Patented Dec.

4, 1951 2,577,364
‘ UNIT~ED°YSTAIES 'O‘FFiICE ;
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,, -; *RIlZODIU:
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M PLATIN'G- :1 . . ‘ .. ,. d . v

vmkir‘rank Herbert Reid, Hounslow, England, assignor: . .. _,

' to The International Nickel Company Inc.,New -- I
York, N.'Y., a corporation._-of Delmyarev > -
‘No Drawing. Application August 18,1948, Serial
, No. 44,978. In Great Brita-in August 19, 1947_

l , ' ~ I

‘This ‘invention relates to the electrodepos'i; phenolfis advantageous because the deposits
tion of rhodium .onto other. metals and ‘to solu should :as a general rule ‘be thicker than‘ the
tions for use therein. ‘ ' vminimum and the risk of inilkiness appearing :be-.
The electrodeposition . of, rhodium onto other fore the desired‘thickness is reached can be elim
metals for decorativecor tarnish-resisting pur inated. It is also to be iinderstoodthat even with
poses is commonly eiiectedwithstheuse of elec the use of phenol the deposits cease to be bright
trolytes of the ‘kindicontaining‘ as the essential at thicknesses, which vary with the composition
constituent rhodium sulphate .or rhodiumphos of the electrolyte and the operatingiconditions.
phate or a mixture ofi-thes'e‘two'comp'ounds to In processe'soi the-kind in question as carried
gether with varying “proportions .of. free sulphuric on hitherto, it ‘is usual ‘to employ a rhodium con
acid or free phosphoric .acid or a mixture there centration of :2'grams per. liter of ‘electrolyte, .a
of. The free acid is" necessary to prevent hy current density of from 2 to a ampere's ‘per square
drolysis of the rhodium compounds in the elec dec'imeter-and an operating temperature of from
trolyte with consequentprecipitation of rhodium room» temperature ‘to ‘about "60° C. but more usuala
hydroxide. ’ ' . . " ' 15; from '35 ‘to 45° ‘C. Incarrying out thepresent
I have found that electrolytes of this kind, invention none of these ?gures is criticaLIbutit
:When operated under normal plating conditions, is preferred to depart from .the prior art prac
tend to furnish rhodium deposits which become tice only to the extent of adding the critical
“milky” in appearance as the thickness increases. amount of phenol. Nevertheless, if desired the
The exact thickness of the deposit at which the rhodium concentration may 'vary' between, say,
desired metallic-brilliance'is lost ‘varies with-the ' about 0.5 and about 5 grams per liter. The free
composition ‘of the electrolyteand ‘the operating acid must always be enough to prevent hydrolysis
conditions. ‘Thus, *depositsfrmn phosphate elec of rhodium compounds, as those skilled in the
trolytes may become milky wh‘enttlieyxare only art will understand. Increase in the free acid
2.5 millionths of an inch thick whereas deposits -25 content above, .say, .20 milliliters of spulphuric
from phosphate-sulphate electrolytes ‘may \re acid per liter decreases the current e?lciency and
main bright until-they are as ‘thick ‘as 10 mil-, so is time-consuming and uneconomic. The cur
lionths of an inch. .Deposits from sulphate elec rent density must,‘ of course, be high enough to
trolytes generally remainlbright until they"v are ensure that the metal on which the deposit is
about .5 to '7 millionths of. an inch thick. Now the being made will not be chemically attacked, but
minimum thickness generally regarded as‘ satis— maybe-less'than12 amps/dmP. High cathodic
_factory in industrialpractice is 5 millionths of an current ‘densities, "say above about ‘5 amps/dmF,
inch and it is desirable that the deposits should tend to cause deterioration olf'ithe electrolyte, so
be two or three times as thick as this. I prefer to avoid their use.
An object of this invention is, to provide a 35 I have found that if ‘the ‘phenolooncentraé
rhodium-plating process by‘ which light deposits ‘tion exceeds 49.3 gram per liter the thickness of
thicker than the prior art deposits can be pro the deposit before slight milkiness appears def
duced. - - "creases when the'lower temperatures are used.
. Another object of this inventionis toqproduce To obtain the'best results at the higher concen
improved rhodium deposits by means of a~eritical 40 trations, therefore, the higher temperatures
amount of phenol in the electrolyte. should be used, e. g.- atlea'st 40° C. with a con
A further object of the invention is to provide centration as high as 0.4 gram of phenol per
a‘novel phenol-containingi- electrolyte for uselin liter. The current e?iciency falls o? rapidly as
rhodium plating. . , ’ >~ the concentration-of phenol increases, the reduc
I have discovered that if a critical amount of > ' tion being more marked at room temperature
phenol (hydroxybenzene) is addedito the electro than at higher temperatures, so the high tem
lyte, the thickness oi.’ the rhodium‘deposits ‘is peratures are desirable for this reason. However,
greatly increased before their characteristic bril at the ‘higher temperatures the electrolyte tends
liance is lost orthey become milky in appearance. to. deteriorate if the cathodic current densityv is
The. phenol concentrationiliesi within the range ' high. For instance one electrolyte containing 0.2
0.07 .to 0.5 gram per- liter. .At concentrations'rbee gram of phenol per liter which had been furnish
low the lower ?gure no signi?cant'improvement ing bright deposits up to 60 millionths of an
is vobtained‘and at’ concentrations above the up inch thick at room temperature and 40° C‘. using
per ?gure the deposits tend to be dark.‘ a current density of 4 amps/din.2 was subse
\It is to "be ‘understood; that bright vdeposits bi' bi quently electrolysed at a temperature of 60° C.
greater than 5-millionths of an' inch ‘thick? and with'a current density of 10 amps/din? ‘for 5
therefore utilisable for some purposes can-be ob minutesand then ‘gave deposits which were slight
tained with some electrolytes, particularly‘the ly milky when theywere only 25 millionth's of an
phosphate-sulphate electrolytes, under "suitable inch-thick. On being again electrolysed at 40° C.
operating conditions, but even then the use of i with a ourrentdensity of *4 amps/elm? it failed
 2,577,864
3 4
to give deposits which remained bright up to 60 EXAMPLEIII'
millionths of an inch thick, but rather the de
posits were severely streaked and milky when A sulphate electrolyte containing per liter 2
they were about 30 millionths of an inch thick. grams of rhodium and 10 mls. of sulphuric acid
To avoid this tendency it is desirable to maintain ' gave the results shown in Table III when elec
the current density in the normal range-of'from T trolysed at a current density of 4 ampsJdmF.
2 to 4 amps/dm?. , 7 Table III
EXAMPLE!‘ . . K
Thick
An electrolyte of the phosphate-sulphate type 10 Phenol - Appear
was prepared by reducing ?ve grams of insoluble No. concu. T631 ‘ ($1118) ?l?sagg ance of
(gms./l.) V ‘ ‘ X10.‘ deposit
rhodium chloride with hydrogen at a low tem
perature, extracting the residue of ?nely divided 0. 1 60 5 27 Bright.
rhodium by heating with“ concentrated sulphuric 0. 3 .60 12 79 D0.
acid, cooling, diluting, ?ltering and precipitating 0. 4
9. 5
'60
60V .
21
i7
118
101
D0.
Do.
rhodium hydroxide 'from the cooled ?ltrate by
neutralization with dilute ammonium hydroxide
solution. The hydroxide was washed'thoroughly, EXAMPLE IV
transferred to a beaker and stirred into a thin A phosphate electrolyte was made by dissolving
cream with water. Solution was readily effected 20 rhodium hydroxide in phosphoric acid and dilut
on adding 5 mls. of 85% phosphoric acid and ing the phosphate solution to give a concentra
warming gently. The resulting‘ solution was tion, per liter, of 2 grams of rhodium and 20 mls.
poured into a mixture of 17 mls. of concentrated of phosphoric acid. On electrolysing this solution
sulphuric acid and 850 mls. of distilled water to with a current density of 4 amps./dm.2 the results
produce an electrolyte containing perrliter 2 25 shown in Table IV were obtained.
grams of rhodium, 20 mls. of sulphuric acid and 5 Table IV
mls. of phosphoric acid.
The electrolyte prepared as described was then
Current Thick
used to deposit rhodium onto cathodes of polished No {31:31:11 Density Toemp. Time llzl?sspf ‘252323;.
nickel, and the results shown by Table I were ob 30 (gms./l.) (313154 ( V09 (“P1159 X1593)?" deposit
tained.
Table I 19_ _ . - nil 4 20 2 2. 5 Slightly
' milky.
20- _ __ 0. 1 - 4 20 v 10 15 Bright.
Current Thick- '
7 No 13:3? Density Ttemp. Time Rn?SSigf ‘Q5831; 35
(gms_I1) (aiming-125).] ( C.) (mms) X1545 deposit The’ metals onto which rhodium may be plated
according to the invention are any that are com
1___ _. nil 3 20 5 7 Milky.
patible with the acid electrolytes and include, be
2_____ nil 2 35 5 15 Do. sides nickel, nickel silver, gold, platinum, pal
3. _ _ _ _ 0. 07 2 60 10 25 Bright.
4_____ 0. 07 2 60 25 45 Do. 40 ladium, copper and brass. ‘ ~ '
I claim: ‘ '
1. In the process for electro-depositing thick
EXAMPLE II ..
plates of bright rhodium on metal using aqueous,
acid electrolyte containing at least‘one rhodium
An electrolyte of the sulphate type was pre 45 compound from the group consisting of rhodium
pared by diluting with water 25 mls. of a‘ sulphate . phosphate and rhodium sulfate in an amount
solution prepared as described in Example I to suii‘icient to provide said electrolyte with about
give a ?nal composition as follows: 0.5 to about 5 grams per liter of rhodium, and
free acid from the group consisting of phosphoric
Rhodium (as sulphate) ______ __grams/liter__ 2 acid and sulfuric acid in an amount sufficient to
Free sulphuric acid ___________ __mls./liter__ 10 ‘ prevent hydrolysis of the rhodium compound but
not exceeding about 20 milliliters per liter of elec
This electrolyte was also used for ‘depositing trolyte; the improvement which comprises in
rhodium onto nickel and the results shown in corporating in said electrolyte about 0.07 to about
Table II were obtained. > >
65 0.5 gram per liter of phenol whereby thick,
Table II light-colored and bright rhodium electro-depos
its are obtained at‘thicknesses of at least about
Current Thick 10 millionths of an inch on metal ‘surfaces by
Phenol Density Temp. Time ness of Appear‘
No. concn. (ampsll (QC ) (mins ) Rh (hm ance of employing the aforesaid phenoll-containingacid
(gmSJl) am!) ' ' X104) deposit 80 electrolyte. ' I > ' I

2. In the process for electro-depositing thick

nil 2 20 6 l0 Milky. plates of bright rhodium on metal using aqueous,
nil 2 40 1. 5 10 ' D0.
acid electrolyte containing at least one rhodium
nil 2 60 1. 5 6 Do.
nil ' 4 20 4. 2 14 D0. compound from the group consisting of rhodium
nil 4 4O 1. 75 ' 7 ‘ Do.
nil 4 60 2. 1 14 Do. 65 phosphate and rhodium sulfate: in an amount
2 4 20 60 131 Bright su?icient to provide said electrolyte with about
0.2 4 60 10 52 D0. 2 grams per liter of rhodium, and free acid from
0. 2 4 60 5 31 ‘ Do.
0. 2 4 60 6 ' 28 Do. the group consisting of phosphoric acid and sul
furic acid in an amount suf?cient to prevent
hydrolysis of the rhodium compound but not ex
The concentrations of phenol quoted above are ceeding about 20 milliliters per-liter of electro
illustrative and may be varied under appropriate lyte; the improvement which comprises incor
operating conditions and still give satisfactory porating in said electrolyte about 0.07 to about 0.5
plating. The e?ect of variation in the phenol gram per liter of phenol whereby thick, light
content is shown by the following example. 75 colored and bright rhodium electro-deposits are
 2,529,364
5
obtained at thicknesses of at least about 10 mil ous, acid electrolyte in electro-depositing rhodi-I
lionths of an inch on metal surfaces by employ um onto metal surfaces.
ing the aforesaid phenol-containing acid elec 5. An electrolyte for use in obtaining thick
trolyte. electro-deposits of bright rhodium on metal
3. A process for the production of thick, bright which comprises an aqueous, acid bath containing
electro-deposits of rhodium on metal which com about 2 grams per liter of rhodium provided by
prises establishing a rhodium-plating electrolyte at least one rhodium compound from the group
containing about 0.5 to about 5 grams per liter consisting of rhodium phosphate and rhodium
of rhodium provided by at least one rhodium sulfate, acid from the group consisting of phos
compound from the group consisting of rhodium l0 phoric acid and sulfuric acid in an amount suf
phosphate and rhodium sulfate, acid from the ?cient to prevent hydrolysis of the rhodium but
group consisting of phosphoric acid and sulfuric not exceeding about 20 milliliters of acid per liter
acid in an amount sufficient to prevent hydrolysis of electrolyte, and about 0.07 to about 0.5 gram
of the rhodium but not exceeding more than per liter of phenol whereby thick, light-colored
about 20 milliliters of acid per liter of electrolyte, 15 and bright rhodium electro-deposits at thick
about 0.07 to about 0.5 gram per liter of phenol; nesses of at least about 10 millionths of an inch
and electrolytically depositing rhodium from said can be obtained on metal surfaces when employ
electrolyte onto said metal at a current density ing the aforesaid phenol-containing, aqueous,
between about 2 and about 4 amperes per square acid electrolyte in electro-depositing rhodium
decimeter and at a temperature between about 20 onto metal surfaces.
room temperature and about 60° C. to produce
thick, light-colored and bright rhodium electro FRANK HERBERT REID.
deposits at thicknesses of at least about 10 mil REFERENCES CITED
lionths of an inch on said metal immersed as
cathode in said electrolyte. The following references are of record in the
25 ?le of this patent:
4. An electrolyte for use in obtaining thick
electro-deposits of bright rhodium on metal UNITED STATES PATENTS
which comprises an aqueous, acid bath contain Number Name Date
ing about 0.5 to about 5 grams per liter of rhodi 1,895,675 Mathers _________ .._ Jan. 31, 1933
um provided by at least one rhodium compound 30 1,981,820 Zimmerman et a1. ___ Nov. 20, 1934
from the group consisting of rhodium phosphate 2,078,014 Oplinger et a1. ____ __ Apr. 20, 1937
and rhodium sulfate, acid from the group con 2,119,304 Viers et a1 ________ __ May 31, 1938
sisting of phosphoric acid and sulfuric acid in 2,250,556 Stareck __________ __ July 29, 1941
an amount sufficient to prevent hydrolysis of the
rhodium but not exceeding about 20 milliliters FOREIGN PATENTS
of acid per liter of electrolyte, and about 0.07 to Number Country Date
about 0.5 gram per liter of phenol whereby thick, 446,393 Great Britain ____ __ Apr. 29, 1936
light-colored and bright rhodium electro-deposits
at thicknesses of at least about 10 millionths of OTHER REFERENCES
an inch can be obtained on metal surfaces when 40 Transactions of the Electrochemical Society,
employing the aforesaid phenol-containing, aque vol. 80 (1941), pp. 494 to 497.