ELECTROFORMING by Carl M. Rodia Consultant, Trumbull, Conn. INTRODUCTION Electroforming is the general term describing the process of electrodepositing a metal on a mandrel producing an independent, mechanically viable, metal object that can stand alone when separated from the mandrel. Although bath chemistry employed in clectroforming is very similar to electroplating chemistry, the equipment and fixturing requirements differ considerably and require close attention if the economies promised by electroforming are to be realized. Whereas electrodeposits are used to enhance the surface properties of a substrate metal or nonconductor, electroforms are usually used as independent objects and are usually separated from the substrate mandrel after electrodeposition. Although good adhesion is invariably a necessity in electroplating applications, separability of electroform from substrate mandrel is always a criteria for success in electroforming. Mechanical or metallurgical bonding of an electroform to its substrate mandrel would negate the purpose of the process. For this reason, electroforming mandrels are usually made of materials that accept passivation processes, and mandrel design follows strict rules avoiding undercuts that would lock electroforms to mandrels. Electroforming can enable the user to manufacture complex shapes and surfaces at low unit cost. Many of the advantages normally associated with thermoplastic molding processes are available with the electroforming process. Seamless objects can be formed as well as complex shapes, which economically defy machining. The virtually perfect surface reproducibility available with electroforming processes makes them ideal for dimensionally exacting applications, such as lens mold production, phonograph record stampers, rotogravure printing plates, holographic embossing plates, and optical memory disk mold cavities, including compact disks (CD) and video disks. Information encoded on the average optical disk comprises impressions having an average mean diameter of 0.2 jm. This tolerance is well within the range of electroforming process accuracy, and disk mold electroforming is by far the most widely used application for the nickel electroforming process today. A variety of metals can be electroformed, offering the product engineer a wide selection of metallic properties from which to choose. In recent years, electroforming of special alloys has added numerous materials to the list of the more commonly electroformed metals, such as nickel, copper, and iron. SUBSTRATE MANDRELS An electroforming mandrel is the substrate, or shape or form the new electroform will take in the process. Mandrels are analogous to molds in the sense that the clectroformed surface will be the exact mirror image of the mandrel’s surface. Mandrels are usually designed to be separated from the electroform and used again and again in a production application. For some special products and applications, the mandrel is used only once and destroyed in the process of separation from its electroform. There are even cases where electroform and mandrel remain together, forming an integral product with both the substrate mandrel and the electroformed appendage working together as major parts of a finished product. Permanent mandrels can be used many times to produce numerous clectroforms. They are usually made of a durable metal, such as nickel, stainless stecl, or brass and can readily accept 378assivation or parting layer, usually a chromate conversion coating. Permanent mandrels are ually machined, cast, or clectroformed themselves to produce the shape to be replicated. jlectroforms produced on permanent or expendable mandrels can usually be used as permanent mandrels themselves, serving as substrates from which other electroforms can be de. Expendable mandrels can be used only once to produce a single electroform. They are destroyed in the process of separation from their electroforms. Expendable mandrels are analogous to “‘lost wax" molds in the sense that the substrate mandrel is destroyed or “‘lost”” in the process of manufacturing the product, Expendable substrate mandrels are used when there is need for only one electroformed jtem, such as in the case of objects of art, restoration work, special components, and so on. ‘They are also used when a particular surface can only be created in a medium that is not ‘durable enough to be used as a permanent mandrel, as in the case of optical disk masters and holographic plate masters. In both these cases, the substrate mandrel can only be recorded onto a photoresist surface. The microsurface topography of these surfaces, though readily ‘reproducible with clectroforming, is totally destroyed by the separation of electroform from the substrate, thereby necessitating production of a new mandrel for each new optical disk or hologram. ‘One redeeming aspect of electroforming disks and holograms is that the electroforms made from expendable photoresist mandrels can themselves be used in subsequent electroforming operations as permanent mandrels, thereby allowing for repeated use and replication of numerous “negatives” and “positives” by alternately treating each electroform as a permanent mandrel for the next generation. Expendable mandrels are typically made of soluble or low-melting-point materials such as aluminum, plastic, wax, glass, or low-melting alloys, such as solders containing tin, lead, and bismuth in varying ratios to yield metals with melting points in the 160 to 280°F range. _ Typical alloys are given in Table I. Other materials commonly used as expendable mandrels are lacquer-coated metals, wood, and paper. In this case, the lacquer seals the substrate, taking on its general shape. It is then _ made electrically conductive by chemical metallization with silver, nickel, or copper or by vapor deposition of these same metals. | All mandrels must receive some kind of surface treatment to ensure a clean separation from the electroform. Permanent metal mandrels made of brass, copper, nickel, stainless steel, aluminum, low-melting-point fusible alloys, and chromium have to be thoroughly cleaned and - Passivated using a chromate dip before electroforming. The passivation process prevents metallurgical bonding at the interface of mandrel and electroform, thereby enabling the two to be separated for subsequent usage. PERMANENT MANDRELS Aluminum as a Permanent Mandrel Aluminum is an amphoteric metal that will not accept adherent electrodeposits unless its Surface is properly treated with an immersion coating of a compatible metal. One popular method of pretreating aluminum is the deposition of an immersion coating of zinc called the zincate process. (Another known method is electroless nickel plating, but it is not Tecommended by the author.) After zincate, the aluminum mandrel is covered with a flash electroplating of copper to stabilize the surface. The zincated and copper-plated aluminum ‘Surface of the mandrel is now ready for the electroforming process selected. 1, Remove all dirt, oil, and grease from the aluminum surface by vapor degreasing. 2. Rinse with running water. 3. Etch the aluminum by immersion in a mild, warm alkaline etching solution. 379Table I. Low-Melting Alloys for Expendable Mandrels ee Melting Point Alloy No. (°F) Bismuth (%) Lead (%) Tin (%) Cadmium (%) a 1 158 50.0 26.7 133 10.0 2 158-190 42.5 37.7 13 85 a 255 55.5 445 _ = a 281-338 40.0 = 60.0 - 5 281 58.0 = 420 — “Eutectic composition. After 10-20 seconds, when gassing is continuous and uniform over the entire surface, remove the aluminum from the etch. 4. Rinse thoroughly in running water. 5. Remove smut from the aluminum surface by immersing it in 50% nitric acid. 6. Rinse in running water. 7. Apply zinc by immersion in the following solution: sodium hydroxide, 75 oz/gal; zinc oxide, 15 oz/gal; ferric chloride, 15 oz/gal; Rochelle salt, 1.3 oz/gal; temperature, 70-80°F. Dissolve the zine oxide in the sodium hydroxide solution, then cool it to room temperature. Before diluting, add predissolved ferric chloride and Rochelle salt and stir. 8. Rinse in hot water (90-1 10°F). 9. Remove zinc coating by immersion in a second 50% nitric acid bath (30-60 sec). 10. Rinse thoroughly in running water, 11. Repeat step 7 (zinc coating) for 10-20 sec. 12. Rinse thoroughly in running water to remove all residual zincate solution. 13, Electrodeposit copper onto the zinc-coated aluminum from a Rochelle salt copper cyanide plating bath: copper cyanide, 6.0 oz/gal; total cyanide, 6.5 oz/gal; sodium carbonate, 4.5 07/gal; Rochelle salt, 8.5 oz/gal; free cyanide, 0.5 oz/gal; temperature, 110-130°F; pH, 10.5 (max); current density, 24 A/ft?. Stainless Steel as a Permanent Mandrel Stainless steel alloys are commonly used as permanent mandrels in electroforming. These alloys have inherently passive surfaces, which facilitate repeated separation of mandrel and electroform in high-volume production situations. The corrosion resistance of stainless steel also adds to the life of the mandrels. Stainless stee! alloys can be machined to extremely close tolerances. The surface finish is extremely durable and resistant to damage and degradation. Products produced on stainless steel mandrels include lens molds, wave guides, screens, and nozzle tubes. Electroplated Metal Mandrels Metals normally not suited for use as electroforming mandrels, owing to their inability to form a passive parting surface layer, may be electroplated with a thin deposit of nickel or chromium. The chromium surface is passive and will facilitate separation of the mandrels from the subsequent electroforms. el is also passive and will readily accept a chromate treatment to ensure the separability of mandrel and electroform. Mild steel, copper, and brass are some of the base metal mandrel surfaces typically enhanced with chromium or nickel. Electroplated mandrels are not used to produce products demanding a high degree of dimensional precision. The plating on the surface of the mandrel can vary in thickness considerably and hence affect the size of the electroform. Plated mandrels are usually used to 380luce consumer products, such as coffee pots, bowls, pen caps, and other scamless containers. Copper and Brass Mandrels Copper and brass have long been chosen by artists and engravers for their work surfaces. ‘These metals are soft and chemically compatible with common photoetching processes. Both ‘metals etch well and can be readily passivated with chromate solutions. Nickel Mandrels "Nickel mandrels are used quite extensively in electroforming applications. Nickel passivates easily, is tarnish and stain resistant, corrosion resistant, mechanically durable, and relatively easier to machine than stainless steels. Nickel mandrels can be produced by the electroforming process and used in high-volume production processes where alternately electroformed positives and negatives can be used to create multiple mandrels from a single original. Nickel mandrels are used extensively in the CD manufacturing process where nickel disk “molds are created by the hundreds each day. Other uses for nickel mandrels are phonograph ‘record stampers, hologram molds, and builders’ hardware, such as switch plates, escutcheons, and plaques. Plastic and Other Nonconductive Mandrels Mandrels made of machined, molded, or case plastics are common. Large sheet stock is typically used for producing surface texturing rollers to emboss floor and wall coverings and ‘other laminatable products. Other applications include slush casting of vinyl rubber products such as doll molds and large detailed sheets such as printing plates. Rigid vinyl sheets were “commonly used in the preparation of mandrels for electrotype printers’ plates. The vinyl sheets were heated and pressed into the original metal type set. The images produced in the hot vinyl sheet by the metal type were metallized and used as the mandrel for electroforming a \onolithic printing plate. Today, this method has been replaced by computer typesetting “methods, but electroforming is still used by the printing industry for the production of fine _ rotogravure printing plates. _Metallization of Nonconductive Mandrels Nonconductive mandrels are quite useful in the electroforming industry. They offer Product design and manufacturing engineers expanded flexibility in product design and engineering. Nonconductive mandrels must be metallized or made electrically conductive so that the electrodeposit can be applied. The mandrel’s surface should be nonporous and mechanically stable and it should not move or have soft spots that can collapse under the Pressures of immersion in an air or mechanically agitated electroforming bath. A thin film of metal is applied to the nonporous surface of the mandrel. This can be done with a chemical silvering or mirroring technique or with similar reduction processes using nickel or copper. “Typically, the process is carried out by spraying the reagent containing the dissolved metal of choice simultaneously with a compatible reducing agent onto the surface of the mandrel. The chemicals combine at the surface, the conductive metal is reduced and coats the surface of the mandrel. Acceptable thicknesses range from 5-15 microinches of silver or copper. ‘An alternative method of metallization is vapor deposition. This technique involves placing the mandrel into a specially equipped vacuum chamber where the metal can be vaporized and Condensed onto the nonconductive surface. The method is widely used in the semiconductor industry, the optical disk industry, and the hologram manufacturing industry where the mandrel "Sizes are commonly small, fitting easily into conventional sized vacuum metallization chambers. 381When vacuum metallization processes are used, the mandrel must be made of a material that will not out-gas in the vacuum chamber. If the mandrel contains volatile material, it will be drawn out in vacuum and inhibit the proper adhesion of the metal deposit. Conventional electroless plating processes are not acceptable for mandrel metallization because they tend to bond strongly to the surface making separation of mandrel from electroform difficult. EXPENDABLE MANDRELS Expendable mandrels are used once and are discarded. Expendable mandrels are used in situations where only one electroform is needed or desired, such as with works of art or in mass production situations where the first clectroform made from the expendable mandrel can be used as a permanent mandrel for subsequent production of multiple copies. Phonograph record stampers, compact disk and video disk stampers, and holographic plates all fall into this category of production, Expendable mandrels are generally made of nonmetallic, nonconductive material and hence require metallization after preparation to accept the electrodeposit. Phonograph record mandrels are aluminum disks coated with a soft lacquer material. Special computer controlled Cutting lathes are used to cut a modulated spiral groove into the lacquer’s surface. After cutting, the disk is metallized with silver and electroplated, usually with nickel. Nonconduetive surfaces such as wood, wax, plaster, or plastic require special cleaning operations and should be made impervious to water absorption if the mandrel is porous in nature. A conductive film, such as reduced silver, is applicd over the mandrel to be electroformed. A sensitizing solution is sprayed on the nonconductive surface until a continuous film is obtained. The surface is rinsed and then the silver and reducer are applied through a double-nozzle gun. Optical disk, compact disk, and hologram mandrels are prepared by laser light exposing certain data points or tracks on a photosensitive medium, then washing away the reacted material, leaving the information etched into the surface of the photosensitive coating. To electroform a negative on this surface it must be made clectrically conductive, This is accomplished by a vacuum metallizing process. Nickel is then clectroformed onto this conductive surface producing the negative plate. Further details are given in the chapter *Metallizing Nonconductors.”” When the electroformed metal negatives are separated from the “lacquer” phonograph record master or the coated optical disk or hologram master, the soft medium is disrupted and cannot be used again. The negative metal electroforms thus produced now serve as the new permanent mandrels from which subsequent “positive” and other “‘negatives” can be electroformed. The ‘‘negatives” produced are uscd for the thin, flat metal molds in the manufacturing of plastic products. DESIGN OF MANDRELS FOR INTERNAL AND EXTERNAL SURFACES Electroforming mandrels are designed to produce the desired pattern, shape, or surface typography on cither the inside or the outside surface of the electroform. When the outside surface of a part is the significant area, the internal surface of the mandrel requires special care. Some helpful suggestions for preparing negative and positive mandrels are provided below. Internal Surface (Negative Mandrel) Sharp internal angles should be avoided in the design. Sharp comers or deep recesses will exhibit very low current density in the electroforming Process and hence will receive proportionately less electrodeposited metal. This will result in a weakness at corners and recesses (Fig. 1). 382<———— NICKEL DEPOSIT <———— MANDREL Fig. 1, Sharp internal corners will create a weakness and should be avoided in the design. Ifacute angles or deep recesses are unavoidable, measures can be taken to compensate for the low deposition rates associated with these areas. Fillets can be used, as illustrated in Fig. 2, The fillet, usually made of solder or other low-melting-point alloy, is applied after the initial electroformed layer is deposited. New metal is then electroformed over the fillet, and -electrodeposition continues until the desired thickness is achieved, Another technique used for compensating for low current density areas in sharp comers and recesses is the use of auxiliary anodes. Auxiliary anodes are small, specially constructed _ metal anodes that are carefully positioned adjacent to the sharp internal angle or recess (Fig. 3). ‘These anodes are usually made of the same material as the primary bath anode system and are _ connected in parallel to the anode circuit. They have the effect of supplying anodic current and _ thaterial in the immediate vicinity of the isolated zone and have the desired compensating _ effect, thereby increasing the electroforming rate and providing a balanced electrodeposit. Auxiliary anodes can be quite useful. They are most helpful in high volume production applications where the cost of the careful engineering of special fixtures can be amortized over hundreds or thousands of electroformed units, _ External Surface (Positive Mandrel) The above precautions also apply to positive mandrels, but to a lesser degree. External Surfaces are easier to prepare than internal surfaces. An electroform intended for production on _ permanent mandrel should be designed with enough draft to permit removal of the mandrel Fig. 2. Fillets can be used when sharp corners cannot be avoided. SOLDER FILLET <—________ SECOND NICKEL DEPOSIT -<—— FIRST NICKEL DEPOSIT —<—_——. MANDREL 383<= PRIMARY ANODE ~<—___—_—. AUXILIARY ANODE <——_ NICKEL DEPOSIT ~<—— _ MANDREL Fig. 3. An auxiliary anode can compensate in low current density areas, especially in high volume applications. without damaging the electroform. If the conformations are such that these conditions cannot be met, expendable mandrels will probably be required, CHOICE OF METAL AND ELECTROFORMING BATHS A variety of metals having properties suitable for electroforming are available. Because many molding processes that utilize thin metal molds involve heat transfer through the mold to a thermoplastic of heat-setting material, the thermal conductivity of the metal selected is significant. Its durability, abrasion, and scratch resistance are also important’ when considering the quantity and quality of the moldings being manufactured. Micro throwing power of the particular bath is significant in certain special applications, such as video disk, phonograph record, and hologram mold electroforming because the tolerances are extremely Tigid. The capability of the metal selected to maintain or form a passive surface is significant if, as in the case of many flat, thin molds, the clectroformed piece is to be used as a mandrel for subsequent electroforming steps, as in the case of Fresnel lenses, optical disks, or phonograph records where the first mandrel is considered a master and subsequent electroformed negatives and positives are made in an expanding “tree” process. A permanent mandrel must be treated to form a parting film on its surface before plating to ensure easy separation afterwards. Common methods of forming separating films involve passivation in chromate solutions, anodic treatment, or application of an absorbed film—only one or two molecules thick—of a colloidal material, such as egg albumen. The metals most commonly used in electroforming are copper, nickel, and iron. Copper Copper is utilized when a highly conductive mold is required, and where the oxidation commonly associated with copper surfaces can be tolerated by the process. Copper, because of its softness, is generally not recommended for use in compression molding operations because deformation of the mold can occur at the high pressures associated with compression molding above the 30,000-40,000 psi range. Although the surface of a copper electroform is not chemically passive, it will readily form a negative separating film onto which subsequent 384ble I. Copper Electroforming Baths smposition Sulfate Fluoborate Copper sulfate (oz/gal) 30-32 — Copper fluoborate (0z/gal) - 30-60 juoboric acid (oz/gal) — topHO3-1.4 sulfuric acid (oz/gal) 6-10 = ¢mperature (°F) 80-110 80-120 Voltage Usually less than 6 412 urrent density (A/ft2) 30-150 75-300 Jaume at 80°F - 29-31 fardness (DPH) 51-170 40-75 fensile strength (psi) 35,000~42,000 17,000-32,000 llongation, 2 in. (%) 5-25 34 Internal stress, tensile (psi) 0-5,000 = gencrations of electroforms can be plated. The passive layer effectively separates the copper from the electroform grown on it, and the two are easily separated when plating is complete. Copper electroformed molds are not recommended for applications utilizing thermoplas- tic molding compounds containing abrasive fillers because copper’s softness leads to rapid wear and scratching under these conditions. Typical formulations are given in Table II. Nickel A great deal of process research and development has been done in nickel plating, “particularly in the sulfamate process, over the past 25 years. The low stress characteristics of the metal, as deposited from this bath, along with inherent ductility, thermal conductivity and relative hardness, and corrosion resistance make it an attractive choice for thin metal molds. Lens manufacturers, phonograph record and video disk manufacturers, and fine printing plate makers have all found nickel to be ideally suited for the high temperature conditions, Formulations are given in Table III. Iron ‘The primary use for iron has been as a substitute for nickel during periods of extreme shortages or restricted usc. Iron baths are classically operated at extremes of high temperature and low pH and hence are objectionable. Iron electroforms are very brittle and must be annealed before use. They also are prone to immediate rust formation and must be chromium Table III. Nickel Electroforming Baths Composition Sulfamate Fluoborate Watts Nickel sulfamate (o2/gal) 40-60 = Nickel fluoborate (0z/gal) — 40-60 _ Nickel chloride (o7/gal) 0-2 = ori acid (o2/gal) 46 3-5 femperature (°F) 100-140 120-130 pH (clectrometric) 35-45 3.0-4.0 Current density (A/F) 25-200 25-100 Tensile strength (psi) 60,000-110,000 56,000-80,000 rdness (DPH) 140-250 130-250 Elongation, 2 in. (%) 5-30 10-32 Internal stress, tensile (psi) 1,000-6,000 15,000-24,000‘Table IV. Iron Electroforming Baths Composition Chloride Fluoborate Ferrous chloride (o7/gal) 30-60 - Calcium chloride (oz/gal) 15-20 — Iron fluoborate (oz/gal) = 20-30 ‘Sodium chloride (oz/gal) — 15 ‘Temperature (°F) 190-200 135-145 pH (clectrometric) 015-15 2.7-3.0 (colorimetric) Current density (A/f*) 20-80 20-100 Baume at 80°F — 19-21 Hardness, Brinell 125-220 — ‘Tensile strength (psi) $0,000-65,000 - Elongation, 2 in. (%) 10-30 = Internal stress, tensile (psi) 15,000-40,000 - plated immediately to preserve the iron surface for molding applications. Typical baths are shown in Table IV. CONTROL OF STRESS IN ELECTROFORMS Nickel Two kinds of internal or residual stress may be present in the electrodeposited nickel during electroforming: tensile, when the deposit tends to contract or pull away from the mandrel at the edges, and compressive, when the deposit tends to expand or become larger than the mandrel. Stress effecis have been studied intensively during recent years because of their importance in preventing curling and cracking around the edges (tensile stress), or in preventing blistering or buckling (compressive stress). Factors found to affect the level of residual stress include bath composition, temperature, current density, grain size of deposit, addition agents, and impurities such as iron, aluminum, and chromium. Most clectroforms should be prepared in an electrolyte controlled to produce deposits having an intemal stress of no more than 1,000-10,000 psi tensile. This will minimize the problem of cracking, blistering, and distortion of the electroform when removed from the mandrel. Sulfamate baths have the inherent advantage of producing oxygen-type addition agents for low internal stress. Because of the sulfur content of deposits made in Watts baths with such additives, it may be necessary to limit the temperatures to which the electroform may be exposed in use to 700°F maximum. At higher temperatures, sulfur-containing deposits suffer embrittlement. Copper Copper is normally deposited with low compressive stress values suitable for electroforming. It is possible to control the stress in deposits from the acid copper electrolyte from 400-2,000 psi tensile, The stresses in deposits from fluoborate copper are slightly higher. Iron Iron deposits from the all-chloride electrolyte can be controlled at 15,000-40,000 psi tensile. Solutions operated at higher temperatures will produce deposits having the lower stress values. Also, the presence of high ferric ion concentration will produce deposits of high stress and low ductility. Deposits produced from the fluoborate electrolyte will have higher stress values, which limit the number of electroforming applications. 386EQUIPMENT There are certain features that are commonly inchided in electroforming equipment systems, which differ from conventional plating equipment. Electroforming tanks are usually designed to accommodate the particular shape and size of clectroforms being produced. Agitation systems are usually included to enhance the high speed deposition. Power supplies just output ripple characteristics consistent with the mechanical properties desired on the formed deposit. Special rectifier controls that automatically raise plating current from initially Jow starting current to high speed levels are also desirable in most production applications where close monitoring of plating conditions is essential. A high degree of electroform thickness uniformity in the electroforming process, as in the electroplating process, can be elusive due to the varying current density from shape to shape. For symmetrical mandrels, the uniformity of electroforming thickness can be enhanced by rotating the mandrel (cathode) in the bath. Rotation has the effect of continuously reorienting the cathode with respect to the anode, thereby eliminating the current density effects in one direction. Shields and auxiliary anodes have been used in conjunction with rotary mandrels to further improve the distribution of the deposits. In the optical disk industry where flat, round Jectroforms of the highest precision are required, clectroform thickness distribution tolerances of plus or minus one micron have been successfully achieved.