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Publication numberUS3809552 A
Publication typeGrant
Publication dateMay 7, 1974
Filing dateNov 8, 1971
Priority dateNov 8, 1971
Publication numberUS 3809552 A, US 3809552A, US-A-3809552, US3809552 A, US3809552A
InventorsKlein G
Original AssigneeMallory & Co Inc P R
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Method for making an anode
US 3809552 A
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Description  (OCR text may contain errors)

G. P. KLEIN May 7, 1974 METHOD FOR MAKING AN ANODE 2 Sheets-Sheet 1 Filed Nov. 8. 1971 L V HM b 1 May 7, 1974 G. P. KLEIN 3,809,552

METHOD FOR MAKING AN ANODE United States Patent 3,809,552 METHOD FOR MAKING AN ANODE Gerhart P. Klein, Manchester, Mass., assignor to P. R. Mallory & Co., Inc., Indianapolis, Ind. Filed Nov. 8, 1971, Ser. No. 196,328 Int. Cl. B22f 3/00 US. Cl. 75-208 R 6 Claims ABSTRACT OF THE DISCLOSURE The process for producing anodes on fixtures comprises the following steps. A stringer with risers of film forming metal welded at right angles to the stringer is lowered into row cavities in an elastomeric mold which have been filled with a film forming metal powder slurry. The risers are centered in the cavities. The powder slurry is frozen with the risers held in registration with the mold pattern. After solidification of the slurry the stringer is withdrawn and the frozen anodes are pulled out of the mold cavities. Predrying preferably with the risers in place prior to freezing removes excess water so that the anodes after thawing will retain their shape and have suificient strength to withstand the limited handling necessary to transfer them to the sintering equipment. Sintering is preferably done in a horizontal furnace, and preferably special fixtures or a belt to hold the stringer in either horizontal or vertical position so that none of the anodes come in contact with any of the parts of the system while the stringers are carried through the furnace for sintering. The stringers are then removed from the belt for further processing.

BACKGROUND OF THE INVENTION In the US. Pat. 3,422,515 method for making porous anodes by freezing wet powder and sintering is described. The result of this process is anodes in the presintered condition without risers. The risers are attached to pre' sintered anodes by welding. Following the welding, the anodes are given a final sintering treatment in vacuum or inert gas atmosphere. After sintering, anodes may be attached to processingbars or stringers by welding.

Even though this process is being used successfully one realizes that numerous operations are required to fabri-- cate anodes on stringers from tantalum powder and wire. Besides the casting of anodes from wet tantalum powder slurry in rubber molds and freezing, several steps are required to obtain presintered anodes, attach risers, resinter the anodes with risers, and finally weld the anodes with risers to stringers.

For several reasons it would be most desirable to produce anodes on stringers without the need of two sintering steps and the welding operation. Firstly, all handling may introduce mechanical damage and/or contamination in sintered anodes and should be avoided. Best results are obtained if sintered anodes are kept separated from each other and are not allowed to touch any processing fixtures, equipment, or other solid structures that can lead to mechanical abrasion or other damage.

Secondly, the welding operation requires a high degree of accuracy in positioning the leads on the anode. Elaborate mechanization is needed for efficient parts handling at this stage.

Thirdly, during final sintering anodes are stacked in crucibles and some degree of sintering between anodes is unavoidable. The resulting inter-anode bonds have to be broken by force which is thought to be harmful to consistant electrical characteristics of finished capacitor devices.

It is an object of the present invention to reduce the number of steps required for the production of capacitor anodes.

It is another object of the present invention to provide,

FIG. 2 is a view of another stage of fabrication in the present invention. I

FIG. 3 is a view of the stringer and risers after insertion into the mold cavity. A FIGS. 4(a) and (b) are views of the stringer and risers after anodes have been frozen therein the mold and the risers have been removed from the mold.

FIG. 5 is a schematic representation of several fabrication steps after the stringers and risers have been removed from the mold.

The process of the present invention eliminates some or all of the shortcomings of the conventional process, and further provides a direct path from the frozen anode to the anode on the stringer with only one sintering operation, elimination of welding of anodes to risers, and elimination of any physical contact between anodes from the time they are removed from the mold in a frozen state to the final capacitor.

A particularly attractive feature is to be seen in the fact that the anodes that are attached directly to a stringer can be electro-processed after application of a band of elastomeric material such as silicon rubber on the risers above the anode. This eliminates the need to use polytetrafluoroethylene washers for control of manganese dioxide build-up.

Anodes thus fixtured can be processed in a variety of ways. Batch processing can be done by combining stringers into processing heads. Linear processing schemes in which rows of anodes pass through subsequent processing stations are particularly attractive for reasons of uniformity of properties, control of profiles of critical process variables (temperature, concentration, etc.) and easy access to individual anodes for in-process control.

SUMMARY OF THE INVENTION The process for producing anodes on fixtures comprises the following steps. A stringer with risers of film forming metal welded at right angles to the stringer is lowered into row pf cavities in an elastomeric mold which have been filled with a film forming metal powder slurry. The risers are centered in the cavities. The powder slurry is frozen with the risers held in registration with the mold pattern. After solidification of the slurry the stringer is withdrawn and the frozen anodes are pulled out of the mold cavities. Predrying preferably with the risers in place prior to freezing removes excess water so that the anodes after thawing will retain their shape and have suflicient strength to withstand the limited handling necessary to transfer them to the sintering equipment. Sintering is preferably done in a horizonal furnace, and preferably special fixtures or a belt hold the stringer in either horizontal or vertical position so that none of the anodes come in contact with any of the parts of the system while the stringers are carried through the furnace for sintering. The stringers are then removed from the belt for further processing.

3 DETAILED DESCRIPTION As can be seen in FIG. 1, stringers 10 with risers 20 attached at right angles are made from film forming metal, including aluminum, tantalum, titanium, and niobium. However, the material is preferably tantalum. The stringer includes a ribbon 11, and the risers 20 are made from wire which preferably includes some kind of barbed hook or head 21 at the free end. The risers 20 are welded to the stringer ribbon 11 as indicated at 12, with accurate predetermined spacing between risers. Typical non-limiting dimensions of the ribbon are: .010" thick, .125" wide, 2.0" long. Typical risers may have the following (non-limiting) dimensions: diameter .020, length .3" to .75", with a head diameter of .030". The spacing between risers is at least .1" center to center.

A rubber mold 30 for anodes is fabricated in a known manner for freezing molded anodes. For example the master pattern may be machined from aluminum or other suitable materials and the mold cast from elastomeric material such as silicone rubber. Mold 30 contains cavities 31 (preferably cylindrical) in a row with approximately the same center to center spacing as the risers on the stringer. The rubber mold contains holes 32 for locating it on a base plate 40 by means of guide pins 33.

Mold 30 is placed on base plate 40. Cavities 31 are filled with water or other freezable liquid preferably carefully excluding trapped air. This may be done, for example, by submerging the mold in water and forcing a jet of water into the cavities. A washing bottle made from elastomeric material such as polyethylene with the nozzle held beneath the surface of the water is suitable for cavities in a single row. Excess water is removed from the mold, for example with a squeegee.

An excess of tantalum powder slurry is placed on the mold and the powder is allowed to fill the cavities. Excess powder may be scraped off with a hard squeegee.

As shown in FIG. 2, a fixture 50 for holding stringer 10 with risers 20 on guide pins 33 is used to guide risers 20 into cavities 31 filled with powder slurry into the position shown in FIG. 3. The risers with the barbed end 21 preferably extend to the bottom of the cavity in cases where the anode diameter is of the order of the diameter of the riser. If the anode diameter is several times the diameter of the riser then the riser need only extend part way into the anode, as discussed hereinafter.

As in the process described in US. Pat. 3,422,515 the slurry contains an excess amount of water which often leads to a collapse of the anodes after freezing and thawing outside the mold. For this reason, the water content of the slurry is preferably reduced for example from 6- 8% to about 4-6%. This is done by drying for example under an infrared lamp, or in a warm air stream. This step is important since too much drying would lead to difficulties on freezing, and subsequent handling, while too little drying would lead to loss of shape and possible falling off risers.

After drying, the whole fixture is placed in a freezer, refrigerator or other system which allows the slurry in the cavities to freeze solidly. A final temperature of C. below freezing is desirable, but it can be anywhere between the freezing point of the liquid, i.e. water, but preferably above the temperature at which the mold material loses its elasticity.

After the slurry has been frozen, fixture 50 holding the stringer is pulled up and the anodes A solidly frozen around the risers will be pulled out of the cavities 31 as shown in FIG. 4. The barbed end 21 (FIG. 1) prevents the risers from being pulled out without the anodes. Extension of the risers to the bottom of the mold in the case of small anodes assures that the anode will come out as a whole. They might otherwise break where the cross section of the frozen mass was reduced by the barbed or headed section of the riser. With larger anodes this is less of a problem. To facilitate removal of larger anodes it may be preferable to use molds with cavities with a slight draft or taper on the walls.

It may be desirable to provide storage between removal from the mold and subsequent sintering for the frozen anodes. They can be stored either while frozen, or in the thawed condition. However because of greater insensitivity to handling the frozen condition is to be preferred. Storage in liquid nitrogen is convenient but may produce some difficulties when the anodes are removed from storage and exposed to the atmosphere. A significant amount of moisture may condense on the anodes and fixture because of the low temperature and this may lead to excess moisture in the anodes and loss of shape as described before. Rapid thawing by exposure to intense infrared radiation can minimize this problem. Otherwise storage at temperature closer to the melting point of the liquid would be more desirable.

The anodes can also be stored in the thawed state as long as drying or additional condensation are prevented. For example, the stringers with anodes can be stored and handled while hanging freely in an atmosphere saturated with moisture. Obviously the stringers must be handled very gently to avoid loss of powder.

The stringers 10 with frozen or moist anodes are transferred to the sintering equipment. For example, a horizontal sintering furnace 60 may be used having inert gas or vacuum. For example, an inert gas such as argon may be introduced through an inlet 66 and exit through furnace extensions 63 and 64. A continuous refractory metal belt 70 driven at constant speed by a suitable power source around wheels 71 and 72 is provided with fixtures to hold individual stringers in either horizontal or vertical position for transport through the hot zone 62 provided by heating elements 61. The stringers must be held in such a way that the anodes A ride freely through the fur-\ nace 60 without touching any part of the system. Prior to entering the extension tubes 63 the anodes are dried for example by means of infrared lamps 73. Reflecting structure or insulation 65 may be used to hold the heat in the furnace. Sintering times vary according to the type of powder used, and whether complete or partial sintering is to be effected. In general however, sintering temperatures of from about 1500 to about 2200 C. may be used. For example, final sintering of 10 micron powder requires 15-30 minutes at 2100 C. whereas 4 micron powder requires only 2-10 minutes at this temperature. Presintering alone requires less time, or lower temperature, or both. Typical presintering conditions for example, are 1850 1950 C. for 110 minutes.

If presintering is to be followed by final sintering in conventional batch type furnaces, then the stringers may be placed on racks and treated as conventional anodes are for sintering.

Electro-processing is done following the procedures similar to those used for anodes on risers made by conventional techniques. An anodic oxide is formed on the anodes according to known techniques. For solid capacitors a solid electrolyte is formed on the oxide, for example, by decomposition of manganese nitrate to form manganese dioxide. The anodes can also be used in wet electrolyte capacitors using known electrolytes such as sulfuric acid.

What is claimed is:

1. In a method of making a body suitable for use as an anode in an electrical device, the steps of shaping using mold means a mass including film forming metal powder and a freezable bonding agent around a headed or barbed portion of an anode riser, freezing the bonding agent to bond together powder around the headed or barbed portion of the anode riser to provide a shaped mass, removing the shaped mass from the mold means, and sintering the shaped mass to form a rigid body including the anode riser suitable for use an an anode in an electrical device.

2. The method of claim 1, wherein the step of removing the shaped mass from the mold means includes applying removal force to the anode riser.

3. The method of claim 1, wherein the step of shaping the mass around the headed or barbed portion of the anode riser includes the step of shaping the mass in a mold cavity prior to freezing the bonding agent of the mass while in the mold cavity and wherein the step of removing the shaped mass from the mold means includes applying removal force to the anode riser.

4. The method of claim 2, wherein the film forming metal powder is selected from the group consisting of Al, Ta, Ti and Nb, wherein the anode riser is of the same material as the powder, and wherein the freezable bonding agent includes water.

5. The method of claim 3, wherein the step of shaping the mass around the headed or barbed portion using a mold means includes the step of placing the headed or barbed portion of the anode riser in contact with the botsom of the mold cavity.

6. In a method of making a body suitable for use as an anode in an electrical device, the steps of shaping using a mold cavity a mass including film forming metal powder 6 and a freezable bonding agent around a headed or barbed portion of an anode riser, freezing the bonding agent to bond together metallic powder around the headed or barbed portion of the anode riser to provide a shaped mass, and removing the shaped mass from the mold cavity by means including the application of force to the anode riser.

References Cited UNITED STATES PATENTS 3,422,515 1/1969 Klein --222 3,424,952 1/1969 Vierow 75-200 3,476,557 11/1969 Fincham 75-222 3,627,520 12/ 1971 Rogers 75-222 LELAND A. SEBASTIAN, Primary Examiner B. HUNT, Assistant Examiner US. Cl. X.R.

mczs I i p Page 1 I a UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 80 5 Dated 7/ Inveritofls) Gerhart P. Klein It is certified that error appears in the aboveidentified patent and that said Letters Patent are hereby corrected as shown below:

Col. 1, line 15 delete film forming metal powder" and after "slurry" insert-"including a freezable bonding agent and filmforming metal powder"- Col. 1, line 37, delete 'the" and substitute therefore ---a---.

Col. 1, lines 43. and 44, delete "one realizes that" Col. 1, line 53, 'delete "all" Col. 1, line 59,- delete "can lead to and substitute therefore ---may result in-. a I

Col. 1, line 60, delete "the" and substitute therefore --a--.

Col. 1, lines Bland 68, delete "consistant" and substitute therefore consistent--.

Col 2, delete lines 6 and 7.

Col. 2. line 25, delete "eliminates" and substitute therefore -"helps minimize---.

Col. 2, 1ine2 6, insert ---of making anodes--after"process".

Col. 2, lines 27-29, delete "provides a direct path from the frozen anode to the anode on the strin%er with onl one sintering operation, elimination of I and substltute t erefore--e iminates the steps nf'-- F PO-1O5O (10-69) I USCOMM-DC suave-ps9 U 5 GOVERNMENT PRINTING OFFICE 8 59. 93 o rage a UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,809,552 Dated 05/07/74 Inventofls) Gerhart P. Klein It is certified that error appears in the above-identified patent and that saidLetters Patent are hereby corrected as shown below:

Col. 2, lines 29 and 30, delete "elimination of any" and substitute therefore helps minimize-- Col. 2, delete the paragraph beginning at line 33 in its entirety.

Col. 2, line 51, delete on fixtures".

C01. 2, lirfi56,'insert ---slurry including-before "film"; same line delete "slurry" and substitute therefore--freezable bonding agent-.

C61. 2, line57, delete "powder".

Col. 2, line 62, delete "water" and substitute therefore freezable bonding agen C61. 3, line after "with" insert-a freezable bonding agent such as-; same line after "other" insert ---suitable Col. 3, line 59, after "the" insert --freezab1e bonding agent of the-.

C01. 3, line 82, delete "liquid, ie" and substitute therefore -freezab1e bonding agent such as, for example,

Col. 4, line 15, delete "can" and substitute therefere -may---.

C01. 4, line 41, after "of" insert ---film forming metal-.

FORM USCOMM-DC 60376-P69 .5. GOVERNMENT PRINTING OFFICE! 8 O I J-TdgU 0 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. i 3, 809, 552 Dated 05/07/74 Inventor-(s) Ger hart P. Klein It is certified that error appears in the above-identified patent and fihat said Letters Patent are hereby corrected as shown below:

Col. 4, line 56, after oxide" insert --layer---; same line delete on and substitute therefore -over- Col. 4, line '58, delete "is formed on the oxide" and substitute therefore -'--.layer is formed over the anodically formed oxide layer-.

sighed and sealed this 4th day of February 1975.

(SEAL) Attest; V

McCOY M. GIBSON JR. 0'; MARSHALL DANN Attesting Officer Commissioner of Patents FORM PC4050 (169) USCOMM-DC 60376-P69 U.$. GOVEINHEINT PRINTING OFFICE: 9 o

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4002473 *Nov 29, 1973Jan 11, 1977P. R. Mallory & Co., Inc.Method of making an anode
US4299627 *Sep 6, 1979Nov 10, 1981Toyota Jidosha Kogyo Kabushiki KaishaCompression molding solid electrolyte, forming oxygen sensor in solid electrolyte, sintering, forming electrode on exterior surface
US8259435Nov 1, 2010Sep 4, 2012Avx CorporationHermetically sealed wet electrolytic capacitor
US8451586Sep 13, 2011May 28, 2013Avx CorporationSealing assembly for a wet electrolytic capacitor
US8514547Nov 1, 2010Aug 20, 2013Avx CorporationVolumetrically efficient wet electrolytic capacitor
US8605411Sep 16, 2010Dec 10, 2013Avx CorporationAbrasive blasted conductive polymer cathode for use in a wet electrolytic capacitor
Classifications
U.S. Classification419/9
International ClassificationH01G9/00, B22F3/00
Cooperative ClassificationH01G9/0029
European ClassificationH01G9/00M
Legal Events
DateCodeEventDescription
Oct 16, 1990ASAssignment
Owner name: U.S. CAPACITORS INC., A CORP OF DE
Free format text: CHANGE OF NAME;ASSIGNOR:ARCOTRONICS INC., A CORP OF DE;REEL/FRAME:005481/0168
Effective date: 19900507
Nov 6, 1989ASAssignment
Owner name: ARCOTRONICS INC., DELAWARE
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:EMHART INDUSTRIES, INC.;REEL/FRAME:005315/0528
Effective date: 19890924