ELECTRONIC SUPPLEMENTARY MATERIAL

for paper:

Spatio-Temporal Organization in Alloy Electrodeposition: a Morphochemical Mathematical Model and its Experimental Validation.

Benedetto Bozzini, Deborah Lacitignola, Ivonne Sgura

Journal of Solid State Electrochemistry

1) gallery of morphological types

In this section we report an extensive selection of spatio-temporal structures published in the literature, classified according to the 6 types defined in Section 4 of the main paper.

1.1 Labyrinth types

3 sub-types of labyrinth have been recognized, documented below: (i) stripe labyrinth, (ii) entangled labyrinth, (iii) “spots and worms labyrinth.


1.2 Waves

1.3 Targets

1.4 Spirals

1.5 Broken spirals


1.6 Mixed type patterns


2) BATHS USED FOR ALLOY ELECTRODEPOSITION EXHIBITING SPATIO-TEMPORAL STRUCTURES

In this section we report the compositions of alloy electrodeposition baths published in the literature, used for investigations into the formation of spatio-temporal structures.

2.1 Ag-Alloys baths

Ag-Sb / Ag-Bi / Ag-Cd / Ag-In / Ag-Sn
bath A / Ag-Sn
bath B
AgNO3 / 0.075¸
0.15M
K4Fe(CN)6 ·3H2O / 0.043¸
0.21 M
KAg(CN)2 / 0.075¸
0.3M / 32¸60mM / 33¸80 mM / 42, 78mM / 78 mM
KCN / 0¸1.85M / 0.56¸1M / 0.25¸1 M / 0.92M / 0.92M
K(SbO)
C4H4O6·3H2O / 4¸50 mM / 0.14¸0.2M
SnCl2·2H2O / 36¸90mM
Sn2P2O7 / 48mM
InCl3 / 0.05¸
0.22M
In(NO3)3 / 0¸0.2 M
BiNO4 / 0.03¸0.09M
K2CO3 / 0.045¸
0.23M
KSCN / 1.5M / 0¸1.24M
KNaC4H4O·4H2O / 0.21M / 0.21 M
KOH / 0.14M
NaOH / 0.64 M
Na2EDTA·2H2O / 0.16M / 0.16M
H2O2 (30%) / 18mM / 18mM
D(+)-Glucose / 0.1 M

Ag-Sb [3-6, 32-40]

Ag-Bi [35, 36]

Ag-Cd [23-25]

Ag-In [2, 26-31]

Ag-Sn [41]

2.2 Non-silver based systems

In-Co [1]

InCl3 0.044M

CoSO4×7H2O 0.5M

(NH4)2H-citrate 0.09¸0.18M

KNa-tartrate 0¸0.024M

Ir-Ru [42, 43]

NaCl-KCl-CsCl (30-24.5-45.5 mol. %) + Ir & Ru chlorides (melt: 4.3 w/o Ir, 2 w/o Ru) 550°C

3) CRYSTAL STRUCTURE OF ELECTRODEPOSITED Ni-P-W-Bi ALLOY

The electrodeposited W 6.9 w/o, P 7.6 w/o, Bi 4.3 w/o Ni-base alloy discussed in Section 2 of the main paper exhibits an X-ray amorphous structure, with evidence of clustering. The X-ray diffractogram, is shown below. XRD measurements were made with a Philips X-PERT diffractometer equipped with a vertical Bragg–Brentano powder goniometer. A step–scan mode was used in the 2θ range from 5° to 90° with a step width of 0.02° and a counting time of 15 s per step. The employed radiation was monochromated CuKα (40 kV – 40 mA).

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