US2680712A - Alkaline zinc plating baths - Google Patents
Alkaline zinc plating baths Download PDFInfo
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- US2680712A US2680712A US240780A US24078051A US2680712A US 2680712 A US2680712 A US 2680712A US 240780 A US240780 A US 240780A US 24078051 A US24078051 A US 24078051A US 2680712 A US2680712 A US 2680712A
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- Prior art keywords
- formaldehyde
- liter
- zinc
- sodium bisulphite
- zinc plating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 238000007747 plating Methods 0.000 title claims description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title description 12
- 239000011701 zinc Substances 0.000 title description 12
- 229910052725 zinc Inorganic materials 0.000 title description 12
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000005282 brightening Methods 0.000 claims description 7
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 0.000 claims description 7
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical class [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 22
- 239000007795 chemical reaction product Substances 0.000 description 12
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 10
- 238000007792 addition Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 229920000768 polyamine Polymers 0.000 description 7
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 6
- 239000002659 electrodeposit Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XUIVKWAWICCWIQ-UHFFFAOYSA-M sodium;formaldehyde;hydrogen sulfite Chemical compound [Na+].O=C.OS([O-])=O XUIVKWAWICCWIQ-UHFFFAOYSA-M 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N 2-propanol Substances CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000283986 Lepus Species 0.000 description 1
- 241000357437 Mola Species 0.000 description 1
- 241001077660 Molo Species 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- JVKAWJASTRPFQY-UHFFFAOYSA-N n-(2-aminoethyl)hydroxylamine Chemical group NCCNO JVKAWJASTRPFQY-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940083608 sodium hydroxide Drugs 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000004296 sodium metabisulphite Substances 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
- C25D3/24—Electroplating: Baths therefor from solutions of zinc from cyanide baths
Definitions
- This invention relates to ⁇ itl-re -eleotrodepo'sition of lzinc from alkali cyanide baths, and v-rnore par#- ticularly to a new type ci addition agent iersuch baths
- bath-'solubleft'son- 'densation polymers prepared from :an aliphatic alkylenepolyarnine (such as ethylenediaininefprepylenediamine and higher member-s of lthis l'series; diethylenetriamina triethyl'enetetramine, ⁇ tetraethylenepentamine and so on; dipropylene- Vtrianiine; N-hydroxyethyl /ethylenediamine LNNJ- ldihydroxyethyi yethylenediaminey Lediamino'- prepa-no1) asonereactant, and furfural, turtura'l sodium bisulphite, formaldehyde, and/or
- reactionprodiiot wasmeatedto '110 C. Then, after cooling .to -roo'x'n temperature, 21'6 g. (2166 inls.) "formaldehyde '(37%) were added andthe reaction product heated 'for l0 minutes .in a Water 'b'a'th to 90 C. The n'al .product was diluted ltO l '.liter. A cyanide Zinc -plating bath containing per .liter l0 to 25 nil.
- Example 1 The reaction product was Vthen'heated for a short .time to C., cooled, and 12156 rg. (125 -molsD lformaldehyde (37%) Werel added under stirring :and the product :again shortly heated to 85 C.
- Example 3 .26 g. 6.0.25 mol.) ,hydroxyethy iethylenedia- :minewand 1g.y (0:5 rmol.) furural-sodium bisulphite (powdered) were mixed. Strong heat levolution occurred-anda dark -broW-n zfresin .resulted which wa-sidissolyed iin water to make .250 ml. 24 -ml.:of this isolation; when-added to f1 liter zinc ybath, .fgave :brilliant electrodcpo'sits 'in fthe high 'current dens-ity range.
- Example 4 To 36.6 g. (0;2'5nroli) ⁇ triethylen'etetranrimewere added 'under :stirring i2() sg. A(025 incl.) formaldefhyde and :then 100 vvag. (0.15 :molo cnrfuralesodiinn 'bisulphite 'The :reaction product .was heated to around C., where-.gasevoluticn volume .increase occurred. 'Therresulting :dark acolored resin was dissolved -to 250 -rl. Only 5I xml. idf this .so'lu-tioli, ⁇ when added fto'l 'liter .zinc .-b'atlli, caused the ormati'nofbrilliant but 1pitted electrodeposits.
- aqueous formaldehyde (37%) (if indicated in the table) was slowly added under stirring and cooling. Then a solution of 1 mol. furfural and 1 mol. sodium bisulphite (0.5 mol. sodium metabisulphite) in 200 ml. of water, aged for at least half an hour, was added under stirring and, if required, cooling. Then the nal formaldehyde (if indicated in the table) was added and the reaction product heated for about 15 minutes at slight boiling. When larger quantities were prepared, external heating was not necessary as the reactions are strongly exothermic.
- reaction products were diluted to 1 liter, and to 15 ml. or" these solutions, equivalent to about 2.5 to 9.5 grams of reaction products, were added to 1 liter plating bath. They all exert a strong brightening action over a wide current density range (approximately 10 to 50 amps./sq. it). Brighteners #10 and #14 seemed to be the best suitable for still zinc plating. .Brighteners and #19 were less good than the average.
- this mixed aldehyde-bisulphite solution was added to the polyamine-formaldehyde reaction product with stirring and the nal mixture heated to boiling, where it was kept for about 10 minutes.
- reaction product was finally diluted to 5 liters.
- this brightener stock solution equivalent to about 6.5 g./liter of reaction product to a standard zinc bath
- uniform bright and blister-free zinc electrodeposits were obtained over a wide current density range (20 to 70 and more amps/sq. it.) and the bath could be easily maintained in good performance by periodic additions of brightener.
- An aqueous alkaline cyanide zinc plating bath containing, in amounts of substantially 2.5 to 9.5 g./liter, as a brightening agent a condensation polymer of an aliphatic alkylenepolyamine with furfural-sodium bisulphite and formaldehyde, 0 to 50% of the latter in the form of its sodium bisulphite compounds.
- An aqueous alkaline cyanide zinc plating bath containing, in amounts of substantially 6-.5 g./liter, as a brightening agent a condensation of triethylenetetramme, N-hydroxyethyl ethylenediamine, formaldehyde, ururalsodium bisulphite and formaldehyde-sodium bisulphite.
- An aqueous alkaline cyanide zinc plating bath containing, in amounts of substantially 6.5 g./liter, as a brightening agent a condensation polymer of 1 mol. triethylenetetramine, 1 mol. N-hydroxyethyl ethylenediamine, 2 mols. formaldehyde, 4 niels. furfural-sodium bisulphite and 2 mois. formaldehyde-sodium bisulphite.
Description
Patented June 8, 1954 U NITED S PATE-N T OFFICE ZINC PLTING BATHS MyronB. Diggin, .Matawan, land Otto Kardos,
Keypor't, N. J., .assignors to Hanson-Van Winkle-Munning Company, Matawan,N. 'J a' coi'- poration of 'New Jersey No Drawing.' 4Application August 37, :1951, Serialy No. 240,280
3 Claims. l
This invention relates to `itl-re -eleotrodepo'sition of lzinc from alkali cyanide baths, and v-rnore par#- ticularly to a new type ci addition agent iersuch baths We have found that certain bath-'solubleft'son- 'densation polymers prepared from :an aliphatic alkylenepolyarnine (such as ethylenediaininefprepylenediamine and higher member-s of lthis l'series; diethylenetriamina triethyl'enetetramine, `tetraethylenepentamine and so on; dipropylene- Vtrianiine; N-hydroxyethyl /ethylenediamine LNNJ- ldihydroxyethyi yethylenediaminey Lediamino'- prepa-no1) asonereactant, and furfural, turtura'l sodium bisulphite, formaldehyde, and/or iormaldehyde sodium bisulphite'as the other reactants exert a strong brightening-action on Athe electrodeposits, vwhen added vin relatively `'small amounts to a cyanide zinc rplating bath,
The vcomposition of 4the yaqueous plating solutions used in our experiments was:
y(ra/gal. Zinc cyanide .f8 :to 12 Sodium cyanide A to 9 :Sodiumhydroxide -8 to 12 Before use, 'the solutions Weretreatedwith'z'inc dust to eliminate metallic impurities. Gur eirperiments were performed at room temperature.
The usual bright dips-can-beappli'edto the zinc plates obtained, but `in many 'cases this is not necessary.
'l `mol. diethylenetriamine reacted With 1 mol. furfural .gave products of ylittle brightening elln ciency; with Zmols. furfural, products of higher We vobtained considerably better addition.
agents by .using the furfural-sodium bisulphite addition'cornpound instead of furiural 'itself Also partial or entire lsubstitution of N-hydroxyethyl ethylene'diamine, NN'-dihydroxyethyl ethylenediamine or 1,3-diarnino-2 propanol for diethylenetriainine (or triethylenetetramine) gavefimproved `results.
Example 1 To 103.2 g. (1 mol.) diethylenetriamine, 96.1 g. (1 mol.) furiural were added under stirring, and
2 the reactionprodiiot wasmeatedto '110 C. Then, after cooling .to -roo'x'n temperature, 21'6 g. (2166 inls.) "formaldehyde '(37%) were added andthe reaction product heated 'for l0 minutes .in a Water 'b'a'th to 90 C. The n'al .product was diluted ltO l '.liter. A cyanide Zinc -plating bath containing per .liter l0 to 25 nil. o'i this b'rightener .solution gave ilarg'e Iarle'as o'f brilliandy 'in the Hull dell, ythe optimum df 'brilliancy occurring at higher current densities with increasing brightener concentration.
Lower and higher amounts of formaldehyde than those indicated above gave less potent brigh'ten'ers. "Tco .lon-g. and :too lhigh heating of these condensation :products iincreased Atheir brightenin'g .efficiency ibut provoked :blistering of the electrodeposits over a steel hase.
Example The reaction product was Vthen'heated for a short .time to C., cooled, and 12156 rg. (125 -molsD lformaldehyde (37%) Werel added under stirring :and the product :again shortly heated to 85 C.
.This dark brown lsyr'upy reactionproduct wla's 'diluted with Water to make 1 liter; 20 to $0 .m1, .oflthis solution, When addedrto 1 liter rzinc bath, .produced bright zinc deposits over a Wide current vdensity Irange.
Example 3 .26 g. 6.0.25 mol.) ,hydroxyethy iethylenedia- :minewand 1g.y (0:5 rmol.) furural-sodium bisulphite (powdered) were mixed. Strong heat levolution occurred-anda dark -broW-n zfresin .resulted which wa-sidissolyed iin water to make .250 ml. 24 -ml.:of this isolation; when-added to f1 liter zinc ybath, .fgave :brilliant electrodcpo'sits 'in fthe high 'current dens-ity range.
Example 4 To 36.6 g. (0;2'5nroli) `triethylen'etetranrimewere added 'under :stirring i2() sg. A(025 incl.) formaldefhyde and :then 100 vvag. (0.15 :molo cnrfuralesodiinn 'bisulphite 'The :reaction product .was heated to around C., where-.gasevoluticn volume .increase occurred. 'Therresulting :dark acolored resin was dissolved -to 250 -rl. Only 5I xml. idf this .so'lu-tioli,` when added fto'l 'liter .zinc .-b'atlli, caused the ormati'nofbrilliant but 1pitted electrodeposits.
When the reaction product was heated only to '70 C. and dissolved to 250 ml., larger brightener additions Were required (14 mL/Iiter), but
pit-free bright zinc deposits were obtained over a Wide current density range (approximately 20 to 50 amps/sqft.) in the Hull cell.
Examples 5 to 19 A great number of reaction products of triethylenetetramine, alone or mixed with N-hydroxyethyl ethylenediamine (or sometimes with NN-dihydroxyethyl ethylenediamine), with furfural-sodium bisulphite (concentrated aqueous solution) and formaldehyde were prepared. The addition agents prepared from triethylenetetramine gave somewhat better results than those prepared from diethylenetriamine or tetraethylenepentamine.
The following table gives the concentration of the reactants in mols. The procedure was as follows:
To the polyamine or the polyamine mixture, aqueous formaldehyde (37%) (if indicated in the table) was slowly added under stirring and cooling. Then a solution of 1 mol. furfural and 1 mol. sodium bisulphite (0.5 mol. sodium metabisulphite) in 200 ml. of water, aged for at least half an hour, was added under stirring and, if required, cooling. Then the nal formaldehyde (if indicated in the table) was added and the reaction product heated for about 15 minutes at slight boiling. When larger quantities were prepared, external heating was not necessary as the reactions are strongly exothermic.
1st or 2nd N-Hy- 2nd or 3rd E Triethyldroxytlilx Resgon Reaction xample enetetraethyl eth- Formal. FmfuraL Step.
mme yl'lga' dehyde sodium lolrlml' bisuiphite e y e l. (l 1. (l 2.0 1.0 2. 2.0 l. 0 0. 5 1. 0 2. 0 1. 0 0. 5 2.0 2. 0 1.() 1. 0 2.0 1. 0 0. 5 0. 5 1.0 2.0 0. 5 0.5 0. 5 2. 1. 0 0. 5 O. 5 1.0 2.0 l. 0 (l. 5 0. 5 2. 0 0. 5 0. 5 2. 0 1. 0 0. 5 0. 5 2. U 2.0 0. 5 0. 5 l. 0 l. 33 0. 5 0. 5 l. 0 2. 66 0. 5 (l. 5 0. 5 2. 0 O. 25 0.75 1. 0 2. 0
Above reaction products were diluted to 1 liter, and to 15 ml. or" these solutions, equivalent to about 2.5 to 9.5 grams of reaction products, were added to 1 liter plating bath. They all exert a strong brightening action over a wide current density range (approximately 10 to 50 amps./sq. it). Brighteners #10 and #14 seemed to be the best suitable for still zinc plating. .Brighteners and #19 were less good than the average.
These addition agents were very stable in the aqueous stock solution, but less so in the zinc plating bath, to which they have to be added periodically in order to maintain a high degree of brightness of the electrodeposits.
However, all these addition agents of high brightening power have a tendency to produce blistering of the zinc deposit on steel in the low current density range, if the plating time is about 10 to 15 minutes and the plated parts are soaked in almost boiling water. This blistering tendency is especially pronounced in older baths replenished several times with brightener.
We have discovered the surprising fact that adpolymer dition of very small amounts of the higher molecular polyamines suppresses this tendency to blistering. This anti-blistering action increases with increasing molecular weight of the polyamine. Thus a polyethylene polyamine of an average molecular weight of 65D is more effective than tetraethylenepentamine, and the latter more than triethylenetetramine. The very small amount of 0.1 g./liter of said polyethylene polyamine was sumcient to suppress this blistering tendency. However, an excess of these higher polyamines reduces the brightness of the electrodeposits considerably.
Complete elimination of this blistering tendency was also obtained by introducing formaldehyde-sodium bisulphite in the brightener molecule.
Eample 20 To a mixture of triethylenetetramine 366 g. (2.5 mols.) and N-hydroxyethyl ethylenediamine 260 g. (2.5 mols.) were slowly added, with stirring, formaldehyde (37%) 375 m1. (approximately 5 mols.). Then an aldehyde-sodium bisulphite solution was prepared as follows: To 2300 ml. of Water were added 375 ml. formaldehyde (5 mols.) then, with stirring, 1500 g. of sodium inetabisulphite (corresponding to 15 mois. sodium bisulphite) and linally 961 g. furfural (10 mola).
After about half an hour of aging, this mixed aldehyde-bisulphite solution was added to the polyamine-formaldehyde reaction product with stirring and the nal mixture heated to boiling, where it was kept for about 10 minutes.
The reaction product was finally diluted to 5 liters. On addition of 10 nil/liter of this brightener stock solution, equivalent to about 6.5 g./liter of reaction product to a standard zinc bath, uniform bright and blister-free zinc electrodeposits were obtained over a wide current density range (20 to 70 and more amps/sq. it.) and the bath could be easily maintained in good performance by periodic additions of brightener.
We claim:
1. An aqueous alkaline cyanide zinc plating bath containing, in amounts of substantially 2.5 to 9.5 g./liter, as a brightening agent a condensation polymer of an aliphatic alkylenepolyamine with furfural-sodium bisulphite and formaldehyde, 0 to 50% of the latter in the form of its sodium bisulphite compounds.
2. An aqueous alkaline cyanide zinc plating bath containing, in amounts of substantially 6-.5 g./liter, as a brightening agent a condensation of triethylenetetramme, N-hydroxyethyl ethylenediamine, formaldehyde, ururalsodium bisulphite and formaldehyde-sodium bisulphite.
3. An aqueous alkaline cyanide zinc plating bath containing, in amounts of substantially 6.5 g./liter, as a brightening agent a condensation polymer of 1 mol. triethylenetetramine, 1 mol. N-hydroxyethyl ethylenediamine, 2 mols. formaldehyde, 4 niels. furfural-sodium bisulphite and 2 mois. formaldehyde-sodium bisulphite.
References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,384,395 Harford Sept. 4, 1945 2,495,629 Chester et al. Jan. 24, 1950 2,589,209 Kardos Mar. 18, 1952
Claims (1)
1. AN AQUEOUS AKALINE CYANIDE ZINC PLATING BATH CONTAINING, IN AMOUNTS OF SUBSTANTIALLY 2.5 TO 9.5 G./LITER, AS A BRIGHTENING AGENT A CONDENSATION POLYMER OF AN ALIPHATIC ALKYLENEPOLYAMINE WITH FURFURAL-SODIUM BISULPHITE AND FORMALDEHYDE, 0 TO 50% OF THE LATTER IN THE FORM OF ITS SODIUM BISULPHITE COMPOUNDS.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US240780A US2680712A (en) | 1951-08-07 | 1951-08-07 | Alkaline zinc plating baths |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US240780A US2680712A (en) | 1951-08-07 | 1951-08-07 | Alkaline zinc plating baths |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2680712A true US2680712A (en) | 1954-06-08 |
Family
ID=22907915
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US240780A Expired - Lifetime US2680712A (en) | 1951-08-07 | 1951-08-07 | Alkaline zinc plating baths |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2680712A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2734026A (en) * | 1951-09-12 | 1956-02-07 | Electrodepositton of copper-zinc alloys | |
| US3454475A (en) * | 1965-07-13 | 1969-07-08 | Du Pont | Electroplating bath and process |
| US3472743A (en) * | 1966-12-19 | 1969-10-14 | Du Pont | Zinc plating baths and additives therefor |
| US3655534A (en) * | 1970-02-24 | 1972-04-11 | Enthone | Alkaline bright zinc electroplating |
| US3883405A (en) * | 1972-07-10 | 1975-05-13 | Gerald H Grossblatt | Zinc plating baths |
| US3915815A (en) * | 1972-11-15 | 1975-10-28 | Reinhard Koch | Alkaline zinc electroplating bath |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2384300A (en) * | 1937-07-03 | 1945-09-04 | Little Inc A | Electrolytic deposition of zinc |
| US2495629A (en) * | 1944-06-02 | 1950-01-24 | Poor & Co | Zinc electroplating |
| US2589209A (en) * | 1948-09-04 | 1952-03-18 | Hanson Van Winkle Munning Co | Dithiocarbamate-aldehyde condensation polymers |
-
1951
- 1951-08-07 US US240780A patent/US2680712A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2384300A (en) * | 1937-07-03 | 1945-09-04 | Little Inc A | Electrolytic deposition of zinc |
| US2495629A (en) * | 1944-06-02 | 1950-01-24 | Poor & Co | Zinc electroplating |
| US2589209A (en) * | 1948-09-04 | 1952-03-18 | Hanson Van Winkle Munning Co | Dithiocarbamate-aldehyde condensation polymers |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2734026A (en) * | 1951-09-12 | 1956-02-07 | Electrodepositton of copper-zinc alloys | |
| US3454475A (en) * | 1965-07-13 | 1969-07-08 | Du Pont | Electroplating bath and process |
| US3472743A (en) * | 1966-12-19 | 1969-10-14 | Du Pont | Zinc plating baths and additives therefor |
| US3655534A (en) * | 1970-02-24 | 1972-04-11 | Enthone | Alkaline bright zinc electroplating |
| US3883405A (en) * | 1972-07-10 | 1975-05-13 | Gerald H Grossblatt | Zinc plating baths |
| US3915815A (en) * | 1972-11-15 | 1975-10-28 | Reinhard Koch | Alkaline zinc electroplating bath |
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