The present disclosure relates to a method for predicting a slagging production position and a slagging production possibility in a furnace, the method including: the analyzing step of analyzing physical compositions of two or more kinds of coal; the phase diagram producing step of producing a phase diagram on the basis of the physical components of the two or more kinds of coal analyzed in the analyzing step; the deriving step of simulating the situation generated when the two or more kinds of coal are co-fired on the basis of the produced phase diagram; and the characteristic analyzing step of analyzing the characteristics in the furnace in the co-firing process of the two or more kinds of coal.

Field
The present disclosure relates to a method for predicting a slagging production position and a slagging production possibility in a furnace, and more particularly, to a method for predicting a slagging production position and a slagging production possibility in a furnace that derives, in the furnace using two or more kinds of coal as fuel, a non-linear melting temperature by coal generated upon co-firing of the two or more kinds of coal, and predicts gas and metals temperatures and heat flux by position in the furnace through computational fluid dynamics (hereinafter, which is referred to as CFD) simulation, thereby predicting the slagging production position and the slagging production possibility in the furnace.
Background of the Related Art
While coal is being burned in a furnace used generally in a thermal power plant, slagging as deposits is formed within the furnace, thereby undesirably causing the efficiency of the furnace to be decreased.
When coal ash is accumulated at a high temperature, in more detail, slagging is generally produced on the outer peripheral wall of a steam conveying tube in the interior of the plant furnace. The production of slagging interrupts heat transfer from fuel gas to the steam conveying tube, thereby reducing the whole efficiency of the thermal power plant.
In some serious cases, the operation of the furnace has to stop due to the existence of slagging, and next, the outer peripheral surface of the steam conveying tube in the interior of the furnace is cleaned or repaired.
If two or more kinds of coal are blended and co-fired, they have different percentages of ten or more elements such as iron, aluminum, natrium, calcium and so on, and accordingly, there is a need to derive the composition of each kind of coal and the melting temperature of the composition and thus to predict a non-linear melting temperature by coal generated in the process of the co-firing of the two or more kinds of coal, thereby recognizing that the production of slagging is in advance prevented when any kinds of coal are co-fired.
In addition, there is a need to derive a non-linear melting temperature by coal generated in the process of the co-firing of the two or more kinds of coal and thus to predict gas and metals temperatures and heat flux by position in the furnace through CFD simulation, thereby predicting a slagging production position and a slagging production possibility in the furnace.

Method for predicting slagging production position and slagging production possibility in furnace

Doosan Heavy Industries Construction Co., Ltd


The present invention relates to palladium-cobalt particles useful as oxygen-reducing electrocatalysts. The invention also relates to oxygen-reducing cathodes and fuel cells containing these palladium-cobalt particles. The invention additionally relates to methods for the production of electrical energy by using the palladium-cobalt particles of the invention.

The present invention relates to palladium-cobalt alloy nanoparticles useful as oxygen reduction electrocatalysts in fuel cells. The palladium-cobalt nanoparticles of the present invention have been found to have at least the same catalytic activity as highly expensive platinum nanoparticles while providing a significantly cheaper alternative to platinum.
A "fuel cell" is a device which converts chemical energy into electrical energy. In a typical fuel cell, a gaseous fuel such as hydrogen is fed to an anode (the negative electrode), while an oxidant such as oxygen is fed to the cathode (the positive electrode). Oxidation of the fuel at the anode causes a release of electrons from the fuel into an external circuit which connects the anode and cathode. In turn, the oxidant is reduced at the cathode using the electrons provided by the oxidized fuel. The electrical circuit is completed by the flow of ions through an electrolyte that allows chemical interaction between the electrodes. The electrolyte is typically in the form of a proton-conducting polymer membrane that separates the anode and cathode compartments and which is also electrically insulating. A well-known example of such a proton-conducting membrane is NAFION®.
A fuel cell, although having components and characteristics similar to those of a typical battery, differs in several respects. A battery is an energy storage device whose available energy is determined by the amount of chemical reactant stored within the battery itself. The battery will cease to produce electrical energy when the stored chemical reactants are consumed. In contrast, the fuel cell is an energy conversion device that theoretically has the capability of producing electrical energy for as long as the fuel and oxidant are supplied to the electrodes.
In a typical proton-exchange membrane (PEM) fuel cell, hydrogen is supplied to the anode and oxygen is supplied to the cathode. Hydrogen is oxidized to form protons while releasing electrons into the external circuit. Oxygen is reduced at the cathode to form reduced oxygen species. Protons travel across the proton-conducting membrane to the cathode compartment to react with reduced oxygen species forming water. The reactions in a typical hydrogen/oxygen fuel cell are as follows:Anode: 2H24H++4e−  (1)Cathode: O2+4H++4e−2H2O  (2)Net Reaction: 2H2+O22H2O  (3)
In many fuel cell systems, a hydrogen fuel is produced by converting a hydrocarbon-based fuel such as methane, or an oxygenated hydrocarbon fuel such as methanol, to hydrogen in a process known as "reforming". The reforming process typically involves the reaction of either methane or methanol with water along with the application of heat to produce hydrogen along with the byproducts of carbon dioxide and carbon monoxide.
Other fuel cells, known as "direct" or "non-reformed" fuel cells, oxidize fuel high in hydrogen content directly, without the hydrogen first being produced by a reforming process. For example, it has been known since the 1950's that lower primary alcohols, particularly methanol, can be oxidized directly. Accordingly, a substantial effort has gone into the development of the so-called "direct methanol oxidation" fuel cell because of the advantage of bypassing the reformation step.
In order for the oxidation and reduction reactions in a fuel cell to occur at useful rates and at desired potentials, electrocatalysts are required. Electrocatalysts are catalysts that promote the rates of electrochemical reactions, and thus, allow fuel cells to operate at lower overpotentials. Accordingly, in the absence of an electrocatalyst, a typical electrode reaction would occur, if at all, only at very high overpotentials. Due to the high catalytic nature of platinum, supported platinum and platinum alloy materials are preferred as electrocatalysts in the anodes and cathodes of fuel cells.
However, platinum is a prohibitively expensive precious metal. In fact, the required platinum loading using current state-of-the-art electrocatalysts is still too high for commercially viable mass production of fuel cells.
Accordingly, there have been efforts to reduce the amount of platinum in electrocatalysts. For example, platinum nanoparticles have been studied as electrocatalysts (see, for example, U.S. Pat. Nos. 6,007,934; and 4,031,292). In addition, platinum-alloy nanoparticles, such as platinum-palladium alloy nanoparticles, have been studied (see, for example, U.S. Pat. No. 6,232,264; Solla-Gullon, J., et al., "Electrochemical And Electrocatalytic Behaviour Of Platinum-Palladium Nanoparticle Alloys", Electrochem. Commun., 4, 9: 716 (2002); and Holmberg, K., "Surfactant-Templated Nanomaterials Synthesis", J. Colloid Interface Sci., 274: 355 (2004)).
U.S. Pat. No. 6,670,301 B2 to Adzic et al. relates to an atomic monolayer of platinum on ruthenium nanoparticles. The platinum-coated ruthenium nanoparticles are useful as carbon monoxide-tolerant anode electrocatalysts in fuel cells. See also: Brankovic, S. R., et al., "Pt Submonolayers On Ru Nanoparticles—A Novel Low Pt Loading, High CO Tolerance Fuel Cell Electrocatalyst", Electrochem. Solid State Lett., 4, p. A217 (2001); and Brankovic, S. R., et al., "Spontaneous Deposition Of Pt On The Ru(0001) Surface", J. Electroanal. Chem., 503: 99 (2001), which also disclose platinum monolayers on ruthenium nanoparticles.
However, the platinum-based nanoparticles described above still require the presence of costly platinum. In fact, most of the platinum-based nanoparticles currently known still require high loadings of platinum.
Accordingly, there is a need for new non-platinum electrocatalysts having electrocatalytic oxygen reduction capabilities comparable to platinum or its alloys. None of the art discussed above disclose non-platinum nanoparticle electrocatalysts with oxygen-reducing electrocatalytic activity similar to platinum. The present invention relates to such non-platinum oxygen reduction electrocatalysts.

Palladium-cobalt particles as oxygen-reduction electrocatalysts


A basic assembly configuration for determination of relevant vegetation parameters includes a high repetitive pulsed excitation laser (1) for the stimulation of chlorophyll fluorescence, a fluorescence detector (3) including an imaging and separation optic (4, 5), a trigger and delay electronic (6) to adjust the laser and appropriate detector timing and a detector electronic (7), consisting of a signal recording and processing module. The assembly can be used for determination of relevant vegetation parameters for agricultural, horticultural and greenhouse application.

The present application is the national stage under 35 U.S.C. 371 of international application PCT/EP98/06815 filed Oct. 28, 1998 which designated the United States, and which international application was published under PCT Article 21(2) in the English language.
This invention relates to a fluorescence detection assembly for determination of relevant vegetation parameters comprising an excitation source consisting in a low power laser device with an excitation wavelength in the red spectral region, a beam forming optical device, a dichroic beam splitter, a basic fluorescence detector system including an entrance optical device receiving fluorescence emission via said dichroic beam splitter and an interference filter blocking out the elastic back scatter signal, an electronic detection device for detecting a fluorescence signal, and an electronic trigger and timing device.
First of all the phenomenon of chlorophyll fluorescence will be discussed now.
The absorbed photosynthetic active radiation (PAR) of the solar irradiation (380 nm less than xcex less than 750 nm) is used by plants primarily to convert the absorbed energy in chemically bound energy (photosynthesis) and stored as chemical energy. This process is directly linked with the uptake of carbon dioxide and the release of oxygen (called primary productivity). Two other pathways are possible for the absorbed energy to keep plants energetically balanced. First, the emission of thermal energy and second, the emission as fluorescence light may be used for regulation.
The thermal energy budget is filled up with solar energy from the visible (VIS) and the short wave infrared (SWIR) range of the solar spectrum. SWIR radiation is directly absorbed by the leaf internal water content. The VIS range contributes via the exciton transfer inside the antenna pigment of the reaction centers (PS I; PS II) and light harvesting complex (LHPC). In this process the absorbed photon energy is transformed to energy quantities required by PS I and PS II. The surplus of energy is stored in oscillating and rotation energy levels and thus finally converted into heat.
At the PS I and PS II the absorbed energy quantities may be used by the so called light reactions, may be transferred to heat or finally emitted as fluorescence light. The emitted fluorescence in the red spectral region is due to the chlorophyll molecules associated to PS I, PS II and the LHPC. The conversion probabilities for heat and fluorescence are considered constant in time, whereas the conversion rate at the light reaction is considered as a function of the state of the reaction center (electron transfer chain) and the phosphorylation state of the photosynthetic active cell membranes. The following Equation (1) will describe the fraction of sun induced chlorophyll fluorescence light (FSun(t)) which is emitted by the reaction centers:                                                         F              Sun                                                  (              t              )                                =                                                    k                Fluorescence                                                              k                  Fluorescence                                +                                  k                  Heat                                +                                                      k                    Photosynthesis                                                                          (                                          Φ                      ,                      M                                        )                                                                        *                                          ∫                PAR                                                                            I                                      Abs                    -                    Sun                                                                                ⅆ                  λ
                                                                                k                    i                                                                          :                                                                          xe2x80x83                                                      conversion                                                        xe2x80x83                                                      probability                                                        xe2x80x83                                                      for                                                        xe2x80x83                                                      fluorescence                                ,                                  heat                                                        xe2x80x83                                                      and                                                        xe2x80x83                                                      photosynthesis                                                                                φ                                                        (                    t                    )                                                                                :                                                                  xe2x80x83                                                state                                                  xe2x80x83                                                of                                                  xe2x80x83                                                the                                                  xe2x80x83                                                reaction                                                  xe2x80x83                                                center                                                                                M                                                        (                    t                    )                                                                                :                                                                  xe2x80x83                                                phosphorylation                                                  xe2x80x83                                                of                                                  xe2x80x83                                                membrane                                                                                I                                      Abs                    -                    Sun                                                                                :                                                                  xe2x80x83                                                absorbed                                                  xe2x80x83                                                spectral                                                  xe2x80x83                                                                  irradiance                  .                                                                                (        1        )
From this formula it can be seen that the behaviour of the time dependent chlorophyll fluorescence gives access to the relative changes of the photosynthetic activity if one assumes that xe2x80x9cxcfx86xe2x80x9d and xe2x80x9cMxe2x80x9d are functions of time.
Detection and interpretation of the chlorophyll fluorescence intensity will be discussed now.
The detection of sun-induced chlorophyll fluorescence is difficult due to the fact that the fluorescence signal is superimposed by the reflected light (passive spectrum). For leaves or plant canopies the fluorescence signal is of the order of only some percent compared to the total signal. Therefore, different measuring techniques applying additional light sources were developed in the past for using the chlorophyll fluorescence for different applications.
In general, a modulated or pulsed light source is added to the sun irradiation xe2x80x9cIAbs-Sunxe2x80x9d inducing a modulated or pulsed fluorescence signal Fadd(t) which superimposes the sun induced fluorescence FSun(t) and the reflected signal IR(xcex). Applying a laser source for excitation the so called laser induced fluorescence (LIF) is generated. Equation (1) is then modified to:                     F        Sun                          (        t        )              +                  F        add                          (        t        )              =                    k        Fluorescence                              k          Fluorescence                +                              k            Photosynthesis                                          (                          Φ              ,              M                        )                                *                  ∫        PAR                                    (                                    I                              Abs                -                Sun                                      +                          I              add                                )                                              ⅆ            λ                    .
The total signal which is normally detected is given by the sum of all fluorescence signals and the reflected signal IR(xcex). With adequate technical set-up the fluorescence signal excited by an additional light source can be separated from the passive spectrum and the sun induced fluorescence even under daylight conditions at distances, ranging from direct contact (Schreiber 1986, Patent DE 3518527, Mazzinghi 1991, EP 0 434 644 B1) to one meter (Chappelle 1995, U.S. Pat. No. 5,412,219) and several hundred meters (Cecchi and Pantani 1995, EP 0 419 425 B1).
The technical challenge for all systems either for contact measurements as well as for remote measurements is to install an excitation set-up strong enough to induce a sufficiently intense fluorescence signal in order to overcome the passive spectrum and weak enough to keep the photosynthetic system in an unchanged physiological status.
In the well known pulse-amplitude-modulation (PAM) fluorometer (Schreiber et al. 1986, Patent DE 3518527) a weak measuring light (light emitting red diode LED) induces the chlorophyll fluorescence via an optical fiber without changing the photosynthetic state of the plant. The fluorescence is transmitted by an optical fiber to a photodiode which detects all fluorescence light above 700 nm. For dark adapted plants no photosynthetic activity is stimulated when the measuring light is on.
Illumination of a dark adapted leaf with an intense flash of several milliseconds up to some seconds duration (called saturating light pulse) gives the maximum available fluorescence (called: Fm) but does not induce photosynthesis. A continuous illumination with non saturating light (called: actinic light) induces photosynthetic activity. After several seconds until minutes of illumination all contributing processes are in equilibrium with the supplied light and thus the fluorescence has reached a steady state value Fs. The transient of the fluorescence during illumination of dark adapted leaves is called Kautzky effect. For example FIG. 1 shows a measured diagram of a Kautzky kinetic of a cucumber plant. The detected fluorescence at 685 nm is exclusively induced by the laser pulses. Illumination with a 500 W halogen spot light influence the photosynthetic state only and thus kPhoto. Its contribution to the fluorescence signal, especially as excitation source, is negligible. The PAM fluorometer is normally operated in direct contact with leaves but can be used also at distances of some centimeters.
Detection and interpretation of the Red Fluorescence Ratio will be discussed now.
When excited by UV light, the typical fluorescence spectrum of a plant exhibits two dominant emission bands (FIG. 2), one from 400 nm-600 nm (called: blue-green fluorescence BG) and one from 650 nm-800 nm (called: red fluorescence; F685, F730). For example FIG. 2 shows a diagram of the fluorescence emission spectrum of a maize plant grown in the greenhouse. The fluorescence at 685 nm and at 730 nm (called: F685 and F730) originates exclusively from the leaf internal-chlorophyll. The blue-green fluorescence (BG) is emitted primarily by phenolic components of the cell walls.
The emission features of healthy plants are closely coupled to the plant morphology, as e.g. the pigment constituents and pigment concentration. Additional features may occur when plants are infected by fungi.
From experiments it is known, that the emissions at 685 and 730 nm are both linked to the photosynthetic system as described before and thus show nearly the same variation in time. In contrast the fluorescence ratio F685/F730 of an individual plant or leaf is constant in time and depends only on the optical properties of the leaf (Equation (2)).                               F685          F730                =                              Ψ            730            685                              A                                xe2x80x83                                                                        ⅇ                                                      -                                          (                                                                        β                                                                                xe2x80x83                                                                              1                                                +                                                  c                          *                          α                                                                                xe2x80x83                                                                              1                                                                    )                                                                          d                                            -              1                                                      ⅇ                                                      -                                          (                                                                        β                                                                                xe2x80x83                                                                              2                                                +                                                  c                          *                          α                                                                                xe2x80x83                                                                              2                                                                    )                                                                          d                                            -              1                                                          (        2        )
with:
"psgr":=spectral fluorescence characteristic @xcex=685 and 730 nm
xcex2:=scattering coefficient @xcex=685 and 730 nm
c:=chlorophyll concentration
xcex1:=specific absorption coefficient @xcex=685 and 730 nm
d:=leaf thickness
A:=constant, also containing the coefficients xcex1,xcex2,c,d.
The fluorescence emission and the pigment absorption bands are overlapping around 685 nm (FIG. 3), hence the emitted (fluorescence-) photons are reabsorbed selectively during their path through the leaf tissue resulting in an exponential dependence of the ratio F685/F730 from the parameter: mean free light path in the leaf, scattering coefficient and chlorophyll concentration. FIG. 3 shows a diagram of the shape of specific absorption (xcex1) of chlorophyll a and the corresponding fluorescence emission spectrum (xcexa8).
The only time dependent variation found in the ratio occurred during the transitions from fully dark adapted plants to light adaptation. This small variation was shown to occur from dark to early morning, from afternoon to evening and during Kautzky kinetic. Under day light no significant dependence or correlation respectively of the red fluorescence ratio and global irradiation could be found. Therefore it is assumed that these changes are related to variations in the optical properties of the leaf tissue. A potential mechanism could be the orientation of the plant organelles (e.g. chloroplasts) towards the arising illumination, but this is matter of further investigations.
Nevertheless, the ratio gives access to measure relative variations of the chlorophyll concentration for a plant species if one assumes a similar morphology for the individual plants. This means that the leaf internal scattering coefficient and the leaf geometry are comparable.
Mazzinghi (EP 0 434 644 B1, 1991 and P. Mazzinghi: xe2x80x9cA laser diode fluorometer for field measurements of the F685/F730 chlorophyll fluorescence ratioxe2x80x9d in xe2x80x9cREVIEW OF SCIENTIFIC INSTRUMENTSxe2x80x9d, Vol.67, No. 10, October 1996, pages 3737-3744, XP000635835, New York, USA) developed an xe2x80x9cinstrument for the two-channel measurements of the fluorescence of chlorophyllxe2x80x9d. This portable and compact system is dedicated for direct contact measurements of the fluorescence ratio F690/F730 (respectively F685/F730) as well as for measurements of the RFD-value at both wavelengths using a helium neon laser or a laser diode as continuous excitation source. When operated in full sunlight the residual background light (passive spectrum), due to the direct reflection of the leaf, must be checked after each measurement separately (and then subtracted) because this light is not completely eliminated by the filter on the probe.
The blue-green fluorescence BG will be discussed now.
The origin of the BG fluorescence is more difficult to identify and is still matter of scientific discussion. The blue-green fluorescence originates mainly from the cell walls in the upper layer of leaves and only a small fraction is emitted from deeper cell layers.
For chloroplasts no blue fluorescence is evident because the red chlorophyll fluorescence is the dominant factor. Nevertheless it is known that NADPH in the chloroplasts is emitting blue fluorescence. Also on the cell level it is shown that fluorescent co-enzymes such as NADH or NAD(P)H are very sensitive bio-indicators of metabolic functions such as the degradation of glucose or respiration. Thus the blue NADPH emission depends on the physiological state of the plant.
For leaves the emission of enzymes and co-enzymes is completely covered by emission of the cell wall where several pant constituents are embedded. As is well-known plant phenolics, ferulic-, chlorogenic- and caffeic acids, as well as coumarins are source of the blue emission and alkaloids and flavonols are source of the green fluorescence.
The detection and interpretation BG fluorescence intensity will be discussed now.
On the basis of the present knowledge about the BG fluorescence there is no commonly agreed interpretation of the overall BG fluorescence intensity. A lot of emitter are clearly identified but their contribution to the total signal is still unknown.
A link to the photosynthetic apparatus, comparable to the description in Equation (1), is only found for the NADPH fluorescence. Assuming a time invariant BG fluorescence of all other emission sources it could be capable to monitor also this transients of the BG fluorescence.
Generally the emission is originated at other plant components, e.g. the epidermal cell layer, especially the cell walls or at the vacuoles, also in the mesophyll cells. All this component do not contain chlorophyll and thus do not contribute to the photosynthesis. Nevertheless the main information, derivable from the BG fluorescence intensity is an estimation of the quantity of emitting plant (tissue) pigments in this spectral range.
Detection and interpretation of the parameter BG fluorescence ratio will be discussed now.
Evaluating the spectral characteristics of the BG fluorescence with special regard to the also monitored red fluorescence provides the possibility to normalize the fluorescence (to the chlorophyll fluorescence) and thus making this measurement resistant to calibration effects and signal fluctuations from successively recorded measurements.
As investigated there are at least four different effects, proved by comparable laboratory or field experiments, which can be differentiated due to the spectral characteristics in the blue, green and red range:
Distinction of mono- and dicotyledone plants (blue-green-red)
Synthesis of UV protection pigments (UV stress) (blue-red) Infection by mildew, rust, . . . (fungi) (blue-green-red)
Detection of leaf necrosis at pine needles (blue-green).
In the case of leaf surface coverage by other organic materials as e.g. during fungal infections the fluorescence emission spectrum of the infected leaf is affected in two different ways:
the auto-fluorescence of the fungi increases (or changes) the BG fluorescence selectively
fungi at the surface lower the red fluorescence by absorbing the excitation light and therefore decreasing the penetration depth. The same effect is seen if the excitation light is diffusely reflected by an additional tissue layer at the plant surface.
The latter behaviour is also known from UV protecting pigments within the epidermal cell vacuoles which hinders the xe2x80x9cUVxe2x80x9d excitation to penetrate deeper cell layers and thus depresses the chlorophyll fluorescence selectively. Usually these pigments (e.g. anthocyanin) are solely absorbers and do not contribute to the total fluorescence signal.
The following preconditions are to satisfy for a successful data collection.
Actinicxe2x80x94non actinic measurement light conditions are to be considered.
Depending of the topic of interest it may be necessary to avoid an influence to the photosystem by the excitation source. In all cases where the fluorescence intensity is relevant for the measurement the excitation must keep the plant system condition. It should be controlled only by environmental parameters as e.g. solar irradiance, vitality or the healthy state.
An a priori excluded influence of the excitation allows a measurement of the illumination and thus an estimation of the vitality or healthy state respectively.
This is mostly irrelevant for measurement of the relative chlorophyll concentration because both emission bands are dependent in the same way, but already in the case of comparing the red fluorescence with the blue fluorescence the different origins of the emission bands indicate the necessity of controlling the emission intensity as far as possible.
On the other hand an undisturbed (by excitation light) photosystem gives the possibility to extract plant specific information by controlling the environmental parameter. The variation of e.g. the light energy supplied or the health state of a plant allows the determination of measurement rules to make an interpretation of the intensity fluctuations feasible. This technique is widely used in the already mentioned PAM fluorometry, or realized by the daily cycle measurements with the far field lidar system.
Beyond that the signal to background ratio (SBR) is to be considered.
The signal to background ratio for the active induced fluorescence is defined as the number of photons passively reflected by the leaf tissue (IR) plus sun induced fluorescence (FSun) plus the emitted fluorescence photons (stimulated by the excitation of the measurement light (Fadd)) divided by the number of photons passively reflected by the leaf tissue (IR) plus sun induced fluorescence (FSun)
To distinguish each contribution one needs to determine both of them. In the far field lidar technique the excitation pulse is as intense that the passive background is negligible in comparison to the induced fluorescence light. The main disadvantages of this method are the high cost for an adequate excitation system (laser), the huge effort to operate the laser (power supply, eye safety restrictions, precision optics) and the uncertainty of the illumination state at the measurement plant position.
Moreover the signal to noise ratio (SNR) must be considered.
For single shot operation the signal to noise ratio defines whether a detection system is able to measure the fluorescence signal with each excitation pulse. The main source of noise defining the SNR are:
the sensitivity of the photon detector
the power of the background signal (St1)
the power of the active fluorescence signal (Flaser)
the operating distance
the entrance aperture of the detection system.
The first source is defined by the detector characteristics, whereas the other three components are dependent on the so called xe2x80x9cshot-noisexe2x80x9d.
Photo multiplier tubes (PMTs), especially in continuous operation, are detectors with extremely low noise levels, clearly below the noise level of the photon (shot) noise even with a high gain level. With an optical system large enough to collect sufficient fluorescence photons to depress the signal distortion by shot noise allows single shot operation. This is mandatory in all cases where the target is rapidly changing.
If the target is located at a fixed position relative to the detection system one may use for instance lock-in technique to separate a noisy fluorescence signal from any noise source independently whether the origin of the noise is shot- or detector noise. In this cases one can reduce the requirements to the optical system (reduction of the aperture) or exchange the photo multiplier tube by a cheaper avalanche or normal photodiode.
A fast repetition rate fluorometer is proposed in U.S. Pat. No. 5,426,306 for measuring in-vivo fluorescence of phytoplankton or higher plants with series of fast repetition rate excitation flashes. The system induces the variable fluorescence in order to derive photosynthetic parameters such as variable fluorescence, effective absorption cross section, rate of electron flow and turnover times of photosynthesis. This device is used for measuring fluorescence of samples as a function of the series of excitation flashes.
A method for the automatic detection of plants by measuring chlorophyll fluorescence intensity was introduced by WO 91/10352. According to this method, fluorescence is excited by a light source at wavelength under 550 nm. The emitted fluorescence is detected with a camera supplied with a broadband edge filter (transmission over 600 nm and blocking below 600 nm). No active background suppression is applied. Therefore, a recommendation is given that the light source is strong enough for picture information and that the radiation of the light source reflected directly from the plant or the substrate does not reach the camera.
It is an object of the invention to provide a cheaper high performance fluorescence detection assembly reducing the necessary excitation power by use of a low power laser sufficiently powerful to stimulate emission of a measurable quantity, and reducing the influence of the background signal.
It is a further object of the present invention to provide a new technical approach to measure well known plant physiological parameters under certain conditions with the most accurate determination of the corresponding measurement and environment conditions.
According to the present invention a fluorescence detection assembly for determination of relevant vegetation parameters is characterized in that said low power laser device provided in the excitation source is a high repetitive pulsed laser device with several nanosecond pulse length and a preferred excitation wavelength in the red spectral region of preferable 670 nm, in that said dichroic beam splitter couples the formed excitation beam co-axially to the optical axis of a receiver optic and directing this formed beam witout optical waveguiding to a vegetation target subject to be investigated, in that said basic fluorescence detector system forms an image of the excitation spot at the sensitive detector area, in that said electronic detection device operates at the doubled pulse repetition rate of said excitation laser source and samples the active fluorescence signal synchronously with the laser emission on the one hand and the passive background signal with a fixed delay in the microsecond range before or after the active signal on the other hand, recording those signals by means of a fast sample and hold circuit coupled to an analog to digital converter which enables a digital signal processing, in that said electronic detection device further comprises means for determining the pure fluorescence signal by subtracting the background signal from the active fluorescence signal electronically or in a post processing procedure, and in that said electronic trigger and timing device synchronizes the laser pulses with the sample intervals of said electronic detection device.
Thus this assembly measures explicitly the background signal. The interesting fluorescence signal Flaser is calculated by subtracting the passive contribution to the total signal.
Flaser=St2xe2x88x92St1
xe2x80x9cSxe2x80x9d is the signal at time (subscript) xe2x80x9ct1xe2x80x9d and xe2x80x9ct2xe2x80x9d
St1=IR+FxcexSun
St2=IR+FxcexSun+Fxcexlaser.
At xe2x80x9ct1xe2x80x9d the active excitation is zero and at xe2x80x9ct2xe2x80x9d the active fluorescence emission is added to the passive signal.
To reduce the necessary excitation power the detection spot and thus also the excitation spot is reduced as far as the contribution of the background signal is reduced to the level of the active fluorescence signal.
These and other features and advantages of the present invention will become more apparent from the following detailed description of exemplary embodiments thereof, as illustrated in the accompanying drawings, in which:

Fluorescence detection assembly for determination of significant vegetation parameters

Deutsches Zentrum fur Luft-und Raumfahrt E.V.


A torch assembly for TIG relaxing an inner surface of a tube to be removed from a tube sheet which comprises a conductive base containing passages for cooling water and for inert gas. A sheath is rotatably mounted to the base and contains a drive shaft fixed to the base. A torch head is fixed to an opposite end of the drive shaft and the drive shaft is embraced by a conductive braid so that electrical power applied to the base is conveyed to the torch head. A torch tip extends radially from the torch head and is used to strike an arc with the inner surface of the tube to be TIG relaxed. Inert gas is supplied through the sheath and to a space around the head which is confined by a gas cap. A hole in the gas cap receives the end of the torch tip so that inert gas bathes the annular space around the tip to protect the arc.

The present invention is generally related to welding torches and more particularly to flexible welding torches.
In nuclear steam generators, the tubes are expanded at the level of their tube sheets to form a tube to tube sheet weld. After the steam generator has been in service for a certain period of time, the steam generator and tubes must be examined for the presence of defects that may have occurred during use. The detection of defects in a tube may require the tube, or a portion of the tube, to be removed to allow for closer inspection of the tube defects and/or for replacement of the tube. By relaxing the tube expansion, removing the tube to tube sheet weld, and cutting the tube to the sample length desired, the tube sample can be removed using a hydraulic jacking sequence. The preservation of any tube defects is vital during the removal of the tube sample. Therefore, it is advantageous to reduce the amount of pull force necessary to remove the tube sample. The most common way of accomplishing this is by making various passes such as vertical, spiral, and zig-zag passes on the inner diameter of the tube with a torch. The melting of the tube inner diameter and subsequent solidification causes the tube to contract and pull away from the tube sheet. A tungsten insert gas (TIG) torch is the most suitable type of torch for insertion into a tube and for producing the necessary heat. TIG torches presently known in the industry require 24 to 42 inches of vertical clearance. This presents a problem when tube samples must be removed from the periphery of the tube sheet since the curvature of the steam generator head provides a limited vertical space. Also, some known TIG torch assemblies require the entry of personnel into the steam generator to position the weldhead on the tube sheet. This is undesirable due to the increased radiation exposure.
Accordingly, there exists a need for a TIG torch assembly that requires little vertical clearance and that can be remotely positioned along the tube sheet after it has been placed inside the steam generator.

Torch for removing steam generator tubes


The combination of a bath/shower enclosure with an innovative curtain arrangement to eliminate splashing water from exiting the enclosure. The curtain arrangement includes at least one elongated, hook and pile type fastening strip positioned along each vertical edge of the curtain, and a complementary number of such fastening strips, angularly oriented to the curtain fasteners, on the enclosure walls, whereby the curtain may be adjustably and temporarily fastened to the enclosure walls.

The invention hereof relates to a shower stall curtain closure, or more particularly to the combination of a shower stall or bath enclosure that requires a flexible type curtain, such as made from plastic, where innovative cooperative means are provided to eliminate splashing of water from the stall or enclosure.
Shower bath curtains are often used with bath tubs to convert the bath tub compartment into a shower compartment. The curtains are suspended on a bar at a suitable height above the outside rim of a bath tub with the lower edge of the curtain placed inside the bath tub and with its edges being located against the end walls of the compartment. It is well known that the above arrangement suffers from the drawback of the shower water escaping through an area of corners defined by the bath tub rim and the end walls of the compartment.
The escaped water cannot only be a hazard to the one exiting the shower, by slipping and possibly injuring oneself on the floor, the water can cause permanent damage to the floor or underlying support surface. This can result in costly repairs.
With this recognition and attending problems known for years, the prior art is replete with devices or proposed solutions in an attempt to contain the water within the shower stall or enclosure. The prior art attempts are reflected in the following U.S. patents:
a.) U.S. Pat. No. 5,148,580, to Dyckow, teaches a kit for use to fasten the outer surface of a shower curtain to an adjacent wall in the shower closure. A sealing protrusion extends from the wall adjacent the fasteners so that, when the outer surface of the curtain is fastened to the wall, the edge of the curtain abuts the protrusion.
b.) U.S. Pat. No. 5,101,522, to Prian, relates to a shower curtain support fixture for hanging a shower curtain above a bath tub which includes a generally U-shaped structure having an elongated main portion and a pair of opposite end portions extending generally transverse to the main portion. A slot is defined in a bottom side of the U-shaped structure extending along its main portion and opposite end portions so as to provide a generally U-shaped guide track in the structure. Shower curtain hanger devices are inserted through the slot and slidable individually along the track provided by the slot. Aligned holes formed through the opposite end portions of the structure facilitate mounting of the structure with its opposite end portions extending in flush relation to oppositely facing bathroom walls disposed at opposite ends of the bath tub, such that a shower curtain hanging from the U-shaped structure by the plurality of hanger devices is extendable into the tub and along a front side of the tub and around front opposite corners thereof to effectively block water from spashing out of the tub over the front side and the front opposite corners of the tub.
c.) U.S. Pat. No. 5,070,551, to Harrison et al., discloses a plurality of wall fasteners positioned along the vertical edges of a shower curtain. The wall fasteners maintain the edges of the shower curtain in contiguity with the shower walls between which the curtain is hung. Thus, the water spray from the shower can not splash past the edges of the shower curtain and the enclosure walls. The fasteners mate with a corresponding fasteners on the shower curtain. Approximately the entire vertical edges of the curtain is, thus, sealed against the shower walls to thereby prevent any water from escaping.
d.) U.S. Pat. No. 4,825,481, to Lonberger, is directed to an arrangement for placing a shower curtain within the opening to a combination shower-bathtub enclosure which utilizes clamps, secured to the side or end walls of the enclosure, for the selective gripping of the free edges of the shower curtain when the latter is in a use condition. The preceding prevents unwanted water spray passage into the area outside of the enclosure and, thereby, overcomes a problem which has been commonly encountered heretofore. The clamps, spring-urged to a normally gripping relationship, serve convenience in use.
e.) U.S. Pat. No. 4,769,862, to Skrzelowski, relates to a shower curtain support defined by a track for slidably suspending a shower curtain across the front opening of a shower stall and around the end corners of the support rearwardly at the front opening. End portions of the shower curtain may be drawn around the corners and inside the shower stall to overlap at least a portion of the surface of the stall end walls in order to prevent leaks. Alternately, a continuous curtain support track is provided in a U-shape or other configuration. End pieces attached thereto support a curtain in a plane parallel to the wall surfaces to prevent spraying or splashing outside the shower area.
f.) U.S. Pat. No. 4,077,072, to Dezura, teaches a device for releasably securing to a bath tub compartment at least one end of a shower curtain arranged such that the part of the shower curtain near one vertical edge thereof is not only secured to the generally vertical wall of the compartment, at least a part of the front portion is also secured to the horizontal rim of a bath tub. The curtain thus forms, on releasably fixing same to the compartment, a corner envelope which effectively prevents undesired escape of shower water.
g.) U.S. Pat. No. 3,808,610, to Mortensen, discloses a shower curtain guard for use particularly in connection with shower enclosures above conventional bath tubs. The guard comprises a vertical bar or rail, attached by a double adhesive medium, to the wall at one or both ends of the tub. The rail is bent inwardly above the tub to hold the lower end of the curtain within the tub while affording a wider shower compartment above the tub. A spongy plastic seal prevents escape of water between the tub and the lower end of the bar to rail. Interlocking fibre patches on the curtain and on the rail, which are separable, secure the curtain so as to prevent water passing outside the compartment.
While the prior art offers proposed solutions for containing water within a shower stall or enclosure, none teach a simple, readily adjustable means to accomplish the goal of preventing splashing water from leaving the shower enclosure. The manner by which this simplicity is achieved in the present invention will become more apparent from the following description.


This invention relates to a layout structure for providing stable power supply to a four-layer motherboard and a main bridge chip substrate. In the invention, on the top signal layer and power path of the bottom solder layer for layout of the main bridge chip and on the power ring, the decoupling capacitors are connected in between the ground bonding pads/solder balls and the power bonding pads/solder balls of the power paths and power rings, so as to provide a stable power supply for the operation of the main bridge chip. In this invention, the ground bonding pad/solder ball connected with each power bonding pad/solder ball can be the closest ground bonding pad/solder ball to the power bonding pad/solder ball. In addition, in the embodiment of the main bridge chip substrate, decoupling capacitors can be disposed at four corners of the power ring or underneath the bonding wires, or can be packaged inside the molding compound.

1. Field of Invention
This invention relates to a layout structure for providing a stable power source More particularly, this invention relates to a layout structure for providing stable power source to a main bridge chip substrate and a motherboard.
2. Description of Related Art
With fast developing technology, the operation speed of computers is getting faster and faster. Taking Intel Pentium 4 as an example, the CPU bus speed can reach 532 MHz (133 MHz×4). This means that the main bridge chip is required to provide higher bus speed on other buses to work with the peripheral components connected to it. The buses include the memory bus with the speed of 333 MHz (166 MHz×2), the AGP bus with the speed of 528 MHz (66 MHz×8) and the main-subalternate connecting bus with the speed of 66 MHz×8. In addition to the high operation speed in requirement, the layout of the main bridge chip substrate as well as the motherboard have to be well designed in order to achieve stable operations for the above devices. Normally, certain design sequences have to be followed during designing the layout of the main bridge chip and motherboard. For example, in order to stabilize a good signal quality on the signal layer, a ground layer has to be provided on the main bridge chip substrate or the motherboard, close to the signal layer, so that all the signals on the signal layer can be referenced to the ground layer.
However, the existing signal-referencing method mentioned above often has some problems depending on how the layout is designed for the main bridge chip substrate and the motherboard FIG. 1 shows a conventional circuit layout for the main bridge chip substrate and the motherboard, wherein there are 4 layers from top to bottom by the top signal layer 11, the ground layer 12, the power source layer 13, and the bottom solder layer 14 respectively. In the conventional layout for the motherboard and the main bridge chip substrate, almost all of the signals in layout are arranged the top signal layer 11, so that the signal lines can be referenced to the ground layer 12. On the other hand, various types of power sources can be obtained through the layout and partition on the power source layer 13. Moreover, the bottom solder layer 14 of the main bridge chip substrate normally contains the solder balls for soldering to the motherboard. Also and, the other circuits for which the signal quality is not critical can also be arranged into this bottom solder layer 14. However, when the main bridge chip needs an even higher bus speed (higher than 1 GHz for example), the layout of the main bridge chip substrate and the motherboard becomes very important because it consumes more power for the relating controllers and the interfaces The layout of the power source is then a rather more important issue.
FIG. 2 shows a schematic diagram of an existing layout structure of the main bridge chip on the power source layer 13 of the motherboard 200, where the partition of the power layer 13 is also indicated in FIG. 2. Furthermore, FIG. 2 also shows many bonding pads which are located at the top signal layer 11 and are connected with the power layer 13 through the vias. It should be noted that the bonding pads must be arranged and positioned according to the locations of the related components. As for the main bridge chip substrate, it is connected with the bonding pad of the motherboard through the solder balls arranged at the bottom solder layer 14, so that the main bridge chip can obtain the related working voltages and proceed the work.
In FIG. 2, it further comprises multiple working connection regions. The CPU working connection region 201 represents the region where the main bridge chip and the CPU are connected together. This region includes the signal bonding pads for connecting to the CPU. The region also includes some ground bonding pads (the black dots) and some CPU power bonding pads (marked with "T"). The CPU power ring 201A, more particularly, represents a region of the power ring on the main bridge chip, wherein the CPU working connection region 201 is connected with the CPU power bonding pads. In addition, the memory working connection region 202 represents the region in which bonding pads are located for connecting the main bridge chip and the memory locates. The bonding pads include the signal bonding pads for connecting the memory (SRAM for example), and also some ground bonding pads as well as some memory power bonding pads (marked with "M"). The memory power ring 202A represents a region of the main bridge chip power ring, which is the region located in the memory working connection region 202 and being connected to the memory power bonding pads. Furthermore, the subalternate bridge working connection region 203 represents the bonding pad region where the main bridge chip and the subalternate bridge are connected. These bonding pads include not only the signal bonding pads connecting to the subalternate bridge chip, but also several ground bonding pads and subalternate bridge power bonding pads (marked as "V"). The subalternate bridge power ring 203A represents a region of the main bridge chip power ring, which is the region connecting the subalternate bridge working connection region 203 to the subalternate bridge power bonding pads. Moreover, the AGP working connection region 204 represents the bonding pad region connecting the main bridge chip and the AGP component. Wherein, the bonding pads include both signal bonding pads connecting the AGP component and the several ground bonding pads as well as some AGP power bonding pads (marked as "A"). The AGP power ring 204A then represents the region of the main bridge chip power ring, which is the region connecting the AGP working connection region 204 and the AGP power bonding pads. It should be noted in FIG. 2 that the ground bonding pads and the signal bonding pads are depicted as black dots 207 and unfilled circles 208 respectively.
Even though the conventional power layer 13 is partitioned in plane according to the layout in FIG. 2, the power layer after partitioning still cannot be fully used. For example, the region 205 represents the actually utilized power path of the CPU working connection region 201. Since the power path 205 is connected at one side of the CPU working connection region 201, the inductance is not uniformly distributed on both sides of the CPU working connection region 201, causing fluctuation of the supplied voltage. In other words, the inductance level is higher for the CPU located further away from the power path 205, and it is lower for the CPU located closer to the power path 205, causing the supplied voltage to be relatively unstable. In addition, from the distribution of power layer 13 shown in FIG. 2, it can be seen that the power rings 201A, 202A, 203A, and 204A all have different widths. For example, the regions indicated in 202B or 202C depict different widths or missing corners, where the inductance levels of these regions are high. Therefore, when operating under high speeds, the power layer 13 often cannot provide current in a timely manner. This results in a rather large ground/bounce effect, further resulting in unstable high-frequency signals, so as to jeopardize the normal data-processing activities of the entire system.

Layout structure for providing stable power source to a main bridge chip substrate and a motherboard


An automatic transmission has an input shaft and an output shaft provided parallel to the input shaft. Above the input shaft is provided a pair of planetary gear mechanisms, an output gear supported on the transmission casing, and two input elements for inputting to the pair of planetary gear mechanisms. The input elements are spaced apart in the direction of the shafts, and the pair of planetary gear mechanisms and the output gear are provided in the space between the input elements. The planetary gear mechanisms are preferably provided respectively facing each side of the output gear with the output gear in the middle. The output gear preferably functions as a connecting member to operably connect with a rotational member of one of the planetary gear mechanisms. The transmission comprises a plurality of frictional engagement elements for selectively operating the planetary gear mechanism according to the driving condition of the vehicle. These engagement elements are preferably clutches of a novel configuration.

Two-shaft type automatic transmissions for motor vehicles are known which combine a torque convertor and a shift change gear mechanism. The power transmission route of the shift change gear mechanism is switched by the selective operation of a plurality of frictional engaging elements such as clutches or brakes, etc., and constructed so that the gear stage is automatically switched in accordance with the driving condition of the vehicle. This type of automatic transmission has an input shaft for inputting engine output over the torque convertor, and an output shaft parallel to the input shaft. For example, Japanese Unexamined Published Patent Application (hereinafter referred to as Kokai) No. 62-93546 discloses an automatic transmission which has an input shaft connected to the turbine of the torque converter and an output shaft disposed parallel to the input shaft. A pair of planetary gear mechanisms, which serve as a shift change gear mechanism, is disposed between a partition wall portion and a rear wall portion of the shift gear casing over the input shaft.
In this type of transmission, in which the planetary gear mechanism is disposed over the input shaft, the mechanism is constructed with a helical gear. Because thrust load is generated following the operation of the planetary gear mechanism, thrust load is applied to the rear wall portion of the shift gear case in the direction of the shape of the helical gear. For this reason, it is necessary to increase the thickness of the rear wall portion, etc., and to improve the strength and rigidity of this portion. This tends to increase the weight and size of the shift gear mechanism.
Also, in order to obtain a plurality of gear stages by connecting the rotational elements of one of the pair of planetary gear mechanisms disposed over the input shaft, connecting members are necessary, which lead to an increase in the number of parts.
Therefore, it is an object of the present invention, in an automatic transmission having an input shaft, an output shaft parallel to the input shaft and a pair of planetary gear mechanisms disposed over the input shaft, to effectively transfer the thrust load generated by the operation of the pair of planetary gear mechanisms to the transmission casing. It is a further object of the present invention to keep the number of parts connecting with the rotational elements of each of the planetary gear mechanisms low.
In the above type of automatic transmission, hydraulic clutches are known, which serve as frictional engagement elements. Such as disclosed in Kokai 62-52249. In the disclosed clutch, in order to improve the releasability of the clutch, a centrifugal balance chamber is formed on one side of the clutch piston opposed to the hydraulic chamber.
In such known clutches, in the side portion of the clutch drum which forms the hydraulic chamber with the other side of the piston, elements for transmitting power to the clutch drum are provided, such as a one-way clutch for regulating the rotation of the clutch drum. A hydraulic clutch which serves as a power transmission device and contains a one-way clutch as above has increased axial dimensions, and thus causes the size of the entire transmission to increase.
It is, therefore yet another object of the present invention, to provide an automatic transmission in which, when a power transmission device such as a clutch and the power transmission elements for the clutch are aligned above the axis of the transmission, the power transmission elements can be arranged so as not to invite any increase in size of the transmission.


A cutting apparatus for slicing semiconductor materials into wafers is disclosed.. The cutting apparatus broadly comprises a pair of spaced-apart co-planar rotatable wheels, a continuous metallic band passing over said wheels, means for driving one of said wheels to move said band unidirectionally through a path encompassing said wheels and through a linear cutting region, means for moving the other wheel towards and away from the driven wheel for tensioning the metallic band, workpiece support means stationed in the cutting region adapted to raise a workpiece to the metallic band at a controlled speed, means for supplying an abrasive slurry to said metallic band in the cutting region upstream of the workpiece, and guide-wipers upstream and downstream of the cutting region each comprising a pair of opposed, laterally and linearly offset wipers for dampening lateral motion of the metallic band, maintaining the band in alignment across the workpiece and wiping the band of abrasive slurry before the band passes over the driven wheel.

This invention relates to a cutting apparatus and is particularly directed to a cutting apparatus for slicing semiconductor materials into wafers.
U.S. Pat. No. 3,599,623, which discloses a closed-loop saw having a continuous band with diamond powder cutting edge, comments on disadvantages inherent in several known techniques such as the scribe-and-break process, sawing with closed wire loops with abrasive slurries, and sawing with reciprocating blades with the workpiece stationary or moved into the saw blade, for severing semiconductor wafers into individual devices. Disadvantages commonly encountered include: difficulty in severing semiconductor materials, particularly friable and expensive materials, into small dies; the inability to produce consistently straight and planar cuts; crumbling of the sides of the cuts; the need for complex and expensive systems; and in the method of the above-mentioned patent, the formation of saw marks on cut surfaces.
It is a principal object of the present invention to provide a cutting apparatus for precision slicing of semiconductor materials with a minimum of kerf loss yielding smooth cut surfaces substantially free of saw marks which normally do not require subsequent lapping.

Cutting apparatus for semi-conductor materials


Metallizing paste is composed, by weight, of 100 parts of Pt, 0.5 to 5 parts of Ag, 0.1 to 1 part of CuO, and 2 to 10 parts of a low thermal expansion fritt, which may also contain up to 100 parts of Au. Another metallizing paste is composed, by weight, of 100 parts of Pd, 0.5 to 4 parts of Ag, 0.1 to 1 part of CuO, and 1 to 10 parts of a low thermal expansion fritt, which may also contain up to 50 parts of Au. A low thermal expansion circuit board with multi-layers is made up to a low thermal expansion substrate such as crystallized glass, A1N, SiC, Si.sub.3 N.sub.4 etc. and metallized layers formed on the surface of the substrate based on the abovementioned metallizing pastes comprising crystallized glass type materials.

This invention relates to metallizing paste for use in multi-layered circuit board for mounting integrated circuits (IC), IC-packages, and so forth thereon. More particularly, it is concerned with metallizing paste adaptable to ceramic substrate materials having a thermal expansion coefficient (.alpha.) of 5.0.times.10.sup.-6 /.degree. C. or lower, such as crystallized glass, alumina-glass composite body, SiC, Si.sub.3 N.sub.4, AlN, and so forth.
In recent years, with development in miniaturization, etc. of various electronic apparatuses and appliances, packaging (or mounting) density of those electrical components such as IC, etc. on the circuit board has become higher and higher. Considering, further, mounting of the power semiconductors, etc., quantity of heat generation on the circuit board becomes much greater.
On account of this, the substrate material to be used is also of ceramic having the thermal expansion coefficient (.alpha.) of 5.0.times.10.sup.-6 /.degree. C. or lower (at a temperature ranging from room temperature to 400.degree. C.), examples of which are SiC, Si.sub.3 N.sub.4, AlN, and so forth. In recent years, there has also been developed the substrate made of crystallized glass material.
For such multi-layered substrates and packages of low thermal expansion coefficient, gold-metallization is usually used, onto which metallized layer metal members (such as leads) are joined by use of brazes such as AuSn or AuSi, or solders such as In/Pb and so on.
In the methods of joining the metal members to the substrates utilizing the brazing or soldering (generally referred to as "brazing" hereinafter) materials as mentioned above, there have been problems in its workability and reliability owing to softening of the brazing material by its reheating during joining of IC chips (at the time of die-mounting). It becomes therefore necessary that the metal member be joined by use of a high temperature brazing material (e.g., pure silver brazing). In this case, the paste for the substrate should also be compatible with this brazing material.
However, the gold metallizing pastes which have conventionally been used for the substrates and so on causes an alloy to be formed between the gold and the softened brazing material, when use is made of a high temperature brazing material such as pure silver braze. On account of this, the gold which has been metallized on the surface of ceramic material is dispersed in the brazing material to lower the bonding strength thereof to become unable to maintain it in a preferred amount and to bring about a problem presenting "eroding phenomenon by the brazing material".
Furthermore, as a method for metallizing ceramics, there has been known the so-called "Telefunken Process" utilizing high melting point metals. However, since these metals are, conductors of a high resistance, they are not suitable for metallizing the multi-layered circuit boards, and others.

Metallizing paste for circuit board having low thermal expansion coefficient


Disclosed is a photographic element comprising a light-sensitive silver halide emulsion layer having associated therewith a cyan "NB coupler" having the formula (I): wherein: ##STR1##. the term "NB coupler" represents a coupler of formula (I) that forms a dye for which the left bandwidth (LBW) using spin-coating is at least 5nm less than that of the same dye in solution form;. Y is H or a coupling-off group;. each Z" and Z* is an independently selected substituent group where n is 0 to 4 and p is 0 to 2;. W2 represents the atoms necessary to complete a heterocyclic ring group; and. V is a sulfone or sulfoxide containing group;. provided that the combined sum of the aliphatic carbon atoms in V, all Z" and all Z* is at least 8. The element exhibits improved cyan dye hue.

In silver halide based color photography, a typical photographic element contains multiple layers of light-sensitive photographic silver halide emulsions coated on a support with one or more of these layers being spectrally sensitized to each of blue light, green light and red light. The blue, green, and red light-sensitive layers typically contain yellow, magenta, and cyan dye-forming couplers, respectively. After exposure to light, color development is accomplished by immersing the exposed material in an aqueous alkali solution containing an aromatic primary amine color-developing agent. The dye-forming couplers are selected so as to react with the oxidized color developing agent to provide yellow, magenta and cyan dyes in the so called subtractive color process to reproduce their complementary colors, blue, green and red as in the original image.
The important features for selecting the dye-forming coupler include, efficient reaction with oxidized color developing agent, thus minimizing the necessary amounts of coupler and silver halide in the photographic element; the formation of dyes with hues appropriate for the photographic use of interest, for color photographic paper applications this requires that dyes have low unwanted side absorption leading to good color reproduction in the photographic print; minimization of image dye loss contributing to improved image permanence under both ambient illumination and conventional storage conditions; and in addition the selected dye-forming coupler must exhibit good solubility in coupler solvents, provide good dispersibility in gelatin and remain stable during handling and manipulation for maximum efficiency in manufacturing processes.
In recent years, a great deal of study has been conducted to improve dye-forming couplers for silver halide photosensitive materials in terms of improved color reproducibility and image dye stability. However, further improvements are needed, particularly in the area of cyan couplers. In general, cyan dyes are formed from naphthols and phenols as described, for example, in U.S. Pat. Nos. 2,367,351, 2,423,730, 2,474,293,2,772,161, 2,772,162, 2,895,826, 2,920,961, 3,002,836, 3,466,622, 3,476,563, 3,552,962, 3,758,308, 3,779,763, 3,839,044, 3,880,661, 3,998,642, 4,333,999, 4,990,436, 4,960,685, and 5,476,757; in French patents 1,478,188 and 1,479,043; and in British patent 2,070,000. These types of couplers can be used either by being incorporated in the photographic silver halide emulsion layers or externally in the processing baths. In the former case the couplers must have ballast substituents built into the molecule to prevent the couplers from migrating from one layer into another. Although these couplers have been used extensively in color photographic film and paper products, the dyes derived from them still suffer from poor stability to heat, humidity or light, low coupling efficiency or optical density, and in particular from undesirable blue and green absorptions which cause considerable reduction in color reproduction and color saturation.
Cyan couplers which have been recently proposed to overcome some of these problems are 2,5-diacylaminophenols containing a sulfone, sulfonamido or sulfate moiety in the ballasts at the 5-position, as disclosed in U.S. Pat. Nos. 4,609,619, 4,775,616, 4,849,328, 5,008,180, 5,045,442, and 5,183,729; and Japanese patent applications JP02035450 A2, JP01253742 A2, JP04163448 A2, JP04212152 A2, and JP05204110 A2. Even though cyan image dyes formed from these couplers allege in various instances improved stability to heat and humidity, enhanced optical density and resistance to reduction by ferrous ions in the bleach bath, the dye absorption maxima (.lambda..sub.max) are too bathochromically shifted (that is, shifted to the red end of the visible spectrum) and the absorption spectra are too broad with considerable amounts of undesirable blue and green absorptions and often lack sufficient stability toward light fading. Thus, these couplers are not acceptable for use in color papers and print applications.
The hue of a dye is a function of both the shape and the position of its spectral absorption band. Traditionally, the cyan dyes used in color photographic papers have had nearly symmetrical absorption bands centered in the region of 620 to 680 nm, typically 630 to 660 nm. Such dyes have rather large amounts of unwanted absorption in the green and blue regions of the spectrum.
More desirable would be a cyan dye whose absorption band is asymmetrical in nature with a steep slope on the short wavelength side, giving less undesired absorption. The half-bandwidth on the short side of the curve, also called the left bandwidth or LBW, is desirably narrowed. Such a dye would suitably peak at a shorter wavelength than a dye with symmetrical absorption band, but the exact position of the desired peak depends on several factors including the degree of asymmetry and the shapes and positions of the absorption bands of the magenta and yellow dyes with which it is associated.
Recently, Lau et al., in U.S. Pat. No. 5,686,235, describe a particular class of cyan dye-forming coupler that has been shown to improve thermal stability and hue, particularly, with decreased absorption in side bands and an absorption band that is asymmetrical in nature. The couplers disclosed as suitable contain a sulfone group bonded to the 2- position of an acetamido group at the 5-position of the phenolic ring and contain a phenylcarbonamido group in the 2-position of the phenolic ring. Other related patents are U.S. Pat. Nos. 5,047,314, 5,047,315, 5,057,408, and 5,162,197.
Although the coupler of Lau et al. provides an advantageous spectra, it is desirable to discover alternative phenolic structures that will accomplish the same result and that may provide other desirable features. Chemical variations may enable advances in the ability to better select the desired curve shape and wavelength of maximum absorption and other properties such as coupler and dye light and dark stability, reactivity etc.
Japanese published application 59-111,645 suggests certain phenolic couplers having an .alpha.-sulfonyl substituent in a 5-carbonamido substituent that forms a dye having a maximum absorption at "about 660 nm" with examples of 657-660 nm. It appears that the spectral curve of the disclosed dyes exhibit the usual broad absorption band but that the curve has been shifted to the long wavelength side in order to reduce the unwanted absorption on the short wavelength side. The disclosed compounds do not provide the desired narrow LBW and shorter wavelength of maximum absorption.
The problem to be solved is to provide an alternative photographic element, compound, and process, employing a cyan dye-forming phenolic coupler which forms a dye having a narrowed LBW and corresponding lower unwanted side absorptions.

Photographic element, compound, and process


A rotary selector switch comprises a generally flat blade mounted for rotation in its own plane about an axis passing through it into and out of contact with one or more of several spaced terminal contacts.

This invention relates to gas-insulated substations and more specifically relates to a novel rotary switch for gas-insulated substations.
In gas-insulated substations a variety of switching functions must be performed and, consequently, a variety of disconnect switch types have evolved. These would include, for example, horizontal switches, breaker switches, tap switches, ground switches and the like. Each of these switches is now made as a separate unitary device and several distinct switch devices are interconnected in any given substation assembly. Each of the distinct switch devices is relatively expensive and requires separate engineering drawings. In addition, each unitary switch takes up space, and limits the substation compactness that can be achieved, particularly at lower voltages. The individual switches must also be provided with respective controls and, frequently, with motor operators, gas monitoring systems, and the like.

Rotary switch for gas-insulated substations


A laundry treatment apparatus includes a drawer. The laundry treatment apparatus further includes a cabinet that is configured to receive the drawer. The laundry treatment apparatus further includes an introduction port that is located in an upper surface of the drawer. The laundry treatment apparatus further includes a drum that is located in the drawer and that is configured to communicate with the introduction port. The laundry treatment apparatus further includes a driving shaft that is located at a bottom surface of the drum. The laundry treatment apparatus further includes a driving unit that is configured to rotate the driving shaft. The laundry treatment apparatus further includes a controller that is configured to control the driving unit. The laundry treatment apparatus further includes an attachment and detachment unit that is configured to connect the drawer to the cabinet in response to a control signal from the controller.

In general, a laundry treatment apparatus is a concept including an apparatus for washing laundry (objects to be washed), an apparatus for drying laundry (objects to be dried), and an apparatus for washing and drying laundry (objects to be washed and objects to be dried).
In a front loading type laundry treatment apparatus (for example, a drum type washing machine), in which laundry is introduced into the laundry treatment apparatus through the front thereof, an introduction port, through which laundry is introduced into the laundry treatment apparatus, is lower than the waist of a user, with the result that the user must stoop to introduce laundry into the laundry treatment apparatus or to remove laundry from the laundry treatment apparatus.