An NFC antenna (“NFC” stands for “near field communication”) includes a ferrite antenna including a primary antenna coil wound on a ferrite core of the ferrite antenna; a loop coil provided in a position where components of a magnetic flux on a non-communication direction side interlink, the magnetic flux being generated by the ferrite antenna; and a loop coil switching unit for switching between a mode for forming a loop of the loop coil and a mode for disconnecting the loop.

1. Field of the Invention
The present invention relates to a near field communication (NFC) antenna well suited for use in RFID (radio frequency identification, which is a generic name of contactless or proximity recognition techniques using electromagnetic waves) and a mobile device including an NFC communication portion and using the NFC antenna
2. Description of the Related Art
Recently, an RFID function is mounted in a standard manner on mobile devices, such as mobile phones. In past and existing techniques, a loop antenna has been used as an antenna of an NFC communication portion to realize the RFID function.
Recently, however, miniaturization or compactness and thinning are strongly demanded for mobile devices. In order to meet the demand, such a loop antenna, which is relatively large in size, cannot be mounted, such that it is difficult to secure a sufficiently necessary communication distance.
In addition, there have been developed ferrite antennas that are smaller in size than loop antennas, but have functional characteristics higher than or equivalent to the characteristics of loop antennas. Further, improvements have been made with respect to the communication distance by improving the reception sensitivity of an RFID LSI (large scale integration) circuit constituting an RFID control portion of the NFC communication portion.
The improvement, therefore, results in increasing the reception sensitivity, thereby making it possible to perform reception even in a remote site. At the same time, however, there occurs a problem in that interference is likely to receive from RFID readers/writers (reading/writing devices) other than a far-end communication device in operation. Particularly, a system employing ASK modulation (ASK: amplitude shift keying) likely to receive disturbance due to interference from other reading/writing devices.
As such, as reader/writer functions are increasingly mounted in various devices, and such devices increases in near sites, communication jamming due to interference increases. In this case, the various devices include, for example, office gate/door control devices (or, entrance/exit control devices), vending machines, green ticket reading machines in trains, notebook personal computers, and mobile phone terminals.
As countermeasures for such interference, it is advantageous to enhance the directivity of an NFC antenna, thereby to concentrate sensitivity on the direction of the far-end communication device, such as reading/writing device. As a method for enhancing the directivity, a method such as described herebelow is known.
FIGS. 5A to 5C are explanatory view showing means or manners for enhancing the directivity of a loop antenna. With reference to FIGS. 5A to 5C, numeral 1 represents the entirety of the loop antenna. As shown in FIG. 5A, the loop antenna 1 is formed in such a manner that a loop-shaped coil 3 is formed on one side of a flexible substrate 2 by printing, for example.
When current (current or induction current of a transmission signal) flows through the coil 3 of the loop antenna 1, as shown by a broken line 4 in FIG. 5B, a magnetic flux occurs spreading in exactly identical patterns to one another on the side having the coil 3 of the flexible substrate 2 and the reverse side. More specifically, the loop antenna 1 exhibits the same characteristics of directivity on the side having the antenna coil 3 of the flexible substrate 2 and the reverse side.
With reference to FIG. 5C, in order to enhance the directivity of the loop antenna 1 along the one direction, a magnetic material 5 having a high magnetic factor is adhered on any of the side, which has the antenna coil 3 of the flexible substrate 2, and the reverse side.
In the configuration thus formed, as shown by a broken line 6 in FIG. 5C, the magnetic flux on the side having the magnetic material 5 passes mainly through the inside of the magnetic material 5, but does not spread on the side having the magnetic material 5. Relatively, however, the magnetic flux on the side without the magnetic material 5 spreads to a long distance. Consequently, the reception sensitivity can be concentrated to the side without having the magnetic material 5, thereby making it possible to enhance the directivity in that direction.
With reference to FIGS. 6A to 6C, a manner for enhancing the directivity of a ferrite antenna will be described herebelow.
In FIG. 6A, numeral 11 represents the entirety of an example of a ferrite antenna. The ferrite antenna 11 of the example is of a bisectional type. As shown in FIG. 6A, the ferrite antenna 11 is configured such that the respective antenna coils 14a and 14b are formed in the manner that a single copper wire 13 is wound about each of two ferrite cores 12a and 12b, and respective antenna coils 14a and 14b are thereby formed.
Alternatively, the configuration of the ferrite antenna 11 can be such that the respective antenna coils 14a and 14b are formed in the manner that the copper wire 13 formed by as a conductive pattern on a flexible substrate is wounded on the respective ferrite cores 12a and 12b. Then, respective assemblies of wire windings on the ferrite cores 12a and 12b are connected together by the copper wire.
As shown by a broken line 15 in FIG. 6B, when the current (current or induction current of the transmission signal) flows through the antenna coils 14a and 14b of the ferrite antenna 11, the current passes through the insides of the respective ferrite cores 12a and 12b, and a magnetic flux occurs spreading in exactly identical patterns to one another on both sides of the ferrite cores 12a and 12b. More specifically, the ferrite antenna 11 exhibits the same characteristics of directivity on both sides of the ferrite cores 12a and 12b.
With reference to FIG. 6C, in order to enhance the directivity of the ferrite antenna 11, a metal plate 16 is disposed close to the ferrite cores 12a and 12b on which the copper wire 13 is wound.
More specifically, when the metal plate 16 is disposed close to the ferrite antenna 11 in the state the magnetic flux occurs as shown in FIG. 6B, overcurrent occurs in the direction of canceling the magnetic flux in the metal plate 16. Then, as shown by a broken line 17 in FIG. 6C, the magnetic flux on the side to which the metal plate 16 is placed close (the side will be referred to as "non-communication direction side") attenuates.
As the magnetic flux on the non-communication direction side is cancelled, self-inductances of the antenna coils 14a and 14b are reduced, whereby the current flowing through the antenna coils 14a and 14b are increased. Then, as shown by a broken line 18 in FIG. 6C, an increased amount of the current causes an increase in the magnetic flux on the opposite side (communication direction side) to the side to which the metal plate 16 is placed close. Consequently, the directivity on the communication direction side is enhanced.
Notes
Referential publications regarding the related techniques being described:
(Patent Document 1) Japanese Unexamined Patent Application Publication No. 2006-197510
(Patent Document 2) Japanese Unexamined Patent Application Publication No. 2006-031508
(Patent Document 3) Japanese Unexamined Patent Application Publication No. 09-200117

Near field communication antenna and mobile device

Sony Ericsson Mobile Communications Japan, Inc.


The liquid drop ejecting device of the present invention comprises a head for ejecting a liquid drop and a controlling device for transmitting a driving signal COM and an ejection datum SI to the head. The head is provided with a memory for storing the ejection datum SI which is transmitted from the controlling device before ejecting the liquid drop. The head ejects the liquid drop according to the ejection datum SI which is stored in the memory and the driving signal which is transmitted from the controlling device. By doing this, it is possible to reduce the transmission of the datum from the controlling device to the liquid drop ejecting head device. Thus, it is possible to provide the liquid drop ejecting device which can manufacture various devices without disturbing the manufacturing efficiency.

1. Field of the Invention
The present invention relates to a liquid drop ejecting device for ejecting a liquid drop such as a liquid resin, a method for ejecting the liquid drop, a liquid drop ejecting head device. Also, the present invention relates to a device which is manufactured according to a method including at least a step for ejecting a liquid drop by using the above device and method for manufacturing a device such as a liquid display device, an organic electroluminescent (herein after called EL) display device, a color filter base board, a metal wiring, a micro-lens array, and an optical element having a coating layer.
2. Description of Related Art
Recently, it is more common that a liquid drop ejecting device for ejecting a fine liquid drop is used for manufacturing devices such an electronic apparatus having a very fine structure, an optical apparatus, etc. For example, a color liquid crystal display device as an electronic apparatus is provided with a color filter which is formed by ejecting fine liquid drops having colors such R (red), green (green), and B (blue) on a transparent base board such as a glass base board in a predetermined pattern by the liquid drop ejecting device. Also, a micro-lens array as an optical apparatus is formed by ejecting a plurality of fine liquid viscous transparent drops of resin on a plurality of sections on the transparent base board. Size and curvature of each micro-lens is controlled according to the time of disposition and the viscosity of the ejection.
Such a liquid drop ejecting device comprises a liquid drop ejecting head device having a liquid drop ejecting head for ejecting a liquid drop and a printing controller for processing the record datum for determining a position to which the liquid drop should be ejected on the base board and generating a driving waveform for driving the liquid drop ejecting head. The printing controller synchronizes the processed record datum and the generated driving waveform so as to transmit the record datum and the driving waveform respectively to the liquid drop ejecting head device. The liquid drop ejecting head device drives the liquid drop ejecting head according to the record datum and the waveform which are transmitted thereto respectively; thus, the controlling operation is performed for ejecting the liquid drop resin.
However, more recently, a larger liquid crystal display device having a finer resolution has been required. Therefore, the record datum which must be processed by the printing controller and transmitted to the liquid drop ejecting head device from the printing controller are increasing greatly. For such a requirement, there has been known a controlling technique for determining whether or not the record datum should be processed according to properties in the record datum (such as "monochrome datum or color datum"). Also, there has been known a technique for reducing a datum which is transmitted from the printing controlling device to the liquid drop ejecting head device by determining a portion in the record datum which is irrelevant to a printing operation so as to omit such an irrelevant portion.
However, the record datum which must be processed in the printing controlling device has increased more greatly recently; thus, there is a concern that a manufacturing efficiency depends on a time for transmitting the record datum from the printing controlling device to the liquid drop ejecting head device. That is, the liquid drop ejecting head can be operated all the time if the time for transmitting the datum from the printing controlling device to the liquid drop ejecting head device is shorter than the time for ejecting the liquid drop from the liquid drop ejecting head. In contrast, if the time for transmitting the datum from the printing controlling device to the liquid drop ejecting head device is longer than the time for ejecting the liquid drop from the liquid drop ejecting head, there is a concern that there is a time in which the liquid drop ejecting head is not operated such that the liquid drop may not be ejected from the liquid drop ejecting head; thus, the manufacturing efficiency may be reduced. Recently, such a case has actually occurred due to the increase of the datum.
In addition, in the above color filter or the micro-lens array, objects to be manufactured such as a pixel or a lens are disposed in a regulated disposition; therefore, it is quite common that the record datum is transmitted from the printing controller to the liquid drop ejecting head device for ejecting the fine liquid drop in a repeated manner. In conventional cases, the datum is transmitted inefficiently such that the record datum is transmitted from the printing controller to the liquid drop ejecting head device during ejecting the liquid drop with regardless to whether or not the record datum has periodicity. Also, there is a problem in that the datum may be converted erroneously and radiation noise may increase if the datum is transmitted more rapidly.

Liquid drop ejecting device and method for ejecting liquid drop, liquid drop ejecting head device, method and manufacturing method for device


A power generating system comprising a heating furnace having an ion burner and positioned on the way of a vertical cylindrical path having a lower gas inlet port and an upper gas outlet port, an axial fan disposed in said path, and a power generator disposed out of said path and interlocking with said axial fan, and wherein a temperature and ion concentration inside said heating furnace are increased by said ion burner, with the result that gas flowed in from said gas inlet port flows through said path upward as a vortical ascending current, and said axial fan is rotated by the vortical ascending current, and said power generator is driven by a rotation of said fan for power generation.

1. Field of the Invention
The present invention relates to a power generating system in which power is generated by energy of a continuous vortical ascending current created artificially.
2. Description of the Related Art
As power generating systems, there are a thermal power generating system, a nuclear power generating system, a hydraulic power generating system and the like. Although these systems are common in the point that power is generated by rotating a turbine of a power generator, energy sources for rotating the turbine are different. In the thermal power generating systems, steam is generated by burning heavy oil or other fuel and the turbine is rotated by energy of the steam. In the nuclear power generating systems, although the turbine is similarly rotated by energy of steam, the steam is generated by heat created by nuclear fission. In the hydraulic power generating systems, the turbine is rotated by energy of water falling from an elevated position. Other than the above systems, there are a wind power generating system in which a power of wind is utilized, a power generating system in which an electric power is generated by chemical reaction between hydrogen and oxygen, and the like.
The present invention is a system in which power is generated by energy different from the energy used in the conventional power generating systems and, in particular, rotating vanes are rotated by a continuous vortical ascending current created artificially (artificial tornado) and a power generator is driven by the obtained rotational force for power generation.
Natural tornado is generated as follows. When air (ionized) specific gravity of which is reduced by solar heat or other heat is ascended to create an ascending current, since atmospheric pressure therein is decreased to generate a low pressure, air is flowing into the ascending current to cancel the pressure difference. In this case, since cold air tends to flow into warm air, the surrounding air colder than the ascending air heated by the solar heat or other heat is flowing into the ascending current, thereby generating vortical current. Once the vortical current is generated, since additional air is flowing into the vortical current in a vortex manner, the rotational force is gradually increased to generate the tornado ultimately.
Further, if a difference in temperature between the ascending current and the surrounding air flowing into the ascending current is small, since the vortical current is generated at a relatively low height, the vortical current is grown, with the result that the low pressure is created in the center of the vortical current, thereby generating a typhoon.
The power generating system according to the present invention, the artificial tornado is created by utilizing the principle of the generation of the natural tornado or the typhoon and the power is generated by energy of the artificial tornado. More specifically, the present invention is constituted as follows.
According to an aspect of the present invention, there is provided a power generating system comprising a heating furnace having an ion burner and positioned on the way of a vertical cylindrical path having a lower gas inlet port and an upper gas outlet port, an axial fan disposed in the path, and a power generator disposed out of the path and interlocking with the axial fan, and wherein temperature and ion concentration inside the heating furnace are increased by the ion burner, with the result that gas flowed in from the gas inlet port is flows through the path upward as a vortical ascending current, and the axial fan is rotated by the vortical ascending current, and the power generator is driven by a rotation of the fan for power generation.
According to another aspect of the present invention, in the above-mentioned power generating system, the heating furnace is further provided with a discharge electrode for maintaining the temperature inside the heating furnace and a particle accelerator for maintaining or increasing ion concentration, and, when the temperature and the ion concentration inside the heating furnace reach predetermined levels, the ion burner is temporarily stopped, and, thereafter, one or both of the discharge electrode and the particle accelerator is driven to maintain the temperature or the ion concentration inside the heating furnace, and, if the temperature or the ion concentration is decreased below the predetermined level, the ion burner is driven again to increase the temperature and the ion concentration inside the heating furnace up to the predetermined levels, and, by repeating the temporary stop of the ion burner, the driving of one or both of the discharge electrode and the particle accelerator and the re-driving of the ion burner, the temperature and the ion concentration inside the heating furnace are maintained to values suitable for generating the vortical ascending current.
According to further aspect of the present invention, in the above-mentioned power generating systems, two or more axial fans are provided in the path and two or more power generators associated with the fans are also provided.
According to further aspect of the present invention, in the above-mentioned power generating systems, the axial fan is designed so that movable vanes thereof are rotated within stationary vanes thereof.
According to further aspect of the present invention, in the above-mentioned power generating systems, there is further provided an auxiliary ion burner disposed at an upper part of the path and adapted to re-heat the gas ascending through the path thereby to promote flow-out of the gas through the gas outlet port.


A centroid calculator calculates the channel virtual center for an adaptive equalizer, based on some type of training signal (e.g., the segment sync of a ATSC-DTV signal), with internal limiting capability that improves its performance. In addition, a centroid calculator with internal limiting capability that improves performance.

The present invention generally relates to communications systems and, more particularly, to a receiver.
In modern digital communication systems like the ATSC-DTV (Advanced Television Systems Committee-Digital Television) system (e.g., see, United States Advanced Television Systems Committee, "ATSC Digital Television Standard", Document A/53, Sep. 16, 1995 and "Guide to the Use of the ATSC Digital Television Standard", Document A/54, Oct. 4, 1995), advanced modulation, channel coding and equalization are usually applied. In the receiver, demodulators generally have carrier phase and/or symbol timing ambiguity. Equalizers are generally a DFE (Decision Feedback Equalizer) type or some variation of it and have a finite length. In severely distorted channels, it is important to know the virtual center of the channel impulse response to give the equalizer the best chance of successfully processing the signal and correcting for distortion. One approach is to use a centroid calculator that calculates the channel virtual center for an adaptive equalizer based on a segment synchronization (sync) signal. Another approach is to use a centroid calculator that calculates the channel virtual center for an adaptive equalizer based on a frame sync signal.


Provided are an apparatus and a method for compensating for an I/Q mismatch using a transmission signal in a wireless communication system. The apparatus includes a coupler, an FFT operator, and an I/Q mismatch estimator. The coupler couples the transmission signal and provides the coupled signal to a reception path, and the FFT operator performs FFT on the coupled transmission signal. The I/Q mismatch estimator estimates I/Q mismatch using a preamble of the FFT-performed transmission signal. The apparatus can compensate for I/Q mismatch in real-time. Since the FFT provided to a reception signal detection unit of a TDD OFDM receiver is used without the need for a separate algorithm for Fourier transform required during an I/Q mismatch estimation process of the conventional art, resources can be saved.

1. Field of the Invention
The present invention relates generally to an apparatus and a method for compensating for I/Q mismatch in a Time Division Duplex (TDD) system, and more particularly, to an apparatus and a method for compensating for a gain mismatch and a phase mismatch between an I-channel (in-phase) and a Q-channel (quadrature), and a mismatch between channels that is caused by DC offset in a receiver of a TDD Orthogonal Frequency Division Multiplexing (OFDM) system.
2. Description of the Related Art
As the bandwidth of a signal used for a digital communication system is widened, an analog/digital converter (ADC) requires a high sampling frequency in order to convert a received analog signal into a digital signal. However, based on the technical limitations of the sampling frequency of the ADC and the reality of high costs in realizing the technology, an analog receiving terminal discriminates a Q-channel from an I-channel to perform quadrature-down-conversion, and performs the analog/digital conversion.
When the I-channel is discriminated from the Q-channel and quadrature-down-conversion is performed as described above, an ADC that uses a lower sampling frequency can be used in place of an ADC performing analog/digital conversion without discrimination of I/Q-channels. However, in the I/Q-channels that are quadrature-down-converted at the analog receiving terminal and analog-digital-converted in a baseband, the performance of a receiver may be reduced due to differences in a gain, a phase, and a DC offset generated during the quadrature-down-conversion.
"Quadrature receiver mismatch calibration," IEEE Trans. Sig. Proc., Vol. 47, No. 11, pp. 3130-133, November 1999 by R. A. Green, R. Anderson-Sprecher, and P. W. Pierre, and "The Correction Of I And Q Errors In A Coherent Processor," IEEE Trans. Aerosp. Electro. Syst., Vol. AES-17, No. 1, pp. 131-137, January 1981 by F. E. Churchill, G. W. Ogar, and B. J, Thompson have proposed methods for applying a square wave to a receiver, and estimating I/Q mismatch using a received signal converted to a complex baseband.
Also, Korean Patent Application No. 10-2000-0004053 titled "Apparatus For Estimating Channel Considering I/Q Mismatch Error And Digital Signal Receiver Having The Same" and Korean Patent Application No. 10-2002-0026853 titled "Method For Estimating And Compensating For I/Q Mismatch And Apparatus Thereof, And method For Estimating And Compensating For I/Q Mismatch And DC Offset And Apparatus Thereof" have proposed methods for estimating and compensating for I/Q mismatch using a predetermined test signal.
FIG. 1 illustrates a receiver for compensating for I/Q mismatch according to the conventional art. Description will be made using an example where a test signal is generated for estimation of I/Q mismatch.
Referring to FIG. 1, the receiver for compensating for I/Q mismatch includes a test signal generator 101, a band pass filter 103, a low noise amplifier 105, I/Q-channel mixers 107 and 108, a local oscillator 109, a phase shifter 111, low pass filters 113 and 114, ADCs 115 and 116, an I/Q mismatch estimator/compensator 117, and a reception signal detector 119.
In operation, the test signal generator 101 generates predetermined test signals in order to estimate I/Q mismatch of the receiver. The band pass filter 103 filters the test signals generated from the test signal generator 101 to pass only signals in a band used for the receiver. After that, the low noise amplifier 105 low-noise-amplifies the signals that have passed through the band pass filter 103.
The I/Q-channel mixers 107 and 108 perform quadrature-down-conversion on the signals from the low noise amplifier 105 for an I-channel and a Q-channel, respectively, to convert the quadrature-down-converted signals into baseband signals. At this point, the I/Q-channel mixers 107 and 108 receive an oscillation signal from the local oscillator 109 and a signal obtained by phase-shifting, at a phase shifter 111, the oscillation signal from the local oscillator 109 by 90°, respectively, to convert I-channel signals and Q-channel signals into baseband signals.
The low pass filters 113 and 114 filter signals from the I/Q-channel mixers 107 and 108, respectively. After that, the ADCs 115 and 116 convert analog signals into digital signals. The I/Q mismatch estimator/compensator 117 estimates I/Q mismatch of the receiver using the signals received from the ADCs 115 and 116, and compensates for I/Q mismatch of received signals using the estimated I/Q mismatch. At this point, the I/Q mismatch estimator/compensator 117 includes a separate Fast Fourier Transform (FFT) algorithm in order to estimate the I/Q mismatch.
The reception signal detector 119 receives a signal where I/Q mismatch is compensated from the I/Q mismatch estimator/compensator 117 to detect a signal.
As described above, the conventional receiver estimates I/Q mismatch using a test signal. That is, since the conventional receiver estimates I/Q mismatch using a separate test signal, the conventional receiver cannot normally receive a signal while the estimation of the I/Q mismatch is performed. Also, since the conventional receiver additionally requires the signal generator 101 for supplying a test signal to the receiver and a separate algorithm for the estimation of the I/Q mismatch is additionally realized at a demodulation terminal, additional hardware and software resources need to be assigned to realize the receiver.

Apparatus and method for compensating for I/Q mismatch in TDD system


A method is provided for synthesizing iron hexacyanoferrate (FeHCF). The method forms a first solution of a ferrocyanide source [A4Fe(CN)6.PH2O] material dissolved in a first solvent, where “A” is an alkali metal ion. A second solution is formed of a Fe(II) source dissolved in a second solvent. A reducing agent is added and, optionally, an alkali metal salt. The first and second solutions may be purged with an inert gas. The second solution is combined with the first solution to form a third solution in a low oxygen environment. The third solution is agitated in a low oxygen environment, and AX+1Fe2(CN)6.ZH2O is formed, where X is in the range of 0 to 1. The method isolates the AX+1Fe2(CN)6.ZH2O from the third solution, and dries the AX+1Fe2(CN)6.ZH2O under vacuum at a temperature greater than 60 degrees C.

1. Field of the Invention
This invention generally relates to electrochemical batteries and, more particularly, to a method for the synthesis of iron hexacyanoferrate (FeHCF, Na1+xFe2(CN)6 (x=0 to 1)).
2. Description of the Related Art
Modern rechargeable lithium batteries have triggered the portable electronic device revolution due to their high power density, long cycle life, and overall reliability. The rechargeable lithium battery consists of a cathode (positive electrode) and anode (negative electrode), separated by a lithium ion (Li+)-permeable membrane. A solution or polymer rich in Li+ is employed to permit facile migration of lithium ions between the positive and negative electrodes. Common positive electrode materials include transition metal oxides such as lithium cobalt oxide (LiCoO2), lithium manganese oxide (LiMn2O4), and lithium iron phosphate (LiFePO4), in addition to various derivatives. Within these materials, Li+ can travel within the interstitial space(s) both freely and reversibly. In general, metallic lithium, alloys, and carbonaceous materials can be utilized as the negative electrode. When the rechargeable lithium battery does not include any metallic electrode, it is referred to as lithium-ion battery (LIB). During the discharge process in a lithium-ion battery, lithium ions are extracted from the negative electrode and subsequently inserted into the positive electrode. At the same time, electrons pass through an external circuit from the negative electrode to the positive electrode to generate electric power. During the charge process, ions and electrons move along the reverse directions and are ultimately restored to their original locations.
Although LIBs have been employed successfully over a broad range of commercial applications, the issue of lithium supply, as it applies to both strain on natural reserves and potential fluctuations in price, has motivated the development of a low-cost, rechargeable battery technology as an alternative to LIB. In light of this, sodium-ion batteries (NIBs) have increased in popularity due primarily to the fact that sodium has similar properties to lithium, but also boasts the benefits of both reduced cost and virtually unlimited availability. However, analogous to LIBs, NIBs require appropriate Na+ host materials. Indeed, significant effort has been devoted towards the direct duplication of Li+ host structures for application as Na+-host electrode materials for NIBs. For example, NaCoO2, NaMnO2, NaCrO2, and Na0.85Li0.17Ni0.21Mn0.64O2 with similar layered-structure to LiCoO2, have been developed for NIBs. Similarly, Co3O4 with a Spinel structure, Na3V2(PO4)3 with a NASICON structure, and NaFePO4 with an Olivine structure have been employed in sodium batteries. In addition, sodium fluorophosphates, such as Na2PO4F, NaVPO4F, and Na1.5VOPO4F0.5 have also been utilized as the positive electrode for sodium batteries.
Overall, it appears impractical to simply adopt conventional Li+ host materials and structures as Na+ host compounds, since sodium ions are larger than lithium ions and, consequently, severely distort the structures of Li+ host compounds during the intercalation process. In response to this, it is critical to develop new Na+ host materials with large interstitial space(s) through which sodium ions can migrate, both easily and reversibly.
It is widely known that Na+ and others ions readily intercalate into metal hexacyanometallate compounds. In general, Prussian Blue and its analogues belong to a class of mixed valence compounds called transition metal hexacyanometallates (TMHCMs). In addition to energy storage, these materials have been identified for applications that include electrochromics, chemical sensors (for nonelectroactive cations and hydrogen peroxide, for example), and advanced biosensors. In general, TMHCMs are characterized by a general formula corresponding to AxM1mM2n(CN)6 where M1m+ and M2n+ are transition metals with different formal oxidation numbers (m and n). In many cases, the TMHCMs can sequester a variety of different ions ("A"=Na+, K+, NH4+, Co2+, Cu2+, for example) as well as various amounts of water (H2O) within the crystal structure.
FIG. 1 is a schematic diagram depicting the crystal structure of TMHCM, which exhibits an open framework and is analogous to that of the ABX3 perovskite (prior art). M1m+ and M2n+ metal ions are in ordered arrangement on the B sites. The large, tetrahedrally coordinated "A" sites can host both alkali and alkaline earth ions (Ax) in addition to species such as ammonium (NH4+) and H2O. The number of alkali (or alkaline earth ions) in the large cages of this crystallographically porous framework may vary from x=0 to x=2, which is dependent on the respective valence(s) of M1 and M2.
Previously, TMHCFs with large interstitial spaces have been investigated as cathode materials for rechargeable lithium-ion batteries,1,2 sodium-ion batteries,3,4 and potassium-ion batteries.5 In aqueous electrolytes containing appropriate alkali metal ions or NH4+, copper and nickel hexacyanoferrates [(Cu,Ni)-HCFs] demonstrated robust cycling with 83% capacity retention after 40,000 cycles at a charge/discharge current density of 17C (1C=150 milliamps per gram).6-8 In spite of this, the materials demonstrated low corresponding capacities and energy densities due to the fact that (1) only one sodium-ion can be inserted/extracted into/from per Cu-HCF or Ni-HCF formula, and (2) the TMHCF electrodes required operation below 1.23 V due to the electrochemical stability window for water. The electrochemical stability window of a substance is the voltage range between which the substance is neither oxidized nor reduced. This range is significant in terms of electrode efficiency since water becomes electrolyzed outside this range, which consequently cannibalizes the electrical energy intended for another electrochemical reaction.
In order to compensate for these shortcomings, manganese hexacyanoferrate (Mn-HCF) and iron hexacyanoferrate (Fe-HCF) were used as cathode materials in non-aqueous electrolyte.9,10 For batteries containing a metallic sodium anode, Mn-HCF and Fe-HCF cathodes demonstrated capacities ˜110 milliamperes hours per gram (mAh/g) when cycled between 2.0 V and 4.2 V.
Despite the significant potential for TMHCFs in secondary battery applications, it has proven extremely difficult to directly synthesize Na1+xFe2(CN)6 (x=0 to 1) through a conventional precipitation process. Specifically, upon addition of Fe2+-containing solution to a solution of ferrocyanide [Fe(CN)64−], Fe2+-ions are almost instantaneously oxidized to Fe3+ ions, yielding a corresponding dark blue precipitate consistent with Na1−xFe2(CN)6 (x=0 to 1).
FIG. 2 is a graph depicting the capacity of a Na1+xFe2(CN)6 (x=0 to 1) electrode, the synthesis of which was unsuccessful using direct mixing of a solution of a Fe2+ source containing Fe(CN)64−. During the first charge, the material generated a modest capacity of 40.85 milliamperes hours per gram (mAh/g), which corresponds to 0.52 Na+ ions per formula unit (fu). Furthermore, thermal gravimetric analysis (TGA) confirmed 2.79 water molecules existing per fu. Thus, the molecular formula can be calculated as Na0.52FeIII[FeII(CN)6]1−y.2.79H2O (y<1), rather than the intended Na1+xFe2(CN)6 (x=0 to 1). Finally, the small Na+ content confirms that a certain proportion of Fe(II) species in Fe(CN)64− was also oxidized during the process. Based upon these results, it would appear as if Na1+xFe2(CN)6 (x=0 to 1) cannot be readily synthesized using a conventional precipitation method.
Hu et al. reported a hydrothermal method to synthesize K2Fe2(CN)6 from K4Fe(CN)6 in a neutral solution.11 However, some practitioners are skeptical of this reported method of synthesizing Na2Fe2(CN)6 due to the fact that sodium ions are smaller than potassium ions and, therefore, harder to retain in the large interstitial space of iron hexacyanoferrates (Fe-HCFs), Further, the reaction is sensitive to solution pH.12-14 In response, Lu et al. demonstrated a modified hydrothermal reaction process to successfully synthesize sodium iron hexacyanoferrate (Na2Fe2(CN)6) directly (U.S. Ser. No. 14/067,038, which is incorporated herein by reference). According to this method, reducing agents are included in the reaction solutions to protect Fe(II) from oxidation during the hydrothermal process.    [1]V. D. Neff, "Some Performance Characteristics of a Prussian Blue Battery", Journal of The Electrochemical Society 1985, 132, 1382-1384.    [2]N. Imanishi, T. Morikawa, J. Kondo, Y. Takeda, O. Yamamoto, N. Kinugasa, and T. Yamagishi, "Lithium Intercalation Behavior Into Iron Cyanide Complex as Positive Electrode of Lithium Secondary Battery", Journal of Power Sources 1999, 79, 215-219.    [3] Y. Lu, L. Wang, J. Cheng, and J. B. Goodenough, "Prussian Blue: A New Framework for Sodium Batteries", Chemical Communications 2012, 48, 6544-6546.    [4]L. Wang, Y. Lu, J. Liu, M. Xu, J. Cheng, D. Zhang, and J. B. Goodenough, "A Superior Low-Cost Cathode for a Na-ion Battery", Angewandte Chemie International Edition 2013, 52, 1964-1967.    [5] A. Eftekhari, "Potassium Secondary Cell Based on Prussian Blue Cathode", Journal of Power Sources 2004, 126, 221-228.    [6]C. D. Wessells, R. A. Huggins, and Y. Cui, "Copper Hexacyanoferrate Battery Electrodes with Long Cycle Life and High Power, Nature Communications 2011, 2, Article number: 550.    [7]C. D. Wessells, S. V. Peddada, R. A. Huggins, and Y. Cui, "Nickel Hexacyanoferrate Nanoparticle Electrodes for Aqueous Sodium and Potassium Ion Batteries", Nano Letters 2011, 11, 5421-5425.    [8]C. D. Wessells, S. V. Peddada, M. T. McDowell, R. A. Huggins, and Y. Cui, "The Effect of Insertion Species on Nanostructured Open Framework Hexacyanoferrate Battery Electrodes", Journal of The Electrochemical Society 2012, 159, A98-A103.    [9]T. Matsuda M. Takachi, and Y. Moritomo, "A Sodium Manganese Ferrocyanide Thin Film for Na-ion Batteries", Chemical Communications 2013, 49, 2750-2752.    [10]S-H. Yu, M. Shokouhimehr, T. Hyeon, and Y-E. Sung, "Iron Hexacyanoferrate Nanoparticles as Cathode Materials for Lithium and Sodium Rechargeable Batteries", ECS Electrochemistry Letters 2013, 2, A39-A41.    [11]M. Hu and J. S. Jiang, "Facile Synthesis of Air-Stable Prussian White Microcubes via a Hydrothermal Method", Materials Research Bulletin 2011, 46, 702-707.    [12] S-H. Lee and Y-D. Huh, "Preferential Evolution of Prussian Blue's Morphology from Cube to Hexapod", Bulletin of the Korean Chemical Society 2012, 33, 1078-1080.    [13] M. Hu, J-S. Jiang, C-C. Lin, and Y. Zeng, "Prussian Blue Mesocrystals: An Example of Self-Construction", Cryst Eng Comm 2010, 12, 2679-2683.    [14]M. Hu, R-P. Ji, J-S. Jiang, "Hydrothermal Synthesis of Magnetite Crystals: From Sheet to Pseudo-Octahedron", Materials Research Bulletin 2010, 45, 1811-1815.    [15] R. K. Patil, S. A. Chimatadar, and S. T. Nandibewoor, "Oxidation of Thiosulfate by Hexacyanoferrate(III) in Aqueous Perchloric Acid Medium—A Kinetic and Mechanistic Study", Indian Journal of Chemistry 2009, 48A, 357-361.
It would be advantageous if Na1+xFe2(CN)6 (x=0 to 1) containing a high concentration of sodium ions could be synthesized using a simple, low-cost process.

Method for the synthesis of iron hexacyanoferrate


The present invention is directed at methods and apparatuses for facilitating the establishment of a reference pressure within a reference chamber of a pressure transducer. The transducer has a housing and a cover, the housing defining a reference chamber and an aperture. A meltable sealing material is disposed on at least one of the cover and the housing. The apparatus includes a pressure chamber that is rotatable between a first position and a second position, a pressure source that is connected to the pressure chamber, a guide that is attachable to the transducer near the aperture, and a heater for selectively heating the pressure chamber to a temperature sufficiently high to melt the sealing material. The cover is positioned in an internal space of the guide. The guide is attached to the transducer near the aperture. The transducer, cover and guide are placed in the pressure chamber, the pressure chamber is rotated to the first position and a pressure is generated in the pressure chamber via the pressure source. After a reference pressure has been established in the reference chamber, the pressure chamber is rotated to the second position. Gravity causes the cover to move within the space towards the aperture when the pressure chamber is rotated to the second position. The heater then heats the pressure chamber to melt the sealing material. Upon cooling, the sealing material forms a seal that seals the reference pressure in the reference chamber of the transducer.

The present invention relates to capacitive pressure transducers. More specifically, the present invention relates to an improved method and apparatus for forming a reference pressure within a chamber of a capacitive pressure transducer assembly.
FIG. 1A depicts a cross-sectional side view of an assembled prior art capacitive pressure transducer assembly 10. FIG. 1B is an exploded view of the upper housing 40, diaphragm 56 and lower housing 60 of FIG. 1A. Briefly, capacitive pressure transducer assembly 10 includes a body that defines an interior cavity. A relatively thin, flexible ceramic diaphragm 56 divides the interior cavity into a first sealed interior chamber 52 and a second sealed interior chamber 54. As will be discussed in greater detail below, diaphragm 56 is mounted so that it flexes, moves, or deforms, in response to pressure differentials in chambers 52 and 54. Transducer assembly 10 provides a parameter that is indicative of the amount of diaphragm flexure and this parameter is therefore indirectly indicative of the differential pressure between chambers 52 and 54. The parameter provided by transducer assembly 10 indicative of the differential pressure is the electrical capacitance between diaphragm 56 and one or more conductors disposed on an upper housing 40.
Capacitive pressure transducer assembly 10 includes a ceramic upper housing 40 and a ceramic lower housing 60. The upper housing 40, which generally has a circular shape when viewed from the top, defines an upper face 41, a central lower face 47, an annular shoulder 42 that has a lower face 42a and an annular channel 43 that is located between the central lower face 47 and the annular shoulder 42. Lower face 42a of the annular shoulder 42 is substantially co-planar with central lower face 47. The upper housing further defines an aperture (or passageway) 48 that extends through the housing 40 from the upper side to the lower side. A metallic conductor 46 is disposed on a center portion of the lower face 47.
The diaphragm 56 is generally a circular thin diaphragm that has an upper face 57 and an opposite, lower, face 59. A metallic conductor 58 is disposed on a center portion of upper face 57 of the diaphragm 56. The diaphragm 56 and the upper housing 40 are arranged so that the conductor 46 of the upper housing 40 is disposed opposite to the conductor 58 of the diaphragm 56. Diaphragm 56 is coupled to the upper housing 40 by a high-temperature air-tight seal (or joint) 70. The seal 70 is located between the lower face 42a of the annular shoulder 42 of the upper housing 40 and a corresponding annular portion of face 57 of diaphragm 56. When sealed, the upper housing 40, seal 70 and diaphragm 56 define reference chamber 52. A reference pressure is established and maintained in the reference chamber 52. Aperture 48 provides an inlet or entry way into reference chamber 52.
The lower housing 60, which generally has a circular shape, defines a central opening 64 and an upwardly projecting annular shoulder 62 that has an upper face 62a. The upper face 62a of shoulder 62 of the lower housing 60 is coupled to a corresponding portion of lower face 59 of diaphragm 56 by a high-temperature air-tight seal (or joint) 76. Seal 76 can be deposited and fabricated in a manner similar to that of seal 70. When sealed, the lower housing 60, seal 76 and face 59 of the diaphragm 56 define process chamber 54.
A pressure tube 66 having an inlet passageway 68 is coupled to the lower housing 60 by a seal, for example, so that the inlet passageway 68 is aligned with the opening 64 of the lower housing 60. Accordingly, the process chamber 54 is in fluid communication, via opening 64 and inlet passageway 68, with an external environment. In operation, the capacitive pressure transducer assembly 10 measures the pressure of this external environment.
Conductors 46 and 58 of the capacitive pressure transducer assembly 10 form parallel plates of a variable capacitor C. As is well known, C=Aεrε0/d, where C is the capacitance between two parallel plates, A is the common area between the plates, ε0 is the permittivity of a vacuum, εr is the relative permittivity of the material separating the plates (e.g., εr=1 for vacuum), and d is the axial distance between the plates (i.e., the distance between the plates measured along an axis normal to the plates). So, the capacitance provided by capacitor C is a function of the axial distance between conductor 46 and conductor 58. As the diaphragm 56 moves or flexes up and down, in response to changes in the pressure differential between chambers 52 and 54, the capacitance provided by capacitor C also changes. At any instant in time, the capacitance provided by capacitor C is indicative of the instantaneous differential pressure between chambers 52 and 54. Known electrical circuits (e.g., a "tank" circuit characterized by a resonant frequency that is a function of the capacitance provided by capacitor C) may be used to measure the capacitance provided by capacitor C and to provide an electrical signal representative of the differential pressure. Conductors 46, 58 can be comprised of a wide variety of conductive materials such as gold or copper, for example, and can be fabricated via known thin and thick film processes or other known fabrication methods. When thin film processes are utilized, conductors 46, 48 may have thicknesses of about 1 μm, for example.
Diaphragm 56 is often made from aluminum oxide. Other ceramic materials, such as ceramic monocrystalline oxide materials, however, may also be used. Capacitance sensors having ceramic components are disclosed in U.S. Pat. Nos. 5,920,015 and 6,122,976.
As noted above, changes in the differential pressure between chambers 52, 54 cause diaphragm 56 to flex thereby changing the gap between conductor 46 and conductor 58. Measurement of changes in the gap permits measurement of the differential pressure. The gap, however, can also be affected by factors unrelated to pressure. For example, the gap can be affected by changes in temperature. Since the components of transducer assembly 10 can be made from a variety of different materials, each of which has its own characteristic coefficient of thermal expansion, temperature changes in the ambient environment can cause the diaphragm 56 to move closer to, or further away from, conductor 46. Fortunately, changes in the gap caused by temperature changes are characteristically different than changes in the gap caused by changes in differential pressure. To compensate for changes in the gap that are caused due to changes in the ambient temperature, it is known to include a second conductor (not shown) that is disposed adjacent to conductor 46 on the lower face 47 of the upper housing 40. In such an embodiment, conductors 46 and 58 form parallel plates of a variable capacitor C1 and conductor 58 and the second conductor form parallel plates of a variable capacitor C2. The two capacitors, C1 and C2, may be used by known methods to reduce the transducer's sensitivity to temperature changes.
The upper housing 40 is positioned so that the lower face 47, and any conductors disposed thereon, are disposed in a plane that is parallel to the plane defined by the conductor 58 (i.e., diaphragm 56) when the pressures in chambers 52, 54 are equal. As discussed above, the capacitance defined by the conductors 46, 58 depends upon the gap (i.e., axial distance) that exists between these opposing conductors. The gap, which is relatively small (e.g., on the order of 0.0004 inches (10–12 μm)), depends, in part, upon the thickness of the seal 70 and the shape and configuration of the upper housing 40 (e.g., the amount that lower face 42a is out of plane, i.e. offset, with lower face 47, if any).
In operation, capacitive pressure transducer assembly 10 is normally used as an absolute pressure transducer. In this form, reference chamber 52 is evacuated to essentially zero pressure, e.g., less than 10−8 Torr, and the reference chamber 52 is then sealed. The reference pressure then serves as a baseline from which a pressure within the process chamber 54 is determined. To maintain the essentially zero pressure within the reference chamber 52, the transducer assembly 10 includes a tube 80, a cover 82, a hold-wire 86, a screen 88 and a getter element 84. As is shown in FIGS. 1A and 1B, the screen 88 supports the getter element 84 within a hollow portion of the tube 80 while the hold-wire 86 maintains the getter element 84 against the screen 88. The hollow portion of the tube 80 is disposed over the aperture 48 of the upper housing 40 so that the getter element 84 is in fluid communication with the reference chamber 52. In addition to supporting the getter element 84, screen 88 also prevents particles from passing into the reference 52 that could adversely affect the operation of the diaphragm 56.
The bottom end of the tube 80 is coupled to the upper face 41 of the upper housing 40 around the aperture 48 by a high-temperature air-tight seal 92, while the cover 82 is coupled to the upper end of the tube 80 by a low-temperature air-tight seal 94. Seals 92, 94 and seal 70, which is located between the shoulder 42 of the upper housing 40 and the diaphragm 56, all assist in maintaining the reference pressure that is established in the reference chamber 52. The high-temperature seal 92 is comprised of a high-temperature glass material while the low-temperature seal 94 is comprised of a low-temperature glass material. To form the high-temperature seal 92, the high-temperature glass material is deposited on the lower end of the tube 80, a corresponding sealing area of face 41, or both. The high-temperature glass material is melted, a force perpendicular to the upper face 41 of the upper housing 40 is applied between the tube 80 and the upper housing 40 and the high-temperature glass material is then allowed to cool (i.e., solidify) thus forming the high-temperature air-tight seal 92. The low-temperature seal 94 is similarly formed between the upper end of the tube 80 and a corresponding sealing area of the cover 82. The high-temperature glass material of the high-temperature seal 92 has a melting temperature that is higher than that of the low-temperature glass material of the low-temperature seal 94. To provide different melting temperatures, the glass materials of the seals 92, 94 can be comprised of different materials or have different amounts of a common material. The melting temperature of the high-temperature seal 92 is higher than the melting temperature(s) of the high-temperature seals 70 and 76 and the melting temperature(s) of the high-temperature seals 70 and 76 is higher than the melting temperature of the low-temperature seal 94.
The getter element 84 is comprised of a material that, when activated, acts to effectively absorb any gaseous impurities that may be present within the sealed reference chamber 52. Thus, when activated, the getter element 84 assists in maintaining the reference pressure at an ultra high vacuum level for long periods of time, e.g., ten or more years.
Although an ultra high vacuum pressure, i.e., essentially zero pressure, is a convenient and useful reference pressure, other reference pressures can also be used. After the reference pressure has been established in chamber 52, the pressure tube 66 is then connected to a source of fluid (not shown) to permit measurement of the pressure of that fluid. Coupling the pressure tube 66 in this fashion delivers the fluid, the pressure of which is to be measured, to process chamber 54 (and to the lower face 59 of the diaphragm 56). The center of diaphragm 56 moves or flexes up or down in response to the differential pressure between chamber 52 and 54 thereby changing the capacitance of capacitor C. Since the instantaneous capacitance of capacitor C is indicative of the position of the diaphragm 56, transducer assembly 10 permits measurement of the pressure in chamber 54 relative to the reference pressure that is established in chamber 52.
The accuracy of the capacitive pressure transducer assembly 10 can depend upon the accuracy at which the reference pressure can be established and maintained in the reference chamber 52. In other words, as the actual pressure within the reference chamber 52 deviates from an intended and designed reference pressure, the performance of the capacitive pressure transducer assembly 10 will correspondingly suffer.
The steps of establishing a reference pressure in the reference chamber 52, activating the getter element 84 and sealing the cover 82 to the tube 80 are typically the last few steps that are performed when fabricating capacitive pressure transducer assembly 10. Thus, the steps of coupling the upper housing 40 to the diaphragm 56 via the high-temperature seal 70, coupling the lower housing 60 to the diaphragm 56 via the high-temperature seal 76, coupling the pressure tube 66 to the lower housing 60 around the opening 64, and coupling the tube 80 (having the screen 88, getter element 84 and hold-wire 86) to the face 41 of the upper housing 40 around the aperture 48 via the high-temperature seal 92 will usually have already been completed before the reference pressure is established.
To establish a reference pressure within the reference chamber 52, the reference chamber 52 is typically subjected to a burn-out and evacuation process and then the cover 82 is sealed to the tube 80. The reference chamber 52 is "burned-out" by heating the inner surfaces that define the reference chamber 52 (including the surfaces of the cover 82, tube 80, housing 40 that are in fluid communication with the reference chamber 52), and the chamber 52 is "evacuated" by drawing an ultra-high vacuum on the reference chamber 52. The burn-out heat vaporizes the contaminants, e.g., volatiles, moisture, that may be present on these inner surfaces while the evacuation vacuum draws the vaporized contaminants and gases out of the reference chamber 52. Since the cover 82 has not yet been sealed to the tube 80, the contaminants and gases are sucked out of the reference chamber 52, the aperture 48 and the hollow portion of the tube 80. Once the burn-out and evacuation process is completed and while the vacuum pressure is continuing to be maintained, the cover 82 is then sealed to the tube 80 via the low-temperature seal 94 to establish the reference pressure in the reference chamber 52.
FIGS. 2A and 2B illustrate a prior art method and apparatus that is used to establish a reference pressure within the reference chamber 52 of a capacitive pressure transducer assembly 10. FIG. 2A generally depicts the burn-out and evacuation process while FIG. 2B generally depicts the process by which the cover 82 is sealed onto the upper end of the tube 80. The apparatus includes a vacuum housing 93 that defines an interior vacuum chamber 95. Referring to FIG. 2A, a low-temperature sealing material 94a is deposited on the upper end of the tube 80. The semi-completed transducer assembly 10, i.e., one that does not yet have the cover 82 sealed to the tube 80, is then disposed in the vacuum chamber 95. [For clarity, the pressure tube 66 has been omitted from FIGS. 2A and 2B and some of the other subsequent figures. The pressure tube 66, however, would typically be coupled to the lower housing 60 prior to the assembly being placed in the vacuum chamber 95.] After the transducer assembly 10 has been placed in the vacuum chamber 95, the vacuum housing 93 is placed in an oven (not shown), a vacuum source (not shown) is coupled to the vacuum chamber 95 and the burn-out and evacuation process of the reference 52 is initiated. During the burn-out and evacuation process, which can last for more than 20 hours, the transducer assembly 10 is heated to a temperature of about 250° C. and an ultra-high vacuum pressure of the order of 10−8 Torr (or less) is generated in the vacuum chamber 95. In FIG. 2A, the burn-out and evacuation of reference chamber 52 (and aperture 48 and tube 80) is indicated by the arrows which extend from the reference chamber 52, up through the aperture 48 and up through and out of the top end of the tube 80.
After the burn-out and evacuation of the reference chamber 52 is completed, the cover 82 is then coupled to the tube 80 by the low-temperature seal 94. Cover 82 is attached and sealed to the tube 80 without opening vacuum housing 93 so as to preserve the vacuum in reference chamber 52. Accordingly, as can been seen in FIG. 2A, prior to initiating the burn-out and evacuation process, the cover 82 is attached to an end of a rod 96 which penetrates into the vacuum chamber 95 of the vacuum housing 93. When the burn-out and evacuation process is completed, the rod 96 can be actuated to bring the cover 82 in contact with the low-temperature sealing material 94a that is disposed on the upper end of the tube 80.
The low-temperature sealing material 94a that forms the low-temperature seal 94 is not melted during the burn-out and evacuation process, i.e., the burn-out temperature is generally set below the melting temperature of the low-temperature sealing material 94a. Moreover, the burn-out and evacuation process should not compromise the seals that have already been formed in the transducer assembly 10 (e.g., high-temperature seals 70, 76 and 92) and, thus, the burn-out temperature should not exceed the melting temperatures of these seals.
A high-temperature dynamic seal 99 (e.g., a gasket) is disposed in the vacuum housing 93 where the rod 96 penetrates the vacuum housing 93. The high-temperature dynamic seal 99 allows to the rod to travel freely up and down while assisting to maintain the pressure that is present in the vacuum chamber 95 of the vacuum housing 93.
Prior to initiating the burn-out and evacuation process, cover 82 is attached to the end of the rod 96 by a low-temperature seal 98. The melting temperature (i.e., melting point) of the low-temperature seal 98, which is lower than the melting temperature of the low-temperature sealing material 94a, is higher than the burn-out temperature and, therefore, does not melt during the burn-out and evacuation process. The rod 96 extends through the high-temperature dynamic seal 99 and, together with the cover 82, is aligned with the tube 80 of the transducer assembly 10.
Referring now to FIG. 2B, after the burn-out and evacuation process is completed, while the pressure in the vacuum chamber 95 is still being maintained, the rod 96/cover 82 is lowered until the cover 82 comes into contact with the low-temperature sealing material 94a. The temperature within the vacuum chamber 95 (as directed by the oven) is then elevated to cause the low-temperature sealing material 94a to melt. This increase in temperature also causes the low-temperature seal 98 to melt and causes the getter element 84 to become activated. To form the low-temperature air-tight seal 94 between the cover 82 and the tube 80, the temperature within the vacuum chamber 95 is decreased until the low-temperature sealing material 94a solidifies and, while the low-temperature seal 98 is sufficiently melted, the rod 96 is pulled away from the transducer assembly 10. Once the low-temperature seal 94 is formed—and the reference pressure in the reference chamber 52 is thus established—the temperature in the vacuum chamber 95 is reduced to ambient temperature, then vacuum source is disconnected and the assembled transducer assembly 10 is removed from the vacuum housing 93.
FIG. 3 illustrates the prior art burn-out, evacuation and sealing process of the apparatus and method of FIGS. 2A and 2B in more detail. In FIG. 3, the x-axis of the process flow represents Time and the y-axis represents Temperature in degrees Celsius. Prior to initiating the burn-out and evacuation process, at Step A of the process flow, the cover 82 is attached to rod 96 via low-temperature seal 98 and the transducer assembly 10, cover 82 and rod 96 are placed in the vacuum chamber 95 (FIG. 2A). During Step A→B, the temperature in the vacuum chamber 95 is raised to a burn-out temperature of 250° C. and the pressure is lowered to an evacuation pressure of 10−8 Torr. Step A→B is completed in three hours. After the burn-out temperature and evacuation pressure are achieved (Step B), the reference chamber 52 is burned-out and evacuated for 20 hours, Step B→C. Shortly before Step C is reached, the rod 96 and cover 82 are lowered so that the cover 82 comes into contact with the low-temperature sealing material 94a that is deposited on the upper end of the tube 80. Once the burn-out and evacuation step is completed (Step C), the temperature in the vacuum chamber 95 is raised to 475° C., Step C→D, which causes the low-temperature sealing material 94a and the low-temperature seal 98 to melt. Step C→D lasts for three hours. The vacuum chamber 95 is then maintained at 475° C. for 30 minutes, Step D→E, to ensure that the low-temperature sealing material 94a and the low-temperature seal 98 are sufficiently melted. The temperature in the vacuum chamber 95 is then lowered to 400° C. over the course of two hours, Step ELF, which causes the low-temperature sealing material 94a to solidify and form the low-temperature air-tight seal 94. The melting temperature of the low-temperature seal 98 is below 400° C. and, thus, the low-temperature seal 98 remains melted throughout Step E→F. Shortly before Step F is reached, rod 96 is raised away from the cover 82 (FIG. 2B). Lastly, the temperature and pressure in the vacuum chamber 95 are brought to ambient conditions over the course of 4 hours and the assembled pressure transducer assembly 10 is then removed from the vacuum chamber 95 of the vacuum housing 93, Step F→G. As illustrated in FIG. 3, the prior art burn-out, evacuation and sealing process can be completed in 32½ hours.
The method and apparatus described above does not necessarily ensure that an accurate reference pressure has been established within the reference chamber 52 of a capacitive pressure transducer assembly 10. For example, it is very difficult to establish and maintain an ultra high vacuum of the order of 10−8 Torr (or less) in a vacuum housing 93 that utilizes a rod 96 and a high-temperature dynamic seal 99 because the pressure integrity of the vacuum housing 93 tends to be compromised by the presence of the high-temperature dynamic seal 99. It also can be difficult or costly to accurately control the positions and orientations of the cover 82 and the tube 80 during the rod actuating mating process. If the cover 82 is not positioned or oriented properly in relationship to the tube 80 during the mating process, the integrity of the low-temperature seal 94 may be compromised or the low-temperature seal 94 may fail entirely.
A need therefore exists for a method and apparatus for accurately establishing a reference pressure within a reference chamber of a capacitive pressure transducer assembly.

Method and apparatus for forming a reference pressure within a chamber of a capacitance sensor


Provided is a conveyor belt cleaning apparatus, and more particularly, to a conveyor belt cleaning apparatus capable of cleaning a conveyor belt by operating in a pneumatic manner using compressed air without using electricity. The conveyor belt cleaning apparatus uses the rodless cylinder so as to enable the steam spray nozzle to perform a reciprocating motion and make it easy to adjust a speed of the steam spray nozzle and adjust a spray range for an object to be cleaned. Further, the conveyor belt cleaning apparatus is structured such that a width in a left-right direction and a height in an up-down direction may be adjusted, such that the conveyor belt cleaning apparatus may be installed on conveyor belts having various sizes, thereby ensuring diversity of use.

A conveyor refers to a mechanical device that automatically and continuously transports materials or items between positions spaced at a predetermined distance in a factory or the like. The types of conveyors include belt conveyors, screw conveyors, chain conveyors, and the like. Among them, the belt conveyor refers to a device that circulates a belt made of rubber, woven fabric, wire mesh, steel plates, and the like and continuously transports objects placed on the belt. The belt is hung on belt wheels and operated in an endless manner as the belt wheels are rotated by an electric motor.
In general, most conveyor belts for transporting goods, food, and the like are contaminated by foreign substances stuck on surfaces of the conveyor belts when the conveyor belts are used over a long period of time. Therefore, it is necessary to remove the foreign substances.
The surfaces of the conveyor belts used by companies certified for food hygiene management by, for example, HACCP (Hazard Analysis Critical Control Points) need to be simultaneously cleaned and sterilized to eliminate a source of contamination.
Korean Patent No. 10-0863066 discloses an exemplary embodiment of a means for removing foreign substances.
That is, a conveyor belt cleaner in the related art includes: a plurality of scrapers having a pair of fitting holes penetratively formed at both sides at a predetermined interval, having tips formed at both sides, and having a friction damping unit at an inner center thereof; two wires fitted into the pair of fitting holes formed in the plurality of scrapers and fixed in position so as to be wound around a surface of a conveyor belt that rotates on pulleys; a wire fixture positioned at one end of each of the two wires in order to support the wires; and a tightening means fitted with the other end of the wires in order to push the plurality of scrapers to one end, in which a discharge hole is formed in a thickness direction in each of the plurality of scrapers.
However, such a cleaning apparatus is basically operated by electricity, and there is a limitation in that the cleaning apparatus is inevitably used only for a conveyor having a belt that is not opened and has a flat bottom surface. There is also a disadvantage in that the conveyor belt is not completely cleaned and sterilized even though the cleaning operation is performed.


Provided herein is a hydrogen chloride salt of 1-(3-/t?r/-butyl-1-p-tolyl-1H-pyrazol-5-yl)-3-(5-fluoro-2-(1-(2-hydroxyethyl)-1H-indazol-5-yloxy)benzyl)urea, crystalline forms of 1-(3-½^butyl-1^-tolyl-1H-pyrazol-5-yl)-3-(5-fluoro-2-(1-(2-hydroxyethyl)-1H-indazol-5-yloxy)benzyl)urea hydrochloride, processes for the preparation of said crystalline forms, pharmaceutical compositions containing a crystalline form of 1-(3-r<i/-r-butyl-1-p-tolyl-1H-pyrazol-5-yl)-3-(5-fluoro-2-(1-(2-hydroxyethyl)-1H-indazol-5-yloxy)benzyl)urea hydrochloride Form B, processes for the preparation of said compositions, pharmaceutical compositions prepared by said methods, and the use of said compositions in the treatment of various diseases and disorders.

1. Field of the Invention
Provided herein is a hydrogen chloride salt of 1-(3-tert-butyl-1-p-tolyl-1H-pyrazol-5-yl)-3-(5-fluoro-2-(1-(2-hydroxyethyl)-1H-indazol-5-yloxy)benzyl)urea, crystalline forms of 1-(3-tert-butyl-1-p-tolyl-1H-pyrazol-5-yl)-3-(5-fluoro-2-(1-(2-hydroxyethyl)-1H-indazol-5-yloxy)benzyl)urea hydrochloride, processes for the preparation of said crystalline forms, pharmaceutical compositions containing crystalline forms of 1-(3-tert-butyl-1-p-tolyl-1H-pyrazol-5-yl)-3-(5-fluoro-2-(1-(2-hydroxyethyl)-1H-indazol-5-yloxy)benzyl)urea hydrochloride Form B, processes for the preparation of said compositions, pharmaceutical compositions prepared by said methods, and the use of said compositions in the treatment of various diseases and disorders.
2. Description of the State of the Art
The myelodysplastic syndromes (MDS, formerly known as pre-leukemia) are a diverse collection of hematological (blood-related) medical conditions that involve ineffective production (or dysplasia) of the myeloid class of blood cells. Patients with MDS often develop severe anemia and require frequent blood transfusions. In most cases, the disease worsens and the patient develops cytopenias (low blood counts) due to progressive bone marrow failure. In about one third of patients with MDS, the disease transforms into acute myelogenous leukemia (AML), usually within months to a few years. The myelodysplastic syndromes include all disorders of the stem cell in the bone marrow. In MDS, hematopoiesis (blood production) is disorderly and ineffective. The number and quality of blood-forming cells decline irreversibly, further impairing blood production
The goals of therapy for patients with MDS are to control symptoms, improve quality of life, improve overall survival, and decrease progression to AML. Treatment options for patients with myelodysplastic syndromes range from supportive care that helps relieve symptoms to aggressive treatment that may slow or prevent progression of the disease. Problems caused by low blood cell counts, such as fatigue and infections, may be treated with transfusions of blood products or the use of growth factors. Chemotherapy may be used to delay progression of the disease. Other drug therapy may be used to lessen the need for transfusions. Certain patients may benefit from aggressive treatment with chemotherapy followed by stem cell transplant using stem cells from a donor. For patients with transfusion-dependent anemia due to low or intermediate-1 risk MDS associated with a deletion 5q cytogenetic abnormality, lenalidomide (Revlimid®) is an approved therapy in the United States. Other treatment options include immunosuppressive agents, low/intermediate intensity chemotherapy (e.g., azacitidine, decitabine, cytarabine), and finally high intensity antileukemic chemotherapy and hematopoietic cell transplantation. Accordingly, there remains a need for new pharmaceutical compositions and methods for treating MDS.
1-(3-Tert-butyl-1-p-tolyl-1H-pyrazol-5-yl)-3-(5-fluoro-2-(1-(2-hydroxyethyl)-1H-indazol-5-yloxy)benzyl)urea (also known as "ARRY-614") is exemplified in WO 2007/089646 and possesses the following structural formula:

1-(3-Tert-butyl-1-p-tolyl-1H-pyrazol-5-yl)-3-(5-fluoro-2-(1-(2-hydroxyethyl)-1H-indazol-5-yloxy)benzyl)urea has been shown to possess potent inhibitory activity against the p38 MAPK and Tie2 protein kinases and therefore could be useful in the treatment of kinase-mediated conditions including proliferative disorders (such as myelodysplastic syndromes), inflammatory diseases, autoimmune diseases, destructive bone disorders, infectious diseases, viral disease, fibrotic disease and neurodegenerative diseases.
1-(3-Tert-butyl-1-p-tolyl-1H-pyrazol-5-yl)-3-(5-fluoro-2-(1-(2-hydroxyethyl)-1H-indazol-5-yloxy)benzyl)urea has been tested in a Phase 1 human clinical trial for myelodysplastic syndromes (MDS) (see R. Komrokji, et al., "Phase 1 Dose-Escalation/Expansion Study of the p38/Tie2 Inhibitor ARRY-614 in Patients with IPSS Low/Int-1 Risk Myelodysplastic Syndromes", 2011 Annual Meeting of the American Society of Hematology, Dec. 11, 2011; which can also be found at: http://www.arraybiopharma.com/_documents/Publication). In this study, a powder in capsule ("PIC") composition of amorphous ARRY-614 was prepared and administered to patients with myelodysplastic syndrome, and inter-patient variability in exposure profiles (concentration/time profiles) and exposure PK parameters (AUC and Cmax) was high. In addition, the clinical study protocol required administration of 12×100 mg capsules per dose (i.e., once daily administration of 12×100 mg capsules), which arose from the inability to achieve a higher drug load per capsule of the amorphous form of the compound. This imposed an undesirably large pill burden on the patients. Due to the limitations of drug load per capsule, only a maximal administrable dose was reached but not a true maximum tolerated dose. A new formulation may provide greater dosing potential if needed.
In order to formulate a pharmaceutically active compound such as 1-(3-tert-butyl-1-p-tolyl-1H-pyrazol-5-yl)-3-(5-fluoro-2-(1-(2-hydroxyethyl)-1H-indazol-5-yloxy)benzyl)urea into a suitably acceptable dosage form, it is desirable that the active compound possess acceptable stability and handling properties in addition to possessing acceptable biopharmaceutical properties such as solubility and dissolution. 1-(3-Tert-butyl-1-p-tolyl-1H-pyrazol-5-yl)-3-(5-fluoro-2-(1-(2-hydroxyethyl)-1H-indazol-5-yloxy)benzyl)urea exists in an amorphous form. It is a BCS Class II molecule with low aqueous solubility (<10 μg/mL) across the typical physiological pH range of 2-8, with a ClogP 6.8 and a calculated pKa less than 3.
Bioavailability is one of the key parameters for many therapeutic indications and can be dependent on the form of the substance to be used in the pharmaceutical composition. Potential pharmaceutical solids of active drugs include crystalline solids and amorphous solids. It is known that the amorphous forms of many pharmaceutical substances exhibit different dissolution characteristics and bioavailability patterns compared to the crystalline forms (Konno T., Chem. Pharm. Bull., 1990, 38:2003-2007). There is often a decrease in solubility of 12-1600 fold in going from an amorphous form to crystalline form (B. C. Hancock and M. Parks, Pharmaceutical Research, 2000, 17(4) 397-404). The identification and selection of a solid form of a pharmaceutical compound is complex, given that a change in solid form may affect a variety of physical and chemical properties, which may provide benefits or drawbacks in processing, formulation, stability and bioavailability, among other important pharmaceutical characteristics. Drawbacks of using the amorphous form of a drug can include the potential of the amorphous solids to lack chemical and physical stability, as well as the risk of form conversion from amorphous to crystalline material at any time during manufacturing and/or storage. In addition, in some cases crystalline salts of the active drug do not form easily and/or are not stable, which is probably due to low pKa values. The pKa value expresses the strength of acids and base, i.e., the tendency for an acid to lose a proton or a base to add a proton (Bronsted J. N., Rec. Trav. Chim. (1923) 47:718).
There remains a need for a pharmaceutical composition suitable for treating proliferative diseases such as MDS.
There also remains a need for a pharmaceutical composition containing a form of 1-(3-tert-butyl-1-p-tolyl-1H-pyrazol-5-yl)-3-(5-fluoro-2-(1-(2-hydroxyethyl)-1H-indazol-5-yloxy)benzyl)urea having increased exposure and increased relative bioavailability.
There also remains a need for a pharmaceutical composition containing a form of 1-(3-tert-butyl-1-p-tolyl-1H-pyrazol-5-yl)-3-(5-fluoro-2-(1-(2-hydroxyethyl)-1H-indazol-5-yloxy)benzyl)urea having reduced inter-patient variability in pharmacokinetic profiles.
There also remains a need for a pharmaceutical composition containing a form of 1-(3-tert-butyl-1-p-tolyl-1H-pyrazol-5-yl)-3-(5-fluoro-2-(1-(2-hydroxyethyl)-1H-indazol-5-yloxy)benzyl)urea having substantially similar pharmacokinetic profiles when administered to a mammal in the fed versus the fasted state.
There also remains a need for a pharmaceutical composition containing a form of 1-(3-tert-butyl-1-p-tolyl-1H-pyrazol-5-yl)-3-(5-fluoro-2-(1-(2-hydroxyethyl)-1H-indazol-5-yloxy)benzyl)urea wherein smaller doses of the composition are required to obtain the same pharmacological effect.
There also remains a need for a pharmaceutical composition containing a form of 1-(3-tert-butyl-1-p-tolyl-1H-pyrazol-5-yl)-3-(5-fluoro-2-(1-(2-hydroxyethyl)-1H-indazol-5-yloxy)benzyl)urea having acceptable pharmacokinetic properties at higher doses.
There also remains a need for a pharmaceutical composition containing a form of 1-(3-tert-butyl-1-p-tolyl-1H-pyrazol-5-yl)-3-(5-fluoro-2-(1-(2-hydroxyethyl)-1H-indazol-5-yloxy)benzyl)urea having an increased rate of dissolution.
There also remains a need for a pharmaceutical composition containing a form of 1-(3-tert-butyl-1-p-tolyl-1H-pyrazol-5-yl)-3-(5-fluoro-2-(1-(2-hydroxyethyl)-1H-indazol-5-yloxy)benzyl)urea that is chemically and physically stable under the conditions in which it is processed, handled and stored.

Crystalline forms of 1-(3-tert-butyl-1-p-tolyl-1H-pyrazol-5-yl)-3-(5-fluoro-2-(1-(2-hydroxyethyl)-1H-indazol-5-yloxy)benzyl)urea hydrochloride


A can filling/seaming device that fills a can with a liquid content and seals the can with a lid by double-seaming allows a filler and a seamer to be integrated in a compact arrangement. A can filling/seaming device includes a filler that fills a can with a liquid content while conveying the can by rotation of a filling turret, a seamer that attaches a lid to the can filled with the content by double-seaming, and a forwarding turret provided between a carrying-out position of the filling turret and a carrying-in position to the seamer to circularly convey the can filled with the content, wherein a lid supply part is provided on the forwarding turret.

A conventional filling/seaming device includes a rotary filling machine (filler) that successively fills a can of a metal material with a liquid content such as a beverage, and a seaming machine (seamer) that successively seals a lid (metal lid) to a flange part of the filled can by seaming. A filler generally used has a plurality of holding parts (pockets) provided at the circular outer circumference of a rotating filling turret to receive and hold a can, and a filling nozzle that moves in synchronization with each of the holding parts is provided above the holding part. Successively supplied cans are sequentially held by the filling turret of the filler and then filled with a prescribed amount of liquid content from the respective filling nozzles while being conveyed by the rotation of the filling turret. The filled cans once removed from the filling turret are transported to a feeding conveyer or a hook-up conveyer and conveyed to the seamer. The seamer sequentially supplies lids to the flange parts of the filled cans supplied from the feed conveyer or the hook-up conveyer, and the flange parts of the cans and the curled parts of the lids are joined by double-seaming by roll processing, so that the lids are attached and sealed to the cans (see PTL 1).

Can filling/seaming device and can filling/seaming method


A computer address translation method and system applicable in CPUs for translating an effective address and a selector address into a physical address under the control of an invalidity signal through a translation lookaside buffer having a stored first address and a stored second address. An effective address and a selector address are simultaneously input to the translation lookaside buffer such that address translation and linear address production are parallel processed, thereby effectively speeding up the address translation process.

1. Field of Invention
The present invention relates to computer architecture in an X-86 system such as a central processing unit (CPU) that can convert an effective address (EA) or logical address into a physical address (PA), and more particularly to a computer address translation system and the translating method.
2. Description of Related Art
Through the use of virtual memory, the X-86 type of computer architecture is now capable of achieving exceptionally high reading and writing speed. Therefore, virtual memory has become an indispensable part of the computer system. However, the address in a virtual memory is implicitly or explicitly programmed by the user into a word referred to as the effective address, hence the effective address must be translated and mapped into a physical address in an actual memory unit to make the virtual memory system compatible. In general, the amount of mappings in translating from effective address to physical address can be very large. To speed up the translating process, address translation is executed using a high-speed memory unit within the CPU. The high-speed memory unit is known as a translation lookaside buffer (TLB). TLB is a special cache memory for address translation whose input is the effective address and the output is the physical address. Generation of the physical address is largely determined by the result of comparing the linear address (LA) to a tag memory residing within the TLB. The tag memory is a content addressable memory (CAM).
FIG. 1 is a block diagram of a conventional computer address translation system. As shown in FIG. 1, first a 32-bit effect address EA is computed by passing through an effective address computational device 10. For example, the base address, offset address and the index address are summed together to obtain an effective address EA within the effective address computational device 10. Next, a selector address SA is input to a segment descriptor cache memory 11, and a 32-bit segment base address Base is output from it. Subsequently, the 32-bit segment base address and the effective address EA are added together to obtain a 32-bit linear address LA. The physical address PA can be determined only after the linear address LA has gone through the inquiries inside a translation lookaside buffer (TLB) 12. For example, the 0-11 bits of the linear address is a segment address, and the 12-bits of the linear address is page address. The page address is input to a tag memory 13 within the translation lookaside buffer (TLB) 12, and then compared with the linear address LA' there. If there is a hit that corresponds to the page base (PB) of the physical address stored in a data memory 14, the 20-bit physical page address is output and then combined with the original 12-bit segment address to form a physical address PA. The data memory 14 also resides within the translation lookaside buffer (TLB) 12 and can be a random access memory (RAM), for example. In other words, a linear address can be obtained only after an effective address is produced, and a physical address can be obtained only after the linear address is released, and hence much processing time is wasted. Because the address stored inside the linear address LA' of the tag memory 13 within the translation lookaside buffer (TLB) 12 is access serially, such processing will generate a critical path, and create a bottleneck in high speed electronic circuit designs.
In light of the foregoing, there is a need in the art for reducing the bottleneck in a conventional computer address translation system.

Computer address translation system and method for converting effective or logical address to physical address


A powertrain testing apparatus for testing performance testing of a powertrain provided with an input shaft and an output shaft that are disposed on different axes. The testing apparatus includes an input motor that replicates rotation of a vehicle-drive engine, an output motor that replicates the load applied to the output shaft in actual service, an input side support having an input connection shaft for connection to the input shaft, an output side support having an output connection shaft for connection to the output shaft, and a vibration generator that replicates vibration transmitted from a road surface in actual service. Vertical and horizontal adjustment units enable inter-shaft distances D1 and D2 between the input connection shaft and the output connection shaft to be changed. Constant velocity joints respectively connect the input motor and the input connection shaft and the output motor and the output connection shaft, thus enabling eccentric positioning thereof.

1. Field of the Invention
The present invention relates to a powertrain testing apparatus for performance testing of a powertrain having an input shaft and an output shaft that are disposed on different axes.
2. Description of the Related Art
Performance testing of powertrains, e.g., an automatic transmission (hereinafter referred to as "A/T"), employs an A/T testing apparatus 9 like that shown in FIG. 6. This A/T testing apparatus 9 includes an input motor 92 that simulates and replicates rotation of an engine, and an output motor 93 that simulates and replicates load that is applied to an output shaft 83 of an A/T 8. The A/T testing apparatus 9 includes a support stand 94 for holding the housing 81 of the A/T 8, an input motor 92 connected to the input shaft 82 of the A/T 8 and an output motor 92 connected to the output shaft 83 of the A/T 8. When the A/T 8 is mounted and connected, tests of the performance of its shifting operations and the like are performed by rotating the input motor 92 at a desired torque and rotational speed. The A/T testing method using the A/T testing apparatus 9 described above may be, for example, like that disclosed in Japanese Patent Laid-Open Publication No. 2001-165282 or No. 2000-258303.
However, as noted above, with the A/T testing apparatus 9 disclosed in the related art, performance testing is carried out with the housing 81 of the A/T 8 in a fixed state. Accordingly, in performance testing using the A/T testing apparatus 9, it is not possible to check what effect vibrations, and the like, transmitted from a road surface, have on the A/T 8. Such vibrations would be transmitted to the A/T 8 if it were mounted in actual travel of a vehicle along a road.
In addition, more particularly, in the case of A/Ts used in front-wheel drive vehicles, inter-shaft distances between an input shaft and a pair of output shafts, that are disposed on an axis that is different from that of the input shaft, vary depending on the type of A/T. Accordingly, there is a need for a testing apparatus that can be easily adjusted for different inter-shaft distances.


An exercise machine and a method for its use in training selected muscle groups by controlled use of brakes to resist crank movement adjustably at specific and adjustable controlled positions in the rotation of a crank. A control system may be incorporated to cause brake mechanisms to apply varying amounts of resistance to a pair of pedal-driven cranks to simulate the efforts required to ride an actual bicycle over a course including various upslopes and down-slopes.

The present invention relates to exercise machines, and in particular relates to an exercise machine incorporating one or more cranks and a method for use of such a machine in training selected muscle groups for athletic or therapeutic purposes.
Exercise machines are well known in which handles or pedals are used to drive cranks connected to flywheels or fans that provide resistance to rotation of the cranks. Various brakes or other mechanisms are used in other exercise machines to provide desired amounts of resistance to rotation of the cranks, varying the resistance in response to operator control, as taught by Owens U.S. Pat. No. 4,934,692, or in response to the length of time during which the exercise machine is operated, or in response to the number of rotations of the crank, as in Johannson U.S. Pat. No. 3,501,142. While such exercise machines are useful in improving the fitness of a healthy user, they are not particularly useful in providing training for rehabilitation of specific muscle groups in injured users or athletes trying to improve function of specific muscles or to improve a particular coordination pattern.
Even though every joint has two sets of muscles working about that joint (generally referred to as the agonist and the antagonist muscles; as they work in opposite directions) for most exercise machines most of the benefit has been to one set of muscles in the legs, the anti-gravity muscles (the hip and knee extensor muscles), and not to their antagonists, the other major set of leg muscles, the hip and knee flexors.
Bicycles and stationary exercise machines which utilize a pair of fixedly opposed cranks driving a flywheel require an initial effort to overcome the inertia of the flywheel or cycle and continued effort thereafter to overcome the continuing effects of friction usually provided by an adjustable brake. A pair of opposed cranks continuously connected to a flywheel, however, may result in flywheel inertia, or torque applied to one crank, being used to make up for weakness of injured muscles working on the opposite crank. As a result, muscles that need to be trained are not forced by the machine to work as much as might be desirable.
Recently there have been attempts to address this weakness of the bicycle and previously known exercise machines, and three recent patents are of note in this regard: Moser, et. al. U.S. Pat. No. 6,234,939, Day U.S. Pat. No. 5,860,329, and Taylor U.S. Pat. No. 5,496,238. The patents of Moser and Day both teach making the two pedals of the bicycle or exercise machine independent from each other to force the use of and thus provide for training of the hip and knee flexor muscles in the pedaling motion, although these two inventors went about this in different ways.
Moser's device, although claiming to be useful for bicycles, gives a description of only a stationary exercise device and achieves its end through dual right and left drive mechanisms. While it would be possible to put such a system on a bicycle it would require substantial modification of a typical bicycle.
Day's solution, while claiming to be useful for an exercise machine, gives a description only of a mechanism to attach to a standard bicycle to make the cranks independent, and it achieves its end by using independent cranks to move a single drive mechanism. Moser's device does describe allowing the user to choose different resistances for the right and left legs on a stationary exercise machine although he does not describe how one would do so on a bicycle. Neither Day nor Moser, et. al. provides significant resistance when pedaling backwards.
The device disclosed by Taylor is specifically intended to train the hip and knee flexor muscles in an independent pedaling apparatus that specifically adds resistance on the "up stroke" of the pedaling motion, but that deliberately provides less resistance on the "down stroke," just the opposite of most cycle type exercise machines.
Some exercise machines are intended to simulate the exercise requirements of an actual bicycle ride, as by increasing braking against crank rotation to simulate climbing a hill, and decreasing braking in order to simulate descending a hill. Such previously available stationary exercise machines, however, fail to realistically simulate many of the variable requirements for effort experienced while actually riding a bicycle, such as needing to overcome the mass inertia of the rider when accelerating or decelerating and the tendency of the bicycle to accelerate when going downhill, even when not pedaling, and improvements are desired.
While some variable resistances are present in currently available exercise machines, many do not simulate the inertia of the bike/rider system which would require the user to put in enough excess energy in order to accelerate. Such system inertia would require approximately 30 seconds for a rider to accelerate to top speed, as in real world riding, compared to the 3-5 seconds it takes on currently available exercise machines where this inertia is ignored or attempted to be simulated with a large flywheel.
Another simulation defect of current machines is the inability to simulate the speeding up that occurs when coasting down hill without attempting to accelerate.
It is therefore desired to provide an exercise machine in which resistance to cranking can be varied for the purpose of training specific muscle groups, and methods for use of such a machine to train selected muscle groups and to simulate more realistically the experience of riding an actual bicycle over varying terrain.

Exercise machine and method for use in training selected muscle groups


An optical sensor includes a graphene layer, a first electrode and a second electrode that are connected to the graphene layer, and an enhancement layer. The enhancement layer is disposed below the graphene layer to enhance the intensity of an optical electric field by surface plasmon resonance. The first electrode and the second electrode are arranged parallel to a first direction. The intensity of the optical electric field enhanced by the enhancement layer is greater on a first electrode side than on a second electrode side with respect to a centerline in the first direction of the graphene layer.

Layered crystals such as graphite have a structure in which atomic layers, serving as structural units, are regularly stacked in a direction normal to the atomic layers. Such graphite exhibits high light absorption, high electrical conductivity, and high flexibility, and thus, the application of graphite to transparent conductive films and flexible devices has been studied. Recently, it has been found that a single atomic layer (graphene), obtained by exfoliation from a bulk graphite crystal, exhibits novel properties, such as high carrier mobility, that are different from those of the bulk crystal. As a result, the development of devices using graphene has been promoted. In particular, by utilizing graphene's high carrier mobility and ability to absorb various wavelengths of light from visible to infrared (2.3% of light per monolayer), high-speed, high-sensitivity infrared sensors that operate at room temperature have been developed.
Although it is preferable to use monolayer graphene in order to utilize its excellent electrical properties (high carrier mobility) when manufacturing a graphene-based optical sensor, it may be difficult to obtain sufficient sensitivity because the amount of light that can be absorbed by the monolayer graphene is small. For this reason, a technique that increases the amount of light absorption of a sensor by subjecting graphene, serving as a light receiver, to antidot patterning (forming a large number of minute holes in graphene) has been suggested.
However, such antidot patterning of graphene decreases carrier mobility in proportion to the amount of the holes formed.

Optical sensor and method for manufacturing same