When the engine load is in a high-load zone, an absolute value control is executed, wherein the actual values of valve timings of an intake valve and an exhaust valve and a valve duration of the intake valve are controlled to coincide with respective target values set based on the operating state of an internal combustion engine. When the engine load is in a low-load zone, a relative value control is executed, wherein an actual value of a valve overlap amount of the intake valve and the exhaust valve is controlled to coincide with a target valve overlap amount obtained based on the target values. Therefore, a control method for the internal combustion engine that is appropriate for the operating state of the engine when the operating state of the engine is in transition is obtained.

A typical internal combustion engine for a vehicle includes a variable valve timing mechanism for changing the valve timing of intake valves and exhaust valves based on the engine operating state to improve the engine output and the exhaust characteristics. The mechanism changes the valve timing of the intake valves and the exhaust valves by changing the relative rotational angle of a camshaft with respect to the crankshaft of the internal combustion engine.
An variable valve duration mechanism has been proposed that changes the valve duration of the intake valves (the crank angle from when each intake valve is opened until when the intake valve is closed) in accordance with the engine operating state (for example, Japanese Laid-Open Patent Publication No. 2001-263015). With the internal combustion engine equipped with the mechanism, the amount of air drawn into engine combustion chambers is adjusted by changing the valve duration of the intake valves. Furthermore, adjusting the intake air amount by changing the valve duration of the intake valves permits the opening degree of an intake throttle valve to be set as large as possible, thus reducing the pumping loss.
Since the valve timing of the intake/exhaust valves and the valve duration of the intake valves are controlled in accordance with the engine operating state, the valve overlap amount of the intake/exhaust valves is appropriately set in accordance with the engine operating state. Since the internal EGR amount, the pumping loss, or the engine combustion state changes significantly as the valve overlap amount changes, the valve overlap amount is desirably controlled appropriately when operating the engine.
There is a predetermined delay in the response of the operation of the variable valve timing mechanism and the variable valve duration mechanism. Therefore, a temporary divergence occurs between the control target values and the actual values of the mechanisms. Therefore, when the control target values are changed in accordance with the change of the engine operating state during a steady operating state where the control target values and the actual values of the mechanisms coincide each other, the operating state of the internal combustion engine shifts into a transition state where the control target values and the actual values of the mechanisms diverge. Then, the operating state of the internal combustion engine shifts into the steady operating state again after a predetermined period has elapsed. When the valve timing of the intake/exhaust valves and the valve duration of the intake valves are independently controlled, the following problems occur when the operating state of the engine is in transition.
That is, when the internal combustion engine shifts from the steady operating state to the transition operating state, the valve timing of the intake/exhaust valves and the valve duration of the intake valves are controlled such that the control target values coincide with the actual values. However, at this time, the valve overlap amount may be controlled to an amount inappropriate for the engine operating state in transition. More specifically, as shown in FIGS. 7A to 7C, when, for example, the engine operating state shifts from a state where the valve overlap amount is desirably set as small as possible (FIG. 7A) to a different state (FIG. 7C), if the valve timing of the intake/exhaust valves and the valve duration of the intake valves are controlled accordingly, the valve overlap amount may be temporarily increased (FIG. 7B). When the valve overlap amount is unexpectedly increased, an internal EGR is excessively performed, leading to deterioration of the engine combustion. As described above, when the operating state of the engine is in transition, the valve overlap amount may be controlled to an amount inappropriate for the engine operating state on each occasion. Therefore, although it is temporary, there is an adverse effect on the engine operation.
To avoid adversely affecting the engine operation, for example, the valve timing of the intake/exhaust valves and the valve duration of the intake valves may be controlled such that the valve overlap amount will not be inappropriate when the operating state of the engine is in transition. However, when such a method is simply employed, although the valve overlap amount is appropriately controlled, the divergence between the actual values and the control target values of the valve timing of the intake/exhaust valves and the valve duration of the intake valves is not promptly eliminated.

Control method and control apparatus for internal combustion engine


A method of forming a microelectronic structure and its associated structures is described. That method comprises forming and patterning a deep uv resist layer on a substrate, etching the substrate in a plasma generated from a gas comprising a carbon to fluorine ratio from about 1:1 to about 2:3 to form substantially vertical sidewalls in the deep uv resist layer.

Resist layers (sometimes called photoresist layers to imply the lithographic processes typically used with them) are frequently used to generate masks during the fabrication of integrated circuits. Typically, a layer of resist material 304 is deposited on the surface of an underlying layer 302 to be patterned, and then the resist layer 304 is exposed to light 300 that is passed through an exposure pattern 301 (see FIG. 3a). The resist material 304 is processed in such a way that the exposed portions of the resist material 304 (or alternately the non-exposed portions) are removed, so that the remaining resist material 304 forms a mask in the shape of the exposure pattern (See FIG. 3b). The patterned resist material 304 includes sidewalls 306 that serve to define circuit features in the underlying layer 302. The sidewalls 306 include a pre-etch sidewall angle 308, that is typically about 90 degrees.
The areas of underlying layer 302 that are not directly covered by the resist material 304 are removed through an etch process, such as a plasma etch, with the mask of resist material 304 preventing removal of those portions of the underlying material that are directly under the resist material 304 (FIG. 3c). Because an etch is a destructive process, the etch may cause deterioration of the resist material 304. This deterioration may uncover additional portions of the underlying material 302 before the etch is complete, thereby etching portions of the underlying material 302 that were intended to be protected from the etch process.
The deterioration is typically greatest at the sidewalls 306 of the resist material 304, i.e., a post-etch sidewall angle 308′ of the sidewalls 306 is less than the pre-etch sidewall angle 308 of the sidewall 306, which results in a sloped resist sidewall 306. Circuit features, such as trenches, that may be etched in a substrate, for example, a low k dielectric material, may exhibit significant sloping because the sidewalls 306 of the resist material 304 that define those features are unintentionally etched away (FIG. 3c). If not treated carefully, excessive resist sloping during plasma etching can cause shorting (because the sloped angle of the resist mask is transferred to the circuit feature) between features such as between metal lines or between trenches, for example, which can leading to device failure.
In addition, resist material that is designed for exposure to light with a wavelength of approximately 193 nanometers (which is commonly used for sub 0.13 micron circuit features) is particularly susceptible to deterioration during the plasma etch. To improve etch resistance, one common approach is to increase the carbon-to-hydrogen ratio in the resist material while maintaining its transparency to exposure light. Several available options have been utilized, such as multi-ringed aliphatic groups, poly methyl methacrylate, or cyclo olefin-maleic anhydride copolymer platforms. However, these approaches have limited success in achieving etch resistance comparable with 248 nm resist, which is commonly used for circuit features greater than about 0.13 microns.
Therefore, there is a need for improved methods of plasma etching that reduce the deterioration of deep ultraviolet (uv) resist material, such as 193 nm resist material, so that underlying features do not exhibit sloping which can lead to device failure. The present invention provides such methods and their associated structures.

Process for low k dielectric plasma etching with high selectivity to deep uv photoresist


A program signal is recorded on a recording medium. The program signal is reproduced from the recording medium. First time information is generated in accordance with lapse of time. Second time information is generated from the reproduced program signal. The second time information represents one of (1) a time at which the program signal was recorded and (2) a time at which the program signal was broadcasted. On-screen information is superimposed on the reproduced program signal. The on-screen information represents (1) a picture portion indicative of a time, (2) a first mark positionally corresponding to the first time information, and (3) a second mark positionally corresponding to the second time information.

1. Field of the Invention
This invention relates to an apparatus for recording and reproducing a signal representative of a program on and from a recording medium such as a hard disk or a semiconductor memory.
2. Description of the Related Art
Personal video recorders (PVR's) are designed to record and reproduce signals representative of programs on and from hard disks. A typical PVR can simultaneously implement the recording of a first program signal and the reproduction of a second program signal on a time sharing basis.
Specifically, the typical PVR can record a signal of a program on the hard disk while reproducing a signal of another program therefrom. In addition, the typical PVR can record a signal of a program on the hard disk while implementing time shift playback which reproduces a head portion or an already-recorded portion of the same program signal from the hard disk.
Furthermore, the typical PVR can implement cache playback as follows. The hard disk is used as a cache disk. A signal representing a currently-broadcasted program is always recorded on the cache disk, that is, the hard disk. An amount of the program signal stored in the cache disk substantially corresponds to a prescribed play time. In the case where a PVR user requires playback from a scene somewhat preceding the current scene, the cache disk is accessed and a portion of the recorded program signal which starts from the required scene is reproduced from the cache disk.
During the implementation of the time shift playback or the cache playback, a program signal reproduced from the hard disk is indicated on a display. Only by watching a program indicated on the display, it is difficult for the PVR user to know whether the indicated program is a currently-broadcasted program or a program represented by a signal reproduced from the hard disk.
In the case where a program visualized on the display during the time shift playback or the cache playback has a superimposed indication of time at the left upper corner of the frame, the PVR user sometimes confuses the indicated time with the present time.

Program-signal recording and reproducing apparatus


A microliter liquid sample, particularly a biological sample, is analyzed in a device employing centrifugal and capillary forces. The sample is moved by capillary forces into one or more metering wells which define the amount of the sample to be analyzed in subsequent steps. The defined amount of the sample is transferred from the metering wells to one or more conditioning and reagent wells for measuring the amount of an analyte contained in each metered amount of the sample.

This invention relates generally to the field of microfluidics, as applied to analysis of various biological and chemical compositions. More particularly, the invention provides methods and apparatus for carrying out analyses, using both imposed centrifugal forces and capillary forces resulting from the surface properties of the passageways in the apparatus
To determine the presence (or absence) of, or the amount of an analyte, such as glucose, albumin, or bacteria in bodily or other fluids, a reagent device is generally used to assist a technician performing the analysis. Such reagent devices contain one or more reagent areas at which the technician can apply the sample fluid and then compare the result to a standard. For example, a reagent strip is dipped into the sample fluid and the strip changes color, the intensity or type of color being compared with a standard reference color chart.
Preparation of such devices is difficult when the sample has a complex composition, as many bodily fluids do. The component to be identified or measured may have to be converted to a suitable form before it can be detected by a reagent to provide a characteristic color. Other components in the sample fluid may interfere with the desired reaction and they must be separated from the sample or their effect neutralized. Sometimes, the reagents are incompatible with each other. In other cases, the sample must be pre-treated to concentrate the analyte of interest. These and other problems make it difficult to provide in a single device the reagents and other components which are needed for a particular assay. The art contains many examples of devices intended to overcome such problems and to provide the ability to analyze a fluid sample.
A different approach is to carry out a sequence of steps which prepare and analyze a sample, but without requiring a technician to do so. One way of doing this is by preparing a device which does the desired processes automatically, but by keeping the reagents separated, is able to avoid the problems just discussed.
Carrying out analysis may involve receiving a sample, selecting a desired amount of the sample, diluting or washing the sample, separating it into components, and carrying out reactions with the sample or its components. If one were to carry out such steps in a laboratory on large samples, it would generally be necessary for a technician to manually perform the necessary steps or if automated, equipment would be needed to move the sample and its components and to introduce reagents, wash liquids, diluents and the like. However, it is typical of biological assays that the samples are small and therefore it follows that the processing steps must be carried out in very small equipment. Scaling down laboratory equipment to the size needed for samples of about 0.02 to 50 μL is not feasible and a different approach is used. Small vessels connected by micron-size passageways are made by creating such features in plastic or other suitable substrates and covering the resulting substrate with another layer. The vessels may contain reagents added to them before the covering layer is applied. The passageways may also be treated as desired to make them wettable or non-wettable by the sample to be tested. The sample, its components, or other fluids may move through such passageways by capillary action when the walls are wetted or they are prevented from moving when the fluids do not wet the walls of the passageway. Thus, the capillary passageways can either move fluids or prevent their movement as if a valve were present. Another method of moving fluids through capillary passageways is by centrifugal force, which overcomes the resistance of non-wettable walls. This simple description provides an overview of microfluidic devices. Specific applications are provided in many patents, some of which will be mentioned below.
An extended discussion of some of the principles used in arranging the vessels and passageways for various types of analyses is provided in U.S. Pat. No. 6,143,248. Additional examples of applications of those principles may be found in U.S. Pat. No. 6,063,589. The microfluidic devices described in those two patents were to be disposed in disc form and rotated on equipment capable of providing varying degrees of centrifugal force as needed to move fluids from one vessel to another. Generally, a sample would be supplied close to the center of rotation and gradually increasing rotational speeds would be used to move the sample, or portions of it, into vessels disposed further away from the center of rotation. The patents describe how specific amounts of samples can be isolated for analysis, how the samples can be mixed with other fluids for washing or other purposes, and how samples can be separated into their components.
Other patents describe the use of electrodes for moving fluids by electro-osmosis, such as U.S. Pat. No. 4,908,112. Caliper Technology Corporation has a portfolio of patent on microfluidic devices in which fluids are moved by electromotive propulsion. Representative examples are U.S. Pat. Nos. 5,942,443; 5,965,001; and 5,976,336.
In U.S. Pat. No. 5,141,868 capillary action is used to draw a sample into a cavity where measurements of the sample can be made by electrodes positioned in the sample cavity.
In U.S. patent application Ser. No. 10/082,415, microfluidic devices were disclosed which have advantages over those previously available. One such device employs multiple U-shaped capillary loops to provide metered amounts of sample liquid for subsequent analysis.
The present inventors have sought an improved method of metering multiple portions of a liquid sample having advantages over the device shown in U.S. patent application Ser. No. 10/082,415. Their solution to the problem is described in detail below.

Method and apparatus for splitting of specimens into multiple channels of a microfluidic device


The method includes a pretreatment step during an operation of a boiler in which in a predetermined period of time before shutdown of the boiler, a part of combustion gas that has bypassed an economizer provided in a flue gas duct for flue gas from the boiler is supplied to an upstream of a NOx removal device having a NOx removal catalyst and mixed with the combustion flue gas from the economizer to generate mixed gas having a predetermined temperature equal to or higher than 360° C. (360° C. to 450° C.), the mixed gas is introduced into the NOx removal catalyst, thereby decomposing VOSO4 adhering to and accumulating on the NOx removal catalyst into V2O5.

As a method of removing nitrogen oxide (NOx) in flue gas discharged from a combustion apparatus such as a boiler, an ammonia catalytic reduction method has been put into practical use, in which ammonia (NH3) is used as a reduction agent to decompose NOx to nitrogen and water, which are harmless to the environment, in the presence of a nitrogen oxide removal catalyst (hereinafter, "NOx removal catalyst").
In the treatment of flue gas from a boiler that uses heavy oil such as fuel oil C with a high sulfur (S) content as a fuel, sulfur dioxide (SO2) with a high concentration is present in flue gas. Therefore, oxidation reaction of sulfur dioxide (SO2) into sulfur trioxide (SO3), which occurs simultaneously with reduction and removal reaction of a NOx removal catalyst, produces sulfur trioxide (SO3) with a high concentration. The sulfur trioxide (SO3) with a high concentration is easily bound to an unreacted portion of NH3, which is used as a reduction agent, in a low temperature region to form acid ammonium sulfate and other compounds, and thus clogging or partial blockages to the interior and piping of various devices such as a heat exchanger in a downstream or the like, thereby increasing a pressure loss. Accordingly, a measure such as performance upgrading of a precipitator needs to be taken.
Furthermore, as a catalyst exhibiting an excellent NOx removal performance and a low SO2 oxidation capability, a type of catalyst having tungsten oxide, vanadium-tungsten oxide or the like supported on titania is available.
Ultraheavy oil, such as Orimulsion (for an oil-in-water type emulsion produced by mixing Orinoco tar, which is ultraheavy oil collected in Orinoco State, Venezuela, with water and a surfactant for easy handling at a normal temperature; trade name of Mitsubishi Corporation), asphalt, and vacuum residual oil (VRO), contains two to three times as much sulfur (S), and five to seven times as much vanadium (V) as in fuel oil C, as shown in Table 1 disclosed in the Patent Literature mentioned below. Furthermore, because the SO2 concentration in flue gas of such ultraheavy oil is very high, there is a problem that a vanadium compound becomes deposited on a surface of the NOx removal catalyst during an operation.
Particularly, it has been confirmed that when a low grade fuel with a sulfur (S) content of 1% by weight or more is used, this tendency is noticeable.
TABLE 1Measurement itemOrimulsionOrinoco oilFuel oil CSpecific gravity—0.9760.889(80° C./4° C.)Viscosity—152834.8(cSt) (80° C.)N (wt %)0.480.630.22S (wt %)2.783.790.97Water content (wt %)28 to 30<0.1<0.1Higher calorificAbout 29400About 4200043680 [10400]power (kJ/kg)[about[about[kcal/kg]7000]10000]Ash content (wt %)0.080.130.01Carbon residue11.8917.48.0(wt %)V (ppm)280 to 350400 to 50050 or lessNa (ppm)40 to 70 60 to 100—(Reference) The Thermal and Nuclear Power, Vol. 465, June 1995
FIG. 5 is a graph of an X-ray diffraction analysis result of a NOx removal catalyst after being operated for 14,400 hours. FIG. 6 is a graph of a relation between a boiler operating time and an increased amount of vanadium pentoxide (V2O5) in an entire catalyst. FIG. 7 is a graph of a relation between a concentration increase of vanadium pentoxide (V2O5) and an SO2 oxidation rate (Non Patent Literature 1). Here, "a.u." in FIGS. 5, 6, and 7 represents a ratio to a reference value, and is not an absolute value.
As shown in FIG. 5, in the X-ray diffraction analysis result in an initial stage of an operation, only titania (TiO) of the catalyst component was produced. However, in the X-ray diffraction analysis result after being operated for 14,400 hours, it was confirmed that vanadyl sulfate (VOSO4) and vanadium pentoxide (V2O5) were produced in the NOx removal catalyst. As shown in FIG. 6, it was confirmed that the concentration of vanadium pentoxide (V2O5) is increased over the course of operating hours.
The vanadium is an active component of the NOx removal catalyst and is a substance that promotes SO2 oxidation reaction as a side reaction. As shown in FIG. 7, in an actual device, there is such a problem that the SO2 oxidation reaction rate is increased with time, and as a result, the amount of corrosive SO3 discharged to a downstream side of the NOx removal device is increased.
In catalyst regeneration treatment for regenerating a NOx removal catalyst at the time of an inspection, therefore, the present inventors have proposed a technique for regenerating a NOx removal catalyst in which after the NOx removal catalyst is first taken out from a NOx removal device, the NOx removal catalyst is then heated under a high temperature condition of, for example, from 450° C. to 600° C. in an electric furnace, vanadyl sulfate (VOSO4) is decomposed into vanadium pentoxide (V2O5), and thereafter the heated NOx removal catalyst is subjected to oxalic acid washing using oxalic acid, thereby dissolving and removing vanadium pentoxide (V2O5), and a technique for decomposing vanadyl sulfate (VOSO4) under a high temperature condition by using sulfuric acid or the like (Patent Literature 1).


A switch device may include a rod movable in association with an operation of a brake pedal, a main body case in which one end side of the rod is disposed, a movable board disposed in the main body case, and a connecting mechanism configured to connect the rod and the movable board. The movable board may be displaceable via the movement of the rod such that a movable contact point of the movable board is in contact with or separate from a fixed contact point. The connecting mechanism may include a protruding portion radially protruding from the rod, and a wall portion provided in the movable board. After pushing the rod into the main body case by a predetermined length, a tooth portion disposed on the protruding portion may mesh with a tooth portion disposed on the wall portion connecting the rod and the movable board.

Japanese Patent No. 4276835 discloses a switch device to be used for detection of a depression operation of a brake pedal.
This switch device includes a rod (pushing bar) moving forward/backward in association with an operation of brake pedal, and a main body case configured by assembling a first case and a second case.
The rod is provided to penetrate through the first case of the main body case in an assembling direction of the first case and the second case, and in this state, the rod is movably supported in an axis line direction along the assembling direction of the first case and the second case.
The rod and a movable board supporting a movable contact point are connected through a lock mechanism in the inside of the switch device. In the switch device, when the rod moves in the axis line direction in association with the operation of the brake pedal, the movable contact point moves in the axis line direction together with the rod to come in contact with a fixed contact point provided in the second case side. Thereby an ON-signal is outputted from the switch device.
For installing the switch device in a state of being capable of detecting the operation of the brake pedal, it is necessary to push the rod into the main body case by a predetermined length.
Therefore in a step of installing the switch device, the movable board in the main body case is necessary to be movable relative to the rod in the axis line direction. It is necessary that after the installation completion of the switch device, the movable board and the rod are connected to be movable together in the axis line direction.
The lock mechanism is an another component from the movable board, and is provided to connect the rod and the movable board supporting the movable contact point to be incapable of rotating relative to each other.
The lock mechanism is configured with a pair of sawtooth lock elements. The lock elements are located on an outer periphery of the rod and on an inner periphery of the lock mechanism respectively.
In the switch device, by rotating the rod around the axis line after the rod is pushed into the main body case by the predetermined length, the lock element in the rod side is caused to be engaged to the lock element in the lock mechanism side. As a result, the movable board having the movable contact point and the rod are connected, and the rod becomes movable in the axis line direction together with the movable board in a state where the rod is positioned correctly in the axis line direction.
The switch device has many components for connection between the rod and the movable board, and further, at the time of pushing the rod into the main body case by the predetermined length, alignment in position between the lock element in the rod side and the lock element in the lock mechanism side is necessary.
Therefore the assembling work becomes complicated, leading to an increase on a manufacturing cost of the switch device.
Accordingly it is required to be capable of providing the switch device at a less cost.


A magnetic flux leakage inspection method generates a magnetic flux parallel to a surface of an inspected object, and detects a magnetic flux that leaks from the surface of the inspected object with a magnetic sensor. The method includes exciting coils that generate an alternating magnetic field having a variable frequency, an exciting coil power source, a magnetic sensor, a lock-in detector, and a signal analyzer that analyzes changes of a signal intensity and a phase of the output of the magnetic sensor with output signals of the lock-in detector. The method obtains cosine or sine as a trigonometric function of a phase obtained by adding to the phase at each measurement point of multipoint measurement, an adjustment phase common to all the measurement points, and displays an analytical value obtained by multiplying the signal intensity and the sine or cosine at each measurement point with any adjustment phase.

A magnetic flux leakage inspection method using magnetism is one of methods that have been used for inspecting a defect of a steel material. The magnetic flux leakage inspection method magnetizes a measured target by direct or alternating magnetization and detects a magnetic flux that leaks from a surface of the measured target mainly using a search coil as a magnetic sensor. Recently, a magnetic resistor device (MR), a hall device, a magnetic impedance device (MI), and the like have begun to be used as the magnetic sensor. In the magnetic flux leakage inspection method using magnetism, when the steel product as the measured target is magnetized by the direct or alternating magnetization, if the measurement target has a defect on a surface, a leakage magnetic flux leakage is generated on the surface. Thus, the magnetic sensor measures a magnetic field component parallel to a surface of the leakage magnetic flux or a magnetic field component perpendicular to the surface of the leakage magnetic flux. A method of magnetizing the measured target includes the direct magnetization and the alternating magnetization using exciting coils. The direct magnetization can uniformly magnetize a cross section of the measured target and thus is mainly used for detecting a defect inside. The alternating magnetization exerts a frequency-dependent skin effect and thus is mainly used for the inspection near the surface of a material. A magnetic sensor with a sensitivity covering a low frequency wave such as the MR, the hall device, and the MI device allows excitation with the low frequency wave and thus is used for detecting a defect deep inside the measured target. The magnetic flux leakage inspection method is generally included in an eddy-current inspection method. The eddy-current inspection method and the magnetic flux leakage inspection method are inspection methods with the same configuration in which the magnetic field is applied to the measured target and the measurement is performed with the magnetic sensor. An eddy-current inspection method applying a low frequency magnetic field and detecting a magnetic field component parallel to a surface of a sample is described in Japanese Patent No. 3987941 (Patent document 1).
The measured target takes various shapes. For detecting a defect of a cylindrical steel pipe and steel bar, it is a common practice to insert the measured target through an encircling coil to be subjected to the alternating magnetization. To inspect a large steel pipe, tank, and the like, since the surface is approximately flat, it is a common practice to attach the exciting coils to a U-shaped yoke member and bring both end portions of the yoke member in contact with the measured target to perform alternating magnetization on the measured target (see, Non-patent documents 1 and 2).
Multipoint measurement data obtained by measuring the measured target at various positions with such a magnetic flux leakage inspection has conventionally been processed as follows. Specifically, an output from the magnetic sensor is directly used as a signal intensity, and a position and a size of a defect are estimated with reference to a change of the signal intensity at measurement positions. Recently, the output from the magnetic sensor has been detected by a lock-in amplifier in synchronization with the exciting coils to analyze a phase in addition to the signal intensity. Specifically, a change of the phase in addition to the change of the signal intensity at the measurement points are graphed to estimate a position and a size of the defect. For example, Japanese Unexamined Patent Application Publication No. 2007-64628 (Patent document 2) describes an analysis method for identifying a depth and a size of a defect from a graph showing a change of a signal intensity.

Leakage magnetic flux flaw inspection method and device

National University Corporation Okayama University


Disclosed is a method for extending a shelf life of vinyl ester resin or unsaturated polyester resin during transportation or general storage. The method includes the step of enhancing an oxygen content of the vinyl ester resin or the unsaturated polyester resin, such that the self-polymerization reaction of reactive functional groups having carbon-carbon unsaturated double bonds of the vinyl ester resin or the unsaturated polyester resin can be minimized, so as to slow down occurrence of a gelation phenomenon of the vinyl ester resin or the unsaturated polyester resin in a long-time transportation or storage, and further to decrease a monetary loss.

1. Field of the Invention
The present invention relates generally to a method for storing vinyl ester resin or unsaturated polyester resin and more particularly, to a method for extending the shelf life of the vinyl ester resin or the unsaturated polyester resin.
2. Description of the Related Art
Carbon-carbon unsaturated double bonds of the molecular structure of vinyl ester resin or unsaturated polyester resin are very easily affected by the impurities contained in the vinyl ester resin or the unsaturated polyester resin or the ambient temperature in the stage of storing the vinyl ester resin or the unsaturated polyester resin, resulting in that the carbon-carbon unsaturated double bonds break to produce free radicals which tend to conduct a chain-reaction polymerization. The higher the ambient temperature increases or the more the storage amount of the vinyl ester resin or the unsaturated polyester resin increases, the more the chain reaction of the self-polymerization through the carbon-carbon unsaturated double bonds occurs easily and extensively. As a result, a gelation phenomenon of the vinyl ester resin or the unsaturated polyester resin caused by the foregoing self-polymerization reaction occurs during transportation or general storage, resulting in a monetary loss due to deterioration of the workability of the vinyl ester resin or the unsaturated polyester resin.
In a conventional method for resolving the aforesaid problem, a free radical inhibitor is added to the vinyl ester resin or the unsaturated polyester resin to minimize the self-polymerization reaction through the carbon-carbon unsaturated double bonds, so as to extend the shelf life of the vinyl ester resin or the unsaturated polyester resin. However, the addition of the aforesaid inhibitor will reduce the reactivity of the vinyl ester resin or the unsaturated polyester resin, thus causing poor problems, for example, the processing time of the vinyl ester resin or the unsaturated polyester resin is increased, such that the whole time for manufacturing a product from the vinyl ester resin or the unsaturated polyester resin is increased, or the vinyl ester resin or the unsaturated polyester resin cannot be cured completely, such that the strength of a product manufactured therefrom fails to satisfy the standard value, undesirably increasing the defective rate. Further, if the additive amount of the inhibitor is excessive, the color of cured vinyl ester resin or cured unsaturated polyester resin becomes darkened, thus the color of a product manufactured therefrom will be darkened, undesirably degrading the appearance of the product.
In another conventional method for resolving the above-mentioned problem, the vinyl ester resin or the unsaturated polyester resin is stored in a freezer during transportation or general storage to reduce the activation energy of the carbon-carbon unsaturated double bonds of the vinyl ester resin or the unsaturated polyester resin, thereby extending the shelf life of the vinyl ester resin or the unsaturated polyester resin. However, the cost for performing the foregoing prior art method is too high, thus undesirably increasing the price of the vinyl ester resin or the unsaturated polyester resin.

Method for extending shelf life of vinyl ester resin or unsaturated polyester resin


A power line indicator accessory configured to simultaneously determine an operating state of a plurality of conductors establishing a circuit connection to a plurality of circuit protection devices such as a fusible switch disconnect devices or modular fuse holders arranged side-by-side in an array. The accessory includes an onboard power supply and a thin, elongated body facilitating its use in tight spaces.

The field of the invention relates generally to fusible circuit protection devices, and more specifically, to an accessory for indicating the status of power lines connecting to an array of fusible switching disconnect devices.
Fuses are widely used as overcurrent protection devices to prevent costly damage to electrical circuits. Fuse terminals typically form an electrical connection between an electrical power source and an electrical component or a combination of components arranged in an electrical circuit. One or more fusible links or elements, or a fuse element assembly, is connected between the fuse terminals, so that when electrical current through the fuse exceeds a predetermined limit, the fusible elements melt and opens one or more circuits through the fuse to prevent electrical component damage.
A variety of fusible disconnect devices are known in the art wherein fused output power may be selectively switched from a power supply. Existing fusible disconnect switch devices, however, have not completely met the needs of those in the art.

Power line indicator accessory for fusible circuit protection device array


A bicycle frame has a front frame, a lower bracket assembly, an upper bracket assembly, a rear frame and a shock absorber. The front frame has a head tube, a down tube, a bottom bracket shell and seat tube. The lower bracket assembly is connected pivotally to the bottom bracket shell and has a lower connecting bracket. The upper bracket assembly is connected pivotally to the seat tube and has two upper connecting brackets. The rear frame is connected pivotally to the upper connecting brackets and the lower connecting bracket of the upper and lower bracket assemblies and has an upper fork, a lower fork and two dropouts. The shock absorber is mounted pivotally between the upper connecting brackets and the lower connecting bracket.

1. Field of the Invention
The present invention relates to a frame, and more particularly to a frame for a bicycle that has a shock absorber to provide smooth operation.
2. Description of Related Art
With reference to FIGS. 5 and 6, a conventional bicycle frame with a shock absorbing capability has a front frame (91), a rear frame (94, 94′) and a shock absorber (90A, 90B). The front frame (91) has a mounting bracket (92) and a driving bracket (93, 93′). The mounting bracket (92) is attached solidly to the front frame (91). The driving bracket (93, 93′) is attached pivotally to the front frame (91) and has a front end and a rear end. The rear frame (94, 94′) is connected pivotally to the front frame (91) and the rear end of the driving bracket (93, 93′) and move ups and pivots the driving bracket (93, 93′) when a shock is transmitted to the rear frame (94, 94′). The front end of the driving bracket (93, 93′) protrudes into the front frame (91). The shock absorber (90A, 90B) is mounted pivotally between the mounting bracket (92) and the front end of the driving bracket (93, 93′) and absorbs any shock transmitted to the driving bracket (93, 93′) from the rear frame (94, 94′).
However, the conventional bicycle frame has the following shortcomings.
1. When the driving bracket (93) in one embodiment of the conventional bicycle frame presses the shock absorber (90A), the shock absorber (90A) is subjected to an angular displacement of up to about 5.67°. In another embodiment of the conventional bicycle frame, the shock absorber (90B) is subjected to an angular displacement of up to about 9.94°.
2. The angular displacement of the shock absorber (90A, 90B) produces lateral friction in the shock absorber (90A, 90B), which causes the shock absorber (90A, 90B) to wear unevenly and eventually fail. Even slight uneven wear of the shock absorber (90A, 90B) can adversely influence the effectiveness of the shock absorber (90A, 90B) and reduce the smoothness and comfort of the conventional bicycle frame.


A method of amplitude modulated electrostatic polymer nanolithography providing rapid creation of features in a polymer film is disclosed. The nanolithography method of the present invention generates features by mass transport of polymer within an initially uniform, planar film via localized softening of attoliters (102-105 nm3) of polymer by Joule heating enabling high data densities upon the surface of the polymer. This localized Joule heating is accomplished by current flow between the cantilever AFM tip and a conductive wafer upon which the layer of polymer is grown or mounted.

The present patent application is related to our copending patent application document "Method of Polymer Nanolithography", AFD 654, Ser. No. 10/817,406 filed on Mar. 25, 2004. The contents of that application are hereby incorporated by reference herein.
The present invention relates generally to nanolithography and specifically to a polymer electrostatic nanolithography method based upon amplitude modulated Atomic Force Microscopy.
The use of nano and micro-scale structuring of polymers, whether as a sacrificial, pattern-transfer layer or as the active component in a nano-device, is integral to nearly every aspect of future material fabrication. Two general areas of interest are polymer patterning for micro/nanofabrication and ultra dense data storage. It is known that a fundamental limitation for the density of magnetic storage media such as computer floppy disks and the like is the so-called superparamagnetic limit that is related to spin—spin interactions. Ultra compact data storage in thin polymer films is a promising alternative to ferromagnetic storage mediums because polymer data storage overcomes this fundamental limitation, enabling ultra dense storage.
Recent nanolithography investigations are based on the spatially selective removal or deposition of polymer. While somewhat successful, the prior art techniques are generally slow to perform. These techniques generally require chemical cross-linking, and/or substantial polymer degradation or ablation to effect. This permanently changes the composition and structure of the media itself, rendering it ineffective for repetitive data storage and retrieval applications.
A recent polymer nanolithography technique is described in U.S. Pat. No. 6,249,747 to Binning et al. The Binning device utilizes a cantilevered tip within an Atomic Force Microscope wherein an electrically conductive material is attached to the cantilever. In use, an electric current is applied to the electrically conductive material in the cantilever, heating the cantilever and the tip, in turn. The tip, thus heated, is selectively applied to a heat deformable film to create pits. The pits are utilized to convey information by the creation of a coherent structure. While this technique is somewhat effective, it has the disadvantage that a specialized tip is required and the application of current to heat the tip slows the overall lithographic process because the cantilever is large, requiring additional time to cool down.
A need exists therefore for a high speed polymer nanolithography method that facilitates rapid polymer feature creation without polymer degradation, cross-linking or removal. Such a method would enable reliable, high speed feature creation, and additionally provide for a ready erasure process and subsequent re-patterning of the polymer film.

Method of amplitude modulated electrostatic polymer nanolithography

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


The present invention provides a process for the preparation of the rosuvastatin intermediate FPP-CHO and its conversion to rosuvastatin and pharmaceutically acceptable salts thereof.

Statins are currently the most therapeutically effective drugs available for reducing low-density lipoprotein (LDL) particle concentration in the blood stream of patients at risk for cardiovascular disease. Thus, statins are used in the treatment of hypercholesterolemia, hyperlipoproteinemia, and atherosclerosis. A high level of LDL in the bloodstream has been linked to the formation of coronary lesions that obstruct the flow of blood and can rupture and promote thrombosis (Goodman and Gilman, The Pharmacological Basis of Therapeutics, page 879, 9th Ed. 1996).
Statins inhibit cholesterol biosynthesis in humans by competitively inhibiting the 3-hydroxy-3-methyl-glutaryl-coenzyme A ("HMG-CoA") reductase enzyme. HMG-CoA reductase catalyzes the conversion of HMG to mevalonate, which is the rate determining step in the biosynthesis of cholesterol. Decreased production of cholesterol causes an increase in the number of LDL receptors and corresponding reduction in the concentration of LDL particles in the bloodstream. Reduction in the LDL level in the bloodstream reduces the risk of coronary artery disease (J.A.M.A. 1984, 251, 351-74).
Currently available statins include lovastatin, simvastatin, pravastatin, fluvastatin, cerivastatin and atorvastatin, which are administered in their lactone form, as sodium salts or as calcium salts. Rosuvastatin calcium is disclosed in U.S. Pat. No. 5,260,440.
Rosuvastatin (7-[4-(4-fluorophenyl)-6-isopropyl-2-(N-methyl-N-methylsulfonylamino) pyrimidin-5-yl]-(3R,5S)-dihydroxy-(E)-6-heptenoic acid) calcium is an HMG-CoA reductase inhibitor, developed by Shionogi for the once daily oral treatment of hyperlipidaemia (Ann Rep, Shionogi, 1996; Direct communications, Shonogi, 8 Feb. 1999 & 25 Feb. 2000). Rosuvastatin is a superstatin, which can lower LDL-cholesterol and triglycerides levels more effectively than first generation drugs. Rosuvastatin calcium has the following chemical formula:

Rosuvastatin calcium is marketed under the name CRESTOR® for treatment of a mammal such as a human. According to the maker of CRESTOR®, it is administered in a daily dose of from about 5 mg to about 40 mg. For patients requiring less aggressive LDL-C reductions or who have pre-disposing factors for myopathy, the 5 mg dose is recommended, while 10 mg dose is recommended for the average patient, 20 mg dose for patients with marked hyper-cholesterolemia and aggressive lipid targets (>190 mg/dL), and the 40 mg dose for patients who have not been responsive to lower doses. WO 03/032995 further discloses a method of preventing dementia by administering rosuvastatin to a patient.
4-(Fluorophenyl)-6-isopropyl-2-(N-methyl-N-methylsulfonylamino)-5-hydroxymethyl-pyrimidine (FPP-OH) is a key intermediate in the synthesis of rosuvastatin. The oxidation of FPP-OH to 4-(Fluorophenyl)-6-isopropyl-2-(N-methyl-N-methylsulfonylamino)-5-formyl-pyrimidine (FPP-CHO) is an important step in the synthesis of rosuvastatin.
EP Patent No. 521,471 and U.S. Pat. No. 5,260,440 disclose the synthesis of rosuvastatin. The oxidation of FPP-OH therein is performed using Tetra Propyl Ammonium Perruthenate (TPAP). Oxidation with TPAP is described in Lenz et al. J. Chem. Soc. PT1, 1997, 3291-3292 and in Ley et al., Synthesis 1994, 639-666. TPAP is an expensive Ruthenium derivative.
There is a need in the art for processes which allow for production of highly pure rosuvastatin in a facile and cost effective manner on an industrial scale.

This patent is subject to a terminal disclaimer.

Process for the preparation of rosuvstatin


Systems and methods provide for assigning pieces of content to time-slots samples for measuring effects of the assigned content. Systems and methods provide for receiving pair-wise content relatedness data that identifies each piece of content as experimental content or control content relative to other pieces of content, and algorithmically assigning experimental or control content pieces to time-slot samples using the content relatedness data, wherein additional content pieces assigned to a particular time-slot sample exclude non-identical related experimental content pieces defined relative to an experimental content piece previously assigned to the particular time-slot sample.

Visual information in a retail environment often takes the form of advertising content. Such content is inherently persuasive, and is typically designed to influence a viewer's attitudes, perceptions, and behaviors in order to create a positive business impact, such as increasing sales, strengthening brand awareness, or engendering consumer loyalty.
In 2002, for example, total spending on advertising content used in retail environments, commonly referred to as Point of Purchase (POP), was estimated at $17 billion in the United States and exceeded $43 billion per year globally. This level of spending has garnered increasing scrutiny among brand owner executives who are demanding greater accountability for their marketing investments.
The need for measurable performance is increasingly urgent as well, because the average tenure of a Chief Marketing Officer has decreased to an estimated 22.9 months according to industry sources. Marketing leaders thus have precious little time to measurably demonstrate results from their marketing efforts. Marketing research, a sub-set of the research industry, has historically used correlational or matched control studies to evaluate advertising content performance against objectives. However, these "best practice" marketing research methodologies do not reliably reveal causation between the marketing message and the business result, as has been widely commented on by marketing analysis experts (e.g., Don E. Schultz, Market Research Deserves Blame for Marketing's Decline, Marketing News, Feb. 15, 2005). Even so, marketing research spending is currently estimated at $8 billion annually in the United States alone, which includes these types of studies.

System and method for assigning pieces of content to time-slots samples for measuring effects of the assigned content


The main object of the present invention is to provide an inorganic nanoparticle being a skutterudite compound, expected to realize the quantum effect, and a method for producing the same.

1. Field of the Invention
The present invention relates to an inorganic nanoparticle of a skutterudite compound that can be used for example for a thermoelectric conversion material and the like.
2. Description of the Related Art
The method for producing an inorganic nanoparticle can roughly be classified into the solid phase method, the liquid phase method and the gas phase method. As a method for producing an inorganic nanoparticle having a narrow particle size distribution, the liquid phase method and the gas phase method as the build up process are effective. In particular, the liquid phase method is excellent, since a chemically homogeneous composition can be provided in the case of two or more kinds of the constituent elements. The liquid phase method can be classified into the coprecipitation method, the reverse micelle method, and the hot soap method. Among them, the hot soap method has been recently attracted attentions as a method for producing an inorganic nanoparticle because it can provide a relatively high crystal property.
As the examples of inorganic nanoparticles produced using the hot soap method, the semiconductor materials showing the light emitting characteristics, such as CdSe, CdS and ZnS can mainly be presented (see the J. Am. Chem. Soc., 115, p. 8706-8715 (1993)). These semiconductor materials are known to show the sharper light emitting characteristics by the quantum effect by processing the same into nanoparticles. Application thereof is discussed mainly in the label field in bio and the display field.
Moreover, as to the magnetic recording material, in order to realize a high density recording by miniaturizing the size, synthesis of the inorganic nanoparticles using the hot soap method has been studied. As the magnetic recording materials produced by the hot soap method so far, specifically, Co, FePt, CoPt3, and the like can be presented (see the Science, 1989, p. 287 (2000)).
On the other hand, although the thermoelectric conversion material is a material for directly converting the heat to the electricity, recently, a theory that the thermoelectric conversion efficiency can be increased by the quantum effect has been made public. Thereafter, the material study has been conducted, and it is known that a high performance of ZT=2.4 by the super lattice structure and ZT=2 by the quantum dot super lattice is provided. Since the high performance by the quantum effect can be expected also by processing the thermoelectric conversion material into the nanoparticles, synthesis of the inorganic nanoparticles using the hot soap method is also studied. As the thermoelectric conversion materials produced so far by the hot soap method, Bi, PbSe, and the like can be presented (see the Mat. Res. Soc. Symp., Proc., 691, G10. 2 (2002)).
The skutterudite compound is a material showing a high thermoelectric conversion performance. Particularly owing to the high mobility, deterioration of an electric conductivity due to interface scattering anticipated at the time of coupling the inorganic nanoparticles is expected to be restrained. The skutterudite compound is a compound represented by MX3 (M: Co, Rh, Ir, X: P, As, Sb). Synthesis of CoSb3 by hydrogen reduction after synthesizing inorganic nanoparticles including the oxides of co and Sb by the coprecipitation method has been reported so far (See Nanostructured Films and Coatings, p. 149-156 (2000)). However, since the particle size of the CoSb3 particles synthesized by this method is 200 nm or more and it should be at least 100 nm or less for realizing the quantum effect, it is difficult to improve the performance. Moreover, a problem is involved in that whether or not the CoSb3 particles are reduced to the center.
Moreover, synthesis of the inorganic nanoparticles of a skutterudite compound having a 100 nm or less particle size has not been reported.

Inorganic nanoparticle and method for producing the same

Abstract: The object of the present invention is achieved by providing an inorganic nanoparticle being a skutterudite compound, having the average particle size in a range of 2 nm to 100 nm.


A method and apparatus are disclosed which incorporate a system for enabling the adaptive modification of the security level of a node in a network based on software use of nodes in the network. The system is particularly applicable to dynamic network i.e. networks in which nodes may be mobile and in which the network topology is not constant.

Current network security is based on the concept of fortification. Sensitive information/hardware is protected from the world outside the network by security software called a firewall that runs on a limited number of computers called gateways that provide the links between the network and other non-trusted networks and/or computers. Reaching within the protected network normally involves crossing one of these firewalls where identity controls are conducted and only legitimate access requests allowed.
This strategy is effective as long as there is no breach in the firewall and control at the gates is efficient. This security technique is well adapted to network architecture where data and communications are carried out over fixed physical wires and cables. In this kind of environment, security measures can effectively be implemented at the entry points to the network that cannot be avoided.
A drawback of this policy is that anything inside the walls is assumed to have successfully passed through a filtering procedure and is therefore implicitly trusted. So as soon as a hostile entity such as a hacker or virus has found a way to avoid all checkpoints it can access and damage anything that was supposed to be protected within the network. Such malevolent entry is often gained via an unsecured or compromised entry point commonly referred to as a back door. However, backdoors are relatively rare and/or difficult to find in well-protected systems. Therefore a hacker or virus needs to be relatively clever to be able to use them as a way of getting inside the secure network.
The efficiency of static firewalls is entirely dependent on 2 elements. The first is their ability to recognise intruders (which is why any anti-virus software has to be kept up-to-date). The second is the topological stability of the network they protect. In other words they are implemented where they are needed i.e. at interfaces with other networks and computers.
Network architecture, which is assumed to be fairly stable in the long term. In other words, the security manager knows where communications from the outside world will come from, and can use this information to prepare the network defences. As a result, computers behind the firewall can run only normal anti-virus software and still be reasonably safe, because serious, deliberate attacks are dealt with by the gateways.
However, emerging technologies such as peer-to-peer architecture and ad hoc communication networks mean that the concept of a static gateway is no longer applicable. For example, switching a mobile, wireless access point on or off at any time and place, and by doing so to join/leave a network of freely interacting devices means that the network topology is unstable.
The security systems for dynamic networks need to be able to cope with the threat of unknown viruses and inventive probing strategies as well as with dynamic topology. In the absence of adaptive defence mechanisms, these networks are vulnerable to new, yet undetectable forms of aggression, but also to attacks emanating from known malevolent entities, due to unexpected exposure of unprotected devices.
In a dynamic network, a node that is at one point safely located far behind the firewall can suddenly become directly exposed due to physical displacements or topological changes. An example of the first case might be a person walking out of office while talking on a mobile phone, and switching from "voice over IP" (presumably using a secure base station protected by the corporate firewall) to the normal cellular phone network. The second situation (topological change) could involve a fixed server that starts acting as the primary access point for external customers after one of its counterpart (normally in charge of automated online support) has failed. In both cases, a device that was once safely behind the firewall without any protection of its own suddenly needs to raise a firewall in order to keep safe and avoid becoming a backdoor.

Method and apparatus for network security

British Telecommunications public limited company


A printed-circuit board arrangement electrically connects the at least one transmitter and/or receiver unit with at least one antenna element, whereas the at least one transmitter and/or receiver unit and the at least one antenna element are at least partially integrated into the printed-circuit board arrangement. In this context, the printed-circuit board arrangement includes different printed circuit boards, which are mechanically connected to one another in a rigid manner. A first part of the printed-circuit board arrangement is formed by at least one printed-circuit board, of which the substrate is made from a first material which is suitable for high-frequency, and a second part of the printed-circuit board arrangement is formed by at least one printed-circuit board, of which the substrate is made from a second material different from the first material, which is still sufficiently suitable for a low frequency and/or for a direct-voltage range.

1. Field of the Invention
The invention relates to a printed-circuit board arrangement with at least one partially integrated transmitter and/or receiver unit and at least one antenna element, which preferably operates in the frequency range for millimeter waves.
2. Discussion of the Background
Printed-circuit board arrangements which can be used in the named context serve to establish electrical contact between the various transmitter and/or receiver units and the corresponding antenna elements, whereas the power supply for the corresponding transmitter and/or receiver units should be secured at the same time. In this context, the printed-circuit board arrangements should be designed so that the overall system can be structured as compactly as possible, and the undesirable emission of interference radiation is reduced to a minimum, whereas the interference immunity of the arrangement as a whole with regard to electromagnetic waves must be secured at the same time.
A printed-circuit board with at least a plurality of antenna elements and a transmitter and/or receiver unit is known from EP 2 144 329 A1. In this context, each antenna element is structured as a patch antenna, which can be excited via a slot with a feeding positioned beneath it. The antenna system operates in the millimeter-wave range.
The disadvantage with EP 2 144 329 A1 is that the printed-circuit board arrangement comprises exclusively substrates which are suitable for the highest frequencies, whereby the structure of the printed-circuit board arrangement becomes expensive.

Printed-circuit board arrangement for millimeter-wave scanners


Providing security-related services for enterprise service requests includes receiving a service request from an endpoint, determining the transaction parameter from the received service request, determining a subroutine for execution based on the transaction parameter, communicating with a data server to execute the subroutine, receiving subroutine results from the data server based on the executed subroutine, applying context-specific rules to the request based on instructive data specified in the subroutine results, determining a response based on the subroutine results and the applied context-specific rules, and communicating the response to the endpoint. Some embodiments may also include accessing transaction rules associated with the transaction parameter, determining an additional subroutine for execution based on the transaction rules, communicating with a data server to execute the additional subroutine, receiving additional subroutine results from the data server based on the executed additional subroutine, and communicating the results to the endpoint.

Enterprises receive service requests from various access channels. Enterprises may experience security-related threats via the various access channels, or in the form of unauthorized service requests. The need for security-related services may be particularly acute in certain business sectors, such as the banking industry. The level of security required may also depend on applicable standards, regulations, business needs, or the severity of the perceived threats.


The present invention relates to a probe tip assembly for testing of integrated circuits or other microelectronic devices. The probe tip assembly may include a plurality of independently flexible contact fingers extending from a support, each contact finger spaced apart from the other contact fingers, and each contact finger terminating in free space at an end distal from the support. A probe may be constructed by attaching the free ends of the contact fingers to electrical contacts on a circuit board and then removing the support from the contact fingers.

The present invention relates to a probe for testing of integrated circuits or other microelectronic devices.
One type of probe utilizes a spaced-apart array of slender needles to contact pads on a device under test (DUT). A signal is provided to the DUT, and the voltages and/or currents at the selected nodes are routed to measurement equipment. A problem encountered with such measurement systems, particularly at high frequencies, is that the close proximity between the needle tips creates inductance that can interfere with accurate measurements. Though this inductance can be reduced by limiting the isolated portion of the probe tips to the region immediately surrounding the DUT, practical considerations make such a design difficult.
Probe structures have been developed to compensate for the inductance at the probe tips. One such design is exemplified by Lockwood et al., U.S. Pat. No. 4,697,143. Lockwood et al. disclose a ground-signal-ground arrangement of strip like conductive traces formed on the underside of an alumina substrate so as to create coplanar transmission lines. These coplanar transmission lines extend from the pads of the DUT at one end to a coaxial cable at the other end. The associated pair of ground traces on each coplanar transmission line is connected to the outer conductor of the coaxial cable and the interposed signal trace is connected to the inner conductor. Areas of wear-resistant conductive material are provided to reliably establish an electrical connection with the respective pads of the DUT. Layers of ferrite-containing microwave absorbing material are mounted about the substrate to absorb spurious microwave energy over a major portion of the length of each ground-signal-ground trace pattern. In accordance with this type of construction, a high frequency impedance (e.g., 50 ohms) can be presented at the probe tips to the device under test. Thus broadband signals of eighteen gigahertz or less can travel with little loss across the coplanar transmission lines formed by each ground-signal-ground trace pattern.
The probing system of Lockwood et al., however, is insufficient to effectively probe non-planar surfaces. Such surfaces might result, for example, if the pads of the DUT differ in height, if a loose metallic particle of minute dimension adheres electrostatically to the surface of one of the pads of the DUT so as to form a non-planar surface irregularity, or when the plane of the DUT is inadvertently tilted slightly with respect to the plane of the coplanar tips of the probing assembly. Further, proper alignment between the needles and the DUT requires careful placement of each needle, a time consuming process.
The alignment limitation between the needles was addressed by Godshalk, U.S. Pat. No. 5,506,515. Godshalk discloses a ground-signal-ground finger arrangement attached to a coaxial cable, as in Lockwood. The fingers, however, are originally formed in one piece, joined together by a carrier tab at the contact ends. Once the fingers are attached to the coaxial cable, the carrier tab is severed and the contact fingers appropriately shaped for contact with the DUT. Godshalk discloses that the relative position of each finger is held in alignment first by the carrying tab, and then by the coaxial cable. Unfortunately, Godshalk's design is limited in that the close placement of a coaxial cable to the finely spaced geometry of the DUT places a limit on the number of coaxial cables, and hence contact fingers, that may be used effectively in the probe. Further, a probe having multiple adjacent coaxial cables, each of which has different flexibilities, may lead to insufficient contact with some of the nodes on the DUT.
Another class of probes that provide clean power to circuits at low impedance are generally referred to as power bypass probes. Another configuration that has been developed to counteract the inductance at the tips of a probe assembly is a power bypass quadrant. The power bypass quadrant minimizes such inductance by providing integrated capacitors or resistor-capacitor networks within the probe.
Strid, U.S. Pat. No. 4,764,723, discloses a power bypass quadrant probe that utilizes an array of ceramic fingers coated with a thin gold or polyimide film to make contact with the DUT. The test signals are routed through a power bypass structure consisting of an RC network. Because of the small geometries near the DUT, the capacitors are located far away from the probe tip, which potentially decreases performance. In addition, the ceramic contact fingers tend to break during probing, particularly when the probe overshoots the contact pads. Further, probing pads that are not coplanar is exceedingly difficult because the ceramic contacting fingers lack flexibility.
Boll et al., U.S. Pat. No. 5,373,231 disclose a probe that includes an array of blades to contact the pads of a DUT. The array of blades extend from a transmission line network traced on a circuit board. An RC network is provided on the circuit board to provide the requisite power bypass, and in some instances, flexible capacitors are located close to, or between the contact blades. Because of the limited geometries near the DUT, the capacitance of the capacitors interconnected between the blades are small, and alone are insufficient to adequately eliminate circuit inductance. Accordingly, a second bank of capacitors with larger values are located away from the probe tip where space is available. Probes utilizing flexible capacitors between the closely spaced blades of the probe have proven to be of limited mechanical durability.
What is desired, therefore, is a configurable, multi-contact probe for high frequency testing of integrated circuits or other microelectronic devices that reduces the inductance at the probe tip to levels acceptable for measurement over a wide range of frequencies. The probe should be sufficiently durable and flexible to reliably and repeatedly probe substantially non-planar devices over time. It is further desired that the probe be easily aligned with the contact points on the device to be tested and that the probe be capable of simultaneously probing a number of such contact points.
The foregoing and other objectives, features, and advantages of the invention will be more readily understood upon consideration of the following detailed description of the invention, taken in conjunction with the accompanying drawings.


The present invention relates to an electrochemical cell and a process for producing a hydroxide solution, sulfuric acid and a halogen gas from a hydrogen halide and a sulfate solution. In particular, the sulfate solution may be an alkali metal sulfate solution, such as sodium or potassium sulfate solution, an alkaline earth metal sulfate solution or an ammonium sulfate solution. The cell and the process may use either an anhydrous or an aqueous hydrogen halide, namely, hydrogen chloride, hydrogen fluoride, hydrogen bromide and hydrogen iodide, to a respective dry halogen gas, such as chlorine, fluorine, bromine, or iodine, to produce hydrogen ions in order to split the alkali metal solution and form the sulfuric acid. The cell has two membrane-electrode assemblies, where an anode is disposed in contact with one membrane, and a cathode is disposed in contact with another membrane. The sulfate solution is fed in between the membrane-electrode assemblies.

1. Field of the Invention
The present invention relates to an electrochemical cell and a process for splitting a solution and producing a hydroxide, sulfuric acid and a halogen gas. In particular, the cell and the process may convert either an anhydrous or an aqueous hydrogen halide, such as hydrogen chloride, to a halogen gas, such as chlorine gas, and a solution such as a sodium sulfate aqueous solution, to form sulfuric acid and sodium hydroxide, along with its co-product, hydrogen.
2. Description of the Related Art
Hydrogen chloride (HCl) or hydrochloric acid is a reaction by-product of many manufacturing processes which use chlorine. For example, chlorine is used to manufacture polyvinyl chloride, isocyanates, and chlorinated hydrocarbons/fluorinated hydrocarbons, with hydrogen chloride as a by-product of these processes. Because supply so exceeds demand, hydrogen chloride or the acid produced often cannot be sold or used, even after careful purification. Shipment over long distances is not economically feasible. Discharge of the acid or chloride ions into waste water streams is environmentally unsound. Recovery and feedback of the chlorine to the manufacturing process is the most desirable route for handling the HCl by-product.
A number of commercial processes have been developed to convert HCl into usable chlorine gas. See, e.g., F. R. Minz, "HCl-Electrolysis--Technology for Recycling Chlorine", Bayer AG, Conference on Electrochemical Processing, Innovation & Progress, Glasgow, Scotland, UK, Apr. 21-Apr. 23, 1993.
Currently, thermal catalytic oxidation processes exist for converting anhydrous HCl and aqueous HCl into chlorine. Commercial processes, known as the "Shell-Chlor", the "Kel-Chlor" and the "MT-Chlor" processes, are based on the Deacon reaction. The original Deacon reaction as developed in the 1870's made use of a fluidized bed containing a copper chloride salt which acted as the catalyst. The Deacon reaction is generally expressed as follows: ##STR1## where the following catalysts may be used, depending on the reaction or process in which equation (1) is used.
______________________________________ Catalyst Reaction or Process ______________________________________ Cu Deacon Cu, Rare Earth, Alkali Shell-Chlor NO.sub.2, NOHSO.sub.4 Kel-Chlor Cr.sub.m O.sub.n MT-Chlor ______________________________________
The commercial improvements to the Deacon reaction have used other catalysts in addition to or in place of the copper used in the Deacon reaction, such as rare earth compounds, various forms of nitrogen oxide, and chromium oxide, in order to improve the rate of conversion, to reduce the energy input and to reduce the corrosive effects on the processing equipment produced by harsh chemical reaction conditions. However, in general, these thermal catalytic oxidation processes are complicated because they require separating the different reaction components in order to achieve product purity. They also involve the production of highly corrosive intermediates, which necessitates expensive construction materials for the reaction systems. Moreover, these thermal catalytic oxidation processes are operated at elevated temperatures of 250.degree. C. and above.
Electrochemical processes exist for converting aqueous HCl to chlorine gas by passage of direct electrical current through the solution. The current electrochemical commercial process is known as the Uhde process. In the Uhde process, aqueous HCl solution of approximately 22% is fed at 65.degree. to 80.degree. C. to both compartments of an electrochemical cell, where exposure to a direct current in the cell results in an electrochemical reaction and a decrease in HCl concentration to 17% with the production of chlorine gas and hydrogen gas. A polymeric separator divides the two compartments. The process requires recycling of dilute (17%) HCl solution produced during the electrolysis step and regenerating an HCl solution of 22% for feed to the electrochemical cell. The overall reaction of the Uhde process is expressed by the equation: ##STR2## As is apparent from equation (2), the chlorine gas produced by the Uhde process is wet, usually containing about 1% to 2% water. This wet chlorine gas must then be further processed to produce a dry, usable gas. If the concentration of HCl in the water becomes too low, it is possible for oxygen to be generated from the water present in the Uhde process. This possible side reaction of the Uhde process due to the presence of water, is expressed by the equation: EQU 2H.sub.2 O.fwdarw.O.sub.2 +4H.sup.+ +4e.sup.- ( 3)
Further, the presence of water in the Uhde system limits the current densities at which the cells can perform to less than 500 amps./ft..sup.2, because of this side reaction. The side reaction results in reduced electrical efficiency and corrosion of the cell components.
Another electrochemical process for processing aqueous HCl has been described in U.S. Pat. No. 4,311,568 to Balko. Balko employs an electrolytic cell having a solid polymer electrolyte membrane. Hydrogen chloride, in the form of hydrogen ions and chloride ions in aqueous solution, is introduced into an electrolytic cell. The solid polymer electrolyte membrane is bonded to the anode to permit transport from the anode surface into the membrane. In Balko, controlling and minimizing the oxygen evolution side reaction is an important consideration. Evolution of oxygen decreases cell efficiency and leads to rapid corrosion of components of the cell. The design and configuration of the anode pore size and electrode thickness employed by Balko maximizes transport of the chloride ions. This results in effective chlorine evolution while minimizing the evolution of oxygen, since oxygen evolution tends to increase under conditions of chloride ion depletion near the anode surface. In Balko, although oxygen evolution may be minimized, it is not eliminated. As can be seen from FIGS. 3 to 5 of Balko, as the overall current density is increased, the rate of oxygen evolution increases, as evidenced by the increase in the concentration of oxygen found in the chlorine produced. Balko can run at higher current densities, but is limited by the deleterious effects of oxygen evolution. If the Balko cell were to be run at high current densities, the anode would be destroyed.
Electrodialysis, a technology based on the use of cation-exchange and/or anion exchange membranes and of an electric field to effect ion separations, has been the subject of many recent books, articles and papers. See, for example, "Membrane Handbook", edited by W. S. W. Ho and K. K. Sirkar, Van Nostrand Reinhold, New York; and "The Green Potential of Electrochemistry, Part 2 Application" by D. Pletcher and N. L. Weinberg, Chemical Engineering, November, 1992, pg. 132-141. In recent years, DeNora Permelec, SpA, of Milan, Italy, has developed the HYDRINA.RTM. process, which generates sodium hydroxide without producing chlorine, using principles of electrodialysis. See "HYDRINA.RTM. Membrane Electrolyzers", published by DeNora Permelec, SpA. In this process, hydrogen and aqueous sodium sulfate are typically fed to a cell, where sodium hydroxide and hydrogen are formed. Commercial applications of electrodialysis now exist in brackish water desalination, treatment of industrial effluents, and in many other areas. See Ho and Sirkar, "Industrial Applications of Electrodialysis and Related Processes", Table 20-1.
A very recent review of salt splitting utilizing electrodialysis was given at the "Conference on Electrochemical Processing, Innovations and Progress", April 1993, Glasgow, Scotland, UK, entitled "Novel Approaches to Salt Splitting" by D. Genders, D. Hartsough and J. Thompson, pp. 21-23. FIG. 1 herein, which is described in this paper, shows a schematic of a three-component cell, shown generally at 1, for splitting sodium sulfate into sulfuric acid and sodium hydroxide. As shown in FIG. 1, cell 1 includes an anode 2, an anion-exchange membrane membrane 4, a cation exchange membrane 6 and a cathode 8. An aqueous solution of sodium sulfate is introduced into a central compartment bounded by anion exchange membrane 4, facing anode 2. Under the influence of an impressed electric field, sulfate ions migrate toward the anode and pass through the anion exchange membrane, where they combine with protons produced from water. The water is introduced into the anode compartment, where, by means of an electrochemical reaction, it is converted into protons and oxygen. Sodium ions from the sodium sulfate migrate through cation-exchange membrane 6 to the cathode compartment, which is also fed with water or dilute sodium hydroxide, whereby they combine with hydroxyl ions formed by the electrochemical reaction of the reduction of water to hydrogen and hydroxyl ion. The products of the electrodialysis are sulfuric acid and sodium hydroxide, and the gases, oxygen and hydrogen. The key to this electrodialysis process is the use of ion-selective membranes, that is, membranes which permit only cations (cation exchange membranes) or anions (anion exchange membranes) to pass therethrough, and reject ions of opposite charge. A number of such membranes are now commercially available, such as a membrane which is made of hydrated, copolymers of polytetrafluoroethylene and poly-sulfonyl fluoride vinyl ether-containing pendant sulfonic acid groups, and sold under the trademark "NAFION.RTM." (hereinafter referred to as NAFION.RTM.) by E. I. du Pont de Nemours and Company of Wilmington, Del. (hereinafter referred to as "DuPont").
The difficulty of disposing of, which includes selling, hydrogen chloride, has been discussed above. In addition, the problem of disposing of large quantities of salts is becoming an increasing concern, in particular, the disposal of sodium salts, especially the sulfate which is formed as a by-product of pulp and paper industries, rayon plants, acid waste neutralization, pharmaceutical processes and other kinds of chemical process. See "HYDRINA.RTM. Membrane Electrolyzers", supra. In order to dispose of hydrogen chloride and sodium salts, several distinct, separate processes have been necessary. Thus, the need exists for a single process and apparatus for an environmentally and economically attractive technique to recycle these materials into useful products, which in many cases, may be key starting materials for other processes.

Electrochemical cell and process for splitting a sulfate solution and producing a hyroxide solution sulfuric acid and a halogen gas