Properties and Comparisons of
Commonly Specified Coatings
   Zinc/Zinc-Alloy, Copper/Alloys, and Some
                Precious Metals
    By: Frank Altmayer
    Technical Education Director, AESF Foundation/NASF
 Data collected from a variety of sources, including ASTM and
 “The Properties of Electroplated Metals & Alloys by Lowenheim”
Properties of Electroplated Zinc
• Density: 7.14 g/cm3                • Not Solderable/brazeable
• Melting Point: 419.53°C/787.15°F   • Weldable (fume problem)
• Brittle up to 100°C,
                                     • Amphoteric
 Malleable 100°C-200°C, Brittle at
                                     • Metal ions are low in toxicity
 >200°C
• Para-magnetic                      • Aquatic toxin (ion)
• Electrical resistance: 5.9 mΩ cm   • Powder is autophoretic
                                     • Incompatibles:
                                         – Chlorates, Chlorine, Acids, Nitrates,
                                           Sulfur, Calcium Chloride, Alkalis
        Bare and zinc
    electroplated fastener
    Properties of Electroplated Zinc
   Sacrificial corrosion protection of ferrous
    substrates
     -   Economical but yields unsightly corrosion
         products (photo)
   Easily chromated to extend service life and
    achieve a desired appearance
   Can be chromated and dyed/painted to produce
    a colored coating
   Lower level of salt spray performance vs. Zn-
    alloys or Cd
   Can grow zinc whiskers that may be a few
    microns in diameter and can grow at rates of
    up to 1 mm per year
        Related to high compressive stress in the
         deposit and environment
        Preventive measures include alloying and
         reduction of stress
        Other metals that can grow whiskers include tin,      Zinc Whiskers, by
         silver, gold, cadmium                              Schtone, Wikipedia photo
Corrosion Resistance of Zinc
                          (From ASTM B633)
 Atmosphere                     Corrosion Rate (μm/year)
 Industrial                            5.6
 Urban nonindustrial                   1.5
 Suburban                              1.3
 Rural                                 0.8
 Indoors                               <<0.5
     Note: The corrosion rate is greatly increased by frequent dew and
              fog, particularly if the evaporation rate is slow.
 Service Condition                                    Min. Thickness, µm
 SC4 (plumbing fixtures, pole line hardware)                 25*
 SC3 (furniture, builder’s hardware, bicycle parts)          12**
 SC2 (tools, zippers, pull shelves, machine parts).          8
 SC1 (buttons, wire goods, fasteners)                        5
                  Corrosion of Zinc
Bare Zinc:
•   White gelatinous corrosion products
•   Zinc oxide plus zinc carbonate
•   Highly porous
                                              Corrosion of bare zinc over steel
•   Corroded fasteners may seize
    – Anti seizing compounds may be applied
• Red rust indicates protection afforded by
  zinc has broken down
Zinc Plus Chromate
• Chromate acts as barrier against
  corrosive
• White corrosion products indicate failure
  of chromate to act as barrier (base metal
  is still protected
• Red rust indicates protection afforded by          Corrosion of zinc plus
  zinc plus chromate has broken down                  chromate over steel
              Galvanic Series
Metal             E° [volts], 25°C E in Seawater @ 25°C
Zn → Zn+2 + 2e-           -0.761               -1.0
                                                    }    0.4V
Fe → Fe+2 + 2e-           -0.440               -0.6
                                                    }    0.1V
Cd → Cd+2 + 2e-           -0.402               -0.7
Co → Co+2 + 2e-           -0.277
Ni → Ni+2 + 2e-           -0.250               -0.15
Sn → Sn+2 + 2e-           -0.136
                                               In a chloride environment,
                                                 cadmium is less noble
                    In a sulfate (acid rain)            than iron
                  environment, cadmium is
                     more noble than iron
Salt Spray Performance of Zinc Alloys
                 Hours to exposure for 12 microns over steel
  Coating                                      Hrs To WR       Hrs To RR
  Bare Cadmium                                      NA         >1000
  Cadmium + Chromate                                672        >1000
  Zinc-Nickel + Chromate (acidic solution)          168        336
  Zinc-Nickel + Chromate (alkaline solution)        >1000      >1000
  Zinc-Tin + Chromate                               672        >1000
  Zinc-Cobalt + Chromate (acidic solution)          168        336
  Zinc-Cobalt + Chromate (alkaline solution)        336        672
                Hours to red rust for 8 microns over steel
          Zn-Ni vs. Zn-Co and Zn-Fe
Parameter      Acid       Alkaline     Acid      Alkaline   Acid       Alkaline
               Zn-Ni       Zn-Ni      Zn-Co       Zn-Fe     Zn-Fe     No-CN Zn
Alloy %        10-12       5-12       0.4-1.0    0.2-0.5     15-50      None
HV100         300-400     200-250                100-170    170-200    80-150
CCE            95-100      45-80      95-100      50-70      70-80      50-80
Throwing        Poor       Good        Poor       Good       Poor      Good
Power
Formability     Poor        Fair       Fair       Good      Good       Good
Solution        Yes         No         Yes         No        Yes         No
Corrosive
to Steel
Appearance    Excellent    Good      Excellent    Good       Fair      Good
                        Zinc-Nickel
Features:
 High salt spray resistance
    – 4-6 Times the performance of zinc alone
 Good Kesternich SO2 performance
    – Zinc-cobalt is better
 Favorable galvanic couple with aluminum
 High abrasion resistance (HV100 =130-450)
 Good formability & weldability
 Excellent corrosion resistance at elevated
  temperatures(up to 180°C)
 Forms temperature stable chromates
                                                Zinc-nickel plus
Limitations:                                    yellow chromate
 Inferior to Zn-Co in SO2 (acid rain)
                  Zinc-Cobalt
Features:
• Co may be unregulated
• Less expensive v. zinc nickel
• Low Co alloys are highly ductile
   -   HV100 =150-200
   -   Parts can be deformed after plating
• Deposit is easier to chromate
Limitations:                                  Automotive parts, zinc-cobalt
                                               plated, illustrating a variety
• Chromates are dehydrated at elevated                of chromates
  temperatures
• Less corrosion resistant vs. Zn-Ni, Zn-Fe
• Lower solderability vs Zn-Ni
• Higher coefficient of friction vs Cd
                         Zinc-Iron
Features:
• Low cost (least expensive of the zinc
  alloys)
• High ductility, suitable for toxing
• Low hardness (HV25 = 80-170)
Limitations:
• Corrosion resistance is heavily dependent
  on the chromate
• Less corrosion resistance vs. Zn-Ni, Zn-Co
   - Corrosion resistance is obtained from
     interaction of chromate and iron (bare Zn-Fe
     @ 0.2-0.5% Fe is no better than bare Zn)
• Prone to delayed blistering
                              Tin-Zinc
Features:
   High Corrosion resistance (especially in
    sulfur atmosphere)
   Chromate performance better that other
    alloys of zinc
   Excellent solderability
   Low coefficient of friction
   Excellent lubricity
   Excellent ductility
   Soft (HV25 =13-28)
   Excellent couple with Al
   Near neutral plating solutions are
    available (pH 5.5-7)
Limitations:
   Tin is expensive
                                               Tin-zinc, as plated and
   Unpleasing appearance                            chromated
 Impact of Zinc Alloys on Hydrogen
    Embrittlement Relief Bake
Coating                    Pass/Fail      Hrs. to Failure
Bare Cadmium               PASS           (3) >200
Cadmium + Chromate         PASS           (1) 183, (5) >200
Acid Zinc-Nickel           FAIL           (3) 0.5, 0.4, 0.5
Acid Zinc-Nickel*          PASS           (3) >200
Alkaline Zinc-Nickel       PASS           (1) 141, (5) >200
Zinc-Tin                   FAIL           (3) 0, 0, 0.2
Acid Zinc-Cobalt           FAIL           (3) 0.8, 5.7, 4.4
Alkaline Zinc-Cobalt       FAIL           (3) 4.5, 4.5, 8.3
   Notes:
   All alloy deposits were chromated
   * Designates an alternate supplier’s process was used
              Electroplated Copper
• Melting Point: 1083°C
• Stable in water, tarnishes quickly in air
    •   Eventually forms a patina and stops corroding
• Ductile, malleable
    -   Elongation is %
    -   Easily buffed/machined
•   Excellent conductor of heat and electricity
•   Hardness is typically HV25 = 50-350
•   Low internal stress
•   Chemically attacked by nitric, hot sulfuric, sulfides
•   Diffusion barrier over brass
•   Heat Treat Stop-off
•   Under-plate for nickel
•   Most commonly plated from sulfuric acid, cyanide or
    alkaline non-cyanide based solutions
                 Electroplated Copper
Property                           General Range High Strength Deposit
UTS (kpsi)                            64 – 90              66 – 93
Yield (kpsi)                                               41 – 57
Elongation (%)                        0 – 40               3 – 18
Hardness (HV)                         48 – 350             131 – 159
Resistivity (micro-ohms-cm)           1.7 - 4.6            1.75 – 2.1
Internal Stress (psi)                 -6,000 - +14,000     +5,000 – +7,000
Fatigue Limit (106 cycles, kpsi)      10 – 20              No data
Notes:
• Thinner deposits from copper sulfate solutions are usually stronger than thicker
• Thicker deposits from cyanide solutions are usually stronger than thinner
• Fatigue limit for copper deposited from a cyanide copper solution (using periodic
  reverse rectification) was twice that for sulfuric acid
                Bronze (Copper-Tin)
Applications:
  • Powertrain, hydraulic and bearing
    components
  • Hardware exposed to marine environments
    (corrosion rate = 0.002ipy)                            Bronze plated
                                                          hydraulic pump
  • Nitride stop-off,                                         cavities
                                                              Photo by F. Altmayer
Most commonly plated alloy: 8-15% Sn
  • High hardness (HV = 350-600)
  • Low coefficient of friction (0.06 on steel vs.
    0.14 for hard chrome)
Color ranges:
                                                                   Wikipedia photo
  • Red (8-10%Sn)
                                                     Bronze plating on a
  • Golden yellow (12-15%Sn)                          German ship hull
                                                           (1914)
  • White (>22%Sn)
                Bronze (Copper-Tin)
                120                                 600
                100                                 500
                 80                                 400
  Resistivity
Micro-ohms-cm                                             HV
                 60                                 300
                 40                                 200
                 20                                 100
                      20   40    60            80
                                Weight % Tin
                  White Bronze
        (55-60%Cu, 25-28%Sn, 14-18%Zn)
Features:
• 55-60%Cu, 25-28%Sn, 14-18%Zn
• Alternative to electroplated nickel
• Bright
• Solderable
• High Hardness (HV340-400)
• Non magnetic
• Effective diffusion barrier             White bronze plated spring
  between gold and copper               loaded washers for electronic
                                                  terminals
Limitations:
• 35% the conductivity of copper
• Cyanide based process
           Properties of Plated Silver
Features:
• Best conductor of heat and electricity of all metals
    -    Electrical resistance = 1.6-1.9 µ-ohms-cm, unless brightened with
         antimony (10 times more resistive)
• Ductile, Malleable
    -    UTS: 34-48ksi
    -    Elongation: 12-19%
•   HV25 = 40-200)
•   Melting point 960.5°C
                                                           Automotive fuse with silver
•   Boiling point 1950 ° C                                      plated contacts
•   Density 10.5 g/cc                                                        Photo by F. Altmayer
•   Excellent reflection of visible light
•    Internal stress: 1500-3500psi (tensile)
•    Anti-galling
•    Anti-bacterial
Limitations:
                                                        Silver sulfide whiskers growing
•       Silver readily reacts with sulfur               out of surface-mount resistors
        producing silver sulfide (Ag2S)                                      Photo by J. Reinhart
     Comparing Plated Precious Metals
Property                         Ag       Au        Rh       Pd          Pt
Color                            White    Yellow    White    White       Grey
Density, g/cm3                   10.5     17-19.3   16-18    11.5-12     21
Melting Point, °C                960      1060      1966     1552        1769
Hardness, HK25                   40-200    50-250   1000     250-500     280-350
Ductility (% elongation)         12-19    0.1-8     1.0      2-8         2-4
Catalytic Activity               No       No        Yes      Yes         Yes
Crystal Structure                FCC      Nano      FCC      FCC         FCC
Visible Light Reflection         Excel.   Poor      Excel.   Good        Fair
Internal Stress Kpsi             0-40     -8-40     70-140   10-100      36
Corrosion Resistance             Poor     Excel.    Excel.   Good        Excel.
Wear Cycles*                     <50      5-200     10,000   50          50
Contact Res. Ohms                <.6      0.3-0.6   0.8      .004-1.1*   .6
Arc Resistance                   Poor     Poor      Excel.   Poor        Poor
Solderability                    Excel    Excel.    Good     V Good      V Good
Thermal Exp. Coeff.              19.7     14.3      8.5      11.8        9.0
Thermal Conductivity**           1.0      0.71      0.21     0.17        0.17
       *Cross wire, 200 g load
       **Cal/cm/sec/°C
Properties of Electroplated Gold
Features:
• Typically alloyed with nickel, cobalt and other
  heavy metals
    -   Additive-free hard gold is available
• Hardness, HK25 =40-90 Pure, 140-250 Alloy                   Gold Plated Contacts
• Extremely malleable
    -   0.5mm diameter pellet can be hammered to >0.5
        square meter
• Highly corrosion resistant to most environments
• Low internal stress: -8,000ksi to +40,000ksi             Gold Whiskers
Liabilities:
• Can grow “whiskers”
• Chemically attacked by: Cyanide, Aqua Regia                          Gold Plate
                                                        Nickel Plate
                                                         Cross Section of Gold over
                                                               Nickel, 1000X
    Properties of Electroplated Gold
Stress:                                     -8500 to +40,000
Contact Electrical Resistance:              0.22-1.74 Milliohm/in2
Electrical Resistivity:                     2.4 micro-ohms-cm
Wear Properties
• Transitional metal Alloys               Best
• Organic Brighteners                     Good
• Semi-metallic Brighteners               Poor
Porosity
• Semi-metallic Brighteners               Best
• Organic Brighteners                     Good               Micro-circuit manufactured
                                                                 using gold plating
• Transitional metal Alloys               Poor
Notes:
•   Porosity of a gold deposit is also related to thickness, temperature, solution
    purity, and current density
•   Gold plating offers excellent corrosion resistance, excellent solderability,
    weldability and infra-red reflectivity
     Electronic Connections
Issues:
•   Corrosive environments
    - Atmospheric
    - Body corrosives (wearables)
                                            High Spot
•   Abrasive Wear
    - Connection cycles may be very frequent
•   Thermal effects
    - Heat dissipation requirements
    - Formation of inter-metallics
    - Diffusion
                                                         Resistance due to
•   Contact Between Mating Surfaces                     current constriction
    - Occurs only at the high spots, creating
       constriction resistance
    - Surface roughness has an impact on contact
       resistance
                                                           Illustration by F. Altmayer
       Electronic Connections
More Issues:
• Connectors are smaller, more dense and often carry
  a higher current density                                    Selectively plated connector
• Soldering nearer to the mating surfaces can heat
  the connectors to ~240°C
• Connectors may need to operate at higher
  temperatures (up to 300°C) vs. older designs                 USB connector
• Co hardened gold is not suitable at > 125°C
• Ni hardened gold is limited to about 200°C
   -   Soft gold over hard gold may allow service at higher
       temperatures
                                                               Apple type connector
                                                          Illustration courtesy of Molex Inc.
                                                          Photo by F. Altmayer
     Electronic Connections
Contact Electrical Resistance (CER):
• Films and abrasive residues from sliding friction increase CER
• Total CER is a combination of resistance due to constriction
  plus film resistance plus the force between mating surfaces
• Mating force may be <10 grams
                                                                 High Spot
             1.0
                                               0.0016” Ni under-plate
        CER 0.5
        (mΩ) 0.4
                                               0.0008” Ni under-plate
             0.3
                      0.0002” Ni under-plate
                 20      50     100      200
                                                                                  Resistance due to
                        Gram Load                                                current constriction
     Deposit          % Au     Resistivity (µΩ-cm) CER (mΩ)
     Pure Gold        100           2.4              0.3
     CoHG             99.5          15               0.6
     NiHG             99.3          11               0.3
                                                         Data from “Gold Plating Technology” by Reid and Goldie
     Electronic Connectors
Soldering Issues:
• Gold dissolves into the solder, bond is created by the
  formation of an intermetallic with the under-plated
  metal/alloy
• Solder containing > 4% Au can be brittle and may form
  a weak joint due to formation of intermetallics with
  (preferentially) Sn and Pb
Surface Roughness:
• Smoother surfaces yield low levels of porosity and
  lower CER values:
      Roughness (RMS)          Pores/cm (CoHG)
             1.6                         60
             5.5                         100
             31.5                        160
                                   Data from “Gold Plating Technology” by Reid and Goldie
    Gold Plating on Connectors
Features:
• Reliability
     -   Especially at current as low as 1 nano-amp
•   Corrosion resistance
•   Wear properties
•   Suitable for low force connections
•   Low/consistent contact electrical resistance
•   Not subject to degradation by fretting
•   Usable at elevated temperatures
Liabilities:
•   Cannot be mated to tin plated surfaces
•   Requires nickel (or other suitable) under-plate   Photo by F. Altmayer
•   Low arc resistance
•   Whiskers can produce short circuits
•   High cost of gold
          Properties of Palladium
Features:
   Melting Point 1555°C, Boiling Point 2200°C
   Density: 11.7-12.02 g/cm3
   Internal Stress: +10,000 to +100,000 psi
   Good Tarnish Resistance
   Hardness: 250-500 HK25
   Contact Resistance, 0.004-1.1 ohms
   Resistivity, 10.7 ohm-cm
   Solderability: excellent
   Thermal Expansion coefficient: 11.8
   Thermal conductivity: 0.17 cal/cm/°C
Liabilities:
   Attacked by HCl and HNO3
   Arc resistance: low
   Low ductility (Elongation: 2-4%)             Palladium plated jewelry
   Relatively Poor Wear Properties
   Polymer Adsorption on Surface
        Palladium-Nickel Alloys
 40 to 99+% palladium
 Bright
 Hard electrodeposits (450 to 600 KHN100)
 Much lower tendency toward micro-cracking
  and polymer adsorption
 Good chemical stability
 Good wear resistance
 Deposit crystal orientation is (100) or (110)
 More economical than pure palladium
 Outperformed by pure palladium deposits in
  applications serving at high temperatures
The End, Thank You!