4616 4620.output

* GB785023 (A)

Description: GB785023 (A) ? 1957-10-23

Improvements in or relating to methods of detecting loose impurities intransparent containers

Description of GB785023 (A)

COMPLETE SPECIFICATION Improvements in or relating to methods of Detecting Loose Impurities! in Transparent Containers We, THE GENERAL ELECTRIC COMPANY LIMITED, of Magnet House, Kingsway, London W.C.2, a British Company, do hereby de clare the invention, for which we pray that a Patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates to methods of detecting loose impurities in transparent containers such as glass bottles when these containers are filled with liquid such as milk. An object of the present invention is the provision of an improved method of detecting the presence of broken glass or other loose foreign matter or impurities in a filled glass milk bottle. according to the present invention, a method of detecting loose impurities or foreign matter in a filled transparent container such as a glass bottle comprises illuminating the container from below so that the bottom of the container is illuminated, rotating the container about its vertical axis to set any loose foreign matter in motion, and rapidly stopping the rotation of the container, any loose foreign matter in the bottom of the container being arranged to be detected Iby photo-electric means responsive to the change in reflected light from a part of the bottom of the container anto which part the foreign matter travels as it spirals inwards after the rotation of the container is stopped. Apparatus for ,detecting loose impurities or foreign matter in a filled transparent container such as a glass bottle, may comprise

means to rotate la container at high speed about its vertical axis, means to illuminate the bottom of the container, photo--electric means arranged to view the bottom of the container and to be responsive to reflected light, and a slide inserted between the bottom of the container and the photoelectric means, said slide being entirely opaque to light except for a narrow spiral slit lying substantially within an image of the bottom of the container arranged to be produced upon the slide by an optical system placed between the slide and the container, the direction of said spiral slit being opposite to the direction of the spiral trajectory executed by the image of a loose impurity after abrupt stoppage of the motion of the container. An apparatus in accordance with the pre sent invention will now be described by way of example with reference to the single figure of the accompanying drawing, which shows a diagrammatic perspective view partly in section of the main elements of the apparatus as used for the detection of broken glass or other loose foreign matter in a filled glass bottle of milk. Referring to the drawing, the apparatus comprises a lightproof box 1 having in its top an aperture 2 over which the bottle 3 is arranged to be placed with its axis vertical so that the bottom of the bottle can be illumi nated by one or more lamps 4 set inside the box 1 towards the top thereof and screened from the remainder of the box. The bottle 3 is arranged to be rotated about its vertical axis at high speed and a chuck (not shown) for gripping the bottle and rotating it may be disposed above the bottle on its axis. Situated directly beneath 'the aperture 2 in the top of the box 1 and below the screening means of the lamp or lamps, is an optical system comprising a lens 5, bellows 6 and a slide 7 in that order, the plane of the lens 5, and the plane of the slide 7 being parallel to the top of the box 1 and the bottom of the bottle 3, and the slide 7 being entirely opaque to light with the exception of a narrow spiral slit 8, 'the spiral ,extending from the centre of the image of the bottom of the 'bottle, formed iby the lens 5 on the slide 7, to a short distance beyond the outside of the image. The spiral slit 8 is arranged to execute at least one revolution in the area covered by the image, in a direction opposite to the spiral executed by the image of a loose impurity after stoppage of the motion of the bottle. Situated below the slide 7 on the axis of the bottle 3 and the

axis of the spiral slit 8 in the slide, is a photo electric multiplier 9 responsive to light re elected from the bottom of the bottle. The photo-.electric multiplier 9 is associated with an electric control circuit (not shown) arranged to reject or pass m-ttk bottles de pending upon whether they contain or do not contain foreign matter and suitable voltage amplifying means will be associated with the photo-electric multiplier. In operation of the apparatus described above a bottle 3 is .placed above the aperture in the top of the Ibox 1 and rotated at high speed. The milk in the bottle also rotates after the lapse of a short period and any foreign matter which is in the bottle is thrown to the outer periphery of the bottom of the bottle 3 as the milk rotates. The bottle 3 is then stop ped rapidly and the milk will continue to rotate on its own for some seconds, gradually coming to rest During the slowing down of the milk, any particle of loose matter such as 10 in the bottom of the bottle will spiral inwardly towards the centre at a rate dependent upon the mass of the particle, a light particle travelling an almost circular path while a heavy particle travels much more directly towards the centre, in a path which may be practically radial. It will Ibe understood that both extremes of path will intersect an oppo sitely-directed spiral. Immediately upon the rotation of the bottle 3 being stopped, the photo-electric system including the multiplier 9 is set in operation so that as any foreign matter 10 spirals inwardly, its image 11 on the slide 7 will pass over that area embraced by the spiral slit 8 and will cause a change in the reflected light received by the photo-electric system including the multiplier 9. This change is adapted to cause such operation of the system that the bottle is rejected. If no foreign matter is present in the bottle, then the photo-electric system does not reject a bottle. One advantage of using the spinning method to cause relative movement between the foreign matter and the wall of a bottle is that if the dirt is initially floating on the top of the milk the spinning aids gravity to make the impurities sink.

As will be appreciated from the above de ascription, the apparatus differentiates between loose foreign matter inside the bottle and dirt or embossing on the outside of the bottle since at the critical time of viewing, the bottle itself is stationary, the only movement being in the milk itself. What we claim is: - 1. A method of detecting loose impurities or foreign matter in a filled transparent con tainer such as a glass bottle which comprises illuminating the container from below so rhat the 'bottom of the container is illuminated, ro tating the container about its vertical axis to set any loose foreign matter in motion, and rapidly stopping .the rotation of the container, any loose foreign matter in the bottom of the container being arranged to be detected by photo-electric means responsive tot he change in reflected light from a part of the bottom of ,the container into which part the foreign matter ,travels as it spirals inwards after the rotation of the container is stopped. 2. Apparatus for detecting loose impurities or foreign matter in a filled transparent container such as a glass bottle, comprising means to rotate the container at high speed about its vertical axis, means to illuminate the bottom of the container, photo-electric means arranged to view the bottom of the container and to he responsive to reflected light, and a slide inserted between the bottom of the container and the photo-electric means, said slide being entirely opaque to light except for ,a narrow spiral slit lying substantially within an image of the bottom of the container arranged to be produced upon the slide by an optical system placed between the slide and the container, the direction of said spiral slit being opposite to the direction of the spiral trajectory executed by the image of a loose impurity after abrupt stoppage of the motion of the container. 3. A method for detecting loose impurities or foreign matter in a filled glass bottle, or apparatus for carrying out the method, substantially as hereinbefore described with refer ence to the accompanying drawing. PROVISIONAL SPECIFICATION Improvements in or relating to methods of Detecting Loose

Impurities in Transparent Containers We, THE GENERAL ELECTRIC COMPANY LIMITED, of Magnet House, Kingway, London W.C.2, a British company, do hereby declare this invention to be described in the following statement: This invention relates to methods of detecting loose impurities in transparent containers such as glass bottles when these containers are filled with liquid such as milk. An object of the present invention is the provision of an improved method of detecting the presence of broken glass or other loose foreign matter or impurities in a filled glass milk bottle. According to the present invention, a

* GB785024 (A)

Description: GB785024 (A) ? 1957-10-23

Composition for eliminating minor element deficiencies in plant growingmedia

Description of GB785024 (A) Translate this text into Tooltip

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The EPO does not accept any responsibility for the accuracy of data and information originating from other authorities than the EPO; in particular, the EPO does not guarantee that they are complete, up-to-date or fit for specific purposes.

COMPLETE SPECIFICATION Composition for Elisz atillg Minor Element Defidencies in Plant Growing Media We, THE Dow CHEMICAL COMPANY, a Corporation of the State of Delaware, United States of America, of Midland, State of Michigan, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us and the method by

which it is to be performed, to be particularly described in and by the following statement: This invention relates to the supplying of trace metals to plant growing media and it has particular relation to compositions including metal salts of trivalent metal chelates of alkylenediamine acetic acids which are water insoluble and capable of releasing their chelated metal through association and/or through exchange with other more strongly bound metals. It is an object of this invention to provide compositions including the metal salts of the trivalent metal chelates of alkylenediamine polyacetic acids which are useful as agricultural aids in overcoming metal deficiencies, i.e. iron chlorosis, both in soils and in plants themselves. Another object of this invention is to provide compositions including carriers which are not metabolized by bacteria. Still another object of this invention is the provision of water insoluble organic metal carriers. Still another object of this invention is the provision of metal salts of trivalent metal chelates of alkylenediamine polyacetic acids which control the activity of the metal ion and which can exchange their chelated metal for other more strongly bound metals. Another object of the invention is to provide metal salts of trivalent metal chelates which have wide utility in the art as metal carriers and which are not metabolized by bacteria. The compounds with which the present invention is concerned have one of the general formul : <img class="EMIRef" id="026700791-00010001" /> where M is a trivalent metal atom other than cobaltic (Co), preferably a ferric, chromic, manganic, or aluminium atom; R is -CWCOO- or -CW.CH2O-; Y is an aikylene or cyclo-alkylene radical which places 2-3 carbon atoms between the indicated nitrogens, preferably ethylene, propylene, trimethylene, isobutylene or cyclohexylene; B is a divalent metal atom which forms a chelate of lower stability with the chelating agent than does the metal M and is preferably a calcium, cadmium, lead, zinc, magnesium, manganous, cupric, ferrous, nickelous, barium, strontium of cobaltous atom; and x represents the charge on the anion and is -4. The method of correcting metal deficiencies in plant growing media is to apply the compounds or compositions which include the compounds in a carrier to an area around the plant. The structure of the metal chelates is dependent to some extent upon the pH and upon the metal M. In the case of trivalent iron, for example, all four substituents on the nitrogen atoms are attached to the central metal. When R represents -CH2CH2OH an alcohol ate link is

probably formed which imparts increased stability to the compounds over the stability of the compounds wherein R represents -CH2-COO- and imparts to these compounds utility as agricultural aids in calcareous soils. Minor element deficiencies of one type or another are known to be universal in existence and to greatly influence the economics iof an area by affecting the growth of vegetation and foodstuffs and of livestock. The elimination of minor nutritional deficiencies can, to some extent, be accomplished by the application of inorganic salts of the deficient metals. The problem of supplying sufficient amounts of metal ions to trees and plants is an important one particularly in those areas in which deficiencies of certain metals exist in the soil and in cases wherein the plants are unable to acquire metals already present in the soil, as in iron chlorosis. Of the several mineral nutritional deficiencies which exist, iron deficiency is one of the most widespread and is most difficult of all nutritional difficulties to correct. Iron chlorosis is found to occur in almost every major fruit growing area in the world and is generally associated with alkaline and high lime soil reaction. Excesses of certain materials such as phosphate and the heavy metals, copper, zinc and manganese also appear to induce iron chlorosis. The liberal use of copper, phosphate and possibly manganese in citrus fertilizers appears to be related to recent increases in iron chlorosis. In the citrus growing areas of Florida, for example, iron chlorosis is widespread and occurs in both acid and calcareous soils. It is the most extensive and serious nutritional problem in acid soils in which most of the citrus is grown. Such deficiencies result in a loss of fruit production and a gradual withering of the tree. At present, such metal deficiencies are treated with a soluble inorganic salt of the deficient metal, said salt being applied to the soil as such or admixed with fertilizer or some inert material, by spraying or by injection. In the case of iron chlorosis, application of sulfur, lime sodium heametaphosphate, sodium tripolyphosphate and tetrasodium pyrophosphate have been tried with little or no success. Our new approach to the problem of mineral deficiencies involves the addition of a metal chelate of the deficient element to the soil or plant and is the first successful means of overcoming iron chlorosis. The compounds of this invention possess a high metal content and possess the important feature of beng able to exchange the chelated

metal with a metal which has the property of becoming more strongly chelated. These compounds, therefore, function in a manner somewhat lilre that of the ion exchange resins now commercially available as is illustrated by the following equation: <img class="EMIRef" id="026700791-00020001" /> Such an exchange is possible when the equilibrium constant of the chelate involving My is greater than that of the chelate involving M1. The present invention involves the discovery of a new class or organic compounds that possess properties eminently suitable for use as agricultural aids. The coordinated metal M is released in small but definite quantities and any action resulting in a removal of the metal M will cause a further dissociation of the metal chelate in accordance with the Law of Mass Action as illustrated in the equation: M+^(Ke)3+3 < oM+s + Kex An important feature of the compounds of the invention is their ability under proper conditions to exchange the central metal atom for another metal atom which is more strongly coordinated. The chelated manganese atom of calcium manganic ethylenediamine tetraacetate for example, is readily replaced by the ferric atom merely by bringing the calcium manganic salt into contact with an iron salt such as ferric phosphate or ferric sulphate, in the presence of moisture or water. When an insoluble iron salt is used, the exchange is readily observed to occur since the original water medium becomes an orange-brown color characteristic of the calcium salt of ferric ethylene diamine tetraacetate. This property permits the compounds of this invention to function in a manner somewhat like that of the ion exchange resins now commercially available. (Y ethylenediamine tetraacetic acid anion) M+ + (M,+3Y) - > 3oM1+3 + (M2Y)X+3 Such an exchange is possible when the equilibrium constant of the chelate involving M2 is greater than that of the chelate involving Ml. Measurements of the equilibrium constants of several chelate compounds of ethylene diamine tetraacetic acid have shown the order of increasing stability to be: - Ba+ < Sr+2 < M+2 < Ga < Mn+Z Fe+2 < L' < ;Co+2 < Zn+ < Cd+2 < Pb+ < Ni+' < Cu+ < Al+' < Fe+3 Any metal in the series will displace any metal occurring below it in the series. This order of stability will hold for the metal salts of the metal chelates. Hence, elimination of iron chlorosis in areas where the iron is present in a non-assimilable form, can be accomplished by adding, for example, the 'calcium calcium chelate to the soil. By an exchange mechanism, the iron is bound up by the chelate and calcium is released

to the soil. The resulting calcium salt of the iron chelate of ethylene diamine tetraacetate is then slowly dissolved by the water in the soil putting the formerly non-available iron in a readily assimilable form. When the metal salts of the trivalent metal chelates of this invention come into contact with water the following reactions occur: (Y represents 'the ethylene diamine tetraacetate anion) <img class="EMIRef" id="026700791-00030001" /> The coordinated metal M is released in small but definite quantities and any action resulting in a removal of the metal M will cause a further dissociation of Ithe metal chelate in accordance with the Law of Mass Action. As a result, a small but definite concentration of the chelated metal M is available in a form that can be assimilated by the plant. These compounds are, moreover, biologically and chemically inert and possess the important feature that, because of their low solubility, they are not easily washed or leached out of the soil las are inorganic salts which are used to treat the metal deficiencies. The compounds possess another advantage in that because of the relative stability of the metal chelate, the chelated metal ions do not exhibit their normal reactions in the presence of precipitating agents. The compounds may, in addition to their direct application to the soil, be combined with compost, cattle fodder, fertilizers or some inert ingredient such as sand (attapulgus clays and vermiculite) to insure uniform distribution in the proportions suitable for application to the soil under treatment. This procedure offers Ithe advantage of a single treatment whereby the necessary elements are added to the soil. Because of their ability to hold two metal atoms, which are different, these compounds possess the novel feature of being able to supply soils, which are deficient in two different metals, with the deficient metals in a single application. Thus, zinc and iron deficiencies can be treated by a single application. of the zinc salt of the iron chelate of ethylenediamine tetraacetate. Another method of application consists in the uo-precipitation of the metal salts on or with resinous materials such as acrylonitrile resins particularly the polyacrylonitrile soil conditioners. In such cases, the metal carrier is readily available to release its metal to the soil and/or to exchange with a metal which forms a stronger chelate; for example, iron will displace 'calcium. When the metal salts of the metal chelates of this invention come into contact with water, the following reactions occur. For the sake of demonstration, the calcium iron salt

CaFe(OH)K will be used. <img class="EMIRef" id="026700791-00030002" /> As a consequence of the above equilibria, a small but definite concentration of Ithe chelate and chelated metal is available in a form that can be assimilated by the plant These compounds are, moreover, biologically and chemically inert. The compounds of this invention possess the added and highly important feature that, because of their low solubility, they are not easily washed or leached out of the soil as are inorganic salts which are used to treat trace metal deficiencies. A second great advantage, the failure of the chelated metal ions to exhibit their normal reactions in the presence of precipitating agents, arises from the stability of the metal chelates. These two features combine to produce a medium which continues to function as a supplier of trace minerals over an extended period even in areas of heavy rainfall. The metal metal chelates of this invention are, under closely controlled conditions such as exist in hot-houses, aids in preventing the occurrence of metal deficiencies. Because of their low solubility these compounds are not readily leached from the soil even in regions of heavy rainfall. The compounds may be added to the soil with the assurance !that their beneficial effects will prevail and continue to operate for an extended period of time. The preferred method of application, which has been found to give satisfactory results, consists in applying the equivalent of 10 grams to 300 grams of chelated metal in a circle of 8 to 10 feet around the tree. Best results have been obtained by the application of 10 to 50 grams of chelated metal per tree. This is especially true of the calcium salts of the iron chelate in treating iron chlorosis in citrus trees on acid soils. Calcareous soils generally require the addition of a substantially greater quantity of chelated metal because of the effect of the higher pH of the soil of the equilibria involved. Satisfactory results have been obtained in calcareous soils by using the metal salts of the iron chelates of N-(2-hydroxyethyl)-N, N1) N1-alkylenediamine trice tic acids which are more stable at higher pB values than are the metal salts of the iron chelates of alkylenediamine tetraacetic acids and do not precipitate the iron as ferric hydroxide. The application of the metal salts of metal chelates eliminate the nutrient mineral deficiencies within 4 to 8 weeks following application; the effects lasting at lelast one year. In many instances new flushes of gmvSth and even flowering have been observed to follow the application of these mineral bearing compounds to the soil around chiorotic trees. As a consequence, applications should preferably be made in the spring or in - late January or

February. In the treatment of iron chlorosis in citrus trees with the calcium salts of the iron chelates of 'this invention, an increase in iron uptake has beenfound to take place. The reason for this is as yet unknown but it is probable that the chelated iron, which is held in a non-precipitable form, is exchanged with cations in the roots. The net result is that the iron is held in a form readily assimilable by the plant roots. Excessive amounts of the metal metal salts are to be avoided since overdoses may produce harmful resltlts. For the purposes of this invention, the pure metal salts are not necessary. The inorganic alkali metal salts present do not interfere in the operation of the products as agricultural aids. In the following examples specific methods illustrating the subject matter of The invention are described. EXAMPLE 1. Ten ounces of the calcium salt of ferric ethylenediamine tetraacetate (40.3 grams of chelated iron) were thoroughly mixed with 5 pounds of sand. The resulting mixture was spread evenly in an 8 foot circle around a mature, severely chiorotic orange tree located on soil having a pH of 4.5, and the treated area thoroughly irrigated. Within a few weeks this tree (A) showed considerable amelioratiolr over a similarly chiorotic but untreated tree, (B) used as control. Tree A continued to show improvement, the characteristic etiolation being completely eliminated over a 12 week period. Control tree B in tbe meantime continued its downward tren:l, -defoliation and finally dieback occurred. EXAMPLE 2. A mature orange tree, suffering from an iron deficiency and growing on a calcareous soil having a pH of 8.5 was treated by- applying a solid carrier !containing 31 Ibs. of the calcium salt - of the iron chelate of N- (2hydroxyethyl)-N, Nl, Nl-ethylenedlamine triacetic acid (containing 225.7 grams of chelated iron) in an 8 to 10 foot circle around the - tree. Complete greening of the chlorotic leaves occurred within 8 weeks and new leaves coming out in the spring were green and appeared about 2 weeks earlier than those on untreated tree. New flushes of growth were also observed on the area covered with the calcium iron salt. EXAMPLE 3. The application of a solid carrier containing two pounds of the calcium salt of the iron chelate of N-(2-hydroxyethyl)-N, Nl, N'- ethylenediamine triacetic acid (129 grams of chelated iron) to a moderately chlorotic mature orange tree standing on acid sail (pH 4.8) produced results similar to those reported under Example 2.

EXAMPLE 4. Four pounds of the zinc salt of the iron chelate of N-(2Thydroxyethyl)-N, N1, N - ethylenediamine triacetic acid (258.0 grams of chelated iron) were mixed with ten pounds of atticulite and evenly distributed on a 50 x 25 foot plot of yellowing celery characterized by a green pattern of the leaves. The pH of the soil was 8.0 and containing sufficient iron which was, however, unavailable to the plants because of the prevailing pH. Within four weeks the chlorotic condition had completely disappeared. The preparation of compositions carrying the heavy metal chelates in a carrier which includes an alkaline earth metal compound, for example, agricultural lime or agricultural limestone, is very rapidly carried out in a manner which avoids the necessity of isolating the chelate salt per se. Thus, the heavy metal chelate of iron, for example, may be formed in its acid form and while it is still in solution it is reacted with agricultural lime or limestone to form the calcium salt of the iron chelate. Operating in this manner, a concentrated solution of iron chelate of ethylene diamine tetraacetic acid is prepared and reacted with the agricultural lime, or limestone. The composition thus obtained comprises excess lime containing the calcium iron chelate in admixture therewith. The amount of excess lime may be varied as desired. Where the solution of the iron chelate is not concentrated, it may be necessary to dry the product somewhat to render it capable of being handled. Where, for example, the sodium salt of rhe chelate is used the prepare the calcium salt in this fashion it may be desired to wash the sodium carbonate or sodium hydroxide out of the lime or limestone composition, because the alkali metals in ionic form generally are not desirable constituents of soil. Thus, where the sodium salt is used the mixture of the lime or limestone with the solution of chellate may be washed with water to wash out the soluble ingredients, which would be sodium hydroxide or sodium carbonate, and leave behind the calcium salt for admixture with the agricultural lime or limestone. The compounds of this invention are all stable non-hygroscopic powders. The metal salts of the trivalent metal chelates of ethylene diamine tetraacetic acid are water insoluble products which readily separate in almost quantitative yields, whereas those of hydroxyethyl)-N,N1,N1 ethylenediamine triacetic acid are soluble in water and are obtained by evaporation of the water. The color of the salt is dependent on the metals present in the molecule. The following table lists some of the metal salts of trivalent metal chelates together with their colors: - (Y= ethylenediamine tetraacetate anion, and X = N- (2-hydtoxyethyl) - ethylenedianline - N,NI,N'- triacetate anion)

TABLE I Compound Color Ca Fe Y Tan Mn Fe X Orange-brow Mn Fe Y Orange-brown Ca Cr Y Violet Ca Al Y White Zn Al Y White The compounds of this invention can be prepared according to any of several modifications, for example, by reacting the proper acid metal chelate, such as calcium dihydrogen ethylenediamine tetraacetate, with a 1:1 molar ratio of the appropriate metal salt, such as aluminum sulfate in an aqueous medium. A method of preparation we have employed consists in reacting a metal chelate, such as zinc diftydrogen ethylenediamine tetraacetate, with the salt of a metal, for example, aluminum sulfate, lying higher in the stability series listed above, whereby a displacement reaction occurs resulting in formation of thc metal salt of the chelate having a higher equilibrium constant. When the pure metal salts of the compounds of this invention are desired, they are conve niently obtained by employing the carbonates or hydroxides of the metals desired in the metal salts. - However, for the purposes of this invention, the pure metal salts are not necessary and the sulfates, chloddes and any other readily available salts may be employed as well as any of the allQali metal salts of the alkylenediamine polyacetic acids. The inorganic alkali metal salts produced do not interfere in the operation of the products as agricultural aids. If desired, however, they can easily be removed by washing vwlth water. In the following examples specific methods illustrating the subject matter of the invention are described. EXAMPLE A Calcium Salt of Aluminum Ethylenediamine Tetraacetate One-half mole of aluminum sulfate was gradually added to a well stirred solution of one mole of calcium disodium ethylenediamine tetraacetate in 1500 milliliters of water at 85" C. and the whole stirred and heated for an additional 2 hours. The white slurry which formed was then cooled to room temperature, filtered, washed with water until a negative sulfate test was obtained, and then dried. A nearly quantitative yield of the calcium salt of aluminum ethylenediamine tetuacetate is obtained. Analysis showed 7.10% aluminum to be present

EXAMPLE B Calcium Salt of Ferric Ethylenediamine Tetraacetate (Pure) One mole of ferrous sulfate hepltahydnate and one mole of calcium disodium ethylenediamine tetraacetate were reacted together as in Example A. About two-thirds of the water was removed by evaporation, the orangebrown slurry cooled, filtered, washed with water to remove sodium sulfate and dried at 80" C. The product, an orange-brown powder, contained 14.2% ircn. The iron is, present in the ferric form because of the rapid oxidation of the initially formed ferrous chelate by oxygen under the reaction conditions employed. EXAMPLE C Calcium Salt of Ferric Ethylenediamine Tetraacetate One-half mole (189 grams) of ferric sulfate and one mole of calcium diso dium ethylenediamino !tetraacetate were reacted together as in Example A. The suspension was heated at 80" -85 C. for one hour and then evaporated to dryness. The resulting buff colored solid contained 9.9% iron. EXAMPLE D Calcium Salt of Aluminum Ethylenediamine Tetraacetate One-half mole of freshly prepared aluminum hydroxide was added ito a slurry of one-half mole ethylenediamine tetraacetic acid in one liter of water at 80"--85" G. The slurry was thoroughly stirred for one-half hour and then one-half mole of calcium. carbonate was gradually added. When evolution of carbon dioxide ceased, the suspension was cooled, filtered and dried. Analysis showed the resulting white powder ItO contain 11.0% calcium. EXAMPLE E Calcium Salt of Ferric N-(2-hydroxyethyl) N,N1,N1-ethylenediamine Tricacetate One mole (278.Q grams) of ferrous sulfate heptahydrate and one mole of calcium, sodium N-(2-hydroxyethyl)-N,N1,N1-ethylene diamine triacetate were reacted together as in Example B. About Itwo-thirds of the water was removed by evaporation, the orange-brown slurry cooled, filtered, washed with water to remove sodium sulfate and dried at 80 C. The product, an orange-brown powder contained 13.9% iron. The iron is present in the ferric form because of the rapid oxidation of the. initial ferrous chelate by oxygen under the reaction conditions employed. EXAMPLE F. Zinc Salt of Ferric N-(24iydroxyethyl)-N,N1,

N1-ethylenediamiae Triacetate One mole of ferrous sulfate heptahydrate and one mole of zinc sodium N-(2-hydroxyethyJ) - N,N1,N1 - ethylenediamine triacetate were reacted together as in Example A and; worked up as in Example E. The yellowbrown powder contained 12.8pro iron. EXAMPLE G Manganous Salt of Ferric N-(2-hydroxyethyl) N,Nl,N'-ethylenediamine Triacetate Same procedure as in Example F but using manganous N-(2 - hydroxyethyl) - N,N1,N1- ethylenediamine triacetate in place of the zinc chelate. The product, a yellow-brown solid contained 8.8% iron. What we claim is: - 1. A composition for application to plant growing media for the elimination and control of trace element deficiencies in the said medi!a which comprises a carrier and a metal salt of a metal chelate having one of the general formulae: <img class="EMIRef" id="026700791-00060001" /> wherein M is a trivalent metal atom other than cobaltic (Go), R is either -CH.COO or --CH,CH,O, Y is an alkylene or cycloalxylene radical which places 23 carbon atoms between the indicated nitrogens; B is a divalent metal atom which forms a chelate of lower stability with the chelating agent than does the metal M; and x represents the charge on the anion and is -4. 2. A composition as ,claimed in claim 1, wherein Y is an ethylene, propylene or trimethylene radical and M is a ferric, chromic, manganic or aluminium atom. 3. A composition in accordance with claim 1 or 2, in which the carrier is sand. 4. A composition in accordance with claim 1 or 2, in which the carrier is a fertilizing material. 5. A composition in accordance with claim 1 or 2, in which the carrier is lime 6. A composition in accordance with claim 1 or 2, in which the carrier is limestone. 7. A composition in accordance with claim 1 Or 2, in which the metal salt is the calcium salt of ferric ethylenediamine tetraacetate. 8. The method of forming a composition useful for application to plant growing media for the elimination and control of trace element deficiencies in the media, which comprises forming a suspension in a carrier of a compound of the general formula I or the general formula II of claim 1, by reacting the corresponding trivalent metal chelate with a basic divalent compound of the corresponding divalent metal. 9. The method in accordance with claim 8, in which the divalent metal is calcium.

10. The method in accordance with claim 8, in which the divalent metal compound is agricultural lime and the metal in the chelate is iron. 11. The method in accordance with claim 8, in which the divalent metal compound is agricultural limestone and the metal in the chelate is iron. 12. Compounds corresponding to the general formulae I or II of claim 1, wherein M is la trivalent metal atom other than cobaltic (Co), R is -CH2COO- or -CwwO'-, B is a divalent metal atom which forms a weaker chelate with the chelating ag

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* GB785025 (A)

Description: GB785025 (A) ? 1957-10-23

Manufacture and use of complex iron salts




PATENT SPECIFICATION 785,025 i k Date of Application and filing Complete Specification: April 20, 1954. No 11405154. Application made in Switzerland on April 20, 1953.

Complete Specification Published: Oct 23, 1957. Index at acceptance:-Classes 2 ( 3), C 212 (A 1: G 1 A: K); 81 ( 1), E 1 C( 5 D: 13); and 111, B 3 (C 1: C 4: F 1). International Classification:-A 611 C 05 c, d, f CO 7 f. COMPLETE SPECIFICATION Manufacture and Use of Complex Iron Salts We, CIBA LIMITED, a body corporate organised according to the laws of Switzerland, of Basle, Switzerland, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: - This invention relates to the manufacture and use of complex iron salts of nitrilotriacetic acid Various salts of trivalent iron with nitrilo-triacetic acid are already known. In volume 249 ( 1942) of the "Zeitschrift fiur anorganische Chemice" is described on pages 301-303, the manufacture of two iron salts. By heating a solution of ferric ammonium sulphate with nitro-triacetic acid there is obtained a salt which is very sparingly soluble in water and contains one mol of nitrilo-triacetic acid bound to one atom of iron This salt is referred to as being noncomplex By reacting a freshly prepared suspension of ferric hydroxide with free nitrilotriacetic acid there is formed an iron salt which is also sparingly soluble in water, and contains a ratio of iron to acid amounting to 2:3 In an article in the Helvetica Chemica Acta, Vol 31, page 333 ( 1948) is described in connection with methods of analysis the formation of complexes between ferric salts and nitrilo-triacetic acid It is stated that when solutions of equimolecular quantities of a ferric salt and the dipotassium salt of nitrilo-triacetic acid are brought together an acid solution is produced which requires one or two equivalents of alkali for neutralisation. The resulting complex ions are referred to as monohydroxo and dihydroxo derivatives of the following formulae lX Fe OHl and lX Fe (OH)2 l in which X represent /V -153 v Coo el coo lPrice 3 PM 1 4 ' 6 d The present invention is based on the observation that the complex ferric compounds of nitrilo-triacetic acid referred to above are stable not only in aqueous solution, 45 but are also obtainable in solid form and easily dissolve in water Accordingly, this invention provides a process for the manufacture of solid water-soluble complex ferric compounds of nitrilo-triacetic acid, in which 50 one atom of iron is present per molecule of acid and which contain 0, 1 or 2 of alkali metal or ammonium ions per ion of nitrilotriacetic acid-iron complex, wherein a ferric salt is reacted with an alkali metal or 55 ammonium salt of nitrilo-triacetic acid in equimolecular proportions

in aqueous solution, the resulting acid is at least partially neutralised by the addition of an alkali metal or ammonium base and the aqueous solution 60 is evaporated to dryness, or wherein a ferrous salt of nitrilo-triacetic acid is oxidised in aqueous solution to the ferric salt, the resulting acid is at least partially neutralised by the addition of an alkali metal or ammonium 65 base, and the aqueous solution is evaporated to dryness. As ferric salts for the present process there may be used any desired water-soluble salts of trivalent iron, for example, ferric 70 ammonium sulphate or ferric chloride. Among the ferrous salts, which may be used for making the ferrous salts of nitrilo-triacetic acid, here is advantageously used ferrous sulphate owing to the ease with which it can 75 be obtained The alkali metal or ammonium salts of nitrilo-triacetic acid may contain one, two or three equivalents of alkali per mol of acid There are advantageously used potassium salts Instead of using the preformed 80 salts, it will be understood that they may be formed in the reaction solution by reacting free nitrilo-triacetic acid with a corresponding quantity of an alkali metal hydroxide or carbonate or ammonia In order to neutralise 85 the acid resulting from the formation of the iron salt there may also be used an alkali r:. > 2 785,025 metal hydroxide or carbonate or ammonia. The quantity to be added depends on whether it is desired to impart to the final product a neutral, weakly alkaline or weakly acid reaction For the method in which oxidation is carried out there may be used any oxidising agent which is capable of converting ferrous salts into ferric salts Advantageously hydrogen peroxide is used The evaporation of the reaction solution in order to produce a dry product is advantageously carried out under reduced pressure. The products so obtained are mixtures of complex ferric salts with other water-soluble salts They are easily soluble in water The complex ferric salts have different constitutions depending on the degree of neutralisation In the light of the information contained in the article in the Helvetica Chemica Acta referred to above it is probable that the products are substantially salts having the following constitutions, when a potassium salt is used for neutralisation: and o vC% Coo OK+ N\ _, _CO When the neutralisation is incomplete a part of the iron salt is in the form of acid, and such salts are to be given the following constitution in analogy with the salts. H+ It has also been found that the watersoluble complex ferric salts of nitrilo-triacetic acid of the invention are valuable agents for protecting plants They can be used for the treatment of diseases caused by a deficiency of iron, because the complex salts are easily taken up by plants and are not adsorbed to any substantial extent by

the constituents of the soil. Accordingly, the invention also provides preparations for protecting plants, which consist of or contain wvater-soluble solid complex ferric compounds of nitrilo-triacetic acid, which contain one mol of acid and one mol of iron and 0,1 or 2 alkali metal or ammonium ions per ion of nitrilo-triacetic acid-iron complex The complex salts may be used as such. Advantageously, however, they are mixed with an inert solid carrier, such as kaolin or talc, or with a solid fertiliser, and are used by scattering the mixture below the plants to be treated It is of advantage to prepare aqueous solutions by dissolving the solid complex compound in water and to use the solutions for watering the plants Also in the case of solutions prepared by dissolving the solid complex ferric salts in water there may be added a fertiliser and/or a pest-combating substance and/or a weed killer. The following Examples illustrate the invention, the parts being by weight unless otherwise stated, and the relationship of parts by weight to parts by volume being the same as that of the kilogram to the litre: EXAMPLE 1. To a suspension of 22 2 parts of nitrilotriacetic acid of 90 per cent strength in 150 parts by volume of water there are first introduced, while stirring, 27 8 parts of crystalline ferrous sulphate and then 20 parts of calcined potassium carbonate There is obtained a solution which is still acid (p H value about 4), in which there are slowly introduced, while stirring, 7 1 parts of hydrogen peroxide of 28 per cent strength diluted with 15 parts by volume of water The temperature rises to 30-35 C and the solution becomes dark in colour After stirring the mixture for one hour at room temperature hydrogen peroxide can no longer be detected and a test portion of the solution remains clear after the addition of sodium carbonate. The whole is then rendered weakly alkaline by -the addition of 6 parts of calcined potassium carbonate, and the solution is evaporated to dryness in vacuo There are obtained parts of a brown powder which is very easily soluble in water, and solutions of which form no precipitate with sodium carbonate at ordinary temperature Instead of potassium carbonate there may be used for the neutralisation an equal quantity of aqueous ammonia solution. EXAMPLE 2. 13.8 parts of potassium carbonate are added 95 to a suspension of 21 2 parts of nitrilo-triacetic acid of 90 per cent strength in 150 parts by volume of water 16 2 parts of pulverised anhydrous ferric chloride are scattered, while stirring, into the resulting 100 solution of the dipotassium salt of nitrilotriacetic acid, and then the whole is

heated for a short time at 809 C After the mixture has been cooled to room temperature, the finely crystalline precipitate of the acid iron 105 salt is formed Upon introducing 13 8 parts of potassium carbonate the latter passes into solution accompanied by the production of a red-brown coloration The p H value of the 785,025 acid, conducted substantially as described in Example 1 or 2 herein. Water-soluble solid complex ferric compounds of nitrilo-triacetic acid, which contain one atom of iron per molecule of the acid and 0, 1 or 2 alkali metal or ammonium ions per ion of nitrilo-acetic acid-iron complex. 6 Water-soluble solid complex ferric compounds of nitrilo-triacetic acid, whenever made by the process claimed in any one of claims 1-4. 7 A preparation for the protection of plants which consists of or contains a watersoluble solid complex ferric compound of nitrilo-triacetic acid containing one atom of iron per molecule of the acid and a 0, 1 or 2 alkali metal or ammonium ions per ion of nitrile-triacetic acid-iron complex. 8 A preparation as claimed in claim 7, which also contains a fertiliser and/or a pestcombating agent and/or a weed killer. 9 A preparation as claimed in claim 7 or 8, which is obtained by dissolving the solid complex compound in water. ABEL & IMRAY, Agents for the Applicants, Quality House, Quality Court, Chancery Lane, London, W C 2. solution is 6 5 By evaporating the solution in vacuo there is obtained a solid salt mixture which is easily soluble in water.


* GB785026 (A)

Description: GB785026 (A) ? 1957-10-23

Metalliferous mono-azo dyestuffs of the benzene-azo-pyrazolone series




PATENT SPECIFICATION Date of Application and filing Complete Specification: April 20, No 11406/54. 785,026 1954. l t ER 2 M Application made in Switzerland on April 21, 1953. Application made in Switzerland on March 29, 1954. (Patent of Addition to No 741,602, dated July 18, 1952). O)O Complete Specification Published: Oct 23, 1957. Index at acceptance:-Class 2 ( 4), P 1 (A 4 83: F 5), P 8 (A 1 B: B 1: C 2: C 3: E). International Classification:-C 09 b. COMPLETE SPECIFICATION Metalliferous Mono-Azo Dyestuffs of the Benzene-Azo-Pyrazolone Series We, CIBA LIMITED, a body corporate organised according to the laws of Switzerland, of Basle, Switzerland, do hereby declare the inventions for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention is an improvement in or a modification of the invention forming the subject of Specification No 741,602. That Specification describes a process for the manufacture of mletalliferous azo,-dyestuffs, wherein one or two monioazo'dyestuffs which are free from sulphonic acid and carboxylic acid groups and correspond to the general formula HO OH VC-N-Q R.-N=N-C| S O 1 N W,, N CH 3 in which R, represents a benzene residue bound to' the azo linkage in ortho-position relatively to the hydroxyl group, and R 2 represents a benzene residue, and in which at least one of the residues R, and R contains an aliphatic group, or a halogen atom, or two moneazoi dyes of which one corresponds to the above formula and the other is ant ortho: orth o$-dioxy-monoazo dyestuff of the benzeneazo-naphthalene series free from: sulphonic acid and carboxyli& acid; groups, is or are treated with an agent yielding cobalt or chromium in such manner that

the resulting metalliferous dyestuff contains, per molecular proportion of dyestuff, less than one atomic proportion of cobalt or chromium. According to the present invention valuable new metalliferous azodyestuffs are made by treating one or two monoeazo-dyeswffs which are free from sulphonic acid and carboxylic lPrice Jiri Sl 4 S 6 d acid groups and correspond to the general formula ( 1) OH I RI-N = N-Pz-R, in which R, represents a benzene residue bound to the azo linkage in orthe-position to the hydroxyl group, Pz represents a 5-pyrazolone residue bound to the azo, linkage in the 4-position, and R represents an, aromatic bicyclic hydrocarbon residue bound directly to the 1-position or by the group -CONH to; the 3position of the pyrazole ring which residue may contain substituents, and in which at least one of the residues R, and R contains a -SO 2 NH group, with an, agent yielding chromium or cobalt under conditions such that a metalliferous azoi dyestuff is formed which contains less than one atom of cobalt or chromium in complex union per molecule of monoiazc-dyestuff Especially valuable results are obtained if monoazedyestuffs are used which are free from sulphonic acid and carboxylic acid groups and which correspond to the formula ( 2) Ira X t/ inl which X represents a chlorine atom or hydrogen atom, and R represents a diphenyl or naphthyl residue. Among these monoazo-dyes tuffs those of the formula ( 3) #o 1 t 3 are especially suitable. The monoazo-dyastuffs corresponding to the above formula and used as starting materials in the present process can be obtained by coupling an ortho-oxy-diazocompound of the benzene series which is free from sulphonic acid and carboxylic acid groups with a pyrazolonc which contains an aromatic bicyclic hydrocarbon residue bound directly to the 1-position or by the group -CONH-to the 3-position cf the pyrazole ring which residue may contain substituents C O N I Sa N and (b) Pyrazolones free from -SONH 2 group's, such as 1-( 7 or P-naphthyl)-3methyl 5 -pyrazolone, 1 ( 21 naphthyl) -3me;thyl-5-pyrazolon-6 '-sulphoni c acid methyl amide, 1-(ocrtho-, mzta or para-benzylphenyl)-3-mnthyl-5-pyrazolone or 1-diphenyl3-m:thyl-5-pyrazolone. As ortho-oxy-diazo compounds of the benzeno series there come into consideration for making thz dyestuffs used as starting materials in the present process diazo compounds of ortho-Gxy-amines of the benzene series of which the benzen'e nucleus may contain, in addition to the hydroxyl group and the amino grcup, further substituents, such as halogen atoms (for example, chlorine), alkyl groups (for example, miethyl), alkoxy groups (for examiple,methoxy),niftro groups, -CO-Alkyl groups (for example CO-CH 3) and acylamino groups (for

example, acetylamino) As examples of amines free from sulphonic acid amide groups, the diazo compounds of which are coupled only with the pyrazolones mentioneld under (a) above, there may be mentioned: 6-Nitro-4-methyl or -4-chloro-2aminc-l-cxybenzene, 6-chiloro-4-methyl or rrmthyl-, 4-chloro or 4-acetylamino-2-aminol-oxybenzene, 5 or 6-nito-2-amino-1-oxybenzene, 4 methyl or 4-chloro-5-nitro'-2amino-l-oxybenzene, 4-nitro-6-acetylamino-2amin o:-1-oxybznzene, 6-nitro -4-acetylamino-2amino-1-oxybenzene, 4: 6-dinitro-2-amino-1oxybenzene, 4: 6 dichloro 2 -amino 1 -oxybenzene, 4 tertiary-amyl-6-nitro-2-aminoloxybenzene, 3-amino-4-oxyacetophenone, 5ritro-3-amino-4-oxyacetophenone, 4-methoxy2-amino-l-oxybenzerne or 6-acetylamino-4chlore 2 -amino-1-lxybenzene, and also 2amino-l-oxybenzen-; 4-carboxylic acid amide. Especially valuable results are obtained with compounds containing a sulphonic acid amide group, such as 4-nitro or 4-chloro-2anmino-1-oxybenzene-5 or -6-sulphonic acid amide, 6-nitro or 6-chloro-2-amino-1-oxyand which contains a -SONH group if such a group, is not present in the diazo comFound. The aforesaid pyrazolones can be made by rathods in themselves known As examples of such pyrazolones there may be mentioned: (a) Components containing a -SO 2,NH, group, such as 1 i -naphthyl 3 -methyl-5pyrazclone-4 '-, -5 '-, -6 '-, -7 ' or -8 ' sulphonic acid amide, 1-fi-naphthyl-3-methyl-5-pyrazolone-6 '-sulphonic acid amide, and also the pyrazolones of the formula #2 <I CO-J/h M 9 benzene-4-sulphonic acid amide, and especially 2-amrino-l-oxybenzene-4 or -5-sulphonic acid antide The diazo compounds of these amnines may be coupled either with the pyra 75 zolones mentioned under (a) above or under (b) above. Coupling of the ortho-oxy-diazo-compounds with the pyrazolones can be carried out by the usual known methods, for example, in a 80 weakly acid to alkaline medium. When the coupling reaction is finished the dyestuffs, for the purpose of metallisation, can easily be separated from the reaction mixture by filtration after the addition of sodium 85 chloride, as they are only sparingly soluble in water They are advantageously used for the metallisation in the form of filter cakes without intermediate drying In some cases it is also possible to carry out the metallisa 90 tion directly in the coupling mixture without intermediate isolation. The monoazo dyestuffs obtainable as described above are in general not especially easily soluble in water when in the form of 95 their alkali metal compounds However, some of them' are sufficiently soluble in that form to enable them' to be used from dyebaths which require noe addition of acid The treatm:ent with an agent yielding chromium or 100 cobalt in accordance with the present invention is carried out in such

manner that a metalliferous dyestuff is obtained which contains less than one atom of chromium or cobalt in complex union per molecule of mono 105 azc-dyestuff Accordingly, the metallisation is advantageously carried out with such an agent yielding chromium or cobalt ard by such a method that a complex chromium or cobalt compound of the desired constitution is oh 110 tained In general, it is of advantage to use less than one, but at least a half, atomic proportion of chromium or cobalt per molecule of monzoazo-dyestuff and/or to carry out the m:etallisation in a weakly acid to alkaline 115 medium Therefore, there are especially suitable these agents yielding chromium or cobalt 785,026 wet fastness and very gobd fastness to light. Specification No 637,404 describes and claims a process for the manufacture of metalliferous dyestuffs free from sulphonic acid groups by the action of agents yielding metal upon azo-dyestuffs which are free from sulphonic acid groups and from carboxylic acid -groups standing in ortho-position to hydroxyl groups and which contain the atomic grouping /0 01/ which are stable in alkaline media, for example, complex chromium or cobalt compounds of aliphatic or aromatic ortho-oxycarboxylic acids, such as lactic acid, citric acid, tartaric acid 4-, 5 or 6-methyl-1-Gxybenzenre-2-carboxylic acid and above all 1-oxybenzene-2-carboxylic acid itself As agents yielding cobalt there are advantageously used simple cobalt salts such as cobalt sulphate or cobalt acetate. Conversion of the dyestuffs into the conmplex metal compounds is advantageously carried out at a raised temperature, under atmospheric or superatmospheric pressure, if desired in the presence of suitable additions, for example, salts of organic acids, bases, organic solvents or other agents assisting the formation of complexes. In one form of the process of the invention a mixture of two different metallisable mono azo-dyestuffs is used as starting material, which dyestuffs both correspond to the formula ( 1). Inl this form of the process it will be understood that the treatment with the agent yielding metal is carried out under conditions such that metalliferous dyestuffs are obtained which contain at least one atom of chromium or cobalt bound in complex union per molecule cf monoazo-dyestuff. The new products of the present process are chromium or cobalt compounds which contain one or two monoazo-dyestuffs in a complex in which the ratio of the number of chromium or cobalt atoms bound in complex union to the number of monoazo-dyestuff molecules bound in complex union to the chromium or cobalt is smaller than 1: 1, and advantageously about 1:2, and in which the meonazo-dyestuff or dyestuffs or ortho:ortho L dioxy-monoazo-dyestuffs free from sulphonic acid and carboxylic acid groups, which correspond to the general

formula ( 1) above. Especially valuable are those chromium and cobalt compounds of this kind which contain two monioazo-dyestuffs of the same constitution, and those wherein the monoazo-dyestuffs correspond to the formula ( 2), and still more so are those chromium and cobalt compounds which contain 2-monoazo-dyestuf Es of the formula ( 3). The new chromiferous and cobaltiferous dyestuffs are soluble in water, and are indeed more soluble than the metal-free dyestuffs used for making them They are suitable for dyeing and printing a very wide variety of materials, but especially fo, dyeing nitrogenous natural materials such as silk, leather and especially wool, and also for dyeing and printing synthetic fibres of super polyamides, super poly urethanes or polyacrylonitrile They are suitable above all for dyeing from a weakly alkaline, neutral or acid, especially acetic acid, bath The wool dyeings so obtained are distinguished by their level character and very good properties of wherein the treatment with the agent yielding metal is conducted in a neutral to alkaline medium and the aforesaid agent is a metal compound which contains an aromatic ortho, oxycarboxylic acid in complex union, and with the use of a proportion of the complexforming metal corresponding to less than one atom for each group, in the dyestuff capable of leading to the formation of complexes. As compared with the pyrazolone dyestuffs disclosed in Specification No 637,404, which are at most sparingly soluble in water, the dyestuffs of the present invention are distinguished by a much better solubility and consequently a greater suitability for dyeing wool from aqueous baths As compared with the dyestuffs of Specification 637,404 whose solubility is sufficient that they are suitable for dyeing wool from aqueous baths, the dyestuffs of the present invention are distinguished by the fact that they yield wool dyeings of much better wet fastness properties. Specification No 678,492 describes and claims monoazo-dyestuffs of the pyrazolone series which are free from carboxylic acid and from sulphonic acid groups and correspond to the general formula 04 ' -4 / I 2 o in which R represents an aromatic residue of 105 the benzene series containing a single sulphonamide group of the formula -5 2 a <' in which R 1 and R 2 each represent hydrogen, an alkyl or an oxyalkyl residue, and which aromatic residue may contain other substituents. 785,026 Specification No 709,495 describes and claims monoazo-dyestuffs of the general formula or X #_l-R A O a in which X represents a sulphonic acid amide group, and R represents the residue of an azo component which is free from sulphonic acid and carboxylic acid groups and is bound to the azo linkage in a position vicinal to a hydroxyl group.

The following Examples illustrate the invention, the parts being by weight: EXAMPLE 1. 47.1 parts of the sodium salt of the dyestuff from diazotised 2 amino 1 oxybanzene-4sulphonic acid amide and 1-( 4 phenylphenyl)-3-methyl-5-pyrazolone are dissolved in 1000 parts of water and 13 3 parts of sodium hydroxide solution of 30 per cent strength After the addition of 120 parts of a solution of sodium chromosalicylate having a chromium content of 2 6 per cent, the whole is boiled for 3 hours under reflux The metallised dyestuff is isolated by evaporating the solution in vacuo It is a water-soluble brown powder which dyes wool from a neutral or acetic acid bath orange tints having very good properties of fastness. The metal-free dyestuff described above is dissolved in 1000 parts of water and 26 6 parts of a sodium hydroxide solution of 30 per cent strength, and, after the addition of 300 parts of a cobalt sulphate solution having a cobalt content of 1 3 Fer cent and heating the mixture for hour at 80-85 C, the cobalt compound of the dyestuff is obtained. It dyes wool from neutral or acetic acid baths brown yellow tints having very good properties of fastness. Similar dyestuffs are obtained by treating the monoazo-dyestuffs, obtained from the diazo: and coupling compcnents mentioned in Columns I and II of the following Table, in the mrnanner described above with an agent yielding thez metal named in Column III In Column IV are given the tints produced on wool with the chromium and cobalt complexes so obtained: 785,026 785,026 II rv red-orange scarlet yellowish brown red-orange yellowish brown, bluish red orange OU S Ox Y, or .a 0,.5/ 1 yea 0,q -2 0,15, 1 8 % OH ll, 602 % OH lll 30, NY, OH .112 S 0, Nt, OR IY,4 S o', NY, III chromium chromium cobalt chromium cobalt chromium #0 1 C-IV. UC.0 p C., I_k Mb #0 W-/V\ elf Ilellc 1 COEXAMPLE 2. parts of well wetted wool are entered at 40-50 C into; a dyebath which contains in 4000 parts of water i part of the chromiferous dyestuff obtainable as described in the first paragraph of Example 1 2 parts of aewtic acid of 40 per cent strength are added, the bath is raised to the boil in the course of hour and dyeing is carried on at the boil for 43 hour Finally the wool is rinsed, with cold water and dried There is obtained an cralnge dyeing of very good fastness to washing and light. The same result is obtained when no acetic acid is added to the dyebath.

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* GB785027 (A)

Description: GB785027 (A) ? 1957-10-23

Improvements in or relating to high frequency current supply arrangementsfor use intelecommunication systems

Description of GB785027 (A)

PATENT SPECIFICATION Inventoir: JOHN BOURA Date of filing Complete Specification April 19, 1955. Application Date April 20, 1954. 7859027 No 11396/54. Complete Specification Published Oct 23, 1957. Index at Acceptance: -Classes 40 ( 4), R 3 D; and 40 ( 5), L 14 B. International Classification: -H 04 j. COMPLETE SPECIFICATION Improvrements in or relating to High l'requency Current Supply Arrangernents for use in Telecommunication Systems We, BRITISH TELECOMMUNICATIONS RESEARCH LIMITED, a British Company, of Taplow Court, Taplow, Buckinghamshire, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: - The present invention is concerned with the supply of carrier current in telecommunication systems, for instance so-called broad-band multi-channel carrier systems where a comparatively large number of different frequencies may be employed corresponding to the various channels. As a matter of convenience and in order to simplify the maintainence of the desired relationship between the different carrier frequencies,

it is usual to derive a number of them from a single master oscillator the frequency of which is very carefully controlled, for instance by the use of a quartz crystal in a special oven maintaining the temperature accurately constant In these circumstances it is obviously very important that the carrier supplies should have the utmost reliability as otherwise there is a danger that a large number of channels might be thrown out of action simultaneously It is accordingly usual practice to provide a stand-by master oscillator together with automatic changeover arrangements to bring in the stand-by supply if any trouble should develop on the normal supply The chief object of the present invention is to provide an arrangement of this type whereby the changeover from one supply to the other is made so rapidly that any loss of signal is negligible. According to the invention, in a carrier current supply arrangement for use in a telecommunication system, two sources of supply are provided from which currents of a plurality of different frequencies are normally available each source being capable of supplying all the frequencies required but being arranged lPrice 3 s 6 dl normally to supply some only of such frequencies, the remainder being normally supplied by the other source, the two sources for each frequency being connected to a common output circuit by way of rectifier networks arranged to be biassed respectively under the control of the common output circuit so that only one source is effective but that on failure of the output the bias is altered so as to render the other source effective. The invention will be better understood from the following description of a preferred method of carrying in into effect which should be taken in conjunction with the drawings accompanying the provisional specification comprising Figs 1 and 2. Fig 1 is block schematic showing the general layout of the carrier supply arrangements, while Fig 2 shows detailed circuits of the changeover arrangements for one particular frequency. Referring now to Fig 1, the supplies for source A and source B are obtained from individual oscillators OA and OB respectively, each of which as mentioned above may be a crystal having its temperature accurately controlled In each case the output of the oscillator is fed to a harmonic generator HGA or HGB arranged to produce the required harmonics and as illustrated it is assumed that five different frequencies a?-e are required from the generator These are separated by the use of suitable filters F Al-FA 5 and FB 1-FB 5 of which only those for frequecies b and e are shown The outputs from the two sources for any one frequency are then extended to linked electronic switches E Al-EA 5 and E Bi-EB 5, details of which are shown in Fig. 2 The linkage between the corresponding members of each pair of

switches is such that at any time one of the switches will be closed and the ohter open, so that the supply is being obtained from one source only The output is then fed to a dual path amplifier such as DP 2 or DP 5 i e an amplifier employing two valves in parallel which, in order to obtain 785,027 enhanced reliability, may be of the type disclosed in Specification No 732,567. The arrangement of the electronic switches is such that certain of the harmonic frequencies are normally supplied from source A and the remainder from source B and conveniently the division can be alternate over the frequency range Thus for instance source A will normally supply frequencies b and d, while source B will provide frequencies a, c and e, If the supply of any one frequency should fail, changeover will immediately take place to the other source The fault may be due to trouble in the equipment relating to that frequency alone or may be due to the failure of the source in which case all the frequencies which it is supplying will fail but the changeover will be made satisfactorily in either case. Considering now Fig 2, it will be assumed that the normal supply extends to input transformer TI and passes by way of the electronic switching or gate circuit to output transformer T 2 and thence to the carrier supply amplifier CSA The stand-by supply is fed to input transformer T 3 and extended by way of its gate to output transformer T 4 and thence to the amplifier The gate circuits each comprise networks of rectifiers and resistors and transformer Ti is centre-tapped with a connection extending to terminal A and similarly transformer T 3 is centre-tapped with a connection extending to terminal B Connections from these terminals extend to terminals A' and B' in the control circuit shown in the lower portion of the figure This comprises essentially two cold cathode gas discharge tubes which are normally extinguished and an electromagnetic relay which is normally released. In the normal conditions of the circuit, terminal A has a higher potential than terminal B and current flows from terminal A over the two halves of the secondary of the transformer TI, rectifiers Wi and W 2, two halves of the centre-tapped primary of transformer T 2, resistor R 2, connection from the junction point of resistors RI and R 2 to the junction point of resistors R 3 and R 4, resistor R 3 rectifiers W 5 and W 6, two halves of the secondary of transformer T 3 to terminal B This current is maintained at a suitable value, for instance 10 ma, and as a result rectifiers W 1, W 2, W 5 and W 6 are biassed to the low resistance condition while rectifiers W 3, W 4, W 7 and W 8 are biassed to the higl resistance condition. Consequently rectifiers W 3 and W 4 form a high impedance shunt and rectifiers Wi and W 2 a low series impedance so that carrier supply is

extended from transformer Ti to transformer T 2 The gate circuit for the stand-by supply is closed however since rectifiers W 7 and W 8 form a high series impedance, while rectifiers W 5 and W 6 form a low impedance shunt across transformer T 3. It will be appreciated that since the circuit is symmetrical, if the potentials of terminals A and B are reversed, the conditions of the gate circuit will be reversed, and the control current will flow by way of the windings of transformer T 3, rectifiers W 7 and W 8, resistor R 4, resistor RI, rectifiers W 3 and W 4 and 70 windings of transformer TI, accordingly there will be a low impedance path between transformer T 3 and T 4 so that the standby supply will become operative while the normal supply will be cut off 75 The connections from the control circuit to terminals A and B may be traced as follows: From IIT+ over normal contact RA 1 and resistor RS to terminal A' and from terminal B' over resistor R 16 and normal contacts 80 RA 3 to HT or earth Changeover is effected by a momentary positive pulse over lead P transmitted from the carrier supply amplifier CSA in the event of failure of the supply This pulse is applied to the grids of the two gas dis 85 charge tubes V 1 and V 2 by way of capacitors Cl and C 2 and rectifier W 9 included in series with capacitor C 2 The priming voltages on the grids are normally just below those needed to produce striking and are determined by the 90 potential dividers comprising resistors R 6 and P.7 and resistors R 11 and R 12 respectively. The capacitors Cl and C 2 are necessary to isolate the two different grid priming voltages and prevent the operating pulse which may 95 have a low impedance source from influencing the priming potentials of V 1 and V 2 The rectifier W 9 prevents the higher grid potential of V 2 from being transmitted to the grid of Vi which might occur and cause the 100 unwanted striking of V 1 when the HT power was first switched on. If a failure of the supply takes place, monitoring equipment in the amplifier CSA causes a pulse to the transmitted which effects the 105 striking of both V 1 and V 2 The current flow through V 2 raises the potential of terminal B' and similarly current flow through V 1 lowers the potential of terminal A' The combined effect of these two changes is to reverse the 110 original polarity relationship of terminals A' and B' and as a consequence current now flows through the gate circuits in the opposite direction with the results previously described, namely that the stand-by source is brought into 115 operation Current flow through V 1 also now operates relay RA which will accordingly change over its contacts Contacts RAI disconnect the anode supply to tube V 2 which is therefore extinguished but the polarising 120 current through the gate circuits is maintained by way

of resistor Ri O Contacts RA 3 disconnect resistor R 16 and contacts RA 2 connect resistor R 13 across tube V 1, this resistor being sufficiently low in value to extinguish V 1 Con 125 tacts RA 2 also supply potential by way of resistor R 17 to a cold cathode diode V 3 which acts as a local visual alarm Resistor R 9 is connected up to provide conditions suitable for the subsequent restoration to normal 130 two sources of supply are provided from which currents of a plurality of different frequencies 60 are normally available each source being capable of supplying all the frequencies required but being arranged normally to supply some only of such frequencies, the remainder being normally supplied by the other source, 65 the two sources for each frequency being connected to a common output circuit by way of rectifier networks arranged to be biassed respectively under the control of the common output circuit so that only one source is effective 70 but that on failure of the output the bias is altered so as to render the other source effective.
