohalic acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, preferably hydrochloric acid can be used. The reaction is carried out by adding a basic compound to the reaction solution containing the compound of formula (4) first to make the solution alkaline (pH range of about 8 to about 10) and then by adding the reactant hydrohalic acid thereto in an amount required to control the pH value of the reaction solution to 7 to 8. As the basic compound, ammonia compound, particularly ammonia gas or ammonia water is used in an amount to make the reaction solution alkaline. When an alkali metal-containing compound is used as the basic compound instead of the ammonia compound, additional purification steps may be required depending on the purpose of the resulting aluminosiloxane compound and thus, not desirable. Through such a neutralization procedure, the oil-miscible and multi-functional compound of formula (5) is obtained.
Finally in Step (iii), the compound of formula (5) is heated under normal pressure and temperatures of 80 to 220xc2x0 C., preferably 100 to 160xc2x0 C. to produce the desired compound of formula (2) which does not have any terminal functional groups.
On the other hand, the aluminosiloxane compound of formula (1) according to the present invention, which is deficient in M, can be prepared by a process characterized in that
(a) the compound of formula (2) is reacted with a compound represented by the followings formula (6)
NRxe2x80x23HXxe2x80x83xe2x80x83(6)
xe2x80x83in which
Rxe2x80x2 is defined as previously described, and
X represents halogen, in a non-polar solvent, or
(b) a compound represented by the following formula (7):
in which
R, Rxe2x80x2 and m are defined as previously described, and
Rxe2x80x3xe2x80x2 represents C1-C6-alkyl, is reacted with aluminum compound and secondary or tertiary alcohol, and then alcohol is removed therefrom.
In process variant (a) above, it is most preferable to use ammonium chloride(i.e., Rxe2x80x2 is hydrogen and X is chlorine) among the compound of formula (6) which is used as a reactant. Reaction is carried out for 3 to 5 hours under normal temperature and pressure because silicone oil may be separated from the resulting aluminosiloxane compound when the reaction mixture is heated. Since the compound of formula (6) is used for the purpose of removing M which is present in the compound of formula (2), it is preferable to use the compound of formula (6) in an equimolar amount to the compound of formula (2). As the non-polar solvent, one or more selected from n-hexane, toluene, tetrahydrofuran, bezene and xylene can be mentioned.
In process variant (b) above, if the compound of formula (7) is used as the starting material, the desired compound of formula (1) is directly produced without any need to use the hydrohalic acid. Here, the same aluminum compound and secondary or tertiary alcohol compound as explained in the process for preparing the compound of formula (2) may be used. When the compound of formula (7) is reacted with aluminum compound and alcohol, the reaction is preferably carried out at temperatures ranging from 60 to 80xc2x0 C.
Although only aluminum compound is exemplified in the above processes according to the present invention, various forms of zinc(Zn) or tin(Sn) compound, such as for example, hydroxides, oxides, alkali metal salts, halides, acid addition salts(sulfate, nitrate, etc.) thereof besides the aluminum compound may be also reacted with siloxane alkali metal salt of formula (3) in the same manner as the aluminum compound to produce siloxane compounds containing various metals.
The present invention will be more specifically explained in the following examples. However, it should be understood that the following examples are intended to illustrate the present invention but not in any manner to limit the scope of the present invention.

Aluminosiloxane compound and process for preparing the same

Samwoo Villa #501, 48-30, Jangchoong-dong 1-ga


Portable electronic devices such as portable telephones, portable computers and the like may obtain power from fuel cells that consume fuel from fuel reservoirs of the portable devices. A network of fueling stations permits users of portable devices to main the devices operational by frequently topping up the fuel reservoirs. Payment systems combine payments for fuel with larger payments for other transactions to avoid the overhead of processing individual payments for very small amounts.

Portable electronic devices such as portable telephones (which include cellular telephones, mobile telephones and other portable telephones), music players, portable computers, personal digital assistants, digital cameras, video camcorders, radio receivers, radio transceivers, navigation devices, combinations of these, and the like are becoming indispensable tools for business and personal affairs. Such devices are referred to herein as "portable devices" or "portable electronic devices". Portable devices are small and lightweight enough to be carried conveniently by a person. There is increasing demand for portable devices that are very compact, light in weight and yet full-featured.
Most portable electronic devices are powered with electricity from batteries. Primary batteries must be replaced once their energy has been consumed. Although they are convenient, primary batteries can be unacceptably expensive for devices that have high energy requirements. Making and disposing of primary batteries both create waste that could harm the environment.
Secondary batteries can be used multiple times and recharged after each use. However, recharging can be inconvenient. The rate at which batteries can be charged safely is limited. Most recharging technologies require from minutes to hours to recharge a secondary battery. Although better secondary battery technologies are being developed, secondary batteries tend to be heavy and can degrade over time. Frequent fast or partial charging can cause the performance of rechargeable batteries to degrade at an accelerated rate.
Fuel cells convert energy from a fuel, such as hydrogen or methanol, into electricity. Fuel cells are an attractive power source for portable electronic devices, in part because they have the potential to provide higher energy densities than most battery technologies. Thus, a fuel-cell-powered device can potentially offer extended runtime and/or higher power output than a comparable battery-powered device. Another advantage of fuel-cells for powering portable devices is that refueling can be accomplished much more quickly than recharging a storage battery. Fuel cell performance remains relatively constant under a wide range of working conditions.
Several fuel cell technologies being developed for portable applications supply fuel in replaceable fuel cartridges. The fuel cartridges are not refillable by a user. Examples of such cartridge-based technologies include:                Mobion™ from MTI MicroFuel Cells Inc. of Albany N.Y.        The power supplies being developed by Medis Technologies Ltd. of New York, N.Y.        U.S. Pat. No. 6,665,549 discloses a system for replenishing power sources for mobile devices that may include a fuel cartridge dispenser.        U.S. Pat. No. 6,326,097 discloses micro fuel cell power chargers that include disposable fuel ampoules or refillable fuel tanks.        US 2004/0146769 discloses a fuel cell cartridge for portable electronic devices.        US2004/0151962 discloses a fuel cartridge for direct methanol fuel cells.        US2005/0023236 discloses a fuel cartridge with a flexible liner that is connectable to a fuel cell.        US2005/0074643 discloses fuel cartridges for fuel cells.        US2005/0022883 discloses a fuel cartridge with a connecting valve for connecting the fuel cartridge to a fuel cell or to a refilling device.
A device that requires pre-filled fuel cartridges for operation has many of the same disadvantages as a device that uses primary batteries for power. Multiple cartridges must be purchased and kept on-hand to maintain the operation of the device. The cost of cartridges becomes a major consideration, especially when used in devices that have high power requirements. The cost of a cartridge can be significantly more than the cost of the fuel contained within the cartridge because cartridges must contain the fuel safely and, provide reliable mechanisms to keep the fuel inside the cartridge until it is desired to supply the fuel to a device and connect to supply fuel to the device without leaking fuel. Further, cartridges should be replaced only when the current cartridge is fully spent. A cartridge that is not completely spent will contain waste fuel with economic, environmental and/or safety implications for disposal
Experience with primary batteries suggests that users will find pre-filled cartridges satisfactory only if the time between cartridge replacements is long or the cost of cartridges is extremely low. Achieving either of these objectives is difficult. Designing inexpensive cartridges is difficult because such cartridges must safely contain flammable fuels. Designing cartridges that are long-lasting requires either large volumes or more-expensive fuel storage technologies.
Some fuel-cell-powered devices have on-board fuel reservoirs. The on-board fuel reservoirs can be refilled with fuel. Non-limiting examples of fuels that could be used to power a fuel-cell-powered device are hydrogen; methanol; formic acid; butane; and borohydride compounds. Fuel can be added to an on-board fuel reservoir either through application of a field refueling cartridge or through the use of a fixed fueling station. For example:                US 2005/008908 describes a portable hydrogen storage device that can be used to transfer hydrogen fuel to a portable electronic device such as a laptop computer.        US2005/0155668 describes a refilling system for fuel cells.        US2004/0175599 discloses fuel cell replenishment using a cartridge.        US2004/0072049 discloses a fuel container and delivery apparatus for a liquid-fuel cell system.        US2004/0205032 describes a network of refilling stations for hydrogen-powered vehicles.        U.S. Pat. No. 6,755,225 discloses a transportable hydrogen refilling station for dispensing gaseous hydrogen from high pressure tanks.        US2003/0021743 discloses a fuel cell refueling station and system.
Providing a portable device having a refillable fuel reservoir does not provide a complete solution to the above problems because of the high cost of fueling stations relative to the portable devices that they service. Even having a home fueling station is not ideal since a portable device may run low on fuel while its user is not at home.
While portable devices powered by fuel have a number of advantages over battery-powered devices, some of which are outlined above, there is a need for cost-effective and convenient ways to replenish the fuel supplies in such devices.

Replenishing fuel cell powered portable devices


A pharmaceutical long acting depot composition is provided as an aid to smoking cessation treatment. The formulation comprises a therapeutically effective amount of varenicline or its pharmaceutically acceptable derivative and pharmaceutically acceptable excipients. The process of preparation of the formulation is also provided.

Smoking is the leading preventable cause of death worldwide. Smoking-related diseases kill an estimated 438,000 Americans each year, including those affected indirectly, such as premature babies of smoking mothers and victims of 'secondhand' smoke. Millions of people in the world have at least one serious illness caused by smoking. Smoking causes chronic lung disease, cardiovascular disease and stroke. Smoking may be a cause of several cancers (in addition to lung cancer) and has been linked to slowed healing of wounds, infertility and stomach ulcers.
Many factors make quitting smoking difficult. Most smokers trying to quit fail several times before they are able to break the habit. Smokers who are trying to quit are faced with social influences that may persuade them to conform and continue smoking. Cravings are easier to detain when one's environment does not provoke the habit. If a person who stopped smoking has close relationships with active smokers, he or she is often put into situations that make the urge to conform more tempting. For example, if an acquaintance offers a cigarette as a polite gesture, the person who has stopped smoking will be more likely to break his commitment of quitting smoking. Smokers with major depressive disorder may be less successful at quitting smoking than non-depressed smokers. Thus, smoking is a notoriously difficult habit to break. Relapse (resuming smoking after quitting) can also happen which has been related to psychological issues such as low self-efficacy, or non-optimal coping responses however, psychological approaches to prevent relapse have not been proven to be successful.
There are various methods of breaking the smoking habit. Smoking cessation therapies are more likely to succeed for patients who are motivated to stop smoking and who are provided additional advice and support. The patients are also provided with appropriate educational materials and counseling to support the quit attempt. Some methods involve medication alone. Most smokers who try to quit, do so without any assistance, however, only 3% to 6% of such attempts are successful. The simplest medication regimen involves administering nicotine in gradually diminishing doses. Nicotine patches or lozenges are used to quit smoking habit. The goal of these slow-release preparations is to maintain the subject in the comfort zone by keeping the blood nicotine concentration constant throughout the day. Over several weeks of treatment, the blood concentration of nicotine is gradually lowered. However, the person trying to quit smoking can easily remove the patches or stop taking lozenges if he or she gets demotivated to quit smoking leading to failure of the treatment.
Varenicline is the first line treatment approved by FDA for use as an aid to smoking cessation. It remarkably binds with high affinity and selectivity at α4β2 neuronal nicotinic acetylcholine receptors which produces agonist activity, while simultaneously preventing nicotine binding to these receptors and this leads to efficacy of varenicline in smoking cessation. Varenicline decreases the urge to smoke and reduces withdrawal symptoms and may help in some relapsed smokers.
Varenicline is available commercially as CHANTIX, an oral immediate release tablet containing varenicline tartrate in the strength equivalent to 0.5 mg and 1 mg free base. The dosage regimen includes administering 0.5 mg once daily on days 1-3 and 0.5 mg twice daily on days 4-7. Once the dosing titration has been successfully completed, patients are advised to take 1 mg twice daily for an additional eleven weeks. Patients that successfully stop smoking under the regimen are advised to take an additional 12 week course of treatment to increase likelihood of long-term abstinence.
US 2006/0084656 provides an intranasal, buccal, sublingual or pulmonary dosage forms of varenicline.
US 2004/0235850 provides storage stable pharmaceutical dosage form of varenicline adducts with certain excipients.
US 2008/0181933 provides a chewing gum composition of varenicline comprising a water insoluble base portion and a water-soluble portion.
However, relative to an oral dosage form, delivery of varenicline via a transdermal composition would be a preferred choice by patients who have difficulty in swallowing tablets, capsules or other solids. Also, the tablet dosage form of varenicline can produce a certain level of nausea in patients. Thus, to reduce these side effects, transdermal composition of varenicline are also provided wherein a gradual release of the varenicline via skin layers might reduce the incidence of nausea and enhance the patient compliance and desirability of the drug to a larger patient population requiring its use.
WO 2007/01296 provides transdermal composition comprising varenicline or its pharmaceutically acceptable salt or prodrug form.
However, it is likely that if the person gets demotivated to quit smoking during the treatment and experience a strong urge to smoke, he or she will stop applying varenicline transdermal patch by removing it from the application site thereby discontinuing the treatment. Hence, adherence to varenicline transdermal patch treatment is often sub-optimal.
Thus, there is an unmet need to provide an alternate dosage form such as a depot formulation, which would provide higher compliance rate along with maintaining therapeutic levels of the drug in the patient's system for days or weeks at a time. A depot formulation may provide convenience for a patient in need of chronic medication. By delivering drug without exposure to the GI tract, the potential issue of drug degradation is also avoided. Moreover, a depot formulation may provide better compliance due to the infrequent dosing regimen and convenience.
Varenicline is therefore a good drug candidate for incorporation into sustained delivery devices, where the patients would be treated for long time periods with just one application. Hence, a drug delivery technology, especially depot preparations which can reduce the total number of such administration and maintain the plasma drug levels for longer time would be preferred. Such reduction in frequency of drug dosing in practice may be achieved by formulating injectable depot system that are capable of releasing drug in a slow but predictable manner and consequently improve patient compliance. Depot injections allow careful control of drug usage (as opposed to orally administered drugs), where overall treatment efficacy and/or side effects may be identified. Furthermore, it is easy to identify defaulters and prepare interventions. These long acting depot formulations of varenicline can have the potential to not only boost the therapeutic benefit in most cases, also reduce any unwanted events, such as reduce the risk of accidental or deliberated overdose and maintain a stable release rate for several weeks, several months or longer to avoid the drawbacks of oral administration such as nausea, poor bioavailability, high frequency of administration, possible toxicity and inadequate individualizable dosing. The long acting depot formulation of varenicline of the present invention can address the problems of fluctuating drug concentration and will provide continuous stimulation of receptors prolonging the duration of action and thus improving patient compliance.

This patent is subject to a terminal disclaimer.


A cleaning composition for cleaning the surfaces of edible fresh fruits and vegetables. The composition comprises water and a preservative, and preferably also a co-solvent with a dielectric constant less than that of water, a surfactant, a flavorant, and a buffering agent to maintain the composition's pH within the range of 2 to 9. The invention further comprises a fibrous wiper impregnated with the cleaning composition for wiping the fresh produce, and a dispenser for storing the impregnated fibrous wiper.

1. Field of the Invention
This invention is directed to a composition for removing residue from the surfaces of edible fresh fruits and vegetables prior to their consumption. The invention also includes a fibrous wiper impregnated with the cleaning composition, and to a dispenser for consumer use for storing the impregnated fibrous wiper.
2. Description of the Prior Art
Compositions for cleaning the edible skins of fresh fruits and vegetables must satisfy two often inconsistent criteria. The compositions must clean the fresh fruits and vegetables and not detrimentally affect the edibility or palatability of the produce.
Several wet wiper products are known which are directed to cleaning human skin. In U.S. Pat. No. 4,772,501 Johnson et al. disclose such a wet wiper product comprising a fibrous wipe saturated with a liquid preservative composition composed of citric acid, sorbic acid and water. A sealed envelope is disclosed for storing the wet wiper product as well as an optional ingredient to moisturize the skin of the user. In U.S. Pat. No. 5,049,440 Bornhoeft et al. disclose an antimicrobially active wet wiper product comprising a fibrous wipe impregnated with a hypotonic liquid preservative composition composed of water, a "naturally occurring organic acid" (citric acid, sorbic acid, etc.), and a "naturally occurring" salt (sodium chloride, etc.), and a sealed envelope to enclose the wiper. A skin moisturizer is disclosed as an optional ingredient. Compositions for cleaning fresh fruits and vegetables, however, are not disclosed.

Composition for cleaning fruits and vegetables

Empire Products Packaging Development, Inc.


Methods for etching a metal layer and a metallization method of a semiconductor device using an etching gas that includes Cl2 and N2 are provided. A mask layer is formed on the metal layer, the etching gas is supplied to the metal layer, and the metal layer is etched by the etching gas using the mask layer as an etch mask. The metal layer may be formed of aluminum or an aluminum alloy. Cl2 and N2 may be mixed at a ratio of 1:1 to 1:10. The etching gas may also include additional gases such as inactive gases or gases that include the elements H, O, F, He, or C. In addition, N2 may be supplied at a flow rate of from 45–65% of the total flow rate of the etching gas, which results in a reduction in the occurrence of micro-loading and cone-shaped defects in semiconductor devices.

1. Field of the Invention
The present invention relates generally to a method of manufacturing a semiconductor device, and more particularly, to a metallization method and a method of etching a metal layer using an etching gas that includes Cl2 and N2, and an etching gas formed of Cl2 and N2.
2. Description of the Related Art
As semiconductor devices become highly integrated, the line width of metal interconnection layers of multilevel metal interconnection structures and the distance between adjacent metal interconnection layers have been reduced while the height of the metal interconnection layers has been increased to increase the aspect ratio. In these semiconductor devices, the metal interconnection layers electrically connect unit devices. The metal interconnection layer may be formed of a material that has a low resistance in order to obtain devices that can operate at a high speed. Aluminum or an aluminum alloy may be used to form the metal interconnection layers.
Although aluminum has excellent electric conductivity, the difference between the etching selectivity of aluminum and the etching selectivity of a photoresist material is small. As a result, the thickness of the photoresist layer is increased. However, when the thickness of the photoresist layer is increased, the throughput of the semiconductor device decreases, and it can become difficult to pattern the photoresist layer. When the thickness of the photoresist layer pattern is reduced to avoid these problems, the regions that are to be protected when patterning the metal interconnection layers cannot be protected. Technology has been developed that uses a hard mask when forming aluminum interconnection layers so that micro-sized metal interconnection patterns for the highly-integrated semiconductor device may be formed.
In an etching process for forming metal interconnection layers that uses a hard mask, a reaction by-product may be formed which may be removed during the etching process or may be deposited on the inner walls of the etching chamber. However, if the reaction by-product is not firmly attached to the inner walls of the etching chamber, the reaction by-product may fall to the surface of a wafer during the etching process, which may cause short circuits between the metal interconnection patterns.
In one conventional method that uses a hard mask to form the metal interconnection layers, the etching gas includes at least one fluorocarbon-based gas such as CF4 or CHF3, as well as Cl2 and BCl3, which have been used in conventional processes where a photoresist layer is used as the etch mask. The fluorocarbon-based gases are used for the passivation of the sidewalls of the metal interconnection patterns. When a fluorocarbon-based gas is used in the etching gas, a by-product deposition layer having low adhesive characteristics may be created in the form of flakes located on the inner walls of the etching chamber. Because the by-product has low adhesive characteristics, the by-product may fall onto the wafer's surface during the etching process. Thus, the number of particles (e.g., contaminants) present on the wafer surface may increase, which reduces yield.
In another conventional method, an etching gas of Cl2/BCl3/N2 is formed by using N2 as a passivation gas instead of a fluorocarbon-based gas, which, as described above, may cause the generation of particles in the etching chamber. However, when this etching gas is used, cone-shaped defects occur on the semiconductor wafer due to the presence of BCl3.
In addition, as the aspect ratio of the metal interconnection patterns increases in a highly-integrated semiconductor device, micro-loading may occur. In particular, micro-loading may vary the etching rate according to the pattern density of regions of a chip on the wafer or may vary the profile shape of the patterns due to a difference in the critical dimension (CD) between a top sectional profile and a bottom sectional profile of the patterns. As the line width of the metal interconnection patterns is reduced, defects may occur due to the micro-loading, which may cause failures in the semiconductor device.

Method of etching a metal layer using a mask, a metallization method for a semiconductor device, a method of etching a metal layer, and an etching gas


The present invention relates to methods and apparatuses for the detection of neural or muscular activity, analysis of the signals and the subsequent stimulating of neural or muscular tissue based thereon. According to a first aspect of the invention an apparatus for producing a muscular action is provided, comprising a combined sensing and stimulation electrode device comprising at least one neurosense electrode means capable of sensing a nerve signal from a peripheral nerve and at least one stimulation electrode means capable of stimulating a peripheral motor nerve fiber, means for receiving and processing the sensed neurosignals to identify a signal indicative of a specific action, especially a component of the gait performed by the patient and for producing a control signal in response thereto, and means for operating the at least one stimulation electrode means in response to the control signal to produce a stimulation of a peripheral motor nerve fiber.

Numerous conditions exist for the human body in which a disease or bodily malfunction have its origin in impaired function of the neuromuscular system, including deficiencies based upon impaired sensory as well as motor activity. In the following the problems addressed by the present invention will be discussed on the basis of the condition known as hemiplegic drop foot, a condition in which a patient is not able to lift, i.e. dorsiflex, the foot during gait, normally based on an Upper Motor Neurone Lesion (UMNL), for which stroke and head-injuries are by far the more prevalent problems with reported prevelances of 12,000/million for stroke and 20,000/million for head injuries.
Quite often persons who suffer a stroke recover a large amount of function following a period of treatment, but a persistent, long-term disability in approximately 10 to 20 of stroke survivors is UpperMotorNeurone-Drop Foot (UMN-DF). UMN-DF typically involves an inability to dorsiflex the foot during the swing phase of gait (Drop Foot), as well as loss of normal hip and knee flexion, and inability to 'push-off' as well as spasticity of the calf muscle group.
An important feature of UMNLs is that electrical excitability of the associated peripheral nerves is still intact, thus facilitating the use of Functional Electrical Stimulation (FES) to restore or enhance gait for some of these cases. As early as in 1961, Liberson and his co-workers proposed application of electrical stimulation (ES) to the common peroneal nerve to correct this condition and using a foot-switch synchronised the application of ES to the swing phase of gait, using a device subsequently referred to as a Peroneal Stimulator (PS) or Drop Foot Stimulator (DFS) [Liberson, W. T., Holmquest, H. J., Scott, D. and Dow, M. (1961) Functional Electrotherapy in stimulation of the peroneal nerve synchronized with the swing phase of gait in hemiparetic patients. Arch Phys Med Rehabil 42, 202-205].
The development of FES-based Drop Foot correction has gone through the following evolutionary stages:    (i) Hard-wired Single-channel Surface Drop Foot Stimulators,    (ii) hard-wired Multi-channel Surface Drop Foot Stimulators,    iiii) hard-wired Single-channel Implanted Drop Foot Stimulators,    (iv) microprocessor-based Surface and Implanted Drop Foot Stimulators,    (v) alternative sensors as replacement for the Foot-switch: (a) artificial sensors, and (b) "natural" sensors.
(i) Hard-wired Single-channel Surface DFS: As indicated above, the first reported use of electrical stimulation for Hemiplegic Drop Foot Correction was in 1961 by Liberson who proposed to elicit dorsiflexion in a hemiplegic foot, synchronised with the swing phase of gait. Liberson's solution, shown in FIG. 1, comprised power and control box (1), a heel-switch (2), when open, during swing, open-circuits the shunt resistor (3), and enables the delivery of stimulus current across the stimulation electrodes (4). The switch when closed, during stance, connects the shunt resistor across the output of the stimulator and no stimulus is delivered to the stimulation electrodes. The delivery of stimulus to the electrodes (positioned for stimulation of the common peroneal nerve) is therefore triggered when the heel-switch opens at heel-off and is terminated when the switch closes at heel-strike. The application of stimulus is thus synchronised with the swing phase of gait. This is an example of a hard-wired stimulator, where the functionality of the stimulator is determined by the wiring of the electronic circuitry. The system performed the essential task of inducing dorsiflexion in the subject's hemiplegic foot at the appropriate point in the gait cycle. Clearly, however, the functionality of the system lacked sophistication and delivered stimuli in a crude fashion compared to the natural performance of the foot-lifter neuromuscular system.
(ii) Hard-wired Multi-channel Surface Drop Foot Stimulators: The first group to present a major technical innovation on Liberson's design was Kralj and his co-workers from the University of Ljubljana in Slovenia. They proposed in 1971 the use of multiple channels of stimulation in the drop foot stimulator and a radio link between the heel-switch and the stimulator [Kralj, A., Trnkoczy, A. and Acimovic, R. (1971) Improvement in Locomotion in Hemiplegic Patients with Multichannel Electrical Stimulation. In: Anonymous Human Locomotor Engineering—A review of developments in the field including advances in prosthetics and the design of aids and controls, pp. 45-50. Institute of Mechanical engineers]. The proposed stimulator had three stimulation channels enabling different muscle groups to be controlled independently, such as ankle dorsiflexors and knee flexors and extensors.
(iii) Hard-wired Single-channel Implanted Drop Foot Stimulators: The next major development in hemiplegic drop foot correction technology was the investigation of the possibilities and practicalities of implantable Hemiplegic Drop Foot Stimulators. Jeglic et al., proposed an implanted DFS (IDFS) aimed at overcoming problems of discomfort due to stimulation pain and difficulties experienced by subjects in correctly placing the stimulation electrodes [Jeglic, A., Vanken, E., Benedik, M., "Implantable muscle/nerve stimulator as part of an electronic brace", in Proc. 3rd International Symposium on External Control of Human Extremities, 1970, pp. 593-603].
Jeglic et al's single channel stimulation device was never successful but may be seen as pre-dating the development of a commercial, implantable, drop foot stimulator by the Rancho Los Amigos Medical Centre/University of Southern California group in California, in conjunction with Medtronic Inc. of Minneapolis [Waters, R. L., McNeal, D. and Perry, J. (1975) Experimental Correction of Foot-drop by Electrical Stimulation of the Peroneal Nerve. J.Bone Joint Surg [A] 57-A (8):1047-1054].
The three elements of this system, shown in FIG. 2, are: an external module with a transmitting antenna and control module (10), an implanted assembly comprising a receiver, pulse train generator and bipolar electrode (11) and a heel-switch (12) located in the shoe. In common with the Jeglic et al. system, the implanted device required no batteries as electrical power was supplied by electromagnetic induction. The antenna transmitted a radio-frequency signal through the skin and this was taped to the skin directly over the implant. Two incisions were required: one on the medial aspect of the thigh to implant the receiver, another on the lateral aspect of the leg, below the knee, to expose the common peroneal nerve. The system was never put on the market, presumable due to the relatively extensive surgical procedures required.
(iv) Microprocessor-based Surface and Implanted Drop Foot Stimulators: The first use of micro-controller/microprocessor technology for DFS systems is thought to be the incorporation of microprocessor technology into the previously discussed Multi-channel Surface Stimulators.
A primary motivation for the development of such multi-channel implantable stimulators was to overcome the particular problem with single-channel implanted systems reported by Waters et al. [Waters, R. L., McNeal, D., Faloon, W. and Clifford, B. (1985) Functional Electrical Stimulation of the Peroneal Nerve for Hemiplegia—Long-Term Clinical follow-up. J.Bone Joint Surg [A] 67-A (5):792-793]. Waters et al found that some of the subjects implanted with the Medtronic implanted single-channel DFS system walked with excessive inversion or eversion following surgery. This problem was due to incorrect positioning of the electrodes as the correct placement of the electrode is difficult to determine during surgery. A balanced dorsiflexion response when the subject is prone does not guarantee that the same response will be obtained when the subject is upright, weight-bearing and walking.
A solution to the problem of incorrect electrode placement during surgery, and of the tendency of the electrodes to move post-surgery was proposed by Kelih et al. [Kelih, B., Rozman, J., Stanic, U. and KLjajic, M. (1988) Dual channel implantable stimulator. In: Wallinga, W., Boom, H. B. K. and de Vries, J., (Eds.) Electrophysiological Kinesiology, pp. 127-130. Elsevier Science Publichers B.V. (Biomedical Division)]. They proposed a dual-channel implantable stimulator enabling control of two-degrees of freedom of foot movement, viz. dorsiflexion and eversion. Thus, post-surgery, when the subject started to walk using the implant, the stimulus level on each channel could be adjusted to obtain balanced dorsiflexion.
(v) Alternative sensors as replacement for the Foot-switch: Since Liberson's development of the first drop foot stimulator until the early 1990s, the sensor used in FES-based Drop Foot Correction system had been the foot-switch, however, it has been proposed by several researchers, that it would be desirable to replace the foot-switch as the gait sensor in DFS systems for the following reasons:
(1) Fundamentally the traditionally foot-switch has been a contact sensor, requiring repetitive contact/non-contact of the wearer's foot with the foot-switch, which has major implications for the reliability of the sensor. With a DFS system, the ultimate application of the system requires that the subject brings the system home and wears it each day. For the wearer to accept this device and to overcome gadget intolerance the reliability of the system must be high and failure of any component of the system over a short period, including the gait sensor, is unacceptable.
(2) The accepted long-term approach to the implementation of FES-based UMN-DF correction systems is the use of implanted systems. For a completely implanted system, the ability to implant the gait sensor is desirable and the foot-switch is unsuitable for implantation.
(3) Finally the information provided to the DFS system by a foot-switch is very limited, namely, presence or absence of contact by a part of the foot with the ground. This type of signal is quite adequate for the hard-wired DFS systems described, but as the sophistication of DFS systems is increased through the use of more complex control algorithms, the limitation of the foot-switch as a gait sensor should become apparent.
For the reasons outlined, several researchers have evaluated alternative gait sensors using either an artificial gait sensor which would be suitable for implantation or using the body's "natural" sensors. Developments in these two research areas will now be discussed.
(a) Artificial sensors as replacement for the Foot-switch: One of the first groups to propose alternatives to the foot-switch as a gait sensor in DFS systems was Symons et al. at the Rancho Los Amigos Medical Centre/USC [J. Symons, D. McNeal, R. L. Waters, and J. Perry, "Trigger switches for implantable gait stimulation," in Proc. 9th Annual RESNA Conference, 1986, pp. 319]. Symons carried out preliminary evaluation of an in-house accelerometer fitted to the greater trochanter process of the femur in a vertical orientation to detect the heel strike event. One of the advantages of accelerometers is that they are miniaturised integrated electronic components and as such are highly reliable and therefore very suitable candidates for implantation, which was the rationale for the evaluation of the accelerometer.
Willemsen et al from the University of Twente in the Netherlands, proposed the used of an integrated accelerometer as a replacement for the foot-switch in an UMN-DF correction system [Willemsen, A. T. M., Bloemhof, F. and Boom, H. B. K. (1990) Automatic Stance-Swing Phase Detection from Accelerometer Data for Peroneal Nerve Stimulation. IEEE Transactions Biomedical Engineering 37 (12):1201-1208]. In their paper, an arrangement of four commercial single-axis accelerometers was placed on the shank of a subject, as shown in FIG. 3. Willemsen et al was able to distinguish between different phases of the gait cycle using the equivalent acceleration at the ankle joint as calculated from four accelerometers placed at locations 30 and 31 and was thus able to detect the onset of swing (push-off) and the termination of swing (heel-strike). Careful attention was paid to the failure rate of detection of push-off and heel-strike. Out of a total of 106 steps, using three hemiplegic subjects, there were errors in only three steps, which is a very good performance.
U.S. Pat. No. 5,814,093 discloses the use of such an artificial sensor arranged corresponding to below the knee of a user. As has been the tradition until now, the (external) stimulation electrodes are placed below the knee joint.
(b) "Natural" sensors as replacement for the Foot-switch: A very elegant and powerful solution to the problems of gait sensors in FES-based UMN-DF correction systems is to use the body's own sensing mechanism. Haugland and Sinkjaer described the use of recordings from a cuff electrode, on the sural nerve, to control the application of stimulus to the common peroneal nerve of a hemiplegic subject [Haugland, M. K. and Sinkjaer, T. (1995) Cutaneous Whole Nerve Recordings Used for Correction for Foot-drop in Hemiplegic Man. IEEE Transactions Biomedical Engineering 3 (4):307-317]. The device is shown in FIG. 4, and consisted of a power and control box 40, a set of surface electrodes 41 for stimulation of the peroneal nerve below the knee, a nerve cuff electrode 42 implanted around the sural nerve 43, having percutaneous wires 44 that with a connector 45 could be connected with the power and control box. To reduce noise in the nerve signal recording an external reference electrode 46 was strapped around the leg. The sural nerve is a sensory nerve which has as it sensory input touch sensors on the lateral part of the foot 47. It was proposed that the conventional heel switch in a DFS system be replaced by a single sural nerve cuff which monitored whether or not the affected foot was supporting weight and used this information to control the application of stimulus in the DFS. Recording nerve signals is referred to as Electroneurography and the corresponding signal is called an ElectroNeuroGram (ENG). It was thus demonstrated that nerve recordings could be used as the basis for the control of a DFS eliminating the need for an external foot-switch and its associated problems.

Method and implantable systems for neural sensing and nerve stimulation


Tyrosine was converted to p-hydroxystyrene in a two-step reaction without purification of individual intermediates. Conditions were determined for bromination of tyrosine in which reactive intermediates were formed. The mixture of these intermediates was used directly in a second step reaction to produce p-hydroxystyrene. The p-hydroxystyrene was further acetylated to produce p-acetoxystyrene in the second step reaction vessel.

Hydroxystyrenes, such as p-hydroxystyrene (pHS; also known as p-vinylphenol) and acetylated derivatives thereof, such as p-acetoxystyrene (pAS), are aromatic compounds that have potential utility in a wide variety of industrial applications. For example, these compounds have applications as monomers for the production of resins, elastomers, adhesives, coatings, automotive finishes, inks and photoresists, as well as in electronic materials. They may also be used as additives in elastomer and resin formulations.
A number of methods for the chemical synthesis of hydroxystyrenes and acetylated derivatives thereof are known. However, these methods generally require expensive reagents, harsh conditions, and give relatively low yields. Examples of starting reagents used in the chemical synthesis of pHS include p-hydroxycinnamic acid (pHCA; Sovish J. Org. Chem. 24:1345-1347 (1959); U.S. Pat. No. 5,274,060), p-hydroxybenzaldehyde (U.S. Pat. No. 4,316,995), ortho or para-hydroxyarylcarboxylic acids (Australian Patent Application No. 7247129), caffeic acid (U.S. Pat. No. 5,324,804), trans-3,5-di-tert-butyl-4-hydroxycinnamic acid (Munteanu et al. J. Thermal Anal. 37:411-426 (1991)), and p-alpha-amino-ethylphenol (U.S. Pat. No. 5,493,062), and hydroxybenzaldehydes and malonic acid (Simpson et al., Tetraheron Lett. 46: 6893 (2005)).
Tyrosine, (S)-2-amino-3-(4-hydroxy-phenyl)propanoic acid, provides a readily available and relatively low cost reagent which has potential of being a reagent for producing pHS. Tyrosine was used as the starting reagent in the synthesis of (S)4-(2-chloro-3-(4-n-dodecyloxy)phenylpropionato)-4′4(2-methyl)butyloxy-biphenylcarboxylate (CDPMBB) in Kumar and Pisipati (Z. Naturforsch. 57a:803-806 (2002)). The initial reaction was diazochlorination of tyrosine by nucleophilic substitution in the presence of sodium nitrite to form (S)-2-chloro-3-(4-hydroxy)phenyl propionic acid. Yields of the reaction were poor, and by-products resulting from nitration or chlorination of the aromatic ring made purification difficult.
Side chain protected tyrosine, tyrosine t-butyl ether, was brominated in the presence of HBr, KBr, and sodium nitrite (Souers et al., Synthesis 4:583-585 (1999)). The presence of the protecting group on the phenol moiety complicates the use of this product as a reagent for producing pHS.
There is a need for a method for the chemical synthesis of pHS from tyrosine which is simple and efficient, that produces product in high yield and avoids the complications of by products generated from the use of a side chain protected tyrosine. Applicants have solved the stated problem by the discovery of a two step reaction for the conversion of tyrosine to brominated tyrosine intermediates coupled with their subsequent conversion to p-hydroxstyrene under basic conditions.

Processes for conversion of tyrosine to p-hydroxystyrene and p-acetoxystyrene


The present invention relates to agriculture and waste management. In particular, compositions and methods relating to soil amendments and organic waste management are provided. In certain aspects, soil amendments, and methods of making soil amendments, and methods for improving crop yields are provided.

Composting is the purposeful biodegradation of organic matter, such as yard and food waste. The decomposition is performed by micro-organisms, mostly bacteria, but also yeast and fungi. There are a wide range of organisms in the decomposer community. Composting organisms require Carbon ("C" or carbohydrates), to provide energy; Nitrogen ("N" or protein), to grow and reproduce more organisms to oxidize the carbon; Oxygen, for oxidizing the carbon, the decomposition process; and water, in the right amounts to maintain activity without causing anaerobic conditions. Certain ratios of these components provide beneficial bacteria with the nutrients to work at a rate that will heat up the compost pile.
During the conventional composting process, considerable water is released as vapor ("steam"), and the oxygen is quickly depleted. The hotter the pile gets, the more often added air and water is necessary. The air/water balance is essential to maintain the high temperatures required to break down the manure and green waste, typically found in a composting mixture. At the same time, too much air or water also slows the process, as does too much C (or too little N). If the pile is built in a short period, and has a good mix of materials (C:N) and a coarse structure, with about 50% moisture, the temperature should rise within days to as high as 60° C. (140° F.). As the temperature of the pile falls, more air is added by turning the pile or using an agitating tool. Typically, moisture is added at the same time. Turning or other aeration is usually needed about every 6-10 days to maintain the highest heat levels until the material is fairly uniformly broken down, and temperatures no longer rebound. A pile that has been maintained at peak temperatures may be ready for maturing in as little as 30-60 days but, generally, 75 days are required to obtain usable compost. The resultant organic compost typically has about 7 lbs of available nitrogen/cubic yard.
Traditional methods of composting, produce large volumes of harmful greenhouse gases including Ammonia, Methane, and Carbon Dioxide. The production of these gases not only generates noxious odors but the release of these gases drastically decreases the amount of available nitrogen and carbon in the composted end-product. Traditional composting is a smelly, slow process requiring a minimum of 30 days under optimal conditions, considerable heat, and frequent turning or aeration of the compost heap. The resulting amendment has lost a considerable amount of its nitrogen and carbon potential through out-gassing. Accordingly, there is a need for improved soil amendments and methods of composting.

Methods and compositions for soil amendments and organic waste management


A method, apparatus, and program storage device for sharing objects with a network server and a database server using a common object model. A first set of objects is stored in a common file accessible by a network server and a database server. A second set of objects is stored in the common file. The first set of objects has network server executable logic and the second set of objects has database server executable logic. The first set of objects are published to the network server and the second set of objects are built in the database server. Building the second set of objects involves building a data link library (DLL) stub for the database server to run intermediate code language on the database server.

1. Field of the Invention
This invention relates in general to programming development environments performed by computers, and in particular, to a shared object model that allows transparent execution on multiple architectures.
2. Description of Related Art
With the fast growing popularity of the Internet and Intranets, especially Web-based networks, there is also a fast growing demand for Internet and Intranet access to databases. However, it is especially difficult to use relational database management system (RDBMS) software with Web-based networks. One of the problems with using RDBMS software with Web-based networks is the lack of programming development environments that can be used to develop both Web-based and RDBMS-based applications.
For example, Web-based networks operate using the HyperText Transfer Protocol (HTTP) and the HyperText Markup Language (HTML). HTTP is the protocol used by Web clients and Web servers to communicate between themselves using these hyperlinks. HTML is the language used by Web servers to create and connect together documents that contain these hyperlinks. This protocol and language results in the communication and display of graphical information that incorporates hyperlinks. Hyperlinks are network addresses that are embedded in a word, phrase, icon or picture that are activated when the user selects a highlighted item displayed in the graphical information.
In contrast, most RDBMS software uses a Structured Query Language (SQL) interface. The SQL interface has evolved into a standard language for RDBMS software and has been adopted as such by both the American Nationals Standard Organization (ANSI) and the International Standards Organization (ISO).
Thus, there is a need in the art for methods of accessing RDBMS software across an Internet or Intranet, and especially via Web-based networks. Further, there is a need for simplified development environments for such systems. For example, current development environments have separate, fragmented, non-associated files for each aspect of the project. These separate files must be pulled together from separate sources to build the project. Another problem with current development environments is an inability to support transparent execution on different architectures. For example, the architecture of RDBMSs accessed via the Internet may be differ substantially, complicating the development environment and the resulting application.

Method, apparatus, and program storage device for sharing objects with a network server and a database server using a common object model

International Business Machines Corporation


The present invention relates to a payment mat that wirelessly communicates with a payment device for payment of items, such as goods and/or services, in a retail environment. A customer presents the payment device within the radiation range of an antenna contained in the payment mat for payment. The payment mat may also include a visual indicator, audio indicator, keypad, transaction display, advertising display, receipt printer, and transaction card reader. The payment mat may be constructed out of a rigid or flexible material. The payment mat may be placed flat on counters in retail stores, nearby cash registers or order entry devices. The payment mat may be placed on drive-thru windows in retail environment, such as quick service restaurants (QSR) or pharmaceutical stores. The payment mat may be placed behind a secure order entry window.

Most retail environments accept cash and credit or debit cards for customer payment of goods or services. Cash transactions require an attendant to make and give change, thereby slowing down throughput of customers. This may be particularly important in retail stores that have heavy customer traffic. Cash transactions also require retail stores to carefully account for such cash to minimize theft, such as counting and making manual deposits into banks. Such deposits often occur in unsafe conditions at night, after the retail store is closed and the cash on-hand is collected and counted.
Credit and debit transaction cards have increased payment speeds over the use of cash, but use of such transaction cards can cause timing delays in their own right. Customers have to reach into their purse or wallet to find their transaction card. Sometimes, magnetic card stripes loose their information requiring the attendant to manually enter the card number and expiration date. Often, transaction card authorization requires communication to a remote host network, taking additional time to receive authorization.
Wireless payment systems, using transponders or other wireless payment devices, such as RFID, have been developed to improve the payment speeds for retail transactions. A wireless payment device may contain an ID that uniquely identifies a customer to the customer's account. The wireless payment device may contain resident memory with storage of a cash balance from which payment can be subtracted. However, use of such wireless payment systems requires communication readers, comprised of electronics and an antenna, for wirelessly communicating with wireless payment devices used by customers for payment. Such communication readers should be located where customers tender payment for purchases. Such communication electronics can be cumbersome to install given the limited amount of space in retail store environments. For instance, quick service restaurants (QSR) have cash registers positioned close together with a minimal amount of space between each. Many of these same QSRs have "drive-thru" window pickups that also have counters with limited space. The counters within restaurants should be clear to allow an attendant to deliver food and other items to the customer. Convenience store counters also have limited space since they often contain cash registers and other goods for sale to customers.
Therefore, a need exists to provide communication readers that are conveniently located and accessible to customers using wireless payment devices for payment and do not occupy large amounts of space on or proximate to the retail counter.

Wireless payment mat device and method for retail environments


A cover assembly for an open top railcar, the assembly having semi-rigid cover reversibly movable between a closed position atop the railcar and an open position alongside the railcar or separate from it. The cover may be connected to the railcar with hinge-latches or linkage arms which permit the cover to be held flat alongside the railcar in an open position, or removed from the railcar during loading and unloading. A load grooming device shapes the load of a loaded railcar to a selected contour. Opening and closing of covers may be continuous and automated, using curved tracks, cranes or mechanical arms to engage and open covers, and conveying devices or vehicles to handle covers during loading and unloading of railcars.

It is known to provide open top railway cars, whether bottom dump hoppers or top unloading gondolas, which may be fitted with removable covers to enclose the top openings. These covers typically may be lifted free of the cars for loading, or, in the case of gondolas, for unloading. Once a load has been loaded or unloaded, the cover may be replaced.
Such covers provide a number of benefits, including product containment, for example, prevention of ingress of dust, which represents an environmental hazard, and prevention of product loss. Other benefits include product protection, for example, protection from rain or snow and protection from debris. Many different granular or powder products may be shipped in this way, including minerals, grains, hazardous waste, coal, and other products.
Typically, such covers are fastened onto railcars with various types of clamps or brackets which fix the cover to the car and prevent it from coming loose in transit, but which allow manual or automatic opening in order to handle the cover.
Covers typically may be manufactured of steel, aluminum, or various composite materials, each of which has its advantages and disadvantages. Covers may be built as a single piece covering the full length and width of the railcar, or as two or more pieces, depending on the material selected and the circumstances of operation. Due to their large size and manner of removal, prior art rail car covers require fixed or mobile heavy equipment for removal and replacement, as well as large areas for moving and stacking removed covers.
The weight of each cover can be significant, ranging from 1500 lbs for a composite cover to as much as 5000 lbs for a steel cover. The cover weight reduces the effective payload of the rail car, thereby reducing the cargo load the user can haul.
In high volume situations, it is often not possible to arrange a suitable method for removal and replacement of covers. For instance, in a coal loading facility, the rail cars typically do not stop moving, but are driven slowly in one long string through the facility under loading chutes and exit the far side of the loading facility which may be several hundred feet away. Slowing or stopping of trains is generally not an option. The logistics of lifting covers off at the entrance to the facility, moving them around the facility to the loadout area at the loading facility exit, and replacing the covers on the railcars, make use of covers very problematic. As a result, to date, no large scale loading operations of this type have been converted to covered cars.
On the unloading end, the problem is similar. For unloading gondola type railcars, high volume operations such as coal will use a railcar dumper, a large device which rotates about the axis of the railcar couplers, completely inverting one or more railcars at a time, while they remain coupled to the cars ahead and behind.
Past and current solutions have included lifting of covers within the dumper building over the dumper itself. This adds time to the dump cycle, and is not suitable for retrofit situations, as dumper buildings typically do not have the space capacity for such a cover lifting mechanism, and many dumpers are constructed with part of their mechanism over top of the car, which would prevent removal of the rail car cover. This solution also would not work at the loading end. Accordingly, a new cover removal system is needed.
Any bulk material cover system may not function if the load is too high or spills onto sills or tail areas of the rail car. Problems in loading are common. A device is needed to groom the shape profile of a rail car load on a continuously moving string or rail cars.
In the drawings, selected embodiments of the invention are illustrated by way of example. It is to be expressly understood that the description and drawings are only for the purpose of illustration and as an aid to understanding, and are not intended as a definition of the limits of the invention.


A button assembly and washing machine having the same, in which the adjacent push buttons are prevented from being pressed together by a user. The button assembly includes a panel, at least two push buttons provided to the panel, and at least one push guide provided on a surface of the panel for preventing the at least two push buttons from being simultaneously pressed together by a user.

1. Field of the Invention
The present invention relates to a washing machine, and more particularly, to a button assembly and washing machine having the same, in which adjacent push buttons are prevented from being incorrectly pressed.
2. Discussion of the Related Art
Generally, in a washing machine, a tub contains water and detergent inside and a laundry is put in a drum installed within the tub. And, the drum is rotated to perform washing, rinsing, and dewatering. The washing machine is an apparatus for removing filth or dirt attached to the laundry using the detergent and mechanical energy applied thereto appropriately. Specifically, a drum, which is horizontally installed within a drum type washing machine, contains detergent, water, and laundry therein and is then rotated by a drive force of a motor to remove filth or dirt attached the laundry. Such a drum type washing machine avoids causing damage or ravel to the laundry, consumes less water, and brings about a washing effect of beating and rubbing.
FIG. 1 shows a perspective view of a washing machine according to a related art. Referring to FIG. 1, a washing machine according to a related art consists of a cabinet 10 forming an overall exterior, an opening 11 formed at a front side of the cabinet 10 for putting/pulling a laundry in/from the washing machine, a door 12 provided to the front side of the cabinet 10 to open/close the opening 11, a tub (not shown) provided within the cabinet 10 to contain water therein, a drum 20 rotatably installed within the cabinet 10 to perform washing on the laundry therein, a multitude of perforated holes formed at a wall of the drum 20 so that the water passes through the perforated holes, a control panel 30 provided to an upper front side of the cabinet 10 to control an operational state of the washing machine, and a detergent input unit 40 for inputting a detergent or additive. Moreover, a button assembly 31 for inputting an operational condition (or operational commands) of the washing machine and a display unit for displaying an operational state of the washing machine are provided to the control panel 30.
The button assembly is explained in detail by referring to FIGS. 1 and 2 as follows. First of all, the button assembly 31 consists of a plurality of push buttons 31a operated by user's push action for an operational condition input of a washing machine and a panel unit 31b on which the push buttons 31a are provided. Moreover, a power switch 31c for power input and a rotary switch 31d for inputting an operational condition of the washing machine by rotation are provided near the push buttons 31a.
The push buttons 31a protrude higher than the panel unit 31b. Once a user presses a specific one of the push buttons 31a, the pressed push button is moved downward to actuate a predetermined switching means. Once the pressing force from the user is released, the corresponding push button is moved upward to return to its original position.
However, in the related art button assembly, when a user presses a specific push button for the operational condition input of the washing machine, another push button in the vicinity of the specific push button is simultaneously pressed, whereby an unwanted operation condition is inputted to bring about a wrong operation of the washing machine. Hence, the user should be cautious to press the specific push button. Moreover, if the push buttons decrease in size in case of a small-sized washing machine, if an interval between the push buttons is narrow, or if a user has a big hand, the above problem becomes more serious.

Button assembly and washing machine having the same


Programmable logic device integrated circuitry having I/O circuitry portions having different maximum speed capabilities and different amounts of programmability for supporting various I/O signaling standards is provided. High-speed I/O circuitry and low-speed I/O circuitry may be provided. The high-speed I/O circuitry may have differential I/O drivers and may not be programmable. Relatively few I/O lines may be connected to the high-speed I/O circuitry. The low-speed I/O circuitry may be programmable so that a user may configure the low-speed I/O circuitry to support different I/O signaling standards. Intermediate-speed I/O circuitry may be provided that is more flexible than the high-speed circuitry and operates at higher maximum I/O data rates than the low-speed I/O circuitry. Transmitter circuitry (output driver circuitry) in the I/O circuitry may be provided with the ability to handle a greater number of different I/O signaling standards than receiver circuitry (input driver circuitry) in the I/O circuitry.

This application relates to programmable logic array integrated circuits ("programmable logic devices"), and more particularly, to input-output circuitry for programmable logic devices.
Programmable logic devices are integrated circuits that may be programmed by a user to perform various logic functions. Some currently-available programmable logic devices have I/O driver circuitry that can be selectively configured to accommodate different I/O signaling standards. This flexibility enhances the usefulness of such devices, because they may be used in various system environments and may communicate with a broader range of other devices than would otherwise be possible. However, substantial performance penalties may arise if the input-output circuitry of a programmable logic device is made too flexible.
On some currently-available programmable logic devices the transmitters (output drivers) in the I/O circuitry may be made more programmable than the receivers (input drivers) to take advantage of the less sensitive nature of the transmitters to performance penalties when adding support for multiple signaling standards. On these devices higher speed I/O circuits may be provided with less programmability to maximize their performance. Performance is enhanced further by reducing the amount of signal conductor area that immediately underlies the flip-chip solder bump pads at the ends of the I/O ines on the programmable logic device.
It is therefore an object of the present invention to provide programmable logic devices that have input-output circuitry with both flexibility and high performance.

Programmable logic device multispeed I/O circuitry


The present invention relates to the preparation of the (S)-(−)-amlodipine and (R)-(+)-amlodipine by means of enantiomeric separation of racemic amlodipine mixture, in which, L- or D-tartaric acid is used as resolution agent, and organic solvent containing 2-butanone is used as solvent. The 2-butanone used in the present invention has the advantage of low boiling point, low toxicity, litter pollution, and the method is suitable for large-scaled production.

Amlodipine is a calcium ion antagonist, which is used for clinically treating hypertension and stable angina. Currently, amlodipine clinically used is substantially the raceme thereof. It is reported that the main pharmacological active ingredient in the raceme is (S)-(−)-amlodipine and the antagonistic activity thereof against calcium ion is about 1000 times to that of (R)-(+)-amlodipine and double to that of the raceme per se by Arrowsmiith, J. E. et al., J. Med. Chem. (1986) 29; 1696-1702. WO93/10779 (Young, J. W.) discloses that the administration of (S)-(−)-amlodipine can reduce the side effects such as acroedema, headache, dizziness etc. as compared with using racemic amlodipine. Accordingly, the therapies of hypertension and stable angina by administrating (S)-(−)-amlodipine have a good market prospect. The other enantiomer, (R)-(+)-amlodipine, has the activity of treating atherosclerosis.
The chemical structure formula of amlodipine is showed by

The method for preparing the enantiomers of amlodipine essentially comprises the resolution of racemic amlodipine. WO95/25722 (Pfizer Pharmaceuticals Limited) provides a method for obtaining the enantiomers of amlodipine by direct resolution of amlodipine using D- or L-tartaric acid as resolving agent and dimethyl sulphoxide (DMSO) as solvent, which has a disadvantage in that a high boiling point of DMSO solvent, i.e. 189° C., tends to cause the recovery of solvent is difficult during the preparation. WO 03/035623 (Sepracor Co.) describes a method for directly resolving racemic amlodipine by using D- or L-tartaric acid as resolving agent and N,N-dimethyl acetamide (DMAC) as solvent. Similarly, it is difficult to recover DMAC due to the high boiling point of about 164-166° C. And since DMAC belongs to the Second Solvent which has high toxicity (Guidance for Industry IMPURITIES: RESIDUAL SOLVENTS, FDA, May 15, 2001), it tends to result in the serious environmental contamination during the preparation.

Method for the enantiomoeric separation of optical active amlodipine

Shijiazhuang Pharmaceutical Group Ouyl Pharma. Co., Ltd.


A constant-velocity joint assembly includes: a first and a second shaft portions respectively provided with a protrusion; a double yoke portion in which a guide hole is formed along an axis direction, the first and the second shaft portions being respectively rotatably connected to both sides of the guide hole with an axis of an upper/lower direction; and a guide portion which is disposed to the guide hole to guide the protrusion and rotates along an inner circumference of the guide hole during rotation of the shaft portions, wherein the first and the second shaft portions respectively comprises: a spider body, a left and a right leg, and an upper and a lower legs; a shaft provided with the protrusion; and a yoke block comprising a block body, and a left and a right connecting member.

U.S. Pat. No. 6,840,864 has been introduced as a double cardan constant-velocity joint assembly.
In a conventional constant-velocity joint assembly a leg portion, i.e., a cross pin which is coupled to a yoke block, i.e., an inner ring is directly connected to a front end of a shaft, so a freedom degree of a front end of a shaft becomes lower so that an improvement of an operation performance is limited. In addition, there are problems in that a productability is deteriorated due to a connection structure and a size of a package becomes larger.
Further, a conventional constant-velocity joint assembly has a limit in a smooth operation of a shaft to an intermediate coupling member due to a structure of an intermediate coupling member. Accordingly, it is needed to change a structure of an intermediate coupling member of a conventional constant-velocity joint assembly to improve performance.

KOREA DELPHI AUTOMOTIVE SYSTEMS CORPORATION


The invention relates to a method for determining whether a same disc is loaded in an optical drive. The method comprises the steps of measuring a time interval between a disc insertion event resulting from a disc insertion command and a disc ejection event resulting from a disc ejection command, comparing the time interval with a predefined value, and indicating that the same disc is loaded in the optical disc if the time interval is smaller than the predefined value.

When a disc is loaded in an optical drive, by means of a tray or not, the first step to be performed is to recognize the disc present in the drive.
The disc recognition procedure involves operations which namely consist of selection of a laser (CD, DVD or BluRay laser) to start disc recognition by way of a substrate thickness measurement, reflection measurement at non-rotating disc, spherical aberration control during disc recognition and initializations, presets, and calibrations of various items such as focus offset, radial tilt, tangential tilt and spherical aberration.
Performing all these operations actually takes a significant amount of time. As timing performance is an important property of an optical drive, the duration and/or number of operations mentioned above should be kept to a minimum.
On the other hand, it is apparent that time could be saved in circumstances where a same disc is still present in the optical drive although the user has given an ejection command but without changing the current disc.
Indeed, under those circumstances, several operations may be skipped such as substrate thickness measurement for selecting the correct laser, spherical aberration adjustment, and radial tilt calibration.
Thus, it can be readily understood that determining whether a same disc is still present in an optical drive may be of the upper importance in assessing the timing performance of an optical drive.
In that context, U.S. Pat. No. 5,974,016 discloses a disc drive equipped with an automatic closing tray wherein a delay is set before the tray is closed, said delay depending on the presence in the tray of an old or a new disc or if the tray is empty. For that purpose, a plurality of sensors at a nest in the tray senses the presence of a disc in the nest and also whether the disc is correctly positioned.
However, it will be appreciated that providing an optical drive with sensors specially dedicated to the determination that a same disc is still present in the drive results in additional costs and technical complexity that are generally hoped to be saved.

Method for determining whether a same disc is loaded in an optical drive


An apparatus is disclosed comprising an audio alert device, a timer, a processor; and a four-wheel drive device for a subject vehicle. The processor may activate the timer when the four-wheel drive device indicates that the subject vehicle has been placed in a four-wheel drive state. The processor may activate the audio alert device so that the audio alert device produces a sound when the timer has reached a limit. The apparatus may include a distance counter. The processor may activate the distance counter when the four-wheel drive device indicates that the subject vehicle has been placed in a four-wheel drive state. The processor may activate the audio alert device so that the audio alert device produces a sound when the distance counter has reached a limit.

Often when driving a four wheel drive vehicle on snowy or icy roadways, a driver will engage a switch or lever to put his or her vehicle in four wheel drive. The driver will often drive the car for any number of miles, totally oblivious to the fact that it is in four wheel drive when, perhaps there is no longer any need that it be in four wheel drive. Driving a car in while it is in four wheel drive causes greater gas consumption, creates more wear and tear on the vehicle, and is more sluggish than driving when in two wheel drive. The current visual alert on four wheel drive buttons do not always serve to remind the driver that he or she might be in four wheel drive because there are so many lights on a dashboard that one particular light might not draw enough attention.


The fiber-optic cable comprises at least one element for high tensile stresses, a cable cladding, and at least one optical transmission element (optical fiber), which is accommodated in a chamber. The thermal contraction of the cable (dL/L) is selected such that it does not differ by more than 30% from the thermal contraction (dL/L) of the optical transmission element used in the range from 20xc2x0 C. to the lower temperature limit value of the cable.

The invention relates to a fiber-optic cable having at least one element for high tensile stress, at least one cable cladding, and at least one element with a chamber receiving at least one optical transmission element having outer dimensions slightly smaller than the dimensions of the chamber.
It is known that optical fiber elements have different thermal coefficients of expansion than the other elements of the cable, particularly the cable sheath, cladding materials of the leads, possible resistance elements against tension or crushing, and so on. When the optical fibers are accommodated loosely in a chamber, then they are coupled to the actual cable solely by friction, and as a consequence of the different thermal coefficients of expansion of the actual cable compared to the optical fiber element, macrobends can arise, which result in an increase in attenuation for the optical fiber element. It is therefore common to give the chamber that accepts the optical fiber elements such ample dimensions that elevations of attenuation due to macrobends are avoided. This very broad method has the disadvantage that the cable cross-section is significantly increased, because the cables known hitherto have always involved some type of xe2x80x9coverdimensioningxe2x80x9d. Additional details of the cable structure, dimensioning and calculation can be found in chapter 9 entitled xe2x80x9cOptical Cable Designxe2x80x9d, Fiber Optic Cables, G. Mahlke and P. Gxc3x6ssing; John Wiley and Sons Ltd., 3rd ed., 1997, pp. 115-158.
U.S. Pat. No. 4,770,489 teaches the loose accommodating of optical fibers in corresponding chambers or tubes. A plurality of tension-resistant elements are additionally provided, which comprise a higher E module than the actual cable and at the same time, a lower thermal coefficient of expansion. For example, fibers that consist of aramide yarn, carbon, or glass embedded in an epoxy resin can be used for these elements. In this way, the operative range of a cable can reach from xe2x88x9220 degrees Celsius to +70 degrees Celsius, instead of from xe2x88x9220 degrees to +60 degrees. This is assuming that the cable structure as such is left unaltered.
U.S. Pat. No. 5,098,177 teaches an optical cable that comprises an element for high tensile stresses. The optical fibers are accommodated loosely in chambers or tubes and comprise a coating of LCP (Liquid Crystal Polymer) whose linear temperature coefficient of expansion is between xe2x88x9215xc2x710xe2x88x926 and 5xc2x710xe2x88x926(1/K). In consideration of the different expansions, a relatively large tolerance range (play) of 0.5% to the wall is provided. This and the coating processes represent an additional outlay, and besides, the outer diameter of the optical fibers is increased by the added coating, so that a part of what is achieved by limiting the expansion behavior is lost again due to the increased space requirement of the optical fiber.
It is the object of the invention to demonstrate how it is possible to reduce, in a simple manner, the space requirement of the chamber within the optical cable that accepts the optical transmission element(s). This object is achieved by a cable having at least one element for high tensile stress, at least one cable cladding and at least one element with a chamber receiving at least one optical transmission element having an outer dimension slightly smaller than the dimension of the chamber and the cable has a thermal contraction (dL/L) in a range from 20xc2x0 C. to a lower temperature, for example xe2x88x9230xc2x0 C., which does not differ more than 30% from the thermal contraction of the optical transmission element.
The invention is based on tuning (synchronizing) the expansion behavior of the cable on one hand and of the optical transmission element on the other hand (in the form of an individual optical fiber, a band of optical fibers or some other elongated optical fiber structure forming a mechanical unit) to one another in the lower temperature rangexe2x80x94which is particularly critical for macrobendsxe2x80x94in such a manner that these deviate from each other only by a predetermined value at the most. In this way, it is possible to create an optimally adjusted xe2x80x9cmovement windowxe2x80x9d for the optical transmission element, this window being optimally small in and of itself, but nevertheless still sufficient to accept macrobends which result from different residual, in particular local, linear expansions (e.g. as a result of bending) and thereby to prevent elevations of attenuation.
In addition to the above solution or independent of it, the fiber-optic cable can also be inventively constructed such that, below 20xc2x0 C., particularly at the lower temperature limit value of the cable (e.g. xe2x88x9230xc2x0 C.,), the disparity between the percentage expansion value of the optical transmission element, on one hand, and the percentage expansion value of an appertaining cable structure, on the other hand, is selected such that the difference of the expansion values is less than xc2x10.03 percentage points, preferably less than xc2x10.02 percentage points, and particularly less than xc2x10.01 percentage points.
The dimensions of the chamber are appropriately so constructed that local bending radii that may result from an additional excess length of the optical transmission element at the lowermost temperature limit value are greater than 70 mm.
In addition to the above solution or independent of it, another course of action consists in thickening the optical transmission element using plastic additives that are connected to it in a mechanically secure manner (for instance, using an additional coating on the optical fiber and/or some other type of material deposition, for instance on the outside on optical fiber bands), such that at low temperatures a preferably slight (e.g. max. 0.05%) adjustment of the expansion to the expansion of the cable structure is achieved.
The invention and its developments are detailed below with the aid of drawings, which represent exemplifying embodiments.