Optimizing Palladium Conversion in Electroless

Palladium Plating of Alumina Membranes

By J.N. Keuler, L. Lorenzen, R.N. Sanderson & V. Linkov

Electroless palladium (Pd) plating on a

alumina membranes was investigated
with the aim of obtaining very high Pd Tetraammine palladium + hydrazine
conversions and pure Pd films. Interac- As above with formaldehyde addes
Tetraammine palladium chloride + hydrazine
tions among operating variables includ- As above with formaldehyde added

Pd mass plated, mg
ing Pd source, temperature, reducing
agent concentration, stabilizer concen- T=64 °C
tration and buffer pH, require proper
choice of these variables to ensure plat-
ing solution stability and to maximize
the conversion of Pd salt to Pd metal. A
preliminary investigation of these vari-
ables readily enabled conversions ex-
ceeding 80 percent to be obtained after
three hr of plating. Near optimal values
(>95%) were also achieved within a
three-hr reaction period for a very spe- Time, hr
cific choice of variables. Surface uniformity and purity of b
the deposited film were excellent. The operating concen-
tration of the stabilizer (Na EDTA) appears to be the most
significant consideration in the plating process. Varying
Na EDTA concentration results in an optimal region of
Pd conversion. Conversions quickly decreased when the
system became unstable or if the system had too great a
Pd conversion, %

stability.

Inorganic membranes covered with a thin electroless Pd film

are mainly used for hydrogenation/dehydrogenation reac-
tions. Palladium films for organic reactions and hydrogen
separation are currently an active area of research.1-3 In this
regard, electroless plating has several advantages over other
methods for creating such thin metal films. The formation of
uniform deposits, either in the bore or on the shell side of
tubular surfaces, to obtain dense, nonporous metal films of Time, hr
minimal thickness are important for creating defect-free Fig. 1—(a) effect of various Pd salts and reducing agents on mass of Pd
catalytic membranes. Several other applications exist for plated; (b) effect of various Pd salts and reducing agents on Pd
electroless Pd thin films, especially in the electronics indus- conversion.
try. These include fabrication of printed circuit boards, low
resistance ohmic contacts, chip-level interconnects4 and se- film impurities. A further unresolved aspect of this plating
lective metal deposition on silicon substrates.5 process is the Pd conversion achieved. Of the few publica-
Several disadvantages of using electroless Pd plating have tions in this regard, Pearlstein achieved 90 percent Pd conver-
been mentioned in the literature; these include low deposition sion after 19 consecutive one-hr depositions.7 By careful
rates, using hydrazine as reducing agent,6 difficulty with film choice of operating conditions and plating chemicals, all of
thickness control, Pd losses because of bath composition1 and the above-mentioned problems can be addressed, yielding
very pure Pd films at a relatively fast rate and with a high
Table 1 percentage of Pd conversion.
Solutions Used for Surface Activation
Background
Sensitizing Activation Electroless plating is the process of covering a substrate with
SnCl 2 · 2H2O 1 g/L Pd(NH3)4(NO3) 2 metal by means of the autocatalytic reduction of metal ions
1.5 mL, 10% solution/L with a reducing agent. It is similar to electroplating; the
HCl (32%) 1 mL/L difference is that a flow of electrons is not supplied by an
HCl (32%) 1 mL/L external source, but rather by the species in the aqueous
solution.

34 PLATING & SURFACE FINISHING

 Table 2 Table 3
Composition of Plating Solutions Plating Solutions Used for Additional
(Values/L) Experimentation
Solutions (Values/L)
1 2 3 4
Pd(NH 3) 4(NO3) 2 25 mL 25 mL — — Pd(NH3) 4(NO3) 2 (10% solution) 27.5 g
(10% solution)
NH 4OH (28%) 200 mL
PdCl2 — — 2.7 g 2.7 g
Disodium EDTA Varied from EDTA:Pd molar
NH 4OH (28%) 200 mL 200 mL 390 mL 390 mL ratio of 6 to 50
Disodium EDTA 20 g 20 g 35 g 35 g Hydrazine (molar ratio to Pd) Varied from hydrazine:Pd
molar ratio of 0.4 to 0.88
Hydrazine (molar 0.80 0.80 0.66 0.66
ratio to Pd) pH buffer (varied from 8 to 12) 100 mL
pH 10 buffer 100 mL 100 mL — — Temp (°C) Varied from 59 to 77 °C
Formaldehyde — 1.5 mL — 1.5 mL
(37%)
The catalysts for electroless plating not only act as plating
Temp (°C) 64 64 64 64
initiators, but have a considerable effect on the smoothness,
coverage, adhesion and surface quality of the deposited metal
film.
Surface Cleaning Catalyzing the inactive surface is done using a combina-
Proper cleaning of the area to be plated prior to activation and tion of tin and palladium. Two processes are commonly
plating is essential. Fingerprints, dirt and particles, such as used:16
ceramic dust, that exist on the surface or in the pores, will
cause nonuniform plating, metal film irregularities or lead to 1. The older, two-step immersion procedure, consisting of
loss in adhesion. a sensitizing step (SnCl/HCl), followed by an activation
Many cleaning procedures for ceramics exist in the litera- step with PdCl/HCl.
ture.8-10 Four cleaning steps usually precede surface activa- 2. The “exchange process,” requiring a catalyzation step
tion (alkaline clean, rinse, etch and rinse again). Etching is with PdCl/SnCl/HCl/HCI (colloids), then acceleration
optional and depends on the surface roughness of the speci- with NaOH or HCl.
men. When glass, plastic or non-porous ceramic is plated,
etching is required. For good metal adhesion, plastics are In recent years, methods have been developed using or-
etched with strongly oxidizing chromic acid solution or ganic solvents and ligands instead of tin4,17 for stabilizing the
chromic acid-sulfuric acid solution.11 The etchant chemically Pd colloids. These processes involve fewer steps and display
modifies the surface, making it hydrophilic and physically superior selectivity compared to the conventional Pd/Sn
roughening it to ensure mechanical locking and chemical catalyzing processes. Moreover, there are fewer adhesion
bonding of metal to plastic. Etching of ceramic and glass is problems compared to those encountered with a Pd/Sn cata-
done with sodium hydroxide12 or fluorides.9-10 Etching is lyst on Si-OH-containing surfaces (silicon, silica and glass).
usually not needed when cleaning porous materials.a Several mixed PdCl/SnCl catalyst solutions are listed in
the literature.16,18 Pd-Sn catalysts are colloids with the core
Surface Activation made from Pd and Sn, surrounded by Sn(II) as Cl- and OH-
Plating on most metals does not require catalytic activation.11 complexes. Accelerators are used to expose the catalytic Pd
Exceptions are stainless steels and titanium, which need to be core by removing the Sn. A method for evaluating catalysts
etched first, and materials (such as lead) that poison the for electroless plating was proposed by Horkans.19
electroless reaction. These exceptions, as well as nonconduc- The two-step procedure deposits more Pd on the surface
tors (ceramics, plastics) must be pretreated to create the than does the exchange process, ensuring a very even metal
catalytic surface required for controlled electroless plating. film over a large surface area after plating. The two-step
process also deposits less tin,19 which is important in obtain-
ing the very high-purity Pd film necessary for catalytic
membranes.

Choice of Chemicals
A limited choice of reductants is available for electroless
Pd conversion, %

plating (dialkylamine borane,20 borohydride, hypophosphite,7

formaldehyde and hydrazine21). Very little has been pub-
lished on the use of borohydride and boranes for the electro-
less plating of Pd. This option was not considered for this
study, because boron is codepsoited with Pd. Formaldehyde
is not a good reducing agent22 because of the small potential

a
Examples include Vycor13 glass, Corning, Inc., Corning, NY, porous stainless steel,14
Fig. 3—Effect of EDTA concentration on Pd conversion. and Membralox, 15 U.S. Filter Corp, Warrendale, PA.

August 1997 35
 Table 4
Pd Conversions for pH 9 & 11 Buffers
(EDTA:Pd molar ratio = 6)

EDTA:Pd (mol
Hydrazine
Buffer pH Temp (°C) (molar ratio) Conversion %
9 59 0.4 19.5

ar ratio)
11 59 0.4 19.0
9 59 0.72 38.7
Hy
11 59 0.72 35.7 dr
az
ine )
9 71 0.4 43.0 :P (°C
d( ture
11 71 0.4 45.5
mo p era
lar em
rat iont
io) lut
So
Table 5 Fig. 4—EDTA:Pd molar ratio required for plating solution stability.
EPd /Pd for various EDTA:Pd
+2

Molar Ratios at 25 °C Five different variables were investigated for their effect
on palladium conversion: Tetra-ammine palladium chloride
EDTA:Pd Molar Ratio 0 6 20 40 or tetra-ammine palladium nitrate, solution temperature, buffer
EPd /Pd (V)
+2 0.83 0.2601 0.2446 0.2357 pH and the concentrations of hydrazine and Na2 EDTA.
Plating temperature was controlled to ±0.5 °C from the
difference between the oxidation and reduction reactions that predetermined temperature of the water bath. The volume of
acts as the driving force. Hypophosphite is commonly used, the plating solution (22 mL per experiment) and the surface
but deposits usually contain in excess of 1.5 percent phospho- area to be plated, were kept constant. Plating was performed
rus,6 thereby reducing film quality. Problems with surface in glass vials precleaned with 6-percent HNO3. The palla-
adhesion of Pd, using hypophosphite, can be encountered in dium solution was allowed to stabilize for at least 8 hr prior
films exceeding 5 mm.23 Hydrazine was judged the most to plating. Both hydrazine and palladium solutions were
suitable and was chosen as our reducing agent. preheated to the predetermined temperature amd mixed, then
Disodium EDTA was used as a stabilizer because it forms the membrane (ends sealed with Teflon™) was added to the
a highly stabile palladium complex. Ammonium chloride can solution.
also act as a stabilizer when using PdCl for the metal salt.
Surface Cleaning
Experimental Procedure A simple cleaning procedure for the membranes, similar to
Ceramic membranes used in this study were supplied by that used by Collins,15 was performed. Membranes were
Potchefstroom University. The membranes consisted of √- sectioned into 5-cm lengths, using a diamond saw. Cleaning
Al2 O3 (70%) and ZrO2 (29%) stabilized with Y2 O3 (1%), comprised
leading to excellent mechanical properties and chemical
stability. The tubular membranes had a 12-mm outer diam- • treatment for 1 min in a 0.1 wt% NaOH ultrasonic bath
eter, wall thickness of about 0.8 mm and nominally the (room temperature)
following properties: 210-nm pore size, 48.5 percent poros- • ultrasonic treatment for 2 min in deionized water
ity and 4.0 m2/g surface area. • rinsing in isopropanol for 10 min
• rinsing in deionized water for a further 10 min
• drying at 110 °C for 8 hr.

Surface Activation
The two-step procedure (although now not much in
use) was chosen for reasons mentioned in the back-
ground section.
The solutions used for surface activation are listed
in Table 1. They are similar to those used by Shu.14 A
Pd conversion, %

fresh sensitizing solution was prepared for each

catalyzation. The activation solutions generally have
an indefinite shelf life.23 All solutions were, how-
ever, used within two weeks. In both cases, metal
salts were dissolved in deionized water prior to
adding HCl, resulting in a colloidal solution (which
favors high tin surface concentrations). Apparently,
T= 71 °C; EDTA-salt:Pd-salt molar ratio = 20:1; hydrazine: Pd-salt molar ratio = 0.721:1
lower tin surface concentrations can be obtained by
changing the mixing order of the sensitizing solu-
tion.19 Dissolving the tin salt in concentrated HCl,
then diluting, results in a true solution and a lower tin
Fig. 2—Effect of buffer pH on Pd conversion. surface concentration.

36 PLATING & SURFACE FINISHING

 • 2 min in sensitizing solution
• 30 sec in deionized water
• 2 min in activation solution
• 30 sec in deionized water

The membranes were then dried at 110 °C, cut

Pd conversion, %

into 8-mm lengths, scrubbed and washed again

in deionized water to remove ceramic dust.
Further drying was done at 110 °C before
beginning electroless plating.

Choice of Palladium Salt

For Maximum Conversion
For the experiments described in Fig. 1a, plat-
ing was carried out for 2 hr, using solutions 1 to
Temp, °C 4, as described in Table 2. The membrane was
then removed, washed with deionized water
Fig. 5—Effect of temperature on Pd conversion. and dried at 110 °C between one and two hr.
The plating and drying processes were repeated
several times. Palladium is reduced in the
following manner:

Pd(ammine complex)+2 + 2e- → Pd 0 (1)

Solution 3 was prepared in the same manner as

Pd conversion, %

Collins.15 The addition of one to two mL/L

formaldehyde are claimed to produce higher
quality films.13 In this study, a white gelatinous
precipitate was formed in the solution.
After establishing tetra-ammine palladium
nitrate without additional formaldehyde as the
best option for high Pd conversion, further
experimentation employed the solution de-
scribed in Table 3. Plating was carried out in 22
mL of solution for three hr. The solution was
slightly shaken every 10 min to improve homo-
Fig. 6—Effect of EDTA on Pd conversion at various temperatures.
geneity. Inductively coupled plasma (ICP) dis-
charge analysis showed that a time of three hr
was sufficient for a nearly complete plating
reaction. The membranes were then removed
from the glass vial, washed with deionized
water and dried for two hr at 200 °C. Conver-
sion was determined by the mass ratio of the Pd
Pd conversion, %

plated on the membrane to the Pd initially

present in the solution; the mass of the latter
had also been recorded, ensuring high accu-
racy.
Ammonium hydroxide is used to provide
stability and OH- for oxidation. The volume
(mL/L) was kept constant, because Athavale
reported that volumes above 100 mL/L had
little effect on Pd deposition (conversion).6

Results and Discussion

The Effect of Pd Salt
Fig. 7—Effect of EDTA on Pd conversion at various temperatures. On Percent Pd Conversion
As seen from Fig. 1b, in the presence of form-
aldehyde, the conversion was very low and decreased to zero
Membrane pieces, 5 cm in length, were sealed with Teflon™ after two plating sessions, making formaldehyde unsuitable
at the ends and only the outer surface was treated. The as a reducing agent in the absence of an osmotic driving force.
following four procedural steps were repeated 10 times, The precipitate is probably a polymerized form of tetraformal
resulting in a brown, evenly distributed catalytic layer over trisazine.24 The intermediate is formed according to the
the entire surface: following reaction:24

August 1997 37
 at high hydrazine concentrations. This phenomenon
can be clearly seen in Fig. 2. Experiments done
outside the pH buffer range of 9 to 11 caused a
sudden decrease in Pd conversion. Pd is then no
longer deposited on the membrane alone, but also on
Pd conversion, %

the surface of the glass vial and onto Pd nuclei

formed in the solution itself. The solution turns black
and no Pd ions are available for plating. Figure 3
shows the comparison between the Pd conversions,
in buffer pH 9 and 11, at various EDTA concentra-
tions. Slightly better conversion results are obtained
with a pH 9 buffer. Below an EDTA to Pd molar ratio
of 20, decomposition took place. Optimum conver-
Molar ratio of hydrazine to Pd-salt sion is obtained with pH buffer values of 9 to 11.
It was previously found that the pH does have a
Fig. 8—Effect of hydrazine concentration on Pd conversion at different EDTA
large influence on the stability of the Pd complex.25
The pH determines the degree of ionization of EDTA.
The fully ionized chelate anion (EDTA-4) forms the
strongest metal chelate (Pd-EDTA) complex. Chelat-
ing agents require high alkalinity to be very effec-
tive.25 In the pH range of 9-11, EDTA -3 and EDTA-
4
dominate and are capable of strong metal bonding.
Pd conversion, %

System Stability
A response surface, using a smooth spline to plot it,
was compiled indicating system stability (Fig. 4).
The molar ratio of EDTA to Pd, on the z-axis,
represents the value at which stability can be guaran-
teed for a specific temperature and hydrazine con-
centration. Values on and above the curve indicate
stability, while those below the curve show probable
instability. Increases in temperature and hydrazine
concentration require a sharp increase in EDTA
concentration to guarantee stability. An unstable
Fig. 9—Effect of EDTA on Pd conversion at various hydrazine concentrations. system is highly unfavorable and will always lead to
low conversions.

Combined Effect of Temperature

N N N & EDTA Concentration on Pd Conversion
4 HCHO + 3H2NNH2 ➝ +4H 20 Plating solution temperature and EDTA concentration are
N N N (2)
interactive parameters. From Fig. 5 it can be seen that the
temperature and EDTA concentrations must be chosen con-
Both the tetra-ammine complexes of palladium chloride and currently to achieve maximum conversion. Figure 5 also
palladium nitrate produce films that grow fairly linearly in shows that low EDTA:Pd molar ratios (6 and 14) cause bath
thickness with time if fresh solution is used every two hr (see depletion at high temperatures (above 66 °C) and a decline in
Fig. 1a). This linear time dependence is very favorable for Pd conversion. Pd conversion from stable solutions increases
controlling film thickness. The chloride salt gives lower as expected with increasing temperature;27 for example, the
conversions; the nitrate form was preferred. case where the EDTA to Pd molar ratio is 30. The figure also
clearly shows the generally higher conversion at a higher
Effect of pH on Conversion EDTA concentration.
Plating was done in an alkaline solution, because hydrazine According to Fig. 6, the EDTA:Pd salt molar ratio has one
is a better reducing agent in an alkaline rather than acidic of three effects. These are best illustrated by the T=71 °C and
medium: T=77 °C curves. First, at low EDTA to Pd molar ratios
(concentrations), conversion is low because of bath decom-
N2H4+ 4OH- → N2 + 4H2O + 4e- E = +1.16 V (3) position. Second, an increase in concentration increases
stability and conversion. Third, when the EDTA concentra-
N2H5 + → N2 + 5H+ + 4e- E = +0.23 V (4) tion is too high, there is a decline in conversion, presumably
because of too great a stability. EDTA to Pd molar ratios
Operating in the pH buffer range of 9 to 11 had little effect on between 20:1 and 40:1 and T ≥ 65 °C result in conversion
the conversion of the metal ion (see Table 4), but is necessary levels greater than 80 percent (at the given hydrazine and
to maintain the correct potential difference for the oxidation buffer pH values).
and reduction reactions. Lower hydrazine concentration (Fig. 7) shows a trend
The use of higher or lower pH buffers resulted in decom- similar to that shown in Fig. 6. The stability limit is achieved
position of the plating solution either at high temperatures or at lower EDTA concentrations (14 molar ratio or lower). In

38 PLATING & SURFACE FINISHING

the stable region, higher temperatures always result in higher ure 10 confirms this. The curves in Fig. 10 have similar
conversions. Maximum conversion at this lower hydrazine shapes, but the higher hydrazine concentration causes a shift
concentration is lower than that shown in Fig. 6, proving that to higher EDTA concentrations required for stability.
hydrazine concentration has a definite effect on palladium Excess hydrazine is required for optimum conversion,
conversion. because hydrazine catalytically decomposes in solution. This
Both temperature and EDTA concentration have an effect subject is extensively covered in the literature.24,29 Thermal
on potential difference. An increase in temperature leads to decomposition increases with increasing temperature and the
an increase in Epd +2/pd, according to the Nernst equation, while presence of the metal catalyst. Decomposition proceeds
increasing EDTA concentration reduces the potential.14 It can mainly by the following reaction:
be concluded that large potential differences will cause
decomposition of the plating solution. This was observed at 3N2 H4 → 4NH3 + N2 (6)
the lower EDTA:Pd molar ratio (value of 6) seen in Fig. 5, for
T > 65 °C, where decomposition took place. EDTA is a very Small amounts of hydrogen are also formed according to:
good stabilizing agent for Pd, with a stability constant of log
KPdEDTA equal to 18.5.28 EDTA effectively reduces the Pd N 2H4 → N2 + 2H 2 (7)
potential (Table 5), stabilizes the Pd ion and results in a
slower reaction rate, high stability and high Pd conversion. The latter reaction becomes more probable with increasing
This extra stability brought on by the higher EDTA concen- pH.29 To obtain maximum conversion and sufficiently high
tration shifts decomposition of the plating solution to higher stability, 40 to 60 percent excess hydrazine is recommended.
temperatures (Fig. 5).
Film Purity
Combined Effect of Hydrazine High-purity films were obtained. Energy dispersive X-ray
& EDTA on Pd Conversion analysis (EDAX) showed only Pd, and small amounts of Al
The complete autocatalytic reaction is: and Zr. The presence of aluminum and zirconium is not
surprising, because they form part of the underlying mem-
2Pd(NH3) 4+2 + N2H4 + 4OH- → 2Pd0 + 8NH3 + N2 + 4H2O (5) brane material.

Stoichiometry predicts that a 0.5 hydrazine to Pd molar Findings

ratio is required for complete reaction. This was not found in 1. Tetra-ammine palladium nitrate was found to be the best
practice, however. Conversion increased with increasing Pd salt with which to achieve high Pd conversions. The
hydrazine concentration (Fig. 8), beyond the expected sto- use of hydrazine as the reducing agent produces the purest
ichiometric value. This was not in agreement with results Pd films.
obtained by Rhoda.27 He obtained the expected stoichiomet- 2. Plating is done in an alkaline solution with a pH buffer
ric value. This is probably because of the higher operating between 9 and 11. The stabilizer (EDTA) and reducing
temperatures we used, resulting in increased hydrazine de- agent perform best in this pH range, while higher and
composition. The exception in this figure, where conversion lower pH buffers tend to cause bath instability and rapid
declines, is because of bath decomposition. No instability conversion decline.
was encountered with hydrazine to Pd molar ratios of 0.56 3. Excess hydrazine (40-60 percent above stoichiometry) is
and 0.4. Higher molar ratio values did cause decomposition required to compensate for thermal decomposition of the
below an EDTA to Pd molar ratio of 14. Figure 9 clearly hydrazine and to ensure high conversions.
indicates an increase in conversion with an increase in hydra- 4. Decomposition of the plating solution occurs more readily
zine concentration at EDTA:Pd molar ratios above 14. Fig- when the hydrazine concentration and temperature in-
crease; in this case, solutions re-
quire high EDTA concentrations to
remain stable.
5. The effect of EDTA concentra-
tion is non-linear—too high a
value results in too stable a com-
plex, while too low a value shows
insufficient stability. Both cause
Pd conversion, %

a reduction in conversion.
6. Pd conversions in excess of 95
percent were obtained, within
three hr, using tetra-ammine pal-
ladium nitrate as Pd salt under
the following conditions: T=77
°C, hydrazine to Pd molar ratio
= 0.72:1, EDTA to Pd molar
ratio = 30 to 40:1 and buffer pH
= 11.

Editor’s Note: Manuscript re-

ceived, August 1996.
Fig. 10—Effect of EDTA and hydrazine concentrations on Pd conversions.

August 1997 39
Acknowledgments About the Authors
The authors wish to thank SASOL and the Foundation for Johan Keuler is a graduate student at
Research and Development for their financial support. the University of Stellenbosch. He ob-
tained a B.Eng. with distinction at
References Stellenbosch in 1995. Some of the un-
1. J. Shu, B.P.A. Grandjean, et al., Can. J. Chem. Eng., 69, dergraduate awards he received include:
1036 (1991). The SA Institute for Chemical Engi-
2. J.N. Armor and T.S. Farris, Proc. 10th Int’l Cong. on neers’ prize for the best final-year chemi-
Catalysts, July 1992, Budapest, Hungary. cal engineering student at Stellenbosch
3. J.N. Armor, Catal. Today, 25, 199 (1995). and the AECI prize for the best first-
4. W.J. Dressick, C.S. Dulcey, et al., J. Electrochem. Soc., year student.
141, 210 (1994)
5. H. Cachet, M. Froment, et al., J. Electrochem. Soc., 139, Professor Leon Lorenzen is professor
2920 (1992). and chair of the Department of Chemi-
6. S.N. Athavale and M.K. Totlani, Metal Fin., 87, 23 cal Engineering at the University of
(1989). Stellenbosch, Banhoek Road,
7. F. Pearlstein and R.F. Weightman, Plating, 56, 1158 Stellenbosch 7600, South Africa. He
(1969). joined the department in 1990 after sev-
8. Y.T. Sasaki, J. Vacuum Sci. and Technol., A, 9, 2025 eral years’ industrial experience in the
(1991). gold and uranium industries, as well as
9. D.W. Baudrand, Plat. and Surf. Fin., 71, 72 (1984). two years’ experience in the aerospace
10. A.K. Graham, Electroplating Engineering Handbook, industry. He holds a B.Eng. in chemical
3rd Ed., Van Nostrand Reinhold, New York, NY, 1971. engineering, an M.Eng., and PhD (Eng.) in metallurgical
11. Kirk-Othmer, Encyclopedia of Chemical Technology, 8, engineering from the University of Stellenbosch and a post-
738, 3rd Ed., John Wiley and Sons, New York, NY, graduate diploma in systems engineering. He has published
1980. as author or co-author 21 papers in international symposia.
12. K. Lin and C. Jong, Mater. Chem. and Phys., 35, 53 Prof. Lorenzen teaches high-temperature thermodynamics,
(1993). electrochemical engineering, mineral processing, project
13. K.L. Yeung, J.M. Sebastian, et al., Catal. Today, 25, 231 and technology management. His research interests include
(1995). all aspects of hydrometallurgy, especially leaching, waste
14. J. Shu, B.P.A. Grandjean, et al., J. Membrane Sci., 77, processing and reactive processes using membranes, resins
181 (1993). and activated carbon.
15. J.P. Collins and J.D. Way, Ind. Eng. Chem. Res., 32,
3006 (1993). Dr. Ronald D. Sanderson is the direc-
16. N. Feldstein, J. Electrochem. Soc.: Electrochem. Sci. tor of the Institute for Polymer Science at
and Technol., 121, 738 (1974). the University of Stellenbosch. He ob-
17. A.M.T. Van Der Putten, J. De Bakker, et al., J. tained a B.Sc. and B.Sc. Hon. at the
Electrochem. Soc., 139, 3475 (1992). University of Cape Town (South Africa)
18. T. Osaka and H. Takematsu, J. Electrochem. Soc.: Elec- and a PhD at the University of Akron. He
trochemical Sci. and Technol., 127, 1021 (1980). has published as author or co-author 90
19. J. Horkans, J. Electrochem. Soc.: Electrochem. Sci. and publications in international journals and
Technol., 130, 311 (1983). holds 18 patents. His main interests are
20. W.V. Hough, J.L. Little, et al., U.S. patent 4,255,194 membranes, separation, reactors and polymers.
(1981).
21. R.N. Rhoda and A.M. Madison, U.S. patent 2,915,406 Dr. Vladimir Linkov completed his
(1959). undergraduate studies in Russia and his
22. I. Ohno, O. Wakabayashi, et al., J. Electrochem. Soc.: PhD in 1995 at the Institute for Polymer
Electrochem, Sci. and Technol.,132, 2323 (1985). Science, University of Stellenbosch. He
23. J.P. Collins, PhD: Catalytic Decomposition of Ammonia has published several papers and is cur-
in a Membrane Reactor, Oregon State University (1993). rently part of a research team at the
24. E.W. Schmidt, Hydrazine and its Derivatives: Prepara- SASOL Centre for Chemistry at the Uni-
tion, Properties, Application, John Wiley and Sons, New versity of Potchefstroom (South Africa).
York, NY, 1984.
25. Ullmann, Ulmann’s Encyclopedia of Industrial Chemis-
try, A10, 96, 5th rev. ed.; VHC Publishers, Germany, Note: Correspondence regarding this paper should be addressed to Professor
1987. Lorenzen.
26. Kirk-Othmer, Encyclopedia of Chemical Technology, 5,
353, 3rd Ed., John Wiley and Sons, New York, NY,
1980.
27. R.N. Rhoda, Trans. Inst. Met. Fin., 36, 82 (1959).
28. L.G. Sillen and A.E. Martell, Stability Constants of
Metal-Ion Complexes, Special Publication No. 17, p.
639; The Chemical Society, London (1964)
29. L.F. Audrieth; The Chemistry of Hydrazine, John Wiley
and Sons, New York, NY, 1951.
40 PLATING & SURFACE FINISHING