A circuit board and a circuit apparatus using the same are provided, which have an improved heat radiation capability near through holes piercing through its metal substrate so as to address a requirement as to heat radiation capability. The circuit apparatus has the circuit board in which a metal substrate having pierced holes is formed as a core member. Protrusions are formed at the top ends of the pierced holes, and round corners are formed at the bottom ends of the same. Insulating layers are formed on both sides of the metal substrate, and wiring pattern layers are formed on the respective insulating layers. The insulator formed on one side of the metal substrate and the insulator formed on the other side of the metal substrate are extended to inside the pierced holes. The joining surface between the extended portions is shifted off the center position of the metal substrate in the thickness direction, toward the same side as where the protrusions are formed. In order to electrically connect the wiring pattern layers, a conductor layer connecting the wiring layers is formed through the metal substrate via the pierced holes, thereby establishing conduction between the wiring layers. A semiconductor chip is connected directly to the top side of the circuit board via solder balls.

1. Field of the Invention
The invention relates to a circuit board and a circuit apparatus using the same. In particular, the invention relates to a circuit board having a substrate consisting primarily of metal as a core member, and a circuit apparatus using the same.
2. Description of the Related Art
While portable electronics equipment including cellular phones, PDAs, DVCs, and DSCs are rapidly becoming more functionally sophisticated, miniaturization and weight savings have become essential in order for these products to be accepted in the market. To achieve this, more highly integrated system LSIs have become sought after. In the meantime, enhanced usability and convenience are also desirable features of such electronics equipment, and increased functional and performance sophistication have therefore been required of the LSIs intended for use in such equipment. Consequently, while the highly integrated LSI chips have facilitated the implementation of a greater numbers of I/Os, miniaturization of the packages themselves has now become imperative. In order to satisfy both of these requirements, there has been a strong demand to develop a semiconductor package suited to packaging semiconductor parts on a board at a higher density. To meet this demand, various types of packaging technologies called CSP (Chip Size Package) have been developed.
Among the known examples of such packages is a BGA (Ball Grid Array). With the BGA, semiconductor chips are mounted on a packaging substrate and molded with resin. Then, solder balls are formed over an area on the other side of the substrate as external terminals. Since the BGA realizes a planar mounting area, it is relatively easy to miniaturize the package. Therefore, the circuit boards need not be designed in narrower pitches, and do not require high-precision mounting technologies. The BGA can thus be used to reduce the total packaging cost, even if the package itself is of a relatively high cost.
FIG. 9 is a diagram showing the general configuration of a typical BGA. The BGA 100 has a structure where an LSI chip 102 is mounted on a glass epoxy substrate 106 via an adhesive layer 108. The LSI chip 102 is molded with sealing resin 110.
The LSI chip 102 and the glass epoxy substrate 106 are electrically connected with metal wires 104. An array of solder balls 112 are formed on the back side of the glass epoxy substrate 106. Through these solder balls 112, the BGA 100 is mounted on a printed wiring board.
In recent years, semiconductor packages (circuit apparatuses) to be incorporated in electronic equipment and the like have required greater miniaturization, higher densities, and increased functionality. The circuit apparatuses have thus grown in heat generation density per unit volume. Such increases in the heat generation density can cause adverse effects on the performance and reliability of the circuit apparatuses, thereby causing significant problems. For this reason, metal substrates and the like having high radiation performance have been used as circuit boards for constituting the circuit apparatuses, instead of the glass epoxy substrate 106. Furthermore, in order to conduct heat to the metal substrates efficiently, resins that contain alumina and other fillers having high thermal conductivities are used to make the insulating layers that constitute the circuit apparatuses. The heat radiation capabilities of the entire circuit apparatuses are therefore enhanced by these means.
FIG. 10 is a sectional view schematically showing the structure of a conventional circuit apparatus disclosed in Japanese Patent Laid-Open Publication No. 2002-335057. With reference to FIG. 10, the circuit board 210 for constituting a conventional circuit apparatus 200 includes a metal substrate 201 as a core member thereinside. Wiring pattern layers 203 and 205 are formed on both sides of the metal substrate 201 via resin insulating layers 202 and 204. For electrical connection between the layers, through apertures called through holes 206 are formed in the thickness direction. The inner surfaces of the through holes are plated with copper or the like, thereby forming an electrical conduction layer 207 for layer-to-layer conduction. In addition, a semiconductor chip 220 is directly connected to one side of the circuit board 210 via solder balls 221.
Resins containing no filler have thermal conductivities of approximately 2 W/(m·K). Filler-containing resins typically have thermal conductivities of approximately 10 W/(m·K), depending on such factors as the thermal conductivity of the filler itself, and the content of the filler. Consider the instance where that a filler-containing resin is used as the internal insulating layers of the metal substrate. The resin insulating layers 202 and 204 are then formed with the metal substrate 201 therebetween, or on the top and bottom surfaces of the same, by thermocompression under vacuum or reduced pressure. In this instance, the resin insulating layers 202 and 204 flow into and fill the through holes 206 from the top and bottom surfaces, respectively.
FIG. 11 is an enlarged sectional view of the circuit apparatus of FIG. 10, showing the vicinity of a through hole in the circuit board. It should be appreciated that the broken line in FIG. 11 indicates the center position (CA) of the metal substrate in the thickness direction.
Since the resin insulating layers 202 and 204 flow into and fill the interior of the through hole 206 from the top and bottom surfaces of the metal substrate 201 at the same time, the joining surface between the resin insulating layers 202 and 204 generally coincides with the center position (CA) of the metal substrate 201 in the thickness direction. While these resin insulating layers are flowing, their resin component and accompanying filler move at different rates of mobility (the mobility of the filler is lower than that of the resin component). The resin inside the through hole 206 thus has areas 202a and 204a where the content of the filler (filler concentration) is lower. Since these areas 202a and 204a have filler concentrations lower than that of the resin insulating layers lying outside the through hole 206, the surrounding areas including the through hole 206 are low in thermal conductivity and low in heat radiation capability.

Circuit board and circuit apparatus using the same


A solid electrolytic capacitor includes: a capacitor element including an anode made of a valve metal having an oxide film formed on a surface thereof, a cathode provided with a valve metal, and a separator provided between the anode and the cathode, the anode and the cathode and the separator being wound around together; a solid electrolyte interposed between the anode and the cathode; an anode lead tab having an oxide film formed on a surface thereof and being fixed to the anode; and a cathode lead tab fixed to the cathode. The oxide film of the anode lead tab has a portion the thickness of which is equal to or greater than 75% but less than 100% of the thickness of the oxide film of the anode.

1. Field of the Invention
The present invention relates to a solid electrolytic capacitor comprising a capacitor element including an anode in which an oxide film is formed on a surface of a valve metal, a cathode furnished with a valve metal, and a separator provided between the anode and the cathode, the anode and the cathode and the separator being wound around together, wherein a solid electrolyte is interposed between the anode and the cathode, an anode lead tab having an oxide film formed on a surface thereof is fixed to the anode, and a cathode lead tab is fixed to the cathode. The invention also relates to a method of manufacturing the solid electrolytic capacitor.
2. Description of Related Art
Electrolytic capacitors that make use of valve metals such as tantalum and aluminum are widely used since they are capable of attaining large capacity with small sized. Among the electrolytic capacitors, solid electrolytic capacitors employing conductive polymers such as polypyrroles, polythiophenes, and polyanilines, or TCNQ complex salts as their electrolytes have attracted attention.
A solid electrolytic capacitor of the foregoing type is fabricated in the following manner (see Japanese Published Unexamined Patent Application No. 6-310381).
First, an anode lead tab that has been subjected to a formation process and a cathode lead tab are fixed to an anode that is made of aluminum foil and has been subjected to an etching process and a formation process, and a cathode, respectively. Thereafter, the anode and the cathode are wound around in a cylindrical form with a separator paper interposed therebetween to form a capacitor element. Further, cut edge formation and a heat treatment is carried out for the capacitor element. Next, the capacitor element is immersed in a solution containing an oxidizing agent and a monomer, and thereafter, thermal polymerization is effected, whereby a conductive polymer layer (a solid electrolyte layer) is formed between the anode and the cathode of the capacitor element. Subsequently, the capacitor element is accommodated and secured in an aluminum case, then the aluminum case is sealed, and further an aging process is performed. Lastly, a base plate is inserted to come into contact with the curled surface of the capacitor, and the lead lines of the capacitor are press-worked and bent to form electrode terminals, so that a solid electrolytic capacitor is completed.
Demands for high-withstanding voltage products of the foregoing solid electrolytic capacitors have been escalating in the market. The solid electrolytic capacitors, however, have a problem that they have poorer self-repairing ability against leakage current (LC) than liquid electrolyte-type electrolytic capacitors. To enable such solid electrolytic capacitors to have an increased withstanding voltage, it is necessary that the withstanding voltage of the dielectric oxide film of the anode foil be high (in other words, the formation voltage for the anode foil needs to be high). Moreover, in the manufacturing process, edges of the anode foil need to be subjected to a formation process again for the same reason. It should be noted, however, that the formation of the edges is a typical process for solid electrolytic capacitors and is not a process that is particularly carried out to increase the withstanding voltage.
Normally, cut edge formation, which is carried out during the manufacturing process, is performed with the same formation voltage as the formation voltage for the anode foil. However, if the formation voltage for the cut edge formation exceeds 200 V (especially over 230 V), the cut edge formation becomes unstable when using a conventional anode lead tab (formation voltage: about 160 V), producing corrosion at many locations in the weld part of the anode lead tab. As a result, the LC characteristics of the solid electrolytic capacitor become unstable.

Solid electrolytic capacitor and method of manufacturing the same


A press working apparatus has a press machine provided with a pair of press dies. The press machine presses a preheated metal slab being transferred in a feeding direction with the press dies mutually opposed to press the metal slab in a direction perpendicular to the thickness of the metal slab. Each press die has a pressing surface facing a respective surface of the metal slab. The pressing surface of each press die has a predetermined length extending in the feeding direction of the metal slab. At least one of the pressing surfaces has a cross section perpendicular to the feeding direction of the metal slab. The shape of the cross section gradually changes along the feeding direction of the metal slab so as to have a predetermined sectional shape for forming the metal slab into a required sectional shape. At least one surface of the metal slab is gradually formed into a predetermined sectional shape as the metal slab is passing through the press machine.

The present invention relates to the field of press working, and in particular, relates to a press working apparatus which can form a metal slab into a ribbed board or a mesh grid such as a reinforcing net.
In the manufacturing of a ribbed steel board consisting of a steel board and reinforcing ribs provided perpendicular thereto, it has thus far been conventional to provide a steel board and ribs, and to weld the ribs to a surface of the steel board.
Furthermore, when manufacturing a mesh grid such as a reinforcing net, it has thus far been conventional to arrange a plurality of steel bars (reinforcing bars) in a net structure, and then to tie the steel bars with tying members such as wires, or to weld each intersection of the assembled steel bars.
However, the above conventional method for manufacturing ribbed steel boards or mesh grids presents problems such as those described below. That is, in order to manufacture a ribbed steel board by the above method, welding is required to form the steel board, and in order to manufacture a reinforcing net by the above method, it is necessary to tie or weld the steel bars, which is troublesome, after arranging the steel bars in a mesh structure. Additionally, since the welding should be performed at many points for a grid or over a long joint in a ribbed board, the work efficiency of the welding is lowered, and quality control of the welding is difficult.

Ishikawajima-Harima Heavy Industries Co., Ltd.


It is intended to provide a method of three-dimensionally culturing normal joint chondrocytes; the production and supply of chondrocytes; and a transplantation material to be used in an injured site in a joint tissue.

When a damage or a defect occurs in a joint cartilage due to some cause, it is rare that the joint cartilage is completely restored and regenerated. One of the reasons includes a nature of chondrocyte. That is, as the joint chondrocytes are highly differentiated, scarcely proliferate and differentiate, their restoration capacity is extremely low. Another reason includes a peripheral inherent environment surrounding the chondrocytes. Since a cartilage tissue lacks a nerve and a blood vessel, no restoration mechanism by hemorrhage, inflammation and granulation is available. Since a periphery of the cartilage tissue is surrounded by extracellular matrix, the chondrocytes can not easily migrate from a healthy site to the injured site.
The injured site in the joint cartilage induces degradation of its periphery and adjacent cartilage with time, finally advances to osteoarthritis, and causes the reduction of joint functions, e.g., pain and mobile limitation. Therefore, various therapeutic methods have been developed as methods of restoring the joint cartilage so far, but this is an actual state that the method of restoring a defect site with complete hyaline cartilage has not been well established at present.
Accompanying with the recent advance of cell engineering, regeneration of the cartilage tissue by autologous chondrocytes has been actively attempted. It is important as a transplantation material applied to the injured site that enough amount of the chondrocytes are maintained, and that the retained chondrocytes can produce the sufficient amount of the extracellular matrix.
However, there is a problem that the chondrocytes dedifferentiate into fibroblasts during the culture when the chondrocytes are isolated from an autologous cartilage piece and subsequently grown in a monolayer culture. Thus, it is difficult to culture the chondrocytes keeping with their character well. As a scaffolding exhibiting a three dimensional structure, biomaterials such as collagen gel sponge, agarose gel, gelatin, chitosan, hyaluronic acid and PGA, PLA and PLGA have been reported, but no material having strength and frictional coefficient corresponding to a cartilage matrix has been developed until now, and a transplantation material having the characters close to the joint cartilage tissue has been desired.

Method of three-dimensionally culturing chondrocytes


A gas combustion type driving tool drives a fastener by combustion pressure when mixed gas of combustible gas and compressed air in a combustion chamber is ignited. The gas combustion type driving tool includes an air ejection valve, and a gas ejection valve. The air ejection valve is configured to eject compressed air into the combustion chamber. The gas ejection valve is configured to eject combustible gas into the combustion chamber. Output related to driving of a fastener is adjustable by adjusting at least one of filling pressure of compressed air or filling pressure of combustible gas.

A gas combustion type driving tool that drives a fastener by combustion pressure of combustible gas is known in the related art. As a method for improving output of such a gas combustion type driving tool, there is an idea that a fastener is driven out by combustion pressure when mixed gas of combustible gas and compressed air is ignited. That is, although air and combustible gas are mixed in the gas combustion type driving tool in the related art, it is studied that, by using compressed air instead of air, a large output may be obtained by energy of compressed air and thermal energy of combustion gas.
Several methods of adjusting the output in such a gas combustion type driving tool are proposed.
For example, JP-A-S50-15177 discloses a method of adjusting output of a gas combustion type driving tool, in which an operation timing of a valve is changed by adjusting pressure operating on a member (the valve) provided between a combustion chamber and a cylinder.
JP-A-S63-28574 discloses a method of adjusting output of a gas combustion type driving tool by changing a volume of a combustion chamber.
There is also a method of adjusting output of a gas combustion type driving tool by using a known driving depth adjustment mechanism.


A method of providing cryptographic information and flow control includes first determining a target domain from an IP address. An organization policy is looked up from a credential store, and an algorithm and credentials specified for the target domain are looked up in a domain-credential map. Any further credentials that are provided and that are permitted by the organizational policy are added. A working key is then generated, and information is received in the form of a receive packet. Any packet header is stripped from the receive packet and the remaining data is encrypted. Key splits are retrieved from the credential store, and are combined to form a key-encrypting key. The working key is the encrypted with the key-encrypting key, and a CKM header is encrypted. The encrypted CKM header is concatenated to the beginning of the encrypted data to form transmit data, and the packet header and the transmit data are concatenated to form a transmit packet. The transmit packet is then provided to a network interface card for transmission on a network.

In an environment in which methods of transmitting information are increasingly public and intertwined, protecting sensitive information has become critically important. Insuring confidentiality, privacy, and restricted access are primary concerns of both government and private organizations. Traditional methods of providing sufficient levels of security lag behind current needs and threaten to block implementation of new information and communication technologies. Furthermore, many methods currently being offered suffer in one or more of the following areas:                Require extremely large investments. While several secure network gateways, interface and VPN devices are available, most are so costly as to exclude them from consideration in all but the most critical applications. It is not uncommon to find devices that would be required at every workstation at a cost of several thousand (and, at times, several tens of thousands of) dollars per unit. Furthermore, most of these devices provide single functionality and must be physically removed or detached for any reconfiguration (providing little "bang for the buck").        Inflexibility. Many current devices provide little if any flexibility in their use, while others offer some flexibility but with varying degrees of difficulty. VPNs either cannot be "re-keyed" to multiple, secure "conferences" or "logical networks", or can only be re-keyed by physically removing or detaching the device. Very few if any provide the ability for a single user or workstation to communicate with multiple VPNs or to communicate through both secure and unsecure channels. Cryptographic algorithms are often pre-loaded and typically cannot be selected dynamically.        Limited Functionality. Most current devices are intended to provide one or two functions, often for a single application. A device provides data privacy but not access control or data separation. Some provide user authentication but cannot verify the authenticity of data received or of the apparent sender, while others do the opposite. Many work only in a Type 1 classified environment, while others can be used only for sensitive but unsecure information.        Extensive Network Infrastructure. Many (if not most) designs for protecting data-in-transit focus on securing the channels of communication rather than the information being communicated. These types of designs require, a priori, that all points between the originator and intended recipient of the data maintain the secure channel. Therefore, specialized hardware and/or software is required throughout the network, presenting extensive maintenance challenges and considerable cost. Furthermore, since these designs introduce multiple points of potential failure, considerably more hardware and maintenance efforts are needed for secondary backup systems, further complicating network design and inflating both initial and ongoing costs.        Extensive Key Management Infrastructure. Many designs require server-based certificate, user, and/or key directories and complicated systems for distribution, replication, authentication, and verification. Such systems are not only complicated to design and implement, but are suspect to load and performance requirements.
If government and commercial organizations are going to be able to exploit the increasingly open networks and technologies, better methods of protecting the information sent through these networks are clearly needed. Although it is not believed that any one technology or any one application of technologies will provide a single complete solution for protecting data in transit, the use of a Constructive Key Management (CKM) system (see U.S. patent application Ser. No. 09/023,672) on a Network Interface Card (NIC) is capable of solving many of the existing challenges for a considerable number of potential applications.

Cryptographic information and flow control


An apparatus for implantation of in vivo sensors includes a housing, a dual-lumen tube extending therefrom, and an in vivo sensor received within one of the lumen of the tube. A needle is received within the other lumens of the tube, and is used to insert the tube through the skin. After implantation, the needle is removed, and the flexible tube and sensor remaining beneath the skin provides the user with reduced irritation and greater comfort. The associated method for subcutaneous implantation of a sensor for use in vivo is also disclosed.

1. Field of the Invention
The present invention relates to an apparatus and method for implantation of an in vivo sensor, and particularly to a minimally invasive method for implanting a sensor.
2. Description of the Prior Art
Certain sensors, such as glucose sensors, are intended for use in vivo, requiring that the sensors be implanted in a fashion consistent with their use. However, it is also desirable that the method of implantation be quick, easy and convenient. The method of implantation is advantageously one which is readily performed both by medical personnel administering to a patient, and also by the person being monitored. Since this person likely will not have medical training, the method should be one which can be performed reliably, such that the readings from the sensor are accurate.
The present invention provides a method which is readily performed for the implantation of a glucose or other sensor, and which uses an apparatus which provides quick and reliable results. While devices have existed for introducing a catheter into small vessels subcutaneously, the introduction of in vivo sensors in this manner has not been suggested.
In U.S. Pat. No. 4,417,886, issued to Frankhouser et al. on Nov. 29, 1983, there is disclosed a catheter introduction set. The Frankhouser patent describes an assembly including a catheter mounted on an introducer needle, with the tip of the needle extending slightly beyond the end of the catheter. A wire guide is received within the needle and attached to a guide tube extending rearwardly from the needle. In use, the needle is inserted into the lumen of the vessel, the spring wire guide is advanced into the vessel, and the catheter is then advanced forwardly to track the spring wire guide into the vessel to the desired position. Thereafter, the spring wire guide and needle are removed.
A comparable device, but without the wire guide, is currently marketed by MiniMed Technologies of Sylmar, Calif. under the name SOF-SET. This device includes a 24 gauge needle received within a short 24 gauge catheter. The needle includes a handle, and is used to introduce the catheter into the body by piercing through the skin. The catheter extends from a support adapted to be secured to the skin. A length of tubing also extends from the support, and communicates with the catheter upon withdrawal of the needle.
Methods and assemblies for the introduction of dual lumen catheters have also been identified. Dual lumen catheters have been noted as providing two means for access to a vessel, such as for withdrawal of blood samples and the infusion of drugs. An introducing needle assembly similar to that described in the Frankhouser patent, but including a double lumen needle, is disclosed in U.S. Pat. No. 4,935,008, issued to Lewis on Jun. 19, 1990. Similarly, the TWIN CATH.RTM. product from Arrow International, Inc., comprises an introducer including a two lumen catheter. One lumen of the catheter is round and receives a needle therein, and the other lumen has a C-shaped cross section and surrounds a portion of the round lumen.

Apparatus and method for implantation of sensors


A method for monitoring a network communications channel to detect specific DTMF triggers transmitted by a network user during either a pre-answer or a post-answer period of a call supported by the channel, and, in response to the detected DTMF triggers, controllably prohibiting the propagation of subsequent DTMF signals transmitted over the channel by the network user. Specifically, possible disruption of a communication between the network user and other parties caused by transmission of DTMF signals is eliminated by advantageously transmitting the DTMF triggers during the pre-answer period of a call. Furthermore, another deficiency of prior network-based arrangements for restricting the propagation of DTMF signals is overcome, as the invention may be practiced without the introduction of any significant propagation delay to a network.

DTMF signals are employed within telecommunication systems to initiate calls, and facilitate control of certain services and/or equipment. The services and/or equipment may be both internal and external to the particular network facilitating a call. For example, codes called "triggers", comprised of one or more DTMF signals, allow network subscribers to control network-based services such as multi-party conferencing. Network subscribers may also need to transmit, via the network, DTMF triggers to equipment and services external to the network, such as answering machines and automated banking services.
Network subscribers have had little control as to the propagation of DTMF signals which they transmit, giving rise to a number of potential problems. For example, assume a network subscriber placed a call to a particular party via a network offering multi-party conferencing in response to a DTMF trigger received from the subscriber. During the course of the call, the conferencing feature allows a subscriber to instruct the network, via a transmitted DTMF trigger, to connect additional parties to the call. The transmitted DTMF trigger would be detected by network-based equipment which would perform the requested connection of the additional party or parties. Unfortunately, like any other audio band signal sent from the subscriber's telephone, the DTMF trigger would also be transmitted to the originally called party. Such audible signals would disrupt any communication with that first called party. For obvious reasons, such disruptions are undesirable.
Arbitrarily blocking all DTMF signals at some point within the network between the network-based equipment to which a network subscriber must transmit DTMF triggers, and the party with whom the subscriber is connected would prohibit DTMF signals from disrupting communications with that party. However, this blocking would also prevent a subscriber from transmitting DTMF triggers to equipment and services external to the network. Previously known network-based arrangements have provided for detecting and selectively blocking a limited number of unique triggers intended for equipment internal to a particular network, while allowing all other DTMF signals to propagate to parties/equipment external to the network. However, these arrangements are limited in their versatility, and cause unacceptable propagation delays within a network.

Method for selectively controlling the propagation of dual-tone multi-frequency signals within a telecommunications network


In some embodiments, the present disclosure pertains to a method for capturing alkenes that includes: associating the alkenes with metal-organic frameworks, where the metal-organic frameworks includes one or more metals and one or more ligands coordinated with the one or more metals, and where the metal-organic frameworks are conductive; and oxidizing the metal-organic frameworks, where the oxidizing results in a capturing of the alkenes by the metal-organic frameworks. Additional embodiments of the present disclosure pertain to a system for capturing alkenes that includes: metal-organic frameworks, where the metal-organic frameworks include one or more metals and one or more ligands coordinated with the one or more metals, and where the metal-organic frameworks are conductive; and an alkene feed source associated with the metal-organic frameworks, where the alkene feed source is configured to deliver an alkene feed to the system.

Extraction of alkenes from various environments and sources (e.g., petroleum) is an energy-demanding process that involves many complex processes (e.g., steam cracking and cryogenic distillation). Alternative methods of alkene extraction that utilize transition metal complexes can improve energy-efficiency, but suffer from poisoning and the reduction in efficiency triggered by additional alkene feed components (e.g., H2, C2H2, CO, and H2S). Moreover, growing environmental concerns require improved methods for separating alkenes from various environmental sources (e.g., petrochemical feedstocks). The present disclosure addresses the aforementioned needs.

Porous scaffolds for electrochemically-controlled reversible capture and release of alkenes


Polyhydroxy amines reacted with fatty acid esters yield polyhydroxy fatty acid amide surfactants, such as the C.sub.11 -C.sub.17 fatty N-methyl glucamides, which may be contaminated with secondary amines. Such amines are acylated by a reaction with acetic anhydride. The resulting "clean" polyhydroxy fatty acid amide surfactants are preferred for use in the presence of oxidants, especially in the formulation of modern, colorless liquid detergents.

The preparation of polyhydroxy fatty acid amide surfactants by the reaction of fatty esters with N-alkylamino polyols is of considerable commercial interest. However, the resulting N-alkylamido polyol reaction products, such as the fatty acid N-methyl glucamides, are often contaminated with residual amounts of unreacted N-alkylamino polyols. Contamination by such materials may be tolerable under many circumstances. For some uses, however, the presence of unreacted N-alkylamino polyols may be undesirable for color and odor reasons. In particular, the manufacturer of modern, clear, colorless, high sudsing detergent compositions which contain polyhydroxy fatty acid amide surfactants (e.g., C.sub.8 -C.sub.22 fatty acid amide derivatives of N-methyl glucamine or N-methyl fructamine) requires an inexpensive source of such materials which have desirable low amino polyol levels. In addition, the manufacture of such detergent compositions, especially the colorless versions, sometimes employs various bleaching agents, such as H.sub.2 O.sub.2, which could potentially oxidize the residual N-alkylamino polyols to undesirable by-products. Manufacturers presumably could arrange for special care to be taken during the reaction in order to minimize the levels of such unreacted starting materials, or employ separate purification techniques. However, the manufacturer of high volume, low-cost chemicals such as home-use detergents can ill-afford special handling techniques or materials which require expensive purification steps.
The present invention solves the heretofore unappreciated problem of contamination by sources of N-alkylamino polyols associated with the manufacture of polyhydroxy fatty acid amides, and thereby affords access to a high quality supply of this class of surfactants which are especially useful in situations where oxidants may be present.

Process for reducing the levels of unreacted amino polyol contaminants in polyhydroxy fatty acid amide surfactants


In high dynamic range (HDR) image creation, a ghost artifact detection method divides the images (brackets) into multiple tiles, and selects one bracket for each tile as the local reference bracket. The local reference brackets are selected via optimization of an objective function which includes both a component that measures exposure quality of individual tiles and a component that measures correlation between neighboring tiles. The minimization can be realized by constructing a graph for the objective function and calculating a minimum cut of the graph using a graph cut algorithm. Graph examples for three and four image sets are given. Ghost artifact detection is then performed on a tile-by-tile basis by using the local reference bracket for each tile. Ghost maps are generated this way and used for HDR image creation. This method minimizes artifacts due to inconsistencies in local reference bracket selection in areas involved in ghost-inducing objects.

1. Field of the Invention
This invention relates to high dynamic range (HDR) imaging, and in particular, it relates to removal of ghost artifact during HDR image creation.
2. Description of Related Art
High dynamic range (HDR) imaging is a technique used in image processing and digital photography to handle sources that have extremely large ranges of brightness (light intensity). For example, an outdoor scene in daylight may include blue sky and sunlit objects as well as objects in shadows; a night scene may include neon lights and brightly lit objects as well as poorly lit objects; an indoor scene may include bright windows as well as darker areas, etc. These scenes pose a challenge for imaging devices such as digital cameras; the dynamic range of the image sensor of currently available digital cameras often cannot adequately image such scenes. If the exposure level is adequate for capturing details of darker areas of the scene, the brighter areas will often be overexposed with details lost; conversely, if the exposure level is adequate for capturing details of brighter areas of the scene, the darker areas will often be underexposed with details lost.
HDR imaging techniques deal with this problem by taking a set of multiple images of the same scene at various exposure levels, and then digitally merging the multiple images to create an HDR image that contains information from the original multiple images, so that details in both brighter and darker areas are adequately expressed in the HDR image. Methods for creating an HDR image from a set of multiple images are generally known.
Bracketing is a technique in photography for taking multiple images of the same scene using different exposure levels or other different setting values such as focus, depth of field, etc. Some cameras can perform autobracketing, i.e., automatically changing the setting multiple times and take multiple images. Each of the multiple images is sometimes referred to as a bracket. Multiple images generated by exposure bracketing can be used to create HDR images.
During HDR image creation, ghosting artifacts can appear when object have moved, appeared or disappeared in between the shooting of the different images (brackets). For example, during the shooting of three brackets, if a person walks into the scene only in the third bracket, then the HDR image created from the three brackets will have a semi-transparent figure of the person over the scene ("ghost"). These objects are referred to as moving objects or ghost-inducing objects in this disclosure.
Methods have been proposed to identify such ghost-inducing objects within the multiple images, so that the images can be processed to reduce or eliminate ghosting effects in the resulting HDR image. Some of these techniques are described in a review paper, A. Srikantha and D. Sidibé, Ghost Detection and Removal for High Dynamic Range Images: Recent Advances, Signal Processing: image Communications, 27(6), pp. 650-662, 2012.
In some known ghost artifact detection method, one of the multiple brackets is selected as the reference image (also referred to as a background image), which is the image that by definition does not contain any ghost-inducing objects. Other brackets are compared to the reference image to determine whether and where ghost-inducing objects are present. An advantage of such a single reference approach is that it simplifies the ghost detection and removal problem, because when processing each non-reference bracket, only two images (the reference bracket and the non-reference bracket) need to be compared to detect non-consistent pixels. A disadvantage, however, is that some large areas of the reference image may be badly exposed (either over or under exposed) and, if used as reference, result in unreliable ghost detection, lost of information and poor quality of the resulting HDR image in the relevant areas.
Thus, a method has been proposed to divide each image into multiple tiles (all brackets are divided into the same tiles), and for each tile, one bracket is selected as the reference image, so that different brackets may be selected as the reference bracket for different tiles. The selected bracket for each tile is referred to as local reference or local background. One such method is described in Gökdeniz Karadag and Ahmet Oguz Akyüz, Color preserving HDR Fusion for Dynamic Scenes, Journal of WSCG 20(2): 155-160 (2012) ("Karadag and Akyuz 2012"). FIG. 2, which is adapted from FIG. 1 of the Karadag and Akyuz 2012 paper, shows an image divided into multiple tiles; tiles labeled "S" (near the upper right hand and lower right hand corners of the image) indicate tiles for which the short exposure bracket will be used as the reference image, and tiles labeled "L" (near the center of the image) indicate those for which the long exposure bracket will be used (this image set had a total of three brackets). For the other tiles, the middle bracket will be used as the reference but for simplicity these tiles are not labeled in FIG. 1. After the reference bracket is selected for each tile, ghost pixels are detected in the non-reference brackets.

Ghost artifact detection and removal in HDR image creation using graph based selection of local reference


Bottom ash and flyash having high LOI is reburned in a pulverized coal furnace. The bottom ash is added to the coal supply before the coal is pulverized. Flyash is added to the pulverized coal stream for injection with the pulverized coal or is separately injected into the furnace at or slightly above the level of the coal burners in the furnace. The bottom ash and flyash is added to the coal in direct proportion of 1% to 3.5% of the coal.

This invention relates to the treatment of coal ash, and particularly to a method for reburning bottom ash and flyash components of coal to remove carbon and provide a usable end product.
Coal fired boilers are widely used to generate steam for producing electricity. A common form of boiler uses a pulverized coal that is injected into a furnace. Millions of tons of coal ash result each year from such operations. The coal ash includes flyash with a minor proportion of bottom ash. Some of the ash is commercially usable in concrete, concrete products, cement production, sewage sludge stabilization, pavement base materials, lightweight aggregate, and other miscellaneous purposes. The remaining coal ash must generally be disposed of by landfilling since it has no commercial value. A principal reason for a lack of commercial value for coal ash is the presence of unburned carbon in the ash. According to ASTM Standard C618, an ash must have a Loss On Ignition (LOI) value no higher than 6% for use in concrete. An upper limit of 3% is more realistic. Higher LOI ash cannot be used because of color problems and concerns for durability under freezing and thawing conditions.
The residual carbon content in the coal ash depends upon a variety of factors including base line furnace operation and boiler design. It also depends upon the source of the coal fuel. For example, subbituminous western coal, when burned, will typically result in a low carbon ash with an LOI of less than 5%.
A variety of methods for dealing with the high carbon flyash problem are currently under investigation. The methods include froth flotation which uses mining technology for separation of materials of different densities, electrostatically-charged belts to separate carbon from the flyash, a fluidized bed separation using acoustical techniques, and combustion of the remaining carbon in the flyash in a fluidized bed boiler designed specifically for that purpose. None of these technologies have demonstrated the ability to completely remove the LOI on a commercial scale, and all of these approaches would require significant capital and operating costs.
It is a principal object of the invention to provide a method of treating high carbon coal ash using existing capital installations, and particularly existing pulverized coal boilers.


According to the process described, old or waste plastics are depolymerized into a pumpable phase and a volatile phase to allow recovery of chemical raw materials and liquid fuel components. The volatile phase is separated into a gaseous phase and a condensate. In order to simplify the process in comparison with the state of the art, the depolymerised product remaining after the volatile phase is separated is also heated together with the condensate or condensate fractions in the presence of hydrogen under pressure and is subjected to hydrotreating, after non-boiling components are removed, to produce syncrude.

1. Field of the Invention
The invention relates to a method for processing recycled or scrap plastics for the purpose of obtaining raw chemical materials and liquid fuel components, by means of depolymerization of the substances being used, at elevated temperature, to produce both a pumpable and a volatile phase, and separation of the volatile phase into a gas phase and a condensate.
2. Description of the Background
In the depolymerization of recycled or scrap plastics, not only melt-viscous depolymerizate, but also a gas phase and a condensate are obtained, and the condensate must be additionally treated with hydrogenation, because of its chlorine content and low stability. With regard to the state of the art, we refer to the PCT application WO 94/22979.
From the aforementioned document, it is evident that the condensable depolymerization products can be subjected to hydrogenating refining on a solid bed catalyst, or also on a moving catalyst, or a bubbling catalyst bed. Such hydrogenating refining represents normal refining processes, which are also referred to as hydrotreating in the technical literature.
The condensates to be subjected to hydrotreating, however, contain non-evaporating components which come from the depolymerizer, because of foaming, spraying, or vapor inclusions, and also those that have been reformed by means of repolymerization, so that direct charging of a catalyst layer arranged in fixed manner in a hydrotreater would result in rapid inactivation of the same, i.e. would result in very high catalyst consumption. In addition, because of the instability of such condensates, coatings would form on heat exchangers, for example pre-heaters, which would prevent sufficiently long times of operation without interruptions. Document WO 94/22979 teaches converting the condensate, for example by hydrotreating it on commercially available Co--Mo or Ni--Mo catalysts arranged in fixed manner, or introducing it directly into chemical, technical or usual refining processes which tolerate chlorine, as a base substance which contains hydrocarbons (syncrude) (see p. 5), where a prior "guard bed" to extend the useful lifetime of the catalyst layer arranged in fixed manner is also taken into consideration (see page 9, line 7, op. cit.).
From the aforementioned state of the art, the technical teaching of a combination of depolymerization, hydrogenating treatment, preferably of distillate components that have been produced, with sump phase hydrogenation, gasification and/or low temperature carbonization can be derived. Here the task of simplifying the process comes up.
A further task is to prevent rapid inactivation of the catalyst charge of the hydrotreating stage.

Method for processing recycled or scrap plastics


Compounds useful as surface coating agents, including compounds of the formula:

The chemical modification of surfaces to achieve desired chemical and/or physical characteristics has been previously described. For example, U.S. Pat. Nos. 4,722,906; 4,973,493; 4,979,959; 5,002,582; and 5,512,329 (each of which is commonly owned by the assignee of the invention described herein, and the disclosure of each is incorporated herein by reference), relate to surface modification by the use of latent reactive groups to achieve covalent coupling of reagents such as biomolecules and synthetic polymers to various substrates. The preferred latent reactive group is typically described as a photochemically reactive functional group ("photoreactive species"). When exposed to an appropriate energy source, a photoreactive species undergoes a transformation from an inactive state (i.e., ground state) to a reactive intermediate capable of forming covalent bonds with appropriate materials.
Such latent reactive groups can be used, for instance, to first derivatize a target molecule (e.g., thermochemically), in order to then photochemically attach the derivatized target molecule to a surface. Such a sequential approach is suitable in many situations, but can lack such attributes as speed, versatility, and ease of use, particularly when used with target molecules that are inherently difficult to first derivatize or under conditions that would result in loss of biological activity.
Latent reactive groups can also be used to prepare photoactivatable heterobifunctional molecules as linking agents, e.g., having a photoreactive species at one end or portion with a thermochemical attachment group at another (see, e.g., the above-captioned '582 patent, and U.S. Pat. No. 4,309,453, Reiner et al.). Such linking agents can be used to either attach nonreactive compounds to a surface or to prime a relatively inert surface in order to render it reactive upon exposure to suitable actinic radiation.
U.S. Pat. No. 5,414,075 (commonly owned by the assignee of the present invention and incorporated by reference herein), describes the use of linking agents to prime a surface to provide the surface with photoactivatable groups. This patent describes a restrained, multifunctional reagent useful for priming a support surface, or for simultaneous application with a target molecule to a support. Reagents such as those described above, including those described in the '075 patent, are generally hydrophobic. As a result, they are of relatively low solubility in aqueous systems, thereby often limiting their usefulness in hydrophilic applications.
U.S. Pat. No. 5,714,360, also commonly owned by the present assignee (and also incorporated herein by reference), describes a chemical linking agent comprising a di-or higher functional photoactivatable charged compound. The linking agent provides at least one group that is charged under the conditions of use, in order to provide improved water solubility, and two or more photoactivatable groups in order to allow the agent to be used as a linking agent in aqueous systems. The "Y group" that provides the core radical is defined as a radical containing one or more charged groups, such as the linear and heterocyclic nitrogen-containing (e.g., quaternary ammonium) radicals exemplified therein. In a preferred embodiment, the charged groups include, but are not limited to, salts of organic acids (such as sulfonate, phosphonate, and carboxylate groups), onium compounds (such as quaternary ammonium, sulfonium, and phosphonium groups), and protonated amines, as well as combinations thereof. The photoreactive species can be provided by two or more radicals of an aryl ketone such as benzophenone.
While the reagents of the art are sufficient, if not preferred, for many applications, there remain applications in which various other properties or attributes, such as water solubility, ease of synthesis and/or hemocompatability, are not optimally provided by the reagents of the art.

Abstract: wherein X1 comprises a first photoreactive species; X2 comprises a second photoreactive species; Y comprises a nonpolymeric core molecule comprising an aromatic group; and Z comprises at least one charged group. The Y core can include an aromatic group such as a benzene radical, the charged groups Z can be independently selected from the organic acids that include sulfonic acid, carboxylic acid, and phosphoric acid, and the photoreactive species of X1 and X2 can independently be aryl ketones, such as those selected from the group acetophenone, benzophenone, anthraquinone, anthrone, and anthrone-like heterocycles, and their substituted derivatives. Examples of such coating agents include 4,5-bis(4-benzoylphenylmethyleneoxy) benzene-1,3-disulfonic acid di(potassium and/or sodium) salt, 2,5-bis(4-benzoylphenylmethyleneoxy) benzene-1,4-disulfonic acid di(potassium and/or sodium) salt (Compound II), and 2,5-bis(4-benzoylphenylmethyleneoxy) benzene-1-sulfonic acid monopotassium and/or monosodium salt.


A method for forming a pre-metallization layer on an underlying micro-structure, and a corresponding micro-structure formed by the method. The micro-structure may be a semiconductor circuit and/or a Micro-Electro-Mechanical Systems (MEMS) device. A first layer of undoped silicate glass is deposited on a micro-structure. Then, a layer of phospho silicate glass is deposited on the first layer of undoped silicate glass. This combination is then densified by applying a temperature to the combination that is sufficient to densify the layer of phospho-silicate glass, while being below the glass flow temperature. After densification, a second layer of undoped silicate glass is deposited on the densified layer of phospho silicate glass. Finally, the upper surface of the second layer of undoped silicate glass is polished using a chemical mechanical polishing process. The result is a dielectric layer of high density and low stress, and that reduces soft errors and defects.

1. The Field of the Invention
The present invention relates generally to micro-structure manufacturing technology. More specifically, the present invention relates to a method and mechanism for manufacturing a pre-metal dielectric layer that is resistant to soft errors and defects.
2. Background and Relevant Art
Manufactured micro-structures are playing an ever more important role in the advancement of civilization. Such micro-structures may include, for example, semiconductor circuits, which are present in almost every device or system that implements some form of electronic logic or function. Micro-structures may also include Micro-Electro-Mechanical Systems (MEMS) devices. Such MEMS devices may include, for example, microscopic devices that accomplish some function using electrical and mechanical principles. General examples of conventional MEMS devices include micro-sensors, micro-motors, micro-gears, or the like. MEMS devices may be manufactured using semiconductor material or non-semiconductor materials.
In recent generations, feature dimension sizes have become smaller and smaller, both for semiconductor circuits and MEMS. Furthermore, the number of metallization layers in a typical semiconductor circuit has increased in order to provide as much circuitry per unit area of die space. In order to selectively isolate the various metallization layers, a dielectric material is typically formed between the metallization layers, with conductive vias formed at the points where connections are desired. In addition, proper selective isolation from the underlying substrate (e.g., a semiconductor wafer) is achieved by fabricating a pre-metallization dielectric layer over the wafer prior to fabricating any metallization layers. Once again, appropriate conductive vias are formed to provide appropriate electrical connections with the underlying substrate.
In order to promote structural integrity and thus reduced defects in the fabricated micro-structure, it is important that each layer be manufactured upon a smooth and flat surface. Accordingly, after manufacturing each dielectric layer (both the pre-metallization dielectric layer and any inter-metallization dielectric layers) it is important to planarize the surface of the dielectric layer prior to forming other structures on top of that surface.
Chemical Mechanical Polishing (CMP) technology combines chemical and mechanical effects to polish the surface of a dielectric layer to be relatively smooth. However, even with such CMP technology, scratching of the dielectric layer surface may occur, thereby introducing non-flat features onto the top surface of the dielectric layer. Such scratches may significantly increase the defects in the finished micro-structure.
One cause of scratching is from the intrinsic stress of the dielectric material. If the dielectric material has intrinsic tensile stress, the dielectric surface will have some concavity, with the level of concavity being dependent on the magnitude of the tensile stress. Similarly, if the dielectric material has intrinsic compressive stress, the dielectric surface will have some convexity, with the level of convexity being dependent on the magnitude of the compressive stress. Such concavity or convexity in the top surface of the dielectric layer means that the more elevated portions of the top surface are more roughly engaged with the CMP polishing pad than other portions of the top surface. This causes the elevated portions to be more susceptible to scratching.
Some dielectric materials use dopants such as boron in order to reduce the flow temperature of the dielectric material. Thus, lower temperatures may be applied to the wafer and allow gravity to flatten the top surface of the dielectric material, to thereby avoid the CMP process. It is desirable to lower the flow temperature since higher temperatures can cause unwanted diffusion to occur thereby changing the electrical or mechanical characteristics of the micro-structure.
However, the use of boron dopants presents some reliability problems, especially for electronic circuitry. Specifically, boron easily decays. When boron10 atoms are struck by photons having certain energy levels, the boron nucleus splits releasing a Lithium nucleus, an alpha particle, and a neutron. The occurrence of these particles can affect the electrical characteristics of any surrounding circuitry. Errors caused by this decay are called "soft errors". Boron dopant decay has been shown to be a source of soft errors in a variety of memories and logic circuitry.
Another important property of a dielectric material is that it be uniformly dense. This is because via holes are often etched through the dielectric material in order to later form conductive vias needed for electrical connections between metallization layers, or with the underlying substrate. However, the etch rate of the dielectric material is a strong function of the density of the material. Accordingly, uniform density of the dielectric material means that the via holes are relatively uniformly etched. This uniform density thereby reduces defects due to incomplete via holes causing an undesigned open circuit.
One conventional technology that achieves highly uniform density involves the use of BoroPhosphoSilicate Glass (BPSG) as the pre-metallization dielectric layer. With the application of heat in the range of from 800 degrees Celsius to 1000 degrees Celsius, the BPSG glass will flow to fill in gaps in the underlying structure with uniform density. Such temperatures do not cause significant adverse diffusion that could degrade the function of the structure. However, the use of BPSG glass has at least two disadvantages.
First, although the density is uniform, its density is also low, which makes the material susceptible to scratching. For example, FIG. 3 shows a cross sectional view of a BPSG pre-metallization dielectric layer with several fractures induced by scratches in its top surface. These scratches may also cause electrical failure. For example, FIG. 4 shows a top view of a BPSG pre-metallization dielectric layer with several dispersed tungsten vias. Between two of the vias, an arching micro-scratch has been inadvertently filled with tungsten, thereby causing an undesigned short between two of the vias. The reduction of scratching would improve the yield in fabrication of the micro-structure.
Second, the presence of the boron material in the BPSG dielectric material may cause the soft errors mentioned above, thereby adversely affecting the electrical performance of any surrounding circuitry.
More recently, High Density Plasma (HDP) Chemical Vapor Deposition (CVD) has been used to form the pre-metallization dielectric layer. This technology allows for the deposition of a dielectric material that fills gaps in the underlying structure, without applying heat, and without the use of dopants. Furthermore, the resulting dielectric material has increased film density, thereby improving its resistance to scratching. However, capital equipment needed to perform HDP CVD processes is expensive. Furthermore, this technology is relatively new, which translates to higher defectivity due the lack of technological maturity. In addition, the use of HDP as the deposition mechanism in active areas may cause plasma-induced damage to the surrounding structure.
Accordingly, what would be advantageous are methods and mechanisms for forming a pre-metallization layer of high density and lower stress, with reduced soft errors, at temperatures that would not cause significant adverse diffusion, and that do not rely on expensive and potentially damaging HDP CVD processes.

Methods for manufacturing a soft error and defect resistant pre-metal dielectric layer


A method of driving a parallel-plate variable micro-electromechanical capacitor includes establishing a first charge differential across first and second conductive plates of a variable capacitor in which the first and second conductive plates are separated by a variable gap distance, isolating the first and second plates for a first duration, decreasing the charge differential to a second charge differential which is less than the first charge differential and in which the second charge differential corresponds to a second value of the variable gap distance.

Micro-electromechanical systems (MEMS) are systems which are developed using thin film technology and which include both electrical and micro mechanical components. MEMS devices are used in a variety of applications such as optical display systems, pressure sensors, flow sensors, and charge control actuators. MEMS devices use electrostatic force or energy to move or monitor the movement of micro-mechanical components. In one type of MEMS device, to achieve a desired result, a gap distance between electrodes is controlled by balancing an electrostatic force and a mechanical restoring force. Typically, digital MEMS devices use two discrete gap distances while analog MEMS devices use variable gap distances.
Such MEMS devices have been developed using a variety of approaches. In one approach, a deformable deflective membrane is positioned over an electrode and is electrostatically attracted to the electrode. Other approaches use flaps or beams of silicon or aluminum, which form a top conducting layer. With optical applications, the conducting layer is reflective while the deflective membrane is deformed using electrostatic force to direct light, which is incident upon the conducting layer.
One approach for controlling the gap distance between electrodes is to apply a continuous control voltage to the electrodes, wherein the control voltage is increased to decrease the gap distance, and vice-versa. However, this approach suffers from electrostatic instability that greatly reduces a useable operating range over which the gap distance can be effectively controlled. In addition, the speed with which the gap distance may be changed depends primarily on the physical characteristics of the MEMS device. When the voltage is changed, the gap distance between the electrodes lags the change of voltage as the MEMS device settles to its final position.

System and a method of driving a parallel-plate variable micro-electromechanical capacitor

Hewlett-Packard Development Company, L.P.


A system is disclosed for a four-stroke internal combustion engine comprising: at least two cylinders; a fuel direct injection device; a variable valve timing system; an engine controller to control valve timing according to load; wherein, below a lower load threshold, a first cylinder is deactivated, an injection of fuel takes place into a combustion chamber of the first cylinder and an inlet valve of the first cylinder is open during a compression stroke. The opening of the inlet valve during a compression stroke of the first cylinder when deactivated allows the substantially homogenous air-fuel mixture therein to escape into the intake manifold and be made available to the second and active cylinder.

Internal combustion engines, in particular internal combustion engines that are used in motor vehicles may be equipped with a fuel injection system. In particular in the case of gasoline injection for applied-ignition engines, a distinction is made between intake pipe injection (also referred to as port injection), in which the injection valve is situated in the intake pipe upstream of an inlet valve of the respective cylinder, and direct injection, in which the fuel is injected directly into the cylinder. Intake pipe injection permits simple production of a homogeneous fuel-air mixture which is introduced into the combustion chamber of the cylinder.
Direct injection may permit different forms of combustion. Firstly, it is possible for a stratified charge to be produced in the combustion chamber of the cylinder, whereby the engine may, in the part-load range, be operated with high efficiency with a "lean" mixture. Secondly, it is also possible for a homogeneous fuel-air mixture to be produced in the combustion chamber, which may be optimal in the full-load range. To permit both combustion with a stratified "lean" mixture and also with a homogeneous mixture, complex interaction is required between the injection nozzle, the geometry of the combustion chamber, the location of the ignition spark and the flow of the gas introduced into the combustion chamber. As a result of realizing different forms of combustion, internal combustion engines with direct injection may more efficiently utilize fuel. A motor vehicle operated using an internal combustion engine with direct injection therefore may exhibit lower fuel consumption than a motor vehicle with a corresponding internal combustion engine with intake pipe injection.
At the transition between the different forms of combustion that may be realized by a direct injection device, provision may be made to ensure the stability of the combustion. Furthermore, different forms of combustion may keep the particle formation in the exhaust gas adequately low both with regard to soot mass and soot particle count such that no particle filter may be used in order to adhere to the applicable exhaust-gas regulations. For this purpose, it is known to provide not only the injection system for the direct injection into the combustion chamber but also a further injection system for an intake pipe injection. A combination of intake pipe injection and direct injection may make it possible to ensure both the stability of the combustion and also an adequate suppression of the soot formation in the exhaust gas. Owing to the plurality of injection systems, however, such a combination of intake pipe injection and direct injection may involve considerable outlay.
It is also known, in order to reduce fuel consumption in the part-load range, for individual cylinders to not be utilized for power generation (selective cylinder deactivation). U.S. 2005/0011485 A1 describes a heavy-duty engine in which, at low load, cylinders can be selectively deactivated. To avoid pumping losses, the inlet valve and the outlet valve of a deactivated cylinder remain closed. This does not permit an adequate reduction of soot formation with simultaneously efficient fuel utilization in different load ranges.
The inventors herein recognize the abovementioned disadvantages and disclose a system and method for the reduction of pumping losses and soot formation with selective cylinder deactivation. A four-stroke internal combustion engine which is operated or controlled in accordance with the disclosure has a multiplicity of cylinders, a fuel direct injection device and a selective cylinder deactivation device. The internal combustion engine is in particular an applied-ignition engine. The internal combustion engine has an injection system which, for each cylinder, comprises at least one injection nozzle for the direct injection of fuel into the combustion chamber of the respective cylinder. The injection system may furthermore comprise one or more injection pumps and corresponding lines and a controller for the control of the injection valves and of the pump or pumps. The internal combustion engine furthermore has a selective cylinder deactivation device, and it is thus possible for one or more cylinders to not be utilized for power generation in the part-load range; the fuel consumption of the internal combustion engine in the part-load range can thus be reduced. It is in particular the case that the injection system is correspondingly designed for realizing the selective cylinder deactivation.
According to the disclosure, in a load transition range of the internal combustion engine, during a compression stroke of a first cylinder which is not utilized for power generation, that is to say which is "deactivated", fuel is injected into a combustion chamber of the first cylinder. The load transition range is in particular a medium-load range which is passed through upon the transition from a part-load range to a full-load range of the internal combustion engine or, conversely, from a full-load range to a part-load range of the internal combustion engine. The injection of fuel takes place in particular during a time period which is short in relation to the duration of the compression stroke, that is to say in relation to the duration of the upward movement of the piston, and said injection of fuel may for example take the form of a main injection or be similar to a main injection of an injection process broken down into multiple partial injections.
Furthermore, according to the disclosure, an inlet valve of the first cylinder is open during the compression stroke in order to make the fuel-air mixture produced by the fuel injection available to a second cylinder, which is utilized for power generation and which is thus not deactivated, for the intake or charge of the combustion chamber of the second cylinder. For this purpose, the inlet valve is open for a period of time which is at least partially subsequent to the fuel injection. The mixture produced by the fuel injection, in particular a fuel-air mixture composed of the air supplied into the combustion chamber and the fuel injected into said combustion chamber, can therefore pass into an intake tract of the internal combustion engine and out of said intake tract into the second cylinder which is utilized for power generation. Within the context of the present disclosure, "intake tract" refers to a region of the internal combustion engine from which the second cylinder is filled with gas, in particular an intake manifold or an intake pipe of the second cylinder. In the case of a supercharged engine, the intake tract may be at elevated pressure, and if an exhaust-gas recirculation system is provided, it may also be possible for a mixture of air and recirculated exhaust gas to be available in the intake tract for the charging of the cylinders. The first cylinder may also be charged from the intake tract. As a result of the compression movement of the piston of the first cylinder, the mixture is forced out of the combustion chamber of the first cylinder into the intake tract and onward into the combustion chamber of the second cylinder. Here, the second cylinder may be operated in the normal mode and thereby contributes to the generation of the mechanical power of the internal combustion engine and to the drive of the first cylinder which is not utilized for power generation. Since the first cylinder is deactivated, the mixture produced in the first cylinder is not ignited, and it is preferably the case that no further injection takes place during the compression stroke after the closing of the inlet valve. The internal combustion engine may comprise further cylinders which can be deactivated or utilized for power generation.
By virtue of the fact that, during a compression stroke of a cylinder which is not utilized for power generation, an injection of fuel takes place into a combustion chamber of the cylinder and an inlet valve of the cylinder is open for the purpose of making the mixture produced therein available to a further cylinder which is utilized for power generation and which is in particular operated in the normal mode, it is made possible for an already substantially homogeneous mixture to be introduced into the second cylinder, into which mixture a further injection of fuel may take place if appropriate. In this way, it is possible both for the stability of the combustion to be increased and also for the soot generation to be reduced, without an intake pipe injection device having a dedicated injection valve or injection system. In this way, it is made possible in a simple manner to increase the quality of the combustion and in particular the exhaust-gas quality, while realizing efficient fuel utilization. According to the disclosure, therefore, selective cylinder deactivation and variable inlet valve actuation are combined with one another to attain the advantages of selective cylinder deactivation with regard to fuel consumption but also to permit the operation of the non-deactivated cylinders with reduced soot formation.
A system is disclosed for a four-stroke internal combustion engine comprising: at least two cylinders; a fuel direct injection device; a variable valve timing system; an engine controller to control valve timing according to load; wherein, below a lower load threshold, a first cylinder is deactivated, an injection of fuel takes place into a combustion chamber of the first cylinder and an inlet valve of the first cylinder is open during a compression stroke. The opening of the inlet valve during a compression stroke of the first cylinder when deactivated allows the substantially homogenous air-fuel mixture therein to escape into the intake manifold and be made available to the second and active cylinder.
The above advantages and other advantages, and features of the present description will be readily apparent from the following Detailed Description when taken alone or in connection with the accompanying drawings.
It should be understood that the summary above is provided to introduce in simplified form a selection of concepts that are further described in the detailed description. It is not meant to identify key or essential features of the claimed subject matter, the scope of which is defined uniquely by the claims that follow the detailed description. Furthermore, the claimed subject matter is not limited to implementations that solve any disadvantages noted above or in any part of this disclosure. Further, the inventors herein have recognized the disadvantages noted herein, and do not admit them as known.

Method and device for controlling a four-stroke internal combustion engine


The present invention relates to an anti-idiotype antibodies directed against the monoclonal antibody (HmenB3) to Neisseria meningitidis serogroup B and hybridomas producing the anti-idiotype antibodies. This invention is also directed to vaccine compositions comprising the anti-idiotypic antibodies in combination with pharmaceutically acceptable carriers. These vaccine compositions can be used to prevent or treat the serogroup B meningococcal disease.

Despite the availability of effective antibiotics, bacterial meningitis is still a devastating disease that threatens the lives of children and young adults. The case fatality rate of bacterial meningitis is very high, approximately 20%, with rapid clinical progression upon following infection, and many patients who recover are left with neurological sequelae. Although there are racial and geographical differences, meningitis due to N. meningitidis remains a leading cause of bacterial meningitis in the world, which includes the United States and European countries (Rosenstein, N. E., et al., N Engl J Med 344, 1378-1388. (2001)).
The complete genomes of both N. meningitidis serogroup A and B has been sequenced respectively (Parkhill, J., et al., Nature 404, 502-506. (2000); and Tettelin H, S. N., et al., Science 287, 1809-1815 (2000)). N. meningitidis is one of the most common causes of bacterial meningitis and is divided into 13 serogroups based on chemically and immunologically distinct capsular PSs. Five serogroups, designated A, B, C, Y, and W-135, has been classified as pathogens in humans. However, meningococcal group B strain accounts for approximately 50% of bacterial meningitis (Ala'Aldeen , D. D. A., et al., Journal of Infection 33, 153-157 (1996); Riedo, F. X., et al., Pediatr Infect Dis J 14, 643-657 (1995); and Rosenstein, N. E., et al., N Engl J Med 344, 1378-1388 (2001)). In comparison to other serogroups, serogroup B meningoccal disease is more prevalent in North America and Europe, for unknown reasons. This creates a public health problem in the United States and Europe.
To date, PS-based conjugate vaccines have failed due to the poor immunogenicity of the capsular PS of NMGB. NMGB PS is a homolinear polymer of N-acetyl (2-8) neuraminic acid, and is structurally similar to polysialic acid of neural cell adhesion molecules expressed in human neuronal tissue (Finne, J., et al., Lancet 2, 355-357 (1983)). Thus, NMGB PS has the potential to induce autoantibodies and lead to autoimmune responses (Finne, J., et al., J Immunol 138, 4402-4407 (1987); and Nedelec, J., et al., J Neuroimmunol 29, 49-56 (1990)). Therefore, such problems make it difficult to develop a vaccine against NMGB.
In an attempt to circumvent this problem, Jennings reported an innovative strategy for overcoming the poor immunogenicity to NMGB PS and the cross-reactivity to NCAM, by substitution of N-propionyl for N-acetyl groups of NMGB PS (Jennings, H. J., et al., JEM 165, 1207-1211 (1987)). N-propionyl neuraminic acid polymer is reported to induce antibodies that cause bacteriolysis in vitro, but a subset of antibodies elicited by N-propionyl neuraminic acid have anti-host antibody activity (Granoff, D. M., et al., Journal of Immunology 160, 5028-5036 (1998); and Pon, R. A., et al., J Exp Med 185, 1929-1938 (1997)). This has made a problem in vaccine stability.
Studies using anti-idiotypic antibodies have focused mostly on increasing the immune response to tumor specific antigens, which do not elicit effective immune response due to their poor immunogenicity, and on the production of bacterial vaccine. For example, anti-idiotypic antibody to the capsular PS of N. meningitidis serogroup C was prepared and immunization of its anti-idiotypic peptide conjugated with carrier protein could elicit Ab to kill the bacteria (Westerink, M. A. J., et al., Proc Natl Acad Sci USA 92, 4021-4025 (1995)). A further example is that the immunization of mice with bacteriophages containing single chain variable fragment (scFv), which was obtained from anti-idiotypic antibody to Streptococcus pneumoniae, showed protective effect against bacterial infection (Magliani, W., et al., Nat Med 4, 705-709 (1998)).
Based on the above references, this inventor developed anti-idiotypic antibody using the properties of HmenB3 in order to provide a vaccine capable of protecting against and treating group B meningococcal disease (Shin, J. S., et al., Infect Immun 69, 3335-3342 (2001)). HmenB3 is a MAb against NMGB PS, which kills NMGB and has no cross-reactivity to NCAM (Shin, J. S., et al., Infect Immun 69, 3335-3342 (2001)).

Vaccine composition for preventing meningococcal disease


Catalytic multiphase reactions are conducted by a process, comprising:

1. Field of the Invention
The present invention relates to a process for conducting catalytic multiphase reactions in a tube reactor. More particularly, the invention relates to a method of preparing vinyl esters by reaction of carboxylic acids with acetylene. Furthermore, the invention relates to the use of the vinyl esters.
2. Description of the Background
Vinyl esters are building blocks for the preparation of copolymers. Vinyl esters of particular industrial importance include those of tertiary C10 acids and also those of tertiary C9 acids. These vinyl esters can be copolymerized with vinyl acetate and then serve as a component for paints. Other vinyl esters of importance include those of 2-ethylhexanoic acid, of isononanoic acid, but also of lauric and stearic acids, for example for the production of adhesives.
The reaction of carboxylic acids with acetylene to form vinyl esters has been known for a long time (e.g. G. Hxc3xcbner, Fette, Seifen, Anstrichm, 68, 290 (1966)), and a review of currently used processes may be found, for example, in Ullman""s Encyclopedia of Industrial Chemistry, Fifth Completely Revised Edition, Volume A2, 430-434.
The reaction of acetylene and vinyl esters can be described by the reaction equation:
Rxe2x80x94COOH+C2H2xe2x86x92Rxe2x80x94COOxe2x80x94CHxe2x95x90CH2.
As catalyst, use is usually made of the zinc salt of the carboxylic acid to be reacted, dissolved in excess carboxylic acid (DE 1238010, DE 1210810). In another method, the reaction is carried out in a paraffinic solvent which has a boiling point higher than the reaction temperature to be employed (e.g paraffin oils) and the concentration of carboxylic acid is to be kept below 5% by weight and the zinc content is to be kept in the range from 0.5-5% by weight, based on the reaction solution. The temperatures employed are generally above 200xc2x0 C., typically from 220-295xc2x0 C. A considerable molar excess of acetylene over the carboxylic acid to be vinylated has to be employed; values of 5-20 mol. of acetylene per mol. of carboxylic acid to be reacted are typical. This means a high circulation of acetylene with the vinyl ester and unreacted carboxylic acid being discharged with the waste gas as a function of their partial vapor pressure, subsequently condensed and separated from one another by distillation.
The formation of low-boiling by-products such as acetaldehyde can lead to resinification of the catalyst. Furthermore, the formation of high boilers due to polymerization of the vinyl ester formed and also the formation of carboxylic anhydrides which no longer participate in the reaction can lead to a reduction in conversion. This can be corrected only by discharging part of the reaction solution or the zinc salt melt, which in turn requires introduction of fresh catalyst. In the examples in DE 1 237 557, it can be seen that at an appropriately high molar excess of acetylene over carboxylic acids of from 5:1 to 20:1, selectivities of from 74.3 to at most 96.1% are achieved. This corresponds to formation of from 3.9-25.7% of by-products.
In engineering terms, the preparation of vinyl esters is a two-phase reaction in which the acetylene forms the gas phase, and the catalyst phase, the carboxylic acid to be reacted, the vinyl ester and any inert solvent form the liquid phase. In order to achieve high conversions, it is, therefore, necessary to employ measures to bring the phases into intimate contact with one another. Such gas-liquid reactions are customarily carried out in bubble columns or stirred reactors. Trickle reactors are also mentioned in the literature. High pressures are specifically not wanted in reactions with acetylene, since acetylene tends to undergo autodecomposition and a gauge pressure of 300 mbar (absolute pressure=1.3 bar) must not be exceeded in the case of pure acetylene. This considerably narrows the choice of reactor. Thus, only short bubble columns or stirred reactors having a small height can be used for the vinylation, since even the static pressure of the liquid can require an acetylene admission pressure of greater than 300 mbar. In addition, the high acetylene circulations which may be necessary require continual recompression of the acetylene.
An alternative is the use of more highly compressed acetylene, in which case the decomposition limit has to be lowered by addition of large proportions of inert gases such as nitrogen. This measure leads to problems in the removal of the tailgas and is also not unproblematical in terms of safety.
For this reason, other processes which avoid or reduce these drawbacks have been developed. Thus, EP 0 622 352 uses platinum metal complexes (in particular those of ruthenium) as catalysts for the preparation of vinyl esters, by means of which the reaction temperature was able to be reduced significantly. However, this process is also preferably carried out at a molar ratio of acetylene/carboxylic acid of from 1.5:1 to 10:1 and at acetylene pressures of from 15-20 bar in order to achieve satisfactory space-time yields. The high price of noble metal compounds necessitates complete circulation of the catalyst without it being decomposed or lost by unintended discharges. A further example of the ruthenium-catalyzed preparation of vinyl esters is given in U.S. Pat. No. 5,430,179.
A completely different process for preparing vinyl esters is transvinylation. Here, an industrially readily available vinyl ester such as vinyl acetate is reacted with the acid to be vinylated in the presence of noble metal catalysts such as Li2PdCl4, forming an equilibrium mixture of vinyl acetate, acetic acid, the carboxylic acid to be reacted and its vinyl ester. Problems here are the difficulty and expense of separating the equilibrium mixtures, the price of vinyl acetate and the formation of contaminated acetic acid.
Taking into account all advantages and disadvantages, the vinylation of carboxylic acids using acetylene in the presence of zinc salts as catalysts, i.e. a multiphase reaction, is on balance the most economical and industrially simplest process.
In the following, the term multiphase reactions is used to describe reactions which proceed with participation of two or more immiscible or only partially miscible fluid phases. This encompasses, for example, reactions between a gas phase and a liquid phase (gl) as in the reaction of acetylene with a carboxylic acid, but also reactions between two liquid phases which are immiscible or have a miscibility gap under the prevailing reaction conditions (ll) and reactions in which both two liquid immiscible or only partially miscible phases and a gas phase participate (gll).
Examples of industrially important gas-liquid reactions (gl) are, apart from the reaction of acetylene with carboxylic acids under consideration here, hydrogenations using homogeneously dissolved catalysts, oxidations using air or oxygen and the hydroformylation of olefins.
Multiphase reactions are generally associated with a series of problems which makes their engineering design significantly more difficult than is the case for simple homogeneous reactions. A few typical problems are described below:
In all cases, the materials have to be brought into very intimate contact with one another in order to minimize the problem of mass transfer: it is necessary to generate a mass transfer area a, between the phases which is as large as possible. On the other hand, the phases have to be able to be separated easily again after the reaction is complete: excessive mixing can lead to problems here. In the presence of two liquid phases, emulsion formation can occur, while in the case of gas-liquid processes it is possible for foaming to occur. In the case of the 3-phase processes mentioned, it is even possible for all of the problems to occur simultaneously.
Apart from a high mass transfer area as, a very high mass transfer coefficient kit should be achieved in all multiphase reactions. Overall, the KLA value, i.e. the product of kl and as in the mass transfer equation
j=kl*as*(C*xe2x88x92C)
where:
j [mol/s]: the molar flow of reacting component through the phase interface (e.g. entry of acetylene into the catalyst phase),
kl [m/s]: mass transfer coefficient,
as [m2]: phase interface area in the reactor,
C* [mol/m3]: maximum solubility of the starting material in the second phase (e.g. acetylene in the catalyst phase) and
C [mol/m3]: actual concentration of the starting material which in turn is coupled to the reaction rate,
should be a maximum.
In view of the above, there is a need for a process for carrying out multiphase reactions which avoids the abovementioned disadvantages and can also be implemented in a simple manner.
Accordingly, one object of the present invention is to provide a process for conducting multiphase reactions which is suitable, in particular, for the preparation of vinyl esters by catalyzed reaction of carboxylic acids with acetylene.
Briefly, this object and other objects of the present invention as hereinafter will become more readily apparent can be attained by a process for conducting catalytic multiphase reactions, comprising:
conducting the catalytic multiphase reactions in a tube reactor, wherein the catalyst is present in the continuous phase and at least one starting material is present in a dispersed phase and the loading factor B of the tube reactor is equal to or greater than 0.8.

Process for carrying out catalytic multiphase reactions, in particular vinylations of carboxylic acids


A decimator for use in digital signal processing has an input line for receiving a sequence of input samples at a first sampling rate and a first register for accumulating input samples for which the order in the sequence is a power of a predetermined number greater than one. A control unit for outputs samples from the first register at a second sampling rate. Typically accumulates input samples for which the order in the sequence is a not power of the predetermined number so that the first register accumulates input samples for which the order of said sequence is a power of the predetermined number combined with a current accumulated value in the second register.

Digital filtering is employed in many areas, for example, in measurement systems, source coding, echo cancellation etc. A relatively common filter function is decimation.
A decimator is a structure that combines samples into a single sample. It typically consists of an electronic hardware structure (ASIC's, FPGA's and the like) or software (DSP's), and can be used in any environment where sampling is possible. The decimation function typically has two objectives, namely reduction of the number of samples and an increase in the accuracy of the samples.
Sometimes a side effect of decimation is the most useful property, namely its low pass characteristic. Fast variations between samples 'disappear', or better, average out. Although the low pass characteristic really is a side effect, it is possible to make a low pass function without reducing the number of samples.
The way that the decimation function performs this operation is relatively straightforward. The samples are mixed together and averaged. The increase in accuracy is related to averaging the spread of the samples.
In electronic and software environments such decimation is a common function, used in many applications. In these fields a few factors typically influence the decimator, typically the input sample rate, the output sample rate, and the allowable chip real estate (hardware) and time (software).
Sometimes these factors are hard to satisfy. For example, it can happen that the input rate has a large dynamic range, whereas the output does not scale along with it. Such an example can be seen in PLL's, where the reference frequency may be as low as in the Hz range, but as high as 10 GHz. Sample processing at 10 GHz is not feasible with current technologies, and only limited processing, such as counting, is really feasible. Still, up to about 1 GHz current technologies can properly handle the processing, albeit at the cost of power and complexity.
The consequence of a large dynamic range for sampling implies that a decimator function may necessarily be flexible. Normally flexibility in a decimator requires extra hardware.
A conventional decimator is a structure with a group of memory buffers. The simplest form of decimator decimates by two. A single memory stores a first sample, which is added to a second sample to yield one combined sample. The second sampler uses a slower sampling rate; twice as slow. Such a structure is shown in FIG. 1.
If the circuit needs to be expanded to three samples being combined an extra memory and an extra adder operation are added. Such an arrangement is shown in FIG. 2, which illustrates decimation by 3. The adder operation can be shared in the time domain, but that in turn requires multiplexing hardware, which requires overhead.
FIG. 3 shows a decimator that does not need to change its sample rate. In such cases it is typically difficult to share adders, unless the decimator runs at much lower speeds than the system clock.
A decimator that averages for instance 128 samples requires a lot of hardware with the above structures. It is possible to change the structure slightly, so that at least the number of adder stages is limited, as is shown in FIG. 4. This structure uses an in-between integrated value, in which each sample is added and after a delay again subtracted. Thus the contribution of a single sample is only temporary, and at the same time the number of adders is limited to two. If this structure is expanded to 128 memory locations, the number of adders does not increase. The structure allows for a high outgoing sample rate. This can be important in certain applications, although they are probably few that do not use sample rate reduction. The structure, however, has a potential flaw if the digital parts are not 100% reliable. For instance, due to the presence of an alpha particle a memory location might change, and thus make a difference between the contents of the memory delay line and the extra integrator. This is unavoidable, and can only be repaired at high extra hardware or software cost. The structure can easily extended to any number of stages.
There is another problem with this structure, and that is the output divider. Only representations that fit well with the division are simple to divide. As such a ternary coding scheme allows simple division by 3. However, most digital hardware is based on binary coding, and thus is only simple to use with divisors that are powers of two; in that case the division is a simple shift, which does not cost any hardware. Most applications use division by powers of two and rate reduction. This can be achieved by using the circuit of FIG. 1 as a repeated module as shown in FIG. 5. This module can be repeated to reduce the sample rate in binary steps.
Which of the above prior art structures is most attractive for a particular application depends on many factors, and is not very easily established. Typical design factors are the process for which the design is intended, the sample rate and the sample size (wordsize). Microcontrollers and DSP's find a load of memory with a round robin structure attractive and fast; memory is low cost. Thus the structure shown in FIG. 4 is quite often most attractive. In hardware the cost of memory is typically not negligible, and the structure shown in FIG. 5 will quite often be more attractive. If the word size is very small, hardware in the form of the structure shown in FIG. 1 may in fact be quite attractive, since the total hardware size is small, even for large decimation numbers.
For all three structures, however, it is not very simple to introduce flexibility. Existing flexible structures normally use a mixed approach, as shown in FIG. 6. This module will normally be designed such that N can only take on powers of two; this somewhat limits the complexity of the module. The structure is now the same type of structure discussed, but not with rate changes of 2 per unit, but some other number N1, N2, N3 etc.
The structures that are relatively common have two or three modules, a fact which illustrates the attractiveness of this approach. The flexibility that typically is required will, even with this structure, require a considerable amount of programming of the constituent parts. In general this is highly unattractive.