The present invention relates to a washing brush for automatic motor vehicle washing systems, comprising a cylindric body on the side outer surface thereof are provided a plurality of bands defining the cleaning elements of the brush. The main feature of the invention is that the band or strip elements extend on the side surface of the cylindric body along direction which are inclined with respect to the axial direction.

The present invention relates to a washing brush to be applied to washing brush assemblies in automatic systems for washing motor vehicles in general.
As is known, automatic systems for washing motor vehicles in general conventionally comprise washing brushes, which are made by coupling, in an axial direction, a plurality of brush elements which are substantially constituted by a cylindric body thereon are coupled band elements comprising cleaning elements formed of a felt or a like material, or a foamed plastics material.
With reference to the diagram shown in FIG. 1, the band elements 1, which are arranged with a substantially vertical arrangement, i.e. parallel to the axis of the cylindric body, provide a vertical discontinuous arrangement perpendicular to the brush movement direction.
In such an arrangement, the controlling motors are supplied with alternating pulses, the uneven amplitudes or values of which make difficult to hold the washing brush in a stable contact condition against the working surface therefor.
Accordingly, the contact gaps provide an objectable noise for a person inside the motor vehicle.
Moreover, it is necessary to frequently adjust the revolution number of the cleaning brush depending on the motor vehicle transiting speed, in order not to leave uncleaned regions along the motor vehicle itself.
Yet another drawback is that, during the rotation of the brush, a person can easily see the central body or tube supporting the cleaning elements, thereby the bush construction appears as a scarcely dense construction, which negatively affects the operating properties of the product.
Yet another drawback is that interspaces are inevitably formed between the several cleaning elements, with a consequent formation of contact lacking spaces on the surfaces to be washed.
Moreover, prior washing brushes generate packaging and transport problems, since it is not possible to provide the cleaning band elements in an ordered manner without bending them according to a small angle thereby frequently deforming the band materials which could render the band elements nearly unusable.
Thus, the packaging cost is inevitably very high.

Washing brush for automatic motor vehicle washing systems


An orth-mode transducer (OMT) assembly, including an OMT common port, an OMT feeder, and a polarization separated core. An input end of the OMT common port is connected to a single polarization antenna, one end of the OMT feeder is connected to an output end of the OMT common port, and an other end of the OMT feeder is connected to the polarization separated core, the OMT feeder has a tubular structure, and horizontal and vertical axes of an inner wall cross section of the OMT feeder are unequal, or a tuning rod is disposed in a tube of the OMT feeder and is perpendicular to an extension direction of the tube, and a vertical polarization port and a horizontal polarization port are disposed in the polarization separated core, the vertical polarization port transmits a vertical polarization wave, and the horizontal polarization port transmits a horizontal polarization wave.

As microwave communication develops, spectrum resources are increasingly scarce. Operators need to pay high spectrum leasing fees to use spectrum resources. Therefore, single polarization transmission is upgraded to dual polarization transmission to improve spectrum utilization, and to double a transmission capacity when spectrum fees are slightly increased or not increased. This becomes the first choice for the operators to upgrade and expand microwave services being used on a live network, as mobile communication services develop.
Cross polarization discrimination (XPD) is a unique and important indicator of the dual-polarized transmission. However, the indicator is not commissioned during production of a single polarization antenna. Consequently, after the single polarization antenna used on the live network is upgraded to a dual polarization antenna, an XPD indicator of the dual polarization antenna cannot meet a requirement.
To resolve this problem, a schematic diagram of possible components of a single polarization antenna is provided. As shown in FIG. 1, the single polarization antenna includes components such as a radome, a reflective surface, a central plate and a mounting bracket, a connection plate, an antenna feeder, and a torque transition section. In the prior art, the antenna feeder can be removed onsite to adjust the XPD. In this way, XPD performance of the dual polarization antenna can meet a specification requirement after the single polarization antenna is reconstructed to the dual polarization antenna.
However, in the prior art, there is a possibility that the antenna feeder of the single polarization antenna cannot be removed or replaced. To be specific, the XPD performance of the reconstructed dual polarization antenna cannot be adjusted, and consequently, the XPD performance of the reconstructed dual polarization antenna cannot meet the specification requirement, reducing feasibility of upgrading and reconstructing the single polarization antenna to the dual polarization antenna through onsite operations.


A fluorochemical ketone compound consists of two terminal, branched, independently fluoroalkylcarbonyl or perfluoroalkylcarbonyl groups and an intervening linear perfluoropolyether segment, each of the terminal groups optionally comprising at least one catenated heteroatom, and the perfluoropolyether segment consisting essentially of at least one tetrafluoroethyleneoxy moiety and, optionally, at least one difluoromethyleneoxy moiety, the moieties being randomly or non-randomly distributed within the perfluoropolyether segment.

Fluorochemical ketone compounds comprise a class of commercially valuable chemical compounds that exhibit a wide range of properties. The compounds as a class are neutral and, in some cases, are surprisingly inert, thermally stable, and hydrolytically stable. Such properties have made them useful as heat transfer agents, as lubricants, and even as fire extinguishing agents.

Fluorochemical ketone compounds and processes for their use


The present invention provides a multi-function coffee maker, comprising at least two brewing accessories including an espresso coffee brewing accessory and a drip coffee brewing accessory, which are interchangeable and each can be loaded within said brewing room of said cover assembly to form an individual brewing chamber. Said multi-function coffee maker further comprises a control circuit including a detection circuit for the brewing accessory. By a water distributor assembly and said control circuit, water flow of suitable pressure is provided into said brewing chamber and the brewing accessory in use is detected automatically so as to initiate a corresponding work mode according to desire.

Brewing drip coffee requires 0-2.5 bar water, while brewing espresso coffee requires 8-10 bar water. The brewing requirement for tea is similar to that for drip coffee. The existing coffee machine such as a coffee maker or a coffee center can be used to make either drip coffee or espresso coffee, but can not be used to make both of drip coffee and espresso coffee in the same machine.


Atomic layers can be formed by introducing a tantalum amine derivative reactant onto a substrate, wherein the tantalum amine derivative has a formula: Ta(NR1)(NR2R3)3, wherein R1, R2 and R3 are each independently H or a C1–C6 alkyl functional group, chemisorbing a portion of the reactant on the substrate, removing non-chemisorbed reactant from the substrate and introducing a reacting gas onto the substrate to form a solid material on the substrate. Thin films comprising tantalum nitride (TaN) are also provided.

It is desirable for metal layers used for metal lines on semiconductor devices to be compatible in various structured forms. To increase the density of devices formed on a semiconductor substrate, a metal layer can be formed as a multi-layered structure. The metal layer can include, for example, aluminum or tungsten. However, the specific resistance of aluminum is about 2.8×10E-8Ωm and the specific resistance of tungsten is about 5.5×10E-8Ωm. Thus, aluminum and tungsten are typically unsuitable for a multi-layer structure. Consequently, copper, which has relatively low specific resistance and good electromigration characteristics, is often used as a metal layer of a multi-layered structure.
Copper can exhibit a very high mobility when compared to silicon and silicon oxide. However, copper can easily be oxidized when it reacts with silicon and silicon oxide. Accordingly, it may be desirable to suppress the oxidization of copper by using a barrier metal layer.
A titanium nitride layer has been used as a barrier metal layer. However, the titanium nitride layer may not be suitable as a barrier metal layer for copper where the titanium nitride layer is desired to have a thickness above 30 nm to restrain the mobility of copper. Since the titanium nitride layer has a resistance proportional to the thickness thereof and a high reactivity, the resistance may be highly increased when the titanium nitride layer has a thickness above 30 nm.
For at least this reason, a tantalum nitride layer is suggested for the barrier metal layer where a tantalum nitride layer may restrain the mobility of copper even when the tantalum nitride layer is thin and has low resistance. Additionally, the tantalum nitride layer may exhibit a suitable step coverage characteristic and a suitable gap-filling property so that the tantalum nitride layer can also be used as a metal plug, a metal wiring, a metal gate, a capacitor electrode and/or the like, in addition to the barrier metal layer. Examples of tantalum nitride layers that can be used as barrier metal layers are disclosed in U.S. Pat. No. 6,204,204 (issued to Paranjpe et. al.), U.S. Pat. No. 6,153,519 (issued to Jain et. al.), and U.S. Pat. No. 5,668,054 (issued to Sun et. al.).
According to the disclosure in U.S. Pat. No. 5,668,054, the tantalum nitride layer is deposited through a chemical vapor deposition process by using terbutylimido-tris-diethylamido-tantalum ((NEt2)3Ta═Nbut, hereinafter simply referred to as "TBTDET") as a reactant. The process is carried out at a temperature above about 600° C. If the process is carried out at a temperature of about 500° C., the specific resistance of the tantalum nitride layer may exceed 10,000 Ωcm. In addition, since the above process is carried out at a relatively high temperature, the semiconductor device can be thermally damaged. Further, it can be difficult to achieve a tantalum nitride layer having the desired step coverage when a chemical vapor deposition process is used.
Recently, an atomic layer deposition (ALD) process has been suggested as a substitute for the chemical vapor deposition (CVD) process. The atomic layer deposition process can be carried out at a relatively low temperature as compared with a conventional thin film forming process and can achieve superior step coverage. Examples of the atomic layer deposition processes for depositing tantalum nitride are disclosed in U.S. Pat. No. 6,203,613 (issued to Gates) and in an article by Kang et al., entitled "Plasma-Enhanced Atomic Layer Deposition of Tantalum Nitrides Using Hydrogen Radicals as a Reducing Agent," Electrochemical and Solid-State Letters, 4(4) C17–19 (2001). As described in the Kang et al. article, a tantalum nitride layer having a specific resistance of about 400 cm, can be formed by an atomic layer deposition process using TBTDET. The deposition is carried out at a temperature of about 260° C. Accordingly, a thin film having a low specific resistance can be formed at a relatively low temperature. In addition, a hydrogen radical obtained by a plasma-enhanced process is used as a reducing agent. Therefore, a power source is applied into a chamber when the deposition is carried out. For this reason, the process described by Kang et al. presents process parameters that may be influenced by the power source applied to the chamber. Thus, while the Kang et al. process can be used to form a thin film having a low specific resistance at a relatively low temperature, the process parameters, which include control of the power source, are added. Moreover, because the Kang et al. process applies the power source directly to a predetermined portion of the chamber to which a semiconductor substrate is placed, the semiconductor substrate can be damaged by the power source.
An ALD process using a tantalum chloride (TaCl5) source in tantalum nitride (TaN) thin film deposition is disclosed in an article by Mikko Ritala et al. entitled "Controlled Growth of TaN, Ta3N5 and TaOxNy Thin Films by Atomic Layer Deposition," Chem. Mater. 1999, 11, pp1712–1218. Additionally, a CVD process using a TBTDET source in TaN thin film deposition is disclosed in an article by Tsai MH et al. entitled "Metal organic chemical vapor deposition of Tantalum Nitride by Terbutyl-imidotris (Diethylamido) Tantalum for Advanced Metallization," Applied Physics Letters, V. 67 N. 8, 19950821.
However, the conventional TaN deposition process can exhibit several potential problems due to the potential problems associated with the sources. For example, the TaCl5 source is generally a halogen source, and the halogen source is a solid state and has a high melting point. Therefore, when the TaCl5 source is employed for the deposition process, particles can be generated and impurities, including chloride, may remain on the deposited TaN thin film which can induce additional problems. When a TBTDET source is used for the depositing process, the deposition rate can be too slow because of a low vapor pressure.
Japanese Laid-Open Patent No. 2002-193981 discloses a method of preparing tertiary amyl imido-tris-dimethylamido tantalum (Ta(NC(CH3)2C2H5)(N(CH3)2)3, (hereinafter simply referred to as "TAIMATA") and a metal organic CVD (MOCVD) process using a solution including TAIMATA as a precursor. According to the method disclosed in Japanese Laid-Open Patent No. 2002-193981, 1 mole of TaCl5, 4 moles of LiNMe2 and 1 mole of LiNHtAm are reacted in an organic solvent at room temperature. The reaction product can be filtered and the solvent used can be removed to prepare TAIMATA. This material can be dissolved into an organic solvent, such as hexane, and thus, the solution obtained can be deposited onto a substrate in a CVD room to form a TaN thin film.
According to the above-described method, however, since the TaN thin film is formed by using only TAIMATA, the formation of the TaN thin film may be uncertain even though the preparation of TAIMATA may be advantageously carried out. When the deposition process is carried out onto the substrate by the CVD process using only TAIMATA, the vapor pressure may not be high enough and the process can be ineffective.

Methods for forming atomic layers and thin films including tantalum nitride and devices including the same


Methods and apparatus for ascertaining whether there is at least a threshold concentration of carbon dioxide in gases being monitored. Reversible hydration of the carbon dioxide to generate excess hydrogen ions and trigger a color change in a pH sensitive indicator is employed in representative embodiments of the invention to provide an indication that the threshold concentration of carbon dioxide is present in the gases. The methods and apparatus may be used to distinguish between tracheal and esophageal intubation of human and other mammalian patients.

Just a few decades ago, an unexpected death or serious mishap during surgery was viewed as a tragic but unavoidable event by patients and their families, and by the public at large. Lawsuits were rare, and settlements were modest.
Today, the average patient in reasonable health who enters a hospital fully expects clinicians to provide care with a near-zero risk of complication or death. If a procedure leads to loss of life or major impairment, the damage is no longer regarded as acceptable, especially when it is thought to be the result of avoidable technical or human failure. These incidents now lead to major malpractice suits against hospitals and physicians.
One of the most important aspects of critical care is the clinician's management of the patient's airway. Typically, this involves placement of an endotracheal (or airway) tube in the trachea of the patient. Oral intubation of the human trachea has become a routine procedure used to maintain a clear airway in most surgical, emergency, and intensive care situations. Intubations are performed in the hospital and in the field by individuals of differing backgrounds and levels of training. Failure to achieve tracheal intubation, resulting in the airway tube being placed in the esophagus and diverting air flow from the lungs, can cause patient complications (morbidity) or death (mortality) and is a continuing source of clinicians' anxiety.
The problem is acute because there are an estimated 18 million surgeries performed under general anesthesia each year in the United States alone. In addition, one million acute heart attack patients and three million trauma patients are admitted to hospitals each year. Most of these patients require mechanical ventilation and thus require tracheal placement of an airway tube.
In addition, there are other situations, typically in the field, where intubations are performed by paramedics or other individuals with less background and training than is typically found among hospital personnel. Misplacement of airway tubes (unrecognized esophageal intubation) by these individuals also contributes significantly to morbidity and mortality statistics.
A review of various anesthesia-related morbidity and mortality statistics indicates that unrecognized esophageal intubation is a problem, even among those members of the medical population specifically trained in the tracheal intubation technique. An analysis of anesthetic accidents reported to the Medical Defense Union of the United Kingdom from 1970-1978 revealed that nearly half of the cases resulting in death or cerebral damage were due to faulty clinical technique. The procedure most often identified as the source of mishap was tracheal intubation with inadvertent esophageal--rather than tracheal--tube placement.
Another reviewer of anesthesia-related medical liability claims in the United Kingdom from 1977 to 1982 listed esophageal intubation as a "main cause" of accidents leading to death or neurologic damage with the largest monetary claims resulting from such mishaps.
An investigation of anesthesia-related deaths in Australia revealed that 69% of these deaths were related to airway mismanagement with esophageal intubation once again identified as a major contributing factor.
In one institution in the United States, unrecognized esophageal intubation was identified as a significant problem in a study of cardiac arrests that had been attributed solely to anesthesia. There were twenty-seven cardiac arrests among 163,240 anesthetic cases over a fifteen year period. Of these twenty-seven cardiac arrests, four were attributed to esophageal intubation.
In the state of Kansas, five malpractice cases involving improper intubation were settled for one million dollars each in 1984-85. Four new cases alleging improper intubation were brought before Kansas courts in the first six months of 1986; at issue were two deaths and two brain-damage cases, all involving patients who were having elective surgeries.
In reviewing malpractice claims brought against anesthesiologists in Washington State from 1971-1982, researchers found that esophageal intubation figured prominently among complications resulting in cardiac arrest, brain damage, and death. Of 192 claims, seven were brought for unrecognized esophageal intubation.
The foregoing makes it clear that a reliable technique for confirming that tracheal intubation has been achieved would be of signal importance to the medical profession. Techniques providing signs which may, in some circumstances, indicate that a successful tracheal intubation has been accomplished include the following:
Direct Visualization
Direct visualization of the vocal cords and observation as the airway tube passes into the trachea is considered by many the "gold standard" of correct tube placement, and this remains one of the more reliable signs. Unfortunately, direct visualization is impossible to achieve in certain patients, even in the most experienced hands, due to a multitude of factors. Clinicians and medics are thus often called upon to make "blind" intubations in which the position or condition of the patient is such that the progress of the tube cannot be followed visually. For example, it may be dangerous to immediately move an accident victim, or there may be insufficient lighting where a patient has collapsed at home. "Blind" intubations are performed in the hospitals as well, especially in patients who are overweight or have anatomical abnormalities. The problem is more common is inexperienced hands and may be associated with haste, poor lighting, or an individual patient's anatomical abnormality. Often, the clinician's view may be obstructed by the advancing tube, by acute angulation of the airway in the back of the patient's throat, or by a loss of depth perception with monocular vision.
Even if visualization of the vocal cords and tracheal tube placement has been achieved, the tube may be inadvertently withdrawn from the trachea before or during securing of the tube or when moving the patient to the lateral or prone position. Additionally, radiographic studies have shown that flexion or extension of the neck can change tube positions as much as five centimeters, resulting in inadvertent extubation which may well not be observed by the clinician.
Chest Movement
Another commonly relied upon method of confirming tracheal intubation is observation of symmetric bilateral movements of the chest wall during ventilation. Some patients, however, have physical conditions in which ventilation is more than usually dependent on diaphragmatic movement as opposed to chest wall movement. Patients with large breasts, obesity, a barrel chest from lung disease, and other conditions tend to develop rigid chest walls. Chest movement can be difficult to evaluate in these circumstances, making assessment of proper tube position by chest expansion unworkable.
More importantly, movement of the chest wall simulating ventilation of the lungs can be seen even with the ventilating tube positioned in the esophagus. Distension of the stomach with air can cause outward movement, mimicking the downward movement of the diaphragm and outward movement of the lower chest. Escape of gas from the stomach through the esophagus with release of bag compression would allow the diaphragm to fall and would move the lower chest inward, creating the false impression that there is exhalation from the lungs. Confirmation of this phenomenon exists in numerous reports and studies. At least one study demonstrated chest movements "identical to those seen when the lungs were inflated" where, in fact, stomach ventilation had been established through an airway tube intentionally inserted into the esophagus.
Breath Sounds
The presence of bilateral breath sounds from a stethoscope placed over each of the lungs would seem to be a strong reassurance of proper tube position based on experience and common sense. However, the literature documents numerous cases involving experienced clinicians where apparently normal breath sounds were present with esophageal ventilation. Air passing through the esophagus has been noted to resemble coarse or tubular breath sounds, and it has been suggested that the combination of esophageal wall oscillation with gas movement and acoustic filtering can produce wheezes similar to the sounds arising from lungs ventilated mechanically or by hand.
Presence of Exhaled Tidal Volume
This method of confirming tracheal intubation can be uncertain because it is possible to have measurable tidal volumes of air moving in the airway tube during spontaneous respiratory efforts with the esophagus intubated and the trachea obstructed. Researchers have documented tidal volumes of up to 180 milliliters and peak flows of greater than fifty liters per minute under these circumstances.
Reservoir Bag Compliance
Another practice commonly employed is noting the characteristic feel of the reservoir bag associated with normal lung compliance during inspiration and the presence of expiratory refilling of the bag during hand ventilation. However, compliance varies widely from one person to another and within the same individual at different times. Repeated filling and emptying of the stomach with esophageal ventilation, leading to inflation and deflation of the breathing bag, can also be mistaken for pulmonary ventilation.
Airway Tube Cuff Maneuvers
With the cuff deflated, the higher pitched sound of air escaping around a tracheal tube, compared to the more guttural of leakage around an esophageal tube, has been used as a distinguishing feature. However, with the cuff of an esophageal tube located near the level of the cricoid cartilage, the distinction in air sounds may not exist. Also, palpation of the airway tube cuff in the neck to verify position has been reported to fail, perhaps because the easily distensible esophagus simply balloons outward with an inflated cuff inside it.
Air Escape
A less commonly performed procedure involves pressing sharply on the chest while listening over the tub=opening to detect "a characteristic feel and sound of expelled air." This procedure is unreliable because of the inability to distinguish between air expelled from the tracheal tube and: (1) air passing through or around an esophageal tube, or (2) esophageal air present from mask ventilation prior to intubation, or (3) air expelled from the nose.
Tube Condensation
Condensation of water vapor in the tube, although less likely with esophageal intubation, can occur and hence is not a reliable sign. Conversely, the absence of condensation normally seen with a tube positioned in the trachea would be reason to look for further proof of correct tube position.
Pulse Oximetry
Although useful in many situations, pulse oximetry may be an untimely indicator of esophageal intubation for several reasons. Researchers have noted normal functioning of a ventilator when connected to an esophageal tube. With the vocal cords relaxed, patients were studied after deliberate intubation of both the esophagus and trachea. Ventilation into the esophagus also caused some ventilation of the lungs, as evidenced by carbon dioxide recordings obtained from the open tracheal tube. This ventilation could significantly slow the onset of oxygen desaturation of the blood after esophageal intubation and could delay recognition of esophageal tube placement until surgery is in progress. Also, the practice of preoxygenation of patients prior to intubation can slow the recognition of an improper tube position using pulse oximetry because the patients' blood is highly saturated with oxygen at the start of the surgical procedure.
End-Tidal Carbon Dioxide Measurement
End-tidal carbon dioxide measurement offers perhaps the most reliable and simplest determination of proper tube placement. It involves the measurement of carbon dioxide concentration during the respiratory cycle. The reliability of carbon dioxide monitoring is based on the assumption that carbon dioxide can be reliably detected in patients with an intact pulmonary circulation and an intubated trachea whereas no carbon dioxide is present in gases exiting from an esophageal tube. Carbon dioxide can be detected initially with esophageal intubation when carbon dioxide has been forced into the stomach during prior mask ventilation. However, the end-tidal carbon dioxide is low in such cases; the wave pattern is irregular; and the carbon dioxide levels rapidly diminish with repeated ventilation, making it easy to distinguish between carbon dioxide from the trachea and that from the esophagus.
The disadvantage of this test is that it takes a relatively expensive monitoring device. Also, this device is too cumbersome for routine use in all settings where it would be needed; and it must be connected to an electrical power source during the intubation procedure. This is disadvantageous because power may not be available where, or when, intubation is needed.
In short, the position of the airway tube employed to achieve tracheal intubation of a patient and thereby manage his or her airway must be checked on each insertion; and there are a large number of tests available to confirm tracheal placement of the tube. However, considerable evidence challenges the relative merits of these heretofore available tests. Also, there has been, up to now, no single device which can or would be used in all situations to detect misplacement of airway tubes in the esophagus. Furthermore, clinical studies have shown that, even with the detection of seemingly proper signs by experienced clinicians, an airway tube may have been placed in the esophagus. Also, a number of the just-discussed techniques for confirming tracheal intubation employ monitoring devices; and those devices each lack one or more of the following attributes, all of which are either required for the monitoring device to be successful or important in obtaining this goal:
Ease of use
The device must be easy to connect to the airway tube, require no more than minimal interpretation of the indication, and require no electrical power.
Sensitive
The device must display an obvious indication of carbon dioxide expired from the lung within thirty seconds.
Reliable
The indicator must not give false-positive readings but may show transitory readings from a limited volume of carbon dioxide or other materials from the stomach.
Inexpensive
The device should desirably sell for less than $1.00 U.S. in large quantities.
Disposable
To avoid cross-contamination, the device should be designed for single patient use.
Clean
The device should be designed to be cleaned during assembly in accordance with ANSI Code 279.2 for tracheal tube connectors and adapters.
Save
The device must not allow components to which it is attached to become disconnected or otherwise impede the normal ventilation of the patient.
Rugged
The device must withstand severe stresses without disconnecting from its mating tube.
Storable
The device must have a shelf life of twenty-four months prior to use without loss of effectiveness.
From the foregoing, it can be seen that undiagnosed esophageal intubation figures prominently in anesthesia-related morbidity or mortality and related malpractice suits. The commonly utilized methods of assessing tube position are all unsatisfactory under the circumstances encountered in tracheal tube placement. Expired carbon dioxide measurement is currently the most reliable means under all circumstances of determining proper tube position, but this method suffers from the requirement that an expensive monitoring device be attached to the airway tube before correct placement can be verified. Thus, the usefulness of this procedure in emergency conditions is limited; and it is relegated to formal hospital settings. There is no inexpensive product currently available which provides a simple test for carbon dioxide expired by the patient through the airway tube to verify tracheal tube placement.

c/o Meridian Medical Corporation, 4811 Forest Ave. SE.


A touch operation management unit detects, at prescribed time intervals, whether or not a touch operation has been performed on a touch operation input unit, and manages the touch operation. A state detection unit detects various kinds of states of a swipe operation performed by the player. A movement instruction acceptance unit accepts a movement instruction among various kinds of touch operations managed by the touch operation management unit. A skill instruction acceptance unit accepts a skill-related instruction among various kinds of touch operations detected by the touch operation management unit. In addition, the skill instruction acceptance unit accepts the designation of a prescribed direction in accordance with the movement direction of a touched position when the swipe transitions from the second state to the third state. A display image generation unit generates a display image for displaying various kinds of controllers. A display control unit executes control for displaying display images for various kinds of games on the display unit.

Recently, in games executed on mobile terminals such as smartphones, images displayed on the mobile terminals are one of the important factors affecting the popularity of the games.
Thus, various attempts have been made at developing technologies for improving the ease of operation of GUIs (Graphical User Interfaces) presented to players.
As a technology for that purpose, there exists, for example, a technology (e.g., see patent document 1) for providing a user interface that behaves as if a player operates a smartphone having elasticity by displaying an object that behaves like an elastic body when the touchscreen is operated.
With the above-described technology, it is possible to issue a plurality of action instructions (e.g., movement of a game character, skill activation etc.) without releasing a finger from the touchscreen during a touch operation.
Patent Document 1: Japanese Unexamined Patent Application, Publication No. 2016-48571

Information processing program, information processing method, and information processing device


A combination lock container (10), suitable for accepting a wine bottle, consisting of an upper housing (12), a lower housing (50), a plurality of tumblers (18A-18E), and externally applied indicia (24). Cylindrical walls, or skirt portions, of each housing nest and engage into one another. Each housing has a key-like feature, consisting of a linear array of tabs with gap spacing between, that projects radially from the outer cylindrical wall surface. The upper housing has a longitudinal slot opening in the cylindrical wall, adjacent to its set of tabs, which can accept the tabs of the lower housing. When the housings are fully assembled, matching tab and gap features on each housing are adjacent and in lateral alignment with respect to each other. A plurality of tumblers, each with an internal annularly formed locking rib, are placed concentrically around the housings. The locking rib wall has a section removed that creates a keyway opening, the width of which is slightly greater than that of the aligned tabs. Located on the tumbler's outer circumference, and directly above the keyway, is a score mark or keyway indicator. Applying a personalized code word to the locking mechanism requires no disassembly. By using the keyway indicator features, indicia may be applied externally such that designated letters of a code word can be applied and aligned directly over the tumbler keyway. Once applied, the indicia conceal the location of the score marks. Locking ribs rotate through and intersect the laterally aligned gaps between the housing tabs, thus axially locking the housings together. When the proper code word is positioned underneath a marker, all keyways fall into alignment with the housing tabs. In this unlocked condition, the housings may be separated and the bottle of wine removed. A slot opening in the upper housing additionally allows the container to be used as a coin bank.

1. Field of Invention
This invention relates to a cylindrical combination lock container.
2. Prior Art
Bottles of wine and spirits are often exchanged as gift items between people. Typically a bottle would be gift wrapped or placed in a decorative tote bag or box and then given as a present. Often times higher quality red wines (or scotch whiskeys) require aging to improve their characteristics. The bottle received is usually just set aside or "cellared" for several years. Although many people enjoy receiving wine, as a gift on its own, it is not particularly novel, fun, or unique. Presenting a special bottle of wine as a gift inside of a combination locking game puzzle (requiring a code word for opening) provides a fun and unique experience for both the gift giver and receiver.
Although the focus presented in this patent application centers around a lockable puzzle container for a wine bottle, there are other commercial applications for a locking container of this sort. For instance, in a different form factor the device could be suitable as a lockable storage container for securing medical supplies, pill bottles, etc. in the household. The container might allow medications to be readily accessible on a kitchen table but out of the hands of children. Alternatively, children might enjoy using a container designed as a piggy bank that can be set up with their own personally chosen code word. The container might also have another novel use as decorative locking container for holding cigars on an office desk top. The form factor of the container can have many variations that are different from and not limited to the shape of a bottle.
There are a number of inventions and products on the market related to securing the contents of bottles. The "Bottle Lock Liquor Locker", patent status unknown, (manufactured by Franklin Machine Products) is a bottle stopper that has three combination dials that when properly aligned will allow removal of the stopper. U.S. Pat. No. 1,358,352 to Wheelock (1920) shows another combination locking closure for an open bottle. Other locking devices that both attach to the bottles and act as theft deterrents are described in US Patent Application US 2006/0043050 A1 to Beldon, Jr. (2006) and U.S. Pat. No. 6,604,643 to Michael et al. (2003). Many devices and inventions have been designed specifically for securing medicine bottles with a programmable combination locking cap or closure. Such combination locking caps can be seen in U.S. Pat. Nos. 3,843,007 to Meyer (1974), 5,277,325 to Yan (1994) and 5,284,262 to O'Nan (1994). Again these devices relate more specifically to a locking cap that fits directly onto the open end of ajar or pill bottle.
There are many patented combination locking devices that allow users to set up or allow permutation of the combinations code. Most involve altering or resetting the tumblers indicia (such as numbers, letters, or symbols) relative to the tumbler internal keyway. Such devices are generally found and more closely related to the field of locks and in particular bicycle cable locks and padlocks. Most of the locking devices in which the combination may be set by an individual tend to be complex in nature and have many mechanical parts. U.S. Pat. No. 6,021,653 to Pimpo (2000) shows a tumbler ring that can be disassembled and have individual indicia plates applied into external slots. U.S. Pat. Nos. 4,615,191, 4,445,348, and 4,354,365 show several variations of two piece tumbler assemblies that allow inner and outer tumblers to have variable radial positions for changing the code. U.S. Pat. No. 6,059,132 to Benjamin describes a combination locking cap that uses flat circular labels to apply indicia. U.S. Pat. No. 6,621,405 B1 describes as word system and computer algorithm for determining a limited set of useable code words for a combination lock. All of the above locking devices require a significant amount of time, assembly effort, and mechanical aptitude on the part of the end user to take apart the device and reset the combination.
More recently, a cylindrical combination locking device called a Cryptex had been introduced into the market place. The Cryptex has been made popular by author Dan Brown's novel "The Da Vinci Code" and its movie version. The book describes the Cryptex as being a cylindrical device used to secure and conceal small rolled up messages or notes on paper held within. It is also described as being similar to a combination bicycle cable lock. There does not appear to be any evidence that the Cryptex was actually invented by Leonardo Da Vinci, but rather that it was fictitiously conceived by the author. There are several commercial replica versions of the Cryptex device available that consist of a cylindrical device with letter coded tumblers. The Cryptex reproductions have held true to this "end use", described in the author's book, and have been designed to do little more than hold rolled up paper notes and possibly small articles such as pieces of jewelry. Many of these ornate and "antique-looking" collector's items are quite expensive and are fabricated from metals, stone, wood, or combinations thereof. Some Cryptex designs require the purchasers to contact the manufacturer and provide a custom code word beforehand to allow the engraving of the chosen letters on to the tumblers during manufacturing. Others Cryptex designs provide features that allow resetting of the combination by disassembly and reorientation of two piece tumblers whereby the internal keyways can be radially adjusted relative to the external portion of the tumbler's indicia. This method of varying the indicia for word permutations with two piece tumblers has been well described in the patents above relating to bicycle cable locks and padlocks. The Encrypta Cryptex puzzle, U.S. Patent Application US 2005/0288082 A1 to De la Huerga, uses wooden blocks, spacers, threaded posts, end pieces, to create a Cryptex. The De La Huerga uses an adjustable two piece tumbler design similar in nature to prior art cable locks. The lock body described (similar to an air cylinder assembly), consists of top and bottom sections, or end caps, with and post connectors or stand-offs extending between the two sections. All of the lock body elements of this design are necessary to retain the tumblers. A more desirable configuration would eliminate these components.
Although the above mentioned patents are discussed as prior art (locks designed for re-combination, combination locking closures for threaded medicine bottles, and Cryptex devices for concealing paper notes), none have strong correlation to the device in this application which pertains to a container that fully locks, encloses, and conceals a wine bottle.


In a winding machine, the space defined by the support cylinders and the winding rolls is sealed and an overpressure is created in this space to relieve the force with which the winding rolls press against the support cylinders. For the purpose, in the area of the two lateral ends of the support cylinders sealing elements are arranged, which for adjustment to various web widths, are axially displaceable and at the same time can be moved away to an area outside the motion range of guide heads and their mounting. In the sealing position of the sealing elements, a fictional-look connection with the support cylinders is avoided.

Such winding machines with support cylinders serve for the axleless winding of longitudinally sectioned webs of material, particularly paper or cardboard onto cores, whereby the winding rolls are positioned in alignment on the support cylinders during winding. Different from the so-called axle winding, wherein a set of winding rolls is held during winding by means of an axle passing through all cores, in the axleless winding two guide heads are introduced from outside into the cores of the outer winding rolls.
With the winding machines with support cylinders known from DE-A 36 18 955, winding rolls with the required winding quality can be produced only up to a certain diameter. The reason for that is that the winding hardness of the roll is influenced by the line load (=contact weight per width of a winding roll) at the two contact lines of the winding roll on the support cylinders.
The winding hardness should be as even as possible for the entire set of winding rolls and over the diameter of each individual winding roll and to have a predetermined value, which is exceeded in the case of the known winding machines with support cylinders from a certain diameter up, due to the increasing contact weight, thereby limiting the maximum diameter of the winding rolls.
In order to relieve the dead load in winding machines with support cylinders with axle winding it is known from German Patent 11 11 496 to create overpressure in the space defined between the support cylinders and the winding roll. For the lateral sealing of this hollow space serve cover plates fitted to the shape of the support cylinders, which plates can be displaced in order to be placed against the frontal side of the winding rolls. The sealing of the bottom portion is done by a cylinder or group of cylinders arranged tangentially with respect to the two support cylinders.
The sealing elements described in German Patent 11 11 496 are not suited for use in winding machine with support cylinders based on axleless winding, since their fastening elements are located within the motion range of the guide heads. Furthermore, a frictional engagement is created between the two support cylinders due to the sealing cylinder pressing thereagainst, which precludes the setting of variable rolling momentums for the purpose of influencing the quality of the winding process.

Winding machine with support cylinders and air pressure relieved wind up rolls


A passively athermal photonic system including a photonic circuit having a substrate and an optical cavity defined on the substrate, and passive temperature-responsive provisions for inducing strain in the optical cavity of the photonic circuit to compensate for a thermo-optic effect resulting from a temperature change in the optical cavity of the photonic circuit. Also disclosed is a method of passively compensating for a temperature dependent thermo-optic effect resulting on an optical cavity of a photonic circuit including the step of passively inducing strain in the optical cavity as a function of a temperature change of the optical cavity thereby producing an elasto-optic effect in the optical cavity to compensate for the thermo-optic effect resulting on an optical cavity due to the temperature change.

The field of integrated photonics seeks to miniaturize optical components, such as modulators, resonators, filters and waveguides, and integrate such optical components onto a single chip in the form of an optical circuit. Many researchers in the field of integrated photonics hope to revolutionize optics in much the same way that miniaturization and integration of the circuits has revolutionized electronics. In the context of high performance computing, for example, optical interconnects would be advantageous in order to improve the bandwidth of communication between computational nodes in supercomputers, and potentially decrease the power consumption of such large scale computers.
In analogous manner to the microelectronics industry, the fabrication of integrated photonic circuits through lithographic, and other highly manufacturable means, seeks to: (1) reduce cost and size, (2) increase complexity, and (3) improve the overall performance of optical systems. Numerous researchers have placed a great deal of effort toward the development of high refractive index contrast (HIC) photonic circuits for their ability to further reduce component sizes and improve performance even further.
While progress has been made in the field of HIC photonic circuits toward the development of practical and low-loss waveguides, high performance filters, resonators and modulators, numerous fundamental challenges remain before widespread implementation of such photonic circuits can occur. For example, HIC photonic circuits, such as those made from silicon, are extremely sensitive to their environment.
Since the refractive index of silicon changes very rapidly with temperature due to the thermo-optic effect, it can be challenging to stabilize the resonance frequency of an optical cavity of a photonic circuit against variations in temperature. If optical cavities were used on microprocessors in order to filter and route optical data on chips, for example, large variations in the local processor temperatures during operation may detune those cavities from their intended resonant frequencies. All of these devices are notoriously temperature sensitive, as changes in both device dimension and refractive index severely impact the performance of the system. Active thermal compensation in the form of a thermal sensor, a heater and a feedback loop, has been pursued as a solution to this problem, however, this is a costly, complex and inefficient solution requiring additional power and components.

Athermalization of resonant optical devices via thermo-mechanical feedback


A clamp assembly is disclosed. The clamp assembly is made with a first clamp part, a second clamp part, a hinge assembly and a fastener. The first clamp part has at least one connection capable of receiving and securing the at least one downhole tool. The first clamp part also has a first inner clamp surface. The second clamp part has a second inner clamp surface extending between the third side and the fourth side. The hinge assembly connects a first side of the first clamp part to a third side of the second clamp part and is configured to permit the first clamp part and the second clamp part to be moved to a closed position and an open position to receive the tubing.

One of the more difficult problems associated with any borehole is to communicate measured data between one or more locations down a borehole and the surface, or between downhole locations themselves. For example, in the oil and gas industry it is desirable to communicate data generated downhole to the surface during operations such as drilling, perforating, fracturing, and drill stem or well testing; and during production operations such as reservoir evaluation testing, pressure and temperature monitoring. Communication is also desired to transmit intelligence from the surface to downhole tools or instruments to effect, control or modify operations or parameters.
Accurate and reliable downhole communication is particularly important when complex data comprising a set of measurements or instructions is to be communicated, i.e., when more than a single measurement or a simple trigger signal has to be communicated. For the transmission of complex data it is often desirable to communicate encoded analog or digital signals. These transmissions can be performed through direct wire connection between the surface and the downhole location(s) or through wireless communications techniques such as electromagnetic waves, pressure or fluid pulses, and acoustic communication.
A tubing is composed of many pipes linked together by connections. There are few nominal sizes for the outside diameter (for example 2⅞ inches, 3.5 inches or 4.5 inches). The outside diameter has a rather large tolerance which is defined by norms edited by the American Petroleum Institute. The connection between pipes, which may be called a "coupling", comprises a thread, and a very large variety of connections exist on the present market. Most of the time, the coupling outside diameters are larger than a diameter of the pipe.
When a device, such as a sensor (temperature, pressure) or a transmitter (for example acoustic transmitter) must be secured on the pipe, such device can either be installed in a carrier (also called a mandrel) placed between two pieces of pipe (see for example, U.S. Pat. No. 7,339,494) or it can be clamped directly along the outside diameter of the pipe, using one or several mechanical collars called "clamps". Usually, the prior art clamps are made of at least two parts which are secured together so that they can be directly installed on the tubing, without engaging the connections.
However, a tool secured outside of the tubing can be exposed to large axial loads and shock when the pipe is moving inside an open hole (whose rugged surface can generate a high friction force when dragging), or when the tool engages a liner. The liner, for example, may be a casing of smaller size located in a lower part of a well. Therefore, the liner forms an abrupt change in diameter with the upper casing. When the tool is an acoustic modem, such acoustic modem has a transceiver assembly which vibrates to introduce axial stress waves into the tubing. In this instance, the acoustic modem should be securely connected to the tubing to maximize the signal transferred from the acoustic modem into the tubing.
As discussed above, clamps are often used for attaching downhole communications tools and/or wires to a downhole pipe. Clamps are well known in the art and take the form of hinged friction collars, hinged collars with set screws, and hinged collars with dogs. See for example, U.S. Pat. No. 6,957,704.
The hinged collar described in the '704 patent has two semicircular bands which are joined at one end by a hinge. At the opposite ends from the hinge, the semicircular bands have a flange through which a bolt extends. Thus, the hinged style stop collar is attached to a pipe by spreading the semicircular bands wide enough to receive the pipe. Rotating about the hinge, the semicircular bands are closed together until a bolt can be inserted through the flanges and tightened. As the bolt tightens, the flanges are drawn closer together so as to squeeze the collar about the pipe.
Moreover, as described/shown in the '704 patent, the hinged collar with set screws also comprises two semicircular bands which together surround a pipe. In this case, however, both ends of both semicircular bands have a hinge. The hinge is made up of corresponding eyelet pieces which are joined by a pin. Thus, the collar is attached to a pipe by placing the semicircular bands on opposite sides of the pipe and mating the hinge eyelets at the ends of the bands. With the hinge eyelets properly mated, pins are inserted into the eyelets. The semicircular bands also comprise set screws which are used to tighten the collar on the pipe. The set screws extend in a radial direction through the bands toward the pipe.
Hinged collars with dogs are again made of two semicircular bands which mate with each other to extend about the circumference of a pipe. Rather than eyelets, two ends of the semicircular bands are joined by interlocking fingers. The opposite ends of the bands have flanges through which a bolt extends. As the bolt is tightened, the flanges are drawn closer together so as to squeeze the bands around the circumference of the pipe. This collar also has several dogs which extend radially through the bands to provide protrusions or bulges on the interior of the bands for engagement with the casing. As the bolt is tightened and the bands are squeezed about the circumference of the pipe, the dogs firmly engage the outer surface of the pipe.
Prior art clamps generally rely on friction to stay in position. Usually made from carbon steel, the surface finish of a pipe can vary with rust and other imperfections. When friction clamps are secured on a rusty surface, resistance to axial load pressures is lowered because rust has low shearing characteristics.
Techniques have been proposed to enhance a shear coupling between a housing of a transmitter assembly and a wall of a tubular string. For example, U.S. Pat. No. 7,595,737 discloses a transmitter assembly of an acoustic telemetry system which is shear coupled to the wall of the tubular string. To enhance the shear coupling between the housing and the wall of the tubular string, external mating surfaces of the housing and the wall may be roughened, serrated, etc. to provide increased grip therebetween.
Clamps with a hinge located on one side of the pipe have uneven distribution of the load, biased to the side of the pipe on which the bolts are located. The load is lesser on the hinge side because most of the force has been absorbed by the friction between the clamp and the pipe.
Pipe diameter varies, because tolerances for pipe diameter are large. Clamps must be capable of fitting even the largest pipe diameter. Prior art clamps contact the pipe mainly on two lines located in the center plane, placing pressure on relatively small areas of the pipe 180° from each other. The pipes, having relatively thin walls, can be deformed into an oval shape.
Despite the efforts of the prior art, there exists a need for a clamp assembly adapted to include improved contact with pipe material, even distribution of load, and more contact points with the pipe. It is therefore desirable to provide an improved clamp assembly with better load bearing, load distribution, and pipe contact features. It is to such a clamp assembly to the present disclosure is directed.

Self-tightening clamps to secure tools along the exterior diameter of a tubing


Provided are a tumor antigen polypeptide having the amino acid sequence as shown in SEQ ID NO: 2 or a variant thereof; a nucleic acid encoding the same; a nucleic acid construct, an expression vector, and a host cell containing the encoding nucleic acid; and an antigen presenting cell presenting the tumor antigen polypeptide on the cell surface and an immune effector cell thereof. Also provided is the use of the polypeptide, nucleic acid, antigen presenting cell or immune effector cell in the diagnosis, prevention and treatment of cancers.

Cancer is a disease in which cell proliferation is out of control due to genetic mutations in cells. At present, it has become a major threat to human health and is one of the main causes of human death. According to the "Global Cancer Report 2014" published by World Health Organization (WHO), cancer patients and death cases were rapidly increased in 2012 worldwide with nearly half of new cancer cases occurred in Asia, most of which occurred in China, and the amount of new cancer cases in China ranks the first in the world[1]. According to data from "Annual Report of Cancer Registration in China in 2012", about 3.5 million new cancer cases every year were reported in China, and about 2.5 million people died therefrom[2]. Therefore, it would be of great clinical value to find a highly effective and specific cancer treatment method.
Traditional treatments for tumor mainly include surgery, radiotherapy and chemotherapy. However, these therapies have serious limitations. For example, the tumor metastasis and recurrence rate after surgical resection is high due to proximal invasion or distant metastasis of cancer cells, and radiotherapy and chemotherapy can cause serious damage to the body's own normal cells, especially hematopoietic system and immune system of the body, and it is therefore difficult for patients who have developed tumor metastasis to achieve better long-term efficacy[3]. With in-depth studies of the molecular mechanism of tumors and further development of biotechnology, targeted drug therapies and immunotherapies play an increasingly important role in the comprehensive treatment of tumors. The targeted therapies mainly include monoclonal antibodies (sometimes classified as passive immunotherapy) and small molecule targeted drugs, and the immunotherapies mainly include cytokine therapy, immune checkpoint monoclonal antibody, adoptive cell transfer and tumor vaccine, etc.[4, 5]. Immunotherapies control and kill tumor cells by activating the immune system of the body and enhancing the anti-tumor immunity of tumor microenvironment, and thus have the advantages of high efficiency and specificity and good tolerance, and have broad prospects in cancer treatment[5, 6].
Vaccines for tumor immunotherapy mainly include tumor cell vaccines, dendritic cell vaccines, protein & peptide vaccines, nucleic acid vaccines, genetic engineering vaccines and anti-idiotype tumor vaccines[7]. The main mechanism of these vaccines in killing a tumor is the initiation of an immune response against tumor-specific antigen in a patient, including antigen-antibody reaction and a CTL-specific killing and the like, among which the CTL-specific killing plays a great role in immune responses to tumors. A tumor-specific peptide is a tumor-specific antigen that primarily causes CTL-specific killing, and includes tumor-specific mutant peptides as well as tumor-specific highly expressed peptides. Wherein, the tumor-specific mutant peptides are only present in tumor tissues of patients and therefore can act as a specific target of tumor immunotherapy, which has the characteristics of good safety and few side effects. Immunotherapies targeting tumor-specific mutant peptides, such as peptide-specific DC-CTL and TIL adoptive transfer, have a good therapeutic effect[8, 9].
Tumor-specific peptides can be recognized by CTL or TIL cells by virtue of the antigen presenting function of human leukocyte antigen (HLA). The human leukocyte antigen is mainly divided into two subtypes I and II. Type I HLA is further mainly divided into three subtypes A, B and C, each of which can be further divided into multiple subtypes depending on its sequence. HLA-A0201 is one of the HLA-A subtypes, and occurs in 13% of the Chinese population, which is a high proportion. Different peptides bind to the HLA-A0201 subtype with different binding affinities. In a tumor patient with a specific HLA subtype, due to the specific HLA subtype, only a portion of mutant peptides can bind to the HLA and be presented to CTL or TIL cells by the HLA.
The CACNA1H gene encodes a protein having a length of 2353 amino acids and a molecular weight of 259,163 daltons, which acts as a subunit of T-type calcium channel Cav3.2, a voltage-sensitive calcium channel, and is involved in the transport of calcium ions into excitable cells and involved in multiple calcium-dependent processes including muscle contraction, release of hormones or neurotransmitters, gene expression, cell movement, division and death, etc.

CACNA1H-derived tumor antigen polypeptide and use thereof


The method of producing lithium titanate anode material for lithium ion battery applications is comprising of: a) mixing of mixed phase having 60-80% anatase and 20-40% rutile of TiO2 as titanium precursor with Li2CO3 as lithium precursor in a stoichiometric ratio of 5:4 and adding with 2 to 5% stearic acid as process control agent as well as carbon precursor; b) milling in horizontal attrition milling unit maintained with the ball to powder ratio of 10:1-12:1 at 250-500 rpm for 0.5 to 2 hrs c) repeating the milling for 40 to 48 times; d) palletisation of the milled powder to a diameter of 30-35 mm under a pressure of 0.5-1 ton; e) annealing under inert atmosphere at a temperature of 700-900° C. for a period of 2-12 hrs; and f) grinding the resultant annealed composite powder to a fine powder. Resultant powder has shown excellent electrochemical properties in terms of charge-discharge, cyclic-stability and rate capability.

Electric vehicle industry expects high energy density lithium ion batteries and therefore researchers are in search of new anode and cathode materials. Present study focuses on development of anode material, which becomes a suitable candidate for high energy density lithium ion battery applications and to design a scalable synthesis technique. Graphite is commonly used commercially available anode (Johnson et al, J. Power Sources 70 (1998), 48-54, Yoshio et al J. Electrochem. Soc. 147 (2000) 1245) and has specific capacity of 372 mA hg−1 (Peled et al, J Electrochem. Soc. 143 (1996) L4). It has voltage plateau of around 0.02 V making it prone to SEI and therefore affecting the electrochemical performance. Many anode materials involved intercalation (Nitta et al Part. Part. Syst. Charact. 31, 2014, 317-336) alloying and conversion mechanism (Obrovac et al Chem. Rev. 144 (2014), 11444-11502) are studied in-depth. Silica becomes one of the most hunted anodes, which becomes the material with highest theoretical capacity around 4200 mA hg−1. Since it accommodates more number of lithium ions it undergoes huge volume expansion, which numbers to be 400% and therefore is difficult to master it. TiO2 in both rutile and anatase form also becomes a promising anode with a capacity of around 350 mA hg−1 but has poor cycle life and rate capability owing to its semiconducting nature. In the present invention, we have chosen LTO as anode material owing to its high specific capacity of 175 mA hg−1 and stable voltage plateau of 1.55V. Since the voltage range is higher than the electrolyte decomposition voltage, it is free from solid electrolyte interface (SEI) formation. It accommodates three lithium ions and hence becomes a zero strain anode. Being a strain free anode, recently LTO has gained attention of many portable and electric vehicle battery industries. Further, long cycle life, high thermal stability (up to 280° C.), abundant and cost-effective Ti source and high rate capability properties of LTO making it more attractive. However, drawbacks such as poor electronic and ionic conductivity limit its electro-chemical performance. Doping with cations, carbon coating and surface coatings have been reported so far to overcome the above said limitations. Wet chemical methods such as hydrothermal (Qiu et al Chinese J of Chemistry, 28 (2010) 911), sol-gel (Shen et al, Materials chemistry and physics, 78 (2003) 437), spray drying (Wu et al, Electrocheima acta 78 (2012) 331), combustion (Prakash et al, Chem. Mater, 22 (2010) 2857) as well as solid state techniques were carried out to synthesize LTO anode. Since lithium titanate is lithiated form of titanium dioxide, there are several reports on synthesis of LTO from TiO2. Prior art reported the synthesis of LTO from either anatase or rutile phases of TiO2. Further, coating of LTO with anatase or rutile TiO2 was also reported to improve the electronic conductivity through the formation of Ti3+ ions. But when TiO2 as such was used as anode material for lithium ion batteries it resulted in poor electrochemical performance due to agglomeration and low packing density of TiO2 nanoparticles. In contrast when TiO2 (mixed phase) was used for the synthesis of LTO, it resulted in excellent electrochemical performance. Though many methods have reported to synthesize LTO, the factors such as (a) cost, (b) scalability and simplicity of material technology determine its commercial viability. Considering the above, in the present invention, we have adopted a sustainable and scalable low cost, energy efficient solid state method for the synthesis of LTO that can be suitable for electric vehicle lithium ion batteries. Since it is a single step large scale process devoid of solvents and large number of precursors, it may be considered as potential process for real application.
Prior-art patents as well as non-patent literature related to the field of present invention available in public domains are discussed below.
Singhal et al. [U.S. Pat. No. 6,827,921 B1/2004] invented a method of synthesizing nano sized lithium titanate from titanium and lithium precursors by refluxing them with an organic solvent followed by heat treatment in inert gas atmosphere. Here anatase TiO2 was used and concluded that the presence of vacant interstitial sites allows diffusion of lithium into TiO2 resulting in the formation of lithium titanate. The wet chemical method involved the use of expensive organic solvents, tedious reflux process and intermediate heating step. Zaghib et al. (U.S. Pat. No. 0,243,467 A1/2007) claimed a method of producing Li4Ti5O12 with metal ion dopants along with carbon coating. The process was found to be multi-step process involving carbon coating of TiO2 followed by milling with lithium precursor. Further, milling period was found to be long (24 h) and involved two step annealing process. Hence the process is tedious and less attractive for commercial applications. Fujimoto et al. (U.S. Pat. No. 6,372,384 B1/2002) reported a method of producing doped lithium titanate for improved load characteristics of lithium ion batteries. It disclosed that the possible phase formation temperature for lithium titanate was around 800-900° C. When the temperature is below 800° C., it resulted in failure of phase formation and when 900° C. exceeds then leads to the formation of impurities phases which degrade the electrochemical performance. Spliter et al. (U.S. Pat. No. 6,890,510 B2/2005) claimed a method of producing pure lithium titanate nano-powders. The technique reported here adapts a combination of wet chemical as well as solid-state technique. The method involved two step calcination and two-step synthesis process was found to be more tedious among the above-mentioned prior art patented works. Amatucci et al. (U.S. Pat. No. 7,211,350 B2/2007) claimed a milling method for producing lithium titanate nano-powders by shorter annealing time. The resulting nano sized lithium titanate anode produced a capacity of 100 mA hg−1 at 10 C rate and was found to be stable over 500 cycles. Though the synthesized material shows promising electrochemical performance, the scalability of the process is concern. Yu et al (U.S. Pat. No. 0,244,439 A1/2012) invented lithium titanate anode containing some of the dopants like potassium or phosphorous and reported to use the technique of ball milling with TiO2 and lithium carbonate as the precursors. The Chinese patent No. CN101587948 B) discloses the synthesis of carbon coated lithium titanate by a two step ball milling and two step annealing process. Initially various inorganic salts of titanium dioxide in single phase were milled followed by annealing at lower temperature. Further the annealed intermediate product was milled with carbon source and calcined under inert atmospheres to form the carbon coated lithium titanate powders.
According to CN102364729 A Lithium titanate was synthesized using a wet milling process followed by two step calcination for carbon coating on lithium titanate powders using activated carbon material. Various solvents for milling and various carbon precursors were used for optimization. The synthesis technique required two step annealing process under oxidizing atmosphere to form activated carbon coated lithium titanate material.
In another Patent application No. CN102664252 A, carbon coated lithium titanate was synthesized using a single step ball milling process. But a mixture of acetylene black and CNT was used as carbon precursor. It is seen that usage of CNT may improve the electrochemical performance, however the difference in the density between LTO and CNT as well as the tedious method and expensive process cost for synthesizing CNTs making the process inefficient.
A two step synthesis process was disclosed in CN103022462 A, where a combination of solid state reaction followed by spray drying was carried out for the synthesis of carbon coated lithium titanate. Multi-step process including slurry preparation, drying, spray drying and annealing seems to be time consuming making the method less attractive and less economical.
As per CN103730649 A, Carbon coated lithium titanate was prepared using ball milling process in which inorganic salts of titanium and lithium are milled together to form the mixture. Further carbon coating was carried out by polymerization process using polymer as carbon precursor under inert atmosphere. This was then followed by spray drying and two step annealing process to produce single phase crystalline, carbon coated lithium titanate anode, which is not attractive for commercial application.
Li et al [Li. et al Int. J. Electrochem. Sci., 6 (2011) 3210-3223] synthesized carbon coated LTO by ball milling technique using amorphous TiO2 nano-clusters as raw material. Unlike in the present invention, where commercial cost-effective TiO2 is used as precursor, here TiO2 synthesized by micro-emulsion process using CTAB as structure directing agent was used for milling. Since the milling technique followed was wet milling in this study, it requires additional heating step to remove the moisture. Further, carbon coating was carried out to improve the electronic conductivity, whereas in the present invention stearic acid used in the milling process plays a dual role, i.e. it acts as carbon source as well as process control agent to improve electronic conductivity and to avoid powder stacking respectively. Spinel Li4Ti5O12 performance highly depends on both the electronic and ionic conductivity, however, developing a low-cost strategy to improve its electronic and ionic conductivity still remains challenging. In study carried out by Yan et al [Yan et al. J. Mater. Chem. A, (2015), 3,11773], a facile cost-saving carbothermal reduction method was followed to synthesize micro scaled surface modified Ti (III) spinel Li4Ti5O12 particles using anatase—TiO2, Li2CO3, and acetylene black (AB) as Ti, Li and carbon precursor respectively. Remarkably, this indigenous design can easily eliminate the influence of the residual carbon, and thus makes it possible to individually study the effect of the Ti (III) on the bulk Li4Ti5O12. The presence of Ti (III) on the surface of Li4Ti5O12 not only improves the electronic conductivity, but also enhances the Li+ diffusion coefficient, therefore decreasing electrochemical polarization and improving the rate performance of LTO. In another study, Li4Ti5O12@CNT composites were prepared by a controlled in situ growth of CNTs on Li4Ti5O12. Since CNTs improve electronbridge between LTO particles, the electronic conductivity of Li4Ti5O12@CNT composites is better than that of pristine LTO and hence Li4Ti5O12@CNT composites show superior lithium storage properties comparable to the pristine Li4Ti5O12. Further, lithium titanate was also prepared by ball milling using micron sized TiO2 particles and lithium hydroxide as Ti and Li precursor respectively. However, the whole process involved a two-step milling, intermediate drying and then annealing again to produce lithium titanate.
It is known that smaller particle size and well crystallinity are both crucial for Li4Ti5O12 to achieve higher capacity and higher rate capability. Considering this, Zhu et al has developed [Zhu, et al. Energy Environ. Sci., 4 (2011) 4016] a facile method to synthesize a carbon-coated nano-sized Li4Ti5O12 by a combination of pre-carbon coating and spray drying. Though micron-size spherical particles used in this study induces large tap density and consequently enhance the volumetric energy density, the commercial TiO2 used for milling was initially carbon coated using sucrose by ball milling followed by carbonization to produce carbon coated TiO2, which was later milled with lithium carbonate to produce LTO. The process is found to be tedious involving multistep milling and annealing and hence it may be less attractive for commercial application. Matsui et al [J. Am. Ceram. Soc., 91 (2008) 1522-1527] synthesized lithium titanate using anatase TiO2 of particle size around 50 nm and lithium acetate as Ti and Li precursors respectively. Unlike in the present invention in which milled powders annealed at once to achieve the desire properties, two step annealing process and carbon coating was carried out in the reported study to produce single phase lithium titanate with improved electronic conductivity. Wang et al [J. Appl. Electrochem 40 (2010) 821-831] developed a modified ball-milling-assisted green solid reaction method followed by two step annealing process to prepare Li4Ti5O12/C composite materials using lithium carbonate, anatase TiO2, and activated carbon as Li, Ti and carbon precursors respectively. Further, hexane was also used as solvent for milling. Though the process employs tedious milling and annealing process to obtain phase pure lithium titanate with 10.6 wt % of carbon content, it still lacks in electrochemical performance compared to the lithium titanate according to the present invention.
Han et al [Han, et al. Appl Phys A 114 (2014) 925-930] reported the synthesis of Li4Ti5O12 by milling method using Li2CO3 and anatase TiO2 as Ti and Li precursor and studied different degree of milling to test the hypothesis that finer starting materials can result in a smaller Li4Ti5O12 particle size and better high-rate discharging capacities. The degree of milling was controlled by using three different ZrO2 ball sizes for high-energy milling (3 h) and 5 mm balls for planetary ball milling (24 h). The results indicated that high-energy milling produced significantly finer starting materials and Li4Ti5Ou particles compared to those produced by ball milling. Here again usage of solvent, intermediate drying step and slow annealing procedure makes the process tedious and time consuming. [Jhan, et al reported [Journal of Power Sources 198 (2012) 294-297] the synthesis of LTO/multi-walled carbon nanotube (MWCNT) composite is prepared by a ball-milling-assisted solid-state reaction and concluded that LTO nanoparticles were confined in the inter space of the MWCNT matrix and MWCNT prevent the aggregation of LTO particles during the calcination process of the solid-state reaction. Further, the entanglement of the MWCNTs and LTO creates an effective conductive network, which improves the conductivity of LTO. Therefore, the entanglement structure improves the electrochemical properties of LTO, such as the rate capability and cyclic stability. In addition, Sol-gel assisted ball milling technique [Yan, et al Journal of Alloys and Compounds 470 (2009) 544-547] was reported to produce lithium titanate where in it was synthesized by adopting sol-gel process, ball milling and then calcination process. The overall process including wet chemical method, intermediate heating, milling and a two step annealing process seems to be complicated, time consuming and expensive process though it exhibit reasonable electrochemical performance. Mechanical alloying is a basic technique used for milling of homogenous mixture of blended precursors and was used for synthesis of various alloying materials. Particularly, high kinetic horizontal rotary or horizontal attrition milling unit is the one that used for the solid state milling of composites with realistic of scalability and used for the production of alloys like Fe—Cr, Ni—Cr or milling of high-speed steel for particle size reduction. Since horizontal attrition milling forms a kinetic energy of 2-3 times higher than that of conventional planetary ball milling, milling time less than one order of magnitude can be reflected in former system in comparison with the later system. The main processing principle of milling is to transfer energy from kinetic collision of balls (Zoz et al Simo36-Paper) to powder. The continuous collection of milled powders without any wastage and environmental friendly condition added further advantages to horizontal attrition milling.
It can be inferred that none of the patents as well as literature matches with the present invention. Most of the patents were dealt with the synthesis of LTO by wet milling in the presence of a dispersing agent and the use of additional carbon coating and external doping for improving the electrical conductivity. Further, reduced atmosphere (H2+Ar) was used for creating oxygen vacancies to produce Ti3+ ions, which increase electrical conductivity in LTO. In contrast, in the present invention, we have adopted horizontal attrition milling, in which milling of Li and Ti (mixed phase) precursors with stearic acid which act as process control agent (PCA) as well as carbon precursor was carried out without external dopant ions, carbon precursor, and reducing atmosphere.

Method of producing high performance lithium titanate anode material for lithium ion battery applications

INTERNATIONAL ADVANCED RESEARCH CENTRE FOR POWDER METALLURGY AND NEW MATERIALS (ARCI)