P o w d e r Technology, 24 (1979) 245 - 250 245

© Elsevier Sequoia S.A., Lausanne - - P r i n t e d in the Netherlands

Cbnracteristics of Electrolytic Zinc Powder Produced from Zinc Dross

I. F. HEWAIDY, H. O. SABRA and E. H. NASSIF

Industrial Metallurgy Dept., Natz'onal Research Centre, D o k k i , Cairo ( U . A . R . )
(Received July 20, 1979)

SUMMARY ticle shape made possible by the reduction

method, are perfectly assured by the elec-
The technology of electrodeposition of trolytic process. Variables permitting precise
z i n c m e t a l p o w d e r f r o m z i n c d r o s s is r e v i e w e d . control of chemical and physical properties of
Electrolysis was carried out utilizing sodium the powder include composition of the elec-
zincate solution obtained by dissolving the trolyte (concentration of metal and pH), tem-
zinc dross in caustic soda and separating the perature of the electrolyte, rate of circulation
undissolved iron residue. The effect of both of the electrolyte, current density, size and
the cathode current density and the zinc ion type of anode and cathode and their distance
concentration on the shape, structure, size, from each other, removal of deposits of the
particle size distribution and specific surface cathode, and additive agents. Although there
area of the produced powder was investigated. are several methods for recovering metallic
zinc from zinc dross, namely the aluminium
and modified aluminium processes [8 - 11],
INTRODUCTION Hewaidy and Nassif [12] prepared zinc pow-
der by electrolysis of sodium zincate solution
Early attempts to utilize zinc dust for the prepared from zinc dross.
fabrication of sintered products have achieved
little success, presumably due to the high
o x i d e c o n t e n t o f t h e p o w d e r . I t is r e c o g n i z e d
t h a t z i n c is e a s i l y o b t a i n e d i n e i t h e r p o w d e r EXPERIIVIENTAL
or sponge form by electrolysis of acidified or
n e u t r a l s i m p l e z i n c s a l t s a s w e l l as t h e alk~line The zinc dross obtained from the galvaniz-
zincate solutions. In the case of non-acidified ing plant in the Egyptian Iron and Steel Com-
s i m p l e s a l t , s p o n g e is o f t e n f o r m e d e v e n a t plex was cut into small parts. Three different
low current densities and high temperature, samples were prepared by treating 10, 20 and
£e. u n d e r t h e inverse c o n d i t i o n s t o t h o s e 30 g of the dross with 5 N sodium hydroxide
usually favouring the deposition of zinc pow- solution. By heating the pulp obtained at
der. Zincate baths are quite suitable for the 7 0 °C a l l t h e z i n c m e t a l w a s d i s s o l v e d , t h e n
production of zinc powder. Deposition of the undissolved residue was separated by
zinc powder from zincate solutions has also filtration. Aliquots of 250 ml of the solution
b e e n i n v e s t i g a t e d ;~y C a l u s a r u [ 1 ] , P a s s e r [ 2 - were subjected to electrolysis in a cell com-
3] and others [ 4 - 5]. Several authors [7] prising a nickel anode and alumininm cathode.
have prepared highly reactive electrolytic zinc The electrodes were firstly degreased, cleaned
dust for the production of hydrosulphltes and and washed thoroughly with disvilled water.
for the hydrogenation of vinyl acetylene to E l e c t r o l y s i s w a s c a r r i e d o u t a t 3 0 °C f o r 1 5
butadiene_ rain at varying amperages ranging between
Zinc powder produced by electrodeposi- 50 and 150 A/ft z of the exposed cathode
t i o n f r o m z i n c a t e s o l u t i o n is c h a r a c t e r i z e d b y surface. The distance between the two elec-
its extreme purity. Moreover, certain advan- trodes was 30 mm. The zinc powder re-
tages of other processes, such as the control covered was washed carefully and dried at
o v e r a p p a r e n t d e n s i t y , p a r t i c l e s i z e , a n d tc a t - I 0 0 °C.
 246

TABLE 1
Screen analysis of zinc powder produced under different conditions

Screen Mean 1 0 g/l z i n c d r o s s 2 0 g/1 z i n c d r o s s 3 0 g/l z i n c d r o s s

analysis particle
(/Am) size 50 A/ft 2 100 150 50 A/ft 2 100 150 50A/ft 2 100 150
(ram)

-- 600 + 500 0.550 0.39 0.45 1.17 1.02 1.99 1.23 0.65 0.76 1.09
- -500 + 250 0.375 8.43 5.14 6.04 9.28 8.16 2.53 10.65 14.60 9.69
-- 250 + 180 0.215 7.02 7.19 7.99 15.62 12.59 5.53 19.10 16.81 15.55
-- 185 + 106 0.143 32.2 18_95 14.13 34.82 27.44 29.24 37.34 34.44 32.70
-- 106 + 75 0.0905 18.26 14.04 14.03 15.80 17.45 17.57 12.04 11.69 17.37
- - 75 + 45 0.060 19_94 26.26 18.62 14.66 17.53 19.65 10.61 12.74 13.14
- - 45 + 0 0.0225 13_76 27.97 38.02 8.80 18.84 24.25 9.61 8.96 10.46

Polished sections of different zinc powder respectively added together. By dividing the
samples were prepared for metallographic summation of the theoretical surface of all
studies. The powder was mLxed with a cold- weight fractions by the total grain weight we
setting resin and mounted in a plastic mould obtain the theoretical specific surface area
under vacuum. The technique was found to (Oi~),
be the most adequate because it forces the
resin to penetrate inside the pores between
giMll
O ~ - - - cm2/g
the particles. Grinding and polishing steps gi
were conducted according to those techniques and the theoretical specific grain number (n K)
usually applied for soft metals.
The particle size distribution was de~er- giM2i
nk - - - particles/g
mined using ASTM standard sieves, sizes 500, gi
250, 180, 106, 75 and 45 pm. Sieving was
carried out for 15 rain using a laboratory sieve The representative diameter is then calcu-
shaker. lated as follows:
The specific surface area, specific grain
number and the representative diameter were
calculated using the conventional method of d. = 10 [/ _ _ (ram)
V n~<Tr
Bindernagel [13]. In this method, the average
diameters of the individual screen fractions, Table 1 is an example of such calculations
din, are calculated by taking the arithmetic for the theoretical specific surface area, the
mean value, based on the mesh sizes of two theoretical grain number and the representa-
consecutive test screens. The percent weight tive diameter of the powder obtained. This
f r a c t i o n s , g~, f o r t h e r e s p e c t i v e s i e v e a n a l y s e s powder was deposited from solutions contain-
are multiplied by the factor M 1 for the theo- i n g 1 0 g/1 z i n c d r o s s , a n d e l e c t r o l y s i n g at 20
retical surface area and by the factor M 2 for A / f t 2.
the theoretical grain number. The factors M1
and M 2 are calculated as follows:
RESULTS AND DISCUSSION
6,-rd 2 6
_ _ -- _ _ (cm 2/g)
M1 d3 a~ dm a D i s s o l u t i o n o f z i n c dross
When compared with the highly reactive
6 m e t a l s , z i n c is h a r d l y a t t a c k e d by water be-
(particles/g) cause of the formation of a passive and dif-
ficultly soluble hydroxide layer on the surface
where dm is the average particle diameter and of the metal. However, the situation is quite
a is t h P t r u e d e n s i t y o f z i n c . E a c h o f t h e c a l - different in either an acid or an alkaline me-
culated theoretical surfaces, and theoretical dium. The amphoteric zinc hydroxide dis-
grain numbers of all the weight fractions are solves in acids to form zinc salts and in alkao
 2,t7

(a) (b)

(c) (d)
lies to give soluble zincates according to the
following equations:
Zn(OH)2 + 2H* > Z n 2÷ + 2 H 2 0
Zn(OH)2 + 201-1- ~ Zn(OH) 2-
T h a t is w h y z i n c d r o s s is r e a d i l y a t t a c k e d
by sodium hydroxide solution giving soluble
zincate, whereas both ferrous and ferric hy-
droxides are precipitated [14]. In this way,
t h e f i l t e r e d s o l u t i o n is a l m o s t p u r e s o d i u m
z i n c a t e w h i c h is f r e e f r o m a n y o t h e r i m p u -
rities and therefore may be efficiently elec-
trolysed to recover zinc powder.
(e)
S h a p e a.~d s t r u c t u r e o f t h e z i n c p o w d e r
Fig. I. Microphotographs of zinc p o w d e r s (x 400). produced
(a) Zinc dross 30 g]l, current density 1 5 0 A/fig; (b)
As the shape of the powder (spheres, fern-
zinc dross 20 g/l, current density 1 5 0 A/ftz; (c) zinc
dross I0 g/I, current density 50 A/ft : (d) zinc dross like, dendritic etc.} has a great effect on the
10 g/l, c u r r e n t d e n s i t y 100 & / f t x ; (e) zinc dross 10 g/i, packing of the powder, it affects then the
c u r r e n t d e n s i t y 150 A / f t 2. kinetics of the sintering process of such a
248

TABLE 2
Example o f screen analysis, surface area and n u m b e r o f particles
~c~ ~c~ M2~x 104 M2"/gix 104
d( m
amto) d u dm
(ram)
gi
(g)
2/g) (partlcles/g) (particles)

0.500-0.600 0.550 0.39 15.3 5.97 0.1609 0.0628

0.250-0.500 0.375 8_43 22.4 188.8 0.5075 4.2782
0.180-0.250 0.215 7.02 39.1 274.5 2.6928 18.9043
0.106-0.180 0.143 32.7 58.7 1890.1 9.1520 294.6944
0.075-0.106 0.0905 18.26 92.8 1694.5 36.0218 657.7581
0.045 - 0 . 0 7 5 0.060 19.94 140.0 2791.6 123.6111 2464.8053
0 -0.045 0.022~ 13.76 375.5 5139.4 2344.038 32253.962
11984.87 35694.464 x 10 4

11984.87 concenErahon of NGOH :200g/L

0~: - - 119_84 cm2/g t e m p e r a t u r e of Darn -ZS°C
100 tlme of depos, rer~a~GI =-=Jm n
3 5 6 9 4 . 4 6 4 X 104 oJrrent dens=ty :SOA/ft 2
n~( = - 356.94 X 104 particles/g concentra:lon of z i n c d r o s s g/L
100 - 10
=ZO

d n = 10 -- I 0 = .<
3 5 6 . 9 4 X 104 X rr
0.0327 cm
,.=
powder. For this reason the effect of the elec- P,
trolytic conditions on the shape of the par-
t i c l e s is o f f u n d a m e n t a l i m p o r t a n c e t o t h e
powder metallurgical processes. The micro-
p h o t o g r a p h s (Fig. 1 a - e) r e v e a l q u i t e c l e a r l y
the dendritic and fern-like shapes which char- 8~ ,~o 2~o 3~ £o ,eo sso

acterize the electrolytic powders. The struc- ME~-'~N PARTICLE S I Z E IJ

t u r e o f t h e p o w d e r p a r t i c l e s is c h a r a c t e r i s t i c a l -
Fig. 2. Particle size d i s t r i b u t i o n o f the zinc powder
ly crystalline. Each particle usually contains produced a t 50 A / f t 2 and different zinc ion c o n c e n -
several individual grains (cryst~llites). trations.
T h e m i c r o g r a p h s l ( a ) - (e) i n d i c a t e t h a t t h e
p a r t i c l e size o f t h e r e c o v e r e d z i n c p o w d e r ef-
fectively decreases with increasing current Table 2 shows the results obtained from
density and decreasing zinc ion concentration. sieve analysis of the various zinc powders pro-
The smallest particle size shown in microphoto- duced under different electrolysis conditions.
graph No. l(e) was obtained by electrodeposi- Figures 2 - 4, reproduced from Table 2, rep-
t i o n o f z i n c p o w d e r u~_ng t h e h i g h e s t c u r r e n t resent plots of the mean par~cle size versus
d e n s i t y ( 1 5 0 A / f t 2) a n d t h e l o w e s t z i n c i o n weight percent for the powder produced at
concentration (10 g/l). 50, 100 and 150 A/ft z respectively. At each
amperage three different concentrations of
Particle size distribution of electrolytic zinc zinc solution were processed, D~mely 10, 20
powder a n d 3 0 g/1. T h e c u r v e s s h o w t h a t t h e p a r t i c l e
The performance of the powder during size decreases by decreasing the zinc ion con-
sintering and the physical properties of the centration in the bath, especi~l!y at higher
finished product are greatly influenced by any cathodic current density.
change in the average particle diameter or in Figures 5 - 7, also reproduced from Table 2,
d i s t r i b u t i o n o f sizes. T h e s p e c i f i c a t i o n s cover- show the effect of cathodic current density
ing particle size and size distribution are on the particle size of zinc powder. The peaks
usually very strict in the field of pcwder o£ the curves are progressively altered to the
metallurgy. s m a l l s i z e a s t h e c u r r e n t d e n s i t y is i n c r e a s e d .
 249

c o n c e n t r a t = o n of NcOH :2OOg/L concentratton Of Nt~0H =200g/L

temperature ot b a t h ;ZS°C temperc2ture of bath =2r~°C
t , m e of d e p o s = t r e m o v c l :tSm=n t,me of deposmt r e r n o v o l ~5mln
current dens:ty :1QOA/ft 2 concentrotlon of z i n c d r o S s = t 0 g / L
concentrot,on of z i n c c r o s s cJ/L current dens:ty A /It2

~ O
• 10 o 50
o 100
150
2O .~ 20

~ ~o

2O 2O

~I e
80 160 2L0 320 z,00 /-80 5E0 ~o ,~o ,Lo ~o '
r.O0 t.BO 560

~E~,'J P~,RTICLE S ZE U MEAN PARTICLE SIZE p

F i g . 3- 9ax~icle size d i s t r i b u t i o n o f t h e z i n c p o w d e r Fig. 5. P a r t i c l e s i z e d i s t r i b u t i o n o f t h e z i n c p o w d e r

produced at I00 A ] f t 2 and di£ferent zinc ion concen- p r o d u c e d a t 1 0 gfl z i n c d r o s s a n d d i f f e r e n t c u r r e n t
trations. densities.

i concentration o f NoOkNoOH =200g/t c o n c e n t r o , , o r of r'{=Oi~ :200g/L

temperature of b Q ttn n =2S°C temper{r_re o f b~{n -ZS°C
hme 0t d e p o s = t rt e r n oovvoo I :15 m l n
hm£ of =15N'*tn
cepcs,t r e m o v a l
I current density =150,cvt~ C0ncertrG°lon of z : ~ dross -~0g/ L

20,
.t0 dross g/L current
•
o
density
50
100
A /f= 2

2C ~50
o

o=
2c

2O 2C

r.80 500

MEAN PARTICLE SIZE ~J MEAN PARTICLE SIZE [J

Fig. 4. Particle size distribution o{ the zinc powder Fig. 6. Particle size distribution o£ the zinc powder
produced at 150 A/~t 2 and different zinc ion concen- p r o d u c e d a t 2 0 gfl z i n c d r o s s a n d d i f f e r e n t c u r r e n t
trations. densi.ties.

T h i s e f f e c t is m o r e p r o n o u n c e d f o r t h e l o w duced from Table 3, demonstrate the effect

c o n c e n t r a t i o n o f z i n c ( 1 0 g/1 z i n c d r o s s ) . of the concentration and of current density
T h i s result is in good a g r e e m e n t w i t h t h e o n t h e s u r f a c e a r e a o f t h e p o w d e r . T h e s e fig-
previous discussions. ures clearly show that changes in surface area
are r o u g h l y p a r a l l e l w i t h v a r i a t i o n s i n p a r t i c l e
=.~/Ji ' f ( 7 ~ e a r e g s i z e , a n d t h i s is a n o r m a l e x p e c t a t i o n i n p o w -
The specific surface area of metal powders der technology.
has a p~onounced effect on the compacting
b e h a v i o u r a n d k i n e t i c s o f s i n t e r i n g as w e l l as REFERENCES
on the degree of oxidation of powder by 1 A_ C a l u s a r u , B u l . I n s t . P o l i t e h . B u c u r e s t i , 1 9 ( 1 9 5 7 )
atmospheric oxygen. Figures 8 and 9, repro- (1 - 2) 353; Chem. Abstr., 53 (1959) 49669.
 25O

TABLE 3
S p e c i f i c s u r f a c e area, n u m b e r o f p a r t i c l e s / g , r e p r e s e n t a t i v e d i a m e t e r f o r z i n c p o w d e r p r o d u c e d u n d e r d i f f e r e n t
conditions

Zinc concentration, g/l 10 20 30

Current density, A/ft 2 50 lC0 150 50 100 150 50 100 150

1. S p e c i f i c s u r f a c e a r e a 1 1 9 . 9 169.5 194.0 96.8 134.3 154.5 93.8 92.3 101.2

(Ok:), c m 2 / g

2. N u m b e r o f p a r t i c l e s 356.9 695.1 920.8 233.7 472.5 601.9 246.7 233.7 271.2

per g (n~) X 104

3. Representative 0.033 0.029 0.026 0.036 0.030 0.029 0.035 0.036 0.035
diameter (dn) , cm

current denslty A /ft 2

concentrat:on OE NGOH --7.03g/L
• 50
temperG'urP of hath :ZS°C
o 100
t:me of depoSrt removal =~5m,n z: 150
concentrotlon of zinc d r o s s = 3 O g / L
current aenslty A/ft z ~'Zl0
- 50 E
° 100
~SO ~ i 90
2O

"~ 170

LL 2 0
~ 150

~- 130
Ld
L~J C_
mli 0
2O

90
80 160 Z&0 320 "~0O 4~0 560 10 20 30
CONCENTRATION OF ZINC DROSS g / L
MEAN PAPT|CLE SIZE U
Fig. 9 . R e l a t i o n b e t w e e n t h e s p e c i f i c s u r f a c e area
Fig. 7. P a r t i c l e s i z e d i s t r i b u t i o n o f t h e z i n c p o w d e r of zinc powder and current densities.
p r o d u c e d a t 3 0 g/I z i n c d r o s s a n d d i f f e r e n t c u r r e n t
densities.
2 M. P a s s e r a n d G . H a n s e l , Wiss. V e r 6 f f . S i e m e n s
concen'rat|on o; z,nc droSS ~. Werken, 18 (1940) 124.
;0
20
3 M. Passer, Kolloid Z., 97 (1941) 272.
3O 4 W. R u t k o w s k i a n d B. W i n s c h , Pr. I n s t . M i n .
~21(
Hutnictwa, 8 (1956) 163; Chem. Abstr., 51
E (1957) 41749.
5 S. C. S h o m e , J. I n d i a n C h e m . S o c . , 3 4 ( 1 9 5 7 )
~tgl 4 0 3 ; C h e m . A b s t r . , 5 2 ( 1 9 5 8 ) 9 2 9 g.
6 C. L . M a n t e l l , J. E l e c t r o c h e m . S o c . , 1 0 6 ( 1 9 5 9 ) 7 0 .
~7{ 7 R e k o r d t , U . S . B u r . M i n e s I n f . Circ., ( M a y 1 9 4 8 )
7466.
~151 8 V . F . L e f e r r e r , J. M e t . , 9 ( 1 9 5 7 ) 1 4 9 5 .
9 A . M a y e r , G a z . C h i m . Ital., 7 7 ( 2 ) ( 1 9 4 7 ) 5 5 .
10 C.J. SmitheIls, Metals Reference Book, Butter-
Eli
G worths, London, 1946, p. 279.
u~ 1 1 M. S c h m i d t , A r c h . M e t a l l k d . , 2 ( 6 ) ( 1 9 4 8 ) 1 9 3 .
'10
1 2 I. F . H e w a i d y a n d E . H . N a s s i f , 2 n d M e t a l l u r g i c a l
C o n f . in A . R . E . , D e c . 1 9 7 8 .
90
S0 I00 150
13 Inge Bindernagel and A. L. Sebaka, Egypt.
Foundryrnen's Soc. Mag., 2 (1975) 56.
CURRENT DENSI ¥'f A/it 2
14 I.M. Kolthoff and E. B. Sandell, Text Book of
Fig. 8. Re]ation between the specific surface area Quantitative Inorganic Analysis, The Macmillan
of zinc powder and zinc dross concentration. Co., New York, 1950.