US440277A - Process of producing crystallized metallic lead plates - Google Patents

Description

(No Model.) 3 Sheets-Sheet l. C. PAYEN.

PROCESS 0E PEODUG'ING SRYSTALLIZED METALLIC LEAD PLATES. No. 440,277. Patented Nov. 11, 1890.

TNEESES. |NVENT|JR= M M (No Model.) 3 Sheets-Sheet 2.

C. PAYEN.

WITNESSEE; lNvlzN'rnRt (No Model.)

o. PAYEN.

3 Sheets-Sheet 3.

PROCESS OEPEODUGING GEYSTALLIZED METALLIC LEAD PLATES.

Patented Nov. 11, 1890.

lill

- l/u IIIHMIIIVIAIIIIIIHNI g NU v INVENTD'R:

UNITED STATESl PATENT Frrcn.

CLMENT PAYEN, OF PHILADELPHIA, PENNSYLVANIA, ASSIGNOR TO THE vELECTRIC STORAGE BATTERY COMPANY, OF GLOUCESTER CITY, NEIV JERSEY.

PROCESS 0F PRODUCING CRYSTALLIZED METALLIC LEAD PLATES.

SPECIFICATION forming part of Letters Patent No. 440,277, dated November 1 1, 1890. Application led January 16, 1888. Renewed April 4, 1889. Serial No. 306,029. (No model.)

To all whom. it may concern,.-

Be it known that I, CLMENT PAYEN, a citizen of the Republic of France, but now residing at the city of Philadelphia., in the count-y of Philadelphia and State of Pennsylvania, have invented a certain new and Improved Process for the Production of Crystallized Metal Lead Plates, of which the following is a specification.

My invention relates to the production of porous crystallized metal lead plates.

The invention consists, essentially, in fusing with a charge ol' chloride of lead a varying quantity or percentage of chloride of cadmium, then discharging the liquid or molten mass into a mold in which in cooling it assumes a crystallized form, and then reducing the same to a metallic state, whereby'a porous crystallized metal lead structure is produced having substantial strength.

In the accompanying drawings I have illustrated apparatus suitable for the conduct of my method of producing crystallized lead plates in such forms, respectively, as I have found practically ecient, and in which- Figure l is a vertical central section through a melting or fusing furnace of my improved construction, showing the crucible pivotally supported therein and operated by a lever for discharging the contents thereof. Fig. 2 is a top or plan view of a mold made in two sections hinged to each other, and showing also the means for clamping the sections together. Fig. 3 is an end view of the mold constructed in two sections with the means for clamping the same together. Fig. 4 is a perspective View of a mold made in two sections hinged to each other, and showing also the interior formation thereof. Fig. 5 is a perspective View of a bivalved mold for framing the crystallized metal plates. Fig. 6 is an end view thereof. Fig. 7 is a top or plan view of said framing-mold and the clamping device thereof; and Figs. 8 and 9 are diagrammatic views showing the first and second electrolytic actions to which the crystallized plates are subjected in order to bring them to a metallic state.

Referring to the accompanying drawings, A is thefurnace, constructed of brick or other material.

B is the grate located and supported in the lower part of the furnace.

D is the drafttine leading to the chimney D.

E is an arch, made of brick or other refractory material, in the upper part of the furnace, which is supported in position on a metallic plate e, with a central opening therein. The plate e is held in position by means of columns f, arranged and supported in the brickwork of the furnace in any suitable manner.

F is a porcelain erucible or melting-pot open at the top, and around the outer circumference of which is formed a layer cl of amianthus, asbestus,`or other similar material, and

between this layer CZ and the metallic pot F is a film or layer of sand f of any desired. thickness. This metallic capsule or pot F is pivotally supported in a central position Within the furnace, and is operated from the outside by a lever f2, attached to one of the journals of the metallic pot, whereby the crucible F may be readily tilted for discharging the contents into a receptacle for further treatment.

H is an inclined hopper provided with a removable stopper h, which permits of the charging of the salts of the metals or other material into the Crucible F.

I is a sliding door, operated in any suitable manner to allow of the discharge of the liquid or molten mass or compound into a suitable mold for causing the same to assume a crystallized form.

Having described and pointed out the characteristic features of a suitable melting or fusing furnace, I will now proceed to describe the first. step in the process of producing a crystallized metal lead plate of a given sizesay from six to eight inches square. I take for the base of the charge chloride of lead, and to which I add two per cent., by weight, more or less, of chloride of cadmium, and I prefer to add the chloride of cadmium before fusing the mass; still it may be added to the chloride of lead while in a state of fusion iny the crucible F, it' so desired. The proportion of chloride of cadmium to the chloride of lead will in each case depend upon the degree of porosity desired in the finished plate. It will vthus be observed that by simply varying the IOD proportions of the chloride or cadmium to the charge of chloride of lead thedegreeof porosity required may be readily obtained. I have found by practical experience when a maximum degree of porosity is desired that the addition of a third chloride to the mass either before or during the fusing step of the process gives excellent results. The third chloride may be one of any of the metals which of itself is not of a deliquescent nature and such as will conduce in conjunction with the chloride of cadmium and chloride of lead to give consistency and strength to the tinished plate, and one which when fused will not be subject to ebullition and continue in such condition while being discharged into the crystallizing-mold, as this would be apt to produce air-bubbles therein and impair to some extent the strength of the structure wh en formed. I have found that the simple addition of chloride of cadmium to the lead chloride enables me to obtain a crystallized plate which is not hygroscopic, and this is a very necessary condition, especially when it is desired to form a lead frame around the plate for the purpose of obtainingagood contact in the electrolysis. After the charge composed of the chlorides of lead and cadmium has been subjected to fusion in the crucible F and the mass or compound has reached a liquid state therein, the crucible is tilted by means of the lever f2, and the sliding doorI at the same time raised sufficiently to permit of the discharge of the molten or liquid mass or compound into the mold M through the mouth on thereof.

The selection of proper material for the mold M is of some considerable importance. The character of the interior surface of the mold is likewise important, and should be perfectly smooth. I have found that the best mold is that made of either brass or bronze. Molds made of malleable iron or cast-iron become deteriorated in a short time by use, while in the use of those made of iron the chloride of lead is apt to adhere to the sides thereof. The same objection has been found to the use of porcelain molds. Those made of lead require the exercise of care in use, owing to the tendency of the metal to melt, yet, nevertheless, good results may be obtained by the use of lead ones with care in the handling of them. The mold to which I give preference is one made of either brass or bronze and composed of two symmetrical sections m and m2, chamfered, as shown, for instance, in Fig. 4, and the two sections united to each other by means of hinges m3, held together by\ means of catches or pawls m6, secured to the extremities of the shaft m5, which is held in bearings m7, formed with one of the sections. These pawls or catches are operated by a lever m4, as shown, for instance, in Figs. 2 and 3. The two sections forming the crystallizing-mold M may be formed so that each will be of a uniform thickness of metal, and the thickness of each section varying from two to ve millimeters, according to the dimensions of' the crystallized metallic' plates to be formed. This similarity and uniform thickness of each section is for some purposes advantageous, for the reason that crystallization therein commences from each side of the mold, and therefore if the two sections are of equal thickness the cooling-point of each will be attained at the same time and the crystals forming in the mass will meet in the middle. The line of cleavage of the crystals will therefore be the same throughout the entire crystallized plate, substantially in parallel columns.

I have found that while it is preferable to have the two sections of the mold of equal thickness, yet at the same time it is not absolutely necessary; but when they are not of equal thickness of metal the cooling off of the material discharged into the same will be unequal, and as a consequence the line of meeting of the crystals will be more to one side of the mold than to the other, which may be advantageous in some instances.

When the molten or liquid mass or compound from the crucible F has been discharged into the casting-mold M, in a few minutes thereafter solidiflcation will take place in the cooling o of the same therein,and the plate cast or formed will become cystallzed. In some instances it maybe well to heat the mold M previaus to charging the molten or liquid mass or compound into the same-say to a temperature of 150 centigrade, more or lessand thereby obtain good results in the crystallization of the plate. /Vhen the plate crystallized has become solid to a greater or less degree, the sections of the mold are unclamped, and the plate then removed into a mold N for casting around the crystallized plate a frame of lead or other suitable material.

The bivalved framing-mold N consists of two sections n and n', made of cast-iron or other suitable material. The section n of the framing-mold N has an upper flange n2 around the sides thereof when in the form of a rect- IOO IIO

angular parallelopipedon and with a beveled i flange or rim n3 formed on the four interior sides of the bottom. With the section lnis formed a funnel-shaped trough or neck n4 for the introduction of material into the mold when the two sections 'n and n are clamped together by means of the pawls or catches a5 and n, rigidly secured to each end of the shaft m7, which is jou rnaledin bearings a8 and n.9, secured to the exterior surface of the section a. These pawls or catches are operated by a lever n10, which causes the pawls or catches ns and "a9 to engage with the strengthening-strip nu, formed with or secured to the exterior surface of the section n. The section n has an interior beveled rim nu, corresponding with the beveled rim n3 of the section n. The four sides or edges of the sections n are slightly deflected downward, and a series of niches or grooves 'm13 are formed in the under edges, constituting air-holes when the two sections are clamped together. In the section n', as shown in Fig. 7, two or more openings nl* are formed at suitable distances apart for the introduction of small pins for holding the crystallized plate in proper position in the mold to allow lead or other suitable material to become cast around the plate in the form, preferably, of a beveled frame, with a tongue or support 11,15, for a purpose to be presently described.

The manner of casting a frame around the crystallized plate will now be explained. The crystallized plate, having been removed from the mold M to the framing-mold N, is placed in the center thereof, so that the beveled rim of the mold will be in close proximity to the four sides of the rectangular-shaped plate, and in this form the section n of the mold is laid upon the same, so as to occupy the position shown in Fig. 7, and the two sections clamped together by means of the lever n10. Pins are now inserted through the small openings n in the section n', in orderto hold the crystallized plate firmly in position. The mold is then elevated and the liquid or molten lead poured in through the funnel-shaped trough n4, passing around the crystallized plate and in cooling off becoming solidly affixed to or cast around the four sides of the crystallized-plate in the form of a beveled frame or border.

IVhen the frame around the sides of the crystallized plate has become perfectly solid, the plate may then be removed from the mold, ready for further treatment or reduction to a metallic state or condition by electrolysis or chemical actions, in the following manner: The crystallized plate formed in the mold N is now placed in a glass canister or other receptacle G, containing water and ten per cent. (more or less) of sulphuric acid, the crystallized plates 2 being immersed in the solution in the glass canister G and alternated with plates of equal dimension of ordinary lead or articial charcoal 3, each having a tongue x, all the crystallized plates 2 being connected through their tongues or supports 07,15 with a wire 4, while the lead or charcoal plates 3 are connected through their tongues 00 with a wire 5, and the two systems of plates insulated from each other by means of the insulatingrods r, made of rubber or other suitable material, and from the canister G by means of the glass insulators 7", mounted on the horizontal bars r2, made of rubber or other suitable insulating material, in the bottom of the glass canister G, as shown, for instance, in Fig. S, the system of crystallized plates being connected or united to the negative electrode s of the dynamo S, while the system of lead or charcoal plates are united to the positive electrode 'n16 of the dynamo S, and in consequence of the electrolytic action which takes place the oxygen and chlorine are separated and caused to attack the system of lead or charcoal plates, while on the system of crystallized plates remain lead and cadmium metallic. The crystallized plates thus treated are then removed and immersed in another glass cannister or receptacle G', containing water and sulphuric acid in about the same proportions as hereinbefore mentioned. In this second receptacle G the crystallized plates are again alternated with others of ordinary lead or artificial charcoal, as in the previousinstance, and the two systems of plates, insulated, respectively, from each other and the glass canister G', are again united by two separate wires 6 and 7, connected with va dynamo S', as in the iirst instance described, with this exception that the negative electrode s is connected with the system of lead or charcoal plates through the tongues Qc, while the positive electrode m17 is connected with the system of crystallized plates through the tongue w15, as shown. in Fig. 9. By this second electrolytic action which takes place the cadmium metallic is deposited on the lead or charcoal plates and the hydrogen escapes and the oxygen is caused to attack the crystallized plates. The second electrolytio action having been permitted to take place, the crystallized lead plates may then be removed from the canister or receptacle G and thoroughly washed and dried in any suitable manner for such uses as required.

It will be found that crystallized metal lead plates produced by this method of treatment with the desired degree of porosity will have as well great consistency and rigidity and may be made of any form or dimension for electrical accumulators and other purposes.

Having thus described the nature and objects of my invention, what I claim as new, and desire to secure by Letters Patent, is

1. The method for the manufacture of a porous crystallized lead plate or other structure, which consists in subjecting the salts of lead and cadmium to fusion, then casting the mass in a mold and allowing it to crystallize therein, and then reducing the same to a metallic state, substantially as and for the purposes set forth.

2. The method for the manufacture of a porous crystallized metal lead plate, which consists in subjecting the chlorides of lead and cadmium to fusion, then casting the mass in a mold and allowing it to cool and crystallize therein, and then reducing the same to a metallic state by electrolytic action, substantially as and for the purposes set forth.

In witness whereof I have hereunto set my hand in the presence of two subscribing witnesses.

CLEMENT PAYEN. Witnesses: v

J. WALTER DOUG-nnss, HERMANN BORMANN.

IOO

IIO

IZO

Images