A toner transportation device according to the present disclosure includes a transportation screw that has a rotational shaft and a transportation fin formed on an outer circumferential surface of the rotational shaft and a toner transportation pipe that has a circular shape in cross section. The transportation screw is rotatably positioned in the toner transportation pipe. A support member is attached to the rotational shaft that has a bearing portion having an annular shape and rotatably fitted onto the rotational shaft and that has a plurality of leg portions radially protruding outward from an outer circumferential surface of the bearing portion. A distance between an axis of the rotational shaft and a tip of each leg portion is greater than a radius of the transportation fin and equal to or less than a radius of an inner circumferential surface of the toner transportation pipe.

The present disclosure relates to toner transportation devices used in image forming apparatuses such as copiers, printers, facsimile machines, and multi-function machines that perform the functions of these devices.
In typical electrophotographic image forming apparatuses, an electrostatic latent image formed on an image carrying body such as a photoconductor drum is visualized by the developing device, typically using a powdery developer. The visualized image (toner image) is transferred to a recording medium and then fixed. Toner remaining on the surface of the image carrying body is removed by a cleaning device so as to form a new toner image. The residual toner removed by the cleaning device is stored in a waste toner bottle. When the waste toner bottle becomes full after a specified number of sheets have been printed, the user is notified of the full state, and the waste toner bottle is replaced and discarded.
A known toner transportation device uses a toner transportation path equipped with a transportation screw located in a pipe-shaped transportation path as a waste toner collection path from a cleaning device to a waste toner bottle. In such a toner transportation path, the locus of an outer circumferential edge of the transportation screw formed while the transportation screw is being rotated may become larger than the inner diameter of the transportation path due to, for example, a dimensional error in the outer diameter of the transportation screw or the inner diameter of the transportation path, or bowing of the transportation screw. In this situation, the transportation screw may not be able to rotate due to an excessive rotational load generated by friction. Thus, the outer diameter of the transportation screw is usually designed to be smaller than the inner diameter of the transportation path.
However, with such a design, there is a clearance (gap) formed between the transportation screw and the transportation path. Thus, when the transportation screw is bowed, the transportation screw swings in the radial directions (becomes eccentric) while being rotated. As a result, the transportation screw hits the inner surface of the transportation path and noise may be generated.
More specifically, when the transportation screw is bowed in a downwardly position, bending due to the weight of the transportation screw itself is added in the same direction as that of the bowing, thereby increasing the amount of deformation. In contrast, when the transportation screw is in an upwardly bowed position, bending due to the weight of the transportation screw itself acts in a direction opposite to the direction of the bowing, thereby decreasing the amount of bowing. Accordingly, when the transportation screw is rotated from the upwardly bowed position, the state of the transportation screw gradually changes from a balanced state, where the amount of deformation is small, into a state where bending due to the weight of the transportation screw increases the bowing. Thus, the transportation screw undergoes significant wave-like deformation while being rotated and hits the inner surface of the transportation path. At this time, noise generated due to the hitting becomes larger as the bowing is increased, the clearance (gap) between the transportation screw and the inner surface of the transportation path is increased, and the weight of the transportation screw is increased.
In view of the above-described situation, a proposed first exemplified toner transportation device has a portion, in which an outer edge of a spiral protrusion (spiral fin) of the transportation screw and an inner face of a cylindrical transportation path are in close proximity with each other. This allows the transportation screw to be stably rotated while part of the outer edge of the transportation screw is in contact with the inner face of the cylindrical transportation path.
A proposed second exemplified toner transportation pipe has a pipe main body having a semi-tubular portion and a semi-tubular lid body joined to the semi-tubular portion of the pipe main body. The plane where the pipe main body and the semi-tubular lid body are joined to each other is substantially flat, and the pipe main body and the tubular lid body are joined to each other by ultrasonic welding so that the toner transportation pipe has good air tightness and dimensional accuracy.
Furthermore, in a proposed third exemplified developer transportation device, a bearing that receives a shaft end portion of a transportation screw has a space so as to allow a developer to pass through the space. Thus, the developer can be smoothly transported while vibration due to rotation of the transportation screw is suppressed.
However, in the first and second examples, there is a limit in setting the clearance between the transportation screw and the cylindrical transportation path due to the dimensional tolerance of component and the assembly tolerance. When bowing of the transportation screw exceeds the clearance, the transportation screw hits the inner surface of the transportation path. Thus, the noise due to the hitting is not necessarily reliably prevented. In the first example, the portion, in which the outer diameter of the spiral fin and the inner diameter of the cylindrical transportation path are in proximity with each other, is formed over the entire periphery at a portion in the axial direction of the cylindrical transportation path. Thus, toner tends to clog the transportation path, thereby increasing the rotational load of the transportation screw. As a result, the fluidity of the toner is decreased by frictional heat, and accordingly, transportation efficiency is degraded. When the toner is left in this state for a long time, there is a possibility of the toner being caked.
With the structure of the third example, since the bearing allows the developer to pass therethrough, vibration at the end portion of the transportation screw can be suppressed. However, it is thought that the above-described deformation of the central portion of the transportation screw caused by bowing of the transportation screw and bending due to the weight of the transportation screw cannot be suppressed. Also in the third example, the bearing has an annular shape, the outer circumferential surface of which is fitted into the developer transportation path and the inner circumferential surface of which slides against a rotational shaft of the transportation screw. Thus, there is a possibility of the entire periphery of the rotational shaft rubbing against the inner circumferential surface of the bearing, thereby increasing the rotational load.
In the above-described situations, the toner transportation path equipped with the transportation screw in the pipe-shaped transportation path is used for the waste toner transportation path from the cleaning device to the waste toner bottle. However, use of the toner transportation path equipped with the transportation screw in the pipe-shaped transportation path is not limited to the waste toner transportation path. In image forming apparatuses, a toner cartridge is provided in order for a developing device to be replenished with toner. A similar situation is also observed in the situation where the toner transportation path equipped with the transportation screw in the transportation pipe is used in a toner replenishment path, which is used when the developing device is replenished with toner from a toner cartridge in accordance with the consumption of toner in the developing device.

Toner transportation device and image forming apparatus equipped with the same


A plastic container that includes a hollow container body having a body opening, a cylindrical finish wall portion surrounding the body opening and extending from the body, with external threads for receiving a closure, and a spout secured to and projecting axially from the externally threaded wall portion. The body, wall portion and spout are of as-molded one-piece or monolithic integral plastic construction. The axial dimension of the spout preferably is greater than that of the externally threaded wall portion of the container finish. The threaded wall portion or the spout has an axially oriented surface that lies in a plane perpendicular to the axis of the container finish for sealing engagement with a closure or cap that is threaded onto the container finish.

Containers constructed of a blow-molded container body with integral finish are conventional in the art. One such container is generally rectangular, and is marketed for dispensing engine oil. The container finish is offset from the centerline of the container at one edge of the top. When the closure or cap is removed from the container, the container is tipped to pour the contents into an engine opening. The recommended method of pouring the contents is with the container finish positioned remote from the engine opening, and then tipped into the opening. However, in use, consumers often position the container finish adjacent to the engine opening before tipping, which often leads to spillage.
It has also been proposed in other applications to provide a pour spout on a container finish by forming the spout in a separate operation and then securing the spout to the container finish in a suitable joining operation. It is a general object of the present invention to provide a container having a finish and pour spout of integral or one-piece construction as molded. Another object of the present invention is to provide a method of constructing such an integral plastic container having a sealing surface on the pour spout or the threaded finish for sealing engagement with a closure. A further object of the present invention is to provide a container and closure package that embodies a container of the described character.
In accordance with one aspect of the present invention, there is provided a method of making a plastic container that includes integrally molding a container body having an opening, an externally threaded cylindrical finish portion extending from the body surrounding the opening, and a spout extending from an end of the threaded portion remote from the container body. The container body, threaded finish and spout preferably are integrally molded in a single blow-molding operation. The spout in the preferred embodiments extends from the container-remote end of the threaded portion of the finish, which is to say that the spout forms an integrally molded axial extension of the threaded portion of the finish. The spout is preferably coaxial with the threaded cylindrical portion of the container finish, and is of either cylindrical construction or conical construction narrowing away from the container body. In the preferred method of the invention, an area of the spout or the threaded cylindrical portion of the container finish is machined following the blow-molding operation to provide an axially oriented surface, either at the free end of the spout or at the upper edge of the threaded portion of the container finish surrounding the spout, for sealing engagement with a closure threaded onto the container finish.
In accordance with another aspect of the present invention, there is provided a plastic container that includes a hollow container body having a body opening, a cylindrical finish wall portion surrounding the body opening and extending from the body, with external threads for receiving a closure, and a spout projecting axially from the externally threaded wall portion forming a continuation or extension of the threaded wall portion. The body, wall portion and spout are of integrally molded plastic construction, which is to say that the body, finish and spout are of as-molded one-piece integral construction, as distinguished from being molded or formed as multiple pieces that are joined together. The axial dimension of the spout preferably is greater than that of the externally threaded wall portion of the container finish. The threaded wall portion or the spout has an axially oriented surface that lies in a plane perpendicular to the axis of the container finish for sealing engagement with a closure that is threaded onto the container finish. The container body is of generally rectangular geometry, with the finish and spout being positioned at an edge of one end.
In accordance with a third aspect of the present invention, there is provided a container and closure package that includes an as-molded integral container body, finish and spout as previously described, and a closure having internal threads axially received over the external threads on the container finish in sealing engagement with the spout or the threaded wall portion of the container finish.

Molded plastic container and container package with integral pour spout


A fully automatic coil binding machine includes a main body, a width adjusting device, a paper clamping device, a resting device, a coil driving device, a cutting device and a driving device. The main body has a coil guiding slot and a guiding row of teeth. The width adjusting device may be used to adjust the width of the coil guiding slot. The paper clamping device has a paper slot, in which a stack of paper may be placed. The binding edge of the stack of paper may rest on the resting device, so that its curvature may be adjusted. The coil driving device may move the coil located in the coil guiding slot along the guiding row of teeth into the paper slot and drive the coil to spin through the holes of the stack of paper.

1. Field of the Invention
The invention generally relates to a coil binding machine. More particularly, the invention relates to a fully automatic coil binding machine.
2. Description of the Prior Art
In the regular coil binding process, first, a row of holes are punched in a stack of paper and then a coil is inserted through the holes. Last, the two ends of the coil are cut up.
As of now, there are two methods to carry out coil binding process: by pure manual labor and by machine. If it is carried out by pure manual labor, such method takes too much time and manpower and hence can not be used to carry out the binding for a large amount of books. Therefore, machine must be used to carry out the binding of a large amount of books. However, in the binding process by machine, the coil can not spin through the holes smoothly because the holes are not oriented at appropriate angle and curvature; therefore, such angle and curvature have to be manually formed at the binding edge before the coil spin through the holes, lowering the speed in the binding process and often resulting in inaccuracy in such angle and curvature.


A lithium ion secondary battery includes a positive electrode, a negative electrode, and an electrolytic solution. The positive electrode contains a lithium composite oxide. The negative electrode contains a material including at least one of silicon Si and tin Sn as a constituent element. The lithium composite oxide includes lithium Li having a composition ratio a, a first element having a composition ratio b, and a second element having a composition ratio c as a constituent element. The first element including two kinds or more selected from among manganese Mn, nickel Ni, and cobalt Co, and including at least manganese. The second element including at least one kind selected from among aluminum Al, titanium Ti, magnesium Mg, and boron B. The composition ratios a to c satisfy the relationships of 1.1<a<1.3, 0.7<b+c<1.1, 0<c<0.1, and a>b+c.

The present disclosure relates to a lithium ion secondary battery using a lithium composite oxide as a positive electrode active material of a positive electrode, an electric tool, an electric vehicle, and a power storage system which use the lithium ion secondary battery.
In recent years, a small-sized electronic apparatus represented by a portable terminal device or the like has become widespread, and a further reduction in size and weight, and a long operation lifespan are strongly demanded. Along with this, a development of a battery as a power source, particularly, a secondary battery, which is small in size and is light in weight, and which can obtain a high energy density, has been progressed. In recent years, this secondary battery has been reviewed for an application for use in a large-sized electronic apparatus such as a vehicle while not being limited to a small-sized electronic apparatus.
As secondary batteries, secondary batteries using various charge and discharge principles have been widely proposed, but among these, a lithium ion secondary battery using occlusion and emission of lithium ions has attracted attention. This is because an energy density higher than that in a lead battery, a nickel-cadmium battery, or the like, can be obtained.
The lithium ion secondary battery includes a positive electrode, a negative electrode, and an electrolytic solution, and the positive electrode and the negative electrode include a positive electrode active material and a negative electrode active material that occludes and emits lithium ions, respectively. As the positive electrode active material, a lithium composite oxide including lithium and a lithium transition metal as a constituent element has been widely used. The selection of the positive electrode active material that is directly related to a charge and discharge reaction has a large effect on a battery performance, such that various studies have been undertaken with respect to the composition of the lithium composite oxide.
Specifically, to obtain a large capacity and a high potential, and to improve charge and discharge cycle characteristics, there is proposed a method in which a lithium composite oxide expressed by LiaMIbMIIcOd (MI includes Mn, Ni, Co, or the like, MII includes Al or the like, 1.1<a<1.5, 0.9<b+c<1.1, 1.8<d<2.5) is used (for example, refer to a specification of Japanese Patent No. 3873717). However, a composition ratio (Li/the sum of MI and MII) of Li with respect to the sum of MI and MII is larger than 1 in a mole ratio.
To ameliorate a loss of a positive electrode capacity caused by an irreversible capacity of an Si-based or Sn-based negative electrode active material, and to sufficiently utilize a high capacity characteristic of the negative electrode active material, there is proposed a method in which a lithium-rich lithium composite oxide expressed by LihMniCojNikO2 is used (for example, refer to Japanese Unexamined Patent Application Publication No. 2009-158415). Here, h=[3(1+x)+4a]/3(1+a), i=[3α(1+x)+2a]/3(1+a), j=β(1−x)/(1+a), k=γ(1−x)/(1+a), 0<a<1, α>0, β>0, γ>0, α+β+γ=1, 0≦x<1/3. This composite oxide is a solid solution expressed by Li1+x(MnαCoβNiγ)1-xO2.aLi4/3Mn2/3O2. However, the cycle characteristics are not sufficiently satisfied.

Lithium ion secondary battery, electric tool, electric vehicle, and power storage system


A method paring a stable, dilute aqueous solution of at least one 3-isothiazolone compound comprising 5-chloro-2-methyl-3-isothiazolone, the concentration of said compound(s) in said solution being about 0.5 to 5% by weight based on solution, comprising introducing about 0.1 to 5% by weight based on said solution, of a ferric salt as the stabilizer is disclosed. Dilute aqueous solutions of about 0.5 to 5.0 parts by weight of at least one 3-isothiazolone compound comprising 5-chloro-2-methyl-3-isothiazolone, about 0.1 to 2.5 parts by weight of a stabilizing, water soluble, non-chelated ferric salt, and about 92 to 99 parts by weight of aqueous solvent, are also disclosed.

1. Field of the Invention
This invention relates to stabilization of 3-isothiazolone compounds present in the form of dilute aqueous solutions.
2. Description of the Prior Art
3-Isothiazolone compounds (hereafter "active ingredient" or AI) are a very important class of microbicides. Several species have been commercialized and are widely used to inhibit the growth of bacteria, fungi and algae. Among the most important species are 2-methyl-3-isothiazolone ("MI"), 5-chloro-2-methyl-3-isothiazolone ("CMI"), and especially mixtures thereof. A 3/1 weight ratio mixture of CMI and MI is used in a wide variety of commercial applications around the world. CMI is naturally unstable and much research has been devoted to stabilizing it in four separate classes of environments: (1) the isolated compound itself; (2) "concentrates" which are about 14 to 25% by weight aqueous solutions of the AI; (3) "dilute solutions" which are about 1 to 5% by weight aqueous solutions of the AI and which are designed to be diluted further when added to a locus; and (4) "use dilutions" which are the end use dilution in the locus to be protected and comprise substantially less than 1% by weight AI.
To stabilize the isolated compound (1), U.S. Pat. No. 4,150,026 teaches making metal salt complexes of isothiazolones. These complexes are taught to greatly enhance the thermal stability of solid isothiazolones, compared to the corresponding uncomplexed isothiazolones. No mention is made regarding the stabilization of aqueous solutions of isothiazolones, i. e., (2) or (3), or the use dilutions (4), against chemical decomposition of the AI.
U.S. Pat. No. 3,870,795 teaches the stabilization of 3-isothiazolone concentrates, i.e., (2), against chemical decomposition by addition of metal nitrite or metal nitrate. Among the useful nitrates are taught those of sodium, potassium, calcium, magnesium, ferric, ferrous, nickel, zinc, barium, manganese, silver, cobalt, and the like, and among the useful nitrites are taught those of sodium, potassium, calcium, magnesium, and the like. The '795 patent discloses that other common anions, including carbonates, sulfates, chlorates, perchlorates, and chlorides, are surprisingly ineffective. The '795 patent also teaches that the isothiazolone can be an aqueous solution of the compound itself, or of the complexes. According to '795, neither the concentrates, nor the complexes, nor non-aqueous 25% by weight solutions of either the compounds or the complexes, are stable unless stabilized with nitrates or nitrites. This patent does not teach stabilization of dilute solutions (3). All of the '795 examples are directed to 25% solutions of the compounds or the complexes thereof. The concentrates are thus taught by the prior art to be stabilized by nitrates or nitrites, irrespective of the metal counter ion, and the present invention is not inconsistent.
Commercial concentrates (2) contain 3:1 mixtures of CMI and MI as the active ingredient and magnesium nitrate stabilizer in an approximate 1:1 weight ratio of stabilizer to AI. Magnesium chloride is also present as a by-product of the neutralization step in the preparation of the isothiazolone.
To stabilize the AI in use dilutions (4), Law et al., U.S. Pat. No. 5,160,527 suggest metal salts (Cu, ferrous, ferric, zinc, manganese, magnesium) of an organic carboxylic acid of at least six carbon atoms, (which are water insoluble) or chelating anions selected from EDTA, 8-hydroxy-5-hydroxyquinolinate, gluconate, o-phenanthroline, quinolinate, N,N-bis(2-hydroxy-5-sulfobenzyl)glycine, lignosulfonate polymers, and polyacrylates. The use dilutions suggested by Law, et al., comprise loci which contain destabilizing components such as amines, reducing agents (e.g., bisulfites), and fuel. These "destabilizing components" react with the AI. Law et al. do not teach any method of stabilizing dilute solutions which consist of the AI and aqueous solvent in the absence of the aforementioned destabilizing components.
Willingham, et al., U.S. Pat. No. 5,118,699, teaches the stabilizing effect of hydrazide compounds for isothiazolones present in metal working fluids and similar loci containing components antagonistic to the AI. Willingham, et al., U.S. Pat. No. 5,142,058, teaches the stabilizing effect of alkyl halohydantoins and the like in similar antagonistic loci, i.e., use dilutions. These Willingham, et al., patents do not relate to stability in dilute solutions.
For dilute solutions (3), there are two conventional methods of stabilization. The first is to use high ratios (e.g., about 15:1) of Mg(NO.sub.3).sub.2 to AI. Mg(NO.sub.3).sub.2 is not effective at lower ratios, i.e., about 1:1. The second is to use a cupric salt as the stabilizer. The cupric salt is conventionally used at a ratio of about 1:10 to AI since only very small amounts of cupric ion are necessary for effective stabilization. The reason use of cupric ion is preferred in industrial situations is that too much nitrate salt is disadvantageous in certain applications or loci.
However, the cupric stabilizer has recently come under question because of government regulatory limits in certain countries on the amount permitted in water discharge streams.
Since dilute solutions have certain advantages over the concentrates (ease of handling, reduced potential for sensitization of workers, and greater flexibility of formulations), it became necessary to find an alternative stabilization method to the cupric ion or high levels of nitrates.


A method and apparatus for accurately transforming coordinates within a first coordinate system (e.g., a two-dimensional coordinate system associated with a substrate (or portion thereof)) into coordinates in a second coordinate system (e.g., a three-dimensional coordinate system of substrate (or portion thereof) tilted within a wafer analysis tool.

1. Field of the Invention
The invention relates to semiconductor wafer processing equipment and, more particularly, to a method and apparatus for tracking the location of defects on a substrate, e.g., a semiconductor wafer or a cleaved portion of a semiconductor wafer, by transforming a substrate coordinate system into a wafer analysis tool coordinate system.
2. Description of the Background Art
Identifying defects on the surface of a semiconductor wafer, such as particulate contaminants and other surface irregularities such as grain structure, is extremely important to integrated circuit manufacturing processes. To eliminate defect sources, defects are identified and analyzed to determine the source of the defect. Thereafter, corrective action can be taken to reduce or eliminate the defect source.
Typically, a defect identification process is accomplished in two steps. First, a laser scanner device scans a wafer with a laser and analyzes the backscatter from the wafer to locate defects on the surface of the wafer. One such laser scanner device is a Tencor SurfScan 6200, manufactured by Tencor Instruments. Secondly, the defect is analyzed to identify the root cause of the defect. The most commonly applied analysis tool is a high magnification imaging system such as a scanning electron microscope (SEM) which is used to identify the defect and/or the source of the defect by inspecting the defect at high magnification. Additionally, the SEM may be accompanied by instrumentation for performing chemical analysis of the defect. Such instrumentation includes an energy dispersive x-ray (EDX) detector. Other tools may include an Auger analysis device, atomic force microscope (AFM), optical spectroscopy device, electron backscattering detector and the like.
Many of these analysis tools can not physically accommodate an entire wafer within the analysis chamber of the tool. As such, the wafer is cleaved into manageable portions and each portion is analyzed separately within the instrumentation. One problem with cleaving a wafer into smaller individual portions and then attempting to analyze each portion is that the defect identified by the laser scanner device is identified in a coordinate system for the wafer as a whole as identified by the laser scanner device. Consequently, when the portion containing the defect is cleaved and placed within the analysis instrumentation, the coordinate system of the wafer that identifies the location of the defect is meaningless and the defect is not readily identifiable and positionable within the field of view of the analysis instrumentation. As such, the wafer analysis instrumentation must scan the entire portion of the wafer to find the defect for analysis.
A solution to this problem is disclosed in commonly assigned U.S. patent application Ser. No. 08/850,954 filed May 5, 1997 (Attorney Docket No. 1785) and incorporated herein by reference. This patent application discloses a method and apparatus for selectively marking defects on a semiconductor wafer. This apparatus fiducializes the wafer such that a two-dimensional wafer coordinate system is generated, then fiducializes the defects on the wafer identifying each defect and selectively marks each defect with an identifiable set of marks. These marks are readily visible via a two-dimensional, wafer analysis tool such that the defect can be easily located and analyzed. As such, when the wafer is cleaved into small portions, each portion containing a defect will have readily identifiable marks surrounding the defect.
Furthermore, the marks themselves can be used as a two-dimensional defect coordinate system for each defect that is contained within a cleaved portion of the wafer. As such, each wafer portion contains a two-dimensional coordinate system for the defect on that portion. The defect is known to be located a predefined distance from the marks. Consequently, a computer file can be generated for each portion of the wafer cleaved from an entire wafer that contains the two-dimensional coordinates of the defects on that portion relative to the defect marking coordinates (i.e., the defect coordinate system).
Although the method and apparatus for selectively marking a semiconductor wafer of U.S. patent application Ser. No. 08/850,954 filed May 5, 1997 (Docket 1785) provides an accurate, two-dimensional coordinate system for a defect and/or a cleaved portion of a semiconductor wafer, there are instances where the coordinate system requires transformation to conform to a particular analysis tool. For example, if the analysis tool is an electron backscattering diffraction (EBSD) analysis tool, the cleaved wafer is generally inserted into the analysis chamber at an angle relative to a horizontal plane. By analyzing the wafer portion tilted at an angle, the EBSD analysis tool has a small footprint within the laboratory and also promotes substantial electron backscattering due to the angle of incidence of the electron beam that scans the wafer portion. Other spectroscopic techniques such as Auger electron spectroscopy, optical spectroscopy and SEM may also tilt the wafer portion to achieve substantially improved signal strength and signal bandwidth. By tilting the wafer portion, the two-dimensional coordinate system associated with that portion is now distorted. Consequently, the defect is no longer directly identifiable by the two-dimensional coordinates of the wafer portion.
Furthermore, the analysis tool depth of field is limited and as such, the tool can only focus upon a small portion of the wafer. Thus, to find defect locations, not only must the tool scan in two dimensions, the tool must scan in a third dimension (focus) to maintain the surface within the depth of field of the tool.
Therefore, there is a need in the art for a method and apparatus that transforms the two-dimensional coordinate system associated with a tilted a wafer (or portion thereof) into a three-dimensional coordinate system of a wafer analysis tool.

Method and apparatus for transforming a substrate coordinate system into a wafer analysis tool coordinate system


Phase change material can be set with a multistage set process. Set control logic can heat a phase change semiconductor material (PM) to a first temperature for a first period of time. The first temperature is configured to promote nucleation of a crystalline state of the PM. The control logic can increase the temperature to a second temperature for a second period of time. The second temperature is configured to promote crystal growth within the PM. The nucleation and growth of the crystal set the PM to the crystalline state. The multistage ramping up of the temperature can improve the efficiency of the set process relative to traditional approaches.

Memory resources have innumerable applications in electronic devices and other computing environments. Continued drive to smaller and more energy efficient devices has resulted in scaling issues with traditional memory resources that are based on using electron charges for data storage and access. Phase change materials (PM) are based on the property of certain compounds to take on one of two or more states based on heat applied to the material. PMs have been made of chalcogenide materials, which exhibit at least two states: a structured crystalline state and a non-ordered amorphous state, depending on characteristics of the application of heat to the material. PMs offer potential advantages for use in memory in that they are nonvolatile, and can potentially scale smaller due to the storage and access of data being based on the structure of the material state instead of on electron charge.
However, access performance in memories based on PMs has historically been significantly worse than that of established memory technologies. Recently, read latency has improved to be comparable to other memory technologies, but write latency continues to result in significant delays. Write latency in phase change memories (PCM) is primarily limited by the set pulse to crystallize or set the PM from its reset or amorphous state. Traditional set algorithms use a fixed ramp rate for either a ramp down approach (first heat the material to the amorphous state, and control the cooling to attempt to change to the crystalline state), or a ramp up approach (controlled increase in temperature to attempt to promote crystallization). These approaches or set procedures attempt to ensure that all memory cells experience an optimal set temperature to minimize the set latency/duration.
Both ramp up and ramp down approaches perform reasonably well in cells with unconfined PM, but are not effective in cells having fully amorphized PM. An unconfined PM refers to a PM that is not fully amorphized in the reset state, and thus always includes crystal nuclei or crystalline region. Thus, the set process is dominated only by crystal growth to transform the amorphous region(s) to the crystalline state based on the nuclei already present. However, to scale PM-based memories to smaller size, cost, and power consumption, the cell size must be decreased. Seeing that the extent to which the cell becomes fully amorphized correlates with PM thickness and/or area of the cell, scaling PM-based memories to smaller geometries results in memory cells that will not set efficiently by traditional set procedures. Thus, traditional set procedures require confined cells to grow crystal, and scaling to smaller geometries reduces the number of nuclei or the amount of crystalline area, which increases set times. The PM will not properly transition to the crystalline state when there are insufficient nuclei or a sufficient crystalline region to promote crystal growth. Thus, traditional set procedures result in very long set procedures, negatively impacting write latency, and/or result in cells that are not set effectively, resulting in higher bit error rate (BER).
Descriptions of certain details and implementations follow, including a description of the figures, which may depict some or all of the embodiments described below, as well as discussing other potential embodiments or implementations of the inventive concepts presented herein.

Multistage set procedure for phase change memory


A dispenser for dispensing folded sheet products from a stack of folded sheet products, includes: an open-ended body, a front panel provided with a dispensing opening, a rear panel, and a transverse panel located between the front and rear panels. The dispenser further includes a support member for receiving the stack of the folded sheet products and at least one locking mechanism located between the support member and at least one longitudinal wall of the open-ended body.

Presently public places, such as restaurants, make available to the consumers dispensers of tissue paper items such as serviettes table napkins, towels or sanitary paper.
In general, a napkin dispenser comprises an open-ended case having a substantially parallelepiped shape and including a front panel fitted with a transverse slot through which the napkins are extracted. The napkins are assembled as a pack inside the dispenser either in a mere juxtaposed manner, or independently of each other, or interleafed with each other. Such dispensers can be set down flat or vertically against a wall.
Common standard dispensers of this type are usually assembled from multiple sections. A body may comprise up to four separate parts, which are assembled by rivets, welds or other means, depending on the material used. In addition, the body may include an end wall and guiding means for a push plate for napkins or the like. These components must also be attached to selected parts of the inner walls of said body. As a rule, the cost of the dispenser and the assembly thereof is directly related to the number of component parts.
In order to refill a dispenser, a user must remove the front panel to access the space into which a stack of napkins is to be loaded. This may either be done by simply removing the front panel, to expose the pus-plate, whereby a new stack of napkins is inserted into the body of the dispenser against the action of the spring loaded push plate. A problem with this type of loose front panel is that it may be difficult to remove, as there is no obvious way to grip the panel. Also, when replacing the front panel after filling, the stack of napkins must be pushed back while the front panel is repositioned and re-attached. This relatively complicated procedure will more often than not cause at least the outermost napkin of the stack to be damaged or displaced relative to the dispensing opening.
In an alternative dispenser, a user must locate and release one or more latches positioned inside the dispenser in order to allow the front panel and an associated holder to be withdrawn from the dispenser for re-filling. Such a dispenser is known from U.S. Pat. No. 4,329,001. As in the above example, a problem with this type of dispenser is that it may be difficult to remove, as there is no obvious way to grip the panel. The user must first know that the front panel is retained by a latch (or latches), and second know where to find said latch. This is not obvious, as the latch is accessed through the dispensing opening, requiring the user to be trained for opening the dispenser, or that the body of the dispenser is provided with instructions for refilling. Apart from detracting from the design and general appearance of the dispenser, such instructions may be worn away with time. A user not familiar with the dispenser may therefore cause damage to the retaining mechanism trying to force the front panel of the dispenser open.
Hence there exists a need for a dispenser provided with means for facilitating an improved method of opening and closing of such a dispenser for the purpose of re-filling.

Apparatus for serially dispensing folder sheet products


Disclosed is a procedure to coat the free surface of Cu damascene lines by a 1-5 nm thick element prior to deposition of the inter-level dielectric or dielectric diffusion barrier layer. The coating provides protection against oxidation, increases the adhesion strength between the Cu and dielectric, and reduces interface diffusion of Cu. In addition, the thin cap layer further increases electromigration Cu lifetime and reduces the stress induced voiding. The selective elements can be directly deposited onto the Cu embedded within the under layer dielectric without causing an electric short circuit between the Cu lines. These chosen elements are based on their high negative reduction potentials with oxygen and water, and a low solubility in and formation of compounds with Cu.

1. Field of the Invention
This invention relates to the general field of copper-based interconnections for integrated circuits.
2. Description of the Prior Art
The industry need for increased integrated circuit (IC) chip performance beyond 0.25 μm technology in conjunction with decreasing feature size is causing migration of interconnect systems to lower resistivity Cu based-conductors. Modem commercial Cu IC chips, which usually contain 4 to 8 levels of Cu interconnections, are generally fabricated by a single and/or dual damascene process. The two most important on-chip interconnection reliability issues are electromigration and stress induced voiding in the Cu interconnect circuit elements. Electromigration in copper metallization for IC chips has been extensively studied. Electromigration and stress induced voiding are the motion of atoms by diffusion in an electrical field and stress gradient, respectively. When an interconnect is electrically stressed in a dc current, the drifting of Cu atoms can cause mass depletion (resulting in a void or an open circuit) or accumulation (resulting in an extrusion or a short-circuit) at the locations where the microstructure and/or materials are varied such that an imbalance of atom flux exists. Hu et al. (Proceedings of 1999 International Interconnect Technology, p. 197) reported that Cu mass transport in Cu interconnects occurs primarily at the surface interface, not at grain boundaries. In Cu interconnection structures the top surface of a line is generally covered by an insulator, e.g., silicon nitride, and the bottom and sides of the line are covered with a liner, e.g. TaN/Ta. The Cu lines are connected to other lines through inter-level vias. Since diffusion at the top Cu/silicon nitride interface is dominant in Cu, then the electromigration flux is constrained to the top interface within an area of δsw, where δs is the effective thickness of the interface region and w is the line width. The relative amount of flux, at constant line current density, j, flowing through the interface region is proportional to the interface area divided by line area ratio, δsw/(wh), or δs/h, where h is the line thickness. The Cu electromigration lifetime τ, is ΔL/Vd=ΔL h kT/(δsDsFe), where ΔL is the critical void length that causes failure, Vd is the void growth rate, Ds is the interface diffusivity, k is the Boltzmann constant, T is the absolute temperature and Fe is the electromigration driving force at the interface. ΔL is generally equal to the inter-level via size. The above equation shows that the lifetime is controlled by the interface diffusivity, Ds. To fully utilize Cu chips as the feature size is scaled to smaller dimensions (which causes higher current densities and even more electromigration), the fast diffusion pathway along interfaces, Ds, must be altered. The intents and purposes of this invention are to modify the property of the top surface of Cu lines in a damascene structure such that fast diffusion can be reduced. This will result in increased circuit lifetime (reliability) due to reduced electromigration or stress-induced failures.
In Cu damascene processing, U.S. Pat. Nos. 4,954,142, 4789,648, and 4,702,792, vias and trenches are etched in an insulator material, metal is deposited to fill these cavities, and chemical mechanical polishing (CMP) is used to remove the excess metal and form metal vias and lines. The metal fill: metal liner, Cu seed layer and Cu main conductor, are produced by a combination of physical vapor deposition and electroplating deposition techniques. The Cu interconnects (lines and vias) are embedded in a dielectric. Hu et al. (Thin Solid Films, 262, p. 84-92, 1995) reported that the Cu interconnections require metal and insulator adhesion/diffusion barrier layers in addition to main Cu conductors. U.S. Pat. No. 6,342,733 discloses the use of an electroless selective deposition film on the top of the Cu surface from a selective group of CoWP, CoSnP, CoP, Pd, CoB, CoSnB, In, NiB and W for reduced electromigration and stress induced migration of Cu wires. E. G. Colgan reported a selective CVD-W film for capping Cu damascene lines (Thin Solid Films, 262, p. 120-123 (1995)) for suppressed Cu hillock formation and oxidation protection. U.S. Pat. No. 5,447,599 teaches the use of Ti/Cu and Cu(Ti) alloy to form TiN(O) by thermally annealing and selective wet etching. U.S. Pat. No. 5,447,887 teaches the use of Cu silicide for improved adhesion between Cu and silicon nitride. U.S. Pat. No. 5,693,563 teaches an etch stop method for a Cu damascene process using a blanket film TiN 50 to 200 nm thick, on the top of a Cu damascene line, followed by patterning TiN using photo-resist and then etching. U.S. Pat. No. 5,968,333 extends the common electroplating method of using pure Cu to fill the trenches/holes to the use of a Cu(Al) alloy. U.S. Pat. No. 6,136,707 discloses the use of multiple Cu seed layers with various deposition techniques for improving main conductor electroplating in Cu or Ag processes. U.S. Pat. No. 6,181,012 teaches the use of Cu alloy seed layer for improving electromigration resistance, and the adhesion/surface properties of Cu interconnections. U.S. Pat. No. 5,023,698 discloses the use of copper alloys containing at least one alloying element selected from group of Al, Be, Cr, Mg, Ni Si, Sn and Zn. U.S. Pat. No. 5,077,005 discloses the use of copper alloys containing at least one alloying element selected from group of In, Cd, Sb, Bi, Ti, Ag, Sn, Pb, Zr and Hf where the weight percent of the alloying element used is between 0.0003 to 0.01. U.S. Pat. No. 5,004,520 discloses the use of a copper foil for film carrier applications containing at least one alloying element selected from group of P, Al, Cd, Fe, Mg, Ni, Sn, Ag, Hf, Zn, B, As, Co, In, Mn, Si, Te, Cr and Zn with impurity concentration from 0.03 to 0.5 weight percent. U.S. Pat. No. 4,749,548 discloses the use of copper alloys containing at least one alloying element selected from group of Cr, Zr, Li, P, Mg, Si, Al, Zn, Mn, Ni, Sn, Be, Fe, Co, Y, Ce, La, Nb, W, V, Ta, B, Hf, Mo and C to increase the strength of the copper alloys. However, none of this prior art discloses the use of Cu interconnections constructed by directly depositing very thin layers of 0.5 to 5 nanometers on the top Cu surface from a selected group of metal elements having both a high negative reduction potential with oxygen and the ability to form compounds with copper. The use of this new innovation will sufficiently improve the Cu interconnects so that Cu ULSI on-chip wiring can be extended to future generations.

On-chip Cu interconnection using 1 to 5 nm thick metal cap

International Business Machines Corporation


A system, including methods and apparatus, for microfluidic analysis of a nucleic acid target in a nucleic acid mixture. The system includes a method to preselect the target from the mixture before amplification. Preselection enriches the mixture for the target by retaining the target on a target-selective receptor and then removing unretained non-target nucleic acids. The preselected target then may be amplified from the enriched mixture and assayed. Devices configured to carry out the method are also disclosed.

Rapid progress in genomic sequencing and proteomics has pushed the biotechnology sector to develop faster and more efficient devices for analyzing nucleic acids in biological samples. Accordingly, the biotechnology sector has directed substantial effort toward developing miniaturized microfluidic devices, often termed labs-on-a-chip, for sample analysis. Such devices may analyze samples in very small volumes of fluid, providing more economical use of reagents and samples, and in some cases dramatically speeding up assays. These devices offer the future possibility of human health assessment, genetic screening, and pathogen detection, among others, as routine, relatively low-cost procedures carried out very rapidly in a clinical setting or in the field.
Despite the potential of microfluidics, the analysis of low quantities of dilute target nucleic acids poses substantial technical problems for microfluidic devices. A typical nucleic acid analysis relies on nonselective isolation of all nucleic acids during initial sample processing. Then, a nucleic acid target(s) may be selectively amplified, generally in the presence of all of the isolated nucleic acids, to allow subsequent assay of the amplified target. However, in many cases the target is isolated in a relatively dilute form during initial sample processing and represents only a tiny fraction of the total isolated nucleic acids. For example, clinically relevant levels of human pathogens may correspond to substantially fewer than one particle or organism per microliter of human blood. Furthermore, a genetic region of interest from a low-titer pathogen or a single-copy gene may represent less than one-millionth of the total DNA isolated from a mammalian sample.
A dilute target that makes up a small fraction of the isolated nucleic acids in a sample may pose at least two problems for amplification of the target. First, because the target is dilute, a relatively large chamber, for example, up to one-hundred microliters or more, may be necessary to hold a fluid volume large enough to include a detectable number of target molecules. As a result, the need for input of a detectable number of target molecules may necessitate additional sample processing before amplification or even preclude the use of some types of microfluidic devices, particularly those that amplify and assay target nucleic acids in sub-microliter volumes. By contrast, a dilute sample in a large volume loses the benefit of microfluidic devices. Second, because the target often represents a tiny fraction of all isolated nucleic acids in the sample, amplification efficiency is reduced by the excess of non-target nucleic acids. For example, side reactions with non-target nucleic acids may slow the rate of target amplification and deplete amplification reagents, resulting at least in a decrease in signal-to-noise ratio or even a complete absence of target signal.

Microfluidic system for analyzing nucleic acids

Hewlett-Packard Development Company, L.P.


This invention relates to a platform (11) and a method for generating electromagnetic field distributions. The invention relates in particular to optical sensors for measuring biological or chemical substances. The platform (11) according to the invention comprises a substrate (13), a structured layer (19) and, positioned between the substrate (13) and the structured layer (19), a multilayer assembly (17), said components being so matched relative to one another that upon appropriate impingement by electromagnetic radiation an electromagnetic field distribution is generated that is at a maximum within the structured layer (19).

This invention relates to a system and a method for generating electromagnetic fields in areas accessible to substances to be irradiated. This invention relates in particular to optical sensors for measuring biological or chemical substances.
Electromagnetic fields are utilized in numerous applications for detecting minute concentrations of substances most typically in liquid samples. There are two basic categories of optical sensors designed to detect substance accumulations on the detector surface: Those used for labeled substances (label methodology) and those that function without such labeling (non-label methodology).
Label methodology encompasses, inter alia, a method whereby the substances to be detected are labeled with a fluorescent dye. Examples of commercially available fluorescent dyes include CY5 for an excitation wavelength of 532 nm, and CY3 for an excitation wavelength of around 635 nm.
While such labeling may be selective, it usually also covers other substances that are present in a sample to be measured. In cases of nonselective labeling, selectivity can be achieved for instance by applying on the surface of the sensor a treatment that allows only the labeled substance that is to be measured to selectively adhere to that surface. When, after full adhesion, the surface is flushed, the intensity of the resultant fluorescence signal provides a quantitative indication of the concentration of the substance to be measured in the sample concerned. Such quantitative information can also be obtained without flushing whenever it is possible to cause a fluorescence-stimulating electromagnetic field to attach itself in concentrated and essentially dedicated fashion to the substances that are to be detected on the sensor surface.
As long as not all of the labeled substances adhering to the surface fluoresce, this general rule applies: the higher the electromagnetic field intensity generated on the surface relative to the impinging light intensity, the better the signal-to-noise (S/N) ratio of the measurement. This has a direct effect on the measuring sensitivity of the sensor. Accordingly, one will try to produce on the surface area concerned as strong an electromagnetic field as possible in relation to the volume to be measured.
Apart from the label-based methods described, i.e. marker-based measuring techniques, non-label methods are widely used as well. In that case, it is for instance a change of the angle of refraction caused by the accumulation of the substance to be measured on the sensor surface that is a factor directly influencing the field distribution in the sensor. That factor has an effect on such optical measuring parameters as the diffraction coefficient or perhaps the waves that pass through a fiber-optic cable, triggering mensurable changes. Here as well it is important that at least segments of the substances being measured have areas accessible to electromagnetic fields.
One possibility to build up that kind of field distribution accessible to the substance being measured is to utilize cross-attenuated electromagnetic waves. In the simplest case a one-time total internal reflection (TIR) is used. To that end, excitation light emanating from the substrate impinges on the sensor surface at an angle that is greater than the critical total reflection angle. This generates on the surface a cross-attenuated field which, declining exponentially, projects from the substrate into the medium to be measured. Technical literature also refers to these fields as evanescent fields, since no light propagates into the medium to be measured but, instead, the field only "projects" into the medium and is thus restricted to the immediate contact surface within the corresponding boundaries.
The so-called depth of penetration, meaning the distance from the contact surface at which the field intensity has dropped to 1/e (where e is the Eulerian coefficient), depends among other factors on the actual angle of incidence and is typically measured in units of the vacuum wavelength of the excitation energy while being of the same order of magnitude.
One way to elevate this type of evanescent field relative to simple total reflection is to cause the excitation light energy to reflect off the contact surface multiple times. For example, if an optical layer of a specific thickness and with a high refractive index relative to the substrate is applied on the latter, it is possible, under certain conditions, for total reflection to take place on both contact surfaces of the layer and for the light propagation to be guided within the layer in a so-called waveguide mode. In a suitably selected waveguide configuration, this leads to an elevated evanescent field on the surface of the waveguide.
It is important in this context that the wave-conducting layer, meaning the layer in which the light wave is guided, have a refractive index that is greater than the refractive indices of the substrate and of the medium next to the waveguide layer. Otherwise there cannot be multiple total reflections nor, consequently, any wave propagation (refer for instance to WO 86/071149). For a given substrate the choice of materials for the wave-conducting layer is therefore limited to high-refraction materials.
Another problem is posed by the fact that the mode propagation and thus the intensity of the field that is available for excitation depends in highly sensitive fashion on the waveguide configuration and possibly existing imperfections. Even minute impurities cause light scattering and a diminution of the intensity of the light passing through the waveguide. That effect is integrally propagated over the entire distance of the light path through the waveguide and even in the case of minute impurities and/or defects it can produce incorrect measurements.
Another difficulty is encountered when coupling the light into the waveguide, which can be accomplished through end-face interfacing, prismatic coupling or via a coupler grating. In all of these it is difficult to ensure constancy in terms of coupling efficiency which, however, should preferably be obtainable for quantitative measurements.
As another problem, the density of the various measuring ranges is limited due to the expansion of the waveguide.
Another way to arrive at an elevated evanescent field is to stimulate so-called surface plasmons. These excitation conditions, generated in metallic layers, propagate in the plane of the layer until they fall apart for instance by absorption in the metal or by scattering. Here again, controlling the evanescent field intensity produced by surface plasmons is quite difficult. And again, there is a limit to the density of the measuring ranges since surface plasmons usually travel over finite distances only before they decay. Moreover, in many cases, metals have stability problems and most of all they tend to age, potentially leading to unreliable measurements.
More recent approaches utilize the well-known effect of the resonant grating with anomalous transmission breaks, for instance as described by Novartis in WO2001/002839 (hereinafter referred to as the Novartis application). As in the case of the waveguide, the substrate is coated with a layer whose refractive index is higher than the refractive index of the substrate, since otherwise there would be no resonance effect. In addition, the surface area of the measuring field is defined by a periodic pattern of channels.
The dimensions of the structures and layers are so chosen that the impingement of coherent light at a particular angle causes a resonance effect whereby transmission is reduced in anomalous fashion, building up the desired evanescent field. The advantage of that approach is that it is not necessary for the light to travel waveguide-style over a long distance, making the system substantially less sensitive to imperfections and centers of scattering. Moreover, compared to waveguide coupling provisions the system can be smaller in size, allowing for a considerably larger number of measuring ranges since for all practical purposes the light does not propagate laterally. This advantage of a potentially greater density of measuring ranges has been stressed most of all in WO2000/75644 by Zeptosens (hereinafter referred to as the Zeptosens application). The Zeptosens application as well provides for continuous modulations in the measuring range, although it is still based on a laminar optical waveguide.
Both the waveguide approach for generating a high field intensity in the surface area and the resonant-grating approach employing anomalous transmission suffer from a drawback in that the field intensity obtained on the surface is a mere fraction of the field intensity present in the highly refractive layer and perhaps in the wave-conducting layer. In these systems, only the cross-attenuated evanescent spurs of the field are accessible.
Another disadvantage lies in the fact that in the cases concerned a highly refractive layer must serve as the terminal surface relative to the surrounding medium. The most progress here has been made in biochemical applications on SiO2 surfaces. With glass substrates, other materials must be used for producing a layer which compared to the substrate has a high refractive index. Examples of the materials employed include TiO2 or Ta2O5. Compared to SiO2, however, these materials have been less widely adopted for biochemical applications. It is possible to coat the high-refraction layer with a thin film of SiO2, which in fact must be very thin since the decline of the evanescent field is exponential in this film as well.

Method for generating electromagnetic field distributions


A method and apparatus for retracting a magnetic brush in an imaging device. The apparatus includes a housing containing carrier beads and toner particles; a magnetic structure at least partly disposed within the housing and generating at least one magnetic field; and an endless sleeve disposed around and rotatable about the magnetic structure, at least a portion of the sleeve extending from the housing. During toner development, the magnetic structure is in a first position for developing a magnetic brush of the carrier beads and toner particles along the portion of the sleeve extending from the housing which forms a developer nip with a photoconductor, and during a period of time when toner development is not to be performed, the magnetic structure is in a second position for retracting the magnetic brush by causing the carrier beads to be positioned against the portion of the endless sleeve extending from the housing forming the developer nip.

1. Field of the Disclosure
The present disclosure relates generally to developing a magnetic brush for transferring toner to a photoconductive member, and particularly to selectively retracting the developed magnetic brush from contact with the photoconductor to substantially prevent background toner development.
2. Description of the Related Art
Electrophotography selectively develops toner to the photoconductor by discharging areas of the photoconductor that correspond to areas to be colored and leaving other areas charged so as to prevent toner development in those "white" areas. For negatively charged toner, these white areas are created by providing a photoconductor charge that is more negative than the developer bias. This difference between the photoconductor and developer biases is called the "white vector." If the white vector is too small, then mechanical development takes place resulting in a haze of toner on areas of the photoconductor that should be white. Increasing the white vector produces a reduction in toner to the white areas, but if the white vector is increased too much there is another increase in toner developed into the white areas. This increased development is the result of high electric field strengths that can result in modifications to the toner charge. The white vector is adjusted to its desired value when the least amount of toner is developed into the white or background areas of the photoconductor. Toner developed into these white areas is called "background toner" and is wasted toner. This toner waste reduces the useful life of a toner cartridge since it represents an undesirable draw of toner for printing.
A typical laser printer will create an image on the page with approximately 0.4 mg/cm2 of print. Background toner with an appropriately adjusted white vector can be about 0.001 mg/cm2. This may seem like an insignificant amount of waste toner, but since the areas of unprinted "white" are typically orders of magnitude larger than the printed areas, this waste toner has greater significance. For color laser printers, the cost to the customer of background toner when printing a white page can, in some circumstances, approach or exceed the cost of a sheet of paper. Most laser printers use white vector to limit development of background toner when the machine is running but not actually developing toner that goes to the printed page. White vector is an effective way to keep the white areas of prints white, but an improved method is needed to prevent toner waste when not printing.

Method and apparatus for magnetic brush retraction in electrophotographic system


A safe delivery system of agriculturally active material is formed using an encapsulation process. A microencapsulated suspension of agriculturally active material includes an encapsulating agent formed from a graft copolymer of starch and at least one vinyl monomer.

1. Field of Invention
The present invention relates to a safe delivery system of agriculturally active material and a process for preparing microencapsulated suspension of agriculturally active material, preferably including pyrethroids wherein the encapsulating agent is a graft copolymer of a starch and at least one vinyl monomer.
2. Description of Related Art
In the agrochemical industry, insecticides are formulated as dust, emulsifiable concentrates, suspension concentrates, wettable powders or wettable granules, and water dispersible granules depending on the properties of the active ingredient and the target pest species and market. Insecticides such as lambda cyhalothrin, cypermethrin, fenvalerate, permethrin, alpha-cypermethrin, and similar compounds, which are moderately toxic in the technical form, have a high skin irritant property and in some cases may provoke an adverse skin reaction such as burning, tingling, numbness or prickling sensation., also generally known as paraesthesia. These skin irritant properties are most pronounced in the areas of an operator's face, hand, and neck during application of these insecticides. For delivering such agriculturally active materials to a target, encapsulation or microencapsulation is one of the safest modes. Encapsulation, or more specifically microencapsulation, is increasingly being used to target specific insects, as it also provides a safer handling of toxic fungicides and insecticides. A microcapsule is a 10−3 m to 10−9 m diameter particle, composed of an inner core material and an outer shell. Microencapsulation of these kinds of agrochemicals can also be advantageous in providing the active material in relatively more concentrated form than the emulsifiable concentrate, wettable powder etc., at the same time reducing the amount of other ingredients such as surfactants, solvents, dye(s) etc.
Microencapsulation of a number of different agriculturally active materials and pesticides has been known for many years by using various processes or techniques for microencapsulation. The general technology for forming microcapsules is divided into two classifications known as physical methods and chemical methods. The physical methods are spray coating, spray drying, pan coating, rotary disk atomization etc. The chemical microencapsulation methods are phase separation, interfacial polymerization, simple and complex coacervation method etc.
The total process of microencapsulation covers three separate steps on a time scale. The first step consists of forming a shell around a core material. The second step involves keeping the core inside the shell material so that it does not release. Also, the shell material must prevent the entrance of undesirable materials that may harm the core. And finally, it is necessary to release the core material beginning at the right time, stage and at the right rate.
Prior encapsulation methods include a process for the preparation of microencapsulated water-immiscible material, including pesticides and other agrochemicals, by interfacial polymerization techniques using one or more polyisocyanates and producing microcapsules having a droplet size of from 0.5 to about 4000 microns, which provides a controlled or sustained release (over weeks) of the active ingredients. This type of controlled released encapsulation is useful in the case of soil application. Whereas, fast release is required in the case of foliar applications.
Another encapsulation method includes a process of encapsulation of a water-immiscible material. i.e. pyrethroid insecticide, within discreet capsules of polyurea prepared from an aromatic diisocyanate. However, the untreated isocyanate, if any, of said isocyanates may cause skin/eye irritation due to its high toxicity
Release rates are governed by the capsule particle size, the thickness of the wall and the permeability of the wall. Small particles with thin walls and low cross-linking density allow the fastest possible release.
Starch is a cheap and natural polymer and is a renewable degradable carbohydrate biopolymer that can be taken from various sources by environmentally sound processes. Starch is hydrophilic and a partially water soluble polymer. Starch-based biodegradable low-density polyethylene (LDPE) films have been used for graft copolymerization of vinyl acetate with ceric ammonium nitrate. Additionally, it is known to graft vinyl acetate and starch acetate with a high degrees of substitution copolymerized to prepare a kind of biodegradable material.

Safe delivery system for agriculturally active material


Improved solutions for watering plant roots and methods of application, the solutions containing in parts by volume (1) humectant from 25 to 75, (2) thickener from 0.2 to 1.5, (3) binder from 0.2 to 5, (4) wetting agent from 0.2 to 2.0 and (5) water 75 to 25.

1. Summary of the Invention
This invention relates to improved solutions for watering plant roots and methods of application, and more particularly, to water soluble solutions for application to grass and other root bearing plants, the solutions including a humectant as its principle constituent and also as additives so that during humid evenings the humectant will act to collect moisture and during hot days the humectant will act to release the collected moisture for feeding the plant roots thereadjacent.
2. Description of the Background Art
In conditions of water scarcity and/or high evaporation loss rates due to high temperatures, low humidity, high winds, etc., soil loses water rapidly. Moisture in the soil is drawn to exposed soil surfaces by capillary action thereby replacing the moisture lost by evaporation into the air. At the same time, moisture drawn from the soil into plant root fibers by osmosis is transpired through the plant stems and leaf systems, and that fraction not converted by photosynthesis is then lost by evaporation from pores of leaf surfaces. Soil can quickly become dehydrated to very low moisture content.
The survival of plants in such conditions thus depends on the amount of soil moisture which is accessible to the plant root systems. This is that fraction of the total soil moisture remaining after losses via the capillary/evaporative process. Since the evaporative losses mean soils are driest near the surface, plants with shallow root systems such as grasses and other small species, are affected more rapidly than deep-rooted plants such as trees, etc.
Where there is a marked change in ground temperatures between day and night, there is a significant air inhalation into porous soils during the night-time cooling (contraction) cycle and exhalation of air and moisture in the heat of the day. This further aggravates the overall evaporative moisture loss.
The invention described herein reduces the losses of moisture from direct evaporation, improves the proportion of soil moisture accessible to plants, and in certain conditions prevents or even reverses the evaporative loss from day/night movement in and out of porous soils.
Commercially available chemical compositions, the literature and patents disclose many compositions and methods for treating plant roots. Note, for example, U.S. Pat. Nos. 3,798,838 to Hashimoto; 4,063,919 to Grano; 4,380,886 to Koslow; 4,469,502 to Heller, and 4,540,427 to Helbling.
The patent to Hashimoto discloses fertilization and irrigation of highly permeable surface soils in semi-arid regions wherein the soils are contacted with an aqueous solution of a water soluble plant nutrient salt and an effective amount of a partially hydrolyzed polyacrylamide to reduce the permeability of the soil without rendering it impermeable to water flow. It has been found that water soluble plant nutrients and the aforementioned partially hydrolyzed polyacrylamide exhibit a synergistic effect to decrease the water permeability of the soils. It has also been found that plants grow better in the treated soil and are more efficient in uptake of nutrients from the soil. These discoveries can be used to conserve water and fertilizer and improve the efficiency of agronomy by contacting the soil with a solution having a concentration of from 0.001 to about 1 weight percent of a polyacrylamide having from 5 to about 80 percent of its amide groups hydrolyzed to carboxylic acid groups and from 0.001 to 5 weight percent of a water soluble, plant nutrient salt.
The patent to Grano relates to a fertilizer rod composition comprising about 100 parts of a polyvinyl alcohol, about 0 to 20 parts of a plasticizer and about 10 to 350 parts of a fertilizer, a process for producing such rod and a product of such process.
The Koslow patent describes a method of promoting the transport of water through medium and coarse grained soils comprising the step of applying to the medium or coarse grained soil a soil amendment composition at a level of less than 20 parts per million parts by weight of dry soil, and preferably less than 5 ppm. The composition comprises a substantially linear, substantially water-soluble hydrophilic polymer having a molecular weight greater than 50,000. A preferred polymer is poly (ethylene oxide) having a molecular weight of 300,000 to 7,000,000.
The Heller patent discloses a process for supplying plants with nutrients uniformly and over a long period of time by the addition of nutrient-charged synthetic resin ion exchangers and mineral fertilizers to the culture medium, according to which the nutrient-charged synthetic resin ion exchangers are employed together with those mineral fertilizers with particle size less than 500 .mu.m which have been coated with massive polyurethanes having a particular water absorbing capacity which is adapted in a particular manner to the water solubility of the mineral fertilizer; furthermore, fertilizers containing nutrient-charged synthetic resin ion exchangers, and the mineral fertilizers coated with the massive polyurethanes having a particular water absorbing capacity.
The Helbling patent discloses a method for improving the water conservation properties of soil. The method increases the ability of the soil to absorb and retain water and acts to stabilize the loosening of break-up of the soil.
In addition, the Merck Index discloses the use of sorbitol and other substances as humectants.
No prior art composition or method of application provides the objects and advantages of the present invention.
It has now surprisingly been found that humectants in aqueous solutions with an appropriate wetting agent function extremely well in improving the watering of plant roots.
It is therefore an object of this invention to provide improved solutions for watering plant roots and methods of application, the solutions containing in parts per volume (1) humectant from 25 to 75, (2) thickener from 0.0 to 1.5, (3) binder from 0.0 to 5, (4) wetting agent from 0.0 to 2.0 and (5) water 75 to 25.
It is a further object of the invention to water lawns and other plant root systems with the aid of a humectant.
It is a further object of the invention to utilize chemical solutions to entrap moisture, then release such entrapped moisture for watering the roots of plants.
It is a further object of the invention to foster ecological objectives by reducing the consumption of water for plant maintenance.
The foregoing has outlined some of the more pertinent objects of the invention. These objects should be construed to be merely illustrative of some of the more prominent features and applications of the intended invention. Many other beneficial results can be obtained by applying the disclosed invention in a different manner or modifying the invention within the scope of the disclosure. Accordingly, other objects and a fuller understanding of the invention may be had by referring to the summary of the invention and the detailed description of the preferred embodiments in addition to the scope of the invention defined by the claims taken in conjunction with the accompanying drawings.