DK141108B - Procedure for Filling Copper Plates for Accumulators. - Google Patents

Description

(11) PUBLICATION NOTICE 1 ^ 1108 DENMARK (»d intci.sh 01 u 4/04 (21) Application No 4718/75 (22) Filed on 20 Oct 1975 l ^ Sl (23) Running Day 20 Oct, 1975 V / (44) The application presented and

the present application was made public on 14 J & n. I98O

DIRECTORATE OF

PATENT & TRADEMARKET (9 Priority requested from it

Oct 18 1974, 45241/74, GB

25 dec. 1974, 55500/74, GB

Oct 15 1575 * 42226/75, GB

Oct 15 1975 # 42227/75, GB

(70 CHLORIDE GROUP LIMITED, 52 Groevenor Gårdene, London SWTW C AU, GB, (72) Inventor: Stanley Charlee Foulkee, 12 Cambourne Drive, Dear, Bolton, Lancashire, GB.

(74) Plenipotentiary in the proceedings:

The engineering firm Lehmann & Ree.

(64) Method of filling the cutting tip with t-H accumulators.

The present invention relates to a method for filling accumulator sheath plates, in particular tubular type accumulator plates.

Tubular plates may have a variety of different types of tubular material and tubular shapes and may have tubes connected to each other or shaped as separate tubes disposed separately on the pins.

An example of such separate pipe arrangements is using woven fabric tubes with a thin outer plastic sheath provided with perforations having a diameter of 1-2 mm at a spacing of approx. 1-2 mm. The plastic sheath is approx. o, l to o, 2 mm thick.

However, the invention will be described with particular reference to pipe arrangements, the tubes being a single pre-formed unit, since this facilitates assembly of the tubes on the pins of the plate.

A conventional method of making tubular sheets includes impregnating fabric tubes with a resin to make them rigid, but still permeable, placing the tubes on a system of lead alloy pins, a pin for each tube, and filling the space between the interior of the tubes and the active material pins, e.g. lead oxide powder from a hopper and shaking the joint to compress the powder into the tube. This approach presents significant problems, including lead oxide wastage, filling weight disparity, and uneven loading, since the active material tends to become too tightly packed at what is at the bottom of the tubes during filling but which is the top of the tubes below the use.

A proposal under British Patent Specification No. 947,796 to reduce these problems is to extrude an active material paste containing a water-soluble thickener into the high pressure tubes. However, this method results in plates having unpredictably variable electrical performance. There is also a tendency for the paste to decompose and lose its fluidity under pressure and also to assume solid form within the machinery if there are intervals or delays in the production process.

Another suggestion according to English Patent No. 1,386.o56 is to inject a metered volume corresponding to the inner volume of the tubular plate of an acidic car accumulator paste into the pipes within a very short period of time, e.g. less than 1.5 seconds. The paste is added to a certain amount of additional water. This is said to form a suspension, but in reality this mixture is a thick paste which does not smooth itself. The pastes listed contain 3 parts of gray lead oxide, 1 part of red lead oxide, 2.96 parts by weight of oxides for each part by weight of acid and water, and o, 6 parts by weight of sulfuric acid of density 1.4 for each part by weight of oxide, i.e. 12.6% of the gray lead oxide was sulfated. Said description indicates that the pastes have dynamic viscosities in the range of 3.ooo to 4.ooo centipoises. There is no indication of the method to be used for measuring viscosity or measuring devices.

The viscosity of the above paste described in British Patent Specification No. 1,386.o56 has been measured on a rotary vane viscometer as described below using the measurement technique also described below.

It has been found that this paste has a torque value (as defined later) on viscosimeter with rotary vane of 1.05 Nm. The paste is not self-leveling, ie. when a mass is deposited as a lump on a flat surface, it does not assume a flat level surface within 3 hours of 24 hours, although small amounts of liquid are separated from the solid parts during that time.

This method has the disadvantage that it requires accurate measurement of the volume of paste to be injected and the paste is so viscous that it must be pressed into the tubes under high pressure.

A similar method is known from German Publication No. 2.25o.748, in which tubular plates for lead accumulators are filled with a paste-shaped active mass by means of a cylinder with a filling opening, through which the paste-shaped mass, due to gravity, falls into the free cylinder space. With a piston, the mass is compressed against a sliding valve which is then opened, whereby the mass is pushed into the tube plates during the movement of the piston.

This need to use a high pressure causes variation of the density of the paste along the tubes, as the paste tends to become too compressed at the inlets of the tubes which are bottom of the tubes during use. Furthermore, it causes difficulties in causing the paste to travel throughout the length of a tube, especially in a deep plate. This significantly limits the size of plate that can be filled. This introduces further problems in making accumulators of the paste and using the accumulators.

The object of the present invention is to reduce the above problems individually and jointly by using a substantially different method and active material composition.

The method of the invention for filling casing sheets for accumulators and batteries comprises introducing an active material composition into the porous casing of the casing plate when the casing is applied to the conductive element of the sheet, and it is peculiar to the method that the active material composition is introduced into the casing as a aqueous sludge comprising an active lead-acid material composition having a torque value measured on rotary vane viscometer in the range of 0.008 to o, o81 Nm at 20 ° C, and wherein the ratio of active lead-acid composition to liquids in the aqueous sludge is not more than 3.5: 1, which aqueous sludge is introduced into the casing at a pressure less than 34 kPa until the casing is filled with the composition, liquid escaping through the casing walls and allowing the pressure to rise to a value above 34 kPa , but not above 69o kPa, after which the pressure is relieved.

The use of a low viscosity sludge introduced into the tubes under the influence of gravity or only a low pressure followed by consolidation when the tubes are filled by allowing the backpressure to build up allows immediate and simple consolidation to be achieved and controlling the degree of consolidation in the tubes and thus the weight of active material introduced into the tubes.

4 U1108

According to the invention, the aqueous slurry preferably has a torque value measured on viscosimeter with rotary vane of 0.008 to 0.50 Nm at 20 ° C. The result is that the immediate and light filling of the tubes is substantially improved without any pressure and minimal layering.

For ease of description, the method will be described essentially with reference to tubular plates.

The ratio of the sludge volume introduced into the tubes to the total internal free volume of the tubes in the sheet is at least 2: 1, such as between 3: 1 and 15: 1. These conditions are preferred because they result in easier and more uniform filling of the pipes.

The internal free volume of the pipes is the volume within the inner diameter of the pipes which is not occupied by the conductive elements.

The aqueous mud comprises a mixture of water and particulate active material. The sludge may not be acidified, or it may be acidified to at least partially sulfate the oxide.

The weight ratio to be used depends on the particular active material being used, the permeability of the pipes being filled, and whether the composition is acidified or not and, if acidified, on the ratio of acid to active material, e.g. the degree of sulfation.

With the non-woven fabric described below, it is preferred to use sludge without acid additives with a ratio of solids to liquids of 2.5: 1 to 3.5: 1 and with partially acidified sludge a solids-to-liquid ratio of 1, 7: 1 to 2.5: 1, the acid having the effect of significantly increasing the viscosity of the sludge. This also contributes to a light and uniform filling of the pipes.

The slurry may contain usual fillers and additives to the active material, such as hydrophobic or hydrophilic silica, as long as the composition continues to have a viscosity, as indicated above. In one arrangement, the tubes are allowed to fill substantially under the influence of gravity, pumping into the tubes under a zero pressure and continuing pumping and allowing the back pressure to build up to a value not exceeding 483 kPa. Thus, the pressure may be in the range of 34 to 344, e.g. 69 to 20o7 and preferably 1o3-2o7 kPa. The time during which the pressure build-up is allowed to occur is not critical. Usually the pressure is only allowed to build up to a set value at which point the pressure is relieved.

Surprisingly, and contrary to the previous proposals, where the entire filling operation is carried out under high pressure, resulting in the active material being layered, the paste being closer to the entrance (which will be the bottom of the tubes during use), w ·.

This arrangement allows the density "of the active material in the tube to increase evenly throughout the tube.

As mentioned above, the ratio of active material to liquids to be used depends on a variety of factors including the nature of the material from which the tubes are made.

A balance must be struck between the need for the material to have a high water permeability to achieve good conductivity during use in the accumulator and the need for the material to retain the active material so as to enable filling to be carried out quickly and the active material to be retained in the pipes. over long periods of use and under shock and vibration conditions. A suitable material is obtained from a non-woven sheet of polyester fibers which is o 2 to 2, 7 mm thick and weighs 12o to 16o grams per gram. cm, has a nitrogen permeability of 8.0 liters / cm / min. and a water permeability of 2 1.5 liters / cm / min. This material is preferably not perforated since its porosity derives from the natural interstices between the fibers from which it is made.

More generally, it is preferred to use a material having a nitrogen permeability in the range of 0.5 to 12, e.g. 1 to 10 or preferably 3 to 9 liters / cm / min. It should preferably have a water permeability of at least 0, 1 liter / cm / min, e.g. o, l or o, 5 to 1.2 or 5 liters per liter. minute or more.

As indicated below, it is preferred to use a sludge composition in which the active material particles have a mean particle size in the range of 5 to 20 microns.

However, material having average particle sizes in the range of 1 to 30 or 5 to 10 microns may also be used.

Referring again to lead acid systems, the lead oxide preferably has substantially all of its particle size particles smaller than 10 microns, e.g. less than 1% by weight is over 2 microns in diameter. Furthermore, less than 1% is less than ο, οοί microns in diameter. Typically, at least 5%, e.g. 95% by weight is less than 1 micron and 5% is less than 1 micron. The oxide may comprise gray lead oxide or red lead oxide or a mixture of gray lead oxide and red lead oxide and preferably a mixture of gray lead oxide of medium particle size 2 microns and red lead oxide of medium particle size 5 to microns. The ratio of gray to red lead may be in the range of 95: 5 to 5:95, although 9o: lO to 5o: 5o, e.g. 33:67, is preferred.

6 141108

The invention will now be explained in more detail with reference to the drawing, in which fig. 1 is a schematic side view of an embodiment of the apparatus according to the invention; FIG. 2 is an enlarged schematic perspective view of the filling box shown in FIG. 1, FIG. 3 is a schematic view of a portion of the lower terminal shown in FIG. 2 in the open position, with only some of the tubes of the plate shown; FIG. 4 is a cross-sectional view taken along line IV-IV of FIG. 3, FIG. 5 is a partial cross-sectional view of a portion of the upper terminal in the open position, as in FIG. 3, FIG. Figure 6 is a front elevational view of rotary vane viscometer used to measure the viscosities of the sludges used in accordance with the invention; 7 is a front elevational view of the vane unit of the viscosimeter of FIG. 6, FIG. 8 is a plan view of the container for use with the viscometer of FIG. 6 to contain the sample whose viscosity is to be measured; and FIG. 9 a plane image made from an optical photographer! of the nonwoven fabric NW described below and used in the Examples. The apparatus shown in FIG. 1 consists of a sludge tank 1o, in which the sludge to be filled in the plate tubes is stored. The tank is equipped with a vane 11 which is located at the bottom of the tank and is driven by a belt and pulley drive 12 by a variable speed motor 13. A vertical feeder tube 15 extends upwardly immediately above the vane 11 to the inlet of a supply pump 16, also driven by a belt and pulley drive 17 from a variable speed motor 18. The outlet of the pump 16 is connected vertically downwards by means of a supply pipe 19 with a plate filling station 20. The supply pipe continues over a pressure gauge 22, a two-way valve 23 and a fish tail manifold 24. The valve 23 either allows the sludge to flow vertically down to the station 20 or can be set to direct the sludge to the tank 1o over a recycling pipe 26 extending downwards immediately above vane 11. Pipes 15 and 26 preferably have the same cross-sectional area.

7 U1108

The mass of the sludge supply is preferably kept at approx. 15o kg, e.g. loo to 2oo kg, and the sludge mass is introduced into each tubular plate, the individual filling liquid being of the order of 4οο-1οόσ grams. More generally, the weight ratio of the active material, e.g.

75 kg, in the continuously mixed sludge supply and the individual filling weight located in the range 13oo: 1 to 25: 1 preferably looo: 1 to 2oo: 1, especially 16o: l to loo: l.

The station 20 has a frame 29 which is rigidly attached to the manifold 24 and carries top and bottom terminals 3o and 31.

Terminals 30 and 31 are toothed and in accordance with the outer surface profile of the bottom and top of the tubular plate as the plate is inserted into the terminals with its open bottom facing towards the manifold 24. The manifold has a discharge nozzle unit of 6.4 mm long copper or other rigid feeder pipes with outside diameters corresponding to the internal diameters of the plate pipes and spaced apart in a straight line, the centers of the feeder pipes lying on the centers of the plate pipes.

Thus, the open ends of the plate tubes fit tightly over the feed lugs and are clamped thereto by the top clamp 30 which may be provided with an elastic sealing liner.

The lower clamp 31 holds the plate in place and tightens the tubes against a thickened end section of the pins. The sides of the plate are completely free. !

The pins are of the usual lead alloy nanotube composition and of the usual structure, being mounted on a top bar at centers corresponding to the centers of the tubes with which they are to be used. They are preferably provided with short axial ribs which are used to center the pins in the tubes and to prevent the pins from being distorted during handling prior to filling.

Station 20 is now described in more detail with reference to Figs. 2 to 5.

As mentioned above, the station 20 has a frame 29 rigidly attached to the manifold 24. This frame is hinged relative to each other along the left side edge, and it is the portion 33 which is rigidly attached to the manifold 24. The top and bottom clamps are each in two parts 3oA and 3oB and 31A and 3IB. 3oA and 31A are disposed on the movable portion 32 of the frame, and 3oB and 31B are disposed on the fixed portion 33 of the frame 29.

The fixed member 33 also carries top and bottom locking lever rods 36 and 37 which are adapted to engage the top and bottom handles 38 and 39 of the movable frame member 32 and lock the filling station in the closed position.

8 141108

The fixed portion 33 of the frame 29 also carries a bottom support rod 42 which has an opening 43 through which the patch 44 of a plate 45 can pass and which helps to set the plate in the correct position in the filling station.

The top and bottom clamps 30 and 31 have toothed profiles which correspond to the outer cutting dimensions of the plate, and the two parts of each clamp define in closed position a series of cylindrical holes 48 which are connected to slots 49 which are twice the the thickness of the fabric 47 in the sheath so as to prevent the sheath from being cut by the clamps.

The bottom clamps 31 press the fabric 47 in the jacket against the extended shoulders 51 on the pins 52 of the plate to ensure a tight closure. (See fig.

3 and 4).

FIG. 5 shows the clamping arrangement at the manifold 24.

A manifold plate 54 has a series of feeder pipes 55 which pass down through it and have narrowed ends 56 extending through openings in a rubber gasket 58. It is elastic in that it is compressible by the finger pressure to only about half its uncompressed thickness. , which is about 3.2 mm thick. The arrangement shown in FIG. 5 shows the sheath 5o in position over the ends 56 of the feeder tubes. However, the arrangement is in fact designed such that the packer 58 is to be compressed by approx.

1.6 mm of the sheath 5o which is pressed into it to bring the top bar of the plate up onto the base bar 42 of the frame (This compression is not shown in the drawing). The clip 3o presses the fabric 47 into the jacket around the ends 56 of the feeder tubes 55 to obtain a good seal at the top.

The pump 16 is one which provides smooth delivery and is of the well-known type, such as that sold under the trade name MONOPUMP, which has a single start screw rotor which fits in a cylinder in the form of a double start screw line with the double pitch of the pitch of the rotor, with the rotor rotating about its own axis in one direction, while its axis orbits the axis of the cylinder in the opposite direction at the same speed. This pump shape provides a positive displacement with uniform flow and prevents the separation of fluids and solids in the composition.

In another arrangement (not shown), the filling station 20 is configured as a double manifold arrangement where each manifold is supplied from the pump 16. The two way valve 23 is replaced by a three way valve and each conduit from the valve 23 to a manifold contains a pressure sensitive valve.

This valve is preferably a pressure relief valve which can be set 2 to any desired pressure, e.g. l, o5 kg / cm, and when this pressure is reached, it will maintain the pressure of l05 kg / cm until it is activated, e.g. manually.

The method will then be for a plate to be inserted into a manifold and the valve 23 to be switched either from recycling or from the other manifold. in 5 seconds and then the pressure 2 will rise to 1.5 oz / cm and held there for 5 seconds. During this time, the operator will have removed the filled plate from the second manifold and inserted a new plate. He can then switch valve 23 either to recycle temporarily or immediately to fill the new plate.

In an alternative arrangement, the pressure relief valve is arranged to switch the pump supply for recycling and release the pressure on the plate as soon as the preset pressure is reached.

During operation, the filling process is performed as follows.

The composition is prepared with the desired composition in the tank 1o using the bucket 11. A tubular plate 5o is assembled, the fabric tubes 47 being placed on the metal pins 52 and placed against the terminals 3oB and 31B of the station 2o with its open bottom ends pressed against the gasket 58 and over the ends 56 of the feeder tubes 55 on the manifold 24. The portion 32 of the frame is then pivoted to the closed position against the portion 33, and the terminals 3o and 31 are thus closed, and the locking arms 36 and 37 are secured over the handles 38 and 39. the valve 23 is rotated to the recirculation position, where the pump 16 is connected to the pipe 26 and the pump 16 is started.The recirculation continues / until the flow is stable. The pressure indicator 22 indicates zero pressure while the recirculation is in progress.

The valve 23 is then switched to connect the pump 16 to the manifold 24. The sludge passes down into the station 20 as the active material fills the interior of the tubes. The valve 23 is held in this position until the tubes have been filled with active material, at which point the pressure indicator indicates a relatively sudden pressure increase. At this point, liquid seeps into droplets over the entire surface of the tubular plate substantially simultaneously. As the pressure rises to the shut-off pressure, additional small amounts of liquid seep out from the plates.

The first liquids tend to be clear, while later liquids also tend to contain active material. When the pressure reaches the desired shut-off value, the valve 23 is switched to recycle the composition of the tank 10 over the pipe 26.

Terminals 30 and 31 are then opened and the filled plate removed and further operations in the process, such as bottom bar insertion, cleaning, drying and electrolytic propagation, are performed on the plate.

The excess sludge in the manifold 24 falls into the tank 1o.

lo 141108

During continuous operation, the pressure rise indicated on the indicator 22 can be used to control the filling cycle, e.g. for activating the valve 23 and opening the terminals 30 and 31 to release them from the manifold 24 and again engage with a new plate in the clamped position. End switches can be arranged to be actuated by the new plate which engages with the manifold 24 to switch valve 23 back to the filling position.

Examples.

Examples of specific plate making methods must now be given there.

The plates were positive plates with 15 tubes, each with a length of 36.8 cm. The bars were made of nonwoven polyethylene terephthalate fibers. This is done as follows:

A thin web (1.5 m wide) of fibers with a mean length of 11.4 cm is produced by carding and a web is produced by laying approx. ten webs to form a continuous length of non-woven fabric (ie 1.5 m wide).

The fibers extend substantially longitudinally in the web, which is folded in zig-zag form as it is taken out of a conveyor moving longitudinally of the web onto a conveyor moving perpendicularly thereon. The fibers thus extend substantially across the length of the web, but due to the migration of the second conveyor, the fibers in adjacent layers are inclined opposite each other at a small angle with the transverse direction.

This material is then impregnated with 5o% by weight of polyacrylic binder. It has a thickness of 0.5, 5 to o, 7 mm and weighs 2 12o to 16o grams / cm.

This material is then transformed into a system of tubes by passing two layers of it through a multiple sewing machine to attach the layers to one another along parallel lines (for example, spaced 13 mm apart) to form pockets or tubes in the usual manner. manner.

This material is then dipped into a phenolic resin and dried. The material absorbs 30% phenolic resin based on the dry weight of the nonwoven material. After cutting the material in length, circular cross-sectional mandrels of 7.29 mm are then inserted between the rows of stitches to form the pockets. It has an air permeability of 2 8, 0 liters / minute / cm and a water permeability of 1.5 liters / minute / cm area. Its structure is shown in FIG. 9th

As shown in FIG. 9, this nonwoven fabric is formed from randomly entangled single fibers. The fibers have a diameter of approx.

25 microns and more generally 2o-5o microns. The gaps between the individual H 141108 fibers are generally smaller than 25 microns and mostly smaller than 10 microns, and furthermore, the material having a thickness of 0.5 to 7 mm has a three-dimensional structure that allows overlap of many individual fibers in a path from side to side of the plate.

Air permeability was measured in the following way: 2

A 2.8 cm diameter (6.16 cm effective cross-sectional area) sample was clamped in place and the time taken for 5o of dry nitrogen to flow through the sample at 20oC under a 1.5cm pressure difference water column, was recorded.

The material is too permeable to mercury porosimetry or air flow through an alcohol-saturated sample to be accurate measurement methods.

Water permeability was measured on the same sample by measuring the time it took for a water column originally 42 ea high and 1 liter in volume to flow through the sample under the influence of gravity.

The lower end of the column during the sample was blocked, and water was introduced over the sample, and then the lower end of the sample was opened to the atmosphere. This material is designated scan the nonwoven fabric NW in Table 1 below.

Another substance was also used. It was a spun woven fabric designated as SW in Table 1 below and has an air permeability of 6.0 liters / cm / minute. It has 17 shooting wires per cm and 22 warp threads. cm. The threads are approx. 25o microns in diameter and the filaments approx. 375 microns in diameter. Microscopic examination shows that the spaces between adjacent warp threads and adjacent bullet threads are approx. 25o microns by 25o microns maximum, but these spaces are crossed by numerous loose fibers extending from the filaments.

The compositions used are listed in Tables 1A and 1B below.

The sludge was made from mixtures of gray lead oxide (mean particle size 2 microns) and red lead oxide (mean particle size 5-microns) mixed in different weight ratios with tap water.

The solid particles in the sludge were of such a nature that less than 1% by weight was above 2 microns and less than 1% were below ο, οοί microns, while 95% by weight was less than 5 microns. These particle sizes were determined by sieving.

The tank lo contains 15o kg of sludge, the bucket 11 with a size of 76 cm by 3.8 cm was rotated at 3o-7o rpm. minute to keep the solids in suspension. Pump 16 was operated at various volumes, as indicated in Table 1A. During recycling, the pressure indicator 22 showed zero pressure. Using the same stirring and pumping conditions, valve 23 was switched to fill position and time. Under which the indicator 22 showed zero pressure was recorded and the total time until the time when valve 23 was again switched to recirculation and the maximum pressure obtained was recorded. These are listed in Table 1A. The inner volume of the tubes was 17 cm.

It is preferred to add acid to at least partially sulfate the oxide. One gram of oxide requires 0.4 ml of sulfuric acid of density 1.4 to achieve this. The mixing of the sludge continues in the storage tank during the acid addition and once this is complete, the filling cycle can continue. Some of the examples in Tables 1A and 1B are of partially acidified compositions.

Example 12 was performed using tubes having a total 3 inner free volume of 5 cm.

_13 141108

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Notes to Tables 1A and 1B.

1) Acid / solid / ratio. It has been assumed that all the acid is absorbed by and reacts with the excess oxide at the stage of first addition, and the acid / oxide ratio thus remains constant until more acid is added, i.e. part of the acid is removed with each paste sample removed.

2) Solid / liquid ratio.

A) These are calculated including all of the acid possibly added as liquid.

B) The weights of removed solids in the samples of the filtrates are disregarded, as the weights of these samples were relatively small and there was no way to easily determine the ratio of solids to liquids in the filtrates.

C) The ratios have been calculated taking into account the amount of liquid removed in the paste in the tubes. These conditions therefore slightly underestimate the content of solids in the sludges.

3) Gray / red ratio. These are assumed to remain constant except when extra gray or red oxide is added.

4) Wet paste in plate. The weight x of the fabric tube, lead pins and a bottom bar were measured. The values given are the wet filled plate after the bottom bar insertion minus x.

5)% precipitation of the sample. This is the height A of the solids in the container divided by the height B of the liquids from the bottom of the container, expressed as a percentage after the sample has been thoroughly shaken for ½ minute and then allowed to settle in a vertical position for 24 hours.

The container is a round-bottomed test tube with an inner diameter of 1.5 cm and at least 9 cm of sludge is placed in the test tube.

6) Half-life of the suspension. This is the time it takes for the level of solids in the sample in the container described under 5) to sink to midway between B and A.

The test is performed by affixing a rubber band with its lower edge at the midway level, ie. (B + A) / 2 cm from the bottom of the test tube, vigorously shaking the tube for at least \ minute, or until all the solids are removed from the bottom of the test tube, and then aligning the test tube and measuring the time from this point to the moment where light is visible for the first time under the rubber band.

7) Pump speed. This is just an option. The volume of sludge pumped through the manifold was measured by varying settings when collecting the mud as it emerged from the manifold. Two measurements were performed for each pump setting. The sludge volume was measured.

A graph was then plotted for 0, 20, 30 and 40 pump settings by volume relative to time in seconds (using a stopwatch). A fairly straight line of the deposited values was formed.

8) Time Until the start of pressure build-up, this is the time from the inlet valve is opened and until the pressure gauge really starts to move instead of just vibrating.

9) Theoretical volume pumped until the start of pressure build-up. This is the time under the eighth column from the left in Table 1A multiplied by the volume reading under the seventh column from the left in Table 1A and is purely theoretical.

10) layering. (Table 3). This is determined by cleaning the plates in sulfuric acid with a density of 1,4 ° for 6 hours followed by drying at 82 ° C for 12 hours.

The top bar and bottom bar were then cut from the plate, and the remaining portion cut into four equal horizontal strips designated A B C and D with A at the bottom bar end of the plate. These were then weighed. The horizontal strips were then cut into four sections of three tubes, omitting every four tubes, and sections were designated 1-4 by 1 at the lap side of the plate. The four sections 1 from each of the horizontal strips were then weighed, and the value given below 1 in Table 3 is this value. The other vertical sections 2,3 and 4 were weighed in the same way.

11) Pin porosity. This is determined by the well-known method of mercury intrusion porosimetry and performed on the same samples as Table 3. Details of this technique can be found in British Patent Specification No. 1,331,257.

The values measured on the rotary vane viscometer for some of the sludges used in the above examples are given below in Table 2.

The viscometer used is shown in Figures 6, 7 and 8.

The apparatus consists of a tripod scan, carrying an electric motor 111 driving a vane unit 12o over a gearbox 112 and a torque converter 119. The speed of the gearbox 112 is sensed by a tachometer generator 113 whose output signal is fed to a digital voltmeter 113A. The voltage signal produced by the torque converter is fed to a curve printer 114. The printer has a variable strip rate and a variable scale.

A sample container 13o is firmly supported on an adjustable table 115 which can be raised and lowered on guides 116 by means of a compressed air cylinder 117.

The sample container 13o has a removable lid 131 disposed over the vane unit 12o. The lid can be secured to the container by an external bayonet lock (not shown).

The vane unit 12o is removably attached to the output shaft 118 ice 141108 on the gearbox 112 and consists of a central rod 121 with a lower projection 122 which rests during use in a hole 132 at the bottom of the container 13o. The bar 121 has a diameter of D5 of 1.3 cm and carries three pairs of vanes 123,124 and 125. The vanes 123 and 125 are perpendicular to the vanes 124. All the blades on the vanes are vertical and thus parallel to the axis of the bar 121. The vanes are arranged on arms 126,127 and 128. The distance D6 from the center of the arm 126 to the projection 122 is 6.5 cm, the distance D7 from the center of the arm 127 to the projection 122 is 3.9 cm, and the distance from the center of the arm 128 to the projection 122 is 1.6 cm. The width of each bucket D3 is 1.2 cm and its height D2 is 1.2 cm and its thickness is 0.1 cm. The distance D4 from the inner edge of each vane to the surface of the rod 121 is 1.5 cm.

The distance D1 between the outer edges of the blades in a pair of blades is 6.8 cm.

The inner height of the container 13o is 8.2 cm and its inner diameter is 8.8 cm.There are four inner shield plates 135 which are arranged at the ends of diameters perpendicular to each other.The thickness Dlo of each spring plate 135 is o, 3o cm and it extends a distance D9 inward of 0.5 cm. The distance D11 between the shield plates on a diameter is 7.65 cm. Each platen extends to the full height of the container.

The container and molding plates are made of smooth stainless steel.

The device is used as follows:

The container is filled to a depth of 8.2 cm with the material to be examined and raised into place clamped to the table 115 and the lid 131 secured.

The curve printer 114 is started and the motor 111 is then started with the exchange set to a low shear rate, e.g. six revolutions per minute. The starting torque and stationary torque are detected by torque converter 119 and the motor and printer run until a stationary value has been recorded for at least two minutes. This is the stationary torque value. The torque value in stationary state is noted and if there was an initial maximum, this ratio is noted. The sample is then removed and shaken with the amount of material being measured and the container refilled. The measurement is then repeated at a higher shear rate, e.g.

18 cycles per minute.This cycle is repeated for as many shear speeds as desired.

The background torque value, namely with the container 13o empty, was found to be o, o55 kgcm at all the shear rates given in Table 2. The same value was obtained when the container was filled with water.

The torque value defined herein, measured on the rotary vane viscometer, is the value of the stationary torque of the sample measured 141108 in the above-described manner on the apparatus described above at a shear rate of 6 turns of the vanes per minute. per minute at an ambient temperature of 20 ° C minus the background value at 20 ° C.

2ο 141108

Table 2

Example Gray Fixed S sulfa Viscosimeter with rotating wing Red fabrics Shear In Moment i Occurrence oxide liquids velocity kg cm of max rpm. mum 2 66:34 2.57: 1 none 6 0.235 No 18 0.194 3o 0.194 42 0.194 4 75:25 2.88: 1 4.o 6 o.912 Yes 24 0.912 No 42 0.912 No 5 75:25 2.39: 1 4.o 6 0.484 Yes 18 0.442 No 3o 0.373 No j 42 0.387 No. lo 75:25 3: 1 - 6 0.194 Yes 18 0.152 Yes 3o 0.166 Yes 42 0.I80

Together 3: 1 2.9o: l 12.6 6 lo.71 Yes Equation Example 1 of British Patent Specification 1,380,865 12 loo: o o.9o: l 17 11 0.138 No

Layering results for the plates prepared in Examples 3,5,8 and 12 are given in Table 3 below. Porosity results for the plates prepared in Examples 3.5 and 8 are given in Table 4 below.

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Example 5 8

Pores between Porosity (%) provided by pores of such dimensions loo - 5o microns o.7 o.8 5o - 25 0.5 o.4 25-12.5 0.6 o.4 12.5 - 6.4 0.2 ol 6.4-3.2 0.3 0.3 3.2-1.6 0.2 0.4 1.6 - o.8 0.4 1.9 0.8 - 0.4 2.2 6.5 0.4 - o.2 4.3 5.4 0.2 - ol 4.1 4.2 ol - o.o5 3.1 2.4 o.o5 - o.o35 o.8 o.5 under o.o35 2.1 1.6 total porosity 19.5 24.9 apparent 5.5 5.0 density true density 6.8 6.6

Claims (10)

23 141108 Patent Claims. A method of filling casing sheets for accumulators and batteries, comprising introducing an active material composition into the porous casing of the casing, when the casing is applied to the conductive element of the sheet, characterized in that the active material composition is introduced into the casing as an aqueous mud comprising an active material. lead-acid material composition having a torque value measured on rotary vane viscosimeter in the range of 0.008 to o, o81 Nm at 20 ° C, and wherein the ratio of active lead-acid composition to liquids in the aqueous sludge is not more than 3.5 : 1, which aqueous sludge is introduced into the casing at a pressure of less than 34 kPa until the casing is filled with the composition, liquid escaping through the casing walls and the pressure thereafter allowing it to rise to a value above 34 kPa, but not above 69o kPa, after which the pressure is relieved. Process according to claim 1, characterized in that the aqueous sludge has a torque value measured on viscosimeter with rotary vane of 0.008 to 0.50 Nm at 20 ° C. 3. A method according to claim 1 or 2, characterized in that the ratio of the sludge volume introduced into the sheaths to the total internal free volume of the sheaths in the plate is at least 2: 1. Method according to claim 3, characterized in that the ratio of the sludge volume introduced into the sheaths to the total internal free volume of the sheaths in the plate is between 3: 1 and 15: 1. Process according to any one of claims 1-4, characterized in that the shell material has a nitrogen permeability in the range of 0.5 to 20 liters / cm / minute. Process according to claim 5, characterized in that the material of the jacket has a nitrogen permeability in the range of 2 to 3 liters per liter / cm / minute. Process according to claim 6, characterized in that the material of the jacket is a non-woven sheet of polyester fibers which is o, 5 to o, 7 mm thick and weighs 12o-16o grams per hour. and has a nitrogen permeability of 8.0 liters / cm / minute. Process according to claim 7, characterized in that the sludge composition is not acidified and has a solids to liquid ratio by weight between 2.5: 1 and 3.5: 1. Process according to any one of claims 1-7, characterized in that the active material is at least partially sulphated before being introduced into the porous sheath of the plates. Process according to any one of claims 1-9, characterized in that the sludge composition is partially sulfated, the degree of sulfation being below 100% and that the sludge composition