CA1088454A - Bright tin-lead alloy plating - Google Patents
Bright tin-lead alloy platingInfo
- Publication number
- CA1088454A CA1088454A CA299,106A CA299106A CA1088454A CA 1088454 A CA1088454 A CA 1088454A CA 299106 A CA299106 A CA 299106A CA 1088454 A CA1088454 A CA 1088454A
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- Canada
- Prior art keywords
- formula
- group
- tin
- lead
- hydrogen
- Prior art date
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Abstract
Abstract of the Disclosure This invention relates to the electrodeposition of tin-lead alloys;
tin-lead alloy plating compositions; tin-lead alloy plating baths; and to processes for the electrodeposition of tin-lead alloys in the presence of:
(a) at least 1 g./l. of at least one polyether of formula Q-(CH2CH2O)n-X wherein:
n represents an integer of from 4 to 100;
Q is chosen from the group consisting of:
(i) an alkoxy group RO of from 4 to 18 carbon atoms;
(ii) an alkyl phenoxy group of formula , wherin R' represents an aliphatic radical of from 8 to 20 carbon atoms;
(iii) an amide group of formula R''CONH-, wherein R'' repre-sents a branched or straight chain aliphatic group of 8 to 18 carbon atoms; and (iv) an amino group of formula
tin-lead alloy plating compositions; tin-lead alloy plating baths; and to processes for the electrodeposition of tin-lead alloys in the presence of:
(a) at least 1 g./l. of at least one polyether of formula Q-(CH2CH2O)n-X wherein:
n represents an integer of from 4 to 100;
Q is chosen from the group consisting of:
(i) an alkoxy group RO of from 4 to 18 carbon atoms;
(ii) an alkyl phenoxy group of formula , wherin R' represents an aliphatic radical of from 8 to 20 carbon atoms;
(iii) an amide group of formula R''CONH-, wherein R'' repre-sents a branched or straight chain aliphatic group of 8 to 18 carbon atoms; and (iv) an amino group of formula
Description
~1)88~59~
BRIGHT TIN-LEAD ALLOY PLATING
Brief Description This invention relates to the electrodeposition of an alloy of tin and lead; plating compositions; plating baths for the electrodeposition of an alloy of tin and lead, and to processes for the electrodeposition of an alloy of tin and lead in the presence of a specific combination of additives.
More specifically this invention provides as a novel combination of additives for electrodepositing an alloy having about 60% tin and about 40% lead from baths containing a water soluble stannous salt and a water soluble lead sal~, at loast one polyether surfactant, and at loast one aromatic aldehyde exhibitillg at least one chloro substituent or at least one compound producing an aromatic aldehyde exhibiting at least one chloro substituent.
Background ; A tin-lead alloy containing about 60% tin and about 40% lead by weight, common:Ly known as "solder-plate", obtained by electrodeposition from a stannous fluoborate-lead fluoborate system, has had extensive application for many years. Some of its applica~ions have been the following:
A. As an easily soldered deposit for making elec~rical connections.
B. As an easily soldered deposit for printed circuitry which is applied on the electrically conductive pattern and which resists attack by various etching solutions used to remove copper from areas where it is not needed in order to leave a conductive pattern.
.
~L~)889~
The alloy has been generally plated from a fluoborate system utilizing certain additives, usua;Lly of organic nature such as peptones and anima:L glue, to --give continuity of deposit, to refine the crystalline structure, and to eliminate the tendency toward loosely adherent, dendritic deposit growth. At best, however, the prior art deposits have been generally dull with a dark cast. The low current density coverage and throwing power also have been generally poor which may be a serious disadvantage particularly in printed circuitry through-hole plating. Another disadvantage of prior art d~posits has been tendency toward staining, tinger-marking on handling and decreased solderability on storage.
It has become a desideratum in the art of solder- ~ -plating, particularly under high production conditions for both rack and barrel plating applications where freedom from staining and decreased solderability are particularly important, to attain a ductile, highly lustrous, uniformly fine-grained deposit throughout a wide cathode current density range.
It has also become a desideratum to obtain highly lustrous deposits which have enhanced resistance to staining and finger-marking, and which will maintain ' their appeaTance and solderability over relatively long time periods of storage.
; . :
.' ~L~)88~S4 This invention relates to a process of producing lustrous, con-tinuous, ductile, fine-grained tin-lead alloy alectrodeposits which comprises passing current from an anode to a metal cathode through an aqueous bath com- -position containing at least one water soluble stannous salt, at least one water soluble lead salt, fluoboric acid, boric acid, at least one polyether surfactant, and at least one aromatic aldehyde exhibiting at least one chloro-substituent or at least one compound producing an aromatic aldehyde exhibit-ing at least one chloro substituent.
The compositions and methods herein are applicable to barrel rack and wire electroplating processes. The concentrations of tin and lead ;
may be varied generally within the limits conventional in this art. ~or example, baths with a stannous tin ion content of S to 55 g/l and a lead ion content of 20 to 30 g/l may be utilized with the a~ditives of the invention horein.
Thus this invention, in a first embodiment, provides a process for depositing a bright, smooth, sound, ductile tin-lead alloy containing from 30% to 50% by weight lead and from 50% to 70% by weight tin which com-prises passing current from an anode to a cathode through an aqueous acidic bath containing at least one water soluble stannous tin salt, at least one water soluble lead salt, and as cooperating add.itives:
~A)(a) at least 1 g/l of at least one polyether of formula Q-(CH2C~I20)n-X wherein n represents an integer of from ~ to 100; Q represents an alkoxy group R0 of 4 to 18 carbon atoms and X is selected from the group consisting of hydrogen, S03M and PO~M2, wherein M is hydrogen or a bath-com-patible cation comprising sodium, potassium, ammonium, magnesium, iead, tin, calcium, caesium, or rubidium; and ~b~ 0.1 g/l to 1.0 g/l of at least one aromatic aldehyde ex-hibiting at least one chloro substituent, or at least one compound producing an aromatic aldehyde exhibiting at least one chloro substituent; or pol~
~B)(a) at least 1 g/l of at l~ast one ~ 4&~ of formula Q-(CH2CH20)n-X wherein n represents an integer of from ~ to 100; Q represents _ 3 _ .
.. .. . . . . : . , . . ,, . . . .:
~o~s~
an alkyl phenoxy group of formula R' ~ 0 , wherein R' represents an alipha~ic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of hydrogen, S03M and PO~M2, wherein M is hydrogen or a bath compatible cation comprising sodium, potassiwn, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one aromatic aldehyde ::
exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at least one chloro substituent; or pol-Je~
(C)(a~ at least 1 g/l of at least one ~y~eb0~ of formula .
Q-(CH2CH20)n-X wherein n represents an integer of from ~ to 100; Q represents -an alkyl phenoxy group of formula R' ~ 0 - , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of S03M and PO~M2, wherein M is hydrogen or a bath-compati-ble cat;Lon comprising so~ium, potass:ium, anunon:ium, magnes:ium, lcad, tinJ cal- ; :
cium, caesium, or rubidium; and . (b) 0.25 g/l to 1.0 g/l of at least one aromatic aldehyde ~ .
exhibiting at least one chloro substituent, or at least one compound produc- .
ing an aromatic aldehyde exhibiting at least one chloro substituent; or (D)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH20)n-X wherein n represents an integer of from 4 to 100; Q
represents an amide group of formula Rl'CONH-, wherein R " represents a branched or straigh~ chain aliphatic group of 8 to 18 carbon atoms; and X is selected from the group consisting of hydrogen, S03M and PO~M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one aromatic aldehyde ex- :
hibiting at least one chloro substituent, or at least one compound producing an aromatic aldehyde exhibiting at least one chloro substituent; or (E)~a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH20~n-X wherein n represents an integer of from ~ to 100; Q
represents an amide group of formula R "CON}I-, wherein R " represents a _ ~ _ , .1 , .
~,. .
, 1(~8~54 branched or straight chain aliphatic group of 8 to 18 carbon atoms; and X
is selec~ed from the group consisting of S03M and P04~12, wherein M is hydro- :
gen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and ;:.
(b) 0.25 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound produe-ing an aromatic aldehyde exhibitin~ at least one chloro substituent; or (F)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH20)n-X wherein n represents an integer of from 4 to 100; Q
represents an amino group of formula R2 ~ C - NH
whcrcin Rl, R2 and R3 each represent a strai~ht or branched alkyl group of Erom 8 to 18 carbon atoms; and tb) 0.1 gtl to l.0 g/l of at least one aromatic aldehyde ex-hibiting at least one chloro substituent, or at least one compound producing ;~
an aromatic aldehyde exhibiting at least one chloro substituent.
In a second embodiment this invention provides a composition for producing bright, smooth, sound, ductile tin-lead alloy electrodeposits containing from 30% to 50% by weight lead and from 50~0 to 70% by weight tin, which comprises an aqueous acidic bath containing at least one water soluble stannous tin salt, at least one water soluble lead salt, and as cooperating additives:
tA)ta) at least 1 g/l of at least one polyether of -formula Q-~CH2CH20)n-X wherein n represents an integer of from 4 to 100; Q represents an alkoxy group R0 of 4 to 18 carbon atoms and X is selected from the group ; consisting of hydrogen, S03M and P04M2, wherein ~l is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, :
;
tinJ calcium, caesium, or rubidium; and t~) 0.1 g/l to 1 0 g/l of at least one aromatic aldehyde ex- :
` 30 `
.. , ~ .
isS.
., ,r~
84S~
. ~ ... .
hibiting at least one chloro substituent, or at leas~ one compound produc-ing an aromatic aldehyde exhibiting at least one chloro substituent; or (B)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH20)n-X wherein n represents an integer of from ~ to 100; Q represents an alkyl phenoxy group of formula R' ~ -, wherein Rl represents an aliphatic radical of from 8 to 20 carbon atoms,and X is selected from the ; :group consisting of hydrogen, S03M and P04M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammoniumJ magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at loast one chloro substituent; or (C)(a) at least 1 g/l oE at loast ono ~olyether o:E :Eormllla Q-(C'II2C1120)n-X whoro:in n roprescnts all integer oE :Erom ~ to l()0; Q rcprosonts an alkyl phenoxy group of formula R' ~ 0 , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of S03M and P04M2, wherein M is hydrogen or a bath-compati-ble cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.25 g/l to 1.0 g/l o:E at least one aromatic aldehyde ex-hibiting at least one chloro substituentJ or at least onc compound producing an aromatic aldehyde exhibiting at least one chloro substituent; or . (D)(a) at least l g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amide group of formula R"CONH-, wherein R" represents a branched or straight chain aliphatic group of 8 to 18 carbon atoms; and X is selected from the group consisting of hydrogen, S03M and P04M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and ;~
: , ~ 38459~ ;
(b) 0.1 g/l to 0.25 g/l of at least one aromatic aldehyde - -exhibiting at least one chloro substituent, or at least one compound produc- :
ing an aromatic aldehyde exhibiting at least one chloro substituent; or ~ :
(E)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH20)n-X wherein n represents an integer of from 4 to 100;
Q represents an amide group of formula R"CONH-, wherein R" represents a branched or straight chain aliphatic group of ~ to 18 carbon a~oms; and X
is selected from the group consisting of S03M and P04M2, wherein M is hydro-gen or a bath-compatible cation comprising sodium, potassium, ammonium, :
magnesium, lead, tin, calcium, caesium, or rubidium; and ~b) 0.25 g/l to 1.0 g/l of at least one aromatic aldehyde --exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at least onc chloro substituent; or (~)ta) at least 1 g/l oE at least one polyothcr surfactant of eormula Q-~CI-l2Cll20)n-X whoro:in n roprosonts an :intcgor o:E Erom ~ to 10(); Q
represents an amino group of Eormula R2 ~ IC - NH
wherein Rl, R2 and R3 each represent a straight or branched alkyl group of from 8 to 18 carbon atoms; and .- 20 (b) O.l g/l to 1,0 g/l o:E at least one aromatic aldehyde ex-; hibiting at least one chloro substitucnt,.or at least one compound producing ~` :
an aromatic aldehyde exhibiting at least one chloro substituent. :
Operable polyether surfactants defined under (a) above, and .:
hcreafter referred to as type A include nitrogen-containing aliphatic poly-ethers characterized by the following general formulae: ;
R,l : ' R2CNH ~CH2CH2)n X (III) 3 .~:
~` '-' .
R~ - CNH(CH2CH20)n - X
~IV) c -: . . . .. . . ..
.. . . . . . . . .. . . . .
~()8~4S4 ...`.
wherein Rl, R2, R3 and R4 each represent a straight or branched chain alkyl group exhibiting 8 to 18 carbon atoms, n is an integer of at least 4 and no .
more than 100, and X is selected from the group consisting of hydrogen, S03M, P04M2 where M is selected from the group consisting of sodium, potas-sium, ammonium, magnesium, lead, tin, calcium, rubidium,caesiumj or any other bath-compatible cation, .,'' :' . ,' '.i'. " .'':, "
', .. . .
"~ :'." . .
~' ,'~, '.
: ''~ ',. ' ,' .
: '`''' ' ' .
`' ' ', ., .... ~, ~ , , . , .: . . . .
s~ :
Polyether surfactants are employed singly in amounts of about l g/l to 10 g/l, and in combination from 10 g/l to 20 g/l.
Typical specific compounds are the following with their concentra- :
tion ranges varying singly from 1 g/l to 10 g/l and in combination from 10 g/l to 20 g/l:
~ ~ 2 2 )15 Nonyl ~
(sold under the trade mark "Tergitol Non-Ionic NP-35") R,l R2-C-NH(C2H40)nS03Na Rl, R2, R3 are each 12-1~ C atoms and R3 n = 15 (sold under the trade mark "Triton QS-15") l~2 C, NlltC2ll4)nll Rl, R2, R3 are each 12-1~ C atoms ancl 3 n 5 1 5 (sold under the trade mark "Priminox R-15") .
The polyether surfactants may be used in the form of aqueous stock : .
solutions.
Thus the polyether surfactant such as "Tergitol Non-Ionic NP-35"
may be added as a concentrated aqueous stock solution, say 100 g/l, in which -form it would be added at a concentration of ~0 ml/l or ~% by volunle.
Chlorinated aromatic aldehydes operable :in the practice of this invention defined under (b) above~ and hereafter referred to as type B are aromatic aldehydes having at least one chloro substituent of the formula:
.
(Cl) l ~ CH0 where n is 1 or 2 ~ ' .
Typical specific compounds are the following with their concentration ranges :
varying from 0.1 g/l to 1 g/l ~nd used singly or in combination:
:: .
S _ . . . , . ................................. , .:
: . : . : .
CHO
o-chlorobenzaldehyde (a preferred compound ~ ~ - Cl because of its cost being relatively low .. .
: l and its easy availability) \~ '':,., ~ CHO
Cl ~ Cl 2,6-dichlorobenzaldehyde CHO
Cl 2,4-dichlorobenzaldehyde ~ J
Cl CHO
3, 4-dichlorobenz zldehyde Cl .
; ', :' CHO ~
m-chlorobenzaldehyde .
Cl . ' :~ Compounds which are effective due to the release of a chlorinated .; .
aromatic aldehyde on being added to the plating bath have the following .
structural con~igurations:
.,~ 0~1 ~. '"
` 10 (1) R-CH-SO3Na ~aldehyde-bisulfite adducts)
BRIGHT TIN-LEAD ALLOY PLATING
Brief Description This invention relates to the electrodeposition of an alloy of tin and lead; plating compositions; plating baths for the electrodeposition of an alloy of tin and lead, and to processes for the electrodeposition of an alloy of tin and lead in the presence of a specific combination of additives.
More specifically this invention provides as a novel combination of additives for electrodepositing an alloy having about 60% tin and about 40% lead from baths containing a water soluble stannous salt and a water soluble lead sal~, at loast one polyether surfactant, and at loast one aromatic aldehyde exhibitillg at least one chloro substituent or at least one compound producing an aromatic aldehyde exhibiting at least one chloro substituent.
Background ; A tin-lead alloy containing about 60% tin and about 40% lead by weight, common:Ly known as "solder-plate", obtained by electrodeposition from a stannous fluoborate-lead fluoborate system, has had extensive application for many years. Some of its applica~ions have been the following:
A. As an easily soldered deposit for making elec~rical connections.
B. As an easily soldered deposit for printed circuitry which is applied on the electrically conductive pattern and which resists attack by various etching solutions used to remove copper from areas where it is not needed in order to leave a conductive pattern.
.
~L~)889~
The alloy has been generally plated from a fluoborate system utilizing certain additives, usua;Lly of organic nature such as peptones and anima:L glue, to --give continuity of deposit, to refine the crystalline structure, and to eliminate the tendency toward loosely adherent, dendritic deposit growth. At best, however, the prior art deposits have been generally dull with a dark cast. The low current density coverage and throwing power also have been generally poor which may be a serious disadvantage particularly in printed circuitry through-hole plating. Another disadvantage of prior art d~posits has been tendency toward staining, tinger-marking on handling and decreased solderability on storage.
It has become a desideratum in the art of solder- ~ -plating, particularly under high production conditions for both rack and barrel plating applications where freedom from staining and decreased solderability are particularly important, to attain a ductile, highly lustrous, uniformly fine-grained deposit throughout a wide cathode current density range.
It has also become a desideratum to obtain highly lustrous deposits which have enhanced resistance to staining and finger-marking, and which will maintain ' their appeaTance and solderability over relatively long time periods of storage.
; . :
.' ~L~)88~S4 This invention relates to a process of producing lustrous, con-tinuous, ductile, fine-grained tin-lead alloy alectrodeposits which comprises passing current from an anode to a metal cathode through an aqueous bath com- -position containing at least one water soluble stannous salt, at least one water soluble lead salt, fluoboric acid, boric acid, at least one polyether surfactant, and at least one aromatic aldehyde exhibiting at least one chloro-substituent or at least one compound producing an aromatic aldehyde exhibit-ing at least one chloro substituent.
The compositions and methods herein are applicable to barrel rack and wire electroplating processes. The concentrations of tin and lead ;
may be varied generally within the limits conventional in this art. ~or example, baths with a stannous tin ion content of S to 55 g/l and a lead ion content of 20 to 30 g/l may be utilized with the a~ditives of the invention horein.
Thus this invention, in a first embodiment, provides a process for depositing a bright, smooth, sound, ductile tin-lead alloy containing from 30% to 50% by weight lead and from 50% to 70% by weight tin which com-prises passing current from an anode to a cathode through an aqueous acidic bath containing at least one water soluble stannous tin salt, at least one water soluble lead salt, and as cooperating add.itives:
~A)(a) at least 1 g/l of at least one polyether of formula Q-(CH2C~I20)n-X wherein n represents an integer of from ~ to 100; Q represents an alkoxy group R0 of 4 to 18 carbon atoms and X is selected from the group consisting of hydrogen, S03M and PO~M2, wherein M is hydrogen or a bath-com-patible cation comprising sodium, potassium, ammonium, magnesium, iead, tin, calcium, caesium, or rubidium; and ~b~ 0.1 g/l to 1.0 g/l of at least one aromatic aldehyde ex-hibiting at least one chloro substituent, or at least one compound producing an aromatic aldehyde exhibiting at least one chloro substituent; or pol~
~B)(a) at least 1 g/l of at l~ast one ~ 4&~ of formula Q-(CH2CH20)n-X wherein n represents an integer of from ~ to 100; Q represents _ 3 _ .
.. .. . . . . : . , . . ,, . . . .:
~o~s~
an alkyl phenoxy group of formula R' ~ 0 , wherein R' represents an alipha~ic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of hydrogen, S03M and PO~M2, wherein M is hydrogen or a bath compatible cation comprising sodium, potassiwn, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one aromatic aldehyde ::
exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at least one chloro substituent; or pol-Je~
(C)(a~ at least 1 g/l of at least one ~y~eb0~ of formula .
Q-(CH2CH20)n-X wherein n represents an integer of from ~ to 100; Q represents -an alkyl phenoxy group of formula R' ~ 0 - , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of S03M and PO~M2, wherein M is hydrogen or a bath-compati-ble cat;Lon comprising so~ium, potass:ium, anunon:ium, magnes:ium, lcad, tinJ cal- ; :
cium, caesium, or rubidium; and . (b) 0.25 g/l to 1.0 g/l of at least one aromatic aldehyde ~ .
exhibiting at least one chloro substituent, or at least one compound produc- .
ing an aromatic aldehyde exhibiting at least one chloro substituent; or (D)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH20)n-X wherein n represents an integer of from 4 to 100; Q
represents an amide group of formula Rl'CONH-, wherein R " represents a branched or straigh~ chain aliphatic group of 8 to 18 carbon atoms; and X is selected from the group consisting of hydrogen, S03M and PO~M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one aromatic aldehyde ex- :
hibiting at least one chloro substituent, or at least one compound producing an aromatic aldehyde exhibiting at least one chloro substituent; or (E)~a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH20~n-X wherein n represents an integer of from ~ to 100; Q
represents an amide group of formula R "CON}I-, wherein R " represents a _ ~ _ , .1 , .
~,. .
, 1(~8~54 branched or straight chain aliphatic group of 8 to 18 carbon atoms; and X
is selec~ed from the group consisting of S03M and P04~12, wherein M is hydro- :
gen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and ;:.
(b) 0.25 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound produe-ing an aromatic aldehyde exhibitin~ at least one chloro substituent; or (F)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH20)n-X wherein n represents an integer of from 4 to 100; Q
represents an amino group of formula R2 ~ C - NH
whcrcin Rl, R2 and R3 each represent a strai~ht or branched alkyl group of Erom 8 to 18 carbon atoms; and tb) 0.1 gtl to l.0 g/l of at least one aromatic aldehyde ex-hibiting at least one chloro substituent, or at least one compound producing ;~
an aromatic aldehyde exhibiting at least one chloro substituent.
In a second embodiment this invention provides a composition for producing bright, smooth, sound, ductile tin-lead alloy electrodeposits containing from 30% to 50% by weight lead and from 50~0 to 70% by weight tin, which comprises an aqueous acidic bath containing at least one water soluble stannous tin salt, at least one water soluble lead salt, and as cooperating additives:
tA)ta) at least 1 g/l of at least one polyether of -formula Q-~CH2CH20)n-X wherein n represents an integer of from 4 to 100; Q represents an alkoxy group R0 of 4 to 18 carbon atoms and X is selected from the group ; consisting of hydrogen, S03M and P04M2, wherein ~l is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, :
;
tinJ calcium, caesium, or rubidium; and t~) 0.1 g/l to 1 0 g/l of at least one aromatic aldehyde ex- :
` 30 `
.. , ~ .
isS.
., ,r~
84S~
. ~ ... .
hibiting at least one chloro substituent, or at leas~ one compound produc-ing an aromatic aldehyde exhibiting at least one chloro substituent; or (B)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH20)n-X wherein n represents an integer of from ~ to 100; Q represents an alkyl phenoxy group of formula R' ~ -, wherein Rl represents an aliphatic radical of from 8 to 20 carbon atoms,and X is selected from the ; :group consisting of hydrogen, S03M and P04M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammoniumJ magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at loast one chloro substituent; or (C)(a) at least 1 g/l oE at loast ono ~olyether o:E :Eormllla Q-(C'II2C1120)n-X whoro:in n roprescnts all integer oE :Erom ~ to l()0; Q rcprosonts an alkyl phenoxy group of formula R' ~ 0 , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of S03M and P04M2, wherein M is hydrogen or a bath-compati-ble cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.25 g/l to 1.0 g/l o:E at least one aromatic aldehyde ex-hibiting at least one chloro substituentJ or at least onc compound producing an aromatic aldehyde exhibiting at least one chloro substituent; or . (D)(a) at least l g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amide group of formula R"CONH-, wherein R" represents a branched or straight chain aliphatic group of 8 to 18 carbon atoms; and X is selected from the group consisting of hydrogen, S03M and P04M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and ;~
: , ~ 38459~ ;
(b) 0.1 g/l to 0.25 g/l of at least one aromatic aldehyde - -exhibiting at least one chloro substituent, or at least one compound produc- :
ing an aromatic aldehyde exhibiting at least one chloro substituent; or ~ :
(E)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH20)n-X wherein n represents an integer of from 4 to 100;
Q represents an amide group of formula R"CONH-, wherein R" represents a branched or straight chain aliphatic group of ~ to 18 carbon a~oms; and X
is selected from the group consisting of S03M and P04M2, wherein M is hydro-gen or a bath-compatible cation comprising sodium, potassium, ammonium, :
magnesium, lead, tin, calcium, caesium, or rubidium; and ~b) 0.25 g/l to 1.0 g/l of at least one aromatic aldehyde --exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at least onc chloro substituent; or (~)ta) at least 1 g/l oE at least one polyothcr surfactant of eormula Q-~CI-l2Cll20)n-X whoro:in n roprosonts an :intcgor o:E Erom ~ to 10(); Q
represents an amino group of Eormula R2 ~ IC - NH
wherein Rl, R2 and R3 each represent a straight or branched alkyl group of from 8 to 18 carbon atoms; and .- 20 (b) O.l g/l to 1,0 g/l o:E at least one aromatic aldehyde ex-; hibiting at least one chloro substitucnt,.or at least one compound producing ~` :
an aromatic aldehyde exhibiting at least one chloro substituent. :
Operable polyether surfactants defined under (a) above, and .:
hcreafter referred to as type A include nitrogen-containing aliphatic poly-ethers characterized by the following general formulae: ;
R,l : ' R2CNH ~CH2CH2)n X (III) 3 .~:
~` '-' .
R~ - CNH(CH2CH20)n - X
~IV) c -: . . . .. . . ..
.. . . . . . . . .. . . . .
~()8~4S4 ...`.
wherein Rl, R2, R3 and R4 each represent a straight or branched chain alkyl group exhibiting 8 to 18 carbon atoms, n is an integer of at least 4 and no .
more than 100, and X is selected from the group consisting of hydrogen, S03M, P04M2 where M is selected from the group consisting of sodium, potas-sium, ammonium, magnesium, lead, tin, calcium, rubidium,caesiumj or any other bath-compatible cation, .,'' :' . ,' '.i'. " .'':, "
', .. . .
"~ :'." . .
~' ,'~, '.
: ''~ ',. ' ,' .
: '`''' ' ' .
`' ' ', ., .... ~, ~ , , . , .: . . . .
s~ :
Polyether surfactants are employed singly in amounts of about l g/l to 10 g/l, and in combination from 10 g/l to 20 g/l.
Typical specific compounds are the following with their concentra- :
tion ranges varying singly from 1 g/l to 10 g/l and in combination from 10 g/l to 20 g/l:
~ ~ 2 2 )15 Nonyl ~
(sold under the trade mark "Tergitol Non-Ionic NP-35") R,l R2-C-NH(C2H40)nS03Na Rl, R2, R3 are each 12-1~ C atoms and R3 n = 15 (sold under the trade mark "Triton QS-15") l~2 C, NlltC2ll4)nll Rl, R2, R3 are each 12-1~ C atoms ancl 3 n 5 1 5 (sold under the trade mark "Priminox R-15") .
The polyether surfactants may be used in the form of aqueous stock : .
solutions.
Thus the polyether surfactant such as "Tergitol Non-Ionic NP-35"
may be added as a concentrated aqueous stock solution, say 100 g/l, in which -form it would be added at a concentration of ~0 ml/l or ~% by volunle.
Chlorinated aromatic aldehydes operable :in the practice of this invention defined under (b) above~ and hereafter referred to as type B are aromatic aldehydes having at least one chloro substituent of the formula:
.
(Cl) l ~ CH0 where n is 1 or 2 ~ ' .
Typical specific compounds are the following with their concentration ranges :
varying from 0.1 g/l to 1 g/l ~nd used singly or in combination:
:: .
S _ . . . , . ................................. , .:
: . : . : .
CHO
o-chlorobenzaldehyde (a preferred compound ~ ~ - Cl because of its cost being relatively low .. .
: l and its easy availability) \~ '':,., ~ CHO
Cl ~ Cl 2,6-dichlorobenzaldehyde CHO
Cl 2,4-dichlorobenzaldehyde ~ J
Cl CHO
3, 4-dichlorobenz zldehyde Cl .
; ', :' CHO ~
m-chlorobenzaldehyde .
Cl . ' :~ Compounds which are effective due to the release of a chlorinated .; .
aromatic aldehyde on being added to the plating bath have the following .
structural con~igurations:
.,~ 0~1 ~. '"
` 10 (1) R-CH-SO3Na ~aldehyde-bisulfite adducts)
(2) R-CH=N-R' ~R' = aliphatic or aromatic group) :
~: ~3) R-CH=N-NHR" (R" = aromatic group such as phenyl) (4) R-CH=N-NHC-NH2 (semi-carbazones) ..
:. O
;. (5) R-CH=N-OH (oximes) (6) R-CH=(OR'")2 (R"' = alkyl group - acetals) ~ In the above compounds, R is an aromatic moiety such as phenyl :' .
,:~
,', : _ 6 _ ., . ~
~0~ 5~
containing 1 or 2 chloro groups directly bonded to the aromatic ring.
Compounds of Type B may be used in the form of stock solutions in appropriate organic solvents (methanol, ethanol, isopropanol, acetone, etc.) or in mixtures of organic solvents (such as methanol plus water plus compounds of Type A, the latter imparting appreciable solubiLizing action).
Although the cooperative use of compounds of Types A and B may give excellent results, particularly under barrel plating conditions, it has also been found that the addition of an aliphatic amine as a further cooperating additive will result in even more uniformly lustrous, pit-free and striation-free deposits.
Compounds which are aliphatic amines or compounds which liberatealiphatic amines on addition to the electroplating bath, defined above under (c~, and hereafter referred to as Type C, are of the formulae:
R-N~12 ~V) / R' where R' R" = hydrogen, alkyl or aromatic groups, and R-N=C R = alkyl group, straight or branched chain with 3 to (VI) R"
Specific and preferred compounds are exemplified by:
CH3(CH2~11NH2 laurylamine CH3(CH2)7NH2 octylamine The aliphatic amine or aliphatic amine producing compounds are used in concentrations ranging from 0.25 g/l to 5 g/l depending on their degree of bath solubility. They may be used in the Eorm of aqu~ous or organ:ic solvent stock solutions or in mixtures of water and organic solvents.
A plating bath of the fluoborate type which may be used in the practice of this invention may consist of the following basic ingredients:
stannous fluoborate [ Sn(BF4)2 ]
lead fluoborate [ Pb(BF4)2 ]
fluoboric acid [ HBF4 ]
boric acid [ H3B03 ]
The stannous fluoborate is usually added as an aqueous concentrate containing typically ~9.6~ by weight of Sn(BF4)2 having a speciEic gravity of 1.60. The lead fluoborate is usually added as an aqueous concentrate contain-.: :
_ 7 ~ 38454 : :
ing typically 50% by weight of Pb(BF4)2 having a specific gravity of 1.75.
The fluoboric acid is generally added as an aqueous concentrate typically 49%
by weight of HBF~ having a specific gravity of 1.37. The boric acid is usually added as a relatively pure grade of powdered or crystalline H3BO3.
The fluoboric acid added in addition to the BF4 anion associated with stannous tin and lead is usually referred to as "free fluoboric acid".
A typical concentration of bath constituents and a preferred bath make-up concentration are as follows, in grams per liter ~g/l):
Range g/l Preferred g/l Sn(BF4)2 110 - 135 135 ( 4)2 37 - 55 46 Equivalent to sn-~2 45 - 55 55 pb~2 20 - 30 25 Free fluoboric acid 100 - 200 120 boric acid 10 - 40 30 ~-Anodes generally consist of a cast or extruded tin-lead alloy containing 60% tin and 40% lead. In order to more consistently obtain an alloy composition at the cathode close to 60-40, the following operating conditions are generally used:
temperature 10C. - 60C.
cathode current density 3.0 ASD (amperes per square dm) anode current density 1.5 ASD
agitation mild mechanical (150 to 700 cm per minute) or slowly rotating barrel (2-5 RPM) Increasing the cathode current density over 3.0 ASD will tend to increase the tin content of the deposit while decreasing the cathode current density below 3.0 ASD will tend to decrease the tin content of the deposit.
Although ideally a 60-40% alloy is desired, in actual commercial operation a i tin content of 60 10% by weight and a lead content of 40 10% by weight are : ~ : . : .. . . :
, ,,: , ,. - . . - :
1~8845~
generally acceptable and this mcans that some variation in tin and lead concentrations and in cathode current density may be tolerated.
This invention also lies in the addition of an anti-oxidant or oxygen acceptor for substantially decreased tendency toward formation of precipitates of stannic basic salts. Operable anti-oxidants or oxygen acceptors include hydroquinone or substituted hydroquinone, pyrocatechol, pyrogallol, catechol, and aromatic sulfinates such as sodium benzene monosulfinate.
These compounds may be used singly or in combination in concentra-tions of about 0.5 g/l to 5 g/l depending on their bath solubility. They may be used in the form of aqueous or organic solvent stock solutions or they may be added directly to the plating bath with stirring to facilitate solution.
According to another of its embodiments, this invention is an .
aqueous solution eor electrodepositing a bright, sound, smooth ductile alloy e tin and lead having about 60% tin and 40% lead comprising: 110 g/l to 135 g/l of stannous fluoborate; 37 g/l to 55 g/l of lead fluoborate; 100 g/l to 200 g/l of fluoboric acid; 10 g/l to 40 g/l of boric acid; and as a novel additive system:
~a) at least 1 g,/l. of at least one polyether of formula Q-(CH2CH2o)n-X wherein:
n represents an integer of from 4 to 100;
Q is chosen from the group consisting of:
(i) an alkoxy group R0 of from 4 to 18 carbon atoms;
(ii) an alkyl phenoxy group of formula R' ~
wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms;
(iii) an amide group of formula R "CONH-, wherein R " repre-sents a branched or straight chain aliphatic group of 8 to 18 carbon atoms; and IRl (iv) an amino group of formula R2- C - N~l - , wherein Rl, R2 and R3 each represent a straight or branched alkyl group of ~,...
_ 9 -, ' ' . ' : . ''; , ' ' ' . .'' ' '' ' ' '~ . . '.' ~ ~ , ", ' ' ' , " .
1~84~S~
from 8 to 18 carbon atoms; and X is selected from the group consisting of hydrogen, S03M and P04M2, wherein M is hydrogen or a bath-compatible cation com-prising sodium, potassium, ammonium, magnesium, lead, tin, ; calcium, caesium, or rubidium; and (b) 0.1 g/l to 1.0 g/l of at least one aromatic aldehyde exhibit-ing at least one chloro substituent, or at least one compound producing an aromatic aldehyde exhibiting at least one chloro substituent; and optionally (c) from 0.25 to 5.0 g/l of at least one aliphatic amine, or a compound producing an aliphatic amine.
The preferred operating conditions, such as pH, temperature, and ; current density may vary depending upon the particular bath composition and the nature of the article receiving the layer of tin-lcad alloy electrodeposit.
tn general, good tin-lead alloy elcctrodoposits nlay be obtained within a speci~ic range of operating conditions.
The tin-lead alloy electroplating processes using the compositions o the invention may be carried out at temperatures of about 10C. - 60 C.
(preferably 15C. - 20C.) either with or without agitation. The temperature of the plating solution is usually the ambient temperature, say 35C. or below, with lower temperatures giving optimum results, such as 15C. - 20C. Using average current densities of 0.5 to 5.0 ASD, tin-lead alloy electrodeposits having average thicknesses of 0.25 - 25 mic:rons may be obtained using plating times which may average 0.1-10 minutes.
In the plating of tin-lead alloy the parts may be plated on racks, i.e. on fixtures holding single or multiple parts which may all be the same or which may be different in size, geometrical configuration, etc. Parts may also be plated in bulk in rotating barrels and in this type of plating, usually used for plating of smaller parts which lend themselves to tumbling action, the barrel loads usually consist of the same part although mixed loads are sometimes plated. Because of the number, size, and shape complexity of parts it is important that the plating bath be so formulated as to provide the -widest possible bright plate current density range. It is also important that ,.
- 1 0 - , ~
it84S~
the limiting current density, i.e. the current density at which ~he deposit ceases to be sound in structure and appearance, be as high as possible to allow for the wide variations in cathode current density which may be encount-ered due to the size and shape complexity of parts. ~-The following examples are submitted for the purpose of illustration only, so that those skilled in the art of tin-lead alloy plating may better understand the operation of the invention. These examples are not to be construed as limiting the scope of the invention in any way.
PLATING TEST CONDITIONS
A. Hull Cell Tests Hull Cell - plastic with a plating solution volume of 267 ml Anode - slab of Sn-Pb alloy (60~ Sn and 40% Pb by weight) Cathode - polished brass 10 cm x 7.5 cm x 1 mm with 5 cm immersed Cell Current - 1 ampere (0 to 7 ASD range) Time - minutes Agitation - magnetic stirrer Temperature - ambient room ~20C. - 25C.) B Life Tosts - 4 liter solution volume-strLp cathodes Plating Cell - rectangular glass battery jar 15.5 cm length, 13 cm width, 26.5 cm depth Solution Volume - 4 liters ~solution depth of 20.5 cm) `, Anode - slab of Sn-Pb cast alloy ~60% Sn and 40% Pb by weight) 9 cm wide, -1 cm thick, 20.5 cm immersed in plating bath Cathode - polished brass 20.4 cm long, 2.54 cm wide, 0.5 mm thick immersed to depth of 18 cm - maintained parallel to the anode at a dis-tance of about 10 cm - bottom of cathode bent to give an inter-nal angle o ~5 facing anode Agitation - moving cathode bar - length of stroke 8 cm - 78 strokes/minute - 11- .. ' .. , , , . ", , , .,, . . ., . - .................. . . . . . ~ ..
.. . . ; , . . , .' :. : . . .: :
45~ :
-total cathode travel 625 cm/minute Temperature - ambient room (20C. - 25C.) Cell Current - varied from 2 to 5 amperes Time - varied from 3 minutes to several hours C. Barrel Plating Tests Barrel - "Plexiglas" (a trade mark) plastic of horizontal hexagonal type - 12.5 cm long with a diameter of about 10 cm - com-pletely immersed in plating bath - operated at 5 RPM
Solution Volume - 4 liters - cooled to compensate for heating effects of current by immersing in solution plastic cooling coils through ~ -which cold water circulated to mainta:in temperature at about 25C
Ccll ~ polyethylene plastic Load - steel nails about 5 cm long with a total load area of about 930 square cm Current - varied from 5 to 25 amperes Time - varied from 15 to 60 minutes .
_AMPLF 1 A stock solution was prepared havlng the following compos.ition:
stannous tin 52 g/l lead 30 g/l .
free fluoboric acid 100 g/l . :
boric acid 25 g/l :
To 267 ml of the above stock solution, there were added the :: .
equivalent of "Tergitol Non-Ionic NP-35" 10 g/l ; "Triton QS-15" 10 g/l o-chlorbenzaldehyde 0.~ g/l On running a Hull Cell test as cLescribed in the above, a lustrous deposit was obtained throughout the entire current density range with a slight tendency -~LS~
toward striation or "ribbing" of deposit in the current density range of 2 to 7 ASD.
Example 1 was repeated using 0.4 g/l of 2,6-dichlorobenzaldehyde in place of the o-chlorobenzaldehyde with essentially the same results obtained.
Example 1 was repeated using 0.4 g/l of m-chlorobenzaldehyde in place o the o-chlorobenzaldehyde with essentially the same results obtained.
A barrel plating test was run using the barrel plating conditions outlined in the above and using a cell current of 20 amperes for 30 minutes to give an average cathode current density o~ about 2 ~SD. Aftcr plating the load of nails was rinsed and dricd, and they had a beautifully lustrous and uni~orm appcarancc. On testing roprcscntative naiLs from the load the deposit ductility and adhesion to the basis metal was excellent. Because of the tumbling and some burnishîng action no indication was obtained of any of the striation or "ribbing" effect indicated by the ~lull Cell tes~s of Examples 1 to 3, inclusive.
The life test was continued for a total electrolysis time of about 300 ampere-hours with variations of current from 5 to 25 amperes per load and ;~
with times ranging from 15 minutes to 1 hour. Periodic replenishment of o-chlorobenzaldehyde easily maintained deposit luster with replenishment additions made on the basis of deposit appearance. Solderabllity tests were made on representative samples from a number of loads and the solderability was found to be excellent.
At the end of about 300 ampere-hours of electrolysis the bath was still performing excellently. A small amount of a white gelatinous sludge of basic stannic salts had precipitated out as would be expected from this type of bath due to some air oxidation of stannous tin, but the amount appeared tolerable and did not adversely affect bath performance.
To the bath of Example 1 there was added the equivalent of 2 g/l of ~O&~B~
laurylamine. On repeating the Hull Cell test, the luster was unimpaired and in fact was more uniform and somewhat more reflective. However, no deposit striations or "ribbing" effects were now noticeable.
Example 5 was repeated using 2 g/l octylamine in place of the laurylamine, with the same results obtained.
4 liters of solution were prepared having the following composition:
stannous tin 55 g/l lead 25 g/l free fluoboric acid 120 g/l boric acid 30 g/l "Iergitol ~on-lonic NP-35" 10 g/l "Triton QS-15" l0 g/l o-chlorobenzaldehyde 0.4 g/l laurylamine 2 g/l Using conditions outlined under Life Tests ~e~, a brass cathode was plated for 15 minutes at 3 amperes to give an average cathode current density of about 3 ASD. The deposit was uniformly lustrous, duc~ile, and free of striations or "ribbing". The deposit also exhibited a remarkable degree of lcvoling as evidenced by the degree of obliteration o basis metal defects ~pits, minor scratches, etc.) and the extraordinary smoothening of the rough sheared edges of the cathode.
The life test was continued for a total of 66 ampere-hours of electrolysis with periodic replenishment additions of o-chlorobenzaldehyde to maintain deposit luster. Plating times were varied from 3 minutes (which would give normally used thicknesses of alloy) to several hours and in general excellent deposits were still being obtained at the end of this electrolysis period Deposit luster was easily maintained with variations of current from 1 to 5 amperes per cathode and deposit ductility remained excellent.
An appreciable amount of a white gelatinous precipitate was formed during the electrolysis period due to air oxidation of stannous tin to stannic 45~L
basic salts but the sludge had surprisingly little or no effect on the luster, smoothness and uniformity of deposits.
The Life Test of Example 7 was repeated using a freshly prepared bath but in addition adding as an anti-oxidant 1.5 g/l hydroquinone.
Excellent results were obtained as in Example 7 but after an electrolysis time of well over 100 ampere-hours the solution remained perfectly clear and free of any opalescence or any precipitate.
The Life Test of Example 7 was repeated using a freshly prepared bath but in addition adding as an anti-oxidant 0.2 g/l of sodium benzene monosulfinate. Excellent results were obtained as in Example 7 but aEter an clectrolysis timc oE well over 100 ampero-hours tho solution remaine~ perfect-ly clear and free of any opalescence or any precipitcLte.
. .:
Although this invention has been illustrated by reference to specific embodiments, modifications thereof which are clearly within the scope of the invention will be apparent to those skilled in the art.
~: ~3) R-CH=N-NHR" (R" = aromatic group such as phenyl) (4) R-CH=N-NHC-NH2 (semi-carbazones) ..
:. O
;. (5) R-CH=N-OH (oximes) (6) R-CH=(OR'")2 (R"' = alkyl group - acetals) ~ In the above compounds, R is an aromatic moiety such as phenyl :' .
,:~
,', : _ 6 _ ., . ~
~0~ 5~
containing 1 or 2 chloro groups directly bonded to the aromatic ring.
Compounds of Type B may be used in the form of stock solutions in appropriate organic solvents (methanol, ethanol, isopropanol, acetone, etc.) or in mixtures of organic solvents (such as methanol plus water plus compounds of Type A, the latter imparting appreciable solubiLizing action).
Although the cooperative use of compounds of Types A and B may give excellent results, particularly under barrel plating conditions, it has also been found that the addition of an aliphatic amine as a further cooperating additive will result in even more uniformly lustrous, pit-free and striation-free deposits.
Compounds which are aliphatic amines or compounds which liberatealiphatic amines on addition to the electroplating bath, defined above under (c~, and hereafter referred to as Type C, are of the formulae:
R-N~12 ~V) / R' where R' R" = hydrogen, alkyl or aromatic groups, and R-N=C R = alkyl group, straight or branched chain with 3 to (VI) R"
Specific and preferred compounds are exemplified by:
CH3(CH2~11NH2 laurylamine CH3(CH2)7NH2 octylamine The aliphatic amine or aliphatic amine producing compounds are used in concentrations ranging from 0.25 g/l to 5 g/l depending on their degree of bath solubility. They may be used in the Eorm of aqu~ous or organ:ic solvent stock solutions or in mixtures of water and organic solvents.
A plating bath of the fluoborate type which may be used in the practice of this invention may consist of the following basic ingredients:
stannous fluoborate [ Sn(BF4)2 ]
lead fluoborate [ Pb(BF4)2 ]
fluoboric acid [ HBF4 ]
boric acid [ H3B03 ]
The stannous fluoborate is usually added as an aqueous concentrate containing typically ~9.6~ by weight of Sn(BF4)2 having a speciEic gravity of 1.60. The lead fluoborate is usually added as an aqueous concentrate contain-.: :
_ 7 ~ 38454 : :
ing typically 50% by weight of Pb(BF4)2 having a specific gravity of 1.75.
The fluoboric acid is generally added as an aqueous concentrate typically 49%
by weight of HBF~ having a specific gravity of 1.37. The boric acid is usually added as a relatively pure grade of powdered or crystalline H3BO3.
The fluoboric acid added in addition to the BF4 anion associated with stannous tin and lead is usually referred to as "free fluoboric acid".
A typical concentration of bath constituents and a preferred bath make-up concentration are as follows, in grams per liter ~g/l):
Range g/l Preferred g/l Sn(BF4)2 110 - 135 135 ( 4)2 37 - 55 46 Equivalent to sn-~2 45 - 55 55 pb~2 20 - 30 25 Free fluoboric acid 100 - 200 120 boric acid 10 - 40 30 ~-Anodes generally consist of a cast or extruded tin-lead alloy containing 60% tin and 40% lead. In order to more consistently obtain an alloy composition at the cathode close to 60-40, the following operating conditions are generally used:
temperature 10C. - 60C.
cathode current density 3.0 ASD (amperes per square dm) anode current density 1.5 ASD
agitation mild mechanical (150 to 700 cm per minute) or slowly rotating barrel (2-5 RPM) Increasing the cathode current density over 3.0 ASD will tend to increase the tin content of the deposit while decreasing the cathode current density below 3.0 ASD will tend to decrease the tin content of the deposit.
Although ideally a 60-40% alloy is desired, in actual commercial operation a i tin content of 60 10% by weight and a lead content of 40 10% by weight are : ~ : . : .. . . :
, ,,: , ,. - . . - :
1~8845~
generally acceptable and this mcans that some variation in tin and lead concentrations and in cathode current density may be tolerated.
This invention also lies in the addition of an anti-oxidant or oxygen acceptor for substantially decreased tendency toward formation of precipitates of stannic basic salts. Operable anti-oxidants or oxygen acceptors include hydroquinone or substituted hydroquinone, pyrocatechol, pyrogallol, catechol, and aromatic sulfinates such as sodium benzene monosulfinate.
These compounds may be used singly or in combination in concentra-tions of about 0.5 g/l to 5 g/l depending on their bath solubility. They may be used in the form of aqueous or organic solvent stock solutions or they may be added directly to the plating bath with stirring to facilitate solution.
According to another of its embodiments, this invention is an .
aqueous solution eor electrodepositing a bright, sound, smooth ductile alloy e tin and lead having about 60% tin and 40% lead comprising: 110 g/l to 135 g/l of stannous fluoborate; 37 g/l to 55 g/l of lead fluoborate; 100 g/l to 200 g/l of fluoboric acid; 10 g/l to 40 g/l of boric acid; and as a novel additive system:
~a) at least 1 g,/l. of at least one polyether of formula Q-(CH2CH2o)n-X wherein:
n represents an integer of from 4 to 100;
Q is chosen from the group consisting of:
(i) an alkoxy group R0 of from 4 to 18 carbon atoms;
(ii) an alkyl phenoxy group of formula R' ~
wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms;
(iii) an amide group of formula R "CONH-, wherein R " repre-sents a branched or straight chain aliphatic group of 8 to 18 carbon atoms; and IRl (iv) an amino group of formula R2- C - N~l - , wherein Rl, R2 and R3 each represent a straight or branched alkyl group of ~,...
_ 9 -, ' ' . ' : . ''; , ' ' ' . .'' ' '' ' ' '~ . . '.' ~ ~ , ", ' ' ' , " .
1~84~S~
from 8 to 18 carbon atoms; and X is selected from the group consisting of hydrogen, S03M and P04M2, wherein M is hydrogen or a bath-compatible cation com-prising sodium, potassium, ammonium, magnesium, lead, tin, ; calcium, caesium, or rubidium; and (b) 0.1 g/l to 1.0 g/l of at least one aromatic aldehyde exhibit-ing at least one chloro substituent, or at least one compound producing an aromatic aldehyde exhibiting at least one chloro substituent; and optionally (c) from 0.25 to 5.0 g/l of at least one aliphatic amine, or a compound producing an aliphatic amine.
The preferred operating conditions, such as pH, temperature, and ; current density may vary depending upon the particular bath composition and the nature of the article receiving the layer of tin-lcad alloy electrodeposit.
tn general, good tin-lead alloy elcctrodoposits nlay be obtained within a speci~ic range of operating conditions.
The tin-lead alloy electroplating processes using the compositions o the invention may be carried out at temperatures of about 10C. - 60 C.
(preferably 15C. - 20C.) either with or without agitation. The temperature of the plating solution is usually the ambient temperature, say 35C. or below, with lower temperatures giving optimum results, such as 15C. - 20C. Using average current densities of 0.5 to 5.0 ASD, tin-lead alloy electrodeposits having average thicknesses of 0.25 - 25 mic:rons may be obtained using plating times which may average 0.1-10 minutes.
In the plating of tin-lead alloy the parts may be plated on racks, i.e. on fixtures holding single or multiple parts which may all be the same or which may be different in size, geometrical configuration, etc. Parts may also be plated in bulk in rotating barrels and in this type of plating, usually used for plating of smaller parts which lend themselves to tumbling action, the barrel loads usually consist of the same part although mixed loads are sometimes plated. Because of the number, size, and shape complexity of parts it is important that the plating bath be so formulated as to provide the -widest possible bright plate current density range. It is also important that ,.
- 1 0 - , ~
it84S~
the limiting current density, i.e. the current density at which ~he deposit ceases to be sound in structure and appearance, be as high as possible to allow for the wide variations in cathode current density which may be encount-ered due to the size and shape complexity of parts. ~-The following examples are submitted for the purpose of illustration only, so that those skilled in the art of tin-lead alloy plating may better understand the operation of the invention. These examples are not to be construed as limiting the scope of the invention in any way.
PLATING TEST CONDITIONS
A. Hull Cell Tests Hull Cell - plastic with a plating solution volume of 267 ml Anode - slab of Sn-Pb alloy (60~ Sn and 40% Pb by weight) Cathode - polished brass 10 cm x 7.5 cm x 1 mm with 5 cm immersed Cell Current - 1 ampere (0 to 7 ASD range) Time - minutes Agitation - magnetic stirrer Temperature - ambient room ~20C. - 25C.) B Life Tosts - 4 liter solution volume-strLp cathodes Plating Cell - rectangular glass battery jar 15.5 cm length, 13 cm width, 26.5 cm depth Solution Volume - 4 liters ~solution depth of 20.5 cm) `, Anode - slab of Sn-Pb cast alloy ~60% Sn and 40% Pb by weight) 9 cm wide, -1 cm thick, 20.5 cm immersed in plating bath Cathode - polished brass 20.4 cm long, 2.54 cm wide, 0.5 mm thick immersed to depth of 18 cm - maintained parallel to the anode at a dis-tance of about 10 cm - bottom of cathode bent to give an inter-nal angle o ~5 facing anode Agitation - moving cathode bar - length of stroke 8 cm - 78 strokes/minute - 11- .. ' .. , , , . ", , , .,, . . ., . - .................. . . . . . ~ ..
.. . . ; , . . , .' :. : . . .: :
45~ :
-total cathode travel 625 cm/minute Temperature - ambient room (20C. - 25C.) Cell Current - varied from 2 to 5 amperes Time - varied from 3 minutes to several hours C. Barrel Plating Tests Barrel - "Plexiglas" (a trade mark) plastic of horizontal hexagonal type - 12.5 cm long with a diameter of about 10 cm - com-pletely immersed in plating bath - operated at 5 RPM
Solution Volume - 4 liters - cooled to compensate for heating effects of current by immersing in solution plastic cooling coils through ~ -which cold water circulated to mainta:in temperature at about 25C
Ccll ~ polyethylene plastic Load - steel nails about 5 cm long with a total load area of about 930 square cm Current - varied from 5 to 25 amperes Time - varied from 15 to 60 minutes .
_AMPLF 1 A stock solution was prepared havlng the following compos.ition:
stannous tin 52 g/l lead 30 g/l .
free fluoboric acid 100 g/l . :
boric acid 25 g/l :
To 267 ml of the above stock solution, there were added the :: .
equivalent of "Tergitol Non-Ionic NP-35" 10 g/l ; "Triton QS-15" 10 g/l o-chlorbenzaldehyde 0.~ g/l On running a Hull Cell test as cLescribed in the above, a lustrous deposit was obtained throughout the entire current density range with a slight tendency -~LS~
toward striation or "ribbing" of deposit in the current density range of 2 to 7 ASD.
Example 1 was repeated using 0.4 g/l of 2,6-dichlorobenzaldehyde in place of the o-chlorobenzaldehyde with essentially the same results obtained.
Example 1 was repeated using 0.4 g/l of m-chlorobenzaldehyde in place o the o-chlorobenzaldehyde with essentially the same results obtained.
A barrel plating test was run using the barrel plating conditions outlined in the above and using a cell current of 20 amperes for 30 minutes to give an average cathode current density o~ about 2 ~SD. Aftcr plating the load of nails was rinsed and dricd, and they had a beautifully lustrous and uni~orm appcarancc. On testing roprcscntative naiLs from the load the deposit ductility and adhesion to the basis metal was excellent. Because of the tumbling and some burnishîng action no indication was obtained of any of the striation or "ribbing" effect indicated by the ~lull Cell tes~s of Examples 1 to 3, inclusive.
The life test was continued for a total electrolysis time of about 300 ampere-hours with variations of current from 5 to 25 amperes per load and ;~
with times ranging from 15 minutes to 1 hour. Periodic replenishment of o-chlorobenzaldehyde easily maintained deposit luster with replenishment additions made on the basis of deposit appearance. Solderabllity tests were made on representative samples from a number of loads and the solderability was found to be excellent.
At the end of about 300 ampere-hours of electrolysis the bath was still performing excellently. A small amount of a white gelatinous sludge of basic stannic salts had precipitated out as would be expected from this type of bath due to some air oxidation of stannous tin, but the amount appeared tolerable and did not adversely affect bath performance.
To the bath of Example 1 there was added the equivalent of 2 g/l of ~O&~B~
laurylamine. On repeating the Hull Cell test, the luster was unimpaired and in fact was more uniform and somewhat more reflective. However, no deposit striations or "ribbing" effects were now noticeable.
Example 5 was repeated using 2 g/l octylamine in place of the laurylamine, with the same results obtained.
4 liters of solution were prepared having the following composition:
stannous tin 55 g/l lead 25 g/l free fluoboric acid 120 g/l boric acid 30 g/l "Iergitol ~on-lonic NP-35" 10 g/l "Triton QS-15" l0 g/l o-chlorobenzaldehyde 0.4 g/l laurylamine 2 g/l Using conditions outlined under Life Tests ~e~, a brass cathode was plated for 15 minutes at 3 amperes to give an average cathode current density of about 3 ASD. The deposit was uniformly lustrous, duc~ile, and free of striations or "ribbing". The deposit also exhibited a remarkable degree of lcvoling as evidenced by the degree of obliteration o basis metal defects ~pits, minor scratches, etc.) and the extraordinary smoothening of the rough sheared edges of the cathode.
The life test was continued for a total of 66 ampere-hours of electrolysis with periodic replenishment additions of o-chlorobenzaldehyde to maintain deposit luster. Plating times were varied from 3 minutes (which would give normally used thicknesses of alloy) to several hours and in general excellent deposits were still being obtained at the end of this electrolysis period Deposit luster was easily maintained with variations of current from 1 to 5 amperes per cathode and deposit ductility remained excellent.
An appreciable amount of a white gelatinous precipitate was formed during the electrolysis period due to air oxidation of stannous tin to stannic 45~L
basic salts but the sludge had surprisingly little or no effect on the luster, smoothness and uniformity of deposits.
The Life Test of Example 7 was repeated using a freshly prepared bath but in addition adding as an anti-oxidant 1.5 g/l hydroquinone.
Excellent results were obtained as in Example 7 but after an electrolysis time of well over 100 ampere-hours the solution remained perfectly clear and free of any opalescence or any precipitate.
The Life Test of Example 7 was repeated using a freshly prepared bath but in addition adding as an anti-oxidant 0.2 g/l of sodium benzene monosulfinate. Excellent results were obtained as in Example 7 but aEter an clectrolysis timc oE well over 100 ampero-hours tho solution remaine~ perfect-ly clear and free of any opalescence or any precipitcLte.
. .:
Although this invention has been illustrated by reference to specific embodiments, modifications thereof which are clearly within the scope of the invention will be apparent to those skilled in the art.
Claims (45)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for depositing a bright, smooth, sound, ductile tin-lead alloy containing from 30% to 50% by weight lead and from 50% to 70% by weight tin which comprises passing current from an anode to a cathode through an aqueous acidic bath containing at least one water soluble stannous tin salt, at least one water soluble lead salt, and as cooperating additives:
(A)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkoxy group RO of 4 to 18 carbon atoms and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound pro-ducing an aromatic aldehyde exhibiting at least one chloro substituent; or (B)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkyl phenoxy group Of formula , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound producing an aromatic aldehyde exhibiting at least one chloro substituent; or (C)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkyl phenoxy group of formula , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.25 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound pro-ducing an aromatic aldehyde exhibiting at least one chloro substituent; or (D)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amide group of formula R" CONH-, wherein R " represents a branched or straight chain aliphatic group of 8 to 18 carbon atoms; and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound pro-ducing an aromatic aldehyde exhibiting at least one chloro substituent; or (E)(a) at least 1 gl1 of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amide group of formula R" CONH-, wherein R'' represents a branched or straight chain aliphatic group of 8 to 18 carbon atoms; and X is selected from the group consisting of SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium, and (b) 0.25 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound pro-ducing an aromatic aldehyde exhibiting at least one chloro substituent; or (F)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amino group of formula wherein R1 R2 and R3 each represent a straight or branched alkyl group of from 8 to 18 carbon atoms; and (b) 0.1 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound producing an aromatic aldehyde exhibiting at least one chloro substituent.
(A)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkoxy group RO of 4 to 18 carbon atoms and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound pro-ducing an aromatic aldehyde exhibiting at least one chloro substituent; or (B)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkyl phenoxy group Of formula , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound producing an aromatic aldehyde exhibiting at least one chloro substituent; or (C)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkyl phenoxy group of formula , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.25 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound pro-ducing an aromatic aldehyde exhibiting at least one chloro substituent; or (D)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amide group of formula R" CONH-, wherein R " represents a branched or straight chain aliphatic group of 8 to 18 carbon atoms; and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound pro-ducing an aromatic aldehyde exhibiting at least one chloro substituent; or (E)(a) at least 1 gl1 of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amide group of formula R" CONH-, wherein R'' represents a branched or straight chain aliphatic group of 8 to 18 carbon atoms; and X is selected from the group consisting of SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium, and (b) 0.25 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound pro-ducing an aromatic aldehyde exhibiting at least one chloro substituent; or (F)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amino group of formula wherein R1 R2 and R3 each represent a straight or branched alkyl group of from 8 to 18 carbon atoms; and (b) 0.1 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound producing an aromatic aldehyde exhibiting at least one chloro substituent.
2. The process according to claim 1 wherein the bath additionally contains from 0.25 to 5.0 g/l of at least one aliphatic amine, or a compound producing an aliphatic amine.
3. The process according to claim 1 for depositing a bright, sound, smooth, ductile alloy of tin and lead which comprises passing current from an anode to a cathode through an aqueous acidic bath containing at least one water soluble stannous tin salt, at least one water soluble lead salt, and as cooperating additives:
(a) at least 1 g/l of at least one polyether surfactant of the formula where R1, R2, and R3 each exhibit 12 to 14 carbon atoms and n is about 15;
and (b) 0.1 g/l to 1 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent or at least one compound producing an aromatic aldehyde exhibiting at least one chloro substituent.
(a) at least 1 g/l of at least one polyether surfactant of the formula where R1, R2, and R3 each exhibit 12 to 14 carbon atoms and n is about 15;
and (b) 0.1 g/l to 1 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent or at least one compound producing an aromatic aldehyde exhibiting at least one chloro substituent.
4. The process for electrodepositing a bright, sound, smooth, ductile alloy of tin and lead which comprises passing current from an anode to a cathode through an aqueous acidic bath containing at least one water soluble stannous tin salt, at least one water soluble lead salt, and as cooperating additives:
(A)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkyl phenoxy group of formula , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at least one chloro substituent, or (B)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkyl phenoxy group of formula , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.25 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound pro-ducing an aromatic aldehyde exhibiting at least one chloro substituent;
(c) 0.25 g/l to 5 g/l of at least one aliphatic amine or a compound producing an aliphatic amine.
(A)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkyl phenoxy group of formula , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at least one chloro substituent, or (B)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkyl phenoxy group of formula , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.25 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound pro-ducing an aromatic aldehyde exhibiting at least one chloro substituent;
(c) 0.25 g/l to 5 g/l of at least one aliphatic amine or a compound producing an aliphatic amine.
5. The process of claims 1 or 4 wherein the polyether surfactant is of the formula where R' is an alkyl group of 8 to 20 carbon atoms, n is an integer 4 to 100, and X is selected from the group consisting of SO3M and PO4M2 where M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium.
6. The process of claim l or 4 wherein at least one polyether surfactant is a nonylphenol-ethylene oxide condensate exhibiting about 15 ethylene oxide groups per molecule.
7. The process of claim 1 or 4 wherein the polyether surfactant is of the formula wherein R is a branched or straight chain aliphatic radical containing 4 to 18 carbon atoms, n is an integer 4 to 100, and X is selected from the group consisting of hydrogen, SO3M and PO4M2 where M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium or rubidium.
8. The process of claims 1 or 2 wherein the polyether surfact-ant is of the formula where R" is a branched or straight chain aliphatic group of 8 to 18 carbon atoms, n is an integer 4 to 100, and X is selected from the group consisting of hydrogen, SO3M and PO4M2 where M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesiu-or rubidium.
9. The process of claims 1 or 2 wherein said aromatic aldehyde either added or to be produced is of the formula where n is 1 or 2.
10. The process of claims 1 or 2 wherein the water soluble stannous tin salt is stannous fluoborate and the water soluble lead salt is lead fluoborate.
11. The process of claims l or 2 wherein said tin-lead alloy is about 60% tin and about 40% lead.
12. The process of claim 2 wherein said compound which is or which produces an aliphatic amine is selected from the group consisting of RNH2 and wherein R is a straight or branched chain alkyl group exhibiting 3 to 20 carbon atoms, R' and R" are hydrogen, alkyl groups, or aromatic groups.
13. The process of claim 2 wherein said aliphatic amine is laurylamine.
14. The process of claim 2 wherein said aliphatic amine is octylamine.
15. A process for depositing a bright, smooth, sound, ductile tin-lead alloy containing from 30% to 50% by weight lead and from 50% to 70% by weight tin which comprises passing current from an anode to a cathode through an aqueous acidic bath containing at least one water soluble stannous tin salt, at least one water soluble lead salt, and as cooperating additives:
(A)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkoxy group RO of 4 to 18 carbon atoms and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium,caesium, or rubidium; and (b) 0.1 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at least one chloro substituent; or (B)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkyl phenoxy group of formula , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound pro-ducing an aromatic aldehyde exhibiting at least one chloro substituent; or (C)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkyl phenoxy group of formula , wherein R' represents an aliphatic radical of Prom 8 to 20 carbon atoms and X is selected Prom the group consisting of SO3M and PO4M2, wherein M is hydrogen or a bath-compat-ible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and b) 0.25 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound pro-ducing an aromatic aldehyde exhibiting at least one chloro substituent; or (D)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amide group of formula R"CONH-, wherein R" represents a branched or straight chain aliphatic group of 8 to 18 carbon atoms; and X
is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, am-monium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound pro-ducing an aromatic aldehyde exhibiting at least one chloro substituent; or (E)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100;
Q represents an amide group of formula R"CONH-, wherein R" represents a branched or straight chain aliphatic group of 8 to 18 carbon atoms; and X
is selected from the group consisting of SO3M and PO4M2, wherein M is hydro-gen or a bath-compatible cation comprising sodium,, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.25 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at least one chloro substituent; or (F)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amino group of formula wherein R1 R2 and R3 each represent a straight or branched alkyl group of from 8 to 18 carbon atoms; and (b) 0.1 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound pro-ducing an aromatic aldehyde exhibiting at least one chloro substituent; and (G) 0.25 g/l to 5 g/l of at least one compound which is or which produces an aliphatic amine; and (H) 0.5 g/l to 5 g/l of at least one anti-oxidant or oxygen acceptor to maintain tin in its divalent stannous form.
(A)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkoxy group RO of 4 to 18 carbon atoms and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium,caesium, or rubidium; and (b) 0.1 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at least one chloro substituent; or (B)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkyl phenoxy group of formula , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound pro-ducing an aromatic aldehyde exhibiting at least one chloro substituent; or (C)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkyl phenoxy group of formula , wherein R' represents an aliphatic radical of Prom 8 to 20 carbon atoms and X is selected Prom the group consisting of SO3M and PO4M2, wherein M is hydrogen or a bath-compat-ible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and b) 0.25 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound pro-ducing an aromatic aldehyde exhibiting at least one chloro substituent; or (D)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amide group of formula R"CONH-, wherein R" represents a branched or straight chain aliphatic group of 8 to 18 carbon atoms; and X
is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, am-monium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound pro-ducing an aromatic aldehyde exhibiting at least one chloro substituent; or (E)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100;
Q represents an amide group of formula R"CONH-, wherein R" represents a branched or straight chain aliphatic group of 8 to 18 carbon atoms; and X
is selected from the group consisting of SO3M and PO4M2, wherein M is hydro-gen or a bath-compatible cation comprising sodium,, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.25 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at least one chloro substituent; or (F)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amino group of formula wherein R1 R2 and R3 each represent a straight or branched alkyl group of from 8 to 18 carbon atoms; and (b) 0.1 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound pro-ducing an aromatic aldehyde exhibiting at least one chloro substituent; and (G) 0.25 g/l to 5 g/l of at least one compound which is or which produces an aliphatic amine; and (H) 0.5 g/l to 5 g/l of at least one anti-oxidant or oxygen acceptor to maintain tin in its divalent stannous form.
16. The process of claim 15 wherein said anti-oxidant compound is an aromatic sulfinate.
17. The process of claim 16 wherein said aromatic sulfinate is sodium benzene monosulfinate.
18. The process of claim 15 wherein said anti-oxidant compound is hydroquinone or substituted hydroquinone.
19. The process of claim 15 wherein said anti-oxidant compound is pyrocatechol.
20. The process of claim 15 wherein said anti-oxidant compound is catechol.
21. The process of claim 15 wherein said anti-oxidant compound is pyrogallol.
22. A process for electrodepositing a bright, sound, smooth, ductile alloy of tin and lead having about 60% tin and about 40% lead comprising passing current from an anode to a cathode through an aqueous acidic bath containing 110 g/l to 135 g/l of stannous fluoborate; 37 g/l to 55 g/l of lead fluoborate; 100 g/l to 200 g/l of fluoboric acid; 10 g/l to 40 g/l of boric acid; and as a novel additive system:
(A)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkoxy group RO of 4 to 18 carbon atoms and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 1.0 g/l of at least one compound which is or which produces a chlorinated aromatic aldehyde of the formula where n is 1 or 2; or (B)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkyl phenoxy group of formula , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one compound which is or which produces a chlorinated aromatic aldehyde of the formula where n is 1 or 2; or (C)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkyl phenoxy group of formula , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of SO3M and PO4M2, wherein M is hydrogen or a bath-compat-ible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.25 g/l to 1.0 g/l of at least one compound which is or which produces a chlorinated aromatic aldehyde of the formula , where n is 1 or 2; or (D)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100;
Q represents an amide group of formula R"CONH-, wherein R" represents a branched or straight chain aliphatic group of 8 to 18 carbon atoms; and X
is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one compound which is or which produces a chlorinated aromatic aldehyde of the formula , where n is 1 or 2; or (E)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 2 to 100; Q represents an amide group of formula R"CONH-, wherein R" represents a branched or straight chain aliphatic group of 8 to 18 carbon atoms; and X is selected from the group consisting of SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.25 g/l to 1.0 g/l of at least one compound which is or which produces a chlorinated aromatic aldehyde of the formula , where n is 1 or 2; or (F)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amino group of formula wherein R1, R2 and R3 each represent a straight or branched alkyl group of from 8 to 18 carbon atoms; and (b) 0.1 g/l to 1.0 g/l of at least one compound which is or which produces a chlorinated aromatic aldehyde of the formula , where n is 1 or 2; and (G) 0.25 g/l to 5 g/l of a compound which is or which pro-duces an aliphatic amine; and (H) 0.5 g/l to 5 g/l of an anti-oxidant or oxygen acceptor to maintain tin in its divalent stannous form.
(A)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkoxy group RO of 4 to 18 carbon atoms and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 1.0 g/l of at least one compound which is or which produces a chlorinated aromatic aldehyde of the formula where n is 1 or 2; or (B)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkyl phenoxy group of formula , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one compound which is or which produces a chlorinated aromatic aldehyde of the formula where n is 1 or 2; or (C)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkyl phenoxy group of formula , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of SO3M and PO4M2, wherein M is hydrogen or a bath-compat-ible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.25 g/l to 1.0 g/l of at least one compound which is or which produces a chlorinated aromatic aldehyde of the formula , where n is 1 or 2; or (D)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100;
Q represents an amide group of formula R"CONH-, wherein R" represents a branched or straight chain aliphatic group of 8 to 18 carbon atoms; and X
is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one compound which is or which produces a chlorinated aromatic aldehyde of the formula , where n is 1 or 2; or (E)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 2 to 100; Q represents an amide group of formula R"CONH-, wherein R" represents a branched or straight chain aliphatic group of 8 to 18 carbon atoms; and X is selected from the group consisting of SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.25 g/l to 1.0 g/l of at least one compound which is or which produces a chlorinated aromatic aldehyde of the formula , where n is 1 or 2; or (F)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amino group of formula wherein R1, R2 and R3 each represent a straight or branched alkyl group of from 8 to 18 carbon atoms; and (b) 0.1 g/l to 1.0 g/l of at least one compound which is or which produces a chlorinated aromatic aldehyde of the formula , where n is 1 or 2; and (G) 0.25 g/l to 5 g/l of a compound which is or which pro-duces an aliphatic amine; and (H) 0.5 g/l to 5 g/l of an anti-oxidant or oxygen acceptor to maintain tin in its divalent stannous form.
23. A composition for producing bright, smooth, sound, ductile tin-lead alloy electrodeposits containing from 30% to 50% by weight lead and from 50% to 70% by weight tin, which comprises an aqueous acidic bath containing at least one water soluble stannous tin salt, at least one water soluble lead salt, and as cooperating additives:
(A)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkoxy group RO of 4 to 18 carbon atoms and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at least one chloro substituent; or (B)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkyl phenoxy group of formula , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at least one chloro substituent; or (C)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkyl phenoxy group of formula , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.25 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at least one chloro substituent; or (D)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amide group of formula R"CONH-, wherein R" represents a branched or straight chain aliphatic group of 8 to 18 carbon atoms; and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound producing an aromatic aldehyde exhibiting at least one chloro substituent; or (E)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amide group of formula R"CONH-, wherein R" represents a branched or straight chain aliphatic group of 8 to 18 carbon atoms; and X is selected from the group consisting of SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead , tin, calcium, caesium, or rubidium, and (b) 0.25 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at least one chloro substituent; or (F)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amino group of formula wherein R1 R2 and R3 each represent a straight or branched alkyl group of from 8 to 18 carbon atoms; and (b) 0.1 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at least one chloro substituent.
(A)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkoxy group RO of 4 to 18 carbon atoms and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at least one chloro substituent; or (B)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkyl phenoxy group of formula , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at least one chloro substituent; or (C)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkyl phenoxy group of formula , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.25 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at least one chloro substituent; or (D)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amide group of formula R"CONH-, wherein R" represents a branched or straight chain aliphatic group of 8 to 18 carbon atoms; and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound producing an aromatic aldehyde exhibiting at least one chloro substituent; or (E)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amide group of formula R"CONH-, wherein R" represents a branched or straight chain aliphatic group of 8 to 18 carbon atoms; and X is selected from the group consisting of SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead , tin, calcium, caesium, or rubidium, and (b) 0.25 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at least one chloro substituent; or (F)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amino group of formula wherein R1 R2 and R3 each represent a straight or branched alkyl group of from 8 to 18 carbon atoms; and (b) 0.1 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at least one chloro substituent.
24. The composition of claim 23 additionally containing from 0.25 g/l to 5.0 g/l of at least one aliphatic amine, or a compound producing an aliphatic amine.
25. The composition of claim 23 which comprises an aqueous acidic bath composition containing at least one water soluble stannous tin salt, at least one water soluble lead salt, and as cooperating additives:
(a) at least l g/l of at least one polyether surfactant of the formula where R1 R2 and R3 each exhibit 12 to 14 carbon atoms and n is about 15; and (b) 0.1 g/l to 1 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent or at least one compound producing an aro-matic aldehyde exhibiting at least one chloro substituent.
(a) at least l g/l of at least one polyether surfactant of the formula where R1 R2 and R3 each exhibit 12 to 14 carbon atoms and n is about 15; and (b) 0.1 g/l to 1 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent or at least one compound producing an aro-matic aldehyde exhibiting at least one chloro substituent.
26. The composition which comprises an aqueous plating bath containing at least one water soluble stannous tin salt, at least one water soluble lead salt, and as cooperating additives:
(A)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 11 to 100; Q represents an alkyl phenoxy group of formula , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at least one chloro substituent; or (B)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkyl phenoxy group of formula , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.25 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at least one chloro substituent; and (C) 0.25 g/l to 5 g/l of at least one aliphatic amine or a compound producing an aliphatic amine.
(A)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 11 to 100; Q represents an alkyl phenoxy group of formula , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at least one chloro substituent; or (B)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkyl phenoxy group of formula , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.25 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at least one chloro substituent; and (C) 0.25 g/l to 5 g/l of at least one aliphatic amine or a compound producing an aliphatic amine.
27. The composition of claims 23 or 24 wherein said aromatic aldehyde either added or to be produced is of the formula where n is 1 to 2.
28. The composition of claim 23 or 24 wherein at least one surfactant is a nonylphenol-ethylene oxide condensate exhibiting about 15 ethylene oxide groups per molecule.
29. The composition of claim 23 or 24 wherein the water soluble stannous tin salt is stannous fluoborate and the water soluble lead salt is lead fluoborate.
30. The composition of claim 23 or 24 wherein said polyether surfactant is of the formula wherein R1, R2 and R3 each exhibit 12 to 14 carbon atoms and n is about 15.
31. The composition of claim 23 wherein said polyether is of the formula RO(CH2CH2O)n-X
wherein R is a branched or straight chain aliphatic radical containing 4 to 18 carbon atoms, n is an integer 4 to 100, and X is selected from the group consisting of hydrogen, SO3M and PO4M2 where M is hydrogen or a bath-compat-ible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium or rubidium.
wherein R is a branched or straight chain aliphatic radical containing 4 to 18 carbon atoms, n is an integer 4 to 100, and X is selected from the group consisting of hydrogen, SO3M and PO4M2 where M is hydrogen or a bath-compat-ible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium or rubidium.
32. The composition of claim 23 or 24 wherein the polyether is of the formula wherein R' is an alkyl group of 8 to 20 carbon atoms, n is an integer 4 to 100, and X is selected from the group consisting of hydrogen, SO3M and PO4M2 where M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium or rubidium.
33. The composition of claims 23 or 24 wherein the polyether is of the formula where R" is a branched or straight chain aliphatic group of 8 to 18 carbon atoms, n is an integer 4 to 100, and X is selected from the group consisting of hydrogen, SO3M and PO4M2 where M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium or rubidium.
34. The composition of claims 23 or 24 adapted to deposit an alloy containing about 60% tin and 40% lead.
35. The composition of claim 24 wherein said compound which is or which produces an aliphatic amine is selected from the group consisting of RNH2 and wherein R is a straight or branched chain alkyl group exhibiting 3 to 20 carbon atoms, R' and R" are hydrogen, alkyl groups or aromatic groups.
36. The composition of claim 24 wherein said aliphatic amine is laurylamine.
37. The composition of claim 24 wherein said aliphatic amine is octylamine.
38. The composition for producing bright, smooth, sound, ductile tin-lead alloy electrodeposits containing from 30% to 50% by weight lead and from 50% to 70% by weight tin, which comprises an aqueous acidic bath con-taining at least one water soluble stannous tin salt, at least one water soluble lead salt, and as cooperating additives:
(A)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkoxy group RO of 4 to 18 carbon atoms and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound pro-ducing an aromatic aldehyde exhibiting at least one chloro substituent; or (B)(a) at least 1 g/l of at least one polyether of formula Q'(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkyl phenoxy group of formula , wherein R' represents an sliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at least one chloro substituent; or (C)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkyl phenoxy group of formula , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of SO3M and PO4M2, wherein M is hydrogen or a bath-compat-ible cation comprising sodium, potassium., ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.25 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound pro-ducing an aromatic exhibiting at least one chloro substituent; or (D)(a) at least 1 g/l of at least one polyether surfacant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amide group of formula R"CONH-, wherein R" represents a branched or straight chain aliphatic group of 8 to 18 carbon atoms; and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at least one chloro substituent; or (E)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amide group of formula R"CONH-, wherein R" represents a branched or straight chain aliphatic group of 8 to 18 carbon atoms; and X is selected from the group consisting of SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or ribidium; and (b) 0.25 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at least one chloro substituent; or (F)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amino group of formula wherein R1 R2 and R3 each represent a straight or branched alkyl group of from 8 to 18 carbon atoms; and (b) 0.1 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound pro-ducing an aromatic aldehyde exhibiting at least one chloro substituent;and (G) 0.25 g/l to 5 g/l of at least one aliphatic amine or a compound producing an aliphatic amine, and (H) 0.5 g/l to 5 g/l of at least one anti-oxidant or oxygen acceptor to maintain tin in its divalent stannous form.
(A)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkoxy group RO of 4 to 18 carbon atoms and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound pro-ducing an aromatic aldehyde exhibiting at least one chloro substituent; or (B)(a) at least 1 g/l of at least one polyether of formula Q'(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkyl phenoxy group of formula , wherein R' represents an sliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at least one chloro substituent; or (C)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkyl phenoxy group of formula , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of SO3M and PO4M2, wherein M is hydrogen or a bath-compat-ible cation comprising sodium, potassium., ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.25 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound pro-ducing an aromatic exhibiting at least one chloro substituent; or (D)(a) at least 1 g/l of at least one polyether surfacant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amide group of formula R"CONH-, wherein R" represents a branched or straight chain aliphatic group of 8 to 18 carbon atoms; and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at least one chloro substituent; or (E)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amide group of formula R"CONH-, wherein R" represents a branched or straight chain aliphatic group of 8 to 18 carbon atoms; and X is selected from the group consisting of SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or ribidium; and (b) 0.25 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound produc-ing an aromatic aldehyde exhibiting at least one chloro substituent; or (F)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amino group of formula wherein R1 R2 and R3 each represent a straight or branched alkyl group of from 8 to 18 carbon atoms; and (b) 0.1 g/l to 1.0 g/l of at least one aromatic aldehyde exhibiting at least one chloro substituent, or at least one compound pro-ducing an aromatic aldehyde exhibiting at least one chloro substituent;and (G) 0.25 g/l to 5 g/l of at least one aliphatic amine or a compound producing an aliphatic amine, and (H) 0.5 g/l to 5 g/l of at least one anti-oxidant or oxygen acceptor to maintain tin in its divalent stannous form.
39. The composition of claim 38 wherein said anti-oxidant compound is an aromatic sulfinate.
40. The composition of claim 39 wherein said aromatic sulfinate is sodium benzene monosulfinate.
41. The composition of claim 38 wherein said anti-oxidant compound is hydroquinone or substituted hydroquinone.
42. The composition of claim 38 wherein said anti-oxidant compound is pyrocatechol.
43. The composition of claim 38 wherein said anti-oxidant compound is catechol.
44. The composition of claim 38 wherein said anti-oxidant compound is pyrogallol.
45. A composition for producing a bright, sound, smooth, ductile electrodeposit of an alloy of tin and lead having about 60% tin and about 40% lead which comprises an aqueous acidic bath containing gas components 110 g/l to 135 g/l of stannous fluoborate, 37 g/l to 55 g/l of lead fluo-borate; 100 g/l to 200 g/l of fluoboric acid; 10 g/l to 40 g/l of boric acid;
and as a novel additive system:
(A)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkoxy group RO of 4 to 18 carbon atoms and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 1.0 g/l of at least one compound which is or which produces a chlorinated aromatic aldehyde of the formula where n is 1 or 2; or (B)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100: Q represents an alkyl phenoxy group of formula , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one compound which is or which produces a chlorinated aromatic aldehyde of the formula where n is 1 or 2; or (C)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkyl phenoxy group of formula , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.25 g/l to 1.0 g/l of at least one compound which is or which produces a chlorinated aromatic aldehyde of the formula where n is 1 or 2; or (D)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amide group of formula R"CONH-, wherein R" represents a branched or straight chain aliphatic group of 8 to 18 carbon atoms; and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one compound which is or which produces a chlorinated aromatic aldehyde of the formula where n is 1 or 2; or (E)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amide group of formula R"CONH-, wherein R" represents a branched or straight chain aliphatic group of 8 to 18 carbon atoms; and X is selected from the group consisting of SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.25 g/l to 1.0 g/l of at least one compound which is or which produces a chlorinated aromatic aldehyde of the formula where n is 1 or 2; or (F)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amino group of formula wherein R1, R2 and R3 each represent a straight or branched alkyl group of from 8 to 18 carbon atoms; and (b) 0.1 g/l to 1.0 g/l of at least one compound which is or which produces a chlorinated aromatic aldehyde of the formula , where n is 1 or 2;
G) 0.25 g/l to 5 g/l of a compound which is or which produces an aliphatic amine; and H) 0.5 g/l to 5 g/l of an anti-oxidant or oxygen acceptor.
and as a novel additive system:
(A)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkoxy group RO of 4 to 18 carbon atoms and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 1.0 g/l of at least one compound which is or which produces a chlorinated aromatic aldehyde of the formula where n is 1 or 2; or (B)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100: Q represents an alkyl phenoxy group of formula , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one compound which is or which produces a chlorinated aromatic aldehyde of the formula where n is 1 or 2; or (C)(a) at least 1 g/l of at least one polyether of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q represents an alkyl phenoxy group of formula , wherein R' represents an aliphatic radical of from 8 to 20 carbon atoms and X is selected from the group consisting of SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.25 g/l to 1.0 g/l of at least one compound which is or which produces a chlorinated aromatic aldehyde of the formula where n is 1 or 2; or (D)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amide group of formula R"CONH-, wherein R" represents a branched or straight chain aliphatic group of 8 to 18 carbon atoms; and X is selected from the group consisting of hydrogen, SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.1 g/l to 0.25 g/l of at least one compound which is or which produces a chlorinated aromatic aldehyde of the formula where n is 1 or 2; or (E)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amide group of formula R"CONH-, wherein R" represents a branched or straight chain aliphatic group of 8 to 18 carbon atoms; and X is selected from the group consisting of SO3M and PO4M2, wherein M is hydrogen or a bath-compatible cation comprising sodium, potassium, ammonium, magnesium, lead, tin, calcium, caesium, or rubidium; and (b) 0.25 g/l to 1.0 g/l of at least one compound which is or which produces a chlorinated aromatic aldehyde of the formula where n is 1 or 2; or (F)(a) at least 1 g/l of at least one polyether surfactant of formula Q-(CH2CH2O)n-X wherein n represents an integer of from 4 to 100; Q
represents an amino group of formula wherein R1, R2 and R3 each represent a straight or branched alkyl group of from 8 to 18 carbon atoms; and (b) 0.1 g/l to 1.0 g/l of at least one compound which is or which produces a chlorinated aromatic aldehyde of the formula , where n is 1 or 2;
G) 0.25 g/l to 5 g/l of a compound which is or which produces an aliphatic amine; and H) 0.5 g/l to 5 g/l of an anti-oxidant or oxygen acceptor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA299,106A CA1088454A (en) | 1971-12-16 | 1978-03-16 | Bright tin-lead alloy plating |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US20888571A | 1971-12-16 | 1971-12-16 | |
| CA157,164A CA1115654A (en) | 1971-12-16 | 1972-11-22 | Bright tin-lead alloy plating |
| CA299,106A CA1088454A (en) | 1971-12-16 | 1978-03-16 | Bright tin-lead alloy plating |
| US208,885 | 1994-03-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1088454A true CA1088454A (en) | 1980-10-28 |
Family
ID=27162421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA299,106A Expired CA1088454A (en) | 1971-12-16 | 1978-03-16 | Bright tin-lead alloy plating |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1088454A (en) |
-
1978
- 1978-03-16 CA CA299,106A patent/CA1088454A/en not_active Expired
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