DECORATIVE CHROMIUM PLATING by Donald L.

Snyder
Atotech USA Inc., Rock Hill, SC
Electrodeposition of decorative chromium is the principal means of imparting the physical and chemical properties of chromium to the surface of less expensive and easier-to-form materials such as steel and plastics. The most desirable properties of chromium as a metal coating are its inherent protective and decorative characteristics. The deposit's high reflectivity is retained in service because of chromium's excellent tarnish, corrosion, wear, and scratch resistance. Decorative chromium is almost exclusively plated over a nickel electrodeposit, which can easily be plated over substrates such as plastics, steel, aluminum, copper alloys, and zinc die castings. Nickel is preferred because it protects the substrate from corrosion, helps give chromium a white color, and is protected from surface oxidation by the chromium. Stainless steel is the only substrate that is frequently plated directly with chromium, but a nickel preplate before chromium is also used. Multiple or single layers of nickel and copper can precede the nickel/chromium deposits depending upon the intended use of the part. Decorative chromium deposits typically are plated in the 2-20-millionths-of-an-inch range. Thicker deposits tend to be duller and contain visible cracks. The traditional chromium deposit is produced from an electroplating electrolyte containing hexavalent chromium ions and has a pleasing bluish white decorative appearance. About 1975, a chromium electrolyte containing the less toxic and less hazardous trivalent chromium ion began replacing many decorative hexavalent chromium electroplating instal~ lations. Depending upon the process, trivalent chromium electrolytes can either produce a metallic white deposit almost identical in appearance to the bluish white hexavalent chromium deposits, or a deep-looking pewter or stainless steel appearing deposit. In almost all chromium plating applications, both hexavalent and/trivalent chromium deposits are interchangeable with each other; however, one or the other process might offer unique advantages. Fluoride will etch substrates, such as steel resulting in iron contamination of the plating bath.

CHEMISTRY FOR HEXAVALENT CHROMIUM

Hexavalent chromium electrolytes require a source of chromium and one or more catalysts in order to plate. The formulation Of the traditional process, called the conventional bath, contains hexavalent chromium and sulfate as the only catalyst. Proprietary additives can be added to the conventional hexavalent chromium plating bath formulation to enhance particular plating operations or the deposit's properties. In most cases, these proprietary processes are called mixed-catalyst baths since the additives contain at least one additional catalyst in addition to sulfate. Fluorides are most commonly used as the second catalyst. Mixed-catalyst baths are used when their special properties are required, but they are more expensive to operate than are conventional processes. They typically plate at faster speeds, have better coverage, have wider bright ranges, and are more tolerant to impurities. They are also less sensitive to current interruptions and can be plated over more passive surfaces. The basic formulations of both types 01~hexavalent chromium processes are very similar. They consist of chromic trioxide (CrO3), which when combined with water forms chromic acid (H2CrO4), and the sulfate ion (SO4) added in the form of sulfuric acid or a sulfate salt. Even though chemically incorrect, in most plating literature solid chromic trioxide is commonly referred to as its hydrated form, chromic acid.

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A number of sometimes conflicting theories have been proposed to explain the very complex mechanism of hexavalent chromium electroplating. Basically, they all resemble the following multiple reactions that are presented in a simplified form. CrO 3 + H20 --> HzCrO4 --->CrO4 -2 + 2H + 2H2CrO 4 --->H2Cr207 4- H20 Deposition reaction: Cr207 -2 + 14H + + 1 2 ( e ) ~ A T --> 2Cr + 7H20 (3)
"-'->

(1) (2)

Cr207 -2 4- 2H + + H20

CAT is a required catalyst, e.g., sulfate and/or fluoride, while (e) refers to an electron. The plating efficiency of reaction (3) is <--20% depending upon the catalyst and the current density. Side reactions: 2H + + 2(e) --->H2(gas) + mist (H2SO 4 4- C r +6 4- H20 ) (4)

This reaction consumes -->80% of the available power. The mist can be trapped within the tank by the use of mist controls or surface tension reducers, Cr207 -2 4- 14H + + 6(e) --->2Cr +3 + 7H20 2Cr +3 + 302 - 6(e) PbO2>2CrO 3 (5) (6)

Reaction (6) is catalyzed by the PbO 2 film on the lead anode. Dilute conventional formulations consist of --250 g/L (33 oz/gal) chromic trioxide ("chromic acid"), with --2.5 g/L (0.33 oz/gal) sulfate. Concentrated conventional baths contain --400 g/L (53 0z/gal) chromic trioxide and 4.0 g/L (0.53 oz/gal) sulfate. In practice, however, concentrations in between these are used. The dilute formulation is extensively used to give good coverage, moderate nickel substrate activation, and consistent current efficiency. It also has a lower cost to originally make up, plates faster, and produces less waste to treat. The concentrated formulation gives better coverage and greater resistance to impurities and requires lower operating voltages; however, it is more expensive to operate because of its higher chromium concentration and the resulting additional chromium to be .waste treated. A critical point in all bath formulations is the requirement for close control of the CrO3/SO4 weight ratio needed to produce consistent plating results. Ratios of between 80:1 and 130:1 are typical, with a ratio of --100:1 being most common for conventional processes. A low ratio results in relatively poor throwing and covering power and an increased limiting current density. Higher ratios result in slow deposition rates, produce dull deposits, have increased covering power, and decreased limiting current density. The addition of a fluoride catalyst necessitates an adjustment in the CrO3/SO4 weight ratio. Ratios of 170:1 to 210:1 are required, with 190:1 being most typical. The chromium concentrations for both the dilute and concentrated mixed-catalyst formulations are the same as for conventional baths; however, the sulfate concentration is lowered. Unlike most plating baths in which the metal, M, is present in solution as a cation, M +, the chromium metal is present as an anion complex, Cr207 -2, which very likely undergoes further complexing with ions such as the sulfate catalyst to permit chromium deposition. Fluoride or silicofluoride ions are extensively used today in mixed-catalyst formulations, especially in proprietary self-regulating baths. The solubility constants of sparingly soluble salts of the catalysts are utilized to control the catalysts' ratio in self-regulating baths because only enough catalyst will dissolve. For this reason, less frequent catalyst analysis is required. Much more routine analyses and chemical control of the catalysts are needed in non-selfregulated formulations since they must be added to the bath as they are depleted. Chromic acid concentrations may be maintained by making frequent specific gravity determinations using a hydrometer. Occasionally, more accurate chromium analyses should

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be conducted by an analytical method specific for chromium. Chromium is consumed and dragged out of the bath. It is replenished by additions of chromic acid since lead anodes are used. Sulfate concentrations should be determined frequently by measuring the volume of the sulfate precipitated with barium. Occasionally, gravimetric analyses should be conducted to confirm the quick, less accurate, centrifuge method. Sulfate concentrations may be raised by adding sulfuric acid. To add 0.05 g/L sulfate (SO4), add 0.0295 ml/L concentrated (66 Bt) H2SO4. Sulfate is both dragged into and out of the tank. To lower the concentration of sulfate by 0.05 g/L of H 2 S O 4, add 0.01 g/L barium carbohate. Sulfate is an impurity in other chemicals such as chromic acid. For this reason, sulfate should be controlled carefully and any sulfate present as impurities should be accounted for.

CHEMISTRY FOR TRIVALENT CHROMIUM

Decorative trivalent chromium, a safer and more efficient system, was developed in the mid 1970s to eliminate some of the problems associated with hexavalent chromium chemistry: high toxicity, low current efficiency, poor metal distribution, lack of coverage around holes, burns in high-current-density areas, and "white-wash." The literature contains far less information on the chemistry of trivalent chromium processes than for hexavalent. This is the result of the relative newness of the commercially successful processes, the proprietorships of the processes, and the wider differences in the chemistries used. Basically, the significant reactions in the trivalent chromium processes are very simple. Deposition reaction: Cr+ 3 + 3(e) -+ Cr Side reaction: Cr +3 --->Cr +6 + 3(e) (8) (7)

Reaction (8) can take place at the anode under some conditions. The electrolytes for trivalent chromium plating solutions differ in chemistry, but they all contain a source of trivalent chromium, which is typically added as the sulfate or chloride salt. They also contain a stabilizing material that combines with the chromium to permit it to plate in the desired form. Salts are also added to increase conductivity in the solution. Wetting agents are used to help in the deposition reaction and to reduce the surface tension of the solution. This reduced surface tension essentially eliminates the formation of a mist at the anode or cathode. Historically, the method used to eliminate the side reaction (8) distinguished the single-cell from the double-cell process. The original single-cell process has built into the bath chemistry and anodes a mechanism to stop this reaction from occurring. A secondary mechanism converts hexavalent to trivalent if any does appear in the solution. Normal addition of additives to the bath is all that is necessary to eliminate hexavalent chromium. The anodes are placed below solution level to eliminate misting. The double-cell process stops the side reaction by isolating the chromium-containing solution from the anode by putting each lead alloy anode into a box with its own chromium-free electrolyte. Because of maintenance problems and the space the anode boxes took from the plating area inside the tank, they have been almost completely replaced, over the last few years, by insoluble metallic catalytic composite anodes with a projected life of 3 to 5 years. Once through the learning curve, control of trivalent chromium plating processes is typically easier than for hexavalent chromium processes. The literature says that an operator should "think nickel plating not chromium plating" when controlling a trivalent chromium process. The troubleshooting guides for trivalent chromium processes are a few lines long compared with several pages for hexavalent chromium. The additives are added based upon

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Table I. Chromium Plating "Pypical Operating Conditions

Trivalent Chromium Hexavalent Chromium

Chromium, g/L Single cell Double cell pH Temperature, F Cathode current density, A/ft2 Agitation Rectifier voltage Anode-cathode ratio Anode material Single cell Double cell Maximum thickness, mil Single cell Room temperature High temperature Double cell Plating rate, rail per rain Single cell (constant) Room temperature High temperature Double cell (average)

4-25 4-15 2.0-4.0 70-120 40-150 Mild air 4-15 2:1 Carbon Lead-7% tin .-0.05 _> I -0.01 0.004-0.007 0.007~.010 _<0.004

100-300 <1 9-120 175-300 Optional 4-12 1: I-3: I Lead-7% tin

_>5

0.00~7

amp-hours, specific gravity, and pH. In addition, chemical analysis on a monthly basis appears to be sufficient for control. At least one of the graphite-anode single-cell process uses a resin to remove all common metallic contaminates directly from the working trivalent chromium solution. This eliminates the problems attributed to metallic contamination. All trivalent chromium processes are far more sensitive to metallic contamination than hexavalant processes. Metallic impurities darken the deposit and alter the throwing and covering powers.

OPERATIONS
The typical operating conditions for trivalent and hexavalent chromium electroplating processes are shown in Table I.

EQUIPMENT
Tank linings for both types of processes must be made from suitable synthetic material such as PVC or plastisol. Hexavalent chromium uses lead-7% tin anodes, which are consumed during plating. Heating and cooling coils for hexavalent chromium processes can be made from the same lead alloy or synthetic materials. The single-cell trivalent process uses graphite insoluble anodes that only need to be replaced when mechanically damaged. The double-cell process uses consumable lead anodes with the anode boxes or insoluble anodes with a recoatable catalytic coating without the anode boxes. Titanium or Teflon spaghetti coils are used for heating and cooling in both trivalent processes. In most cases, a plating line adequately designed for one process can be used for another after thorough cleaning. For trivalent chromium processes, lead and hexavalent chromium

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Table H. Trivalent and Hexavalent Chromium Comparison

Trivalent Chromium Hexavalent Chromium

Throwing power Covering power Current interruptions Rectifier ripple Deposit structure (microdiscontinuous) Single cell Double cell Ease of burning Ease of rinsing Color buffing requirement Filtering requirement Single cell Double cell Conditioning/dummying Single cell Double cell Passivity of nonplated surfaces Color of deposit Single cell Ambient temperature Elevated temperature Double cell Elevated temperature Waste treatment Relative safety Misting Odor Removal of impurities

Good Good Completely tolerant Completely tolerant Microporous and microcracked Microporous and microcracked Very hard Easy Never Only after chemical purification Daily with carbon Never Start up and routinely Needs postdip Pewter or stainless steel Metallic white Metallic white Easy Similar to nickel Almost eliminated Almost eliminated Easy

Poor Poor Intolerant

Intolerant
Special processes required Easy Moderate Occasional Never Start up each day "Chromate" surfaces Blue-white

Moderate Similar to cyanide Heavy Strong and dangerous Hard

must .be completely removed since they both act as poisons. For hexavalent chromium processes, small amounts of trivalent chromium act as a poison. The current carrying capacity of the plating racks must be designed for the highest amperage they will carry. They must also be designed so that the parts on the racks will utilize the bath's plating benefits and minimize the bath's negative plating characteristics. The plating amps for hexavalent chromium processes are at least twice those used for trivalent processes so the racks must be heavier to carry the current. In general, racks designed for hexavalent chromium processes can be used in trivalent processes, but the reverse is not true. Since trivalent chromium processes will not "bum" and they have greater covering and throwing powers than hi xavalent processes (see Table II), the parts can be placed closer together on the racks and high current density areas can face the anodes. This increases productivity and makes shielding and robbing of the part's high current density areas, as is required for hexavalent chromium processes, unnecessary. Auxiliary anodes are sometimes necessary with hexavalent processes to obtain coverage in the recesses, but typically unnecessary in trivalent processes. Trivalent chromium processes do not require scrubbers and, if the room is adequately ventilated, tank ventilation is typically not used. This is due to the almost complete elimination of misting and odor with trivalent chromium processes due to a built-in mist suppressor, the low chromium concentration, and the greatly reduced toxicity and oxidizing properties of trivalent as compared with those of hexavalent of chromium. Trivalent chromium solution drains and rinses

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easily, thus greatly reducing the amount of chromium drag-out, ff any solution does dry on the part, it is less hazardous since the chromium is in the trivalent state. It also does not stain the part.

SOLUTION MAINTENANCE
The best waste treatment method is to minimize the amount of solution dragged out of the plating tank. Secondly, return as much dragged-out material as possible back to the tank. Any plating solution that cannot be recovered must be waste treated. Even though this reduces plating solution waste, reduced drag-out keeps contaminants in the plating solution complicating the requirement to maintain a pure enough plating solution to obtain the required deposit properties. Due to hexavalent chromium's poor draining characteristics and its misting, a large amount of solution is unavoidably removed from a decorative chromium plating tank. Vacuum evaporators and ion exchange are examples of methods used to return dragged-out hexavalent chromium back to the plating tank to save chemical and waste treatment expenses; however, due to the difficulty of removing metallic impurities from hexavalent chromium plating solutions, it is common to send a solution containing an excess of metallic impurities out for recovery. Trivalent chromium is much more sensitive to metallic impurities than hexavalent chromium; however, the chemistry of most trivalent chromium processes makes it easy to remove metallic impurities thus eliminating the need to ever discard it for normal metallic contamination. Atmospheric evaporators are extensively used to return all the trivalent chromium that can be captured back to its plating tank. In most trivalent chromium processes, metallic impurities can be removed quickly by chemical precipitation or slowly by dummying. The most effective way for at least one trivalent process is to use a resin treatment directly on the plating solution to remove all common metallic impurities. This eliminates the buildup of metallic impurities and excludes any change in deposit color or properties associated with metallic impurities. If a trivalent chromium plating solution has to be waste treated its cost is approximately one-tenth that of treating hexavalent chromium. Hexavalent chromium processes are essentially insensitive to organic contamination since the hexavalent chromium ion destroys most organics. In the process trivalent chromium ions are formed. Trivalent chromium is also formed at the anodes. Being a contaminant, trivalent chromium must be reconverted back to hexavalent chromium. The most common way is to dummy at a high cathode current density (e.g., anode current density of 12 A/ft 2, cathode current density of 600 A/ft2). Trivalent chromium processes are also relatively insensitive to organic impurities but sometimes organics must be removed. Occasional carbon filtering is sufficient for some processes while routine carbordperoxide treatments are needed for others.

CORROSION PROTECTION
Decorative chromium deposits play an important role in the base metal protection provided by nickel/chromium systems. They offer hardness, appealing color, tarnish resistance, wear resistance, and corrosion resistance. Even though decorative trivalent and hexavalent chromium deposits are used interchangeably, there are some important differences. When corrosion resistance is important, most specifications encourage or require microdiscontinuous chromium deposits. With a controlled pattern of microscopic pores or cracks-the corrosion potential between the chromium and underlying nickel deposits is spread out over thousands of corrosion sites. This reduces the anodic current on the nickel at any one site greatly reducing the individual corrosion rate. This results in a fine pattern of active corrosion sites uniformly spaced over the surface. A typical standard will specify a minimum

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Table I l l . D e c o r a t i v e B l a c k C h r o m i u m F o r m u l a t i o n s
Bath A Bath B Bath C

Chromic acid, g/L Fluosili~:ic acid, g/L Acetic acid, g/L Barium acetate, g/L Temperature, F Current density, A/ft2

250
-216 7.6 100

340
0.34 -11 70

250
0.25 ---

40-90

200

90 150-450

of 10,000 micropores per square centimeter or over 30 microcracks per millimeter. Without microdiscontinuity all the corrosion potential would be centered in a few sites resulting in unsightly, irregularly spaced, large corrosion sites. All trivalent chromium deposits are microdiscontinuous as plated. Deposits under about 20 millionths are microporous. Deposits over about 25 millionth are microcracked. Hexavalent chromium deposits must undergo special treatments to produce microdiscontinuity. Chromium plated over very fine inert particles that are codeposited in a nickel strike over the bright nickel deposit is the typical way of producing microporous chromium. Lightly spraying the hard, brittle chromium deposit with hard 60 to 80 mesh particles produces microporous chromium at the contact points. If microdiscontinuity is not induced, hexavalent chromium will typically macrocrack (visible to unaided eye) in service if plated over 20 millionth in thickness. Most chromium specifications requiring corrosion protection specify between 10 to 12 millionths of chromium. "Crack-free" hexavalent chromium depositswill typically macrocrack in service since, like all chromium deposits, t h e y are hard and brittle. Specifications used in North America have essentially eliminated microcracked deposits from use. Microcracked deposits tend to lose their reflective appearance much faster than microporous deposits. Trivalent chromium solutions do not impact short-term corrosion protection by "chromating" the unplated sections of a part as hexavalent chromium ions do. Postchromium plating corrosion inhibiting treatments must be used to obtain an equivalent to this protection.

DECORATIVE BLACK CHROMIUM

Thin black chromium deposits are used for functional and decorative applications. Important functional applications include solar energy collectors for heat production and anti-glare surfaces. Decorative functions include furniture, plumbing fixtures, optical equipment, boat equipment, and builders' hardware. The decorative jet black finish enhances users' appeal for the product and so its popularity depends upon the customers' changing desire for black finishes. Except for a decrease in wear resistance, black chromium deposits offer a surface with properties similar to that of regular chromium deposits. In addition, black chromium deposits
T a b l e IV. H e x a v a l e n t C h r o m i u m B a r r e l F o r m u l a t i o n s
Bath A Bath B 340

Chromic acid, g/L Sulfate, g/L Fluosilicate, g/L Temperature, F Voltage Time of plating (minutes to produce 10 millionths)

525

7 90-105 6-18 8

0.98 6 Room-95 6-18 I0

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have a greater degree of microporosity, which helps absorb oil and paint. This property improves its corrosion resistance, wearability, and appearance. Most black chromium processes are proprietary because of the difficulty of obtaining consistent plating characteristics and deposit properties. In many applications, plating black chromium over regular chromium is recommended. For all decorative and most functional black chromium deposits, the typical thickness is - 1 0 millionths of an inch. Three general formulations are given in Table III. Low carbon steel anodes can be used with plating times of up to 10 min. Most formulations will only produce a maximum deposit thickness and then stop plating due to the nonconductive nature of the deposit. To produce black deposits, barium salts are typically added to remove any traces of sulfate. Hexavalent chromium formulations are more common but trivalent chromium formulations are available.

BULK CHROMIUM PLATING

Plating racks are typically used to hold parts, transfer parts to and from the plating solution, and to carry the direct current to the part. Very small parts such as eyelets, screws, nuts, and bolts have high labor costs when placed individually on racks so they are sometimes bulk plated in barrels or trays; however, even under the best of plating conditions, the chromium reject rate can be very high. This is due to incomplete coverage and black/gray deposits mostly resulting from poor cathode contact and current interruption. Both hexavalent and trivalent chromium processes can be used for bulk plating of parts. Hexavalent chromium has been used primarily and special proprietary formulations have been developed that can produce near 100% coverage if precise control is used. Table IV contains typical barrel hexavalent chromium formulations. Since current interruptions are not avoidable in barrels and trays, stalk complexed-fluoride-containing solutions are normally used. It is extremely important that the bright nickel used prior to chromium not be passive. This is typically accomplished by plating a minimum of 0.1 rail of nickel in the same barrel and, with a few rinses in between, transferring the parts directly into the chromium tank. Since the parts are not held by a rack, poor or no contact with cathode leads is common. Contact must depend upon gravity, while being dampened by the solution, to hold the part against the cathode contact points. To increase the likelihood of good contact sod satisfactory plating, platers use low current density, low temperatures, and specially designed barrels and trays. Cathode contact points in barrels are constructed from wire mesh, solid steel liners, button contact points less than an inch apart, o r steel bars that tumble the parts as they move. Large barrels with small loads also help to increase the frequency of contact and reduce temperature buildup inside the confined space of the barrel. In general, the highest practical current density possible, without burning, should be used. Screw and spiral design plating equipment are also used. The parts are put into the barrel at one end and transferred through the barrel for plating inside the threads of the screw. This permits a continuous flow of plated parts. Vibratory agitation and centrifugal force barrels are also available. In all cases, the barrels must be constructed so that the hydrogen gas generated during plating can escape from the barrel rather than being trapped and possibly exploding. Tray plating requires that parts be layered onto a metallic screen and vibrated or tumbled during plating. Trivalent chromium solutions have recently been used for barrel and tray plating of chromium. Since current interruptions do not hurt the deposit in trivalent chromium processes, and burning is never a problem, this technology will probably be much more popular in the future.

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