Chapter 14 Plating on Plastics

John J. Kuzmik

The plating of non-conductors has been achieved for many years. Articles plated were mainly decorative, and adhesion of the plate t o the substrate was minimal. In the early 1960s' due to technological advances in chemical processing techniques, plating on plastics began on a commercial level. Industries that utilize plated plastics include the automotive, plumbing, appliance and electronics. One of the early plastics to be plated on a large scale was polypropylene, which gave adhesion values of over 20 pounds per linear inch. Even though adhesion was excellent, other problems occurred that ultimately led to the demise of plating polypropylene. These problems included (1) failure t o pass thermal cycling due to its high coefficient of linear thermal expansion (i.e., the amount i n inches per inch the part shrinks in the mold-68 t o 9 5 x lO-'in./in./" c for polypropylene); (2) brittleness after plating due to notch sensitivity (a phenomenon whereby a crack in the plate will propagate through a normally flexible plastic, causing it t o break easily); and (3) "sink" marks caused by the plastic shrinking i n the mold, especially over bosses and ribs and showing up as dimples or "sinks" after molding. Some of the reasons various industries are interested in plating plastics include (1): Lowercost No secondary operations (i.e., no deflashing or buffing) Design freedom (i.e., the ability to mold large and complex parts) Weight reduction

Weight reduction became a very real benefit to the automotive industry when the gasoline crunch occurred in the early 1970s. Many plastics are plated today, including:
0

ABS Polypropylene Polysulfone Polyethersulfone Polyetherimide Teflon

377

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ELECTROLESS PLATING

Polyarylether Polycarbonate Polyphenylene oxide (modified) Polyacetal Urea formaldehyde Diallyl phthalate Mineral-reinforced nylon (MRN) Phenolic Some typical applications of plated plastics are shown in Figs. 14.1 and 14.2. Several of the above-mentioned resins have little or no adhesion and/or unacceptable appearance. Of the resins listed, ABS, acrylonitrile-butadienestyrene, has found the widest acceptance in the plating industry. ABS is a terpolymer thermoplastic that has an acrylonitrile-styrene matrix with butadiene rubber uniformly distributed in it. This quality makes it unique for plating, as the butadiene can be selectively etched out of the matrix (Fig. 14.3), leaving microscopic holes that are used as bonding sites by the electroless plate. Other factors influencing the choice are: Lowcost Low coefficient of thermal expansion Ease of molding Good metal adhesion to the substrate Good appearance after plate Because ABS is the most widely plated plastic, it will be the material mainly referred to in this chapter. Scanning electron micrographs of ABS surfaces are shown in Fig. 14.4. Quality plating on plastics involves the following three basic steps: Molding-converting plastic pellets into the desired part. Preplate-processing the molded part through an electroless bath in order to render it conductive. Electroplating-building additional metal thickness using current. Because of the importance of molding, which must be done properly to insure a part with the high quality necessary for plating, it will be advantageous to mention some general guidelines that should be followed. Molding consists of transforming the plastic pellets into the shape (part) to be plated. A mold of the part must be built and in doing so, certain design features must be taken into account for the finished part. These include (2): Gates (fill areas) should be put in a non-appearance area. Integral parts should be used to avoid welded joints. Ribs and bosses should be designed to eliminate sink marks. Texturing can be used to break up large flat surfaces and hide any defects, such as scratches.
0

379

Fig. 14.1-Typical applications of plated plastic parts.

Fig. 14.2-More appiicalions of plated plastic parts.

Draft angles should be at least one degree (1") for easy removal of the part from the mold. Parting lines (where the mold opens) should be put in a non-significant area if possible. Close tolerance fits must include the final plate in the initial part design. Wall thickness should be sufficient to insure rigidity. Plate uniformity, which results from current density distribution, must be considered in the initial design. Use no 90" angles, no V grooves, keep letters close to the wrface, make angles as large as possible, and crown large flat surfaces (Figs. 14.5 and 14.6).

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Fig. 14.4-SEM photomicrographsof ABS: (left) as molded; (right) after etching.

Some other design considerations are: location of drainage holes, no blind holes, and rack contact areas on the part. If the above features are taken into account when designing a mold, a part suitable for plating should be produced. These are not all the considerations, but some that must be looked at. Certain molding parameters should also be followed to insure good parts. Some of these are (2): Highly polished mold-Poor mold surfaces can cause defects in the molded part such as pits, which show up in the final plate and cause rejects. Proper drying of resin-Moisture in the resin can cause "splay" or delamination on the part, which may result in a blister. Proper melt temperature-If the melt temperature is too low, stress can be incorporated in the part, which could cause uneven etching and possible thermal cycle failure. Consult the resin manufacturer for the proper parameters.

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i Fig. 14.5-Design considerationsfor plating thlckness unlformity: (left) 90 angles and V-grooves result in poor current distribution; (right) suggested design.

Fig. 14.6-Sharp corners(a) result in poor plating uniformity;(b) rounded corners, both Internal and external,Improvecoverage. Expansive surfaces (c) should be crowned fora convex surtace as In (d).

Proper mold femperafure-If the mold is too cold, skinning can occur, that is, the first material to hit the mold hardens instantly and the hot material under it flows, causing a surface skin that may cause delamination. Proper fill speed-A fast fill speed can overpack a mold, thus making it harder toetch, resulting in adhesion loss. Best resultsareobtained using a slow fill speed. These are some of the more obvious parameters t o be considered when molding a part to be plated. The mold design and molding parameters are extremely important to insure good parts that are free of stress and other imperfections. Most plastics can be evaluated for stress. In polycarbonate and other clear plastics, stress can be detected using polarized light. ABS is immersed in glacial acetic acid for one minute, rinsed and dried. Any peeling indicates delamination, white areas depict stressed areas, which usually etch differently than the rest of the part, causing adhesion and thermal cycle problems. Cracks or actual breakage of parts indicate severe stress and should not be plated at all.

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ELECTROLESS PLATING

The type of mold release used can have a profound effect on the molded part. For example, silicon-type mold releases (materials sprayed on the molded Surfaceto help in the removal of the molded part) should not be used, as they are extremely difficult to remove and usually lead to adhesion failures (blisters) or misplate because they hindered the processing solutions from performing their functions properly. Molders who mold plastic parts for plating generally do not use a mold release. If it is essential to use one, a stearate or soap type may be used sparingly. The addition of fillers (4) to the resin can create problems when plating of the parts is involved. In some cases fillers are added to the resins to increase strength (i.e., glass fibers), to impart color (i.e., carbon black or titanium dioxide), or for fire retardancy (organic phosphates, antimony oxide). In any case, problems can arise. Glass, for example, usually gives a rough surface to the finished part. Titanium dioxide can build up in the processing tanks and cause a rough surface after plating. Some of the fire retardants and other fillers can leave a non-adherent fiim on the surface that results in no adhesion after plating. If the film can be removed prior to catalyst, good results are usually obtained. Other fillers such as calcium carbonate are added to facilitate etching. These fillers are preferentially etched out of the surface to create bonding sites required for adequate adhesion. If these particles are large, a poor surface results. Generally, a happy medium is reached where adhesion is adequate and the surface is acceptable. Mineral-reinforced nylon is one such material. When parts are molded, they are ready to be plated, as there is no secondary operation required. Parts are racked and run through the processing solutions, which include cleaners and/or predips, etching, neutralization, preactivation, activation, acceleration, and finally electroless plating (see Fig. 14.7). These steps are known as the preplate cycle (5).

CLEANERS
Cleaners are used for removing light soils such as fingerprints, dirt, and other debris from the parts. They are usually mild alkaline cleaners. In some cases, a highly wetted chromic acid solution may be used to insure complete wetting of a part in knurled or lettered areas prior to etching. This will minimize pinpoint skips in these areas. Cleaning prior to etching is optional and generally not used if parts are reasonably clean. Troubleshooting these materials usually only involves chemical analysis to insure they are up to concentration.

PREDIPS
Predips, which are generally solvents, such as dimethylformamide for polysulfone, are used prior to etchants for two types of plastic problems. The

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Fig. 14.7-Process

steps in plating plastics.

first use is to help improve the surface of a normally plated but poorly molded, highly stressed part. This is done on ABS and its alloys by slightly swelling the surface, allowing the etchant to more uniformly attack the surface. By using a predip, non-uniform etch conditions are reduced on a stressed part, giving better overall adhesion. As stated earlier, proper molding can eliminate stress as well as the need for a predip in the above case. The second use of predips is to attack or swell the surface of normally hard to etch plastics. These materials include polypropylene, polycarbonate, polysulfone, and others. This swelling action of the predip enables the chemical etchant to readily attack the surface of the normally resistant resin. Generally, a different solvent is needed for each resin in order to be successful. Troubleshooting the predips involves analysis to insure proper balance.

ETCHANTS
Etchants are usually strong oxidizing solutions that eat away the plastic Surface to varying degrees, accomplishing two purposes. First, the surface area is greatly increased, making the part turn from a hydrophobic (water-hating) to a hydrophilic (water-loving) material. Second, the microscopic holes left in the surface of the plastic by the etchant provide the bonding sites for the deposited metal. These sites are needed for adhesion between the plastic and the metal. When ABS is exposed to an etchant, the butadiene is selectively removed, thus leaving small holes or bonding sites. Commonly used etchants for ABS are: Chromium trioxide-375 to 450 g/L Sulfuric acid-335 to 360 g/L This is the so-called chrome-sulfuric version, or,

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ELECTROLESS PLATING

Chromium trioxide-900+ g/L This is the all chrome version, which tends to give a finer, more uniform etch. Both types are used in production. All-chrome etchants require several milliliters of sulfuric acid per liter of etchant to retard tank deterioration if chemical lead is used. It is also desirable to have about 40 g/L trivalent chromium in a new all-chrome bath to avoid over-etching the ABS surface. Etchants are generally operated at 140 to 160 F for 4 to 10 minutes on ABS. Other plastics may require higher or lower temperatures and times. Polycarbonate, for example, uses an etchant at 170 F for 10 minutes, while mineral-reinforced nylon (MRN) uses one at 105 F for 2 minutes. As the chrome-based etchants are used, the following reduction reaction occurs as the plastic is attacked:

+ 3eCr+6

Cr+ reduction

After a certain build-up of Cr (about 40 g/L in the chrome-sulfuric type etchant), the etchant starts to lose its ability to perform properly. Adding more Cr+6 in the form of chromium oxide extends the life of theetchant for a while, but it is better to eliminate the excess Cr. This can be done in two ways: Decant part or all of the etchant and rebuild it. This method may cause a waste disposal problem if provisions for the spent material are not made. The excess trivalent chrome can be electrolytically regenerated. This can be accomplished by using porous pots containing an electrolyte of 10 to 50 percent byvol HrSO,. Copper or stainless steel cathodes are then inserted in the pots. The tank or lead straps may be used as the anode. The usual anode to cathode ratio is 2:l. The voltage used is 9 to 12 Vat a temperature of 100 to 155 F. The current is 100 to 150 amps for a 15-cm-diameter by 45-cm-long porous pot. Efficiency of this regeneration process is best when more than 20 g/L of trivalent chromium are present in the bath. The reaction involved is: Cr

- 3e- - Crth
oxidation

at the anode. Using this method and a flash evaporator for the rinses results in a tight closed loop system. One problem with this system is that all impurities in the etch such as dissolved metals and titanium dioxide filler are returned to it. This causes a build-up of impurities that eventually results in problems such as stardusting, a fine roughness usually occurring on the shelf of a part. The etchant is the most critical step in obtaining an acceptable finished part. An underetched part can result in poor adhesion and possible skip plate. Overetching a part can degrade the surface causing poor adhesion and cosmetics. Some problems that may be encountered are shown in Table 14.1.

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Table 14.1 Troubleshooting Etchants for Electroless Nickel

Problem
Shiny parts after electroless nickel Poor adhesion

Cause
Underetching

Solution
Increase time Increase temperature

High Cr3 Overetching

Check chemistry Decrease time Decrease temperature Check chemistry

Dull or almost black parts after

electroless nickel Poorsurface-low adhesion with black layer on plastic and metal Stardusting or roughness on part Chemistry good, but parts have low adhesion and look shiny out of electroless nickel Parts warp out of etch

TiO, build-up Poor molding Mold release on part Temperature too high Too much tension on rack

Install spray rinse after etch Check parts for stress

Lower temperature Check rack tension and adjust or change rack Check chemistry and rebalance bath Check with glacial acetic acid to confirm. Reduce etch time and/or temperature. Use a predip

CrOl additions do not show up in analysis Poor adheion at gate area only

HISOI too high CrOI is salting out

Part stressed at gate

NEUTRALIZERS
After etching, the parts are thoroughly rinsed in water and then put into a neutralizer. These are materials such as sodium bisulfite or any of the proprietary products available that are designed to eliminate excess etchant from the parts and racks, usually by chemical reduction. Hexavalent chromium ( C P ) is harmful in the ensuing steps. Even with excellent rinsing, etchant may be trapped in blind holes. If this is not rinsed out or reduced to trivalent chromium (Cri3), skip plate can occur as a result of bleedout of etchant in subsequent steps. Neutralizers are generally cheap to make up and are usually dumped and remade on a regular basis. They are usually run at 70 to 110 F for 1 to 3 minutes with air agitation. Troubleshooting is relatively simple, as seen in Table 14.2.

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Table 14.2 Troubleshooting Neutralizers for Electroless Nickel Problem

Cr'' seen dripping off parts coming out of neutralizer

Cause
Bleed-out of blind holes on rack tips Bath spent

Solution
Check chemistry Check bath color-if orangish, dump Increase air and/or temperature Check rack tips As above

Drip skip noted after electroless nickel

Bleed-out of hexavalent chromium

PREACTIVATORS
After neutralization and rinsing, a preactivator may be employed for certain resins, such as polypropylene or polyphenylene oxide. These proprietary materials are designed primarily to enhance activator absorption. Generally they do not reduce hexavalent chromium. Preactivators help make otherwise unplateable resins plateable by conditioning the resin surface by forming a film or changing the surface charge. One must be careful in selecting a preactivator, as excessive conditioning can lead to resist overplate and rack plating. Typical parameters for these baths are 70 to 120" F for 1 to 3 minutes. if the partsarefullycovered out of the electroless plating bath, the preactivator is doing its job. Troubleshooting guidelines for preactivators are given in Table 14.3.

ACTIVATORS
Activators or catalysts, as they are sometimes called, are materials that in most cases contain some precious metal such as palladium, platinum or gold. The early version of activation was a two-step procedure. Step 1 was a stannous chloride/hydrochloric acid solution in which the stannous ion (Sn") was adsorbed onto the surface. The part was then rinsed well. Step 2 was a palladium chloride/hydrochloric acid solution which, when the part with the stannous ion was immersed in it, caused the Pdt22 ion to be reduced to Pd" according to the following reaction: Sn"

+ Pd''

- Sn"

+ Pd"

PI

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Table 14.3 Troubleshooting Preactivators for Electroless Nickel

Problem
Skip or no plate out of electroless bath

Cause
Bleed-out of Cr'6 Preactivator out of spec

Solution
Use better rinsing Increase air Check chemistry of bathif spent, dump Lower temperature and/or time Check chemistry

Rack or resist overplate

Temperature too high Concentration too high

The Pd sites formed the catalytic surface needed to deposit the chemical nickel. Present day catalysts are essentially the earlier two step version combined. In other words, the palladium chloride, stannous chloride and hydrochloric acid are in one solution. What we get is a palladium-tin hydrosol, which is a solution of complex ions and colloidal particles whose activity and stability depend on the chloride and stannous ion concentrations (6,7). A typical working activator bath today would consist of the following: Stannous chloride-6 g/L Palladium (metal)-20 to 100 ppm Chloride ion-2.5 to 3.5 N The chloride ion may be maintained with hydrochloric acid or sodium chloride. When processing a part, the first noticeable change will be evident after the activator. The part acquires a tan to brownish color. This coloration, unless the part is black, can easily be seen and is an indication the activator isworking. The absence of a coloring on the part usually indicates a problem that can result in skip plate and possibly low adhesion. The primary purpose of activators is to provide catalytic sites on the plastic surface. The usual operating conditions for the activator bath are 80 to 95" F for 2 to 5 minutes. Because this is the most expensive bath in the system, care is taken to analyze regularly. Even when the bath is not being used, analysis for tin is required, as tin is continually oxidized to the stannic ion (Sn")). When almost all the stannous is oxidized, the bath "falls out". Troubleshooting tips for the bath are given in Table 14.4.

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ELECTROLESS PLATINQ
~~ ~~

Table 14.4 Troubleshooting Activators for Electroless Nickel

Problem
Silver mirror seen on bath surface Roughness on parts

Cause
Low stannous ion
Particulates in the bath

Solution
Reolenish stannous ion Batch filter to the bath. (Expect to lose 2-3% due to absorption on the filter Raise stannous level Install spray rinse after activator Make up a new bath

Stannous may be low

Solution clear or tea colored Rack plate and/or stop-off overplate Skip plate after electroless bath Blotchy surface (light and dark areas Parts very dark Parts very light

Bath fell out due to low stannous, impure HCI, or an addition of HNO) High temperature High concentration Low temperature Low concentration Stress in Dart High temperature Low temperature

Lower temperature Check chemistry Raise temperature Check chemistry Confirm with glacial acetic acid Lower temperature Check chemistry Raise temperature Check chemistry Agitate parts

ACCELERATORS
After rinsing following theactivator, metallic palladium is present on the surface of the part surrounded by hydrolyzed stannous hydroxide. Theexcess stannous hydroxide must be removed from the part before the palladium can act as a catalyst. The role of an accelerator is just that. It is to remove the excess tin from the part while leaving the palladium sites intact for the deposition of the electroless bath. Tin will inhibit the action of the electroless bath, resulting in skip plate. This step is important, as too short a time in bath, as well as too long a time, can cause skip plate. These baths are usually organics or mineral acids. The biggest problem with accelerators is the effect of metallic contamination. Most proprietary baths contain a built-in reducer to eliminate any hexavalent chromium. Chromium may be dragged through the line in blind holes or bad

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rack tips. These contaminants, such as hexavalent chromium, iron, and other metals, can cause the accelerator to become over-aggressive. This causes the accelerator to remove not only the stannous tin, but also palladium. When this occurs, skip plate can be the result. Some materials are designed to minimize the effect of these contaminants. Accelerators are usually run at 110 to 140" F for 2 to 5 minutes. Some problems that may occur are as shown in Table 14.5.

Table 14.5 Troubleshooting Accelerators for Electroless Nickel

Problem
No plate on edges of part

Cause
Over-acceleration High temperature Under-acceleration Low temperature

Solution
Check chemistry Lower temperature Lower time Check chemistry Raise temperature Increase time Agitate parts in solution When parts come out of the activator brown, but are clean after the accelerator, contamination and/or high temperature may be the problem. In this case, lower the temperatureor make up a new bath. If parts are brown out of the accelerator, under-acceleration is probably the cause. In this case, increase the time, temperature, and/or agitation

Parts have no plate in major areas or slow takeoff in the electroless that goes from the edges inward
No plate at all out of electroless bath

Contamination that causes aggressiveness

High temperature

Check chemistry

ELECTROLESS PLATING
After rinsing, the parts are put into the final step in the preplate cycle. This is the electroless bath, which deposits a thin, adherent metallic film, usually copper or nickel, on the plastic surface by chemical reduction. This is accomplished by using a semi-stable solution containing a metal salt, a reducer, a complexor for the metal, a stabilizer and a buffer system. When idle, the baths are stable, but

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when a palladium-bearing surface is introduced into the solution, a chemical reduction of metal occurs on the palladium sites, and through autocatalysis, continues until the part is removed. The basic reactions for copper and nickel are:

CU"

2HCHO + 40H- J2HC00- + 2H:O + Cu" + H:

[41

The electroless nickel used is an alkaline bath, usually partially complexed with ammonium hydroxide. It is operated at 80 to 100" F for 5 to 10 minutes at a pH of about 9.0. Nickel thickness can range from 8 to 12 pin. and should have a resistance of 50 to 20 ohmdin. The pH is controlled with ammonium hydroxide. If an electroless copper is used, it is usually reduced by formaldehyde and complexed by various materials, depending on the supplier. Copper baths are operated at 100 to 140' Fat a pH of 12 to 13. The thickness ranges from 20 to 50 pin. For most applications, electroless nickel is adequate, as the primary function of the electroless bath is to render the surface conductive. The automotive industry has done studies that show that electroless copper tends to exhibit less of a tendency to blister in a humid, corrosiveenvironment (7,8). Becauseof this, most exterior automotive parts are processed through electroless copper. Nickel baths are relatively easy to control, while copper baths generally require automatic analysis for control. Copper baths are more susceptible to problems than nickel. Some troubleshooting hints are given in Tables 14.6 and 14.7. In all cases, if an automatic controller is being used to analyze and add the necessary chemicals to the bath, the first thing to check is the controller if something is out of spec. Be sure the pumps are working and the reagents and/or replenishment solutions are not used up. When the controller is operating properly, over-the-side additions of chemicals are rare. Following the electroless deposition, the parts are generally run through an electrolytic copper or Watts nickel strike (9). The purpose of the strike is to build up the thin electroless deposit prior to subsequent electroplating. This build-up, usually to 0.0001 in., prevents "burn-off", the loss of contact between the part and the rack tips. The electrolytic strike is usually followed by ar: electrolytic bright acid copper plating solution, which is normally a proprietary product. This step will build a copper thickness to about 0.0005 to 0.001 in. and give a bright surface. Copper, being ductile, will act as a buffer layer between the plastic substrate and the final plate as the part sees large thermal changes. This buffer layer helps prevent blisters and/or cracking of the plated deposit. If good corrosion and abrasion resistance is desired, as for an exterior automotive part, the next step will be an electrolytic semi-bright nickel plating

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Table 14.6 Troubleshooting Electroless Nickel Plating Baths Problem

Skip plate

Cause
Low reducer Low temperature Contamination Particulates in bath

Solution
Check chemistry Raise temperature Check for contamination Filter bath Install spray rinse after bath Agitate work Increase time Increase temperature Check bath rate Check chemistry Check racks Lower temperature Check chemistry

Roughness

Burn-off in strike

Electroless coating too thin

Bad racking. not enough contacts Bath overactive High temperature High reducer Palladium contamination Low complexor Tank plate-out Low stabilizer pH out of range High stabilizer Low reducer Low temperature Contamination

Clean and strip tank Check stabilizer Check chemistry

Bath sluggish

Raise temperature Check for contamination

solution. Normally 0.0003 to 0.0008 in. of semi-bright nickel are plated, followed by an electrolytic bright nickel plating solution, which will deposit about 0.0002 to 0.0004 in. of metal. The deposit from the latter bath is generally very specular. For the best corrosion resistance, a layer of about 0.0001 in. of microporous nickel can be electrolytically deposited on the bright nickel, followed by an electrolytic chromium deposit from either a hexavalent or trivalent bath. This layer,onlyabout5to 10millionthsofan inch thick, isthefinalstepinproducinga finished part. Be aware that if the surface of the substrate is pitted, scratched, dented, or marred in any way, electroplating will enhance these blemishes. Care must be taken when handling and racking plastic parts to avoid damaging them (1). Parts are usually plated to meet various service conditions, which are:
SC7-Mild. Includes indoor exposure to normally dry, warm atmosphere and subject to minimal wear and abrasion. SCP-Moderate. Indoor exposure where moisture condensation occurs. Examples are kitchen and bathroom fixtures.

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Table 14.7 Troubleshooting Electroless Copper Platlng Baths

Problem
Bath slow-dark deposits

Cause
Low copper Low caustic Low formaldehyde High stabilizer Low tern perature Too much air High caustic High formaldehyde Low stabilizer High temperature High loading factor Tank plate-out Low complexor

Solution
Check chemistry, plating rate

Increase temperature Decrease air Check chemistry, plating rate Add stabilizer Lower temperature Decrease work in bath Clean and strip tank Increase air Check chemistry

Bath overactive-dark, deposits

grainy

Roughness on parts-precipitate forms when additions are made

SC3-Severe. Includes frequent wetting by rain or dew, and in some cases strong cleaners and salt solutions. Examples are outdoor furniture, bicycle parts, and hospital furniture. Sc4-Very severe. Includes likely damage from dents, scratches, and abrasive wear in addition to being in acorrosive environment. Examples are boat parts and exterior automotive parts. The various plate thicknesses required for each type of service are given in Table 14.8. Chromium is not theonlyfinish that can beapplied to plated plastics. Once the electroless is put down, any plate combination can be used. Final finishes can be brass, gold,, silver. or any of the other finishes put on plated metal articles. After plating to thedesired specification, most platers perform quality control testing on plated parts. These tests include:

Adhesion (Jacquet Test)

The part, usually one with a flat surface, is plated with 1 mil of bright acid copper. A 1-in.-wide strip is cut and the plate is separated from the plastic at one end. The plate is then pulled at 1 in./min at 90" to the surface. Values obtained in pounds per linear inch are recorded. ABS, for example, has from 5 to 15 Ib/linear in. pull.

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Table 14.8 Minimum Plating Thickness Requirements Under Various Service Conditions
Total

Service
SCl sc2

Copper
0 6 mils 0 fi mils 0 6 mils 0 6 mils

nickel
-03 mils
0 6 mils

Chromium
10 pin 10 pin 10 Uin
10 p i n

sc3
sc4

09 m i l s 1 2 mils

Thermal Cycling
Because various plastics have various coefficients of thermal expansion, some do not readily pass this test, even though adhesion is good. To counteract this, more copper may be plated on the part to act as a cushion. I n thermal cycling, the part is first put into an air-circulating oven for 1 hr at 180" F. The part is then removed and held at room temperature for 15 min. The 2 0 ' F for 1 hr. This is repeated a part is then placed into a cold chamber at minimum of three times. Loss of adhesion, blisters, or cracking indicate a failure. Part design and molding can also affect thermal cycling. This test was designed for ABS and does not necessarily apply to other substrates.

C.A.S.S.
The C.A.S.S. ( l o ) , or Copper Accelerated Acetic Acid Salt Spray Test, checks the corrosion resistance of the final plate. This test is generally performed in a cabinet, according to ASTM 6-368. Requirements are as follows: SC1-None SC2-1 8-hr cycle SC3--2 16-hr cycles SC4-3 16-hr cycles Failure is indicated by white or green corrosion. The above are the most widely used tests. Others include:

N.S.S. (10)-5 percent neutral salt spray, which is also used in another corrosion test-ASTM 6-1 17. Plate thickness-Checking plate thicknesses by either a destructive or non-destructive method. Outdoor exposure-Setting industrial samples in environments they will be normally exposed to.

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C.S.A. 8-125, LRP-15 (11)-A Canadian test for plumbing goods that includes 450 cycles of dipping the parts in alternating hot (175' F) and ambient (70' F) water baths for 40 seconds. One cycle is 40 seconds in the hot water, and 40 seconds in the ambient water.
New technologies in plating on plastics are leaning toward plating engineering resins for printed circuits. Resins with high strength and heat distortion are also being looked at to replace metals i n functional as well as decorative roles.

ELECTROMAGNETIC INTERFERENCE SHIELDING

EM1 shielding is another area where plating-on-plastics technology can be utilized. Electromagnetic interference is electrical "noise" generated by a piece of electrical or electronic equipment that causes a problem of interference with the operation of another piece of electrical or electronic equipment. An example is the annoying lines on a TV set caused when an electric razor or other small appliance is in use. Sources of EM1 are shown in Fig. 14.8. Some of the more common sources of EM1 are:
0 0 0

0 0 0

Airplanes Computers Electric motors Ignition systems Power lines Radio and television transmitters Videogames Lightning

Some equipment affected by EM1 "noise" includes: Radio and television receivers Computers Telephones

In the early days of electronic packaging, MI radiation emitted from equipment was not a major concern. Today, these emissions are subject to controls, it has become necessary to redesign and effectively shield electronic equipment. The electromagnetic radiation spectra, which covers a wide range of frequencies, is shown in Fig. 14.9.
Metal enclosures were used for many years as the main shielding material. This provided structural integrity as well as a shielding function. Some drawbacks of metal were weight and design limitations. As housings for electronic equipment changed from metal to plastic, it became necessary to apply shielding to protect the equipment. Several types of technical approaches have been used in an attempt to effectively solve the shielding problems of plastic housings. One such method could be the use of electroless-plated

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Fig. 14.8-Sources

of EM1 and RFI.

Fig. 14.9-Electromagnetic radiation spectrum.

copper and/or nickel. The process used would be similar to that presently used to plate on plastics. Steps would include:
1. 2. 3. 4. 5.

Pretreatment (if necessary) Rinse Etch Rinse Neutralize

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Fig. 14.10-Attenuation as a function of thickness of metal deposits.

6. Rinse 7. Preactivate (if necessary) 8. Rinse 9. Activate 10. Rinse 11. Accelerate 12. Rinse 13. Electroless copper 14. Rinse 15. Activate 16. Rinse 17. Electroless nickel 18. Rinse 19. Dry The electroless copper (Step 13) generally would be deposited to a thickness of 40to60millionthsof an inch.Thecopperisaveryeffectiveshieldby itself, but because of its corrosive nature, an electroless nickel (Step 17) topcoat of about 10 to 20 millionths of an inch is applied to retard the corrosion. Nickel can be used by itself, but itsshielding effectiveness is much lower than that of copper or copper/nickel. It is also an excellent base i f the article is to be painted. Electroless shielding is applied i n general to both sides of a plastic enclosure, which assures the best protection against the transmission of electromagnetic radiation (Fig. 14.11). Still, techniques have been developed to apply the electroless coatings only to the inside of the enclosure, to allow the use of color-molded finishes. Shielding effectiveness is the ability of the method used to absorb or reflect the unwanted "noise" signal, typically over a frequency range of 14 K H z to 1

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397

Fig. 14.1 1-Double-sided shielding

Table 14.9 EM1 Shielding Effectiveness

Attenuation
0 to 10 dB 10 to 30 dB 30 to 60 dB 60 to 90 dB 90 to 120 dB and above

Shielding effectiveness
Very little Minimal Average Above average Maximurntostate-of-the-art

GHz. This is called attenuation, which is a function of theelectrical conductivity of the shield used, measured in decibels (dB). Attenuation as a function of the thickness of the metal deposits is shown in Fig. 14.10. Shielding values for various attenuation levels are shown in Table 14.9. The electrical conductivity required to satisfy the minimal functional requirements are expressed in surface resistance (ohmdsquare) as follows:
EM1 shielding-Less than 1 ohm/square RFI (radio frequency interference)-Less than 10 ohms/square ESD (electrostatic discharge)-50 to 100 ohmdsquare
This allows performance to be measured in surface resistance as well as dB. Some of the other technologies presently being used to shield plastic housings are given in Table 14.10.

398

ELECTROLESS PLATING

Table 14.10 Coating Techniques for EM1 Shielding Of Plastic Housing

Method
Zinc arc spray

Advantages
Good conductivity Hard, dense coat Effective over a wide frequency range Good conductivity Conventional equipment Resists flaking Conductive oxide Easy to apply Conventional equipment Resists flaking Economical Easy to apply

Disadvantages
Need special equipment Adhesive problems Coating cracks May distort the housing Expensive

Conductive painfs Silver

Nickel

Multiple coats needed for good conductivity Thickness problems Questionable attenuation Multiple coats needed for good conductivity Thickness problems Oxidation reduces conductivity Size limited to vacuum chamber Base coat needed Expensive special equipment Low thickness Expensive equipment Microscopic cracking May distort housing High power needed Complex parts are difficult to coat Labor intensive Material expensive Poor attenuation Surface usually poor Tendency to oxidize Difficult to mask Multiple-step process Limited to Lertain resins

Copper

Conventional equipment Resists flaking Economical Easy to apply

Vacuum metallizing

Good adhesion Good for all plastics Not limited to simple designs Familiar technology Good conductivity Good adhesion

Cathode sputtering

Foil application

Die cut to part shape Good conductivity Good for experimentation

Conductive plastics

No secondary operation

Silver reduction

Good conductivity Low initial cost Uniform thickness Good for all size and shape parts Good conductivity Resists chipping Can be electroplated for metallic appearance Can be painted

Electroless plating (copper and/or nickel)

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399

As can be seen above, besides electroless plating, numerous other methods of shielding are available. The success of plating on plastics technology is dependent on the industry and its requirements.

REFERENCES
1. J.L. Adcock, Electroplating Plastics, American Electroplaters and Surface Finishers Society. 2. Design and Converting Techniques for Plating Cycolac Brand ABS, EP3510, Marbon Division, Borg-Warner Corporation, Technical Bulletin, (May 1967). 3. Glossary of Terms, Thomas H. Ferrigno, ed.; Fillers and Additives Committee, Society of Plastic Industry. 4. Plating on Plastics 11, Technical paper-Society of Plastics Engineers, Connecticut Section. 5. A. Rantell and A. Holzman, Mechanism of Activation of Polymer Surfaces by Mixed Stannous Chloride/Palladium Chloride Catalysts, Division of Metal Sciences, Polytechnic of the South Bank, London SElOAA (February 12, 1973). 6. C.H. deMinjer and P.F.J. v.d. Boom, The Nucleation with SnCI?-PdCI Solutions of Glass Before Electroless Plating, Phillips Research Laboratories, Einhaven, Netherlands. 7. R.G. Wedel, Plating, 62(3), 235 (Mar. 1975). 8. R.G. Wedel, ibid., 62(1), 40 (Jan. 1975). 9. Metal Finishing Guidebook-Directory Issue, Metals and Plastics Publications, Inc., One University Plaza, Hackensack, NJ 07601. 10. ASTM 8-117, 15-22; ASTM 8-368, 164-169, Part 9, American Society for Testing and Materials, Philadelphia, PA. 11. CSA Standard 8-125, LRP-15, Canadian Standards Association, Ontario, Canada. 12. E.B. Saubestre, Plating, 52(10), 982 (Oct. 1965). 13. E.B. Saubestre, Modern Electroplating, p. 636 (1974). 14. W.P. Innes, Plating, 58(10), 1002 (Oct. 1971). 15. H.Narcus, ibid., 55(8), 816 (Aug. 1968). 16. Plating of Plastics with Metals, Chemical Technology Review, Noyes Data Corporation, Vol. 27 (1974). 17. Plating on Plastics, Extended Abstracts (1965-1971), The International Nickel Company, Inc. 18. James L. Adcock, Products Finishing, p. 51 (May 1982). 19. Gerald Krulik, lndustrial Finishing, p. 16 (May 1983). 20. Gerald Krulik, Products Finishing, p. 49 (Oct. 1983).