IE42755B1 - Manufacture of battery plates - Google Patents

Description

This invention relates to the manufacture of batt ery plates especially those of tubular type and is concerned in particular with the filling of the tubes of such plates, : and novel apparatus for carrying . out the method.

Tubular plates can have a variety of different types of tube material and tube configurations and can have tubes joined together or formed as separ10. ate tubes which are separately located on the spines.

One example of such separate tube arrangements utilizes woven fabric tubes having a thin outer plastic sheath provided with perforations about 1-2 . mm across spaced apart by about 1 to 2 mms. The plastic sheath is about 0.1 to'0.2 mms thick.

The invention, though not limited to such arrangements, however is described with particular reference to tube arrangements in which the tubes are a single . preformed assembly since this facilitates assembly of the tubes'onto the spines of the plate.

A conventional method for making tubular plates involves impregnating fabric tubes with a resin to render them stiff though still permeable, locating . the tubes on an array of lead alloy spines, one spine I. to each tube, and filling the space between the interior of the tubes and the spines with active material e.g. lead oxide powder from a hopper and shaking the assembly to compact the power in the tube.

. This method has considerable problems including . . . 437SS . . . . . waste of lead oxide powder, inconsistency of filling weight, and unevenness of filling, the active material tending to become over consolidated at what is the bottom of the tubes during filling but is the top of the tubes in use.

One proposal, in British Patent Specification No. 947,796, for reducing these problems was to extrude an active material paste containing a water soluble thickening agent into the tubes under high pressure. However, this method resulted in plates which had unpredictably variable electrical performance. There was also a tendency for the paste to break down and lose its fluiditiy under pressure and also to go solid inside the machinery if there were any intervals or delay in the production sequence.

Another proposal, in German Auslegeschrift No. 2,243,377 1s to inject a metered volume, corresponding to the internal volume of the tubular plate, of an acidic automotive battery paste into the tubes within ’a very short space of time e.g. less than 1.5 seconds.

The paste has a certain amount of additional water added to it. This is alleged to form a suspension but in fact this mixture is a thick paste which is not self levelling. The pastes which are disclosed contain 3 parks grey lead oxide, 1 part red lead oxide, 2.96 parts by weight of oxides to each part by weight of acid and water and 0.06 parte by weight of 1.Λ specific gravity sulphuric acid for each part by weight of oxide, i.e. 12.6% of the grey lead oxico was sulphated. The specification describes the pastes as having dynamic viscosities in tl··.:· range 3000 to 4000 centipoises. No indication is given .43755 of what method of measurement of viscosity or measuring apparatus is to be used.

We have measured the viscosity of the above paste described in German Auslegeschrift/2,243,377 on a . rotating vane viscometer as described below using the measurement technique described below.

Vie find that this paste has a rotating vane viscometer torque value (as defined herein) of 0.-775 lbs ft. The paste is not self levelling; that is . when a mass is deposited as a lump on a flat surface it does not assume a flat level surface.within a period of 24 hours, though small amounts of liquids separate outfrom the solids during this period.

The process has the disadvantages of requiring . accurate metering of the volume of paste to be injected and the paste is so viscous that it has to be forced into the tubes under high pressure.

This need to use high pressure results in variation ·· in density of the paste along the length, of the tubes, , the paste tending to become over consolidated at the inlets to the tubes which are the bottoms of the tubes in use. In addition it introduces difficulties in getting the paste to travel the full length of a tube, especially in a deep plate. This severely limits . the size of plate which can be filled. This introduces further problems in production of batteries from the paste and in use of the batteries.

We have discovered that these problems can severally and collectively be reduced by using a . radically different active material composition, - 4 43785 apparatus and method in which a pourable liquid slurry of very low viscosity is poured or fed into the tubes under gravity and then, when the tubes are full, preferably consolidated by allowing the back pressure to build up. By controlling the value to which the back pressure is allowed to rise, the degree of consolidation can be varied as desired and a very even consolidation achieved.

According to one aspect of the present invention a method for preparing enveloped plates for batteries by introducing an active material composition containing water into the porous envelope of the plate, when the envelope is assembled on the current conducting element of the plate is characterised in that the active material of the composition is introduced into the envelope as an aqueous slurry, which has a rotating vane miscometer torque value (as defined herein) of less than 0.006 and preferably not more than 0.004 lbs. ft., at 20°C, the aqueous slurry being introd uced into the envelope at a pressure of less than 5 p.s.i. until the envelope is filled with the composition, liquid issuing through the walls of the envelope, the pressure then being allowed to rise to a value above 5 p.s.i. but not in excess of 100 p.s.i. whereafter the pressure is released. The active material is preferably a lead oxide active material and the ratio of solids to water in the composition is preferably from 2.5:1 down to 0.4:1. by weight.

The term envelope covers arrays of separate tubes as well as arrays of tubes joined together or formed from sheets of material in addition to covering any envelope effective to form a bag or pocket around the current collecting element or elements of the plate and effective to filter out active material as a bed around the current conducting element or elements.

According to a preferred form of the present invention, a method of filling enveloped plates, preferably tubular plates, for batteries, preferably lead acid batteries, which comprises introducing an active material composition ihto the porous envelope of an enveloped plate e.g. the tubes, when the tubes are assembled on the current conducting element of the plate, e.g. the spines, is characterised in that the active material composition is fed into the envelope as an aqueous slurry comprising a lead acid active material composition, which has a rotating vane viscometer torque value of less than 0.006 lbs. ft. at 20°C, the said aqueous slurry being intro uced into the envelope at a pressure of less than 5 p.s.i. until the envelope is filled with the composition, liquid issuing through the walls of the envelope, the pressure the being allowed to rise to a value above 5 p.s.i. but not in excess of 100 p.s.i. whereafter the pressure is released, and in which the envelope is disposed in a substantially vertical plane, so that the solids can settle to the bottom of the envelope under gravity, the aqueous slurry containin a ratio of active material to water in the range 2.5 : 1 t 0.4 : 1 in parts by weight, the material of the envelope being selected to filter out active material whilst allowing passage of liquids, the solids thus being at least partially retained within the envelope and the liquids at least partially passing out through the walls of the envelope. 4S758 For ease of description the process will be described essentially with reference to tubular plates.

The ratio of the volume of slurry which is fed into the tubes of the enveloped plate to the total internal free volume of the tubes or the enveloped plate is preferably at least 2:1 and desirably at least 3:1, 4:1, or 5:1, preferably 5:1 to 15:1 or more preferably 6:1 to 10:1.

The internal free volume of the tubes is that volume within the internal diameter of the tubes which is not occupied by the current conducting elements.

The aqueous slurry comprises a blend of water and particulate active material. The slurry may have had no acid added to it and may be substantially free of sulphate.

The weight ratio of solids to liquids in the slurry within the above defined range which is best used depends on the particular active material which is being used, and the permeability of .the tubes which are being filled.

Preferably, the aqueous slurry comprises a blend of particulate active material e.g. lead oxide and water in a weight ratio in the range 0.5:1 to 1.5:1 or 2.0:1, more preferably 1:1 to 1.8:1 or about 1.5:1.

A slurry with a 0.1:1 oxide ratio had a density of 1.1 gr./cc.; 0.5:1 a density of 1.4; 1:1 a density of 1.7; 1.5:1 a density of 2.15 and 2.0:1 a density of 2.35 grams per cc. The slurry preferably 43755 has a density of less than 2.5 grams per cc.

The solid particles in the slurry were such that less than 1% by weight were above 200 microns, and less than 1% were below 0.00T microns, 95% by weight were less than 50 microns. These particle sizes were determined by sieving.

With the non-woven fabric described below we prefer to use non-acidified slurries having a solids to liquids ratio of 2.0:1 to 0.5:1 e.g. 1.5:1 to 0.7 : 1.

With the spun-woven fabric described below we prefer to use non-acidified slurries having a solids to liquids ratio of 2.5:1 to 1:1.

With the woven fabric described below we prefer to use non-acidified slurries having a solids to liquids rat Tn excess of 2.0:1 e.g. in the range 2.4:1 to 2.5:1.

The slurries useful in accordance with the present invention have viscosities substantially the same as that of water, that is as compared with conventional battery pastes and the pastes proposed by Bohle in German Auslegesch: 224,337. The viscosities of the slurries in accordance with the present invention cannot be measured by a Brookfie viscometer because the solids separate out on standing.

Slurries useful in accordance with the present invention are readily pourable and the solids settle 4375B out rapidly from the liquid phase, namely in less than 15 minutes on standing.

Thus the compositions are characterised by having a rotating vane viscometer torque value (as defined . herein) of less than 0.006, preferably not more than 9,004 lbs. ft. at 20°C.

The suspension half life (as defined herein) of the slurries is preferably not more than 15 minutes preferably in the range 1 to 10 minutes.

. The slurries have viscosities substantially independent of shear rate that is to say they are not thixotropic gels and whilst the viscosities fall with increase in shear rate this fall is not pronounced and a gel does not form when the shear force is · removed.

The slurry can contain conventional fillers and additives for the active material such as hydrophobic or hydrophilic silica, e.g. 0.1% to 0.5% by weight based on the oxide. The introduction of the slurry into the tubes . is preferably carried out under gravity i.e. at zero pressure or at a pressure of less than 5 psi until the .tubes are filled with the composition, the pressure then being allowed to rise to a value not in excess of 100 psi and the pressure thereafter being released.

. In one arrangement, the tubes are allowed to fill substantially under gravity and then the ρτ-essure is allowed to build up to apply pressure to the active material in the filled tube for only a fraction of the time.taken to fill the tube. Thus the pressure may be . in the range 5 to 50, e.g., 10 to 30 psi, applied, e.g. for one-tenth to one half the time taken to fill the tube or for a time equal to that taken to fill the tube. Thus the tube 43755 may take 5 to 15 seconds to fill and the pressure may be, applied for 1 to 5 seconds.

In another arrangement the pressure is applied for longer periods of time. In this arrangement, · the tubes are allowed to fill substantially under gravity by .the slurry being pumped into the tubes under zero back pressure, once the tubes have filled the pumping is continued and the hack pressure allowed to build up to a value not in excess . of 70 psi. Thus the pressure may he in the range 5 to 50, e.g. 10 to 30 psi. The weight of oxide in the tubes can be adjusted by adjusting the pressure build . up ,as is indicated in the examples. Usually the pressure is merely allowed to build up to a set value · at which point the pressure is released.

Surprisingly and in contrast to the prior proposals where the whole filling operation is carried out under high pressure, which results in the active material being stratified, the paste being more dense nearer the . inlet, this arrangement enables the density of the active material in the tube to be increased evenly throughout the tube without stratification occurring.

The material of the tube as indicated above is select to have a filtering action on the active material used.

. However this does not mean that all the active material is removed from the liquids issuing from the tubes merely that a proportion is retained within the tubes.

As mentioned above the ratio of active material to liquids which should 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 provide good conductivity in use in the battery and the need - 10 4373s for the material to have a good filtering action so as to enable filling to be carried out rapidly and the active material to be retained in the tubes over long periods of use and under conditions of shock and vibration. One suitable material is made from a non-woven batt of polyester fibres which is 0.5 to 0.7 mm. thick and weighs 120 to 160 grams per sq. cm. This is not perforated, its porosity being derived from the various gaps between the fibres from which it is made. It has an air permeability (as hereinafter defined) of 8.0 litres of nitrogen/sq. cm./minute, and a water permeability (as hereinafter defined of 1.5 litres of water/sq. cm./minute.

More broadly, it is preferred to use a material having an air permeability in the range 0.5 to 20 preferably 1 to 10 or more preferably 3 to 9 litres of nitrogen/sq. cm./ min. Desirably, it should also have a water permeability of at least 0.01 litres of water/sq. cm./min, preferably 0.1 to 0.5 to 1, 2 or 5 litres of water sq. cm./minute or more.

One preferred material is a spun woven fabric having 15 to 25 weft threads per cm. and 15 to 25 warp threads per cm., and an air permeability (as defined herein) of 5 litres of nitrogen/sq. cm./minute.

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

However, material with average particle sizes in the range 1 to 30 or 50 or 100 microns can equally well be used so long as the tube material still has adequate filtration action. Active material of higher particle size such as 4S7SS granulated material, e.g., of particle size 0.1 to 1.0 mm can be used and if desired blends of active material of differing particle size can be used.

The active material may be any desired for the particular battery being made and, whilst the invention is described with reference to lead acid batteries, the teach of the invention concerning the necessary requirements for the active material composition and the material of the envelope, whereby filtration filling is achieved and a bed of active; material is built up from the bottom of the envelope (the top in use) can be applied to other electrochemical systems.

Referring again to lead acid systems the lead oxide preferably has substantially all of its particles having particle sizes less than 100 microns, e.g., less than 1% by weight are above 200 microns in diameter. In addition, less than 1% is below 0.001 micron in diameter. Typically at least 50%, e.g., 95% by weight, is less than 50 microns 50% by weight is less than 10 microns and 5% is less than 1 micron. The oxide may be grey lead oxide or red lead oxide or blends of grey lead oxide and red lead oxide.

For example the active material may comprise a blend of gre lead oxide of average particle size 20 microns and red lead oxide of average particle size 5 to 10 microns. The ratio of grey to red lead may be in the range 95:5 to 5:95 through 90:10 to 33:67 e.g., in the range 66:34 to 33:67, especially 33:67, is preferred.

Preferably, the tubes are clamped at the top and bottom so that the liquids can escape out from the whole area of the tubes. 427S5 Desirably, a supply of the slurry composition is continuously mixed during the filling and a minor proportion of the slurry supply is introduced from this continuously mixed supply into each tubular plate.

The supply of slurry composition is preferably delivered by a pump which gives smooth delivery and maintains the slurry in suspension and the slurry, in the intervals between introduction into a tubular plate, is recirculated from the outlet of the pump back to its inlet, e.g., via a recirculating tube, connected to the pump outlet, and an agitated storage tank, from which a supply tube extends to the pump inlet.

In a first form of the method, the slurry is introduced from a pump into one tubular plate then when that plate is filled is continuously recirculated from the outlet of the pump to the pump inlet and is then introduced into another tubular plate.

The apparatus for carrying out the method in accordance with the invention preferably comprises at least one filling station comprising means for supporting the envelope of a plate assembled on its current conducting element, the envelope comprising at least one porous tube, in a substantially vertical plane and a filling manifold adapted to be juxtaposed to the top of the supporting means whereby an aqueous slurry of active material composition may be introduced into the envelope of a plate located in the said supporting means, the apparatus further comprising a slurry storage tank adapted to contain a supply of active material slurry, and provided with agitation means for 3755 \ΐ;Jmaintaining the active material in the storage tank in sus- t' pe'nsion as a slurry, and delivery means connected between the storage tank and each filling station for delivering the slurry from the storage tank to the manifold of a selected filling station, and means positioned below the means for supporting the enveloped plates for collecting the liquids issuing through the walls of the envelopes, the delivery meai including recirculating means for recirculating the slurry ti the storage tank when the slurry is not being delivered to IQ a filling station, a pressure responsive valve being located in the delivery means to each filling manifold on the inlet side of each filling manifold, the or each pressure respons valve being arranged to actuate automatic switching of the slurry supply from the manifold to the recirculating means and to release the pressure in the delivery means to the manifold as soon as a preset pressure is reached.

The delivery means may comprise a pump having an inlet pipe communicating with the storage tank and valve means, referred to herein as the recirculating valve, commun· icating with the outlet of the pump for directing the slurry from the pump outlet to a filling station, or when more than one station is used, to a selected station, or for recirculal the slurry to the storage tank.

The means for supporting the plate are preferably adapl to support tubular plates and comprise a frame rigidly secure to the filling manifold and carrying top and bottom clamps arranged to releasably clamp the plate to the frame.

The clamps may be toothed and conform to the outside surface profile of the bottom and top of the tubular plate.

At least the top clamp is preferably provided with a resilient sealing liner. 437SS The manifold is preferably adapted for use with tubular plates and then preferably has an outlet nozzle assembly consisting of rigid feed tubes spaced apart in a straight line with their centres on the centres of the tubes of the plate and having external diameters corresponding to the internal diameters of the tubes of the plate. Thus the tubes are preferably arranged vertically so that the slurry is fed in under gravity.

The feed tubes may extend through a resilient gasket, the dimensions of the frame in relation to the plate being such that the end of the plate has to be forced up into the gasket in order to locate the plate in the supporting means.

Preferably at least two filling stations are provided for each pump and slurry storage tank and the recirculating valve is a three way valve.

In another arrangement at least two filling stations are provided for each pump and slurry storage tank and the manifolds are fed via individual supply lines by a common feed pipe connected from the outlet of the pump to a recirculating pipe for feeding slurry to the storage tank and valve means are provided for selectively connecting each individual supply line to the feed pipe.

The or each pressure responsive valve may be arranged to actuate automatic switching of the recirculating valve or the valve means connecting the or each manifold to the common feed pipe to the recirculating position and to release the pressure on the plate as soon as a preset pressure is reached.

The pump preferably comprises a rotor in the form of a single start helix fitting in a cylinder in the form of a double start helix of twice the pitch of the rotor, in which the rotor turns about its own axis in one direction, whilst its axis orbits about the axis of the cylinder in the opposite direction at the same speed.

In a further hroader aspect of the invention the metii is not restricted to the filling of tubular sheathed plates. Thus other shapes of sheath can be used, e'.g. » envelope shaped sheaths hnd in this case the grid need 5 · no longer he in the form of a comb of spines but could he a conventional cast grid or a reticulated plate, e.g. an expanded metal mesh or a sheet with apertures punched through it, it could even he a solid plate so long as the necessary current collecting function was adequately TO carried out.

The sheath can he of flexible material or of rigid or stiff material but at least when the sheath is flexible it is preferred to support its faces with porous support means, e.g. rigid foraminous sheets, meshes or grids during the filling operation so as to keep the plate substantially parallel sided whilst permitting the liquids to pass through.

With this arrangement the inlet manifold also has to he modified so that, instead of a row of tubes which plug Into the ends of the individual tubes of the sheath, a single or double tubular slot is provided to plug into th open bottom end of the sheath. A double slot arrangement which nests over the end of the grid and affords a pair c slots extending along either side of the grid and can be clamped thereto may have advantages over a single slot arrangement.

The end of the sheath can be sealed with an elongate bottom bar after filling. This can consist of an interne plug gripping the end of the grid and an external clip oi 164 37 55 integral flange on the plug arranged to grip the outside of the envelope and hold it in against the plug.

In another alternative instead of an inlet manifold of fixed tubular outlets or fixed slots an arrange5. ment of retractable filling tubes extending down into the sheath can be used. The arrangement would start with the filling tubes fully extended down into the sheath around the spines (which now need not have centering fins since the filling tubes . perform this function). As the active material issues from the ends of the tubes the tubes are withdrawn up along the sheath and finally halt at the open top end of the sheath where they may be momentarily clamped and then released to complete filling of the plate.

. Clearly however this arrangement is more complicated than the arrangement in which the slurry is merely fed in at the tops of the tubes and this simple arrangement is much preferred. 17. 4S75S The invention may he put into practice in various ways and. two specific embodiments and certain modifications will be described by way of example with reference to the accompanying drawings, in which:5. Figure 1 is a diagrammatic side elevation of one embodiment of apparatus in accordance with the invention Figure 2 is an enlarged diagrammatic perspective view of the filling box shown in Figure 1; Figure 3 is a diagrammatic view of part of the 10. lower clamp shown in Figure 2 in the open position, showing only some of the tubes of the plate; Figure 4 is a cross-sectional plan view on the line IV-IV of' Figure 3‘; Figure 5 is a part cross-sectional view of part of 15. the upper clamp in the open position, as in Figure 3; Figure 6 is a general front elevational view of the rotating vane viscometer used to measure the viscosities of the slurries used in the invention; Figure 7 is a detailed front elevational view 20. of the paddle assembly of the viscometer of Figure 6; Figure 8 is a plan view of the container for use with the viscometer of Figure 6 for containing the sample whose viscosity is to be measured; and Figure 9 is a plan view produced from an optical 25. photomicrograph of the non-woven fabric, described below and used in the examples.

Figure 10 is a front elevation of a preferred form of satellite filling station for use in a modificatiom of the invention in which a central slurry preparation . station supplies slurry to a number of satellite filling stations. _ 18 _ Figure 11 is a side elevation of the satellite filling station shown in Figure 10, Figure 12 is a plan view of the satellite filling station shown in Figure 10, . Figure 13 is a plan view of the central slurry preparation station referred to above in connection with Figure 10, Figure 14 is a side elevation of the station shown in Figure 13, . Figure 15 is a front elevation of a preferred form of filling manifold and upper clamp as used in the filling station shown in Figure 10, Figure 16 is a plan view of the filling manifold shown in Figure 15, . Figure 17 is a cross sectional view on the line XVII - XVII of Figure 15, Figure 18 is a front elevation of a preferred form of bottom clamp as used in the filling station shown in Figure 10, and . Figure 19 is a vertical cross section on the line XIX - XIX of Figure 18. 43755 The apparatus consists of a slurry tank 10 in which the slurry to be filled into the plate tubes is stored.

The tank is fitted with a paddle 11 located at the bottom of the tank and driven by a belt and pulley drive 12 from a variable speed motor 13. A vertical feed tube 15 extend up from just above the paddle 11 to the inlet to a supply pump 16 which is 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 a supply pipe 19 to a plate filling station 20. The supply pipe proceeds via pressure gauge 22 in a two-way valve 23 and a fishtail manifold 24. The valve 23 either permits the slurry to flow vertically downwards to the station 20 or can be positioned to direct the slurry to the tank 10 via a recirculating tube 26 which extends down to just above the paddle 11. The tubes 15 and,26 are preferably of the same cross-sectional area.

The mass of the supply of slurry is preferably maint ed at about 150 kg., or more broadly 100 to 200 kg., and the mass of slurry introduced into each tubular plate, the individual filling weight, is of the order of 400 to 1,000 gm. More broadly, the weight ratio of the active material, e.g., 75 kg., in the continuously mixed slurry supply to the individual filling weight is in the range 200 :1 to 25 :1, e.g., 160 : 1 to 100 : 1. 43785 The station 20 comprises a frame 29 rigidly secured, in relation to the manifold 24 and carrying top and bottom clamps 30 and 31.

The clamps 30 and 31 are toothed and conform to the . outside surface profile of the bottom and top of the tubular plate since the plate is inserted in the clamps with its Open bottom end facing the manifold 24. The manifold has an outlet nozzle assembly consisting of l/4 inch long copper or other rigid feed tubes with external diameters corres10. ponding to the internal diameters of the plate tubes and spaced apart in a straight line, the centres of the feed tubes being on the centres of the plate tubes.

Thus the open ends of the plate tubes fit snugly over the feed tubes and are clamped thereto by the top elamp 30 , which may be provided with a resilient sealing liner.

!· The lowei- clamp 31 holds the plate in position and I ί ί 3755 presses the tubes against a thickened end section on tbe spines. The faces of the plate are completely free.

The spines are of conventional lead alloy compositioi and of conventional . structure being located on a top bar at centres corresponc to the centres of the tubes with which they will be used. They are desirably provided with short axial fins which are used to centre the spines in the tubes and to prevent the spinqs being distorted during handling prior to fillii . The. station? 20.will now be described in more detail with reference to Figures 2 to 5, As mentioned above, the station 20 comprises a frame ’ I rigidly secured in relation to the manifold 24. This fra is in two parts 32 and 33 hinged to each other along the . left hand edge, and it is the part 33 which is rigidly attached to the manifold 24. The top and bottom clamps a each in two parts 30A and 30B and 31A and 3 IB· 30A and 3 are carried by the movable part 32 of the frame 29 and 30 „ and 31B are carried by the fixed part 33 of the frame 29.

. The fixed part 33 also carries top and bottom lockin levers 36 and 37 which are arranged to engage top and bot handles 38 and 39 on the movable frame part 32, and lock filling station closed.

The fixed part 33 of the frame 29 also carries a bot . support bar 42 which has an aperture 43 through which the lug 44 of a plate 45 can pass and which assists in regist ing the plate in the filling station.

The top and bottom clamps 30 and 31 have toothed profiles which conform to the external ahtat . dimensions of tne .plate ami ihe two portions of each c.i.ai, - 22 when closed define a row of cylindrical holes 48 connected by gaps 49 twice the thickness of the fabric 47 of the sheath so as to prevent the sheath being cut by the clamps.

The bottom clamp 31 presses the fabric 47 of the sheath against the broadened shoulders 51 of the spines 52 of the plate to ensure a tight seal. (See Figures 3 and 4).

Figure 5 shows the clamping arrangment at the manifold 24. A manifold plate 54 has a row of feed tubes 55 passing down through it and having narrowed ends 56 which extend through apertures in a rubber gasket 58. It is resilient being compressible by finger pressure to only about half its uncompressed thickness, which is about J inch thick. Figure 5 shows the sheath 47 in position over the ends 56 of the feed tubes. However, the arrangement is in fact such that the gasket 58 has to be compressed by about l/16th inch by the sheath 47 being farced up into it in order to get the top bar of the plate onto the bottom bar 42 of the frame.

(This compression has not been shown on the drawing).

The clamp 30 presses the fabric 47 of the sheath around the ends of the feed tubes 56 of the feed tubes 55 to achieve a good top seal. Thus the tubes are filled whilst vertical with their top bar at the bottom.

The pump 16 is one which gives smooth delivery and is of the well known type, such as that marketed under the trade mark MONOPUMP, which comprises a rotor in the form of a single start helix fitting in a cylinder in the form of a double start helix of twice the Ditch of the rotor, in which the rotor turns about its own axis in one direction whilst its axis orbits about the axis of the 43755 cylinder in the opposite direction at. .the same speed.

This form of pump gives a positive displacement with uniform flow, and prevents the separation of liquids and solids in the slurry.

. In another arrangement (not shown) the filling station 20 is formed as a twin manifold arrangement eacj manifold being fed from the pump 16. The two way valve is replaced by a three way valve and each line from · valve 23 to a manifold contains a pressure responsive · valve.

This valve is preferably a pressure release val· which can be set to any desired pressure e.g. 15 psi an when this pressure is reached will hold the pressure at US. psi until actuated, e.g. manually. 2-5. The procedure would then be for a plate to be inse: in one manifold and the valve 23 switched either from recirculation or from the other manifold. The plate would fill e.g. in 5 seconds and then the pressure would to 15 psi and be held there for 5 seconds. During this 2θ· time the operator would have removed the filled plate from the Other manifold and inserted a new plate. He c then switch the valve 23 either to recirculate momentar or immediately to fill the new plate.

In an alternative arrangement the pressure responsive lease valve is arranged to switch the pump supply to recirculation and release the pressure on the plate as soon as the preset pressure is reached. - 2443755 ι In operation,, the filling process is as follows.

The slurry is made up to the desired composition in the tank 10 by use of the paddle 11. A tubular plate 50 is assembled,the non-woven fabric tubes 47 being located » on the metal spines 52,and it is positioned against the clamps 30B and 313 at the station 20 with its open bottom ends pushed up against the gasket 58 and over ends 56 of the feed tubes 55 of the manifold 24. The part 32 of the frame is then swung closed against the part 35 and the . clamps 30 and 31 thus closed and the locking arms 36 and 37 secured over the handles 38 and 39· The paddle 11 is kept in operation and the valve 23 is turned to the recirculating position connecting the pump 16 to the tube 28 and the pump 16 is switched on. Recirculation is carried out . until the flow is steady. The pressure indicator 22 indicates zero pressure whilst recirculation is occurr'inn.

The valve 23 is then switched to connect the pump 16 to the manifold 24. The slurry passes down through the ..station 20, some of the active material settling into the . interior of the tubes whilst excess liquid and active material drains through the fabric 47 of the tubes and back into the tank 10. The valve 23 is maintained in this position until the tubes have filled with active material at which point the pressure indicator indicates a . relatively sudden increase in pressure. The valve 23 is then switched to recirculate the slurry to the tank 10 via the pipe 26.

The clamps 30 and 31 are then opened and the filled 43755 plate removed and the further processing operations such as bottom bar insertion, pickling, drying and electrolytic formation carried out on the plate.

The excess slurry in the manifold. 24 falls down into 5. the tank 10.

In continuous operation, the pressure rise indicated by the indicator 22 could be used to control the filling cycle, e.g., to activate the valve 23, and open the clamp: 30 and 31 to disengage it from the manifold 24 and re-engi , a new' plate in the clamped position. Limit switches couli be provided, wiiich would be activated by the new plate engaging the manifold 24 to divert the valve 23 back to t' filling· position. 26. 43755 . In the modification shown in Figures 10 to 19 two or more, e.g. three, satellite filling arrangements as shown in Figures 1 to 5 are supplied with slurry from a central slurry reservoir and make-up . tank which is mounted on a balance so that it can be continuously weighed. The reservoir is continuously stirred and is provided with a float controlled water supply so as to maintain the volume of slurry constant. The slurry starts off at an oxide to . water ratio of 1.5:1. Each satellite filling arrangement is supplied with slurry by a variable speed pump. Once the weight of the reservoir has dropped by 1200 lbs and the oxide water ratio has fallen to 1.2:1 the pumps to the satellites are switched off. - 800 lbs of red oxide and 400 lbs of grey oxide are added. The oxide water ratio in the satellites falls to about 1:1 whilst this is being done. When the feed from the reservoir to the satellites is recommenced the solid/liquid ratio is reestablished.

. In this arrangement it is preferred to increase the volume of the tank 10 in the satellite filling arrangement so that when the supply from the main tank is switched off during replenishment the oxide to water ratio does not fall too much. Thus the . mass of slurry is proferably in the range 500-625 kg and thus the weight ratio of the active material in the slurry to the individual filling weight (e.g. 200 - 1200 grams) is in the range 1300:1 to 200:1 e.g. 1000:1 to 250:1. The mixing of the slurry 50. continues in the reservoir during the oxide addition and once this is completed the pumps to the satellites are switched on again. -27 43755 The central slurry preparation station 100 is shown in Fieures 13 and 14. The preferred, form of satellite filling apparatus 130 is shown in Figures 10 to 12 and 15 to 19.

Three such identical filling apparatus 130 are preferably 5 by the central station 100 by a pumped supply pipe 101 and a pumped or gravity return pipe 102.

The central station comprises a circular slurry tank 103 on a base plate 104 via a load cell 105 and a pair of cross spring flexures 106. The load cell and flexures are placed on the comers of an equilateral triangle. A vertical paddle 107 is mounted for rotation about a vertical axis in a horizontal plane at the bottom of the tank 103 and is driven by a motor 108 so as to maintain the solids in suspension in the tank 103· The tank has a lid 109 with a shrouded aperture Is (ηό|; shown) through which a powder supply mechanism 111 can tip powder into the tank 103.' The powder supply mechanism 111 consists of a hoist 112 ] a cradle 113 arranged to engage a drum 114 of active material and lift it up and around a circular path and tip it into the tank at the position 115 shown in chain lines in Figure 14.

The mechanism 111 is enclosed in a shroud 116 as indicated in chain lines in Figure 14. The tank 103 is kept topped up with water by means of a ballcock 117· We refer now to the preferred form of filling apparatus as shown in Figures 10 to 12. This is closely similar in gene: arrangement to the apparatus shown in Figures 1 to 5 and the same reference numerals will be used for the same parts.

Thus the slurry tank is fitted with a paddle 11 located ι the bottom of the tank and driven by a variable speed motor 3q 13 via a gear box 131. A vertical feed pipe 15 with a filter 140 at its lower end extends up from just above the paddle 11 to the inlet to a MONOPUMP supply pump 16 driven by a variable speed motor 18.

The outlet 132 of the pump 16 is connected to a common supply pipe 133 which extends past a pair of inlet valves, 134 and 135 to a pair of filling manifolds 136 and 137, on to a recirculation pipe 138 which extends down to the slurry tank 48755 The valve 134 is under the control of a pneumatic cylinder 141 and crank 142 and is arranged to always be either open to the manifold or on bypass. The valve 135 is similarly arranged. The valve 135 is under the control of a similar cylinder 143 and crank 144.

The valves 134 and 135 supply the manifolds 136 and 137 via pipes 146 and 147 which extend up from the valves to the manifolds so that any settlement in these pipes will tend to be in the region of the valves 134 and 135 and can be readily flushed out. Pressure gauges 148 and 149 are placed in the pipes 146 and 147 and are arranged with pressure cut off devices so that as soon as the pressure in the pipe 146 or 147 reaches a predetermined value, which can be preset as desired, the cylinder 141 or 143 is automatically actuated and the supply from the pump is switched to bypass and is returned via pipes 133 and 138 to the tank 10.

The cylinders 141 and 143 are also arranged to be under the control of switches actuated by a door 150 ( though this can be bypassed if desired). The doer on being closed over one manifold e.g. 136 in Figure 12 switches the valve 134 from bypass to .feed and the slurry is supplied to the manifold 136. When the pressure rises and outs off,the door can then be swung ta the other side to actuate the valve 143 for the other filling manifold 137.

The filling manifolds 136 and 137 are associated with bottom clamps 152 only one of which is shown in Figure 10 for clarity in the drawings. The manifolds and bottom clamp are mounted on a backing plate 155 (see Figure 31) which is inclined backwards at a slight angle to the vertical so as to facilitate insertion of plates into the clamps and to prevent the plates falling out before the clamps are closed.

The filling manifolds are shown in greater detail in Figures 18 and 19. 29. 43755 Referring first to Figures 15 to 17 the manifold consists of a manifold body 160 bolted to the mounting pla 155 and affording a rectangular horizontal slurry distribu cavity 161 which is fed from the rear by a central port 16 to which the pipe 146 or 147 is connected. At the middle 0 the top face of the cavity 161 there is a port 163 in whic the pressure gauge 148 or 149 is located.

A row of nozzles 167 extends down from the bottom fa of the cavity 161 out of the body 160 and it is over these short nozzles that the fabric tube is fitted and to which it is clamped. The clamping is achieved by a movable fron clamp face 170 carried in a frame 130 which is secured by vertical bolts 171 to the body 160. The inside face of th clamp 170 is a series of rounded teeth as in Figure 5 but the teeth are chamfered as shown in Figure 17 by the reference numeral 172.

The front clamp 170 co-operates with a movable rear clamp 175 and the two clamps are actuated by a pair of pne ic cylinders 176 mounted on pistons 177 which are secured the front clamp 170.

The cylinder 176 is secured to the rear clamp 175 and thus when they are actuated to force out the piste 177, they drive the clamp face 175 rearwards towards the mounting plate 155, and simultaneously drive the front cla 25 170 forwards. The amount of such travel can be varied by means of the adjustable stops 178. The clamp 175 has a round toothed top edge 180 which clamps the rear edge of t fabric to the nozzles 167 and this edge 180 is also slight chamfered as shown in Figure 17. The clamp 175 also has a grooved skirt 181 to assist location of the plate in the c Thus, the plate can be rested on the skirt 181 in the corr grooves and then slid up into the clamp.

Referring now to Figures 18 and 19 the bottom clamp consists of a back frame 190 bolted to the mounting plate 4275& but separated therefrom by a spacer 191 so that liquids issuing from a plate in the clamp can flow down behind it.

A pair of side flanges 192 are bolted to the back frame 190 and a front frame 193 is hingedly attached by pivots 194 to these flanges. At least one of the flanges also carries a stop 195 to prevent the front frame 193 moving through more than 90° from the closed position. The front frame is held in the closed position or in the open position by an overcentre spring arrangement, a spring 197 extending on each side of the clamp from a pin 198 on the front frame to a pin 199 on the rear frame.

A finger grip 200 is attached to the outside top edge of the front frame. The opposed inside top edges of the back frame 190 and the front frame 193 carry co-operating θ round toothed clamps 202 and 203 both of which have their top inside edges chamfered as indicated at 204 and 205. The clamps are so dimensioned as to press the fabric of the tubing tight against the broadened shoulders 207 of the current collecting spines. 2θ A horizontal bar or projection 208 extends out below the clamp 203 and is arranged to support the top bar of a plate and has a gap down through which the lug of the plate can extend.

Each satellite filling apparatus is provid-d with a work bench 220 and sink adjacent to the tank 10. Part of the work bench 220 is shown cn the right hand side of the tank 10 in Figure 10 of the drawings. This provides an area where the plant operator can insert a bottom bar in the ODen end of each plate, e.g. a conventional plastic e.g, nolyethylene plug which is hammered onto the ends of the spines. A balance may also be provided to enable the operator to check the weight of each filled plate.

A monopump (not shown) is located under Lh·? work bench in the supply line 101 from, the -bank 103 to the tank 10 and is arranged to pump about 10 gallons of slurry per minute 43755 into the tank 10, which has a capacity of about 30 gallons.

The return pipe 102 is a gravity return and the filling apparatus 130 is thus preferably raised on staging about one foot above the floor level. A pumped return could however be used if desired.

If desired a larger tank eg of 50 gallons can be used. Thus the slurry in the tank 10 is desirably replaced about every 5 to 15, e.g· 10, minutes.

The apparatus is used as fellows.

The slurry is made up to the desired composition in the tank 103 and then pumped continuously via pipe 101 by the pump 230 into the satellite tanks 10 and recirculated therefro by an overflow pipe arrangement 231 connected to the return pipe 102.

The weight of slurry in the tank 103 is continuously or periodically measured by the load cell 105 and when it has dropped to a preset value a warning is given to the operator.

The slurry in the tanks 10 is continuously mixed and pumped by the pump 16 through the circuit; pipe 15, pump 1 pipe 132, valve 134 on by-pass, valve 135 on by-pass, pipe 138 A plate comprising fabric tubes assembled on the current conducting spirits having dimensions appropriate to the top and bottom clamps being used is located in one filling manifold e.g. 136 and the top and bottom clamps closed. The door 150 is now shut and if the automatic arrangement js in operation, the cylinder 141 switches the valve 134 to connect the pump 16 to the manifold 136. The plate fills, the pressur in the manifold cavity l6l builds up and at the preset value triggers the pressure gauge 148 which in turn actuates the cylinder 141 which moves the valve 134 back to by-pass.

As soon as the door 150 was shut, the operator could fit another plate into the manifold 137. Thus, as soon as the first plate has filled, he can start filling the next plate either before or after removing the first plate. The cycle 5 can then be continued until the main tank 103 needs replenishing and this can if necessary be carried out by another plant operative.

At the end of a shift or whenever the filling station is to be left, it is prudent for the slurry to be pumped from the tank 10 back into the tank 103 and the filling station to be thoroughly cleaned and its pipe work flushed out with water The .invention in its preferred form has referred to the plates being filled while in a substantially vertical plane and whilst in Figures 1 to 5 the plates are filled whilst lo vertically disposed, in Figures 10 to 19, and as shown in Figure 11, the plates may be filled equally well when disposed at an angle of about 5° to the vertical.

It will be appreciated therefore that so long as the bed of active material can be built up evenly from the end 2q remote from the inlet end with the space between the spine and the sheath being sufficiently evenly filled on both sides so as not i.o impair electrical performance, the exact angle at which the plate is disposed whilst filtration filling occurs is not critical.

Thus, whilst it is clearly prudent to maintain the plate at a steeply inclined angle, there is considerable room for variation. The angle wi1! clearly vary depending on the length and diameter of the plate and the size of the spines.

Thus, a very narrow annular space is being filled and so long as the maximum horizontal distance from side to side across th? inclined tube is not many times, e.g. not more than 10 times the minimum transverse dimension of the tube 3342755 or envelope, one may anticipate that no significant adverse effect on evenness of filling should arise.

Thus, in general, it may he-possible to fill the tubes when they are inclined at angles of as much as 60° to the vertical though angles of up to only 20° to the vertical are probably more prudent.

The invention extends in its broader apparatus scope to a number of additional aspects.

Thus, in one alternative at least two filling stations 10 are provided for each pump and slurry storage tank and the manifolds are fed by a common feed pipe connected from the outlet of the pump to the recirculating pipe and valve mean are provided for selectively connecting each manifold to the feed pipe.

In another modification the top clamp comprises a fixed toothed face and a moveable co-operating toothed face arranged to be moved away from the fixed face while remaining parallel thereto by pneumatic or hydraulic means. In addition, in order to assist in liquid flow from tubes, at least one, and 2θ preferably both, of the opposed faces of the lower edge -f the top clamp or the top edge of the bottom clamp, or preferabl both clamps, is chamfered.

The rear face of the top clamp preferably carries a groov member depending therefrom to assist location of a plate in the clamp.

In one form of the invention the bottom clamp has a front clamp face which hinges down from a back clamp face and biassin, means are provided and are arranged to bias the front plate either to the closed position or to a fully open position. 34. 42?S$ The invention also extends to plant for filling enveloped battery plates which comprises a central slurry preparation statin’ and at least one filling apparatus in accordance vzith earlier aspects of the invention and means for feeding slurry from the central station to the filling apparatus.

The means for feeding slurry preferably comprise means for continuously feeding slurry to the or each filling apparatus and return means foi1 returning slurry to the central station whereby the slurry can be continuously circulated.

The slurry preparation station preferably comprises a tank, weighing means for enabling the tank to be weighed, agitating means to enable the slurry to be kept in suspension, and active material ziupply means and liquid supply means.

The weighing means preferably incorporate a load cell located below the tank.

The agitating means preferably comprise a paddle arranged to rotate at the bottom of the tank. The invention alfso extends to a method of using the plant which comprises continuously feeding slurry from the central preparation tank to each filling 2θ apparatus and back to the central tank at a rate such that the contents of the slurry tank of the filling apparatus i.s replaced at least every hour and preferably at least every half hour and more especially every 5 to 15 minutes.

In another alternative embodiment (not shown) the three fillinq 25 apparatuses arranged around the central slurry preparation station are instead arranged in a straight line with the central station either at the end of the line or in the line between adjacent filling apparatus. Up to six.filling apparatuses may be supplied with slurry from one central station. The suoply pipe 101 and the return pipe 102 in this case are both supplied with a pump e.g. Ίη a MONOPUMP and may be constructed of 1 inch internal diameter hose or pipe.

. EXAMPLE I An example will now be given of a specific plate production technique. This example is carried out on t apparatus described with reference to Figures 1 to 5.

The' plates were positive plates having 15 tubes eac 5. 9 inches long. The tubes were made of non-woven polyethylene terephthaiate fibre. This is made as foil A thin web (1.5 metres wide) of fibres having an average length of 4i inches is produced by carding, and fleece is produced by layering approximately ten webs to . form a continuous length of non-woven fabric (also 1.5 metres wide).

The fibres extend generally longitudinally in the w which is pleated in a zig-zag fashion as it is taken off from a conveyor travelling in the direction of the lengt . of the web onto a conveyor travelling at right angles thereto. Thus the fibres extend substantially transversely to the length of the fleece, but due to the travel of the second· conveyor the fibres in adjacent ., layers are oppositely inclined at a small angle to the . transverse direction.

This material is then impregnated with 50/» by weigh of polyacrylic binder. It has a thickness of 0.5 to 0, mm. and weighs 120 to 160 grams/sq.cm.

This material is then converted into an array of , tubes by passing two layers of it through a multiple sewing machine to secure the layers together along parallel lines (for example, spaced about 2 to the inch) to form pockets or tubes in the conventional manner. - 364 3 7.55 This material is then dipped in a phenolic resin and dried. The material picks up 30# of phenolic resin based on the dry weight of the non-woven material.

After cutting the material to length circular , section mandrels 0.287 inches in diameter are then inserted between the rows of stitches to form the pockets. It has an air permeability of 8.0 litres/min/sq.cm. and a water permeability of 1.5 litres/min/sq. cm. area.

Its structure is shown in Figure 9 of the accompanying . drawings.

As can be seen in Figure 9 this non-woven fabric is made up of randomly entangled individual fibres. The fibres have a diameter of about 25 microns or more broadly 20 to 50 microns. The gaps between individual fibres are . . in general less than 250 microns and mostly less than 100 microns and moreover the material in having a thickness of 0.5 to 0,7 mms has a three dimensional structure permitting the overlap of many individual fibres in any ., one path from face to face of the sheet. The material , has an excellent filtering activity for use in accordance - 36a 42755 with the present invention since whilst it permits pass of both liquids and solids in tube shape it rapidly fil •with active material when this is fed or poured into th tubes under gravity.

, Air permeability was measured as follows:A sample 2.8 cm. in diameter (6.16 sq.cm, effective cross-sectional area) was clamped in position and the ti for 50 1. of dry nitrogen to flow through the sample at under a.pressure difference of 0.6 inches (1.5 cms) watf . gauge was recorded.

The material is too permeable for mercury porosimeor air flow through an alcohol saturated sample to be accurate measurement techniques.

However, air permeability is known to be an accura 15. reflection of the filtering capacity of a material and materials suitable for use in this invention can be selected by measurement of their air permeability.

Water permeability was measured on the same samp. by measuring the time taken for a column of water . initially 42 em. high and 1 litre in volume to flow under gravity through the sample.

The downstream end of the column below the sampl was blocked off, the water introduced above the sampl and then the downstream end below the sample opened t . atmosphere.

The slurry used in this example 1 was made up from a mixture of 1 part grey lead oxide by weight (average particle size ?0 microns) and 2 parts red lead oxide by weight (average particle size 5 to 10 microns) mixed in . 1.5:1 weight ratio with mains water. 42753 The tank 10 contained 150 kg. of slurry, the paddle 11, 30 inches by 1.5 inches, was rotated at 50 to 70 rpm, to maintain solids in suspension. The pump 16 was run at a volume throughput of 9·5, or more broadly 4 to 5 10 litres/minute, during recirculation the pressure indicator 22 showed zero pressure. Using the same stirring and pumping conditions, the valve 23 was switched to the fill position. The indicator 22 showed zero pressure for 5 seconds, and 15 psi after a further io second when the valve 23 was again switched to recirculation. The internal volume of the tubes wan 105 cc.

The volume of slurry passed through the plate was 0.8 litres i.e. the ratio of slurry volume to internal plate volume was 7.6:1.

Flow rates below 4 litres per minute were found to give rather slow filling rates and this reduced the productivity of the process, flow rates above 13 litres per minute were found with these particular cells to give rather low filling weights for the plates. - 38 4 STS 5 Thus whilst the slurry is introduced into the top ends of the tubes they fill from the bottom upwards, ar oxide layer building up the tube evenly, and water and some oxide emerging through the fabric of the tube main] . at the level of the top surface of the active material j the tube. However, liquid also emerges through the whc filled length of the tube as well, and it is believed tl· further liquid is forced out of the whole length of the tube once the back pressure starts to build up.

. The plate was then dried. The plates were weighec and the weight was 450 - 20 grans. The plates were then, pickled in conventional manner. Numerous plates were made in this way. Some were dissected an weighed, there being no significant weight variation *5· between the top, middle and bottom of the tubes. Oth had their electrical characteristics measured snd compared with dry powder shaken plates using the same ’ active material. These plates are referred to as standard plates.

. The plates in accordance with the present invent had substantially the same discharge duration at the first and also at the tenth discharge in a standard charge/discharge procedure as did the standard plates Plates with, individual internal tube volumes in the range 50 to 250 cc. can readily be filled.

Me have found, as mentioned above, that the degree of densification and thus the total dry fill weight of . the tubes can be controlled by control of the pressure which is allowed to build up at the end of the filling period.

Thus using the same slurry and tubes as described above, we have found that if the pressure is only allowed . to build up to 5 or 7 P3i, the weight is 420 grams ± 5$s if the pressure is allowed to build up to 15 psi, the weight is 450 grams ± 5$ and. if the pressure is allowed to build up to 35 psi, the weight is 500 grams ± 5$.

. Moreover, the tubes are still filled evenly without stratification using those fill weights.

The active material in the tubes at 450 grams filling weight has a density of 4.3 grams/ce.

When this example was repeated using a paste of . 3 parts oxide to 1 of water, (which had a density of 3.5 grams/cc), the material was essentially extruded into the tubes which filled in less than 1 second. No significant amount of liquor passed through the tubes,and the plates on testing demonstrated significant . stratification of density in the tubes. - 40 43755 Examples 2-27 These were carried out on the apparatus described with reference to Figures 1 to 5 using the method described for Example 1.

. The tubes were made in the same way as described for the non woven tubes of Example 1 except that they were 14,5 inches long rather than 9 inches long.

The non woven fabric tubes of Example 1 were used for certain of the Examples as indicated hy the letters . N-W in Tables IA and IB and 2A and 2B below. Two other fabrics were also used.

One was a spun woven fabric, referred to as S.W. ir Tables IA and IB and 2A and 2B below and having an air permeability (as herein defined) of 6,0 litres/sq,cm./mi . It has 17 weft threads per cm and 22 warp threads per cr The warp threads being about 250 microns in diameter anc the weft threads being about 375 microns in diameter.

' Microscopic examination indicates that the gaps between adjacent warp threads and adjacent weft threads are aboi . 250 microns by 250 microns maximum but these gaps are bridged by numerous loose fibres extending out from the threads. The effective filtering capability of the fabric' is thus much enhanced.

The. other fabric was a woven fabric, referred to ai . W., in Tables IA and IB and 2A and 2B below and having £ air permeability (as herein defined) of 15.2 litres/sq. cin./minute.

It has 18 weft threads per cm and 22 warp threads per cm. The warp and weft threads being about 250 micrc in diameter. Microscopic examination indicates that the gaps between adjacent warp threads and adjacent weft threads are about 250 microns by 250 microns and are not occluded by fibres extending out from the threads. The . filtering capability of this fabric is thus much less than that of the spun woven fabric.

The compositions used are indicated in Tables IA md IB and 2A and 2B below.

The slurry was made from mixtures of grey lead . oxide (average particle size 20 microns) and red lead oxide (average particle size 5 to 10 microns) mixed in various weight ratios with mains water.

The solid particles in the slurry were such that less than 1% by weight were above 200 microns, , and less than 1% were below 0.001 microns, 95% by weight were less than 50 microns. These particle sizes were determined by sieving.

The tank 10 contains 150 kg of slurry, the paddle 11, 30 inches by 1.5 inches, was rotated at 30 to 70 . rpm, to maintain solids in suspension. The pump 16 was run at various volume throughputs as indicated in Tables IA and 2A. During recirculation the pressure indicator 22 showed zero pressure. Using the same stirring and pumping conditions, the valve 23 was . switched to the fill position, and the time for which the indicator 22 showed zero pressure recorded and the total time up to when the valve 23 was again switched to recirculation and the maximum pressure reached recorded. These are given in Tables IA and 2A. The total internal 50. free volume of the tubes was 170 cc. - 42 42755 Table 3 below gives stratification results for certain of the examples and measurements of the porosity of the active material for certain of these examples.

. Example 7 concerns the.woven tube Vf. Examples 6 9, 12, 15, 16, 19, 22 and 23 concern the spun woven tube SW, the remaining examples concern the non-woven tube HW. The tubes in all the Examples fill in the manner described for Example.1, that is the solids are . filtered out and the solids level gradually rises up the tubes with the bulk of the liquids issuing from the tubes at the solids level which is current at the moment in question.

Table V Sh Ρ 3 βνπ w Λ o Sn 0) VH rH 3 Sh-PP g ra 5 Hi tfl Ο > P, bo 00 m OJ o o CM 1 m rn c m o o S m in rd ω Εη·ρη . 3 ra Ρ ω·π ο ω Ο W r-t 1 φ S Fi ·Η OJ ft ra •rl OP Sh ftCJ EhVh ? ft a) Eh 1 co 1 4· O rd failed to fill the solids were not filtered out from the slurry - vo rd m rd o rd 00 in rd CM CM in β» φ 0 (h W P O ra O ri β Sh S3 N Eh p Φ peri Eh o CM rd m 0- CM rd O in m O m m m -i CM in \O in 8 rd Theoretical volume pumped, to start of pressure build up CCS 1 t o 00 σ> δ m is CM rn CM nj to 8 IS rd CO CM I960 m CM H VO IS o rn m 7962 Oft £°£3 . p ra d a φ ft ton o S to a> ή φ •rl P Sh 3 r-l ra Eh M ftPEH 1 m CM 1 00 o m σ\ £ m CM VO rd O in IS CM in vO Pump volume cc/sec rn m - m OJ OJ rd = = 122.5 Pump speed o o O = s = = s P = c s Type of tube I = = = fo fi 1 fo fi 1 fo g & , s* 1 Vh φ US O Si p bo Φ 3ft ftd d ri Ο ®·Η 3-rip M OT Ρ Ρ Ο o k G) N Solids liquids rd O\ --4 H rH '-0 r-f rd rd H OJ rd s. H pH m m rd 0.89:1 0.67:1j r-d p OT 6 0.71:1 r-i O Ο- Ο r-i ω ό rd rd m d Grey Red IS VO rn rn = = = = = = - = = = = = ojdurexg cm in -ΐ m vo ' IS co ch o r-f rd rd OJ V m T— V ’ ί, Table IB Φ •Ρ β Φ d o •ΗΉ-μ i ra H OH ra a 1 1 1 1 1 1 1 1 1 1 1 1 1 •HP® M ra p, •P fi Φ o -P S «I Φ fi ΧγΙΉ-Ρ I , 1 1 1 | | •ΡΟΗ •Ρ ·Η ω co φ φ ο •Η Ή Ρ. 1 ra Η ο β ra fi 1 1 1 1 1 1 1 1 1 1 1 1 1 ro 3 Φ wrap) •Ρ fi Φ φ 0 w Φ Ρ Vp i> H > η a ♦ d , • d •ρ S C'-'O I 1 I 1 1 1 1 1 1 nvn Ρ W •4· CM φ fr- W φ Ιί-Ρ fi.fi ra •Ρ 60S 1 1 1 I 1 1 1 1 1 I 1 1 1 •Η Φ fi fa ? Μ φ φ ω •ρ -ρ a in o in <0 o VO Cb o co VO VO -ρ ra cd 8 CM n cb fb 1 CM m CM o m IO Φ (!) fi Η fi > ρ,-Η ρ, bO CO σ» VO Cb co Cb c- Ov OV vo to fr- τί ‘Φ fi Ο Η o Φ β 3 fi d H H H o φ o fb fb (b (b •Ρ o m -: — η j: s m & m m r*. in m tn Ha in . m in vo ov VO W o a o ro o - Φ Fh r·-» ο: ω in o Cb ω Ov ov H m Lf\ o CO co co in in o vo o VO o fr- (I) H Vi) vO (b o H in vo in o O ω fr- fr- vo in tr\ » (> w £>» a o in m m in •4 •ΐ 4- cvi o φ 3 c fi fi •Ό C5 U) H sqdDiexa CM tn in vO fr- /15 co OV 10 11 12 m H H Table Pressure at shut off of valve psi gauge O tn CM rH o m o tn in rn H . C m rH σ» OJ rH in rn i-r o Sdh 3 a>H Λ 01 Ή ui ® ° wd 1 hi sm&cr H o • kD 1 1 1 1 1 1 Cb 1 m rl 1 CJ tf 1 ® e. „ 3w rt ω w ρ +> 0 tl e> o oSi!f.iJ« H +> O CO I in «1 IS o IS in • o rH 1 H OJ ί IS OJ 1 OJ ¢0 : Theoretical Volume pumped to start of pressure build up CCS in tf GJ tf CD H co kD m 1 .1 in tn is · co in co O s rH rn m tf rH in rl IS rH m tn tf rH o cn tf o Οϊ tf Time to start of pressure build up Tl secs o N in • H o rn ί 1 o • U3 o IS OJ rH IS rH rl -tf H 1 IS. « rl rl tf fl) o S fl> ft 3 ω ids 3 ρ o fi ko in GJ CM H m gj N H in OJ OJ rl in GJ OJ rH m GJ CJ rH in GJ OJ H in * GJ GJ rH in OJ GJ H in GJ GJ rH m GJ CJ H m OJ OJ rl m OJ OJ rH * m CJ GJ ri Pump speed O tf o tf o tf O tf O tf O -tf o O -tf O -tf O -tf O -tf O Oj tf Type of tube h* CO s FX i—i £ r-r CQ § 3 H δ F--1 •r- 5 >* r’ I o Sh fl) N 1 1 I I 1 1 1 1 1 1 1 Solids liquids rH ω tf GJ in tf GJ (H o O CJ rH IS 0D rH rH tf' r-l H rl H rH H CO O rH rH r- o ri rH in o • rH rH tf in o r-l Uh o iH l'\ .•J iH fl >> 41 (4 ϋ Ό fl) PJ tf m kO kO m kO kD tf m kO kD 7n kO kD tf in Ή kO -tf m .* kD kD tf in kD kD -tf rn kD kD tf rn ώ kD c- o r-i j sxduiexa m rH kO rH S iH CO rHr · 3 rH C\J CJ tn CJ £ m fj ' D • J 1 0J Ah Table 2B 1 l 1 ® - 1 -p « J o ca o | M τϊ 1 *i*P-P Λ 2 » 1 - Η Ο Η ώ ti r* I , -d 3® ΐ 1 r+β ! 11 1 1 12 mins 1 1 in in 1 1 1 in o' 1 m 6 •P f4 ' 1 , 1 co I 1 os rt 1 1 CM CM i life of sample sus- pension mins 1 1 1 1 1 tn rt 1 1 1 in • CM 1 OJ 1 % Settlement Sample i' 1 1 > 1 tn OS 1 1 00 LO 1 1 1 rt tn 1 VD CO tn t> I Q) I -p 5 £& .2 H rt § rt Φ fe fo ? hO OS o o rt rt co CM 1 1 CM tn tn $ c- 1 tn H .1 LD tn CM in tn LO Wet paste in plate grams LD O cn 8 in in co LD o tn cn in LD OS t- lA cn to cO co ia to 03 tn m LD o ts- cn cn oo csi tn cn CM tn LD TJ Ή Ο rt «ί B 0 a s. - Water ml os b- co in CM os b- co in CM os b- co o m m o tn o tn o rt in co in b- o in co tn ο- ο in 00 £ o in CO in o- os OS CM Os LD os o o o o CM in o σ os rt M B •d ?s Q) fe is \ tn tn tn· LO in CM o o LO in o. o os in os vo CM in tn tn tn rt un O CO m >, £ 0 ro fe fe δ ω CM <δ LD £ tn O\ in m b~ CM irs O o tn tn CM apduiBXJl in rt LO rt b- rt co rt rt o CM rt CM CM CM tn CM < CM IP. CM LO CM b- CM /•7 - . <7 42755 (Λ % deviation Ai fe-Q 1— OJ + 1 As ΪΙ ^4' V- co rs. O G d- I to CO +T σ + 1 AS as CO G + 1 AC <± O + 1 β Qj S m CO CM rd m rd Φ S OA cn ( 30 a 00 *7» CM CM CM m CM KA CM vo 0A vo 00 CM CM O S co OA cn I) o co CM CM CM CM CM KA CM rn CTi in 0> (S CM KA rd ts cn cn C> 30 O co CM CM cm KA CM KA CM CM O OA OA CM rd S CM CO oa OA C^ n o 00 CM CM CM KA CM m CM CM m VO OA O o o rd ts σι cn 2) Ci 00 CM CM CM CM CM m CM .o •rH JR P ti it tt tt te. tt •H CM rd rd KA rd •4 CM Φ +1 +1 +1 +1 +1 +1 +1 d a ti rH in OA CTi rd OA φ IS OA (Λ cn s O ts a CM CM CM CM CM KA CM P (0 rn •4· cn CM in o rd CM rd < 1 + 1 1 1 1 1 1 a ci $ O\ m m o VO OA m M ϋ IS σ) (Ti tn is ω s •H O CM cm CM CM CM nj CM -μ a ti 0 S m •4 m cn vD ώ •rl Η Μ ts cn OA cn s OA s tfcdl CM CM CM CM CM CM CM •H 4-3 d ., j Cl CO m n in CM -4 O f-'. VO m rn o a> o CO β CM CM CM KA CM m CM •P OQ H r—t OA OA co •4 m o Q is OA cn Ci is rd co s CM CM CM KA CM rn CM 1 φ Φ p rq Ό ti ·Ρ th Φ Φ Φ Φ Φ aj Φ jG β fi fi fi fi ri a Π.Ψ4 O o o Q O o o o rd O fi fi fi fi fi fi 0 ω fi 0) 0 β ti η ω ti to -d rd H H H rd rd H d -η •H 3 oi s- rd IS •tf in O1 OA rd o tn VO . Ο -H * • • • • • • WH CM H rd rd rd o rd Md «4 >4 4 Φ|Φ »n rn ka ?<\ KA rn c β|β »* · ·· ·» • * ·· ol VO VD vo vo vo vD a VD VD VD VD VD VD o r! Φ rd ί-1ι a m co cn o CM 4 VO ti a rd rd rd cm CM CM CM ~ Notes on Table IA and IB and 2A and 2B and Table 3. 1) Solid/liquid ratios.

A) The weights of solids removed in the samples of the filtrates have been ignored since the weights of these . samples were relatively small and there was no way of easily determining the ratio of solids to liquids in the filtrates.

B) The ratios have been calculated ignoring the amount of liquids removed in the paste in the tubes.

. These ratios therefore slightly underestimate the solids content of the slurries. 2) Grey/red ratios. These have been assumed to remair constant except when extra grey or red oxide is added. 3) Wet paste in plate. The weight of the fabric tube, . lead spines and a bottom bar was 645 grams. The values quoted are the wet filled plate plus a loose bottom bar minus 645. 4) % Settlement 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 had been thoroughly shaken for i minute and then allowed to settle in a vertical position for 24 hours.

. The container is a round bottomed test tube of 1.5 cms internal diameter and at least 9 cms of slurry are placed in the test tube.

) It life of the suspension. This is the time . taken for the solids level of the sample in the container described under 5) above to sink to halfway between B and A.

The test is carried out by placing a rubber band with its bottom edge at the halfway level i.e.

. (B + A) / 2 cms from the bottom of the test tube, shaking the tube vigorously for at least | minute or until all the solids are displaced from the bottom of the test tube and then righting the test tube and measuring the time from that instant to the . instant when light is first visible under the rubber band. 6) Pump speed. This is merely a setting. The volume of slurry pumped through the manifold was measured at varying settings by collecting the . slurry as it cane out of the manifold. Two measurements were made for each pump setting. The volume of slurry was measured.

A graph was then plotted for the 0, 20, 30 and 40 pump settings of volume against time in seconds . (using a stop watch). A reasonable straight line plot was obtained. 7) Timo to start of pressure build up. This is the time between the inlet valve being opened and the pressure gauge actually starting to move rather . than merely flicker^.

TABLE 4 Example 18 20 24 Pores between porosity (%) provided by pores having such dimensions 100 - 50 microns 0.9 0.7 0.6 50 - 25 0.8 0.4 0.4 25 - 12.5 0.2 0.1 0.2 12.5 - 6.4 <· 0.2 0.1 0.2 6.4 - 3.2 0.1 0.1 0.1 3.2 - 1.6 » 0.4 0.3 - 1.6 - 0.8 » 0.2 0.1 0.5 0.8 - 0.4 1.3 1.1 2.3 0.4 - 0.2 3.3 4.9 4.9 0.2 - 0.1 5.5 4.6 4.1 o.i - 0.05 3.3 3.2 3.6 0.05 - 0.035 ” 0.8 0.9 0.9 below 0.035 2.1 1.0 1.2 Total porosity 19.1 17.5 19.0 Apparent density 5.5 5.6 5.4 True density 6.8 6.7 6.7 50a 48755 8) Theoretical volume pumped, to start of pressure buildup. This i3 the time under the eighth column from the left of tables ΙΑ, 2Λ, 11A, 12A and 13A multiplied by the volume reading under the seventh column from the left of . tables ΙΑ, 2A, 11A, 12A and 13Λ and is purely theoretical. 9) Stratification. (Table 3) This is determined by pickling the plates in 1.40 specific gravity sulphuric acid for 6 hours followed by drying at 180°F for 12 hours.

The top bar and the bottom bar were then cut off the . plate and the remainder cut into four equal horizontal strips labelled ABC 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 each leaving out every fourth tube and labelled 1 to 4 . with a 1 at the lug side of the plate. The four sections 1 from each of the horizontal strips was then weighed and the value given under 1 in Table 6 is this value. The other vertical sections 2, 3 and 4 were weighed in the same way. . 10) Pencil porosity, (Table 5) This is determined by the well known technique of mercury intrusion porosimetry, and .is done on the same samples as table 3. Details of this technique are given in our Patent Specification No. 35310.

The rotating vane viscometer values for certain of 2F, the slurries used in the above examples are given below in Table 5.

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

The apparatus consists of a frame 110 carrying , an electric motor 111 driving a paddle assembly 120 via a gear box 112 and a torque transducer 119. The speed in the gear box 112 is sensed by a tachogenerator 113 the output of which is fed to a digital voltmeter 113A. The voltage signal produced by the torque trans35. ducer is fed to a chart recorder 114. The recorder has - 51 4 2755 a variable chart speed and a variable scale.

A sample container 130 is clampably supported on ·' an adjusted table 115 which can be raised and lowered on guides 116 by a pneumatic cylinder 117.

. The sample container 130 has a detachable lid 131 located above the paddle assembly 120. The lid can be secured to the container by an external bayonet lock (not shown).

•The paddle assembly 120 is removably attached to . the output shaft 118 of the gear box 112, and consists of a central rod 121 having a lower boss 122 which in us nests in a hole 132 in the bottom of the container 130. The rod 121 has a diameter D5 of 1.3 cms and carries 3 pairs of paddles 123, 124 and 125. The paddles 123 and . ' 125 are in the same plane and are at right angles to the paddles 124. All the blades of the paddles are vertical and thus parallel to the axis of the rod 121. The paddl are carried on arms 126, 127 and 128. The distance D6 from the centre of the arm 126 to the boss 122 is . 6.5 cms, the distance D7 from the centre of the arm .127 to the boss 122 is 3.9 cms and the distance D3 from the centre of the arm 128 to the boss.122 is 1.6 cms.

The width of each paddle D3 is 1.2 cms and its height D2 is 1.2 cms and its thickness 0.1 cm. The . distance D4 from the inside edge of each paddle to the surface of the rod 121 is 1.5 cms.

The distance Dl between the outside edges of the paddles in a pair of paddles is 6.8 cms.

The internal height of the container 130 is . 8.2 cms and its internal diameter is 8.8 cms. There are four internal baffles 135 ’located at the ends of diameters at right angles to each other. The thickness DIO of each baffle 135 is 0.30 cms and its inward extent D9 is 0.5 cms. The separation Dll · of the baffles on a diameter is 7·65 cms. Each 43755 baffle extends the full height of the container.

The container and baffles are made of smooth stainless steel.

The apparatus is used as follows: . The container is filled to a depth of 8.2 cms with the material under test and raised into position, clamped to the table 115 and the lid 131 secured.

The chart recorder 114 is started and the motor 10. Ill is then started with the gearing set for a low shear rate e.g. 6 rpm. The start up torque and steady state torque are detected by the torque transducer Π9 and the motor and recorder run until a steady torque value has been recorded for at least 2 minutes.

. This is the steady state torque value. The torque value at the steady state is quoted and if an initial peak was present this fact is noted. The sample is then removed, shaken with the bulk of the material being measured and the container refilled. The measurement is . then repeated at a higher shear rate e.g. 18 rpm. The cycle is repeated for as many shear rates as desired.

The background torque value namely with the container 130 empty was found to be 0.004 lbs ft at all the shear rates quoted in Table 2. The same value was obtained when . the container was filled with water.

The rotating vane viscometer torque value as defined herein is the value of the steady state torque value of the sample measured in the above described manner on the above described machine at a shear rate of 6 revolutions of . the paddles per minute at ambient temperature of 20°C. minus the background value at 2O°C.

TABLE β Example Grey Red oxide Solids liquids /ύ Sulphation of grey oxide Rotating X’ane ~v siTear*i Torquerisco’; pre of rate rpm lbs ft Comparison Example 1 of lerman Auslezeschrift. 75:25 2.90:1 12.6% 6 3.47 5 2,243,377 2 33:67 1.49:1 none 6 0.005 I 42 0.004 I 17 66:34 2.00:1 none 6 0.008 I 24 66:34 0.54:1 none 6 0.004 I 26 100:1 1.65:1 none 6 0.006 I 24 0.005 I 42 0.005 I I The viscosity values quoted herein are used to characterise the slurries as being readily pourable and of low viscosity. The values quoted in Tables 5, 7, 10 and 15 are the observed values and are not the torque values (as defined herein) which are used to characterise the preferred slurries.

It will be appreciated that to convert the observed torque values of Tables 5, 7, 10 and 15 to the torque values (as defined herein) the background value of 0.004 should be subtracted from the observed values. Certain examples, e.g. 2 and 24 in Table 5 and 17, 26, 34, 54, 55 and 56 in Table 15 have values the same as the background value. Thus their observed torque value is not greater than the background value in the measurement carried out and they fulfil the preferred viscosity characteristic of having a torque value (as defined herein) of less than 0.006 lbs. ft. at 20°C.

He have found that at ratios of oxides to water above 2.5:1 the filtration process does not occur and the process is much more difficult to control. Thus there is a tendency for the plates to become overfilled and too dense and for the tubes to be filled unevenly large pockets and gaps being liable to occur and also regions of lower density distributed unevenly through the plate.

At ratios of oxides to water below 0.4 to 1 the time taken to fill the plate becomes excessively long and the weight of oxides which can be introduced with the tubes tends to fall to unacceptably low values.

Thus it is preferred for the weight of wet paste in the plates used in Examples 2 to 27 to be at least 800 grams preferably in the range 800 to 950 grams.

As can be seen from Table 5 the viscosity of the aqueous slurries used in accordance with the present invention are all very low and are substantially the same as that of water as compared with the viscosity of conventional battery pastes and the paste of Example 1 of German Auslegeschrift No. 2,243,377, Thus as compared with a rotating vane viscometer torque value for the German specification of 3.5 lbs. ft. typical pourable self levelling slurries of the present invention have values below 0.010 lbs. ft. and more especially not more than 0.080 lbs. ft.

'—, Examples 28 to 35 These are examples of high viscosity mixtures and are given by way of comparison only and are not in accordance with the present invention.

These are examples of the use of formulations which have a rotating vane viscometer torque value (as herein defined) of 0.006 lbs. ft. and above.

Examples 28 to 32 were carried out on the apparatus of Figures 1 to 5. Example 33 was carried out on the apparatus of Figures 10 to 19 . This apparatus diffei from the earlier apparatus only in the rate of delivery of the monopump, the use of a preset pressure responsii switch which automatically cuts off the supply of slurry soon as the pressure in the supply tubes to the manifold reaches a preset value and in certain engineering features.

The proportions of ingredients and the conditions used for these examples are given in tables 6A and 6B below. 2o The viscosities of the formulations used are give in tahle 7 and the stratification results for Example 33 in table 8.

None of these formulations filled hy the filtrati filling technique, they all filled from the inlet end downwards. Some formulations, such as example 30, were too thick for them even to be capable of being pumped in the tubes. In example 31 not all the tubes filled propei As can be seen from table 8, the density of the active material i.n the plate of Example 33 varied by considerab) amounts namely +20% compared with the maximum variation in table 3 of +4%.

We have also found that use of these higher viscoi pastes tends to introduce problems of occasional blocking of the machinery during use. 43755 Table 6Ah'So „ ω w > μ ® rd 3 η μ n s ω ™ ρ μ o i> p, ho ω ρ -d H . 3 Λ M’H o φ offlri ι ® 6 R'd ? , ra •Η ΟΛ & ? Pt (fl IH ω ®. o p w ΡΉ 3 li Η O W S IS I tJ •H 3 -Ρ Μ H +? Η Ρ « -H ω οχ) ρ ο ρ P > ω Ρ P A o ftiap ® h S , ω £ (β 3 0 O 3 3 Ή Φ ft •PM ¢) t «rt S d Φ Ή •π -μ p d h Eh W p<,QH I «Η φ Φ O ti £J UO 0) λ α ·υ Η ο Φ -H P -rt £ X CO -P -P o w W li τί •rt •rt 3 rrt σ* O •rt CO rrt ί>ϊrd Φ Φ P p;i ϋ O‘[dU’C££[ O fA o irt irt Φ O lA o O CM o rtf -P CO rn ω 1 1 vo CM o • <0 CA σν fA •rt lA P Φ hO O -P 1 co VO ΓΑ 1 CM o •rt ί 1 rrt CM o o •P 1 m rrt IA CM CM H IA CM CM rrt 1 co E>- LA CM CM rrt O o CM O rtf O o O CM O O rtf f5 s = = - Φ a 0 CJ = LA ES < fA O' σ\ tS· rrt H m rrt i> lA « CM rrt o co OJ rd O > • o rrt fA I'- d rrt O' « a IA CM rtf rn IA CM o m r- ω \Ό IA V- LO 'Ό o 1 1 fl) (J Ολ CM Ct ff) r-i IA CM IA IA n·, 43755 • Table ID I I 1 I &0- β rt in rt e 1 rt 1 ω 1 ts > φ rt rt Φ ω 00 lO .cn P 1 o β 1 IS 00 Cd Cd 1 1 1 cn b- rt oo kO kD o I lh kD rt O o O o I o o c rt Cd cn o 00 kD c- o CM cn co o cn in o 00 rt cd Cd in 0- O o rs. kD js- o cn kD lo σ LO CM CM LO © oo ad r— rt «3* o t—· cn r— o cn kD Ό o rs. kD CO 10 r-r* m •d* •d* CO tn cn o rt CM CM fn m fn I : 87131 90900 7000 272 TABLE 7 4 2 7 5 S Example Grev Red oxide Solido iiquiciij % Sulphation of grey oxide _Rotating vane m yhearnri'orau'F” dscometer presence of peak rate rpm lbs ft Joinparicon Example 1 of 3erman Auslegeschrift 2243377 75:25 2.90:1 12.6 ' 6 3.47 Yes 28 II 3.30:1 none II 0.014 29 66:34 2.57:1 II II 0.017 30 75:25 2.86:1 3.75 II 0.066 31 II 0.70:1 9 It 0.012 32 66:34 0.73:1 II 'II 0.010 33 100:0 0.90:1 17 II 0.010 no ctf •Η ί> τι kOkO Η OJ + I ε-t α ω 0) ιη S • σ> η <ι* in CM β .ο •Η ^S Ul cos'd *d.-rl ·η·ΰ r-ί o4 O.-rl WH >'d φ:φ O< Φ H Pf (tf β ο tf ιη σι CM m tfιη kb tf coo HCM + I in m H CM in cO co o' IX) IS H σι o o o o H in m It has been mentioned above that other electrochemically active materials besides lead acid active materials can be used with the process of this invention.

Clearly the components used in such alternative arrangements must be compatible with each other. Thus, for example, when alkaline negative active materials are to be used the spines should be made of a metal having adequate chemical corrosion resistance to the alkaline environment, e.g. steel current collecting spines of round or strip section could be used, and these may he nickel plated and the polyester fabric tubes could be replaced by polyamide, e.g. nylon, fabric tubes. Preferred examples of alkaline electrochemically active materials include nickel hydroxide for the positive plate and cadnium hydroxide for the negative plate. These typically contain a proportion of electrically conductive material, e.g. graphite sufficient to ensure adequate conductivity; preferably 5 to 15% by weight of graphite is used. Steel may be used as the current collecting element and can also be used as the envelope for the active material in a suitable porous form to enable the filtration filling to be achieved. Other alkaline electrochemically active materials include iron oxide for the negative active material.

The nickel hydroxide may also have nickel particles or flakes distributed through it to enhance its conductivity.

The iron oxide may also have conductive materials incorporated in it to ’improve its conductivity.

The electrolyte is typically aqueous potassium hydroxide which may contain a small proportion of lithium hydroxide.

A variety of lead acid electrochemically active materials have already been mentioned including grey lead oxide and red lead oxide. Grey lead oxide comes in a variety of forms having different contents of lead and lead monoxide (Pbo) and particle sizes depending on the method by which it is made.

Hardinge oxide which is made by ball milling lead billets has a lead content of about 20-40%, e.g. 30% and a PbO content of about 80-60%, e.g. 70%.

It is subjected to air classification, the coarser particles being returned for regrinding. It has an average particle size of 15 to 25 preferably 20 microns.

Tudor oxide is another oxide which is made by milling but this is not subjected to air classification it has an . average particle size of 30 to 50, preferably 40, microns.

Oxide produced by the roasting process (e.g. the Barton pot process) has an average particle size of 12-15 microns.

The invention in enabling chemically inert envelopes to be used does not preclude the filling of the tubes with metallic forms of the active materials and their chemical or electrolytic conversion to electrochemically active form within the envelope and thus in its broadest aspect includes such an arrangement. The term active material composition thus includes materials capable of being converted to electrochemically active form within the porous envelope either before assembly into the cell or after assembly into 1θ the cell.

Many other electrochemically active couples exist which have been proposed for use in batteries.

The process has been described with reference to secondary or rechargeable systems so far. It is, however, ls equally applicable to primary battery systems where the active materials or one of them can be enclosed in a porous envelope and can be introduced into the envelope as a liquid suspended, preferably aqueous, slurry.

The liquid used as the suspension agent in the slurry is most readily^aqueous and this is clearly preferred on grounds of cost, safety and inertness. However, if an aqueous vehicle would introduce problems it could be replaced by any other liquid vehicles appropriate to the active material being used.

Examples of other battery systems with which the process could be used are thus listed in the following Table 9.

The active materials listed below would be used in particulate form of particle size appropriate to achieve filtration filling with the porous envelope which would be used. 427 55 Battery Positive Negative Primary or System Electrode Electrode Electrolyte Secondary Comments & nJ ϋ ο g td ϋ ft Ο o 3 tn .. to tn Cd rri dP tfl ft ® ®+> ® ta ft o> ft ft >> a ft OH OJ Ο P tfl Η ω ο ftPP tn td η) ο tfl tn Ο O ftp tfl £ •Η □ d o tu ω ftd n Λ oh P ft ft ρ ο d Ori ω tu tnH tn tn (Β·Η tfl ra*H 'H-S£ ft M® 3§£ tfl s d ft ft cd o a O -rl •tn ft M ft Ή X Ο I •H ca ω £0 p o cu Λ d O a> ra 3 Wrd IQ >><0 H-p ra ttfdJH •pgra ra -p o HSU (Dp Φ +3 ο o cu 3 § ftPP o (fl P . ft-H ft tn tb £ o tfl o o O o β β β β •H •H •H •Η N ESI N Ν o ft •H CQ (conti nued) fi •Η η fi · © hOΦ wfifi 3 ©fi fi © ·Η >, Ο -φ > Ο Φ r—i fi fi 'H Ofi μ fi hflhO 03 © Ofi Ο © fi © Μ -Η μ © hOfi ·Η •φ fi ·Η Η ο δ fi ΟΦ £ > © fi 03 fi 3 3 μ fi fi-Φ © >.© Ο-Η ω ©fifi ho fi © βμΒ fi © rl Tl H (fl ft Φ hfl © © Φ fi fifi O ωμ 3 · o fi © 3 βμ ra ω to-φ fiOOOOtO-Ht», E-ifi o ra ho 3 fi fi β . o >> P 8 fi ω fato fi •Η (0 < © Ή o o © W ΤΑΒΤ.κ 9 (continuation) © +5 s H O fi μ o ω $ ΰ) Η Φ φ •Η *Ρ·Ρ χ 2 φ ο a ρ Ρ ο Ο fi Ο Ο •Η 0 Φ •Ρ Ο Λ ft Φ © ti o ΐ j? (3 •Η ·Η ·Η 0 ·Η •Η 0 0 0 β X 0 β 0 0 0 Ο Ο 0 •Η = Φ Φ Φ Φ Ρ Φ Ρ +3 Ρ β^ί Ρ 0 οοο 0 <ί PM ΡΜ 04 /β ΡΜ ω ©.Ό > ο •H fi μμ ο ο ω ω ω η 0Η © © η > ρ •Η fi μμ •η ο ω © Ο Η CUM !? β © © μ μ μ ω Φ >1 Μ m g I: Ρ β *Φ Φ Ο ififi Μ -¾ β Ο k Η ft ο © Ο ·Η 3 fi ιη·^. ί Ο Ο © © μ fits ra fi ο ffl'Hfl Ο © h0 X fi fi r-l fi ο ω fi η 3 ·Η Η Φ Ο SS-fifi Ο ο •Η ω © fi ω φ £ O 3 hO OK fi'— 3 © Ο fi fi Ή © X £ o fi ra fi μ r-t © •η ω © ft >Γΐμ ft ο © o fifi θ O © © © μ οι fi © ra •h S wo firj © Ο Pi (ϋ M 33 ,β ΦΡγΟ Ο JM Φ Ο β β Ο ο β ο 0 65' 427&S Experiments have shown that nonwoven tubular plates can be filled, by the filtration filling process using either positive alkaline active material or negative alkaline active material.

Thus we have found that conventional negative alkaline active material( containing by weight 76% cadmium hydroxide 5% cadmium metal, 15% iron oxide, 2% graphite and 2% paraffin) can be introduced under gravity alone into the same non woven, NW, tubular plates as were used in Examples 2 to 27. io We have found that active material to watei; ratios in the range 0.75:1 down to 0.2:1 produce slurries which fill from the bottom end of the tubes back up to the inlet with good even distribution of active material in the tubes. The solids in these slurries settle out relatively rapidly in similar manner to the lead acid slurries described above and are all readily pourable liquids.

Similarly conventional positive alkaline active materia . compositions(containing by Weight'85% nickel hydroxide and 15% graphite (a blend of powdered graphite and flake graphite))when used in the same ratios of solids to liquids,! slurried which fill from the bottom ends of the tubes back up to the inlet with good even distribution of the active material in the tubes.

The solids in these slurries again settle out relatively rapidly in similar manner to the lead acid slurrie described above and are all readily pourable liquids. .

Experiments on the application of pressure to the slurry indicated that the amount of active material introduce into the tubes could be increased by tbe application of pressure in a way similar to that demonstrated above in connection with lead acid active materials.

Another factor which must be borne in mind if one is to achieve successful filtration filling is the relationship between the slurry particle size and the permeability, structure and pore dimensions, i.e. filtering capability, of the material from which the porous envelope is made. Thus with a highly porous envelope such as the woven envelope described in connection with Examples 2 to 27 and Example 7 in particular, the mixture of 33:67 Hardinge grey oxide to red lead oxide, which has a relatively low particle size, at a solids to liquids ratio of only 1.35.:1, as under Example 7; failed to fill the woven plate, the bed of active material failing to build up inside the tubes.

However, when 100% grey Tudor oxide, of average particle size 40 microns, at solids to liquids ratios in the range 2.5:1 to 2.0 :1 is used these woven tubes, W, can be filtration filled satisfactorily. These tubes can also be filled satisfactorily using this range of solids to liquids ratios for slurries in which the Tudor oxide to red lead oxide ratios are 80:20, 60:40, 40:60 and 20:80. · These tubes can also be filled with Hardinge oxide and 80:20 Hardinge oxide to red lead oxide mixturesat these solids to liquids ratios. 43755 The invention has been described so far with reference to non acidified lead acid active materials. However, lead acid ac materials can also be used which have had aqid added to them to ; at least partially sulpha’te them. •5 vje have observed that the addition Qf acid has a pronounced effect on the viscosity of the slurry within certain degrees of : sulphation.

The reason for this effect is not known for certain and whilst the invention is not dependant on any particular theory ‘10 it ig thought that this may be due to variations in the degree of hydration and thus intramolecular or intraparticulate interacl with variation in.the amount of intermediate sulphate oompounds which may be present in the acidified slurries. The figures fo: rotating vane viscometer torque values given in table IQ below clearly demonstrate this variation in viscosity with variation of degree of sulphation.

TABLE 10 Bresence of peak ' ra φ H . ra φ ΪΗ ra Φ ra Φ ra Φ X ra φ in p bp cv » .o Hg SP M· p rt OJ •ri mx? J o%> e ON · . ω ft •rip · > td Rio fri H O • o o 10 CM in vo • tn 0\ tn in • o in tn tn • o 0 o •H •P & Pf g tS-to o o CM o o VD o co o o rt ’ra »d •rl rt O CQ to •Φ •rl O* rt rt ·· tn rt • tn rt • tn rt ·· tn rt ·» tn rt »· tn ώ « S' ° W 0 OJ-cJ0 . ripi r-1 O H W OoK o CM in rri VD in CD in CM rt VD io C— R a> a> p B td ,, a » o Λ O'* O O & VD \o tn in o CM O VD rt tn rt •o p to jJo ie bo-ri a rilri Id ,® o JL, Is to no O o o CM s = = = - • (1) SH f-t O. R fi · p to o tri X « if) M — —....... · tri O rri CM 6 rt M O rt o 6 r-l in ό rt 10 ό rl -·” I $ w Φ β g • Φ W ω β ft β φ •Ρ ο ϋ ο φ ο § Λί ο Ό +> φ *ϋ *0 Φ β φ •Ρ § Ο Η £ φ fi Φ fi Ο acid and the water liberated, by the reaction of H?S0r with PbO to produce PbSO/ 2755 Care must thus be taken to use a system, in which the solids to liquids ratio is kept sufficiently low, so that the percentage sulphatic used does not cause the slurry, when used with the particular fabric envelope involved, to fail to filtration fill.

We have also found that, at least when using the non-woven fabric NW described above with a wide range of lead acid slurries, slurries which have a rotating vane viscometer torque value (as herein defined) of less than 0.010 lbs.ft. at 20°C appear to fill by filtration filling whilst slurries having such torque values of 0.010 and above fill by injection filling. Thus, though the invention in its broadest aspects is not limited to the use of slurries having torque values below 0.010, the use of such slurries is very much preferred.

We give certain illustrative non-limiting examples of acidified slurry formulations which filtration fill in the following Examples 34 1 1 gram of grey lead oxide requires 0.4 mis of 1.4 specific gravity sulphuric acid to achieve 100% sulphation.

With grey lead oxide containing 30% lead and 70% lead oxide the degree of sulphation Y is given by the equation: volume of 1.4 sp. gr. HgSO^ in litres Y = 216.4 X weight of grey lead oxide in kilogrammes 2θ EXAMPLE 34 to 42 These were carried out on the apparatus described with reference to Figures 1 to 5.

The proportions used and conditions and results are given in Tables Ila and lib below. These examples all use 100% Hardinge Oxide with solids to liquids ratios of 1.28 : 1 down to 0.43 : 1 and non woven tubes.

It will be observed that with these acidified slurries somewhat lov values are obtained for the wet paste in.the plate as compared with the acidified slurries of Examples 1 to 27. However, as can be seen from Table 14 below, the active material in the tubes is merely of lower dens and possesses good distribution and no harmful stratification.

The viscosities of slurries used in Examples 34 and 38 are given i Table 15. 3755 TABLE HA - ’ - 4 P « M- O 2 <+— φ ·ι- Ctn Or- ω 3 40 H CO tA -1 . tf CM 0 tA rM in tA CM tA tn to o. to 0 p > cn i- d o x: .. .1 3 H in in 1 ® E-t „ Xj W -rt Τ’, CM CO • rM 0 O « H 1 m tf 1 co rM rM 1 co a m •ri © 0 ft •Η O ft fr fc ftCM E-tM S ft 3 ri EM —®-®-- o 0 © in S 0) in O © 0 • ri 0 ra Ρ .λ CM I cn O 1 tf CM •ρ θ ό ω ο o tr- rM rM tA rM O -rl c a CCM ra EMP 0 ft-ri EM (Λ rM nJ ϋ 1 -3 •rl P 0 H P A ra-ri 0 03 ri 0 3 kO kO in A 0 ra -p C £ tn co co O O CO O o 3 ft © ft Q tf kO cn cn m tA tA CA CO 0 H S a 0 n m tf tf 00 cn cn t— O ft o 3 OM J4 ft et !* ft-P 033 ch ra P o o A 3 P 3 43 © 3 CM kO O υ ρ CM rM a nJ 0 »rl ς> K\ tA tf tf t- rM rM , •Η P H 3 Η φ E-i (0 ftP> &c Ul 0 0 in in in in in in fl 0 • « ·- • • CO ft 3 n 04 CM CM CM CM oo co CM firIK CM CM CM CM CM c— C- CM t— 3 O U 1—1 H H H H H At !> O 3 ft 0 Q 0 O O 0 O O 0 0 O 0 3 ft tf tf tf tf tf CM 04 tf CM A W 0 0 Oi >sfii ft 3 % g g g ·>. g g g 1 s IH Ο p 3 O •H P 5 in in m m in in in 0 0 ft • « * • « • * • » i-l H rM r-M rM rM rM rM tf tf . 3 ts.ra w H rM rM (~ΐ rM rM rM rM H w ·· ·· ·· »· k. ·· ·· ♦« ·♦ CO tf CM Cn tr- kO tf IA 04 •rl 3 CM CM CO r— tf tf tf tf tf rM cs1 • • • • « • • • • O •ri rM ,-4 O 0 O O O O Q ω Pl () O O 0 O O 0 p r*' -χ \ X \ \ \ O X X (1) 3 Q 0 0 0 0 0 C) 0 ?[ 0 C J O 0 0 0 0 O 0 0 O fti r-i rM rMr-4 H rM rl ,- I jL/i.wp le 4- tA kO c— CO r M tA tA CA tA hn cn O tf OJ ____ . __ . ... —.tf— ifc TABSE IIB 18755 fi o . QJ -id -p ra OJ tip 1 •Η -P ft 1 I 1 I 1 1 I 1 .-i’ci o m -p P QJ 0 0 -P QJ ti o tn VD CO o •P -P | vo 1 • • * • -Ρ H tn IS 1 ! CM in OA OJCp ·Η ”4- KA CM CM VRCQ O (¾ fi QJ 0 O •H ft I ra h S ra c <4d ti P Q> τφι o ra ra ft 1 1 11 1 1 1 I +3 P 0 xt vD vo VD 0 0 VO VD -Φ • • • • VO • • ' ·· 00 ts ts • I •P ft cn σ» 00 vo in tn in OA -p s s- c- VD in QJ ti AS.cotn 0 •P ti -P ·· co O vD fi X! 03 vo xt cn in •ρ ω π 1 tn vo i 1 cn rd rd Η ·Η ti co I tn rd CM CM •id 0) R ω 0 QJ ra •Ρ P 0 t\l cn tn •tf· cn rd tn O CM p io nJ Hi Ολ co . co CM (-- VO cn CM KA 03 i d fi H fi p,.r| p, i!fl •0 -4- ω in s co xt S- S d o O o CO o o O o o •r I o O o co CO o o o o ϋ rd I.M CM CM CM CM CM CM CM CM ti M F-i m VO tn tn tn OA cn C5A tn 0 .1 CO rl rl tn tn tn o -P Ί rd tn tn tn «4- xt Xt is ti r-j ΣΛ CM r-l rd rd o O O OA r - a • \1 CM tn tn tn in in in xt ra G OS rf Φ P Ph tO 1 1 1 l t 1 t 1 CQ S>0 VO cn r-l co xt o OA VD CM CD ti CA O *n Cn ts ‘-Ό rd OJ O M h IS ω H rn rl tn U) f cb 'ί) OA r- ifA . t •j- ΓΑ CM . 1 o f\J CM tsl CM CM CM Ol 'M οχώιιηχρ t ΙΛ j ζζ. CD rn n- f·' co t.'S tn O r-l - -*V * ‘-1 w . *-*· 1.,, .7......1 Examples 43 to 50 Those were carried out on the apparatus described with reference to Figures 1 to 5.

The proportions used, conditions and results for these , examples are given in Table 12A and 12b below. These Examples use high proportions of red lead with solids to liquids ratios of about 1.6:1 and non-woven tubes, NW.

Stratification results are given in Table 14.

The viscosities of sLurries used in Examples 44,: 47 , 48 and. 50 are given in Table 15.

The degree of sulphation quoted in Table 12A has been obtained merely by replacing the weight of grey lead by the weight of red lead. The slurries of Examples 47 to 50 were made up by adding grey lead oxide to the slurry of Example 46. ‘ Μ ...... wr <73 ω £ «> “ >: · S 2+j ο·ρ· . } Q- rtJ o CM 1 in in rt 20 o tn o tn o rt 0 EM Λ 1 ·Η <Λ Φ ο ra Φ rt 1 υ 0 fe -rl Φ fe ft ,Φ Η ΟΛ H 3 PrC\l &4<η £ Pt ra d Ε-: m • LO rt 1 CM • CM in • o tn in • co rt t> r- 1 φ φ ο fe ra ·ρ<Η ρ ti rt ο ra φ w ίϋ φ ra fe υ φ ο $ ο·η p fe Pcm ΕΗ-Ρ φ ft-H ei in ”4* *4* in * LO CM LO LO in t*- *4· in LO CM CM rt CM rt in rt r-t Π) ο 1 τ) Η -ρ to Η to -ρ ρ ω ·Η ο © © Η d 0 d ο Ρ β ©-Ρ Ρ,ο ο 3 ft ra ft tun S ω > Β o d ο Η P Pt &t > pt-p 0 3 3 O tn *4- cn 1 in LO rt *4· If tn co o CM o co σ' tn rt LO tn rt LO 1 - 00 CM 1 Pr to d © 1 P rti Pt0H PH odd ri tn .a *4· tn rt ώ in tn 1 Φ ο 0 Φ ftp ra §Η\ poo ft ί> ο in CM CM rt in CM CM rt in CM CM rt in CM CM rt in CM CM rt tn CM CM rt in • CM CM rt in • CM · CM rt Ό Pr 0 θ ω· d Pr Pt ra O o o *4· o *4· O •4· O vf- O O ?4“ Γ-Ι / w § 0 0 Pl |O ΡίΉ d pop g g fe fe g fe fe » -1 E4 P o ί I rt p νΛω >- o * o co rt O (0 rt O γ- γ- ο CM js. O CM E> O CM C— • o CM Ο- Ο ra Ό •H rt o CQ ra •H •rl rt tn LO rt f—1 cn in rt rt in in rt r-l O m rt rt CM L0 rt r-1 co LO rt rt tn LO rt rt σ\ in rl >3 Q) rl C> rt Φ Ph O o rt \ O O Q rt \ o O © r-l o o 1-1 \ O rt O cn \ cn Ch xf· rt ω LO Ό r-1 aidcrexfl m ’ 1' -3- LO •si t- •3 $ O'» O m TABLE 12A .. 74 TABLE 12B Φ •Ρ r: ra ο β >1-1 Ρ (0 ΦΗ C {μ·Ηϋ •Η «Η Ρί Η 03 rt|N Ο Μ 1 1 1 1 1 1 Ρ β φ φ 0 Ρ Φ (β Η ft I I 1 1 1 1 1 Ρ Ρ Ρ Η ΟΜ·Η m ο ft 03 W ft β ϋ Φ φ Ο •Η Φ «Η Η ·Η a ra •Η Ρ< 1 03 Η 0 03 β σι mo 1 1 vo in Ϊ 1 <Κ α! 3 φ 4ι ο μ ο ρ. rd «4* Ρ β φ 0 Φ Φ Η r-d CJ tn S- ρ a VO I 1 1 S oo I t φ ra \S.ra to Φ Ρ ft Ρ ft Ρ ιη m CM Ρ W) Β I t 1 I m O Η -ft lfl o CM 1 I •Η Φ U £ Μ tn CM φ φ ra ρ ρ a ρ ra nJ nt CM ω Ch s CO <· tn 00 φ nJ ft η ft CO CM Ch H co co CM H :3 ftp ft ta CO m s S IS IS S CO O o o o O Ό o m m o o o o O O rJ < E rd CM CM H rd rd rd rd Ui tn tn ih ih ch VO vo fl) VO o O f') ' > ω >0 -P · CM CM m m m K\ ,-1 r I ra rd o> Ch (0 ω CO Cf) s F- £= β r-d r-d rd H r-! rd t- to <- CM m oo co s- m 0 tn m tn rn <—1 Ch m VO ό ra m •4- ts th CM tn Ch in φ h rd o «3* h- s m CM CM [ti 1.:0 tn in CM CM CM CM CM CM w S3 Φ nJ o Ch rd S- Sq M 1 1 I J ;·> - i -M- ’ d O tffl O ?’ - CM r··’ tn tn m m otdiJiTTZI-T rn -4 77 i 1 m VO -4 s <1 CO o m 4S7SS Examples 51 to 55 These were carried out on the apparatus described with reference to Figures 10 to 19.

The proportions used, conditions and results for these 5 examples are given in Tables 13A and 13B below. These examp: use high proportions of grey lead oxide and higher degrees of sulphation than Examples 34 to 42, with non-woven tubes.

Stratification results are given in Table 14 and the viscosities of slurries used in Examples 51, 54, 55 and. 56 are given in Table 15.

TABLE 13A Φ ρ μ rt 2 fH ω ,ε< ο φ .ρ. W CG > tf> 3 Ο «μ —ι c. «J r k-P'i-l c' (Xi ft} O > O OJ CM CM o CM 20 20 o CM 42755 Φ 1 - H H CG Φ O CG Φ H E-ί ϋ 13 f-l -rl Φ tl ft | Φ •rt O A tl 2 ftCM CG CH «η “·: ft w φ ε-ί lA CM 1 1 1 CM φ Φ O tl Φ -p Λ, Φ Ο ·η s5 h d cm vi [-IP ffl PrH *“ LA VD o A 1 LA o H 1 LA o rrt 1 LA A- irt ti o •rl Ρ 1 Pi Ρ P BJ 3 ffl ffl Ό Π) ffl p a ω ρ Ρ Ό ui o 3 ft® Mr-1 υ fflH S Ρ·Η W ,3 O 3 O ρ,ρ o ra P 1 O O VD Ϊ I 1 1 rt •rt μ μ 2 A Ert CO ftrQ Crt 1 rt- 1 1 1 LA 0) o a ® Pi 3 ra 0H\ poo (P !> ffl o o CM O LA rrt o o irt O O rrt o o rrt O O A XJ ft Φ £ Φ 3 ft ftro O rt* o CM O O O O ffl ffl Ά A s g •jw g *3- g g •τ». g £ o •rt μ d Λ P< rrt 2 \Xcn A- VD r-4 A- VD rrt A- VD rrt VD VO irt j—1 VD A VD O rrt (G fd •rt ,-4 o ω w 'd •rt 2 σ* •rt A rrt σ\ rt· Q frt co rt· o- 1—1 co rt* d rrt o LA O ,rt CM lA O A CO r> • a >> Q) tl rb XJ Φ ft' o o o rrt o 6 a r-i -o CG O -4 CO d CA ·» ala rt- lA CO rrt LAlA IA rt' IA Si· Example rrt IA CM LA IA LA LA · ir\ VO LA P 0 Φ H β Φ •H ft r*t 0 M β r 0 P β Φ φ 0 P Φ Φ Γ1 β P P P r-l Φ •rl x β ο •Η Φ β Η Φ ftft 0 0* Q-f Φ β 4« Ο CO 0 Φ «Α •Η Η Ρ β Φ . 0 0 HH Ρ ft 45 § φ φ \&co ω tn γCM frCM frvo vo φ ρ Φ Ρ β,β 2 ρ ω s Η ·Η Φ •Η Φ.β ft £ UD Φ .Ρ Ρ 0 φ 0rl β (3 ρ,-Η ft fciO ο CM ιη σι CM tn σι CM in o tn σι o tn vo in tn rtf · •Η Η Ο 0 <3 Ο Ο ΙΛ tn Ο Ο ιη tn ο ο ιη tn o o in tn o o in tn o o in tn β Φ Ρ φ Η S ο ο σ\ ο cn ο ο σι ο σ ο ο σι ο σι o o σι o σι o o σι o σι o o cn o cn τ$ Φ· φ β « ω o tn vo co o in CM fr· in tf* VO H tn >αΠ φ φ β β cb Μ ιϊΛ Γ•ί* • h νο tn νο tn «Φ co •4* Ο tn fr* in CO H ^f· ογώπΒΧΚ Η tf.

CM η m in - VD cn tn m co •tf σι tn in in vp in TABLE 14 / 1 3 lA LA LA LA ri OJ C— LA 0- OJ Φ « • • • • K CO LA tf LA o LA OJ tA tA tA tf LA tf LA LA Ut\ H ΙΧΛ tA tA kO $ CJ tA ΓΑ tA LA C- LA tf LO rM in ' tA CJ tA tA CO tf kO co LA LA LA in OJ • kD kO 0- • « 00 tA tA tA CM LA .OJ..... -3- LA LA LA LA f • • • LA ΟΛ c- kO LA fri « tA tA tA tA tf IA LA 3 ' 0 •ri P ri rM tf vD cn cn tf •ri rM 0J 0J OJ rM CM j 0) 0- a LA tA tf O + rM Cm rM CM + - + + + + LA 3 OJ LA LA • » 0- Φ tf A- LA tA t> • s . tf lA LA LA LA tf 0- fi LA t tA 0J rM 0- cn CM rM I o tf rM CM rM tA — -r tom j tA rM co tA LA kD LA LA tf tf kD LA tf LA LA kD kD CO P C\J CM OJ 3 •o O o CO t> tA H LA tf tA P tf 0- tf tf kD kD· kD kD CO ri o CQ 1 OJ - tf GJ CJ OJ •ri Ό o ’OJ o o~ tA kD tA o •r- O -J- kD lA tf kD kD tf LA P T AJ OJ OJ ri. P ft o OJ CO cn tA rM CD kD 0- CO o ft tA kO LA tA tf tf tA tf LA EM OJ OJ OJ 3 o rM P 3 O Ο- Ο CJ 0- t- t> A- kD rM kD Pi Q o kD kD kD kD kD O rM rM rM rri rri rri rM 3 W Pi 1 1 pL PL ra H rM rri rM rri rM «· »· ra 3 • a • a • a a< «a • o CJ CO 3 •ri CJ tA cn cn CO CO LA LA 0- •H tf kD LA tf tf tf • • « r-l σ1 a • • • • • O o o O •ri o ,M rM o o o CQ fi • •LA tf o o o LA · • •LA r-l ·. 3 • a »a CO • LA LA · (D d ·· . ) kO r-M o o o ·♦ tf Γ-» • tf ε-ι ri - t • a) o o o CM CO lA tf o » co rri H CO LA r-M o rri 0 Ph fj ri CJ tA o fri OJ fA tf IA •D M tf •J- Ll\ lA lA [A (A IA LA W t 4275S •79 43755 TABLE 15 Example Solids % su'l- Rotating vane vipcometer Kecr Oxide Liquids pha- tion G-tiear rate rpm Torque Ihs.ft pce.sencc of peak 34 10Q 1.28:1 1.5 6 0.008 No 29 0.008 NO 42 0.007 No , 39 100:1 0.47:1 1.5 6 0.005 No 24 0.005 No 42 9.006 No ' 4-1 100:1 0.43:1 4.0 6 0.004 No 24 0.004 No 42 0.004 No '44 0:100 1.59:1 0.18 “e 0.004 No 24 0.005 No 42 0.005 . No 47 . 9.9: 1.62:1 0.72 6. 0.004 NO 90.1 24 0.005 No 42 0.005 No • 48 18.6; 1.68:1 0.72 6 0.004 No 81:9 24 0.004 No 42 0.004 NO 51 100:0 0.49:1 16.7 6 0,005 No 24 0.005 NO 42 0.:.005 No 54 92:8 0.50:1 16.6 6 0.006 No 24 · 0.004 No 4 o Cw 0.004 No 55 84.5:15.5 0.52:1 16.1 6 0.007 No 24 0.005 No 42 0.005 NO < 56 55.5:44.5 0.78:1 10.6 6 0.006 ITO 24 0.005 no 0.003 Wo Footnote: As to the viscosity values see general statement under Table 5.

Comparison of the stratification results in Table 8 and Table 14 makes it clear that plates vzhich are filtration filled (Table 14) have significantly lower degrees of stratification than plates which are injection filled (Table 8), a Notes on Tables 11A and 11¾ to 1¾ and 15¾ 1) fi Sulphation. It has been assumed that all the acid is absorbed by and reacted with the excess oxide at the stage when it is first added and thus the fi sulphation remains constant until more acid is added i.e. a proportion of the acid is removed vzith .Iq each sample of paste which is removed. 2) Solid/liquid ratios.

These are calculated including the whole of any acid added as liquid.

The effect of presulphation of the lead acid active material lo has been described with reference to three areas of the possible theoretical range of slurry compositions. These are 100$ grey oxide with solids to liquids ratios of 1.5:1 toO.4:land degrees of sulphation in the range 1.5 to 4.0$ (Examples 54 to 42); OjlOO grey to red to 20:80 grey to red with solids to liquids ratios in the range 1.5:1 to 1.7S'l and degrees of sulphation in the range 0.05 to o.8$ (Examples 45 to 50); and 100:0 grey to red to 55 : 45 grey to red with 3olids to liquids ratios in the range' 0.4:1 to 0.8:1 and degrees of sulphation of 10$ to 17$ (Examples 51 to 56).

It is believed that there are many other formulations for 2b presulphated lead acid active materials which will be effective to give filtration filling and the reader, with the teaching given herein, of the effect of aeid on viscosity and the effect of variation of the ratio of solids to liquids, and of the effect of acid on viscosity and the effect of variation of grey oxide to red oxide ratio and the effect of variation in permeability of the porous envelope, will readily be able to select an appropriate formulation and an appropriate material for the porous envelope.

Claims (53)

1. A method for preparing enveloped plates for batte by introducing an active material composition containing liquids into the porous envelope of the plate, when the 5 envelope is assembled on the current conducting element o the plate, characterised in that the active material of t composition is introduced into the envelope as an aqueous slurry, which has a rotating vane viscometer torque value (as defined herein) of less than 0.006 lbs. ft. at 20°C, 10 the aqueous slurry being introduced into the envelope at a pressure of less than 5 p.si. until the envelope is fil with the composition, liquid issuing through the walls of the envelope, the pressure then being allowed to rise to value above 5 p.s.i. but not in excess of 100 p.s.i. wher 15 after the pressure is released.

2. A method as claimed in Claim 1 in which the envel is an array of tubes arranged side by side with a current conducting element located in each tube.

3. A method as claimed in Claim 2 in which the ratio 20 of the volume of slurry which is fed into the tubes of th enveloped plate to the total internal free volume of the tubes of the enveloped plate is at least 2:1.

4. A method as claimed in Claim 3 in which the ratio is between 3:1 and 15:1. 25

5. A method as claimed in any one of Claims 1 to 4 in which after the envelope has filled the back pressure in the supply of slurry to the envelope is allowed to bui up to a pressure in the range 5 to 50 p.s.i.

6. A method as claimed in Claim 5 in which the time ι 30 which the pressure is allowed to build up is from one-teni of the time taken to fill the envelope up to a time equal to that taken to fill the envelope. ' 82

7. A method as claimed in Claim 5 in which the envelope is filled in 5 to 15 seconds and the pressure is allowed to build up for 1 to 15 seconds.

8. A method as claimed in any one of Claims 1 to 7 in which the material of the envelope has an air permeability (as defined herein) in the range 0.5 to 20 litres of nitrogen/ sq. cm/minute.

9. A method as claimed in Claim 8 in which the material of the envelope has an air permeability (as herein defined) in the range 3 to 10 litres of nitrogen/sq. cm/minute.

10. A method as claimed in Claim 9 in which the material of the envelope is a non-woven batt of polyester fibres which is 0.5 to 0.7 mm thick and weighs 120 to 160 grams per sq.cm., has an air permeability (as herein defined) of 8.0 litres of nitrogen/sq, cm/minute.

11. A method as claimed in any one of Claims 1 to 10 in which the aqueous slurry comprises an aqueous blend of particulate active material and liquids, the weight ratio of the solids to the liquids being in the range 1:1 to 1.8:1.

12. A method as claimed in any one of Claims 1 to 11 in which the slurry has a density of less than 2.5 grams/cc.

13. A method as claimed in any one of Claims 1 to 1.0 in which the slurry composition is non-acidified and contains grey lead oxide and red lead oxide in a range of ratios by weight of 66:34 to 33:67 and the weight ratio of solids to liquids is in the range 2.0:1 to 0.5:1.

14. A method as claimed in Claim 13 in which the weight ratio of solids to liquids is in the range 1.5:1 to 0.7:1. . 42755

15. A method as claimed in Claim 8 in which the mate: of the envelope is a spun woven fabric having 15 to 25 weft threads per cm and 15 to 25 warp threads per cm and a nitrogen permeability (as defined herein) of 5 litres oi nitrogen/sq. cm/minute.

16. A method as claimed in Claim 15 in which the slurry composition is non acidified and contains grey leac oxide and red lead oxide in a range of ratios by weight oi 66:34 to 33:67 and the weight ratio of solids to liquids is in the range 2.5:1 to 0.9:1.

17. A method as claimed in any one of claims 1 to 10 in which the active material is a lead acid active materia which is at least partially sulphated before being introdi into the porous envelope of the plates.

18. A method as claimed in Claim 17 in which the degree of sulphation of the active material is less than 17% by weight.

19. A method as claimed in Claim 18 in which the degree of sulphation of the active material is in the ranc 0.05% to 16.7%.

20. A method as claimed in Claim 17 in which the acti material is grey lead oxide, which is sulphated, the degree of sulphation being up to 4% and the ratio of solic to liquids is in the range 1.3:1 to 0.4:1.

21. A method as claimed in Claim 17 in which the acti material is grey lead oxide containing red lead oxide in a amount up to .45% by weight and the lead oxides are sulphated, the degr of sulphation being in the range 10% to 17% and the solids to liquids ratio is below 0.8:1,

22. A method as claimed in Claim 17 in which the acti material is red lead oxide containing grey lead oxide in an amount up to 20% by weight and the lead oxides are sulphated, the degree of sulphation being up to 0.8% and the solids to liquids ratio is not more than 1.7:1.

23. A method as claimed in any one of Claims 1 to 16 in which the active material has an average particle size in the range 1 to 100 microns.

24. A method as claimed in Claim 23 in which the active material has an average particle size in the range 5 to 20 microns.

25. A method of filling enveloped plates for batteries which comprises introducing an active material composition into the porous envelope of the plate, when the envelope is assembled on the current conducting element of the plate, characterized in that the active material composition is introduced into the envelope as an aqueous slurry, comprising a lead acid active material composition, which has a rotating vane miscometer torque value of less than 0.006 lbs. ft, at 20°C, the said aqueous slurry being introduced into the envelope at a pressure of less than 5 p.s.i, until the envelope is filled with the composition, liquid issuing through the walls of the envelope, the pressure then being allowed to rise to a value above 5 p.s.i. but not in excess of 100 p.s.i, whereafter the pressure is released, and in which the envelope is disposed in a substantially vertical plane so that solids can settle to the bottom of the envelope under gravity, the aqueous slurry containing a ratio of active material to water in the range 0.1:1 to 2.5:1 in parts by weight, the material of the envelope being selected to filter out active material whilst allowing passage of liquids, the solids being at least partially retained within the envelope and the liquids at least partially passing out through the walls of the envelope.

26. A method as claimed in Claim 25 in which the envelope is clamped at the top and bottom whilst the slu is introduced into the liquids at least partially passir out through the walls of the envelope.

5. 27. A method as claimed in any one of Claims 1 to 2 in which

6. 10 28. A method as' claimed in Claim 27 in which the w< ratio of the active material, in the continuously mixed slurry supply to the individual filling weight (as heredefined) is in the range 1300:1 to 25:1.

29. A method as claimed in any one of Claims 1 to ; 7. 15 inwhiGh the supply of slurry composition is delivered by a pump to a filling manifold, which feeds a plate, f an agitated supply of slurry in a storage tank, the sai pump being one which gives smooth delivery and maintain the slurry in suspension and the slurry, in the interva 8. 20 between introduction into an enveloped plate via the filling manifold, is recirculated from the outlet of th pump, via a recirculating tube connected to the pump outlet, to the storage tank, and thence, via a supply t to the pump inlet. 9. 25

30. A method as claimed in Claim 1 and substantial! as specifically described herein with reference to any o of Examples 1 to 6, or 8 to 25.

31, A tubular plate for a lead acid battery wheneve filled by a method as claimed in any one of Claims 1 to 43735

32. Apparatus for filling enveloped plates for batteries by the method claimed in Claim 1 comprising at least one filling station comprising means for supporting the envelope of a plate, assembled on its current conducting element, the envelope comprising at least one porous tube, in a substantially vertical plane and a filling manifold adapted to be juxtaposed to the top of the supporting means whereby an aqueous slurry of an active material composition may be introduced into the envelope of a plate located in the said supporting means, the apparatus further comprising a slurry storage tank adapted to contain a supply of active material slurry, and provided with agitating means for maintaining the active material in the storage tanks in suspension as a slurry, and delivery means connected between the storage tank and each filling station for deliver ing the slurry from the storage tank to the manifold of a selected filling station, and means positioned below the means for supporting the enveloped plates for collecting the liquids issuing through the walls of the envelopes, the delivery means including recirculating means for recirculating the slurry to the storage tank when the slurry is not being delivered to a filling station, a pressure responsive valve being located in the delivery means to each filling manifold on the inlet side of each filling manifold, the or each pressure responsive valve being arranged to actuate automatic switching of the slurry supply from the manifold to the recirculating means and to release the pressure in the delivery means to the manifold as soon as a preset pressure is reached.

33. Apparatus as claimed in Claim 32 in which the delivery means to the manifold comprises a pump having an inlet pipe communicating with the storage tank and va' means, referred to herein as the recirculating valve, 5 communicating with the outlet of the pump for directing slurry from the pump outlet to a filling station or for recirculating the slurry to the storage tank.

34. Apparatus as claimed in Claim 32 or Claim 33 in which the means for supporting the plates are adapted to support tubular plates and comprise a frame rigidly secured to the filling manifold and carrying top and bot clamps arranged to releasably clamp the plate to the frai

35. Apparatus as claimed in Claim 34 in which the . clamps are toothed and conform to the outside surface pr I s of the bottom and top of the tubular plate.

36. Apparatus as claimed in Claim 34 or Claim 35 in which at least the top clamp is provided with a resilien sealing liner.

37. Apparatus as claimed in any one of Claims 32 to 20 36 adapted for use with tubular plates in which the manifold has an outlet nozzle assembly consisting of rig feed tubes spaced apart in a straight line with their ce on the centres of the tubes of the plate and having exte diameters corresponding to the internal diameters of the 25 tubes of the plate.

’ 38. Apparatus as claimed in Claim 37 in which the fe tubes extend through a resilient gasket, the dimensions of the frame in relation to the plate being such that th end of the plate has to be forced into the gasket in ord 10. 30 to locate the plate in the supporting means.

39. Apparatus as claimed in any one of Claims 33 to 38 in which at least two filling stations are provided for each pump and slurry storage tank and the recirculating valve is a three way valve,

40. Apparatus as claimed in any one of Claims 33 to 38 in which at least two filling stations are provided for each pump and slurry storage tank and the manifolds are fed via individual supply lines by a common feed pipe connected from the outlet of the pump to a recirculating pipe for feeding slurry to the storage tank and valve means are provided for selectively connecting each individual supply line to the feed pipe.

41. Apparatus as claimed in Claim 38 in which the pressure responsive valve is a pressure relief valve.

42. Apparatus as claimed in Claim 38, 39, 40 and 41 or Claims 39, 40 and 41 in which the or each pressure responsive valve is arranged to actuate automatic switching of the recirculating valve or the valve means connecting the or each manifold to the common feed pipe to the recirculating position and to release the pressure in the supply line to the plate as soon as a preset pressure is reached.

43. Apparatus as claimed in any one of Claims 33 to 42 in which the pump comprises a rotor in the form of a single start helix fitting in a cylinder in the form of a double start helix of twice the pitch of the rotor, in which the rotor turns about its own axis in one direction, whilst its axis orbits about the axis of the cylinder in the opposite direction at the same speed. 43755

44. Apparatus as claimed in Claim 34 in which the top clamp comprises a fixed toothed face and a movable co-operating toothed face arranged to be moved away froir the fixed face, while remaining parallel thereto, by pneumatic or hydraulic means.

45. Apparatus as claimed in Claim 34 or Claim 44 ir which at least one of the opposed faces of the lower edc of the top clamp or the top edge of the bottom clamp is chamfered.

46. Apparatus as claimed in any one of Claims 34 or Claim 44 or Claim 45 in which the rear face of the top clamp carries a grooved member depending therefrom to assist location of a plate in the clamp.

47. Apparatus as claimed in any one of Claims 34, 1 45 or 46 in which the bottom clamp has a front clamp fa< which hinges down from a back clamp face and biassing means are provided and are arranged to bias the front plate either to the closed position or to a fully open position.

48. Apparatus as claimed in Claim 32 and substantii as specifically described herein with reference to Figures 1 to 5 or Figures 10 to 12 and 15 to 19.

49. Plant for filling enveloped battery plates whii comprises a central slurry preparation station comprisii a tank, weighing means for enabling the tank to be weigl agitating means to enable the slurry to be kept in suspension, active material supply means and liquid sup] means, and at least one filling apparatus as claimed in any one of Claims 32 to 48 and means for feeding slurry from the central station to the manifolds of the fil1 ini apparatus. 43755

50. Plant as claimed in Claim 49 in which the means for feeding a slurry comprise means for continuously feeding slurry to the or each filling apparatus and return means for returning slurry to the central station whereby the slurry can be continuously circulated.

51. Plant as claimed in Claim 49 or Claim 50 in which the weighting means incorporate a load cell located below the tank.

52. Plant as claimed in Claim 49, 50, 51 in which the agitating means comprise a paddle arranged to rotate at the bottom of the tank.

53. Plant as claimed in Claim 49 substantially as specifically described herein with reference to Figures 13 and 14 and Figures 1 to 5 or Figures 13 and 14 and Figures 10 to 12 or Figures 13 and 14 and Figures 10 to 12 and 15 to 19.