US3841982A - Method to improve the brightness of zinc from an alkaline zincate electrodeposition bath - Google Patents
Method to improve the brightness of zinc from an alkaline zincate electrodeposition bath Download PDFInfo
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- US3841982A US3841982A US00333927A US33392773A US3841982A US 3841982 A US3841982 A US 3841982A US 00333927 A US00333927 A US 00333927A US 33392773 A US33392773 A US 33392773A US 3841982 A US3841982 A US 3841982A
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 21
- 239000011701 zinc Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title description 26
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 title description 13
- 238000004070 electrodeposition Methods 0.000 title description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- -1 NITROGEN HETEROCYCLIC COMPOUND Chemical class 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 10
- 238000009713 electroplating Methods 0.000 claims abstract description 7
- 238000005282 brightening Methods 0.000 claims abstract description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 14
- 239000001257 hydrogen Substances 0.000 abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical class [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 6
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- 125000002837 carbocyclic group Chemical group 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 230000003381 solubilizing effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002659 electrodeposit Substances 0.000 description 3
- UHGULLIUJBCTEF-UHFFFAOYSA-N 2-aminobenzothiazole Chemical compound C1=CC=C2SC(N)=NC2=C1 UHGULLIUJBCTEF-UHFFFAOYSA-N 0.000 description 2
- QZTYKRLAEBXDQS-UHFFFAOYSA-N 4-amino-3h-1,3-benzothiazole-2-thione Chemical compound NC1=CC=CC2=C1NC(=S)S2 QZTYKRLAEBXDQS-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 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
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002699 waste material Substances 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
Definitions
- X is S- or A is independently selected from the group consisting n is or 1; when n is 0, nitrogen is doubly bonded to carbon in A; with the proviso that when n is 0, A is R and R are independently selected from the group consisting of hydrogen, alkyl of l to 4 carbon atoms, phenyl; and may be joined to form a six membered aromatic carbocyclic ring and R is hydrogen, alkyl of 1 to 4 carbon atoms or phenyl.
- Zincate plating baths have been used as a means of electrodepositing zinc without employing cyanide ions due to the difficulty in disposing of cyanide ions in waste efiluent.
- Some conventional zinc brighteners produce a bright deposit but only over a narrow current density range.
- the high current density areas generally resulted in a spongy or burnt deposit. It has been found through the combination of brighteners employed in the present case to obtain not only a bright deposit, but also a deposit over a wide current density area.
- a method for obtaining a bright zinc electrodeposit over a wide current density area from a zincate electroplating bath by employing a combination of additives, the first being a polyethyleneimine and the second one being a heterocyclic nitrogen containing compound.
- X is S or I NR,
- A is independently selected from the group consisting n is 0 or 1; when n is 0, nitrogen is doubly bonded to carbon in A; with the proviso that when n is 0, A is R and R are independently selected from the group consisting of hydrogen, alkyl of 1 to 4 carbon atoms, phenyl; and may be joined to form a six membered aromatic carbocyclic ring and R is hydrogen, alkyl of 1 to 4 carbon atoms or phenyl.
- Zincate plating baths are those which generally contain zinc oxide and caustic, such as sodium hydroxide.
- the amount of sodium hydroxide that may be employed ranges from 50 to 250 grams/liter, preferably from about to about 200 grams/liter, while the amount of zinc oxide ranges from 5 to 50 grams/liter, preferably from about 8 to about 30 grams/liter.
- the processing parameters are such that normally atmospheric temperature and pressure is employed, although temperatures up to 55 C. may also be employed, and even more preferably 15 to about 45 C.
- the cathode current density ranges from about 5 to 25 amps per sq. ft. while the anode current density ranges from about 10 to 35 amps per sq. ft. where the zinc deposition can occur with agitation.
- agents may also be present in the bath, such as those described in the above patents.
- suitable agents may be anisaldehyde, glue, polyvinyl alcohol and the glycerol ester of polyvinyl alcohol wherein these alcohols have a molecular weight of 5,000 to 20.- 000.
- Other polymers that may be employed are gelatin, peptone, and the like.
- chelating agents or agents which can form a complex with the metal zinc in the bath may also be employed, such as nitrilotriacetic acid and the various alkali metal salts, such as the sodium salt, ethylenediaminetetraacetic acid, and its water soluble salts, such as sodium, and the like.
- the polyethyleneimine that may be used in the present case has a molecular weight ranging from 1,000 to 400,- 000, preferably 600 to 60,000 where the percentage of primary, secondary and tertiary nitrogen atoms is about 25, 50, and 25% respectively.
- a zincate bath that may be employed in the present invention is as follows:
- the bath pH may be adjusted by adding NaOl-I.
- Some of the nitrogen heterocylic compounds that may be employed in the present invention are as follows.
- water solubilizing group any substituent on the six membered carbocyclic ring which will improve the water solubility of the compound.
- Such groups are hydroxy, alkoxy, such as methoxy or ethoxy and the like, carboxy, amino, and the like.
- R may be other groups which are not detrimental to the electrodeposition of zinc such as chloro, bromo, cyano (CN), nitro and the like.
- EXAMPLE 1 A zincate plating bath was formulated containing the following components and was used to electrodeposit zinc onto a steel substrate at a cathode current density of ASP and a temperature of 75 F.
- the initial bath pH is about 14.
- EXAMPLE 2 Zincate plating bath similar to the above was also prepared but further including 0.1 g./l. of polyvinyl alcohol. A bright zinc deposit was obtained over a broad current density range following the procedure of Example #1.
- Example 3 The procedure of Example #1 was followed, except that the bath also contained 0.1 grams/liter of anisaldehyde with equivalent results being obtained.
- Example 4 The procedure of Example #1 was followed, except that the bath also contained 0.1 grams/liter of anisaldehyde and 0.1 grams/liter of polyvinyl alcohol with equivalent results being obtained.
- An aqueous alkaline electroplating bath comprising inc oxide, alkali metal hydroxide, polyethyleneimine having a molecular weight of from 1,000 to 400,000 and being present in a concentration of 0.2 to grams per liter and a zinc brightening amount of a nitrogen heterocyclic compound of the formula:
- A is independently selected from the group consisting of 11 is 0 or 1; when n is 0, nitrogen is doubly bonded to carbon in A; with the proviso that when n is O, A is R and R are independently selected from the group consisting of hydrogen, alkyl of 1 to 4 carbons, phenyl; and may be joined to form a six membered aromatic carbocyclic ring which may be substituted and R is hydrogen, alkyl of 1 to 4 carbon atoms or phenyl.
- a method of depositing bright zinc from a zincate electroplating bath comprising electrolyzing the bath of Claim 1 for a period of time suflicient to form a bright zinc deposit onto a cathodic surface.
- a cyanide free alkaline zincate electroplating bath comprising zinc oxide, alkali metal hydroxide, polyethyleneimine having a molecular weight of from 1,000 to 400,000 and being present in a concentration from 0.2 to 100 grams per liter and a zinc brightening amount of a nitrogen heterocyclic compound of the formula:
- X is S- or l lR and A is independently selected from the group consisting of n is O or 1; when n is 0, nitrogen is doubly bonded to carbon in A; with the proviso that when n is 0, A is R and R are independently selected from the group consisting of hydrogen, alkyl of 1 to 4 carbon atoms, phenyl; and may be joined to form a six membered aromatic carbocyclic ring which may be substituted and R is hydrogen, alkyl of 1 to 4 carbon atoms or phenyl.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
1. AN AQUEOUS ALKALINE ELECTROPLATING BATH COMPRISING INC OXIDE, ALKALI METAL HYDROXIDE, POLYETHYLENEIMINE HAVING A MOLECULAR WEIGHT OF FROM 1,000 TO 400,000 AND BEING PRESENT IN A CONCENTRATION OF 0.2 TO 100 GRAMS PER LITER AND A ZINC BRIGHTENING AMOUNT OF A NITROGEN HETEROCYCLIC COMPOUND OF THE FORMULA:
X<(-A=N OR -N(-R3)N-C(-R2)=C(-R1)-)
WHEREIN X IS
-S- OR >N-R3, AND
A IS INDEPENDENTLY SELECTED FROM THE GROUP CONSISTING OF
>C-N(-R3)2; >C=S; -C(=S)-R3; >C=N-R3 AND >CH2
N IS O OR 1; WHEN N IS 0, NITROGEN IS DOUBLY BONDED TO CARBON IN A; WITH THE PROVISO THAT WHEN N IS O, A IS
>C-N(-R3)2; >C-S(R)3 OR >CH2
R1 AND R2 ARE INDEPENDENTLY SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, ALKYL OF 1 TO 4 CARBONS, PHENYL; AND MAY BE JOINED TO FORM A SIX MEMBERED AROMATIC CARBOCYCLIC RING WHICH MAY BE SUBSTITUTED AND R3 IS HYDROGEN, ALKYL OF 1 TO 4 CARBON ATOMS OR PHENYL.
X<(-A=N OR -N(-R3)N-C(-R2)=C(-R1)-)
WHEREIN X IS
-S- OR >N-R3, AND
A IS INDEPENDENTLY SELECTED FROM THE GROUP CONSISTING OF
>C-N(-R3)2; >C=S; -C(=S)-R3; >C=N-R3 AND >CH2
N IS O OR 1; WHEN N IS 0, NITROGEN IS DOUBLY BONDED TO CARBON IN A; WITH THE PROVISO THAT WHEN N IS O, A IS
>C-N(-R3)2; >C-S(R)3 OR >CH2
R1 AND R2 ARE INDEPENDENTLY SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, ALKYL OF 1 TO 4 CARBONS, PHENYL; AND MAY BE JOINED TO FORM A SIX MEMBERED AROMATIC CARBOCYCLIC RING WHICH MAY BE SUBSTITUTED AND R3 IS HYDROGEN, ALKYL OF 1 TO 4 CARBON ATOMS OR PHENYL.
Description
United States Patent Office Patented Oct. 15, 1974 3,841,982 METHOD TO IMPROVE THE BRIGHTNESS OF ZINC FROM AN ALKALINE ZINCATE ELEC- US. Cl. 204-55 R 36 Claims ABSTRACT OF THE DISCLOSURE An aqueous alkaline electroplating bath comprising zinc oxide, alkali metal hydroxide, polyethyleneimine and a zinc brightening amount of a nitrogen heterocyclic compound of the formula:
wherein X is S- or A is independently selected from the group consisting n is or 1; when n is 0, nitrogen is doubly bonded to carbon in A; with the proviso that when n is 0, A is R and R are independently selected from the group consisting of hydrogen, alkyl of l to 4 carbon atoms, phenyl; and may be joined to form a six membered aromatic carbocyclic ring and R is hydrogen, alkyl of 1 to 4 carbon atoms or phenyl.
CROSS REFERENCE TO RELATED CASES This case is a continuation-in-part of US. Ser. No. 244,938, filed Apr. 17, 1972, now abandoned.
BACKGROUND OF THE INVENTION Zincate plating baths have been used as a means of electrodepositing zinc without employing cyanide ions due to the difficulty in disposing of cyanide ions in waste efiluent. Previously, it had been difficult to electrodeposit a bright zinc deposit from a zincate bath over a wide current density area. Some conventional zinc brighteners produce a bright deposit but only over a narrow current density range. The high current density areas generally resulted in a spongy or burnt deposit. It has been found through the combination of brighteners employed in the present case to obtain not only a bright deposit, but also a deposit over a wide current density area.
It has also been found that with conventional brigheners relative large amounts are required to obtain brightness while with the components of the present invention relatively less amounts are needed to obtain a bright deposit.
Some zinc brighteners have been described in US. 3,296,105; US. 3,317,412; US. 3,393,135; US. 3,472,743 and German 1,232,800.
SUMMARY OF THE INVENTION A method is described for obtaining a bright zinc electrodeposit over a wide current density area from a zincate electroplating bath by employing a combination of additives, the first being a polyethyleneimine and the second one being a heterocyclic nitrogen containing compound.
DESCRIPTION OF PREFERRED EMBODIMENTS A method is described for obtaining a bright zinc deposit from an alkaline bathpreferably a cyanide free alkaline zincate bath wherein the bath contains polyethyleneimine and a brightening amount of a nitrogen heterocyclic compound of the structure:
wherein X is S or I NR,; and
A is independently selected from the group consisting n is 0 or 1; when n is 0, nitrogen is doubly bonded to carbon in A; with the proviso that when n is 0, A is R and R are independently selected from the group consisting of hydrogen, alkyl of 1 to 4 carbon atoms, phenyl; and may be joined to form a six membered aromatic carbocyclic ring and R is hydrogen, alkyl of 1 to 4 carbon atoms or phenyl.
Zincate plating baths are those which generally contain zinc oxide and caustic, such as sodium hydroxide. The amount of sodium hydroxide that may be employed ranges from 50 to 250 grams/liter, preferably from about to about 200 grams/liter, while the amount of zinc oxide ranges from 5 to 50 grams/liter, preferably from about 8 to about 30 grams/liter.
The processing parameters are such that normally atmospheric temperature and pressure is employed, although temperatures up to 55 C. may also be employed, and even more preferably 15 to about 45 C. The cathode current density ranges from about 5 to 25 amps per sq. ft. while the anode current density ranges from about 10 to 35 amps per sq. ft. where the zinc deposition can occur with agitation.
Other agents may also be present in the bath, such as those described in the above patents. Examples of such suitable agents may be anisaldehyde, glue, polyvinyl alcohol and the glycerol ester of polyvinyl alcohol wherein these alcohols have a molecular weight of 5,000 to 20.- 000. Other polymers that may be employed are gelatin, peptone, and the like. In addition, chelating agents or agents which can form a complex with the metal zinc in the bath may also be employed, such as nitrilotriacetic acid and the various alkali metal salts, such as the sodium salt, ethylenediaminetetraacetic acid, and its water soluble salts, such as sodium, and the like.
The polyethyleneimine that may be used in the present case has a molecular weight ranging from 1,000 to 400,- 000, preferably 600 to 60,000 where the percentage of primary, secondary and tertiary nitrogen atoms is about 25, 50, and 25% respectively.
A zincate bath that may be employed in the present invention is as follows:
The bath pH may be adjusted by adding NaOl-I. Some of the nitrogen heterocylic compounds that may be employed in the present invention are as follows.
TNH; s H N N n N s T511 K TNH: H N
' l uHs s =s /N HZN j Tsn s s -sH -s-on3 n l HzN H l CH3 CH3 \FNH mom HzN If 1? H H n N N Ts-orn H H-sn nm N N E N S S H S H 71 1 HzN -N N m B4 --N wherein R is a water solubilizing group.
By water solubilizing group is meant any substituent on the six membered carbocyclic ring which will improve the water solubility of the compound. Such groups are hydroxy, alkoxy, such as methoxy or ethoxy and the like, carboxy, amino, and the like. In addition, R may be other groups which are not detrimental to the electrodeposition of zinc such as chloro, bromo, cyano (CN), nitro and the like.
EXAMPLE 1 A zincate plating bath was formulated containing the following components and was used to electrodeposit zinc onto a steel substrate at a cathode current density of ASP and a temperature of 75 F.
Sodium hydroxide 140 grams/liter; zinc oxide -12 grams/liter; polyethyleneimine (1,200 molecular weight) 2 grams/liter, nitrilotriacetic acid trisodium salt 1 gram/ liter; and Z-amino-benzothiazole 0.03 grams/liter.
After plating rod like structures in a typical barrel plating apparatus for 25-30 minutes a uniform bright zinc deposit of 0.2-0.3 mil thickness was obtained. The initial bath pH is about 14.
EXAMPLE 2 Zincate plating bath similar to the above was also prepared but further including 0.1 g./l. of polyvinyl alcohol. A bright zinc deposit was obtained over a broad current density range following the procedure of Example #1.
EXAMPLE 3 The procedure of Example #1 was followed, except that the bath also contained 0.1 grams/liter of anisaldehyde with equivalent results being obtained.
EXAMPLE 4 The procedure of Example #1 was followed, except that the bath also contained 0.1 grams/liter of anisaldehyde and 0.1 grams/liter of polyvinyl alcohol with equivalent results being obtained.
EXAMPLE 5 A cyanide free alkaline zincate bath was formulated as follows:
G./l. NaOH 140 ZnO 15 Z-mercaptobenzothiazole 0.03 polyethyleneimine (1200 molecular wt.) 3
Following the procedure of Example #1 equivalently good results were obtained.
What is claimed is:
1. An aqueous alkaline electroplating bath comprising inc oxide, alkali metal hydroxide, polyethyleneimine having a molecular weight of from 1,000 to 400,000 and being present in a concentration of 0.2 to grams per liter and a zinc brightening amount of a nitrogen heterocyclic compound of the formula:
i 3)n wherein X is -S- or I!\IR3; and
A is independently selected from the group consisting of 11 is 0 or 1; when n is 0, nitrogen is doubly bonded to carbon in A; with the proviso that when n is O, A is R and R are independently selected from the group consisting of hydrogen, alkyl of 1 to 4 carbons, phenyl; and may be joined to form a six membered aromatic carbocyclic ring which may be substituted and R is hydrogen, alkyl of 1 to 4 carbon atoms or phenyl.
2. The bath of Claim 1 wherein R and R are joined to form a six membered aromatic carbocyclic ring.
3. The bath of Claim 2 wherein the carbocyclic ring is substituted by an amino group.
4. The bath of Claim 2 wherein the carbocyclic ring is substituted by a bath solubilizing group.
5. The bath of Claim 1 wherein the nitrogen heterocyclic compound is present in an amount ranging from about 0.005 to about 5 grams/ liter.
6. The bath of Claim 1 wherein X is S.
7. The bath of Claim 1 wherein X is -I IRa.
'8. The bath of Claim 1 wherein A is 9. The bath of Claim 1 wherein A is 10. The bath of Claim 1 wherein A is 11. The bath of Claim 1 wherein A is 12. The bath of Claim 1 wherein n is 0.
13. The bath of Claim 1 wherein R is hydrogen.
1-4. The bath of Claim 1 wherein R and R are hydrogen.
15. The bath of Claim 1 wherein the nitrogen heterocyclic compound is aminobenzothiazole.
16. The bath of Claim 1 wherein the nitrogen heterocyclic compound is an amino-2-mercaptobenzothiazole.
17. The bath of Claim 1 wherein the nitrogen heterocyclic compound is 2-imino, 3-a1kyl benzothiazole.
18. A method of depositing bright zinc from a zincate electroplating bath comprising electrolyzing the bath of Claim 1 for a period of time suflicient to form a bright zinc deposit onto a cathodic surface.
19. The method of Claim 18 wherein R and R are joined to form a six membered aromatic carbocyclic ring.
20. The method of Claim 19 wherein the carbocyclic ring is substituted by an amino group.
21. The method of Claim 19 wherein the carbocyclic ring is substituted by a bath solubilizing group.
22. The method of Claim 18 wherein the nitrogen heterocyclic compound is present in an amount ranging from about 0.005 to about 5 grams/ liter.
23. The method of Claim 18 wherein X is S.
24. The method of Claim 18 wherein X is ALB.
'25. The method of Claim 18 wherein A is J a)z- 26. The method of Claim 18 wherein A is 27. The method of Claim 18 wherein A is -.iJ-s (R3). 28. The method of Claim 18 wherein A is 29. The method of Claim 18 wherein n is 0.
30. The method of Claim 18 wherein R is hydrogen.
31. The method of Claim 18 wherein R and R are hydrogen.
32. The method of Claim 18 wherein the nitrogen heterocyclic compound is aminobenzothiazole.
33. The method of Claim 18 wherein the nitrogen heterocyclic compound is an amino2-mercaptobenzothiazole.
34. The method of Claim 18 wherein the nitrogen heterocyclic compound is 2-imino, 3'alkyl benzothiazole.
35. The method of Claim 18 wherein the cathodic surface is metallic.
36. A cyanide free alkaline zincate electroplating bath comprising zinc oxide, alkali metal hydroxide, polyethyleneimine having a molecular weight of from 1,000 to 400,000 and being present in a concentration from 0.2 to 100 grams per liter and a zinc brightening amount of a nitrogen heterocyclic compound of the formula:
wherein X is S- or l lR and A is independently selected from the group consisting of n is O or 1; when n is 0, nitrogen is doubly bonded to carbon in A; with the proviso that when n is 0, A is R and R are independently selected from the group consisting of hydrogen, alkyl of 1 to 4 carbon atoms, phenyl; and may be joined to form a six membered aromatic carbocyclic ring which may be substituted and R is hydrogen, alkyl of 1 to 4 carbon atoms or phenyl.
References Cited UNITED STATES PATENTS 2,853,444 9/1958 Pye et a1 204- R X 2,892,760 6/1959 Giindel et a1 204-44 3,267,010 8/ 1966 Creutz et a1 20452 R 3,672,971 6/1972 Senge et al. 204-55 R 3,723,263 3/ 1973 Rosenberg 204-55 R FOREIGN PATENTS 1,243,488 6/1967 Germany 204-55 R 1,263,445 3/ 196 8 Germany 20455 R a GERALD L. KAPLAN, Primary Examiner
Claims (1)
1. AN AQUEOUS ALKALINE ELECTROPLATING BATH COMPRISING INC OXIDE, ALKALI METAL HYDROXIDE, POLYETHYLENEIMINE HAVING A MOLECULAR WEIGHT OF FROM 1,000 TO 400,000 AND BEING PRESENT IN A CONCENTRATION OF 0.2 TO 100 GRAMS PER LITER AND A ZINC BRIGHTENING AMOUNT OF A NITROGEN HETEROCYCLIC COMPOUND OF THE FORMULA:
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US00333927A US3841982A (en) | 1972-04-17 | 1973-02-20 | Method to improve the brightness of zinc from an alkaline zincate electrodeposition bath |
| NL7304246A NL7304246A (en) | 1972-04-17 | 1973-03-27 | |
| FR7311420A FR2180708B1 (en) | 1972-04-17 | 1973-03-29 | |
| DE2318984A DE2318984C2 (en) | 1972-04-17 | 1973-04-14 | Aqueous alkaline bath and process for the deposition of shiny zinc coatings |
| CA169,009A CA1009178A (en) | 1972-04-17 | 1973-04-16 | Method to improve the brightness of zinc from an alkaline zincate electrodeposition bath |
| GB1826373A GB1387529A (en) | 1972-04-17 | 1973-04-16 | Method to improve the brightness of zinc from an alkaline zincate electrode-position bath |
| IT49467/73A IT983031B (en) | 1972-04-17 | 1973-04-16 | METHOD FOR STORING BRIGHT ZINC ELECTROLYTES AND BATHROOMS USED IN IT |
| AR247599A AR197894A1 (en) | 1972-04-17 | 1973-04-17 | AQUEOUS ALKALINE ELECTROPLATE BATH |
| JP48042757A JPS4917324A (en) | 1972-04-17 | 1973-04-17 |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US24493872A | 1972-04-17 | 1972-04-17 | |
| US00333927A US3841982A (en) | 1972-04-17 | 1973-02-20 | Method to improve the brightness of zinc from an alkaline zincate electrodeposition bath |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3841982A true US3841982A (en) | 1974-10-15 |
Family
ID=26936902
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00333927A Expired - Lifetime US3841982A (en) | 1972-04-17 | 1973-02-20 | Method to improve the brightness of zinc from an alkaline zincate electrodeposition bath |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US3841982A (en) |
| JP (1) | JPS4917324A (en) |
| AR (1) | AR197894A1 (en) |
| CA (1) | CA1009178A (en) |
| DE (1) | DE2318984C2 (en) |
| FR (1) | FR2180708B1 (en) |
| GB (1) | GB1387529A (en) |
| IT (1) | IT983031B (en) |
| NL (1) | NL7304246A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5084542A (en) * | 1990-05-31 | 1992-01-28 | E. I. Du Pont De Nemours And Company | Epoxy/isocyanate crosslinked coatings containing 1,3-disubstituted imidazole-2-thione catalysts |
| US6656606B1 (en) | 2000-08-17 | 2003-12-02 | The Westaim Corporation | Electroplated aluminum parts and process of production |
| WO2013056996A1 (en) * | 2011-10-19 | 2013-04-25 | Basf Se | Formulations, use thereof as or to produce dishwashing detergents, and production thereof |
| CN103842559A (en) * | 2011-10-04 | 2014-06-04 | 杰富意钢铁株式会社 | Production method for zinc-electroplated steel sheets |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5332771B2 (en) * | 1973-12-10 | 1978-09-09 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1480997A (en) * | 1966-05-25 | 1967-05-12 | Schering Ag | Alkaline zincic brightening bath, free of cyanides |
| DE1935821B2 (en) * | 1969-07-15 | 1972-03-16 | Riedel & Co, 4800 Bielefeld | PROCESS FOR THE PRODUCTION OF A GLOSS ADDITIVE FOR ALKALINE CYANIDE-FREE ZINC BATHS |
-
1973
- 1973-02-20 US US00333927A patent/US3841982A/en not_active Expired - Lifetime
- 1973-03-27 NL NL7304246A patent/NL7304246A/xx unknown
- 1973-03-29 FR FR7311420A patent/FR2180708B1/fr not_active Expired
- 1973-04-14 DE DE2318984A patent/DE2318984C2/en not_active Expired
- 1973-04-16 GB GB1826373A patent/GB1387529A/en not_active Expired
- 1973-04-16 CA CA169,009A patent/CA1009178A/en not_active Expired
- 1973-04-16 IT IT49467/73A patent/IT983031B/en active
- 1973-04-17 JP JP48042757A patent/JPS4917324A/ja active Pending
- 1973-04-17 AR AR247599A patent/AR197894A1/en active
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5084542A (en) * | 1990-05-31 | 1992-01-28 | E. I. Du Pont De Nemours And Company | Epoxy/isocyanate crosslinked coatings containing 1,3-disubstituted imidazole-2-thione catalysts |
| US6656606B1 (en) | 2000-08-17 | 2003-12-02 | The Westaim Corporation | Electroplated aluminum parts and process of production |
| US6692630B2 (en) | 2000-08-17 | 2004-02-17 | The Westaim Corporation | Electroplated aluminum parts and process for production |
| CN103842559A (en) * | 2011-10-04 | 2014-06-04 | 杰富意钢铁株式会社 | Production method for zinc-electroplated steel sheets |
| CN103842559B (en) * | 2011-10-04 | 2016-11-09 | 杰富意钢铁株式会社 | Manufacturing method of electrogalvanized steel sheet |
| WO2013056996A1 (en) * | 2011-10-19 | 2013-04-25 | Basf Se | Formulations, use thereof as or to produce dishwashing detergents, and production thereof |
| US8574374B2 (en) | 2011-10-19 | 2013-11-05 | Basf Se | Formulations, their use as or for producing dishwashing compositions and their preparation |
| KR20140088566A (en) * | 2011-10-19 | 2014-07-10 | 바스프 에스이 | Formulations, use thereof as or to produce dishwashing detergents, and production thereof |
| RU2607085C2 (en) * | 2011-10-19 | 2017-01-10 | Басф Се | Compositions, use thereof as or for preparing agents for dish washing and preparation thereof |
| KR101884618B1 (en) | 2011-10-19 | 2018-08-02 | 바스프 에스이 | Formulations, use thereof as or to produce dishwashing detergents, and production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2180708B1 (en) | 1977-04-29 |
| GB1387529A (en) | 1975-03-19 |
| DE2318984C2 (en) | 1982-11-11 |
| CA1009178A (en) | 1977-04-26 |
| AR197894A1 (en) | 1974-05-15 |
| NL7304246A (en) | 1973-10-19 |
| IT983031B (en) | 1974-10-31 |
| DE2318984A1 (en) | 1973-11-08 |
| JPS4917324A (en) | 1974-02-15 |
| FR2180708A1 (en) | 1973-11-30 |
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Legal Events
| Date | Code | Title | Description |
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| AS | Assignment |
Owner name: OXY METAL INDUSTRIES CORPORATION Free format text: CHANGE OF NAME;ASSIGNOR:OXY METAL FINISHING CORPORATION;REEL/FRAME:003967/0084 Effective date: 19741220 |
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| AS | Assignment |
Owner name: HOOKER CHEMICALS & PLASTICS CORP. Free format text: MERGER;ASSIGNOR:OXY METAL INDUSTRIES CORPORATION;REEL/FRAME:004075/0885 Effective date: 19801222 |
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Owner name: OCCIDENTAL CHEMICAL CORPORATION Free format text: CHANGE OF NAME;ASSIGNOR:HOOKER CHEMICAS & PLASTICS CORP.;REEL/FRAME:004126/0054 Effective date: 19820330 |
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Owner name: OMI INTERNATIONAL CORPORATION, 21441 HOOVER ROAD, Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:OCCIDENTAL CHEMICAL CORPORATION;REEL/FRAME:004190/0827 Effective date: 19830915 |
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| AS | Assignment |
Owner name: MANUFACTURERS HANOVER TRUST COMPANY, A CORP OF NY Free format text: SECURITY INTEREST;ASSIGNOR:INTERNATIONAL CORPORATION, A CORP OF DE;REEL/FRAME:004201/0733 Effective date: 19830930 |