A compact, efficient and disposable capillary blood drawing device by which a patient's tissue can be punctured and a blood sample collected by the same reliable device. The blood drawing device includes the integral connection of a solid core needle and a spring in which potential energy is initially stored. A release of the potential energy from the spring correspondingly causes the needle to be driven into contact with the patient's tissue to make a puncture therein. When the spring assumes an at rest position, the needle will be safely withdrawn in and shielded by the blood drawing device to avoid an accidental needle stick and the possible spread of disease. The blood drawing device also includes a flexible bladder in which blood from the puncture can be collected, under suction, and selectively expulsed, under compression, for medical examination and diagnostic purposes.

Prior art lancing devices are known by which to puncture a patient's skin and to collect a sample of the patient's blood for medical evaluation and diagnosis. However, separate devices are commonly used to first puncture the patient's skin and then collect the blood sample. An additional device may also be needed to dispense an adequate volume of blood from the collector so as to permit a suitable medical examination of the sample. Obviously, the need for separate lancing, collecting and dispensing devices increases medical costs and reduces efficiency. Moreover, the disposal volume is also significantly increased when separate lancing and collecting devices must be safely discarded. Likewise, the preparation of such prior art devices for use (e.g. arming the lancing device with a removable tissue puncturing needle) may be complicated and require special skill and/or care.
In some cases, access is available to the tissue puncturing needle before and/or after the patient's tissue has been punctured. Therefore, both sheathing and resheathing steps may be required to adequately shield the tip of the needle. In other cases, there is no easy way to reliably isolate the blood sample in the blood collection device from the outside environment. Consequently, an accidental needle stick from the lancing device or the premature expulsion of blood from the collecting device could lead to the spread of a contageous and possible life threatening disease. That is to say, the lack of any protective means or the misuse of said protective means with conventional lancing and blood collecting devices will subject health care workers to increased risk of disease during the handling, use and disposal of such conventional devices.


In one aspect, the present invention provides catalysts for the carbonylation of heterocycles. The inventive catalysts feature metal-ligand complexes having cationic functional groups tethered to the ligand, wherein the tethered cationic groups are associated with anionic metal carbonyl species. The invention also provides methods of using the inventive catalysts to affect the ring opening carbonylation of epoxides.

Catalytic carbonylation of epoxides, aziridines, thiiranes, oxetanes, lactones, lactams and analogous compounds have been shown to be useful for the synthesis of ring expanded products of such compounds. The early catalyst for the carbonylation of epoxides was based on the use of [Co2(CO)8]. EP-B-0 577 206 by Drent and Kragtwijk relates to a process for the carbonylation of epoxides to form beta-lactone in the presence of [Co2(CO)8] and a hydroxy substituted pyridine compound. Alper and co-workers (J. Org. Chem. 2001, 66, 5424-5426) reported increased activity of carbonylation and selectivity for beta-lactone using combinations of [PPN]+[Co(CO)4]− and neutral metal complexes (PPN=bis(triphenylphosphine)iminium).
Further improvement of activity of carbonylation disclosed in U.S. Pat. No. 6,852,865 relates to bimetallic catalysts of the general type [metal complex]+[Co(CO)4]− for the ring-expanding carbonylation of epoxides, aziridines, thiiranes, oxetanes, lactones, lactams and analogous compounds.
Nonetheless, there remains a need for catalysts that have increased activity that will further reduce the catalyst cost in the carbonylation of epoxides, aziridines, thiiranes, oxetanes, lactones, lactams and analogous compounds.

Catalytic carbonylation catalysts and methods


A two-dimensional optoelectronic array module contains metal, semiconductor metal, or P-I-N photodetectors which detect light, and converts it to electrical signals provided to conventional integrated circuitry contained on the same wafer. The circuitry processes the electrical signals, and drives an array of vertical cavity lasers on another wafer through solder bumps which carry driver signals and connect the two wafers together. The detectors are thin membranes formed by etching intrinsic silicon wafers, and have anti-reflective coatings and Schottky metal contacts. The module is cooled via microchannels.

1. Field of the Invention
This invention relates to apparatus and methods for converting light to electrical current for utility in intelligent optical relays. That is, this invention relates to apparatus and methods for detecting optical signals, processing the data with electronic circuits and emitting the processed data again as optical signals. More particularly, this invention relates to optical relay structures and processes which utilize thin membrane photodetectors formed on a silicon wafer which is cooled with microchannels.
2. Description of the Related Art
Silicon photodetectors are known in the art. Most photodetectors are P-I-N type (p-type - intrinsic - n-type silicon layers). To obtain high responsivity, the intrinsic layer of P-I-N photodetectors must be around one to three times the absorption length (for 830 nm light, the thickness would be around 10 to 30 micrometers). Such detectors have a slow response time (around 1 microsecond), unless a large voltage is applied. Furthermore, the layer structure is not compatible with that of standard electronic circuits. Metal-semiconductor-metal photodetectors on thin membranes overcome these disadvantages by being fully compatible with standard electronic circuits, simpler to fabricate, and thinner, therefore, faster. In addition, both metal contacts can be placed on the same side of the wafer. Metal-semiconductor-metal detectors are known in the art. See "Nanoscale Ultrafast Metal-Semiconductor-Metal Photoconductors," by Y. Liu et al, Proc. Device Research Conference, paper VIB-1, Cambridge, Mass., June 1992. However, use of the thin membrane as an absorbing region, surface texturing, and operation at 830 nm wavelength are not taught by this reference. The use of surface texturing traps light better, allowing a thinner membrane to be used, and thereby increasing the bandwidth of the device.
It is known in the prior art to flip chip bond vertical cavity lasers. An article describing this process is "High-power Vertical-cavity Surface Emitting Lasers," by F. H. Peters et al, Electronics Letter, Vol. 29, 1983. It is known to use microchannels to cool silicon wafers. See, for example, "High-Performance Heat Sinking for VLSI," D. B. Tuckerman et al, IEEE Electr. Dev. Lett., Vol. EDL-2, P. 126, 1981. Other types of cooling include U.S. Pat. No. 5,163,179, by Pelligrini, which discloses an IR detector capable of passive cooling because of its structure and material. Etching opens the active area of the detector, and the detector is illuminated from the back. Also, U.S. Pat. No. 4,754,139 by Ennulat et al discloses an IR detector array cooled, in part, by positioning each detector over an air filled or evacuated chamber.
Light trapping in a silicon detector by roughening the surface with sandblasting is known. For instance, see U.S. Pat. No. 3,487,223 for "Multiple Internal Reflection Structure In A Silicon Detector Which Is Obtained By Sandblasting," by A. E. St. John. Etching silicon membranes is also known in the art. "An Etch-Stop Utilizing Selective Etching of N-Type Silicon by Pulsed Potential Anodization," S. S. Wang et al, Journal of Microelectromechanical Systems, Vol. 1, pp 187-192, and "Fabrication of Novel Three-Dimensional Microstructure by the Anisotropic Etching of (100) and (110) Silicon," by E. Bassous, IEEE Transaction on Electron Devices, Vol. ED-25, pp 1178-1184, are two articles describing this process.
U.S. Pat. No. 5,223,081 by Doan discloses a method of roughening a silicon substrate comprising the steps of depositing a metal layer on the substrate, heating to form a metal silicide layer, and etching to remove the metal and metal silicide.
U.S. Pat. No. 5,162,251 by Poole et al discloses a two-step method for abrasively thinning a silicon CCD. The CCD is mounted to a glass substrate for support and to allow backside illumination.
U.S. Pat. No. 4,983,251 by Haisma et al discloses a method of manufacturing semiconductor devices comprising polishing a support body and a monocrystalline semiconductor body, providing an insulation layer, connecting the bodies, heat treating them, and etching the semiconductor body to a thin layer (to prevent circulation currents).
U.S. Pat. No. 4,160,045 by Longshore discloses a method for producing a rough photosensitive surface by depositing islands of indium on the surface and bombarding with ions.
Reactive Ion Etching (RIE) is a standard and highly reproducible dry etching process used in the silicon microfabrication industry. It creates shallow textured surfaces with high light trapping capacity by the nature of micron-sized corrugation that are formed during this process.
Back illumination of photodetectors is known in the art. U.S. Pat. No. 4,784,702 by Henri discloses a P-I-N photodiode of amorphous silicon. The P and N layers are formed by multilayers rather than doping. The diodes may be illuminated from either side. U.S. Pat. No. 3,758,797 by Peterson et al discloses a solid state bistable switching device. The silicon layer may be illuminated from the backside.

Two-dimensional optoelectronic array module

The Regents of the University of Colorado


A torque wrench having a handle and an output shaft is disclosed. The output shaft may be constrained to turn only unidirectionally due to a ratchet. Rotation of the output shaft may be permanently disabled by an internal mechanism. Torque imposed on the output shaft may be limited by a torque responsive cam clutch. The handle forms or is part of an enclosure enclosing internal components such as the ratchet, the internal disablement mechanism, and the torque responsive cam clutch. A seal between the body and the output shaft prevents ingress and egress of lubricants and contamination between the inside of the body and the output shaft.

Tools for certain operations require a fairly high degree of precision. Illustratively, some operations require precise torque values to be applied to fasteners. One of the most effective ways to accomplish this goal is to provide a self-limiting torque wrench having a mechanism for limiting maximum applied torque. With such a mechanism, a user can freely turn the wrench without having to pay attention to the amount of torque being developed. Free turning of the wrench may entail alternating direction of wrench rotation, since that can be performed conveniently with one hand, without requiring that the hand be removed from the tool.
In some usages and environments, such a torque wrench can develop serious deficiencies. For example, in the field of high precision assembly, a torque wrench may go out of calibration to a degree unacceptable to assembly or fabrication standards. In another example, a torque wrench used in medical procedures such as installation of inserts in the human body may become internally contaminated, or may start to leak lubricant.
There exists a need for a torque wrench which overcomes the problems facing manually used wrenches.

Shaft ratchet release and sealing mechanism


A radiation imaging system includes pixel array, scanning circuit to scan rows of the pixel array, and readout circuit to read signals from the pixel array. Each pixel includes converter to generate electric signal corresponding to radiation and transistor connected to the converter. The readout circuit reads signal from the converter via the transistor. The system performs image capturing modes and conditioning mode of conditioning a threshold voltage of the transistor. In the conditioning mode, the scanning circuit supplies, to a gate of the transistor, an OFF voltage different from OFF voltages in the image capturing modes. The scanning circuit scans the rows in units of at least one row in the image capturing modes, and scans the rows in units of at least two rows in the conditioning mode.

Field of the Invention
The present invention relates to a radiation imaging system.
Description of the Related Art
A radiation imaging apparatus includes a panel in which a plurality of pixels for detecting radiation are arranged, and a readout circuit for reading out signals from the panel. Each pixel can include a converter for converting radiation into an electric signal, and a transistor connected to the converter. If the radiation imaging apparatus is irradiated with radiation through a subject, signals corresponding to the emitted radiation are accumulated in the converters, and the readout circuit reads out, via the transistor, signals corresponding to the accumulated signals. This obtains a radiation image. In a state in which the radiation imaging apparatus is not irradiated with radiation, noise components can be accumulated in the converters. An image corresponding to the noise components can be read out as an offset image.
The radiation imaging apparatus can obtain an image from which the noise components are removed, by calculating the difference between the radiation image obtained by detecting the irradiated radiation and the offset image obtained in the state in which the radiation imaging apparatus is not irradiated with radiation. However, if the state of the radiation imaging apparatus when obtaining the radiation image is different from the state of the radiation imaging apparatus when obtaining the offset image, it is impossible to correctly remove the noise components from the radiation image. Japanese Patent Laid-Open No. 2011-101693 describes a radiation image forming apparatus which has an imaging enable state and a sleep state, and causes a readout IC to perform a readout operation by supplying power to the readout IC in the sleep state or when transiting from the sleep state to the imaging enable state.
As described above, each pixel of the radiation imaging apparatus includes the converter and the transistor connected to the converter. If an OFF voltage (a voltage for turning off the transistor) is applied to the gate of the transistor of the pixel for a long time, a threshold may shift. If the threshold of the transistor of each pixel shifts, the influence of the shift appears in a radiation image as fixed pattern noise.


According to the invention, a cartridge filter for cleaning liquids and gases from mechanical impurities comprises compartments containing filtering cartridges, a pressure difference indicator and a control unit. The compartments are provided with cover plates having pipes for filtering and cleaning the compartments containing the cartridges, perforated guides and a spring device for locking the cartridges. The filter is also provided with mechanisms for moving the compartments and cover plates and a device for storing and replacing the filtering cartridges. The filter according to the invention enables an improved productivity owing to the elimination of manual operations of disassembly, replacement of cartridges and assembly of the filter, compliance with sanitary requirements and reduction of losses of filtered product.

A growth of production in various industries and increased requirements to the quality of products, as well as an increase in labour productivity, improvement of labour conditions in the manufactures using toxic products result in the need to provide new high-performance filters eliminating manual labour.
Known in the art is a filter (U.S. Pat. No. 3,447,684, Cl. 210-108 of June 3, 1969) having two alternately operating filtering elements and a pilot valve for automatically switching over the supply of filtered fluid. When the filter is contaminated, a pressure difference sensor operates to control a pilot valve switching mechanism. The pilot valve returns a portion of the outflowing filtrate for regenerating the filtering element by the reverse flow.
Known in the art is a filter manufactured by "AMF Cuno Incorporated" for filtering liquids and gases through throw-away thin-walled filtering cartridges having a pre-set pore size. The cartridges are placed in tightly sealed compartments or a number of compartments interconnected by a distribution device. During filtering, a fluid being cleaned passes through the walls of the cartridge to be filtered, and contaminants remain in the cartridge walls. As the particles accumulate, the resistance offered by the cartridge increases and the throughput capacity of the filter decreases. To maintain optimum throughput capacity of the filter, the flow of a product being cleaned is switched over to another compartment containing new cartridges, and the filtering cartridges are replaced manually in the disconnected compartment.
"AMF-Cuno" manufactures filters having one, two, three, nine, eighteen, forty two and two hundred fifty six cartridges. The filters comprise a casing having a removable cover plate and perforated guides in the form of tubes for fixing the cartridges and for removal of filtrate.
The filter has a low productivity owing to the need in manual operations of disassembly of the filter, replacement of cartridges and assembly of the filter. Much time being spent for replacement of cartridges, the number of concurrently operating filtering cartridges should be increased. Non-uniform washing of cartridges in multicartridge filters results in losses of product being filtered. In addition, sanitary conditions are not complied with during disassembly and replacement of cartridges.

Sevastopolsky prospekt, 83, korpus 1, kv. 49


Disclosed herein is a semiconductor integrated circuit device equipped with a memory circuit, which realizes the speeding up of its operation and low power consumption thereof in a simple configuration. At input/output nodes of a sense amplifier including a CMOS latch circuit for performing an amplifying operation in response to an operation timing signal, a pair of first precharge MOSFETs brought to an on state during a precharge period to thereby supply a precharge voltage, and select switch MOSFETs for connecting the input/output nodes and each complementary bit line pair in response to a select signal are provided. A second precharge MOSFET for short-circuiting the complementary bit line pair is provided between the complementary bit line pair. A memory array is provided which includes dynamic memory cells each comprising an address selecting MOSFET and a storage capacitor, each of which is provided between one of the complementary bit line pair and a word line intersecting it. The thickness of a gate insulating film for the second precharge MOSFET is formed thin as compared with that of a gate insulating film for the selecting MOSFETs.

The present invention relates to a semiconductor integrated circuit device, and to a technology effective for application to a semiconductor integrated circuit device equipped with a memory circuit.
It has been reported from the result of a known-example search subsequent to the completion or achievement of the invention of the present application that as ones related to such complementary bit-line precharge as described in the invention of the present application, there have been provided (1) gate boost precharge, (2) Unexamined Patent Publication No. 2000-100171 cited or listed below as a Patent Document 1, and (3) Unexamined Patent Publication No. Hei 10(1998)-178161 cited or listed below as a Patent Document 2. (1) is intended to boost the gate of a precharge MOS transistor to VPP (word line voltage) to thereby speed up a precharge operation for the purpose of speeding up of bit line precharge. (2) is intended to dispose only a short MOS transistor of a precharge circuit outside a shared MOS transistor to thereby speed up a precharge operation for the purpose of speeding up of bit line precharge. (3) aims to reduce a threshold voltage of a transistor of a precharge circuit to thereby speed up a precharge operation for the purpose of speeding up of bit line precharge.    Patent Document 1:            Unexamined Patent Publication No. 2000-100171            Patent Document 2:            Unexamined Patent Publication No. Hei 10(1998)-178161

Semiconductor integrated circuit device operating at high speed and low power consumption


A floral rack, particularly designed to hold floral stand flower arrangements which relate to a prior invention. The rack has a multi-level configuration and may be hung on a wall peg through a hole at one end or placed horizontally on a shelf and a suitable surface or easily transported. The rack is light weight, being made of polystyrene sheet material. The multi-level rack has a long surface with a rim on three sides, and two or more trays mounted, spaced above the bottom surface. This permits a number of floral stand arrays to be loaded and held in position for separate access and removal by a customer, without disturbing other floral stands.

This invention relates to sales racks for display of floral arrangements, and particularly to racks for the display and transportation of Floral Stand flower arrays.
An earlier patent application entitled "Floral Stand" by this inventor, describes flower holders that do not require a vase or dish, and may be mounted horizontally or vertically. These flower holders are mounted on bases made of rigid plastic sheet which are rectangular in shape.
The standard available display racks and transportation holders do not lend themselves to efficient display or carrying of the "Floral Stand" type arrangements. In part, this is due to the flat, sheet bases of the floral stands, which can occupy more space than is readily available on a shelf. The available racks also are not designed to take advantage of the ability of the floral stand arrays to be held and displayed in other than upright position. For these reasons, it was found advantageous to produce a rack configuration suited to the display and transportation of the floral stand flower holders.
The present invention is a floral rack, designed to hold the floral stands or anything having the appropriate bases. The rack is designed as a multi-level configuration. The configuration may be hung on a wall peg through a hole at one end, or placed horizontally on a shelf or suitable surface, or easily transported. The multi-level rack has a long surface with a rim on three sides, and at least two short racks mounted, spaced above the bottom surface. This permits a number of floral stand arrays to be loaded, held in position and to be separately accessed for removal by a customer, without disturbing other floral stands.
Accordingly, it is a principal object of this invention to provide a device that will hold floral stands efficiently for display and transportation;
Another object of this invention is to provide a device that will hold efficiently, any flower holder or article having a flat rectangular base of suitable size.
An advantage of the present invention is its light weight and low cost, relative to presently available means for display and transportation.
Further objects and advantages of the present invention will be apparent from study of the following portion of the specification, the claims and the attached drawings.


A network system in which a client device is connected to a server via a LAN. A CPU in the client device obtains date data of respective still picture files from the respective servers and generates representative thumbnail picture. Subsequently, the CPU in the client device generates a directory of a still picture taken on each photographing date, associates the directory with the thumbnail picture of the representative picture of each photographing date, and then displays a list of the representative thumbnail pictures. When a user selects the representative thumbnail picture which is taken on a date identical with a desired still picture from the respective thumbnail pictures, the CPU in the client device obtains all still pictures which are to be stored in the directory associated with the selected representative thumbnail picture from a storage medium in the server, and then generates thumbnail pictures of the still pictures.

1. Field of the Invention
The present invention relates to a network system in which a client device is connected to a server and particularly relates to a network system which enables a user to look for a still picture which the user wishes to view in numerous still pictures stored in the server from the client device.
2. Description of the Related Art
Conventionally, a network system conforming to DLNA guideline (Digital Living Network Alliance guideline, which is a technical specification to connect audio-visual (AV) equipments, personal computers, and information appliances to each other for cooperative usage by using home LAN (Local Area Network) (home network), abbreviated as DLNA hereinafter) is known as the above network system. In the DLNA, a DMS (Digital Media Server) which records, stores, and provides contents is provided as the server, and a DMP (Digital Media Player) which reproduces the contents of the DMS is provided as the client. Once hooked up to a network, both DMS and DMP are operational, and the DMP finds the DMS in the network and obtains a list of the available contents automatically. Thus, once the above DLNA compliant equipment is hooked up to the network, the contents of other equipments are available automatically. For example, a network attached storages, which are file service machines, personal computers, DVD/HDD recorders, and video cameras can be used as the DMS, and AV equipments such as television receivers, notebook computers, and personal digital assistants (PDA) can be used as the DMP, and moreover, one equipment may have functions of both DMS and DMP.
Each still picture file stored in the above DMS is normally provided with a file name, which is automatically created in each digital camera for each data of still pictures which are taken with the digital camera, and is stored in a storage medium such as IC card of the digital camera temporarily, and subsequently, transmitted from the storage medium to be stored in the DMS.
The digital camera automatically creates the file name in accordance with DCF (Design rule for Camera File system) and records the still picture file for the still pictures, which are taken with the digital camera, in the storage medium. In the DCF, each digital camera manufacturer adds an arbitrary character to three directory numbers to set a directory name and arranges three arbitrary characters, four directory numbers, and an extension sequentially to set the file name. Moreover, data of the above file include a photographing date and time, so that a photographing date and time of each still picture is stored in the file data.
Normally, it is uncommon for the user to determine the directory name and a hierarchy of the pictures by himself/herself when storing the still picture taken with the digital camera in the server, and the still picture file for the still pictures, which are taken with the digital camera, is often stored in the recording medium with the directory name which is automatically created in the digital camera when taking the picture.
In the DMP connected to the network of the above DLNA, when the user wishes to view a still picture of a photograph, which is taken with the digital camera, in the contents which are stored in each DMS connected to the network, a search process shown in FIG. 7, for example, is performed: the user operates the DMP to specify the DMS (S101), further specify the directory of the still picture stored in the specified DMS (S102), and search the directory whose name is identical with that of the directory created automatically in the digital camera and move down the hierarchy sequentially for search, so that the still picture which the user wishes to view is found and displayed (S103). However, in the above search process, when still pictures which are taken with digital cameras of different manufacturers are mixedly stored in the server, for example, it is difficult to determine what types of the still pictures are in each directory based on simply the directory names created in each digital camera.
Consequently, in the conventional process for searching the still picture, the user is required to remember which directory the desired still picture is stored in the DMS, and unless the user remembers the directory in which the desired still picture is stored, it is difficult to search the desired still picture easily. Moreover, because capacities of a storage medium of the picture data such as a memory card using a nonvolatile memory, a HDD (hard disk) using magnetic disks, and so on get larger, a total amount of the still picture files which can be stored in the respective storage mediums in the digital camera and the server increases dramatically. As a result, the time for searching the desired still picture file in many still picture files stored in the storage medium gets even longer, so that a means for searching the desired still picture more easily is coveted.
As shown in Japanese Laid-Open Patent Publication No. 2004-96582, there is a known picture file management method which creates a directory in a storage medium in accordance with a date on which pictures in the picture files are taken (photographing date), arranges number symbols which represent the photographing date so as to set a name of the directory for each directory, and stores the picture file of the picture whose photographing dates corresponds to the directory. This picture file management method enables an easy storage management of the picture file. However, unless the user remembers which picture is taken on the photographing date, the desired picture file cannot easily be found just by seeing the name of the picture file which is made up of the number symbols which represent the photographing date.
There is a known recording apparatus which encodes data as an encoded data of a predetermined codec level and codec class to classify a codec with a predetermined encoding system and makes a storage medium store the encoded data as a file whose name represents the codec level of the encoded data (refer to Japanese Laid-Open Patent Publication No. 2006-165918, for example). However, in this apparatus, when the name of the encoded data file in a directory which includes letters representing the codec encoding system is displayed, a thumbnail is located in an area immediately in front of the file name, and the presence and absence of this thumbnail shows whether or not the encoded data can be decoded by the codec of the apparatus, so that it is not easy to find the desired still picture file only by the directory name.
There is a known digital camera which transmits picture data taken with the digital camera to a personal computer in a home network and a server on Internet via a network so that the picture data are stored in the personal computer and the server and the picture data in the digital camera is stored more certainly (refer to Japanese Laid-Open Patent Publication No. 2003-319309, for example). In this digital camera, the still pictures are stored in a holder (directory) whose name includes a photographing date, however, the desired still picture cannot immediately be found just by seeing the holder name.


High purity and ultrapure bisphenol A is prepared in a novel process.

Bisphenol-A is a feedstock or intermediate product for the commercial production of various polymers including the polyarylates, polyamides, polyetherimides, polysulfones and polycarbonates, epoxy resins and modified phenol-formaldehyde resins. Colorless and high purity bisphenol-A has to be used to produce high quality polycarbonates.
Polycarbonates are in turn essential engineering plastics. They have excellent resistance to high temperatures, high impact resistance and good insulation resistance. These polymers play a more and more important role in the industrial fields such as, for example, chemical, mechanical and electric/electronic engineerings. Recently, laser data storage discs have found widespread applications in the industries such as, for example, computer and video-audio industries since optical data storage techniques have a variety of tremendous advantages. The feedstock for the production of an optical data storage substrate must be a polycarbonate which is prepared by means of nearly colorless and ultrapure bisphenol-A (the content of bisphenol-A is higher than about 99.99% by weight). An ultrapure bisphenol-A not only has higher purity but also should satisfy the extremely strict standards with respect to color, transmisivity, ash and iron contents or the like. This raises higher requirements in relation to the synthesis and purification of bisphenol-A than the production of usual polycarbonate grade bisphenol-A.
Bisphenol-A is produced by the condensation reaction of phenol and acetone, using an excess of phenol, in the presence of an acidic catalyst optionally with a promotor. ##STR1## The reaction product mixture contains unreacted phenol and acetone, water formed during the reaction and by-products in addition to bisphenol-A.
The by-products which are formed during the condensation reaction of phenol and acetone include predominantly 2-(2-hydroxyphenyl)-2-(4-hydroxyphenyl)propane (hereinafter sometimes also simply identified as "2,4-BPA" or "o,p-BPA") and the Dianin's compound. Additionally, there are present in the reaction mixture small amounts of 2,4-bis [2-(4-hydroxyphenyl)isopropyl]phenol (hereinafter also sometimes identified as "triphenol"), polyphenol and some undesirable coloring substance. The presence of such by-products and impurities in a bisphenol-A product results in a decrease in the quality or performance properties of for example resins that are manufactured by making use of bisphenol-A.
In general, a process for the production of bisphenol-A comprises two essential stages, namely synthesis of bisphenol-A by means of the condensation reaction of phenol and acetone and subsequent purification of the resulting reaction mixture containing bisphenol-A.
The methods conventionally used in the synthesis of bisphenol-A include predominantly a "hydrochloric acid catalyzed method" and an "ion-exchange resin catalyzed method".
In the hydrochloric acid catalyzed method, hydrochloric acid as a catalyst is highly active and used in a small amount. The rate of the hydrochloric acid catalyzed reaction and the conversion of the starting materials, in particular acetone are high. However, the hydrochloric acid catalyzed method suffers from the disadvantages such as, for example, the strong corrosion of the acidic reaction solution on the apparatus used for the performance of the condensation reaction of phenol and acetone. Therefore, this process requires that the equipment for carrying out the condensation reaction and the subsequent treatments be made from particular types of materials. Additionally, the low selectivity of the reaction to the desired product and the decomposition of the obtained bisphenol-A are attributed to the presence of acidic substance during the distillation. Furthermore, a complicated purification installation is required for recovery of hydrochloric acid subsequent to the reaction and for purification of the obtained reaction product.
Moreover, the desired BPA product is susceptible to contamination. More importantly, all the equipment that is brought in contact with acidic substance must be made from special corrosion-resistant materials.
In some instances, sulfuric acid, sulfur compounds or other substances are employed as a cocatalyst or a promotor to improve the hydrochloric acid catalyzed method in some aspects but this has not overcome the disadvantages of the method for the production of bisphenol-A using an acid as a catalyst in general.
Alternatively, the ion-exchange resin catalyzed method employs a non-corrosive reaction system. Therefore, this method allows a variety of materials to be used for the manufacture of the reaction and successive treatment equipment and reduces in turn the expenditure of capital on the equipment to a great extent. Moreover, since an ion-exchange resin usable as a catalyst is generally insoluble in the reaction mixture system, it is easily separated after the condensation reaction and a quality bisphenol-A product can be thus obtained. In recent years, the conversion of the starting materials and selectivity to the desired bisphenol-A product have been improved to an important extent as the catalyst technology that is intimately associated with the ion-exchange resin catalyzed method advances continuously. As a result, this method is more and more extensively used in the synthesis of bisphenol-A. A great number of patents, patent applications and other publications have described the ion-exchange resin catalyzed method and in particular some of operation steps, specific resins and equipment used therein. For example, U.S. Pat. Nos. 3,073,868, 3,153,001, 3,172,916, 3,234,221, 3,873,275, 3,936,507, 4,054,611, 4,156,089, 4,209,646, 4,212,997, 4,215,011, 4,294,994, 4,308,404, 4,346,247, 4,354,046, 4,391,997, 4,400,555, 4,445,409, 4,471,154, 4,487,430, 4,492,807, 4,590,303, 4,740,634, 4,798,654, 4,847,433, 4,918,245, 4,950,806, 4,954,661, 5,087,767[also JP No. 64-332, 802(Kokai)], 5,105,026, and 5,124,265; GB 159,668, 1,183,564, 1,340,869 and 2,053,019; DE 2,733,537; EP 0,144,735A, 0,268,318A, 0,319,326A3[CN 1,034,361A and also JP No. 62-304,941(Kokai)], 0,324,080, 0,329,075, 0,330,146, 0,332,877, 0,343,349 and 0,442,122A; JP No. Sho 36-23,335(Kokoku), 38-1,368(Kokoku), 40-7,186(Kokoku), 47-43,937(Kokoku), 49-48,319 (Kokoku), 50-13,334(Kokai), 54-159,378(Kokai), 55-27,1 08(Kokai), 56-46, 831(Kokai), (Kokai), 57-88, 137 (Kokai), 60-122,004(Kokai), 61-78,741(Kokai), 62-148,441(Kokai), 62-178,532(Kokai), 63-56,335(Kokai) and 63-60,227(also CN 1,002,560C); SU 715,100 and CN 1,034,360A, 1,035,282A, 1,036,559A, 1,048,987A, 1,059,480A and 1,069,961 are concerned with the ion-exchange resin catalyzed methods more or less or some operation steps as well as the equipment and resin catalysts employed therein.
There have been proposed many processes for obtaining high purity bisphenol-A through the removal of the impurities or by-products which have formed during the condensation reaction.
In order to synthesize bisphenol-A in accordance with the ion-exchange resin catalyzed method, the following purification process is generally used: removing water, unreacted acetone and phenol from the liquid condensation reaction mixture by fractional distillation at a reduced pressure, then cooling the residual liquid mixture to precipitate bisphenol-A in the form of adduct crystals of bisphenol-A with phenol, further separating the resulting adduct crystals from the mixture containing by-products and impurities and finally removing phenol from the adduct crystals to obtain a high purity bisphenol-A product. Further, many processes are already provided for the treatment of the mother liquor from which the adduct crystals have been separated.
One of the methods for removing phenol from the adduct crystals of bisphenol-A and phenol is distillation method wherein phenol is distilled out at a reduced pressure. However, it is impossible to remove all the phenol present in the adduct crystals by making use of the distillation method. Therefore, it is necessary to perform a stripping step in a subsequent procedure as described in JP Nos. 47-43; 937(Kokoku) or 40-7, 186(Kokoku) or to conduct a recrystallization step with heated water as described in JP No. 57-88,137(Kokai).
More specifically, U.S. Pat. No. 3,049,569 to Francis N. Apel et al. describes a process for the production of ultrapure bisphenol-A comprising the steps of continuously contacting a mixture of acetone and excess of phenol with a substantially insoluble cationic exchange resin catalyst, separating the effluent from the reaction zone into two streams, isolating the reaction by-products and bisphenol-A from the first stream, dehydrating the second stream and recycling the reaction by-products, acetone and phenol which have been isolated to the reaction zone. According to Apel, a conversion of about 50% by weight is the most desirable since it provides yields of about 99% of the theoretical yield of bisphenol-A. The resulting reaction mixture contains only about 15% by weight of bisphenol-A. Therefore, the mixture must be concentrated and the recycle quantities are extremely large. Moreover, the purity in the order of about 99% is obtained (about 99.7% is obtained in the example).
U.S. Pat. No. 3,873,275 to Richard C. Bennett describes in general a crystallization apparatus and method wherein the mother liquor recirculation rate and the size of crystal particles removed through a fine crystal destruction circuit are independently regulated so that undesirable fine crystals removed from the slurry body undergoing crystallization and the residence time thereof are regulated to provide a product of substantially improved size uniformity. However, the Bennett apparatus is considerably complicated and the performance of the apparatus is difficult to be adjusted or controlled.
U.S. Pat. No. 4,209,646 to Caluire R. Gac et al. describes a process for purifying diphenylol propane (bisphenol-A) by preparing a liquid of from about 10% to about 50% by weight diphenylol propane, phenol and less than about 15% by weight of water at a temperature of from about 70.degree. C. to about 100.degree. C. and applying a reduced pressure such as from about 20 to about 120 mmHg thereto which corresponds to the vapor pressure of the mixture while simultaneously cooling the same to precipitate almost pure diphenylolpropane in the form of crystals. However, the obtained diphenylolpropane still contains up to about 2% by weight of impurities and the coloration of the diphenylolpropane crystals corresponds to 30APHA after melting.
U.S. Pat. No. 4,215,011 to Lawrence A. Smith, Jr. discloses a catalyst system for use in a reaction-distillation column comprising a plurality of closed cloth pockets containing a particulate catalytic material arranged and supported in said reaction-distillation column by a wire mesh that is intimately associated with said closed cloth pockets. This complicated arrangement of catalytic particles is particularly provided for use in the separation of isoolefins from streams containing mixtures of at least one isoolefin and the corresponding normal olefin. This patent is especially useful for the separation of isobutene from a stream containing normal butenes. It is not known to be useful or to have ever been used in the preparation of bisphenol-A.
U.S. Pat. No. 4,294,994 to Ming K. Li describes a method for removal of phenol from the adduct of bisphenol-A and phenol by subjecting the adduct feed at a temperature of from about 50.degree. to about 150.degree. C. to spray drying conditions such as at a temperature of from about 150.degree. to about 250.degree. C. with a small amount of liquid carrier having a boiling point below that of phenol and recovering the bisphenol-A product from the released phenol. The purity of the obtained bisphenol-A product, as shown in example 2 provided by Li, is up to about 99% by weight though it is obviously disadvantageous that the adduct of bisphenol-A and phenol experiences high temperature effect of up to about 250.degree. C. whereby degradation or undesirable reactions thereof usually occur.
U.S. Pat. No. 4,308,404 to Arien Kwantes et al. proposes an improved continuous process for preparing bisphenols such as bisphenol-A from phenol and acetone in the presence of an acidic ion-exchange resin catalyst in a reaction zone comprising a series of reactors wherein a part of the effluent from at least one reactor with the exception of the last reactor is recycled to the preceding reactor, preferably to the first reactor, and the ratio of the recycled stream to the stream fed to the following reactor (the recycle ratio) is in the range of from about 0.1:1 to about 10:1. Nevertheless, the Kwantes' manner of operation undoubtedly results in a substantial reduction in the reaction rate as the condensation reaction proceeds.
U.S. Pat. No. 4,351,966 to John W. Flock relates to a process for recovery of phenol from the tarry residue derived during the manufacture of bisphenol-A. According to Flock, the bisphenol tar is treated at temperatures of from about 200.degree. to about 500.degree. C. and atmospheric pressure to recover all of the trapped phenol and the phenol liberated from a variety of phenol-based compounds. Flock uses so-called molecular sieve catalyst, that is cryctalline hydrated silica-alumina catalyst.
U.S. Pat. No. 4,354,046 to Glem R. Ladewig et al. provides a process for improving the purity and yield of bisphenol-A by feeding the crude bisphenol-A containing any unreacted phenol and acetone as well as the water formed during the condensation reaction removed from the condensation reactor to a crystallizer, adding an organic solvent such as toluene and water, heating the resulting mixture to form a single liquid phase, cooling the liquid phase to obtain crystals of bisphenol-A, separating the solvent and water from the resulting mother liquor, mixing phenol with the mother liquor, contacting the mixture with a cation-exchange resin catalyst or hydrochloric acid to convert the impurities to bisphenol-A, removing phenol from the mixture and recycling the remainder and the separated phenol to the crystallizer and the condensation reactor, respectively. It can be obviously seen that the product yield of p,p-bisphenol and the conversion of the total impurities are about 95%, respectively.
U.S. Pat. No. 4,391,997 to Ashok K. Mendiratta describes a process for the production of bisphenol-A comprising reacting phenol and acetone in the presence of a cation-exchange resin as a catalyst in a continuous reactor system in which the reaction temperatures increases along the length of the reactor or alternatively, the reaction takes place in a series of reactors operated at progressively increasing temperatures to produce a condensation reaction mixture of bisphenol-A, phenol, acetone, water and phenol/acetone condensation reaction by-products which may be then treated by any conventional means to form a bisphenol-A product having limited quantities of coloring substance and other condensation reaction by-products or impurities. It is attempted according to Mendiratta's teachings to reduce the amount of by-products or impurities and the material losses, thereby improving the material usage and the quality of BPA in the system employed. However, the conversion and selectivity of the acetone reaction is also remarkably limited. Actually, at a phenol to acetone molar ratio of about 10.7:1 and the temperature of about 90.degree. C., the conversion of acetone remains constant at about 69%. Under steady operation conditions, p,p-bisphenol-A is formed in yields of about 94+ percent and p,p-BPA plus o, p-BPA are formed in combination in yields of from about 98+ to about 99+ percent (based on p,p-BPA, o, p-BPA and other minor by-products). The selectivity of p,p-BPA is believed to be possibly as great as only about 96% (based on p, p-BPA, o,p-BPA and other minor by-products).
U.S. Pat. No. 4,400,555 to Ashok K. Mendiratta provides an improved bisphenol-A synthesis reactor system using a multiple acetone injection technique in a cation-exchange resin catalyzed bisphenol-A production process. Ashok K. Mendiratta intends to yield high material usage and to improve bisphenol-A product color or hue as well as to reduce the equipment capital expenditure/operating costs involved with recovery and recycling of excess phenol for the same overall phenol to acetone ratio charged to the reactor system. In operation, 25-75% of the feedstream of acetone is injected to the first reactor or the beginning of the reactor and the remainder is injected to the subsequent reactors or along the length of the reactor and all of phenol is charged to the first reactor or the beginning of the reactor. It is believed that this procedure allows a high relative phenol concentration to be maintained during most of the condensation reaction process while the overall phenol to acetone molar ratio is reduced to be as low as possible. According to Mendiratta, the conversion and selectivity to p, p-BPA of acetone reaction are significantly limited [the yield of p, p-BPA is about 94+ percent and the yield of p,p-BPA and o,p-BPA in combination is only from about 98+ to about 99+ percent (based on p,p-BPA, o,p-BPA and other minor by-products)] by means of the multiple acetone injection system.
U.S. Pat. No. 4,471,154 to Frederick C. Franklin suggests a staged and fluidized bed distillation reactor including a reactor vessel containing a plurality of trays vertically spaced from one another and interconnected by means of respective downcomers for conducting reaction liquid downward from tray to tray, at least some of said trays further containing a quantity of a particulate catalyst which is confined within a containing volume by a screen in connection to each of the trays and fluidized by the action of vapor. When operation is started, a stream of vapor and a stream of liquid pass through the respective trays containing the catalyst thereon upward and downward, respectively. The lower and higher boiling materials are removed from the upper and lower portions of the distillation reactor, respectively. It is evident in view of teachings of Frederick C. Franklin that this patent is focused on conducting a reaction of reactants A and B by providing a staged and fluidized bed distillation reactor rather than on improving the purity and hue or color of a bisphenol-A product and at the same time simplifying the process for the production of bisphenol-A.
U.S. Pat. No. 4,492,807 to Viney P. Aneja suggests that up to about 15% by weight of water and up to about 15% by weight of an organic liquid be simultaneously added to a mixture comprising impure bisphenol-A and phenol. The organic liquid should not react with bisphenol-A or phenol and dissolves a substantial proportion of the impurities or by-products formed in the synthesis of bisphenol-A. Preferred organic liquids are toluene and acetone. The Aneja's invention is advantageous in that a pronounced increase in recovery of bisphenol-A such as up to about 90% recovery is obtained without a significant sacrifice in product purity. Obviously, the recovery and purity are not so improved as expected.
U.S. Pat. No. 4,590,303 to Ashok K. Mendiratta is concerned with a method for the preparation of bisphenol-A from phenol and acetone wherein from about 5% to about 70% by weight of acetone feed per hour based on the weight of total acetone feed charged to the condensation reactor per hour, preferably from about 10 to about 40% by weight is diverted and delivered to the rearrangement reactor so that the product distribution of the condensation reactor effluent is substantially maintained. It is reported that as a result of diversion of the total acetone feed to the rearrangement reactor, improved acetone conversion is realized and BPA productivity is enhanced. However, the highest overall acetone conversion is about 65% by weight, though there may be increase of about 35% in acetone conversion.
U.S. Pat. No. 4,740,634 to Isabel M. Gones de Matos et al. discloses a special aspect of the process for the preparation of bisphenol-A wherein water is added to the mixture comprising bisphenol-A, from about 0.5 to about 15 percent by weight of diphenol isomers and other impurities but essentially no phenol. The resulting mixture is brought to a temperature sufficient to melt the solid material present therein and then cooled to a temperature below about 90.degree. C. to form bisphenol-A crystals which are thereafter separated, washed and dried to obtain a bisphenol-A product. However, thus obtained bisphenol-A product has an initial absorbance of 0.111 and contains only less than about 99.5 percent by weight of p, p-BPA even if it is further purified by contacting with an organic solvent.
U.S. Pat. No. 4,798,654 to Shigeru Iimuro et al. teaches a process for preparing bisphenol-A comprising distilling the intermediate adduct of bisphenol-A and phenol at a temperature in a range from about 160.degree. C. to about 200.degree. C. in a dephenolization column, recovering phenol from the top of the distillation column and bisphenol-A from the bottom of the distillation column and recycling a part of bottom liquid to the adduct feed of bisphenol-A and phenol. It is said in the Iimuro disclosure that plugging of the distillation column is prevented and continuous operation for a long period of time such as one year is possible. However, the phenol content of the bisphenol-A product taken out of the bottom of the dephenolization column is still up to about 2%.
U.S. Pat. No. 4,847,433 Gaylord M. Kissinger provides a process for preparing dihydric phenols such as bisphenol-A which process is based on the finding that there are significant quantities of acidic impurities derived from the acidic ion-exchange resin catalyst in the stream which is recovered from the catalyst. These impurities are believed to cause the bisphenol-A product to disappear (breakdown). Therefore, Kissinger suggests that acid neutralizing effective amounts of a carbonate of a Group II--a metal or transition metal of oxidation number +2 be added with barium carbonate being particularly preferred. Data as to the purity of in particular bisphenol-A and the conversion of acetone are not found in the Kissinger's disclosure.
U.S. Pat. No. 4,918,245 to Shigeru Iimuro et al. describes a process for the preparation of bisphenol-A. According to '245, (1) one mole of acetone is reacted with 4 to 12 moles of phenol in the presence of a sulfonic acid type cation exchange resin catalyst modified with a mercapto group--containing compound such as mercaptoethylamine to convert from about 20 to about 60% of acetone, and (2) the reaction mixture containing unreacted acetone is successively reacted in the presence of the hydrochloric acid catalyst. However, the drawback of '245 is that the hydrochloric acid catalyst is used and even so the purity of the p,p-BPA thus obtained is only about 98.3% as shown in only one example of this invention.
U.S. Pat. No. 4,950,806 Shigeru Iimuro et al. describes a process for crystallizing an adduct of bisphenol-A with phenol from a phenol solution of bisphenol-A in the presence of water, said process comprising the steps of controlling the concentration of bisphenol-A in said solution by removing a portion of the phenol from said solution or adding phenol to said solution according to feedback control based on the measurement of solution density to obtain an adjusted solution containing from 20 to 50% by weight of bisphenol-A, and feeding the adjusted solution to the crystallizer to form a solution having a temperature of from about 35.degree. C. to about 70.degree. C. and maintaining the inside wall of the crystallizer at a temperature higher than that of the solution, provided the temperature difference is smaller than 5.degree. C. This patent is also disadvantageous in that hydrogen chloride is used as a catalyst and the reaction mixture issued from the reaction system must be concentrated.
U.S. Pat. No. 4,954,661 to Shigeru Iimuro et al. discloses a method for preparing high purity or high quality bisphenol-A by recovering in a high yield bisphenol-A from the mother liquor from which the adduct of bisphenol-A with phenol has been separated and removing coloring substances and other impruities. According to the first aspect of Iimuro's invention, a portion of the by-products which are not recovered as bisphenol-A are withdrawn from the reaction system with the same being prevented from recycling to any process or recycling the same to each process is minimized and therefore the bisphenol-A can not contaminated with such by-products due to the accumulation thereof. Furthermore, sinceall the withdrawn portions of the by-products which can be recovered to obtain bisphenol-A may be returned to the principal reaction process, it is possible to increase the productivity of each process to the maximum extent. This patent only teaches an overall process which involves operations such as concentration, crystallization and cleavage or cracking, etc. subsequent to the condensation reaction of phenol and acetone.
U.S. Pat. No. 5,087,767 to Kenichi Okamoto et al. suggests a method for preparing 2,2-bis(4-hydroxyphenyl)propane comprising reacting acetone and phenol in the presence of an acidic ion-exchange resin as a catalyst wherein the reaction of acetone and phenol is performed while removing a part of the water generated during the reaction from a mixed solution containing acetone and phenol by a pervaporation method with a selectively water-permeable membrane such as porous glass, silica, alumina and ceramic membranes. According to the method described in this patent, the water generated through the reaction can rapidly be removed simultaneously with or alternatively to the reaction by a pervaporation operation and, therefore, the catalytic activity of the ion-exchange resin is not impaired at all. Moreover, any complicated operations associated with dehydration are not required. Thus, the acidic ion-exchange resin catalyst can continuously be used over a long time period without any treatment for the regeneration thereof. Further, according to the method of this patent, bisphenol-A can be economically prepared from acetone and phenol in a high conversion rate and good yield. However, as shown in the illustrative examples, the capacity of removing water is not strong so that after about 8 hours of the condensation reaction in a batch stirred reactor the conversion of acetone or the yield of p, p-bisphenol-A amounts to about 75% for an inorganic-organic composite membrane, about 80% for an organic membrane and about 90% for an inorganic membrane.
U.S. Pat. No. 5,105,026 to Joseph B. Powell is concerned with improvements to the purity of a bisphenol product in a bisphenol by-product isomerization process wherein isomers of bisphenol are isomerized to the desired bisphenol product. During the isomerization, acidic resin fines elute from the acidic ion-exchange resin isomerization catalyst into the reaction effluent. These resin fines can be filtered effectively and without contamination by a bed of solid particles such as alumina or carbon. The removal of resin fines improves the product quality and yield by eliminating resin particulates and reducing acid catalyzed cracking of bisphenols during successive purification and finishing steps.
U.S. Pat. No. 5,133,942 Edward M. Jones provides an arrangement for concurrently carrying out chemical reactions in a distillation column reactor, separating by fractional distillation the reactants and reaction products, removing the reaction catalyst from a distillation column reactor and replacing the used catalyst with fresh and/or regenerated catalyst. The distillation column contains a plurality of suitable liquid-vapor contact trays. Each of said trays have a downcomer and weir associated therewith, said downcomer connecting each said tray to the tray below each said tray. A solid particulate catalyst is supported on at least a portion of said trays by wire mesh or screen or filter medium and submerged to approximately the depth of the liquid on said trays. The vapor rising through the liquid on the trays tends to keep the particulate catalyst in the form of suspension in the liquid. Obviously, there are a lot of chemical reactions which can not be carried out because the reaction temperature of the reactants and the distillation temperature of the component or product to be separated out by fractional distillation are not consistent with each other or there is a great difference therebetween.
EP 0,319,326A3 to Shigeru Iimuro et al. provides a process for preparing 2,2-bis (4-hydroxyphenyl) propane (also bisphenol-A) of high purity. Actually, Shigeru Iimuro et al. simply suggests a pretreatment step before the adduct of bisphenol-A with phenol, in particular that obtained by the condensation reaction of acetone and phenol and subsequent treatments such as, for example distillation or concentration and crystallizations of the resulting reaction mixture is subjected to the dephenolization operation. According to the Iimuro's invention, the adduct is washed with phenol which itself is obtained as a by-product when the adduct of bisphenol-A and phenol is decomposed to give a bisphenol-A product. It is reported in the Iimuro's description that the hue of bisphenol-A obtained by the decomposition of the washed adduct is about 10 APHA and the purity of the bisphenol-A product was believed to be satisfactory as a material for use in the manufacture of an optical storage polycarbonate. However, the purity of the bisphenol-A product is not specifically given in the Iimuro's disclosure.
JP No. 61-78,741 assigned to Mitsui Toatsu Chemicals, Inc. describes a process for the production of 2,2-bis (4-hydroxyphenyl) propane (BPA) wherein the mixed reaction solution containing phenol and acetone is brought into contact simultaneously or alternatively with an ion-exchange resin and a dehydrating agent. The provided examples as a consequence, reports that after about 8 hours of the condensation reaction in such a manner the conversion is at most about 95% and the purity of the obtained bisphenol-A product does not exceed about 97.5%.
CN 1,069,961A is directed to the preparation and purification of the adduct crystals of bisphenol-A and phenol, crystallization means and process for the preparation of a high quality bisphenol-A product. According to the teachings of this patent application, the reaction mixture issued from the condensation reaction of acetone and excess phenol is passed through a plurality of crystallization treatment stages and the adduct of bisphenol-A and phenol which is meanwhile crystallized and separated in the respective crystallization stages is brought into intimate contact with a phenol product which is already purified in accordance with a specific manner to wash and purify the adduct crystals thoroughly. Thereafter, phenol is removed from the adduct crystals by means of for example evaporation, extraction and steam stripping. It is asserted in the disclosure of this application that bisphenol-A having a high purity, a good hue (less than 15 APHA), good storage stability and resistance to coloration when it is melted may be obtained. Obviously, there is only stressed in the application the performance of the crystallization operation of the already formed adduct crystals of bisphenol-A and phenol rather than how to increase the purity of the obtained bisphenol-A through the improvements to various operation steps with a simplified reactor system and subsequent treatment means.
Although the bisphenol-A product obtained after the purification operations in accordance with the ion-exchange resin catalyzed method may meet the requirements as to the quality of bisphenol-A usable for the manufacture of conventional polycarbonates, there is heretofore unknown an ultrapure bisphenol-A product having a purity of such as, for example, more than about 99.95% or even about 99.99% sufficient for use in the manufacture of for example optical data storage materials.
Since the processes for the synthesis of higher purity bisphenol-A according to the ion-exchange resin catalyzed methods so far proposed in the literature such as in the above-mentioned patents and patent applications use higher molar ratios of phenol to acetone which is in general higher than about 8:1 and at the same time there are some limitations to the reaction temperature and residence time, etc., the concentration of bisphenol-A in the resulting liquid condensation reaction mixture is very low, typically below about 15%. Therefore, the liquid condensation reaction mixture must be concentrated before it is cooled to precipitate adduct of bisphenol-A and phenol in the form of crystals. Heretofore, there has been no proposal for omitting the concentration step since direct crystallization of the highly dilute condensation reaction solution undoubtedly results in very low yield of bisphenol-A and fully unacceptable color or hue of more than 15 APHA, thereby reducing the purity of thus obtained bisphenol-A product significantly. To concentrate the reaction mixture means that the process stream is subjected to strong thermal effect once more, thereby leading possibly to the decomposition or secondary reactions of the desired reaction product to form coloring substance because the liquid condensation reaction mixture from the reactor system contains slightly acidic impurities.
Moreover, the ion-exchange resin catalyzed methods as described in for example the above-mentioned patents or patent applications are still disadvantageous in that the condensation reaction rate is low and the residence time of feedstocks is long in the reactor system. The after treatment is complicated and highly loaded due to the high ratio of phenol to acetone and large amount of recycle unreacted phenol stream. In some instances, the reactor systems used are difficult to assemble or disassemble. For the bag construction as described in U.S. Pat. No. 4,487,430, some liquid may flow through the spaces between the bags.
Therefore, it is always desirable to further improve the conventional processes or some steps thereof in various aspects or further to develop novel processes for producing higher and higher quality (purity and coloration, etc.) bisphenol-A products to meet great demand in industrial applications although there have been a great number of processes for the production of bisphenol-A (BPA) which have shown separately some advantages over their respective preceding processes and have been described in a variety of patents and other publications such as those mentioned above.

Process for the production of high purity and ultrapure bisphenol-A


The present invention is directed to a hair styling device for providing lift to a mass of undifferentiated hair stands on a scalp region comprising: a bundling means for gathering hair strands into hair bundles; a reservoir, in fluid communication with the bundling means, comprising a styling composition; and a means to hold and further align the hair strands along and beyond the bundling means.

The use of hair styling devices for styling hair is well known and many attempts have been made to provide devices such as hair rollers, curling irons and flat irons with structures to improve the results obtained in curling, straightening, and setting hair with the aid of air or heat.
In order to achieve a desired lift and volume to the hair, attempts in the past have used the combination of hair styling products such as mousses, gels and sprays in combination with a hair styling device such as a dryer, curling iron, or flat iron. However, the result of using this method is cumbersome and results in a very limited and not long-lasting through the day hair style.
It has now surprisingly been found a single hair styling device can achieve this unmet need. The present invention discloses a hair styling device for providing lift to a mass of undifferentiated hair stands on a scalp region comprising: a bundling means for gathering hair strands into hair bundles; a reservoir, in fluid communication with the bundling means, comprising a styling composition; and a means to hold and further align the hair strands along and beyond the bundling means.
This approach allows for the delivery of a thin layer of active on the hair, close to the scalp and results in a long-lasting hair style throughout the day. This approach also eliminates the problems associated with the use of too much styling product all over the hair, which will have a negative impact on the hair feel. The hair styling device of the present invention allows a user to put larger amounts of active (localized deposition) in a specific area to provide lift and volume benefits while minimizing feel tradeoff.

Device for achieving lift and volume to hair


A substrate is filled with a reagent that presents a stable free radical character, and that is capable of producing a visible reaction in the presence of at least one free radical scavenger analyte of the skin.

The present invention relates to methods and devices that make it possible to evaluate the potential of the skin, including the lips, for scavenging free radicals, said potential also being referred to as "antioxidant potential."
Harmful free radicals are molecules that have a very short half-life, in the range 1 nanosecond (ns) to 1 millisecond (ms), and that are therefore very unstable and very reactive.
It is known that the ability of the skin to protect itself from external aggression such as exposure to ultraviolet rays, pollution, or other types of biological or chemical aggression, can depend in particular on its epidermal content of non-enzymatic antioxidants that are capable of scavenging the free radicals.
Thus, vitamin E is a known antioxidant for protecting the skin and for preventing it from aging, and it is often found in cosmetic formulations.
Depending on the individual, the concentration in the skin of antioxidants such as molecules with a thiol group, ascorbate, tocopherol, tocotrienol, uric acid, vitamin A, ubiquinone 10, spermine, and the like can vary, e.g. depending on age, skin type, diet, degree of exposure to ultraviolet rays, etc.
At present, common apparatus for monitoring free radicals directly is exceedingly expensive.
It has been proposed to use neutral sensor molecules called spin-trap that react to give radical-like molecules that are more stable and thus measurable by Electron Spin Resonance (ESR).
The formation of lipid peroxides or of squalene peroxides as indicators of cutaneous stress has been studied in the publication "Ultraviolet A induces generation of squalene monohydroperoxide isomers in human sebum and skin surface lipids in vitro and in vivo": S. E. Mudiyanselage, M. Hamburger, P. Elsner, J. J. Thiele, J. Invest. Dermatol. June 2003; 120(6) 915-22, and in German patent application DE 10 164 553.
The article "Evaluation of free radical scavenger effects of Helianthus annus extract using new ex vivo stripping methods," P. Mondon and al. in "Cosmetics, aerosols & toiletries" in Australia May 20, 1999, describes a method consisting in taking a sample of the stratum corneum, and in extracting therefrom the antioxidants the reaction of which with a colored reagent that is 1,1-Diphenyl-2-Picryl-Hydrazyl (DPPH) is carried, the bleaching of the reagent being monitored using a spectrophotometer at 517 nanometers (nm).
DPPH is a stable free radical, which, in the presence of one or more radical scavengers, loses its free radical character with a reduction in its color.
As a result of its stable character, DPPH has also been used in Electron Paramagnetic Resonance (EPR) techniques for measuring the free radical scavenger activity of the human epidermis, as described in the article "HPLC analysis of vitamin E isoforms in human epidermis: Correlation with minimal erythema dose and free radical scavenger activity": J. Fuchs, S. Weber, M. Podda, N. Groth, T. Herrling, L. Packer, R. Kaufmann, Free radic. Biol. Med. Feb. 1, 2003; 34 (3): 330-6.
Current analysis techniques implementing DPPH remain relatively complex and costly.

Method of evaluating the potential of the skin for scavenging free radicals


A single continuous dough sheet (12) is conveyed by a conveyor (20) up an incline to a dough tension and drive system (38). In the system (38), the dough sheet (12) passes around a lower drive roller (40), around an intermediate drive roller (42), and around an upper drive roller (44). The dough sheet (12) extends at a downward angle to an idler roller (80) which directs the dough sheet (12) generally vertically downward in a flat condition. A wishbone pushing element (82) having a rounded V-shape forms the first face of the dough sheet (12) into a generally V-shape having two wings. The wings of the V-shape are then guided by an aligning element (96) such as laterally spaced rollers (98, 100) which roll on the opposite face of the wings to form a folded, two-ply continuous dough sheet (14). The angular relationship of the legs (84, 86) of the pushing element (82), the lateral spacing of the rollers (98, 100 ) of the aligning element (96) and the three dimensional positioning of the pushing element (82) and the aligning element (96) can be adjusted to insure that the free edges in the folded continuous dough sheet (14) are aligned relative to each other.

The present invention generally relates to apparatus and methods for flipping and aligning a flexible, continuous sheet, particularly to food processing apparatus and methods for flipping and aligning a dough sheet into a folded, two-ply continuous sheet, and more particularly to apparatus and methods for flipping and aligning a dough sheet for the preparation of a snack product by conventional deep fat frying.
One type of snack product which has gained wide market acceptance is the "puffed" snack piece. In certain methods of preparation, a cooked farinaceous dough is formed into a single continuous dough sheet. This dough sheet is then run through a piece forming apparatus which includes an opposed pair of rollers at least one of which has depressions which stamp out the desired shape and size pieces from the dough sheet. After formation of the dough pieces, the pieces are dried under controlled conditions from a moisture content of about 18% down to a moisture content of between 12% and 14% to form a pellet called a half product piece. The moisture content of the half product piece is sufficiently low to exhibit extended shelf stability. The snack product is prepared from the half product piece by conventional deep fat frying. The frying of the half product piece generates steam volumes inside of the half product piece to puff the half product piece resulting in a light, puffed snack piece having surface corrugations
The sale of snack food products is a highly competitive business. The novelty of snack food products decline rapidly, as new and different types of snack foods are introduced to maintain or increase market share. Puffed snack pieces can be varied in various ways such as by changing the shapes, sizes, and surface corrugations of the pieces or by changing the composition of the dough from which the half product pieces are prepared. Another variation is to have the puffed snack piece of a hollow structure, with the hollow configuration resulting from the fabrication of the half product pieces from a two-layer laminated dough sheet.
One method of forming a laminated dough sheet is to fold a single continuous dough sheet into a two-plied dough sheet. However, the formation of such a two-plied dough sheet continuously from a single dough sheet presents many problems. In particular, even though the free edges of the folded sheet are initially aligned, the free edges will tend to travel relative to each other upon continued operation of a folding device. This problem is particularly severe as the speed of operation of the machinery increases. The failure to provide an evenly folded two-ply dough sheet results in improper feeding into the dough piece former. At the one, misaligned free edge, defective half product pieces are formed. At the other end, an excess of dough material is fed to the piece former resulting in either generation of scrap material, deformation of formed pieces, or both.
Accordingly, it is an object of the present invention to provide novel apparatus and methods for the continuous creation of a two-plied sheet from a single sheet.
Another object of the present invention is to provide novel apparatus and methods for folding a dough sheet and aligning the folded sheet into a two-plied sheet.
Yet another object of the present invention is to provide novel apparatus and methods for continuously fabricating a two-plied dough sheet from a single dough sheet. In this regard, the free edges of the folded sheet are aligned even with continuous and high speed operation.

Method of flipping and aligning a dough sheet


Imaging of a turbid object utilizes interference among the modulation wavefronts of a plurality of modulated light rays propagating through the object by diffusion and having predetermined phases relative to one another. A computer controlled phase and amplitude selecting device, such as a zone plate, is used to modulate light rays at appropriate phases in order to obtain constructive interference only at a predetermined portion of the object, including one or more preselected voxels. The rays reflected from (or diffusively transmitted through) the predetermined portion are received simultaneously at a detector, thus providing simultaneously all the data necessary to describe or image the portion. A single detector element may be used to detect the scattered reflected or transmitted light from the portion and to generate a signal representing the amplitude and phase characteristics for the modulation wavefront, thereby to provide absorption (and other) characteristics descriptive of the portion. An array of detectors may be used to detect the light from a plurality of individual voxels simultaneously and to provide such characteristics for each of the voxels. By dynamically controlling the phase and amplitude selecting device, the voxels selected for imaging are changed without mechanical scanning. Light rays having different frequencies may be modulated to provide complete absorption spectra for an arbitrarily selected portion of the object.

Numerous techniques and devices are known and available for imaging structures within opaque or turbid objects, such as biological tissue.
For example, X-ray imaging has been widely used to provide shadow images of obstructed structures. Such imaging relies on opacity of dense materials, such as bone structure, relative to surrounding tissue, to attenuate the intensity of X- radiation passing directly through the object to a recording medium, such as photographic film or fluorescent media. The recording medium is exposed to a spatial pattern of radiation corresponding to the intensity of the incident attenuated radiation, thus providing data or shadow image representation of a spatial distribution of internal structural components of differing size and density at different locations in the object being imaged.
In order to obtain a three dimensional view of the imaged object it is necessary to irradiate the object sequentially from all angles, using complex mechanical scanning devices for changing the relative positioning of the source and detector with respect to the imaged object, as with computerized tomography, in order to enable imaging of a single "slice". Other imaging techniques use still other forms of ionizing radiation, such as gamma radiation, to obtain similar results. In addition to these disadvantages, it is necessary to introduce contrast agents into the sample in order to image soft tissue. Such a process adds to the complexity of imaging living subjects.
Similarly, magnetic resonance imaging techniques and ultrasound imaging techniques are known, providing information in the form of images descriptive of the position, size and shape of objects. In NMR (nuclear magnetic resonance) imaging a spatially varying magnetic field is applied to the object while in ultrasound imaging a sonic wave is applied to the object. Mechanical scanning may be necessary for ultrasound imaging in order to apply and to receive the waves to the selected segment to be imaged. Moreover, two dimensional N.times.N imaging using NMR exploits the frequency domain and the phase domain, and N sequential data acquisitions are required in the phase direction for such imaging. The acquired data detected by an RF pickup coil are then processed to provide an image of the internal structure of the object.
Moreover, there are known techniques for use of light beams for producing an image, wherein one or more light rays travel through an object and the exiting rays are passed through a zone plate to a detector array to provide information relative to the internal structure of the object. Such techniques, however, are subject to significant errors in attempting to image a preselected site. Specifically, resolution is a function of the wavelength. Typical wavelengths for laser generated light are in the range of 0.5 to 1.0 micron. Thus, in order to use a beam of coherent light to image a selected element of an object it is necessary to position the object with extreme accuracy. Positioning errors of less than a micron result in significant errors.
In order to obtain resolution of the order of 1 mm it would be necessary to use electromagnetic radiation having wavelengths in the range of 1 to 10 cm. However, use of this band of frequencies would expose the object to radiation in the microwave region. Such radiation is particularly susceptible to absorption by water in the tissue being imaged. As is known, electromagnetic radiation in the microwave region is thus typically used for heating and cooking. Accordingly, it could be quite harmful to attempt direct optical imaging utilizing electromagnetic radiation having wavelengths appropriate for standard resolution.
Additionally, similarly to X-ray and gamma imaging, known attempts at imaging using rays of partially coherent light rely on shadow-imaging, utilizing only the relatively small number of "prompt" photons which pass directly through the object, in a relatively straight line and with minimal deflection and diffusion. However, a much larger number of photons which pass through the tissue, and which thus potentially carry much more information, are ignored. These are photons which pass through the tissue by the wave diffusion process, hence passing more slowly, at attenuated intensity and undergoing scattering and interference with one another. For various reasons such diffusive rays have been overlooked by the prior art as a source of imaging information.
The theory of propagation of intensity modulated laser beams in turbid media by photon diffusion has been studied and equations have been developed describing wave propagation characteristics. Specifically, attenuation and phase delay of the modulated wavefront have been described in a homogeneous medium, for diffusive waves having a coherent front. The equations were tested for description of photon migration in turbid media, and were used in conjunction with a frequency domain analysis to determine linear scattering and absorption coefficients of a homogeneous, infinite, turbid medium. Fishkin et al., "Diffusion of Intensity Modulated Near-Infrared Light in Turbid Media", Tissues, SPIE, Los Angeles, January, 1991.
In a more recent development, it has been proposed to image tissues using intensity-modulated near-infrared light provided by a pulsed laser, using the increased distance of maintained coherence for diffusional waves and the greater depth of propagation for the lower frequency intensity modulation wavefront than for the higher frequency optical field wavefront. Nonetheless, the reported technique has not contemplated a manner in which a particular volume of interest (voxel) at a desired depth may be selected for imaging.
In summary, the known imaging methods and devices suffer from various drawbacks. For example, known techniques do not permit simultaneous imaging of all points of a desired volume of interest within an object. Nor are the known techniques capable of providing information beyond the presence and shape of various structures within an imaged volume. Moreover, where reflectance imaging is used, signals from voxels close to the object surface tend to overwhelm the photodetector, so that selection of deeper voxels is made impractical. Further, various techniques of the prior art require mechanical scanning of an object in order to image a desired voxel, rely on sequential data acquisition, and are incapable of imaging a voxel in real time. Others of the known methods require exposure to ionizing radiation, administration of radioactive contrast or tracing agents, may be invasive in nature, expensive to administer, and suffer from various other deficiencies.
There is accordingly a need for method and apparatus for obtaining data descriptive of characteristics of a turbid medium, and more specifically of tissue, and of its internal structure, which are not subject to the deficiencies of the prior art.
There is a more particular need for a method and apparatus for imaging an object utilizing electromagnetic radiation and permitting resolution in the range of 1 mm, while avoiding use of radiation having wavelengths in the range of 1-10 cm and the harmful effects thereof.
There is a more specific need for a non-invasive method and apparatus for imaging an object, free of requirements for exposure to ionizing radiation and administration of contrast or tracing agents, free of a need for mechanical scanning, and capable of simultaneously providing imaging data representative of a selected volume of interest.
Moreover, there is a need to be able to reflectively image voxels which are deep within the object, without overwhelming the photodetector by signals from voxels close to the surface.
There is still a further need for a method and apparatus for obtaining images or data descriptive of characteristics of a selected voxel of an object by exposure to intensity modulated light beams or other non-ionizing radiation, wherein the acquired images or data are descriptive of characteristics or physical parameters in addition to physical size or presence of structures within the object.

Method and apparatus for imaging a physical parameter in turbid media using diffuse waves

The Government of the United States of America as represented by the Secretary of the Department Health and Human Services


A portable sanitizer dispenser for use with a cellular phone includes a hand sanitizer dispenser configured to releasably engage at least one surface of a cellular phone. The sanitizer dispenser includes a compressible cavity defined therein configured to retain a sanitizer therein. The sanitizer dispenser further includes a nozzle disposed on an outer surface thereof. The nozzle is in fluid communication with the compressible cavity such that when pressure is applied to the compressible cavity, sanitizer is expelled from the nozzle.

Technical Field
The present disclosure relates to dispensers and, more particularly, to portable hand sanitizer dispensers.
Description of Related Art
Humans interact with hundreds if not thousands of objects every day. Manipulating or touching these objects transmits pathogens, such as viruses, bacteria, fungus, and the like, and in doing so, fosters the spread of sicknesses and disease. As such, the use of hand sanitizers, such as PURELL®, SHBAN™, Germ-X®, and similar alcohol based or alcohol free liquids or gels that effectively kill 99.9% of these pathogens has become more prevalent. However, hand sanitizers are typically dispensed through the use of pump bottles, touch free dispensers, and other large dispensers incapable of truly portable use. Therefore, one is unable to sanitize his/her hands frequently or after handling objects that may transmit pathogens unless a dispenser is nearby and handy, thereby promoting the spread of disease.
Therefore, a need exists for portable hand sanitizer dispensers that may be easily carried and deployed with minimal effort.

Devices and methods for dispensing hand sanitizer


Controlling network services using palm sized computers is described. A program on the palm sized computer is used to access a registry of network services that may be available. The registry includes descriptions for various services. Each description includes at least a reference to program code that can be downloaded to the palm sized computer. Executing this program causes the palm sized computer to issue commands directly to the specific network services needed. In some cases, these network services include application services for running desktop applications that the palm sized computer could not execute.

1. Field of the Invention
This invention relates to the field of networked computer. In particular, the invention relates to a system and method to control network devices using a palm sized, or otherwise reduced functionality, computer.
2. Description of the Related Art
Palm sized computers, also referred to as Personal Digital Assistants (PDAs), are portable devices which perform an array of personal management tasks such as calendar management and address book storage. The adoption of palm sized computers has been rapid. Some palm sized computers are able to interface with conventional computing devices, such as PCs, on an as-needed basis. For example, palm sized computers such as 3Com's Palm Platform.TM. computers can upload personal appointments to a PC-based calendar.
Palm sized computers generally have the following characteristics. Relative to desktop and laptop computers, palm sized computers have limited processing, display and input capabilities. As a result of these limitations, palm sized computers do not run the same applications as desktop or laptop computers. Other limitations of palm sized computers include limited battery life and lower bandwidth communications with other devices.
One big advantage of palm sized computers is their portability. Therefore, it is desirable to be able to access desktop functionality from palm sized computers.

System and method using a palm sized computer to control network devices


In connection with a rear window shade, elastomeric profiled strips are assigned to the guide rails in which the pull rod is guided. The profiled strips are capable of holding the respective end of the pull rod in the guide rail in a substantially rattle-free manner.

Rear window shades for motor vehicles are known in the prior art. Today, a rotatably seated winding shaft installed under the rear window ledge is usually a part of these shades. An edge of the shade web is fastened to the winding shaft and can be pulled out through a slit in the rear window ledge. Since the shade web is not rigid in itself, it is necessary for the shade web to be guided. To this end, guide rails, in which a pull rod arrangement is guided, extend at the sides of the side to be shaded. The pull rod arrangement is fastened to the front edge of the shade web, i.e. to that edge which travels the greatest distance when the window shade is extended and retracted.
The guide rails have an approximately C-shaped cross section, so that an undercut channel is created, which opens to the outside via a slit. The slits of the two guide rails face each other. The pull rod arrangement can include guide bodies that can be guided in the guide rails in such a way that the guide bodies cannot be pulled out at right angles to the longitudinal axis of the guide rail.
Although as a rule the guide bodies are pre-tensed by springs, and a spring motor force also acts on the pull rod arrangement which attempts to wind the shade web up on the winding shaft, such arrangements are not completely free of rattles. Force components, which are effective perpendicularly with respect to the plane defined by the extended window shade, are primarily only absorbed by the frictional connection which is used between the guide bodies and the actuating devices for transporting the pull rod arrangement along the guide rails. The forces can easily become larger, and the guide bodies can rattle in the transverse direction. The question as to whether this noise will develop depends on the position of the window shades, the installed position, the jarring being generated because of road conditions, and other factors.
Freedom from rattling cannot be completely assured by means of the previous solutions.

Window shade with a rattle-free guidance system


A method for time lapse electric logging in a cased hole in which electrodes are implanted in the casing or the hole is completed with a gravel packed non conductive, perforated liner that allows an open hole logging tool to be used for time-lapse logging. Thereafter, the implemented electrodes or a self-potential (SP) logging tool are used to monitor a steam-flooding EOR method by detecting two-phase flow with time lapse logging. A potential drop between the surface and zones of interest is measured with electrodes installed in a non-conductive casing or the SP logging tool.

In the production of crude oil, it is sometimes found that the crude oil is sufficiently viscous to require steam injection into the petroleum reservoir. Ideally, the petroleum reservoir would be completely homogeneous and steam would enter all portions of the reservoir evenly. However, it is often found that this does not occur. Instead, steam selectively enters a small portion of the reservoir while effectively bypassing other portions of the reservoir. Eventually, "steam breakthrough" occurs and most of the steam flows directly from an injection well to a production well, bypassing a large part of the petroleum reservoir and producing significant amounts of wasted heat.
It is possible to overcome this problem with various remedial measures, e.g., by using foam or by plugging off certain portions of the injection well. For example, see U.S. Pat. Nos. 4,470,462 and 4,501,329 which are hereby incorporated by reference herein. However, to institute these remedial measures, it is necessary to determine which portions of the reservoir are selectively receiving the injected steam. This is often a difficult problem.
Various methods have been proposed for determining how injected steam is being distributed in the wellbore. D. E. Bookout et al. in a publication entitled "Injection Profiles During Steam Injection", SPE Paper No. 801-843 C, pp. 1-16, dated May 3, 1967 summarizes some of the known methods for determining steam projection profiles.
The first and most widely used of these methods is known as a "spinner survey". In this method, a tool containing a freely rotating impeller is placed in the wellbore. As steam passes the impeller, it rotates at a rate which depends on the velocity of the steam. The rotation of the impeller is translated into an electrical signal which is transmitted up the logging cable to the surface where it is recorded on a strip chart or other recording device.
As is known to those skilled in the art, these spinners are greatly affected by both the quality and the rate of steam injection into the well. Steam quality and rate decrease with depth leading to unreliable and unreproducible results.
Radioactive tracer surveys are also used in many situations. With this method methyl iodide (131) has been used to trace the vapor phase. Sodium iodide has been used to trace the liquid phase. Radioactive iodine is injected into the steam between the steam generator and the injection well. Injected tracer moves down the tubing with the steam until it reaches the formation, where the tracer is temporarily held on the face of the formation for several minutes. A typical gamma ray log is then run immediately following the tracer injection. The recorded gamma ray intensity at any point in the well is then assumed to be proportional to the amount of steam injected at that point.
Vapor phase tracers have variously been described as alkyl halides (methyl iodide, methyl bromide, and ethyl bromide) or elemental iodine. The arrival of the radioactive tracer is a function of steam quality. Since quality decreases with depth then most of the material would be dissolved in the liquid phase in the lower portion of the injection well leading to unreliable measurements.
Although these methods can be utilized, what is needed is a simple and efficient method for determining the rate of steam injection and the quality of the steam injected. It is important to determine which intervals of the formation are accepting steam and the quality of the steam both at the injection wellbore and at an observation well away from the injector.

Method including electrical self potential measurements for detecting multiphase flow in a cased hole


An optical fiber tube includes a core material having multiple nylon filaments twisted with each other in a helical manner, a plurality of single strand optical fibers mounted around the core material and twisted with the core material in a helical manner, a tubular protective film mounted around the plurality of single strand optical fibers, and a plastic sleeve mounted around the protective film.

1. Field of the Invention
The present invention relates to an optical fiber tube, and more particularly to an optical fiber tube for a decorative light.
2. Description of the Related Art
A first conventional optical fiber tube for a decorative light in accordance with the prior art shown in FIG. 7 includes a core (81 ) and a cover (80) around the core (81). The core (81) and the cover (80) are both made of transparent materials with different refractive indexes. The refractive index of the core (81) is greater than that of the cover (80). When the incident angle of the light entering the core (81) is greater than a limiting angle, the light will be fully reflected and can then be propagated in the core (81).
A second conventional optical fiber tube for a decorative light in accordance with the prior art shown in FIGS. 8 and 9 includes a core material (90) made of polyvinyl chloride (P.V.C.), multiple single strand optical fibers (91) around the core material (90) and having multiple optical fibers (910) twisted with each other, a transparent tubular protective film (92) mounted around the single strand optical fibers (91), and a transparent plastic cover (93) mounted around the protective film (92). However, the optical fiber tube cannot be bent due to the rigidity of the core material (90), thereby decreasing the versatility of the optical fiber tube.
The present invention has arisen to mitigate and/or obviate the disadvantage of the conventional optical fiber tube.

Optical fiber tube for a decorative light

15th Fl.-D, No. 81, Sec. 1, Hsintai 5th Rd.