Tetrakis(fluoroaryl)borate.magnesium halide (Ar.sub.4 BMgX) expressed by General Formula (1): ##STR1##. where each of R.sub.1 -R.sub.10 represents a hydrogen atom, a fluorine atom, a hydrocarbon group, or an alkoxy group, provided that at least one of R.sub.1 -R.sub.5 represents a fluorine atom and at least one of R.sub.6 -R.sub.10 represents a fluorine atom, X represents a chlorine atom, a bromine atom, or an iodide atom, and n represents 2 or 3, is treated with alkali metal salts of carboxylic acid and/or alkali earth metal salts of carboxylic acid. Then, a tetrakis(fluoroaryl)borate derivative (Ar.sub.4 BZ) is produced by reacting treated Ar.sub.4 BMgX with a compound generating monovalent cation seeds (for example, N,N-dimethylaniline.hydrochloride). Consequently, it has become possible to provide a purifying process of separating/removing impurities from Ar.sub.4 BMgX readily and efficiently, and a process of producing inexpensive Ar.sub.4 BX efficiently.

A tetrakis(fluoroaryl)borate derivative is an useful compound as, for example, a co-catalyst for promoting the activity of a metallocene catalyst (polymeric catalyst) used in a cationic complex polymerization reaction, or a photopolymeric catalyst for silicone. Also, tetrakis(fluoroaryl)borate.magnesium halide is an useful compound as an intermediate for producing the tetrakis(fluoroaryl)borate derivative. Recently, the metallocene catalyst has been receiving considerable attention as a polyolefin polymeric catalyst.
A producing process of tetrakis (pentafluorophenyl)borate.magnesium bromide, which is a kind of tetrakis(fluoroaryl)borate.magnesium halide, from bromopentafluorobenzene through the Grignard reaction is disclosed in, for example, Japanese Laid-open Patent Application No. 247980/1994 (Tokukaihei No. 6-247980).
Also, in Japanese Laid-open Patent Application No. 247981/1994 (Tokukaihei No. 6-247981), a process of synthesizing tetrakis(pentafluorophenyl)borate.lithium from pentafluorobenzene using an organic lithium compound and boron halide first, and thence reacting the resulting compound with N,N-dimethylaniline.hydrochloride is disclosed as a producing process of a tetrakis(pentafluorophenyl)borate derivative, which is a kind of the tetrakis(fluoroaryl)borate derivative.
Further, a producing process of the tetrakis(pentafluorophenyl)borate derivative by reacting tetrakis(pentafluorophenyl)borate.magnesium bromide with N,N-dimethylaniline.hydrochloride is disclosed in U.S. Pat. No. 5,473,036.
However, Japanese Laid-open Patent Application No. 247980/1994 (Tokukaihei No. 6-247980) neither discloses nor implies the separation/removal of magnesium halide, a by-product produced with tetrakis(pentafluorophenyl)borate.magnesium bromide, from the reaction series. If the tetrakis(pentafluorophenyl)borate derivative is produced from tetrakis(pentafluorophenyl)borate.magnesium bromide containing magnesium halide as impurities, and used as a co-catalyst of the metallocene catalyst, for example, the activity of the metallocene catalyst deteriorates considerably. The process disclosed in Japanese Laid-open Patent Application No. 247980/1994 (Tokukaihei No. 6-247980) is a producing process of tetrakis(pentafluorophenyl)borate.magnesium bromide containing magnesium halide as impurities. Thus, tetrakis(pentafluorophenyl)borate.magnesium bromide obtained through this process can not be used as an adequate intermediate for producing the tetrakis(pentafluorophenyl)borate derivative.
If typical alkali treatment is applied to tetrakis(pentafluorophenyl)borate.magnesium bromide to remove magnesium halide from tetrakis(pentaflurorphenyl)borate.magnesium bromide obtained by the process disclosed in the above publication, magnesium hydroxide is produced. Since magnesium hydroxide turns a post-treatment solution into gel, the solution can not be filtered. In other words, since magnesium halide can not be removed by the typical alkali treatment, it is difficult to separate tetrakis(pentafluorophenyl)borate.magnesium bromide obtained in the above process, or to obtain a highly-pure tetrakis(fluoroaryl)borate compound after the treatment.
Thus, there has been an increasing demand for a purifying process for separating/removing impurities, such as magnesium halide, from tetrakis(fluoroaryl)borate.magnesium halide readily and efficiently.
On the other hand, the process disclosed in Japanese Laid-open Patent Application No. 247981/1994 (Tokukaihei No. 6-247981) has the following problems:
(1) since the reaction series must be kept at -65.degree. C. or below, not only special equipment is required, but also the cooling cost is high; PA1 (2) the process demands an expensive organic lithium compound (t-butyl lithium), which is a dangerous compound because it may ignite when reacted with water and the like; PA1 (3) the process also demands expensive boron halide (boron trichloride), which is very difficult to handle because it is in the gaseous state and corrosive. Thus, the process disclosed in the above publication can not be readily adopted for industrial use. PA1 the impurities, such as magnesium halide, can be readily and efficiently separated/removed from tetrakis(fluoroaryl)borate.magnesium halide by treating tetrakis(fluoroaryl)borate.magnesium halide with, for example, alkali metal salts of carboxylic acid and/or alkali earth metal salts of carboxylic acid; and PA1 an inexpensive and highly-pure tetrakis(fluoroaryl)borate derivative, which is useful as, for example, a co-catalyst of the metallocene catalyst or a photopolymeric catalyst for silicone, can be produced efficiently by reacting a tetrakis(fluoroaryl)borate compound obtained through the above purifying process with a compound generating monovalent cationic seeds. PA1 1 alkali metal salts of carboxylic acid and/or alkali earth metal salts of carboxylic acid; PA1 2 an acid; PA1 3 an acid followed by alkali metal hydroxide and/or alkaline earth metal hydroxide; or PA1 4 an acid followed by alkali metal salts of carboxylic acid and/or alkaline earth metal salts of carboxylic acid. PA1 with an ether compound expressed by General Formula (6): EQU R.sub.11 --O--Y--O--R.sub.12 (6) PA1 where each of R.sub.11 and R.sub.12 represents a hydrocarbon group which may include a substituent group containing a hetero atom, and Y represents a hydrocarbon bivalent group. PA1 1 alkali metal salts of carboxylic acid and/or alkali earth metal salts of carboxylic acid; PA1 2 an acid; PA1 3 an acid followed by alkali metal hydroxide and/or alkaline earth metal hydroxide; or PA1 4 an acid followed by alkali metal salts of carboxylic acid and/or alkaline earth metal salts of carboxylic acid. PA1 ether solvents, such as diethyl ether, diisopropyl ether, dibutyl ether, and anisole; PA1 aliphatic hydrocarbon solvents, such as pentane, hexane, and heptane; PA1 alicyclic hydrocarbon solvents, such as cyclopentane and cyclohexane; PA1 aromatic hydrocarbon solvents, such as benzene and toluene; etc. PA1 alkali metal salts of saturated aliphatic monocarboxylic acid, such as sodium formate, potassium formate, sodium acetate, potassium acetate, sodium propionate, and potassium propionate; PA1 mono- or dialkali metal salts of saturated aliphatic dicarboxylic acid, such as sodium oxalate monobasic, sodium oxalate dibasic, potassium oxalate monobasic, potassium oxalate dibasic, sodium malonate monobasic, sodium malonate dibasic, potassium malonate monobasic, potassium malonate dibasic, sodium succinate monobasic, sodium succinate dibasic, potassium succinate monobasic, and potassium succinate dibasic; PA1 alkali metal salts of unsaturated aliphatic monocarboxylic acid, such as sodium acrylate, potassium acrylate, sodium methacrylate, and potassium methacrylate; PA1 mono- or dialkali metal salts of unsaturated aliphatic dicarboxylic acid, such as sodium maleate monobasic, sodium maleate dibasic, potassium maleate monobasic, potassium maleate dibasic, sodium fumarate monobasic, sodium fumarate dibasic, potassium fumarate monobasic, and potassium fumarate dibasic; PA1 alkali metal salts of aromatic monocarboxylic acid, such as sodium benzoate and potassium benzoate; PA1 mono- or dialkali metal salts of aromatic dicarboxylic acid, such as sodium phthalate monobasic, sodium phthalate dibasic, potassium phthalate monobasic, potassium phthalate dibasic, sodium isophthalate monobasic, sodium isophthalate dibasic, potassium isophthalate monobasic, potassium isophthalate dibasic, sodium terephthalate monobasic, sodium terephthalate dibasic, potassium terephthalate monobasic, and potassium terephthalate dibasic; etc. PA1 alkaline earth metal salts of saturated aliphatic monocarboxylic acid, such as calcium formate, barium formate, calcium acetate, barium acetate, calcium propionate, and barium propionate; PA1 alkaline earth metal salts of saturated aliphatic dicarboxylic acid, such as calcium oxalate, barium oxalate, calcium malonate, barium malonate, calcium succinate, and barium succinate; PA1 alkaline earth metal salts of unsaturated aliphatic monocarboxylic acid, such as calcium acrylate, barium acrylate, calcium methacrylate, and barium methacrylate; PA1 alkaline earth metal salts of unsaturated aliphatic dicarboxylic acid, such as calcium maleate, barium maleate, calcium fumarate, and barium fumarate; PA1 alkaline earth metal salts of aromatic monocarboxylic acid, such as calcium benzoate and barium benzoate; PA1 alkaline earth metal salts of aromatic dicarboxylic acid, such as calcium phthalate, barium phthalate, calcium isophthalate, barium isophthalate, calcium terephthalate, and barium terephthalate; etc. In the present invention, the alkaline earth metal salts of carboxylic acid include carbonates, such as calcium carbonate and barium carbonate. Note that, however, in the present invention, the alkaline earth metal salts of carboxylic acid do not include magnesium salts of carboxylic acid. PA1 inorganic acids, such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and carbonic acid; PA1 organic acids, such as formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, and succinic acid; etc. PA1 water; PA1 ether solvents, such as diethyl ether, diisopropyl ether, dibutyl ether, and anisole; PA1 aliphatic hydrocarbon solvents, such as pentane, hexane, and heptane; PA1 alicyclic hydrocarbon solvents, such as cyclopentane and cyclohexane; PA1 ester solvents, such as methyl acetate and ethyl acetate; PA1 aromatic hydrocarbon solvents, such as benzene and toluene; treating tetrakis(fluoroaryl)borate.magnesium halide with the acid followed by the hydroxide or carboxylate is not especially limited. For example, the acid can be readily separated from a solution of the tetrakis(fluoroaryl)borate compound by a simple manipulation, such as liquid separation (oil-water separation). After the treatment, the tetrakis(fluoroaryl)borate compound is obtained in the form of a solution dissolved into the solvent. PA1 alcohol solvents, such as methyl alcohol and ethyl alcohol; PA1 ketone solvents, such as acetone and methyl ethyl ketone; etc. PA1 1 a process of treating tetrakis(fluoroaryl)borate.magnesium halide with carboxylate; PA1 2 a process of treating tetrakis(fluoroaryl)borate.magnesium halide with an acid; PA1 3 a process of treating tetrakis(fluoroaryl)borate.magnesium halide with an acid followed by the hydroxide; and PA1 4 a process of treating tetrakis(fluoroaryl)borate.magnesium halide with an acid followed by the carboxylate. PA1 ammonium cations, such as n-butyl ammonium, dimethyl ammonium, trimethyl ammonium, triethyl ammonium, triisopropyl ammonium, tri-n-butyl ammonium, tetramethyl ammonium, tetraethyl ammonium, and tetra-n-butyl ammonium; PA1 anilinium cations, such as anilinium, N-methyl anilinium, N,N-dimethyl anilinium, N,N-diethyl anilinium, N,N-diphenyl anilinium, and N,N,N-trimethyl anilinium; PA1 pyridinium cations, such as pyridinium, N-methyl pyridinium, and N-benzyl pyridinium; PA1 quinolinium cations, such as quinolinium and isoquinolinium; PA1 phosphonium cations, such as dimethylphenyl phosphonium, triphenyl phosphonium, tetraethyl phosphonium, and tetraphenyl phosphonium; PA1 sulfonium cations, such as trimethyl sulfonium and triphenyl sulfonium; PA1 iodonium cations, such as diphenyl iodonium and di-4-methoxy phenyl iodonium; PA1 carbenium cations, such as triphenyl carbenium and tri-4-methoxyphenyl carbenium; PA1 monovalent cations of metals other than alkali metal and alkali earth metal; etc. PA1 quaternary ammonium compounds, such as tri-n-butylamine.hydrochloride, N,N-dimethylaniline.hydrochloride, N,N-dimethylaniline.sulfate, and tetramethyl ammonium chloride; PA1 nitrogen-containing aromatic heterocyclic compounds, such as pyridine hydrochloride, quinoline.hydrochloride, N-methyl pyridine iodide, and N-methyl quinoline iodide; PA1 quaternary phosphonium compounds, such as n-butylphosphonium bromide and tetraphenyl phosphonium bromide; PA1 sulfonium compounds, such as trimethyl sulfonium iodide; PA1 iodinium compounds, such as diphenyl iodinium chloride; PA1 carbenium compounds, such as trityl chloride; etc. PA1 water; PA1 ether solvents, such as diethyl ether, diisopropyl ether, dibutyl ether, and anisole; PA1 aliphatic hydrocarbon solvents, such as pentane, hexane, and heptane; PA1 alicyclic hydrocarbon solvents, such as cyclopentane and cyclohexane; PA1 ester solvents, such as methyl acetate and ethyl acetate; PA1 aromatic hydrocarbon solvents, such as benzene and toluene; PA1 alcohol solvents, such as methyl alcohol and ethyl alcohol; PA1 ketone solvents, such as acetone and methyl ethyl ketone; etc. PA1 a method of mixing the tetrakis(fluoroaryl)borate compound and cation seed generating compound with the reaction solvent; PA1 a method of mixing the cation seed generating compound or a solution thereof with a solution of the tetrakis(fluoroaryl)borate compound; PA1 a method of mixing the tetrakis(fluoroaryl)borate compound or a solution thereof with a solution of the cation seed generating compound; etc. PA1 substituents containing oxygen atoms, such as an alkoxy group, an aryloxy group, a cycloalkyloxy group, and an acyloxy group; PA1 substituents containing nitrogen atoms, such as a dialkyl amino group; PA1 substituents containing sulfur atoms, such as an alkylthio group and an arylthio group; etc. PA1 The hydrocarbon bivalent group is preferably a bivalent group selected from the group consisting of an alkylene group having up to six carbon atoms as a carbon chain linking two oxygen atoms, namely, a methylene group possibly having a substituent, an ethylene group possibly having a substituent, a trimethylene group possibly having a substituent, a tetramethylene group possibly having a substituent, a pentamethylene group possibly having a substituent, and a hexamethylene group possibly having a substituent. It is more preferable that the substituent in the bivalent group is an alkyl group having up to six carbon atoms. PA1 ethylene glycol dialkyl ether, such as 1,2-dimethoxy ethane, 1,2-diethoxy ethane, ethylene glycol di-n-propyl ether, ethylene glycol diisopropyl ether, ethylene glycol di-n-butyl ether, ethylene glycol diisobutyl ether, ethylene glycol di-sec-butyl ether, ethylene glycol di-t-butyl ether, ethylene glycol dipentyl ether, ethylene glycol dineopentyl ether, ethylene glycol dihexyl ether, ethylene glycol diheptyl ether, ethylene glycol dioctyl ether, ethylene glycol dinonyl ether, and ethylene glycol didecyl ether; PA1 ethylene glycol dicycloalkyl ether, such as ethylene glycol dicyclopropyl ether, ethylene glycol dicyclo butyl ether, ethylene glycol dicyclopentyl ether, ethylene glycol dicyclohexyl ether, ethylene glycol diheptyl ether, ethylene glycol dicyclo octyl ether, ethylene glycol dicyclo nonyl ether, and ethylene glycol dicyclo decyl ether; PA1 unsymetric ethylene glycol methyl alkyl ether, such as ethylene glycol methyl ethyl ether, ethylene glycol methyl isopropyl ether, and ethylene glycol methyl butyl ether; PA1 diethylene glycol dialkyl ether, such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol diisopropyl ether, diethylene glycol dibutyl ether, diethylene glycol dipentyl ether, diethylene glycol dihexyl ether, diethylene glycol diheptyl ether, diethylene glycol dioctyl ether, diethylene glycol dinonyl ether, and diethylene glycol didecyl ether; PA1 triethylene glycol dialkyl ether, such as triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol diisopropyl ether, triethylene glycol dibutyl ether, triethylene glycol dipentyl ether, triethylene glycol dihexyl ether, triethylene glycol diheptyl ether, triethylene glycol dioctyl ether, triethylene glycol dinonyl ether, and triethylene glycol didecyl ether; PA1 ethylene glycol dialkyl ether having an acyloxy group, such as diethylene glycol monoethyl ether acetate and diethylene glycol monoethyl ether methacrylate; PA1 ethylene glycol dialkyl ether having an alkylthio group, such as ethylene glycol di-2-methylthio ethyl ether; PA1 ethylene glycol dialkyl ether having a dialkyl amino group, such as ethylene glycol di-2-dimethyl amino ethyl ether; PA1 ethylene glycol diaryl ether, such as ethylene glycol diphenyl ether; PA1 diethylene glycol diaryl ether, such as diethylene glycol diphenyl ether; PA1 triethylene glycol diaryl ether, such as triethylene glycol diphenyl ether; PA1 ethylene glycol dibenzyl ether; etc. PA1 ether solvents, such as diethyl ether, diisopropyl ether, dibutyl ether, and anisole; PA1 aliphatic hydrocarbon solvents, such as pentane, hexane, and heptane; PA1 alicyclic hydrocarbon solvents, such as cyclopentane and cyclohexane; PA1 ester solvents, such as methyl acetate and ethyl acetate; PA1 aromatic hydrocarbon solvents, such as benzene and toluene; etc. PA1 a first producing process, in which, after tetrakis(fluoroaryl)borate is obtained by removing the polyfunctional ether from the tetrakis(fluoroaryl)borate ether complex, the resulting tetrakis(fluoroaryl)borate is reacted with the cation seed generating compound; PA1 a second producing process, in which, after the tetrakis(fluoroaryl)borate derivative.ether complex is obtained by reacting the tetrakis(fluoroaryl)borate ether complex with the cation seed generating compound, the polyfunctional ether is removed from the resulting tetrakis(fluoroaryl)borate derivative.ether complex.
In the process disclosed in U.S. Pat. No. 5,473,036, magnesium hydroxide is produced as a by-product with the object product, that is, the tetrakis(pentafluorophenyl)borate derivative. Since magnesium hydroxide turns a post-treatment solution into gel, it is difficult to separate (isolate) the tetrakis(pentafluorophenyl)borate derivative from the solution. Thus, there arises a problem that the tetrakis(pentafluorophenyl)borate derivative can not be produced efficiently.
In other words, the conventional producing processes have a problem that an inexpensive and highly-pure tetrakis(fluoroaryl)borate derivative can not be produced efficiently. Hence, there has been an increasing demand for a process of producing an inexpensive and highly-pure tetrakis(fluoroaryl)borate derivative efficiently.
Therefore, it is a first object of the present invention to provide a purifying process of separating/removing impurities, such as magnesium halide, from tetrakis(fluoroaryl)borate.magnesium halide readily and efficiently. Also, it is a second object of the present invention to provide a process of efficiently producing an inexpensive and highly-pure tetrakis(fluoroaryl)borate derivative, which is useful as, for example, a co-catalyst of the metallocene catalyst or a photopolymeric catalyst for silicone.
A producing process of tetrakis(pentafluorophenyl)borate, which is useful as an intermediate for producing the tetrakis(pentafluorophenyl)borate derivatives of various kinds, has been known.
For example, a process of obtaining tetrakis(pentafluorophenyl)borate.lithium by reacting pentafluorophenyl lithium, which is produced by reacting pentafluorophenyl bromide with butyl lithium at -78.degree. C. in dry pentane, with tris(pentafluorophenyl)borate at -78.degree. C. in dry pentane is disclosed in p245, J. Organometallic. Chem., 2, (1964).
Also, aforementioned Japanese Laid-open Patent Application No. 247981/1994 (Tokukaihei No. 6-247981) discloses a preparing process of tetrakis(pentafluorophenyl)borate.lithium used in the producing process of N,N-dimethyl anilinium.tetrakis(pentafluorophenyl)borate from N,N-dimethylaniline.hydrochloride as follows.
That is, the above publication discloses a preparing process, in which pentafluorophenyl lithium is produced initially by reacting pentafluorophenyl bromide with t-butyl lithium at -65.degree. C. in dry diethyl ether, and then tetrakis(pentafluorophenyl)borate.lithium is prepared by reacting the resulting pentafluorophenyl lithium with boron trichloride at -65.degree. C. to -55.degree. C. in dry pentane.
However, the process disclosed in p245, J. Organometallic. Chem., 2, (1964) has a problem that the yield of tetrakis(pentafluorophenyl)borate.lithium is low (43%). Also, since the process disclosed in aforementioned Japanese Laid-open Patent Application No. 247981/1994 (Tokukaihei No. 6-247981) has the above-explained problem, it can not be readily applied to industrial use.
On the other hand, aforementioned Japanese Laid-open Patent Application No. 247980/1994 (Tokukaihei No. 6-247980) discloses a process of obtaining the tetrakis(pentafluorophenyl)borate derivative by reacting pentafluorophenyl magnesium bromide, which is a Grignard reagent, with a boron trifluoride.diethyl ether complex.
Also, aforementioned U.S. Pat. No. 5,473,036 discloses a process of obtaining tetrakis(pentafluorophenyl)borate.magnesium bromide by reacting pentafluorophenyl magnesium bromide, which is a Grignard reagent, with a boron trifluoride.diethyl ether complex, and a process of obtaining N,N-dimethyl anilinium.tetrakis(pentafluorophenyl)borate by reacting tetrakis(pentafluorophenyl)borate.magnesium bromide with an aqueous solution of N,N-dimethylaniline.hydrochloride.
However, in the process disclosed in Japanese Laid-open Patent Application No. 247980/1994 (Tokukaihei No. 6-247980), magnesium halide, such as magnesium bromide fluoride (MgBrF), produced as a by-product with tetrakis(pentafluorophenyl)borate.magnesium bromide, is not separated/removed from the reaction series and remains therein as impurities. Thus, as previously mentioned, if the tetrakis(pentafluorophenyl)borate derivative is produced from tetrakis(pentafluorophenyl)borate.magnesium bromide containing magnesium halide as impurities and used as a co-catalyst of the metallocene catalyst, for example, the activity of the metallocene catalyst deteriorates considerably.
Further, in the processes disclosed in U.S. Pat. No. 398,236 and Japanese Laid-open Patent Application No. 247980/1994 (Tokukaihei No. 6-247980), resulting tetrakis(pentafluorophenyl)borate.magnesium bromide is colored with a coloring component derived from the Grignard reaction. Thus, if the tetrakis(pentafluorophenyl)borate derivative is produced from tetrakis(pentafluorophenyl)borate.magnesium bromide obtained in either of the above processes, there arises a problem that the coloring component remains in the tetrakis(pentafluorophenyl)borate derivative (the tetrakis(pentafluorophenyl)borate derivative is colored).
The producing process of tetrakis(pentafluorophenyl)borate derivative disclosed in U.S. Pat. No. 5,473,036 also has the following problem. That is, in the above process, a post-treatment solution is turned into gel by magnesium hydroxide produced as a by-product. Thus, it is difficult to filter the solution and isolate the tetrakis(pentafluorophenyl)borate derivative from the solution. Also, to isolate the tetrakis(pentafluorophenyl)borate derivative in the above process, a crude product must be crystallized again using a chlorine solvent, such as chloroform and dichloroethane.
As has been explained, since tetrakis(fluoroaryl)borate.magnesium bromide obtained by the conventional processes contains the by-product salts and coloring component as impurities, it can not be used as an adequate intermediate for producing the tetrakis(fluoroaryl)borate derivative. Hence, there has been an increasing demand for a tetrakis(fluoroaryl)borate derivative which can be used as a suitable intermediate for producing the tetrakis(fluoroaryl)borate derivatives of various kinds.
It is therefore a third object of the present invention to provide a tetrakis(fluoroaryl)borate ether complex as a new material which can be used suitably as a co-catalyst of the metallocene catalyst, a cationic polymerization initiator, an intermediate for producing the tetrakis(fluoroaryl)borate derivatives of various kinds and the like, and a producing process of the same.
Also, the conventional producing processes of the tetrakis(fluoroaryl)borate derivative from tetrakis(fluoroaryl)borate prepared using an organic lithium compound or a Grignard reagent has a problem that an inexpensive and highly-pure tetrakis(fluoroaryl)borate derivative can not be produced efficiently.
It is therefore a fourth object of the present invention to provide a producing process of an inexpensive and highly-pure tetrakis(fluoroaryl)borate derivative efficiently. Also, it is a fifth object of the present invention to provide a producing process of highly-pure tetrakis(fluoroaryl)borate. Further, it is a sixth object of the present invention to provide a tetrakis(fluoroaryl)borate derivative.ether complex as a new material, which is useful not only as an intermediate for producing the tetrakis(fluoroaryl)borate derivative, but also as a co-catalyst of the metallocene catalyst (polymeric catalyst) used in the cationic complex polymerization reaction, and a producing process of the same. Furthermore, it is a seventh object of the present invention to provide a producing process of an inexpensive tetrakis(fluoroaryl)borate derivative from the tetrakis(fluoroaryl)borate derivative.ether complex efficiently.
To fulfill the first and second objects, the inventors of the present invention conducted an assiduous study on the purifying process of tetrakis(fluoroaryl)borate.magnesium halide and the producing process of the tetrakis(fluoroaryl)borate derivative. In due course, the inventors achieved the present invention when they discovered that:
In other words, to fulfill the above objects, a purifying process of tetrakis(fluoroaryl)borate.magnesium halide of the present invention is characterized by treating tetrakis(fluoraryl)borate.magnesium halide expressed by General Formula (1): ##STR2##
where each of R.sub.1 -R.sub.10 represents a hydrogen atom, a fluorine atom, a hydrocarbon group, or an alkoxy group, provided that at least one of R.sub.1 -R.sub.5 represents a fluorine atom and at least one of R.sub.6 -R.sub.10 represents a fluorine atom, X represents a chlorine atom, a bromine atom, or an iodide atom, and n represents 2 or 3, with:
According to the above process, magnesium halide, such as magnesium bromide fluoride, produced as a by-product during the producing process of tetrakis(fluoroaryl)borate.magnesium halide through the Grignard reaction can be turned into water-soluble or water-insoluble magnesium salts (that is, in the state of salts other than magnesium hydroxide). Thus, the salts can be readily and efficiently separated/removed from tetrakis(fluoroaryl)borate.magnesium halide through oil-water separation, filtration or the like. In short, the impurities, such as magnesium halide, can be readily and efficiently separated/removed from tetrakis(fluoroaryl)borate.magnesium halide.
When tetrakis(fluoroaryl)borate.magnesium halide is treated with the purifying process 1, 3 or 4, alkali metal salts and/or alkali earth metal salts of tetrakis(fluoroaryl)borate can be obtained. When tetrakis(fluoroaryl)borate.magnesium halide is treated with the purifying process 2, hydrogen compound of tetrakis(fluoroaryl)borate can be obtained.
A producing process of a tetrakis(fluoroaryl)borate derivative of the present invention relates to a producing process of a tetrakis(fluoroaryl)borate derivative expressed by General Formula (2): ##STR3##
where each of R.sub.1 -R.sub.10 represents a hydrogen atom, a fluorine atom, a hydrocarbon group, or an alkoxy group, provided that at least one of R.sub.1 -R.sub.5 represents a fluorine atom and at least one of R.sub.6 -R.sub.10 represents a fluorine atom, Z.sup.+ represents a monovalent cation seed, and n represents 2 or 3, and is characterized by reacting a tetrakis(fluoroaryl)borate compound obtained by any of the purifying processes 1-4 with a compound generating monovalent cation seeds.
According to the above process, an inexpensive tetrakis(fluoroaryl)borate derivative can be produced efficiently from the tetrakis(fluoroaryl)borate compound obtained through any of the above purifying processes, namely, alkali metal salts, alkaline earth metal salts, and hydrides of tetrakis(fluoroaryl)borate. The resulting tetrakis(fluoroaryl)borate derivative does not contain the impurities, such as magnesium halide, and therefore is so pure that it can be used suitably as, for example, a co-catalyst of the metallocene catalyst used in the cationic complex polymerization reaction or photopolymeric catalyst for silicone.
Also, to fulfill the third object, the inventors of the present invention conducted an assiduous study on the tetrakis(fluoroaryl)borate ether complex and the producing process of the same. In due course, the inventors discovered that an inexpensive and highly-pure tetrakis(fluoroaryl)borate ether complex as a new material, which can be suitably used as an intermediate for producing the tetrakis(fluoroaryl)borate derivatives of various kinds, can be obtained at high yield by reacting tetrakis(fluoroaryl)borate with a particular kind of ether compound.
In addition, the inventors achieved the present invention when they also discovered that even when tetrakis(fluoroaryl)borate.magnesium halide containing a coloring component derived from the Grignard reaction and by-product salts, such as magnesium bromide fluoride (MgBrF) produced as a by-product in the Grignard reaction, is used as a raw material, that is, tetrakis(fluoroaryl)borate, a tetrakis(fluoroaryl)borate ether complex can be obtained in the form of highly-pure crystals, from which the coloring component and by-product salts can be readily separated/removed.
In other words, a producing process of a tetrakis(fluoroaryl)borate ether complex of the present invention relates to a producing process of a tetrakis(fluoroaryl)borate ether complex expressed by General Formula (4): ##STR4##
where each of R.sub.1 -R.sub.10 represents a hydrogen atom, a fluorine atom, a hydrocarbon group, or an alkoxy group, provided that at least one of R.sub.1 -R.sub.5 represents a fluorine atom and at least one of R.sub.6 -R.sub.10 represents a fluorine atom, each of R.sub.11 and R.sub.12 represents a hydrocarbon group which may include a substituent group containing a hetero atom, Y represents a hydrocarbon bivalent group, M represents a hydrogen atom, alkali metal, alkaline earth metal, or alkaline earth metal halide, n represents 2 or 3, and m represents 1 when M represents a hydrogen atom, alkali metal, or alkaline earth metal halide, and 2 when M represents alkali earth metal, and is characterized by reacting tetrakis(fluoroaryl)borate expressed by General Formula (5): ##STR5##
where each of R.sub.1 -R.sub.10 represents a hydrogen atom, a fluorine atom, a hydrocarbon group, or an alkoxy group, provided that at least one of R.sub.1 -R.sub.5 represents a fluorine atom and at least one of R.sub.6 -R.sub.10 represents a fluorine atom, M represents a hydrogen atom, alkali metal, alkaline earth metal, or alkaline earth metal halide, n represents 2 or 3, and m represents 1 when M represents a hydrogen atom, alkali metal, or alkaline earth metal halide, and 2 when M represents alkali earth metal,
According to the above process, an inexpensive and highly-pure tetrakis(fluoroaryl)borate ether complex as a new material suitably used as, for example, a co-catalyst of the metallocene catalyst, a cationic polymerization initiator, or an intermediate for producing the tetrakis(fluoroaryl)borate derivatives of various kinds, can be produced at high yield.
Also, according to the above process, even when a raw material, that is, tetrakis(fluoroaryl)borate, contains the impurities, a highly-pure tetrakis(fluoroaryl)borate ether complex from which the impurities are removed can be obtained. The tetrakis(fluoroaryl)borate ether complex obtained through the above process is so pure that it can be used suitably as, for example, a co-catalyst of the metallocene catalyst, a cationic polymerization initiator, or an intermediate for producing the tetrakis(fluoroaryl)borate derivatives of various kinds.
Further, to fulfill the fourth through seventh objects, the inventors of the present invention conducted an assiduous study. In due course, the inventors achieved the present invention when they discovered that an inexpensive and highly-pure tetrakis(fluoroaryl)borate derivative can be produced efficiently when both a particular kind of tetrakis(fluoroaryl)borate ether complex and a compound generating monovalent cation seeds are used as a starting material.
In other words, to fulfill the above objects, a producing process of the tetrakis(fluoroaryl)borate derivative of the present invention expressed by General Formula (2) above is characterized by using both the tetrakis(fluoroaryl)borate ether complex expressed by General Formula (4) above and a compound generating monovalent cation seeds as a starting material.
According to the above process, since the tetrakis(fluoroaryl)borate ether complex expressed by General Formula (4) above, which can be readily and highly purified compared with tetrakis(fluoroaryl)borate, is used as the starting material, the tetrakis(fluoroaryl)borate derivative expressed by General Formula (2) above can be produced efficiently with high purity at low costs.
In addition, to fulfill the above objects, a producing process of tetrakis(fluoroaryl)borate expressed by General Formula (5) above is characterized by removing the ether compound expressed by General Formula (6) above from the tetrakis(fluoroaryl)borate ether complex expressed by General Formula (4) above.
According to the above processes, since the tetrakis(fluoroaryl)borate ether complex expressed by General Formula (4) above, which can be readily and highly purified compared with tetrakis(fluoroaryl)borate, borate ether complex expressed by General Formula (4) above with a compound generating monovalent cation seeds.
According to the above process, the tetrakis(fluoroaryl)borate derivative.ether complex expressed as General Formula (7) above as a new, useful material for an intermediate in producing the tetrakis(fluoroaryl)borate derivative can be produced.
Further, to fulfill the above objects, a producing process of the tetrakis(fluoroaryl)borate derivative of the present invention expressed by General Formula (2) above is characterized by removing the ether compound expressed by General Formula (6) above from the tetrakis(fluoroaryl)borate derivative.ether complex expressed by General Formula (7) above.
According to the above process, the tetrakis(fluoroaryl)borate derivative expressed by General Formula (2) above can be produced from the tetrakis(fluoroaryl)borate derivative.ether complex expressed by General Formula (7) above efficiently at low costs.

Method for purifying tetrakis (fluoroaryl) borate/magnesium halide, tetrakis (fluoroaryl) borate/ether complex and process for preparing the same, and process for preparing tetrakis (fluoroaryl) borate derivative


An automatic matchplate molding machine, used to form sand cope and drag molds, includes a basin former to create a pouring basin in the cope mold. The basin former includes a two-piece liner, one of the pieces being a relatively short and inexpensive plastic sleeve which may be replaced at a relatively low cost when wear occurs. Air passages in the liner channel air into the center of the liner, creating a swirling air current, thereby blowing loose sand out of the liner.

This invention relates to a molding machine and more particularly to an automatic matchplate molding machine of the type in which a pattern plate is located between cope and drag flasks adapted to be filled with sand and adapted to be rammed upwardly toward a squeeze head in order to pack the sand and form cope and drag molds in the cope and drag flasks, respectively. A machine of this general type is disclosed in Hunter U.S. Pat. No. 4,840,218.
The pattern plate of such a machine carries an upwardly projecting sprue former which forms a sprue in the cope mold. Coacting with the sprue former is a basin former which creates a pouring basin in the upper side of the cope mold around the sprue. The basin former is carried by the squeeze head and telescopically receives the sprue former when the cope flask and the pattern plate are rammed upwardly toward the squeeze head. When the two formers are telescoped together, a small sand core may be created in the basin former and may fall downwardly into the pouring basin and the sprue when the cope flask and the cope mold are retracted downwardly from the squeeze head.
To prevent loose sand from falling downwardly when the cope flask and cope mold are retracted, a one-piece plastic liner with means for injecting pressurized air through the side of the liner has been employed to blow sand in the basin former out of the upper end thereof and away from the mold. A liner of this type is disclosed in Hunter U.S. Pat. No. 5,069,268. During operation, the liner telescopically receives the sprue former and, as a result of repeated sliding of the sprue former within the liner, the latter wears and eventually must be replaced. The one-piece liner of the '268 patent is comparatively large and thus is relatively expensive to replace.

Two-piece liner for use in a matchplate molding machine


A semiconductor package is disclosed for an integrated circuit die (52). The integrated circuit die is electrically connected to the package substrate by either die solder balls (53a), or wirebonds (53b). The package substrate (50), a single sided printed wiring board, has a thick metal core (100), consisting of a base metal, a core capacitor, and one or more thin build up layers.

A semiconductor package mounts an integrated circuit die, and provides electrical and thermal connections between the die and an electronic subsystem, while also providing mechanical and environmental protection to the die. A ball grid array package performs these functions by mounting the die on a substrate. The electrical pads of the die are attached to conductive traces on the substrate. Electrical connections between the die and the substrate have been made by wirebond, solder balls, or TAB. The conductive traces on the substrate fanout from the die to an array of package pads. Each package pad has a package solder ball, which makes electrical contact to a pad on an electronic subsystem circuit board. The substrate is mounted flush to the circuit board, separated by the diameter of the package solder balls. The substrate has been fabricated in various technologies; such as printed wiring board, multilayer ceramic, or polyimide flex circuit.
A known problem with ball grid array package is mechanical fatigue of the package solder balls. There is a thermal coefficient of expansion (TCE) mismatch between the package and the circuit board. During power on/off cycles the package and board heat at different rates, and operate at different temperatures, so their expansion and contraction is not uniform. The difference in expansion causes strain across the package solder balls, resulting in reliability fails from fatigue. It is advantageous to match the TCE of the package to the TCE of the circuit board, thereby minimizing differences in expansion and the strain across the solderballs and reducing reliability failures from fatigue.
In a cavity up design the die is mounted on one side of the substrate and electrical connections to the circuit board are made on the opposite side of the substrate. The electrical connections between the die and the substrate are made by wirebond, TAB or solder balls. As the electrical connections to the die and the circuit board are on opposite sides, it is necessary to include and provide electrical vias through, and connecting both sides of the substrate. As the pitch of the array of package pads is reduced from 1.27 mm or 1.0 mm to 0.8 mm, 0.65 mm, or 0.5 mm, the through via consumes a larger percentage of area on the substrate. This blocks the routing of the conductive traces, and requires the use of a more expensive substrate technology.
For solder ball attached die there is also a TCE mismatch, this time between the die and the substrate. Again, it is advantageous to match both TCEs, the TCE of the die to the TCE of the substrate to reduce the fatigue failure of the die solder balls, and improve reliability. However, the TCE of a silicon die is 2 ppm/C and the TCE of a typical circuit board is 18 ppm/C, so it is not possible to match the TCE of the substrate to both the die and the circuit board. However it is beneficial to be able to engineer and design the TCE of the substrate to obtain optimum reliability.
Also for a solder ball attached die, the back of the die is exposed and a heatspreader may be attached to improve the thermal performance. The structure (substrate/die solder balls/die/adhesive/heatspreader) sandwiches the die between the substrate and the heatspreader. This sandwich structure is mechanically complex, and the components have different thermal TCE and often operate at different temperatures. Compared to a structure without a heatspreader, there is more stress on the die solder balls in the sandwich structure during thermal cycles and an increase in reliability failures. Again, it is beneficial to be able to engineer and design the TCE of the substrate to obtain optimum reliability.
There is a trade-off in adjusting the TCE of the substrate to match the die for improved die solder ball reliability and to match the circuit board for package solder ball reliability. Key factors when evaluating fatigue are the attached area (size of die and package) and the diameter of the solder balls (both die and package), which provide the separation between materials with different TCEs. When the pitch on the solder balls (die or package) is reduced, the diameter of the solder balls must also be reduced, and the distance is less between the materials with different TCEs. This reduced distance increases the stress on the solderballs, and therefore will cause higher fatigue for a given TCE mismatch. Therefore as technology shrinks it becomes increasingly beneficial to have the ability to engineer and design the TCE of the substrate for an optimum reliability.
In a cavity down design the same side of the package is used to mount the die and to make electrical connections to the circuit board. However, as the package is mounted flush to the circuit board, there is limited space to contain the integrated circuit die 10. Typically a hole is stamped, punched, or milled in the substrate 11 and then the substrate is attached to a support member 12 with an adhesive 13. The support member provides mechanical rigidity and is also a thermal heatspreader. The substrate is typically a polyimide flex circuit or a printed wiring board. The support member has a recess 14, which provides a space to contain the die. The multi-step process; fabricate substrate, excise hole, and laminate heatspreader increases package cost and design complexity. As an option, the support member is electrically connected to the substrate circuitry to improve performance. This electrical connection requires additional process steps and materials during the substrate attachment process, and therefore adds cost. In U.S. Pat. No. 5,420,460 (Massingill) the edge of the stamped hole 15a is outside the recess, and in U.S. Pat. No. 5,869,889 (Chia et al) the edge of the stamped hole 15b is inside the recess. The die is adhesively attached to the support member, and wirebonds 16 electrically connect the die to the circuitry on the substrate. The recess, die and wirebonds are coated with epoxy encapsulation 17 for environmental protection. Package solder balls 18 are attached to the array of package pads to complete the package.
The process of making the recess, removes a portion or all of the substrate in the recess area, and therefore removes the capability of having substrate circuitry in the total recess area. As the circuitry has been removed, the ability for attaching a die with solder balls is not available, and solder ball attached the die are not used.
As the clock rates and power of semiconductor die increase, power supply noise becomes a more serious problem. It becomes desirable to attach decoupling capacitors close to the die to minimize the effective inductances in the power supply distribution system. Approaches to accomplish this include mounting discrete capacitors on the subsystem circuit board adjacent to, or under the package, mounting discrete capacitors on the package, or providing thin organic dielectric layers in the package substrate. A drawback of discrete capacitors is the series inductance of the capacitors and the inductance from the routing to connect the capacitor limit its effectiveness to frequencies below 300 Mhz. A drawback of thin organic dielectric layers is the capacitance per unit area is small, typically less than 1 nF/cm^2, and is insufficient control power supply noise.
Consequently a need exists for a cavity-down ball grid array package, that allows substrate circuitry, does not have through vias, includes an integral electrically connected heatspreader that does not sandwich the die, mounts the die without a recess, allows electrical connections to the die with wirebond, TAB, or solder balls, allows the TCE of the substrate to be adjusted for optimum reliability, and provides a capacitor layer for controlling power supply noise.


A disk drive that has a plurality of heads coupled to one or more disks. The heads have air bearing surfaces that compensate for a radial crown and a radial camber of an adjacent disk to maintain a flying height at a relatively constant level across the disk surface. By way of example, the air bearing surfaces may have crown and camber sensitivities that are opposite in sign from the crown and camber sensitivities created by the disk. The opposite sensitivities offset the sensitivities of the disk to maintain an essentially constant flying height as the head moves across the surface of a disk.

1. Field of the Invention
The present invention relates to a head of a disk drive that compensates for a radial crown and radial camber of a disk to maintain a constant flying height across the surface of the disk.
2. Background Information
Hard disk drives contain a plurality of magnetic heads that are coupled to rotating disks. The heads write and read information by magnetizing and sensing the magnetic fields of the disk surfaces, respectively. Each head is attached to a flexure arm to create a subassembly commonly referred to as a head gimbal assembly ("HGA"). The HGA's are suspended from an actuator arm. The actuator arm has a voice coil motor that can move the heads across the surfaces of the disks. There are typically heads adjacent to the top surfaces of the disks, also referred to as the UP heads, and heads adjacent to the bottom surfaces of the disks, also known as DN heads.
The disks are rotated by a spindle motor of the drive. Rotation of the disks creates an air flow within the disk drive. Each head has an air bearing surface that cooperates with the air flow to create an air bearing between the head and the disk. The air bearing eliminates or minimizes the mechanical wear between the head and the disk. The height of the air bearing is commonly referred to as the flying height of the head.
Because of manufacturing defects a disk may have a radial slope also known as disk crown and radial curvature also known as disk camber. The crown and camber of a disk may vary the flying height of the air bearing as the head moves radially across the disk surface. The variation in flying height may produce errors in writing or reading data. The crown and camber of the disk increases the flying height for the UP head and decreases the flying height for the DN heads. It would be desirable to provide heads that compensate for the crown and camber of a disk. This UP/DOWN trend difference can make it difficult to compensate for the variations in flying height when writing and reading data.

Flying height compensation for up/down bit error rate trend difference


Methods of making supported monolithic gold (Au) catalysts that can be used for generating a hydrogen-rich gas from gas mixtures containing carbon monoxide, hydrogen and water via a water gas shift reaction, and for the removal of carbon monoxide from air at a low reaction temperature via its oxidation reaction are described. Methods of making highly dispersed gold catalysts on washcoated monoliths and the stabilization of monolithic catalyst supports by the addition of a third metal oxide, such as zirconia (ZrO2), lanthanum oxide (La2O3), or manganese oxide (MnxOy). The catalyst supports and/or washcoats may include a variety of transition metal oxides such as alpha iron oxide (α-Fe2O3), cerium oxide (CeO2), ZrO2, gamma alumina (γ-Al2O3), or their combinations.

1. Field of the Invention
Embodiments of the invention relate to methods of preparation of supported monolithic gold (Au) catalysts that are used for generating a hydrogen-rich gas from gas mixtures containing carbon monoxide, hydrogen and water via a water gas shift reaction, and for the removal of carbon monoxide from air at a low reaction temperature via its oxidation reaction. More particularly, embodiments of the invention include methods for the preparation of highly dispersed gold catalysts on washcoated monoliths and the stabilization of monolithic catalyst supports by the addition of a third metal oxide, such as zirconia (ZrO2), lanthanum oxide (La2O3), or manganese oxide (MnxOy). The catalyst supports and/or washcoats may include a variety of transition metal oxides such as alpha iron oxide (α-Fe2O3), cerium oxide (CeO2), ZrO2, gamma alumina (γ-Al2O3), or their combinations.
2. Technical Background
Hydrogen (H2) or H2-rich compositions are an indispensable feedstock for many chemical and energy-generating processes, including the refinery processes in petrochemistry and the production of chemicals such as ammonia and methanol. These compositions are also applied in proton exchange membrane (PEM) fuel cells for generating electricity, etc. (see W. Ruettinger, O. Ilinich and R. J. Farrauto, J. Power Sources, 2003, 118, 6-65).
H2 is an environmentally benign material as it is non-poisonous and the use of H2 in many energy-generating processes, such as that in (PEM) fuel cells, does not emit any pollutant, as the sole product of H2 oxidation is water. The use of fuel cells complement environmental regulations that are getting increasingly stringent, whereby cleaner, renewable and non-pollution processes and products are demanded. Moreover, in addition to the growing global demand for H2 production and distribution, the need to obtain higher H2 purity is also increasing. For example, the maximum allowable carbon monoxide (CO) concentration in the H2 gas feed of a PEM fuel cell has dropped from a value of 100 ppm, as required in the 1990s, to the current value of 10 ppm or even 1 ppm. The presence of CO could poison the platinum (Pt) electrodes in the Fuel cells (see W. Ruettinger, O. Ilinich and R. J. Farrauto, J. Power Sources, 2003, 118, 6-65).
H2 is commonly produced by splitting water and steam, reforming of fuels (methane or mixtures of hydrocarbons), or as a by-product of steam reforming of naphtha. The former process is very energy-consuming and is not applicable for large scale production unless cheap electricity is available. Therefore, in industry, most H2 (above 90%) is produced from the steam reforming process, which produces a synthesis gas comprising H2, carbon dioxide (CO2), and CO. Using methane (CH4) as an example, the reaction can be expressed as:2CH4+3H2O→7H2+CO+CO2 The CO concentration is usually above 10% in the synthesis gas, thus, it is still not directly applicable in a fuel cell or in the production of ammonia, etc.
To separate H2 from CO, a reaction called the Water Gas Shift (WGS) reaction is used in industry to convert CO into CO2:CO+H2O→CO2+H2
The current industrial WGS process is composed of a two-stage reaction: the high temperature (HT) WGS reaction, using ferro chromium (FeCr) as the catalyst at a working temperature in the range of from 350° C. to 500° C., and the low-temperature (LT) WGS process, using copper zinc (CuZn) as the catalyst at a working temperature in the range of from 200° C. to 260° C. After the steam reforming reaction of a fuel such as methane, the CO concentration in the synthesis gas can be lowered to about 2% to 4% after the HT-WGS reaction, and further lowered to a value between 0.1% and 1% after the LT WGS process (see L. Lloyd, D. E. Ridler, M. V. Twigg, in: M. V. Twigg (Ed.), Catalyst Handbook, seconded, Wolfe Publishing, Frome, 1989, pp. 283-338). This means that the CO conversion in the latter process should be above 50% to 95%, if the CO concentration is around 2% after the HT-WGS reaction. Since the WGS reaction is exothermic and reversible, it is not favorable to reach such a low CO concentration at high temperatures, in accordance with thermodynamics.
Both the FeCr and CuZn catalysts need to be reduced or activated in situ before use (see W. Ruettinger, O. Ilinich and R. J. Farrauto, J. Power Sources, 2003, 118, 6-65). Also, they are pyrophoric after activation, i.e. they spontaneously generate heat to dangerously high temperatures when exposed to air. Unfortunately, residential or mobile fuel cell systems are often operated with frequent start/stop operations. Therefore, the existing industrial FeCr and CuZn catalysts clearly cannot meet these dynamic requirements, as they will then experience unacceptable rapid deactivation under these operation conditions due to their pyrophoric nature (see R. J. Farrauto et. al. Catal. Rev. 2007, 49, 141-196; and R. Borup, J. Meyers et. al. Chem. Rev. 2007, 107, 3904-3951). In addition, in the production and handling process, as well as the post-reaction treatment, of the chromium-promoted iron catalyst, the presence of chromium is a potential danger to health, and a problem to the environment.
Other developed catalyst systems usually need a higher reaction temperature to convert CO into CO2 via the WGS reaction. For instance, U.S. Pat. No. 5,030,440, reports a Pt and Pt-containing catalyst formulation which needs a reaction temperature above 550° C., while U.S. Pat. No. 5,830,425 discloses a chromium-free iron/copper catalyst that requires a reaction temperature above 300° C. Some other metals such as cobalt (Co), ruthenium (Ru), Palladium (Pd), Rhodium (Rh) and nickel are also tested for WGS reaction, and methanation of CO (CH4 formation from CO and H2) is usually observed as described in U.S. Pat. No. 7,160,533. Furthermore, all of these catalysts cannot fulfill the requirement for frequent stop/start operations.
Therefore, in recent years, research efforts have been made to further lower the WGS reaction temperature, while maintaining the high catalytic activity. It is not only because the low reaction temperature favors a higher CO conversion, according to the thermodynamic equilibrium of the WGS reaction, but also the necessity to lower the temperature of the H2-stream fed to a PEM fuel cell to be as close as that of the operation temperature of the PEM fuel cell, which is around 80° C. Also, as mentioned above, the new WGS catalysts should be able to endure the repeated start/stop operations.
It is reported that supported Au catalysts on α-Fe2O3 exhibited good WGS activity in the temperature range of from 120° C. to 200° C., at a gas hourly space velocity (GHSV) of 4000 h−1 (see D. Andreeva, V. Idakiev, T. Tabakova, A. Andreev, J. Catal. 158 (1996), 354-355). Some other supported Au catalysts on CeO2, TiO2 and ZrO2 were later reported to be used in LT WGS reaction (see D. Andree, Gold Bulletin, 2002, 35, 82-88; H. Sajurai, T. Akita, S. Tsubota, M. Kiuchi, M. Haruta, Appl. Catal. A: General, 2005, 291, 179-187; Q. Fu, H. Saltsburg, M. Flytzani-Stephanopoulos, Science, 2003, 301, 935-907). The use of mesoporous catalyst supports such as mesoporous ZrO2 can further improve the catalytic performance of the catalysts (see V. Idakiev, T. Tabakova, A. Naydenov, Z. Y. Yuan and B. L. Su, Appl. Catal. B. Environ. 63, 178 (2006); V. Idakiev, T. Tabakova, K. Tenchev, Z. Y. Yuan, T. T. Ren and B. L. Su, Catal. Today 128, 223 (2007). A recent U.S. Pat. No. 7,375,051, describes Au supported on sulfated ZrO2 for WGS reaction. At 200° C. and at a GHSV of 4000 h−1, the CO conversion could reach 96%, and after a 20 hr reaction, it was slightly decreased to about 95%. Clearly, the Au catalyst is promising for WGS reaction at low reaction temperatures. Other examples can be seen in US Patent Application No. 2006/0128565A1, where Au/Lanthanum oxides were used for WGS reaction.
The methods developed for the preparation of the supported Au catalysts include the co-precipitation (CP) method and deposition-precipitation (DP) methods (see M. Haruta, S. Tsubota, T. Kobayashi, H. Kageyama, M. J. Genet, B. Delmon, J. Catal. 1993, 144, 175) in which HAuCl4 is used as the precursor, and sodium carbonate (Na2CO3), sodium hydroxide (NaOH) or urea (see R. Zanalla, S. Giorgio, C. R. Henry and C. Louis, J. Phys. Chem. B. 2002, 106, 7634) as the precipitating agents respectively, chemical vapor deposition method (see M. Okumura, S. Nakamura, S. Tsubota, T. Nakamura, M. Azuma, M. Haruta, Catal. Lett., 1998, 51, 53-58), and a Au-colloid-based two-stage method employing tetrakis(hydroxmethyl)-phosphonium chloride (THPC) as the reducing and capping agent (see D. Grunwaldt, C. Kiener, C. Wogerbauer, A. Baiker, J. Catal. 1999, 181, 223-232), and a sonicated-assisted method (Z. Zhong et al, Patent Application No. WO2007/055663 and Z. Zhong, J. Lin, S. P Teh, J. Teo, F. M. Dautzenberg, Adv. Funct. Mater, 2007, 17, 1402-1408), etc.
One factor that determines the catalytic performance of the supported Au catalysts for CO oxidation is the Au particle size. The Au particles should be below 5 nm, and for CO oxidation, the optimum Au particle size should be about 3 nm (see M. Haruta et al, Catal. Lett. 1997, 44, 83; M. S. Chen, D. W. Goodman, Science, 2004, 306, 252). The above methods in most cases can control Au particles below 5 nm. A number of supported Au catalysts (in powder form) have been prepared for CO oxidation (or selective oxidation of CO in the presence of H2) by these methods such as those described in US Patent Application No. 2006/0165576, which reported the use of Au supported on Al2O3, Fe2O3 etc, in the selective oxidation of CO; US Patent Application No. 2007/0190347 A1 which describes Au/CeO2 catalyst applied in CO oxidation in air for treating tobacco smoke; and WO 2007/055663 A1 which also describes supported Au catalysts used in CO oxidation.
However, for these powder catalysts, when they are packed into bed particulate form, a large pressure drop will be created during the catalytic reaction, thus limiting a high speed flow of reactant gases. Moreover, the catalyst beds are vulnerable to severe breakage resulting from stresses that are induced by the frequent start and stop operations required for mobile fuel cell systems (see R. J. Farrauto, Y. Liu, W. Ruettinger, O. Ilinich, L. Shore, T. Giroux, Catal. Rev. 2007, 49, 141-196).

Gold catalysts for co oxidation and water gas shift reactions


A display driving device supporting a low power mode according to an aspect of the present disclosure that is capable of minimizing power consumption when driving in the low power mode includes a plurality of output buffers connected to data lines to precharge the data lines with a first data signal corresponding to a black image when a precharge horizontal line is driven in a display panel including a first region where a standby image is displayed and the second region where the black image is displayed, the precharge horizontal line being included in the second region, and a gamma voltage generator connected to the data lines to output the first data signal to the data lines when other horizontal lines other than the precharge horizontal line in the second region are driven.

With the advancement of the information society, requirements for a display device for displaying an image are increasing in various forms. According to such requirements, various types of display devices such as an organic light emitting display device (OLED), and the like as well as a conventional liquid crystal display device (LCD) are being used.
The display devices described above are also applied to mobile terminals such as a mobile phone, a smartphone, a tablet computer, a laptop computer, and a wearable device. As shown in FIG. 1, a recently developed mobile terminal supports a low power mode that always displays a standby image 110 such as a clock, weather, or calendar designated by a user on a display device 100 when the mobile terminal is not in use, for example, an always on display (AoD) mode.
When the mobile device operates in the low power mode, the display device 100 is divided into a first region 120 where a black image is displayed and a second region 130 where the standby image 110 is displayed to reduce power consumption.
At this time, an output buffer (not shown) of each of source channels in the first region 120 where the black image is displayed is not turned off and maintains a turned-on state in order to represent a black voltage corresponding to a black gradation. However, even though the output buffer of each of the source channels outputs the black voltage, power is continuously consumed, and thus there is a problem that there is a limit to reduction of power consumption in the low power mode.

Device and method for driving display supporting low power mode


The use of bandwidth constrained wireless links in mobile networks necessitates the use of bandwidth saving header compression schemes. In these schemes, a compressor and a decompressor collaborate to code bulky IP headers into streamlined compressed headers. The gain of establishing the compressed header state in a greedy manner, without the compressor waiting for the decompressor's acknowledgment is evaluated. The impact of header compression on the traffic pattern, and the consequences on the channel allocation or connection admission control are also evaluated. A decision method for channel allocation or for connection admission control are proposed that maximizes the bandwidth utilization of the channel while providing some performance guarantees in terms of delay.

With the immense growth of the Internet and of mobile networks, the convergence of the two networks is considered inevitable. In a mobile Internet, the problem of efficiently carrying the Internet Protocol (IP) over mobile networks is critical, since the IP protocol has enjoyed the comfort of relatively higher bandwidth links and lower transmission errors. In a mobile network, such as a wide-area cellular network, lower link bandwidth necessitates that the IP header overheads are minimized in order to better utilize the link capacity to deliver useful payload to applications. The challenge for header compression in such links is to be robust against higher channel errors and also be sensitive to longer Round-Trip Times (RTTs). The [rohc] working group in the IETF has undertaken work to specify a robust header compression protocol for operation over lossy links with longer latencies.
Briefly, a robust header compression algorithm functions using a compressor and a decompressor. The compressor begins by sending packets with Full IP headers, until it gains sufficient confidence that the decompressor has received the required information, called Full Context. The point of such a determination is to allow subsequent header compression to operate with as small number of header bits as possible. This context initialization phase is important since it forms the basis for both the compressor and the decompressor to progress towards spectrally efficient state using a consistent reference state. However, it creates a bursty traffic pattern, consisting of some Full Header packets that require a large amount of bandwidth, followed by some compressed packets that require a significant smaller amount of bandwidth. Bandwidth allocation or Connection Admission Control (CAC) is thus complicated by the Header Compression scheme. Allocating the minimal amount of bandwidth or accepting the maximum number of connections while giving enough room for the header compression context initialization burst is a difficult task, yet of tremendous importance.
It is with respect to these considerations and others that the present invention has been made.

IP header compression dependent connection admission control and/or channel allocation


Microwave absorption in a varying magnetic field is investigated near electron cyclotron resonance with a network analyzer which is capable of swept frequency measurements, and of measuring reflection and transmission coefficients from 0.045 to 18 GHz, with greater than 80 dB dynamic range. The experimental conditions are such that the plasma is generated in a modified Penning discharge in a magnetic mirror configuration. A microwave beam is caused to propagate along the axis of the magnetic mirror field in the plasma column. The microwave beam is attenuated near the electron cyclotron resonance frequency, providing microwave absorption over a range of frequencies spanning the electron cyclotron frequencies present in the axially varying magnetic field. The attenuation, along with hot-plasma effects, are measured as a function of frequency by the network analyzer.

The present invention relates generally to aircraft protection and antidetection systems and more specifically the invention pertains to a plasma cloaking device which provides microwave absorption using a varying magnetic field.
Traditional aircraft antidetection systems are divided into two broad categories: active systems (which generate radar jamming signals); and passive systems, which rely on some characteristics of the vehicle to reduce the radar return. When the radar jamming transmitter is located on the target aircraft, the jamming signal transmitted by the aircraft can sometimes act as a beacon to the radar tracking system. Passive systems, which include the use of radar absorbing materials on the vehicle's surface, are limited in their ability to reduce the vehicle's radar cross section.
The task of providing a microwave absorption system which can reduce the detectability of satellites and aircraft, and which can protect targets from directed energy weapons is alleviated, to some extent, by the systems disclosed by the following U.S. Patents, the disclosures of which are incorporated herein by reference:
U.S. Pat. No. 3,127,608, A. L. Eldridge, Object Camouflage Method and Apparatus;
U.S. Pat. No. 3,713,157, Henry August, Energy Absorption by a Radioisotope Produced Plasma;
U.S. Pat. No. 3,773,684, Alvin M. Marks, Dipolar Electro-Optic Compositions and Method of Preparation; and
U.S. Pat. No. 4,791,419, Gary R. Eubanks, Microwave Absorbing Means.
The August patent, Energy Absorption by a Radioisotope Produce Plasma, which describes a means of attenuating electromagnetic radiation passing through an ionized gas plasma adjacent to a body, teaches placing a radioisotope material on a surface of the body in contact with the gaseous medium surrounding the object. Such radioisotope material ejects energetic particles and quanta into the medium and causes ionization of the gas, forming an ionized gas plasma sheath around the object. This plasma sheath would absorb any electromagnetic energy entering it or would so distort any incoming signal that it would be unrecognized as a radar signal upon its return to its source. This patent also suggests superimposing a DC magnetic field upon the plasma in order to enhance attenuation.
The plasma around the object is constantly replaced by the continuous release of energetic particles and quanta into the gaseous medium surrounding the object. Additionally, this patent predicts a decrease in the plasma density as the distance from the object increases, providing impedance matching and a resulting decrease in the reflectivity of the plasma sheath.
The Eldridge Patent, Object Camouflage and Apparatus, teaches rendering an object invisible to radar by use of an ionized gas cloud surrounding the object. A particle accelerator is used to continuously ionize the gas immediately in front of the object and the object's forward progress through the ionized gas cloud provides the necessary coverage of the object. This patent teaches that the ionized gas cloud will attenuate and refract any incident electromagnetic waves, which effectively makes the object invisible to radar.
The Marks Patent, Dipolar Electro-optic Compositions and Method of Preparation, teaches using a suspension of dipolar particles as a light-controlling means. The particles are in suspension and are oriented by the application of an external electric or magnetic field. This patent teaches a method for creating such a device in which the particles are evenly distributed throughout the suspension, have a fast orientation response upon application of the appropriate exterior field, and are sufficiently transparent or reflective to electromagnetic radiation, depending upon orientation, to allow use of the device as a practical light-controlling device.
The Eubanks Patent, Microwave Absorbing Means, defines a device which is designed to absorb the microwave radiation used in traffic control radar by using a microwave antenna connected to a microwave absorbing means. This patent teaches winding a wire around a fluorescent light bulb as a helical microwave antenna. Each end of the antenna is then electrically coupled to the absorbing tube (fluorescent light bulb) so that the microwave radiation received by the antenna is transmitted to the absorbing tube where it is then absorbed by the gas contained within the tube.
While the above-cited references are instructive, they do not acknowledge that a varying magnetic field in proximity with a plasma produces dramatic microwave absorption. More specifically, microwave absorption is enhanced when the varying magnetic field is produced near electron cycloton resonance.
The August reference discussed above teaches the use of a plasma to attenuate radar signals and suggests superimposing a DC magnetic field on the plasma as a means of enhancing attenuation. The Eldridge reference teaches using an ionized gas cloud to cloak an object, but fails to disclose or predict the use of a magnetic field with the ionized gas cloud to increase attenuation of the incident radar signals.
The Eubanks reference teaches the absorption of radar signals so as to reduce or negate any reflected signal, but this reference neither claims nor predicts the use of a dipolar magnetic field supplied with a weak plasma to absorb incoming radar signals. There are no plasmas in this reference.
The Marks reference is not concerned with the absorption of radar signals at all, but is a light-controlling device. There is no plasma present in this reference and a magnetic field, if present, is used for the sole purpose of controlling the orientation of dipolar particles in suspension.
While the above-cited references are instructive, there remains the need to provide a system capable of cloaking a target using a dipolar magnetic field supplied with a weak plasma to absorb probing radar signals. The present invention is intended to satisfy that need.

The United States of America as represented by the Secretary of the Air Force


Analytics-based optimized maintenance operations for a hyper-converged infrastructure are described. An example includes instructions to establish an order for a sequence of maintenance operations including collecting data points that relate to high availability of multiple nodes in a storage infrastructure; performing analysis of the collected data, including discovery of groups of nodes that don't have mutual relations with other paired nodes; receiving a request to perform a maintenance operation for the plurality of nodes; generating an ordered sequence of groups of nodes for the maintenance operation based at least in part on the analysis of the collected data, each group including one or more nodes; and performing the maintenance operation for the plurality of nodes according to the sequence of groups of nodes, wherein the maintenance operation includes a power cycle for each of the plurality of nodes.

A hyper-converged infrastructure (HCI) is in general a software-defined information technology infrastructure in which all elements are virtualized. An HCI includes a combination of varied servers and storage devices in the software defined data center architecture. Within such an infrastructure there are commonly clusters, with each cluster including a set of nodes.
During life cycle management for a hyper-converged cluster it is often necessary to provide a power cycle (reboot) of each node in order to install upgrades. However, it is common for there to be overlapping pairs of data in high availability (HA) nodes, thus preventing such nodes from being rebooted at the same time.
A conventional system may perform an upgrade of multiple HCI nodes of a cluster in a sequential schedule of individual nodes. However, such an upgrade schedule is inefficient because it only allows the upgrade of one node at a time, thus requiring a long time period to complete the upgrade. Further, this maintenance process generally does not take into account how data is synchronized between nodes, or how the data storage and processing that are required to be offloaded from nodes during a power cycle can be best provided, thus further reducing efficiency and increasing the risk of faults occurring in the upgraded nodes.

Maintenance operations based on analysis of collected data

Hewlett Packard Enterprise Development LP


A fornix manipulator includes a collar and stabilizer. The collar has a first end and a second end, the second end having an opening and diameter greater than the first end and the first end having an opening to receive a cervix into the collar. The stabilizer has a base portion defining a guide hole and a plurality of prongs extending from the base portion to contact the first end of the collar.

1. Field of the Invention
The present disclosure relates to a formix manipulator, and more particularly, to a device that delineates and deviates the vaginal formix while preserving access to the cervix and supporting the vaginal wall to create a platform or plane for dissection.
2. Description of the Related Art
In some medical procedures, the vaginal formix may need to be delineated and/or deviated away from other vital organs. In addition, the formix and neighboring vaginal wall may need to be supported to provide a platform or plane for dissection. Many medical procedures require manipulation of the formix. These include but are not limited to: hysterectomies; colpotomies; vaginal suspensions; colpoplexies; and resections of vesicovaginal fistulas, pelvic endometriesis, cancer, fibroids, and adhesions.
For example, in a hysterectomy, a surgeon cuts through the vaginal formix to detach and remove the cervix and uterus from the body. Here, the vaginal formix must be precisely delineated to prevent injury to the vaginal wall and neighboring vital organs, such as the bladder, bowel, or ureters. In addition to delineating the formix, the surgeon may also have to deviate or move the formix away from vital organs during incision. If organs are connected to the vaginal wall or formix, the surgeon may also have to dissect or cut the connecting tissue. This requires supporting the formix and vaginal wall together to provide an adequate platform or plane for dissection.
FIG. 1A-C illustrate the location of the formix. FIG. 1A is a sagittal cross-section of a female pelvis. The cervix 103 opens into the uterus 104, and the ovaries 105 are connected to the uterus 104. On one side of the vagina 107, toward the front of the body, is a bladder 112 and a urethra 106 leading from the bladder to an outside of the body. On another side of the vagina 107, toward the rear of the body, is the rectum 109 between intestines 110 and the anus 108 which opens from the rectum 109 to outside the body.
FIG. 1B is a view of the cervix 103 from the vaginal canal. FIG. 1C is a simplified view of the uterus 104 from within the abdomen 111. Surgeons may access the uterus 104 and other organs from the abdominal cavity 111.
The formix 100 is a cylindrical ring of tissue encircling the cervix 103 and lower uterus 104. The lowest cylindrical ring is the intra-vaginal formix 101, The intra-vaginal formix 101 encircles the cervix 103 and is visible from the vaginal canal, as illustrated by FIG. 1B. The intra-vaginal formix 101 is located between the vaginal wall 102 and the cervix 103, as illustrated by FIGS. 1A and 1B.
The upper-most cylindrical ring of the formix 100 is the intra-abdominal formix 113. When viewed from the abdomen, as in FIG. 1C, the anterior half of the intra-abdominal formix 113 may be visible, but it is neither demarcated nor obvious to the human eye. It is therefore indicated with a dotted line. The ring of the intra-abdominal formix 113 passes between the uterus 104 and rectum 109, and also passes between the uterus 104 and bladder 112, as indicated by FIG. 1.
The length of the formix 100, or the distance between the lowest and upper-most cylindrical rings (i.e. the intra-vaginal formix 101 and intra-abdominal formix 113, respectively) is indicated by dotted lines in FIG. 1.
Several problems and injuries may result when using conventional devices, known as uterine manipulators, to manipulate the formix 100. These problems include imprecise formix delineation and deviation; vaginal shortening; and abdominal deflation. Injury can also result from blocked cervical access and blind cervical retrieval; device insertion and retrieval; and lack of a platform while dissecting vital organs away from the formix and vaginal wall.
FIGS. 2A and 2B illustrate a first conventional device to perform uterine manipulation, and FIG. 3 illustrates a second conventional device. In the first conventional device 210, a first cup 211 has a first end 213 positioned at or near the intra-vaginal formix 101. The second device 310 has a similar shape, with a single cup 311 having a first end 313 positioned at or near the intra-vaginal formix 101. When pressure is applied against cups 211 or 311, their respective first ends 213 and 313 push the intra-vaginal formix 101 against the intra-abdominal formix 113. Eventually, the first end bulges through the formix 100 into the abdomen as a distended ring of formix tissue. The bulging ring formed by the first ends delineates the circumference of the formix 100 when viewed from the abdomen.
Conventional devices may misestimate the location and diameter of the vaginal formix 100, causing inaccurate delineation. The diameter of the first ends 213 and 313 of devices 210 and 310, respectively, may be greater than the diameter of the intra-vaginal formix 101. Here, first ends 213 and 313 do not delineate the intra-vaginal formix 101, but the upper third of the vaginal wall 102. In addition, the length of the cervix may be greater than the depths of the cups 211 and 311, respectively. Here, first ends 213 and 313 would not delineate the intra-vaginal formix 101, since the length of the cervix 103 would prevent the ends 213 and 313 from reaching the intra-vaginal formix 101. Rather, the devices would delineate the upper third of the vaginal wall.
When conventional devices misestimate the location and diameter of the vaginal formix 100, the surgeon cannot precisely deviate the formix away from other vital organs when operating inside the abdomen 111.
Inaccurate delineation can also lead to vaginal shortening. If a surgeon seeks to cut through the circumference of the formix 100, the inaccurate delineation may cause the surgeon to cut through the vaginal wall 102, instead of in the formix 100 itself. When a surgeon cuts the vaginal wall instead of the formix 100, the length of the vaginal canal decreases.
Conventional uterine manipulators are also ill-suited for laparascopic and robotic surgeries that require abdominal inflation, also known as inflation of the peritoneal cavity. In laparoscopic and robotic surgeries, a camera and surgical tools are inserted through a navel port or small incisions on the lower abdomen. A constant supply of air or gas is pumped into the abdomen to inflate the abdomen. The inflated abdomen creates space for the surgeon to maneuver the camera and instruments without injuring vital organs. However, when a surgeon makes an incision through the vaginal formix, gas escapes from the abdomen through the vaginal canal. When the air leaks out, the abdomen disinflates, making it difficult to maneuver instruments and increasing the risk of organ injury.
Conventional uterine manipulators do not prevent abdominal disinflation. Rather, incised tissue retracts from the point of the incision and creates a hole or space between the device and tissue for air to escape. In the first device 210, since the first end 213 of the first cup 211 has a diameter greater than the second end 214, the tissue of the vaginal wall 102 retracts from the incision at the first end 213 toward the second end 214. A space forms between the vaginal wall 102 and first device 210. Consequently, air escapes from the abdominal cavity 111. The second device 310 attempts to prevent air leakage by inflating a balloon 312 within the vagina 107. However, air may continue to leak, and at the same time, the cervix 103 cannot be accessed from the vagina 107.
Conventional uterine manipulators block access to the cervix from the vagina 107. For example, the first device 210 blocks access to the cervix 103 with both the first and second cups 211 and 212, and the second device 310 blocks access to the cervix 103 with the balloon 312. Consequently, if the cervix 103 and attached uterus 104 must be retrieved from the vagina 107 after a hysterectomy, the surgeon must first remove the uterine manipulator and then reach into the vagina 107 to blindly feel around for the cervix 103. At times, the surgeon pulls and tears the incised formix 100 or vaginal wall 102. In robotic operations in particular, this may add significant time to the procedure, since it requires the surgeon to scrub before reaching in.
Conventional uterine manipulators pose injury risks in removal. For example, the cups 211, 212, and 311 may get stuck in the vaginal canal when the uterine manipulator 230 or 330 is extracted from the vagina 107. This may occur since the diameter of the cups may be larger than a diameter of the vaginal opening. To retrieve the cups, the surgeons must blindly reach and fish for the cups. At times, the surgeon may pull and damage tissue, or the surgeon may have cut the vaginal opening to remove the cups.
Conventional uterine manipulators also pose injury risks upon insertion. Since the devices are of predetermined diameters with the first end larger than the second end, the tissue of the vaginal wall 102 may be damaged when the vagina 107 has a smaller diameter than the diameters of the first ends of devices 210 and 310.
Conventional uterine manipulators do not provide a platform or plane for dissection. For example, when performing a hysterectomy, the surgeon may need to dissect vital organs such as the bladder 112 and the rectum 109 away from the vaginal wall. These vital organs are connected to the vaginal wall 102 and at times the formix 100. Thus, heat from cauterizing the formix 100 may travel through the tissue and injure the these organs if not dissected away. In the first device 210, cups 211 and 212 become narrower at their intersection 210, and therefore do not provide a surface or plane on which to perform a dissection. The second device 310 likewise does not provide a surface for dissection since there are spaces or holes in cup 312. The lack of a platform or even plane increases the risk of injury to vital organs in hysterectomies as well as other operations that require resections, such as operations to remove endometriosis, cancer, fibroids, pelvic adhesions, and vesicovaginal fistulas.

Minimally Invasive Surgical Technologies, Inc.


An imaging apparatus according to the present invention can generate an image from an output of an image sensor to record the image as an image file, and record first information and second information onto the image file as additional information. Accordingly, the imaging apparatus can provide a user or a staff person of a repair center with useful information regarding a failure, repair, and replacement that conventionally could not be provided.

1. Field of the Invention
The present invention relates to an imaging apparatus such as an interchangeable lens type digital camera, and a lens unit.
2. Description of the Related Art
As a conventional technological idea, for example, Japanese Patent Application Laid-Open No. 2004-356847 discusses a method for recording a failure detected by a camera onto a captured image as text data. Japanese Patent Application Laid-Open No. 2004-356847 further discusses a technique of printing out failure information along with printing of the captured image to notify a user of it.
However, the conventional art discussed in the above described Japanese Patent Application Laid-Open No. 2004-356847 still has a problem to be solved for an interchangeable lens type digital camera. Especially, a problem may arise when a failure is attributed to a lens unit, not a camera unit. More specifically, it is difficult for a user possessing a plurality of lens units to find out which lens unit is the cause of a failure. For example, in a company in which a large number of lenses of the same type are possessed and a plurality of users shares them, such as a newspaper publishing company and a news service agency, it is extremely difficult for a user and a staff person of a repair center to find out which lens is the cause of an error.

Imaging apparatus, lens unit, and methods for controlling the same


A new Osteospermum plant named ‘OSTZ0001’ particularly distinguished by the light yellow-orange to red-orange bi-colored inflorescences held well above the foliage on relatively long peduncles, medium-deep green foliage, semi-upright plant habit with relatively vigorous growth habit.

The present invention comprises a Osteospermum, botanically known as Osteospermum ecklonis and hereinafter referred to by the variety name 'OSTZ0001'.
'OSTZ0001' is a product of a planned breeding program. The new cultivar has light yellow-orange to red-orange bi-colored inflorescences held well above the foliage on relatively long peduncles, medium-deep green foliage, semi-upright plant habit with relatively vigorous growth habit.
'OSTZ0001' originated from an open pollination occurring in the summer of 2006 in a controlled environment in Enkhuizen, Netherlands. The female parent was the unpatented, proprietary plant designated '60145', with bronze flower color, and more mounding and less upright plant habit, with more branching.
The male parent of 'OSTZ0001' is not known.
The resulting seeds were sown in Enkhuizen, Netherlands in March 2007. 'OSTZ0001' was selected as one flowering plant within the progeny of the stated cross in August 2007.
The first act of asexual reproduction of 'OSTZ0001' was accomplished when vegetative cuttings were propagated from the initial selection in October 2007 in a controlled environment in Enkhuizen, Netherlands.


Multi-level wager games are described in which play at higher levels in the game continues even if the player does not achieve a winning result for play at a given level. Such play at the higher levels may be completed automatically in an autocomplete mode, without any additional player interaction. A payout is awarded if the outcome of play at any of the higher levels is a winning result in accordance with a special pay table designed for such autocomplete mode. In one embodiment, the special pay table is constructed such that the odds of obtaining a winning result in the autocomplete mode are less than the odds of obtaining a winning result for play at the first level. For example, in a two level poker game, if the player loses in the first level with only a pair of sixes (pair of Jacks or better needed for a winning hand in the first level), the cards in the second hand are revealed and the player obtains a winning result for second level hand only if the hand is dealt a Royal Flush.

This disclosure relates generally to wager games such as poker, slots and dice games, and more particularly to wager games that are capable of being played at multiple levels or rounds. Such games typically provide for progressively larger payouts at each successive level if the player continues to achieve a winning result and advances to the next level.
Multi-level wager games are known in the art and described in the patent literature, including U.S. Pat. No. 6,612,927 (Slomiany et al.) and U.S. Pat. No. 6,648,163 (Moody). In one version of a multi-level poker game, a first round of poker, such as five card draw poker, is played at a first level. If the player does not obtain the minimum poker hand ranking in the first level or round, the game is over and the player does not advance to a second level or round. However, if the player obtains a hand with a minimum poker hand ranking, such as a pair of Jacks or better, a winning result is deemed to have been achieved and the player wins according to a pay table. The player then advances to play at a second level of the game. The attraction of this game, referred to sometimes as "multi-level poker" or "multi-strike poker", is that the pay table for the second round is typically higher than the pay table for the first round. For example, the pay table for the second round might be double the pay table for the first round. Stated differently, if the player has a winning hand at the second level they would win twice as much at the second round as they would in the first round for the same poker hand.
As a method of adding additional excitement to the game, the game can be extended to additional levels, such as a third level and a fourth level, with the player only advancing to the next level if they continue to achieve a winning hand (i.e., a poker hand with a minimum poker hand ranking). However, the pay table for the third and subsequent rounds continues to escalate, e.g., at each successive level the pay table doubles again. A lucky player that wins at each level up to and including the fourth level has a potential for an enormous payout, particularly if they have a good or great hand at the highest level. The risk the player faces is that if the player loses at any level, the game is over, they forfeit their wager on the levels that they did not get to play, and they only retain their winnings for the level(s) at which they had the minimum poker hand ranking, if any, less their initial wager.
The concept of poker played at multiple levels, as described above, can be extended to other card wager games, and to other non-card wager games, such as slots or dice games such as Bunco, as set forth in the aforementioned '927 U.S. patent. Such games can be played in a variety of formats, such as using video gaming terminals, at a card table, or in an on-line gaming format where a player plays at a computer workstation and communicates with a gaming server associated with a casino website over a network such as the Internet.
There is an ongoing need in the art for providing new and exciting games for players, including new and exciting improvements to multi-level wager games. This invention provides for an improved method and apparatus for playing multi-level wager games, and is applicable to dice, poker, slots, and other types of games capable of being played in a multi-level format.

Multi-level wager games with autocomplete


According to an embodiment(s), a current detection circuit has first and second main electrodes, a vertical structure output transistor that includes a first control electrode where a control signal is supplied thereto, a third main electrode that is connected to the first main electrode, a second control electrode that is connected to the first control electrode, and a vertical structure detection transistor that has a fourth main electrode. The current detection circuit has a voltage supply circuit that supplies a divided voltage of a voltage between the first and second main electrodes to the fourth main electrode.

A current detection circuit has conventionally been disclosed that senses an output current of an output transistor by using an N-channel-type MOS transistor. However, in a case where an N-channel-type output transistor is used on a high side, a charge pump to supply a switching signal that controls on/off of an output transistor is needed. A charge pump generates a high-voltage switching signal, so that a high electromagnetic interference (EMI) measure is demanded. Furthermore, an attempt to use a multi-source P-channel-type MOS transistor that has a vertical structure on a high side is executed. In such a case, a source of an output transistor is directly connected to a power source terminal, so that a voltage drop that is caused between the source of an output transistor and the power source terminal is minute. Hence, in a case where an amplifier that responds to an output current is provided on a source side of a detection transistor that detects the output current, its offset voltage greatly influences a current sense ratio for detecting an output current and causes reducing of accuracy of the current sense ratio.

TOSHIBA ELECTRONIC DEVICES & STORAGE CORPORATION


Disclosed herein is an apparatus and method for controlling a fault in a lighting network. The apparatus includes power selection units respectively provided in a plurality of lighting units connected to one another over a network, each power selection unit being configured to compare a reference voltage with an output voltage sensed from power supply signals input from power supply units respectively provided in a lighting unit, located ahead of a faulty lighting unit, and the faulty lighting unit if a fault occurs in the lighting unit, and to select supply power to be supplied to the faulty lighting unit. Lighting control units control driving of the faulty lighting unit using the selected supply power.

1. Technical Field
The present invention relates generally to an apparatus and method for controlling a fault in a lighting network and, more particularly, to an apparatus and method for controlling a fault in a lighting network, which use a daisy-chain network topology based on a Recommended Standard 485 (RS485) communication scheme.
2. Description of the Related Art
Recently, the importance of the Light Emitting Diode (LED) lighting industry has gradually increased. In the past, most operations for lighting were implemented merely by turning on and off a single lighting lamp using a single switch. However, recently, such a lighting scheme has developed into a centralized scheme in which a central control unit controls a plurality of lighting devices over a network.
In order to implement such a lighting network, various types of topological structures can be used. First, RS485 communication enables a topology to be configured in a bus manner and enables a plurality of devices to be simultaneously connected to the bus, so that one-to-many communication or many-to-many communication can be realized. Such a structure is widely used in lighting networks at the present time.
In detail, bus structures that can be implemented using an RS485 communication scheme include a tree bus structure, a star structure, or a daisy-chain bus structure.
First, the tree bus structure is characterized in that the current of signals can be weakened while data transmitted from a lighting control device is reaching a lighting device in a final stage, so that an effective range of 1.2 km of the RS485 communication scheme may not be guaranteed. Therefore, such a tree bus structure is useful for the control of a small number of lighting devices, but causes a problem in connecting and operating a plurality of lighting devices in conjunction with one another.
Next, the daisy-chain bus structure can be configured such that data transmitted from a lighting control apparatus disclosed in Korean Patent No. 100870733 (Date of registration: Nov. 20, 2008) entitled "Remote lighting control apparatus and method," is connected to a neighboring lighting device, and that lighting device is connected to its neighboring lighting device, so that the individual lighting devices can be connected in series. Such a daisy-chain bus structure is advantageous in that the loss of current is low and the influence of noise is less, and in that the length of a cable can be reduced because the individual lighting devices are connected in series. However, such a daisy-chain bus structure is problematic in that when a fault occurs in a single lighting device, none of the lighting devices may be normally operated.

Apparatus and method for controlling fault in lighting network

Electronics and Telecommunications Research Institute