GB2231063A - Electroless plating composition containing saccharin - Google Patents
Electroless plating composition containing saccharin Download PDFInfo
- Publication number
- GB2231063A GB2231063A GB8904435A GB8904435A GB2231063A GB 2231063 A GB2231063 A GB 2231063A GB 8904435 A GB8904435 A GB 8904435A GB 8904435 A GB8904435 A GB 8904435A GB 2231063 A GB2231063 A GB 2231063A
- Authority
- GB
- United Kingdom
- Prior art keywords
- composition
- amount
- present
- saccharin
- conversion
- 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.)
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- 239000000203 mixture Substances 0.000 title claims description 35
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 title claims description 19
- 229940081974 saccharin Drugs 0.000 title claims description 17
- 235000019204 saccharin Nutrition 0.000 title claims description 17
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 title claims description 17
- 238000007772 electroless plating Methods 0.000 title description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 70
- 229910052759 nickel Inorganic materials 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000007747 plating Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 12
- -1 nitrate ions Chemical class 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000004310 lactic acid Substances 0.000 claims description 6
- 235000014655 lactic acid Nutrition 0.000 claims description 6
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 claims description 4
- 229910001453 nickel ion Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical group FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 230000007306 turnover Effects 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical group 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 229940046892 lead acetate Drugs 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- MQLJIOAPXLAGAP-UHFFFAOYSA-N 3-[amino(azaniumylidene)methyl]sulfanylpropane-1-sulfonate Chemical compound NC(=N)SCCCS(O)(=O)=O MQLJIOAPXLAGAP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910001096 P alloy Inorganic materials 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- PHJJWPXKTFKKPD-UHFFFAOYSA-N [Ni+3].[O-]P([O-])[O-] Chemical compound [Ni+3].[O-]P([O-])[O-] PHJJWPXKTFKKPD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008364 bulk solution Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
Description
0 e, --:
1 PLATING COMPOSITION AND PROCESS This invention relates to the production of black electroless nickel deposits.
Electroless nickel plating has been known for some time. Articles coated with an electroless nickel deposit are disclosed, for example, in US-A3088846. There is at present a general commercial need, dictated partly by questions of fashion, for black electroless nickel deposits, primarily but not exclusively for decorative use. Such deposits are typically required on, for example, exposed metal components and/or casing of televisions, video cassette recorders and hi-fi equipment.
EP-A-0094127 proposes a solution to the problem of producing black electroless nickel deposits. it discloses that an electroless nickelcoated article can be treated in a bath comprising chromate ions, phosphate ions and optionally sulphate ions and subjected to periodically reversed current. EP-A0094127 suggests that the electroless nickel can be deposited from a bath marketed by Enthone under the trade name ENPLATE 415. (The word 11ENPLATE11 is a trade mark.) It has been found,, however, that deposits formed by the ENPLATE 415 bath and subsequently converted only give a properly black layer when the electroless plating bath is older than 1, but not more than 3, metal turnovers. (A metal turnover is reached when a plating bath has plated out that weight of metal ions which were present 2 in the bath originally; during plating the bath is replenished with metal ions, and generally with reducing agent.) Because the electroless plating bath can only effectively be used for two metal turnovers, and neither of them being the f irst one, if the deposited nickel is subsequently to be blackened, there is considerable wastage of plating bath materials, unless the plating bath is used for other purposes during the first and after the third turnover.
It has now been discovered that the presence of saccharin in an electroless nickel plating bath enables nickel to be deposited throughout the bath life and that the deposited nickel-phosphorus alloy can subsequently be blackened uniformly, or at least in a better manner than has been hitherto been possible.
According to a first aspect of the present invention, there is provided an electroless nickel plating composition which comprises saccharin. The saccharin will generally be present in an amount effective to enable deposited nickel to be subsequently blackened.
It is to be understood that references in this specification to a "nickel deposit" include references to a deposited alloy of nickel and some other element, such as phosphorus, as will typically be produced in electroless nickel plating.
The source of nickel may be nickel sulphate or any other convenient soluble nickel salt. The amount of 3 nickel present in the bath may range from 0.1 to 50 g/1, for example 1 to 25 g/1, typically 2 to 10 g/1.
In electroless metal plating baths, the metal ion is reduced not by electricity but by a chemical reducing agent. Any suitable reducing agent for nickel ions can be used in the bath, but in practice the preferred reducing agent will probably be sodium hypophosphite, which gives rise to a nickel phosphorus deposit. The reducing agent may be present in the electroless plating composition in an amount of from 1 to 100 g/1, for example 5 to 50 g/1, typically 20 to 40 g/1.
In order to avoid premature reducti6n of the nickel ions in bulk solution, it is usual for an electroless nickel plating composition to include a complexor for the nickel ions. Any convenient complexor can be used, but lactic acid is a preferred complexor. (It is to be understood that references in this specification to lactic acid or any other weak organic acid include references to lactate or other corresponding ions, as the exact species present will naturally depend upon pH.) Other complexors which might be useful apart from lactic acid include succinic acid, glycolic acid, malic acid and citric acid. The complexor may be present in an amount of from 1 to 100 g/1, for example 5 to 50 g/1 and typically 20 to 40 g/1. other complexors, including mixtures, can be used.
The saccharin will generally be present or added to the bath in soluble form. A suitable soluble form of saccharin is sodium saccharin, but other soluble salts may be used. The saccharin should be present in the bath in at least 0.7 g/1 for good results. Further, if 4 there are more than 2 g/1 present, it has been found that sometimes this can give rise to a mottled effect after blackening. Between 1.0 and 1.8 g/1, for example 1.5 g/1 has been found to be a particularly suitable amount of saccharin. As further guidance, it has been found experimentally that, for bath maintenance, the addition of between 25 and 200 mg saccharin per gram of nickel consumed has been found to give good results; preferred proportions are between 75 and 125 ing saccharin per gram of nickel, with the addition of about 100 Tag saccharin per gram of nickel being apparently optimal.
A buffer may be present in the bath. The buffer may be an acetic acid/acetate system, although any other buffer, for example based on a weak organic acid and its salt, may be used. The buffer may be present in an amount of from 1 to 50 g/1, for example 5 to 40 g/1, typically 20 to 30 g/1. If sodium acetate is used as the buffer, it may be supplied as the trihydrate salt.
The composition may additionally contain one or more stabilisers. In appropriate amounts, lead has been found to be a suitable stabiliser for electroless nickel systems. Lead may be supplied as lead acetate or as any other suitable soluble lead salt. Lead may be present in an amount of from 0.1 to 5 mg/1, for example 0.2 to 3 mg/1, typically 0.5 to 1.5 mg/1.
Sulphur-containing compounds form another class of useful stabilisers. One useful compound from this class is 3 - ( (amino- iminomethyl) thio) 1-propane sulphonic acid, although others may be used. The sulphur-containing compound may be present in an amount of from 0.1 to 10 mg/1, for example 0.2 to 5 mg/1, typically 0.5 to 3 mg/1.
The pH of the electroless nickel plating composition will usually be on the acid side. It may range from 3 to 6, for example 4 to 5.5, typically 4.5 to 5.
According to a second aspect of the invention there is provided a process for preparing a black electroless nickel deposit, the process comprising contacting a substrate for the deposit with an electroless nickel plating composition comprising saccharin and forming a conversion layer comprising chromium. The conversion layer may comprise phosphorus and optionally sulphur. The conversion layer may in particular comprise a hydrated basic chromium phosphate which comprises the components CrP04 and Cr(OH)3, wherein Cr2(S04)3 may be present and in which the weight ratio CR: P: S = 1: (0. 2 to 1. 5): (0 to 0. 5).
In the formation of the electroless nickel deposit, the temperature of the plating composition may range f rom 40 to 99%, for example 60 to 950C, ' typically 85 to 900C. Plating may take place for any convenient length of time, such as f rom 5 minutes to 5 hours, depending on the thickness required. Plating periods of from 20 minutes to 2 hours are usual, with periods of from 30 to 45 minutes being typical to obtain a deposit thickness of about 10 microns.
The conversion layer may contain chromium, phosphorus and sulphur, in which the ratio of CR:P:S = 1:1(0-0.2).
6 The conversion layer will generally be formed on an electroless nickel plated article treated with periodic reverse current, as described in EPA-0094127, which, insofar as the law allows, is herein incorporated by reference. The frequency of current reversal may range from 0.1 to 50 Hz, for example 0.5 to 25 Hz, typically about 1 Hz.
The ratio of the time for which the electroless nickel plated article is the cathode and the time for which it is the anode for a given current cycle (tcat/ tan) need not be equal to 1. A tcat/tan ratio of from 0.05 to 20 may in general be suitable, but a tcat/tan ratio of less than 1 is preferred. Tcat/tan ratios of between 0. 1 and 0. 8 inclusive have been found to be the most acceptable.
The current density may typically range from 0. 1 to 1 ASD, for example 0. 2 to 0.5 ASD, typically about 0.25 ASD.
In an important preferred feature of the invention, it has been found that if nitrate ions are present in the conversion composition, the performdnce is improved: improvements in the throwing power have been observed, and the tendency of greenish colours to be formed in high current density regions was significantly reduced. The conversion composition therefore preferably contains nitrate ions, which may be added as nitric acid. From 1 to 10 ml/1 nitric acid (65%) has been found to be suitable, f or example 5 to 10 ml/l, with about 7.5 ml/1 being optimal.
7 The chromate ions in the conversion composition may be present in an amount of from 1 to 40 g/1 Cr03, for example 2 to 20 g/1, typically 5 to 15 g/1. Phosphate ions may be present in an amount as would be provided for by the addition of from 1 to 60 ml/l, concentrated phosphoric acid, for example from 2 to 40 ml/l, typically 10 to 30 ml/l. Sulphate ions may be present in an amount provided by from 0 to 10 ml/1 concentrated sulphuric acid, for example 0.1 to 5 inl/l, typically 0.5 to 3 ml/l.
other preferred features of the conversion composition and the conversion process are to be found in EP-A0094127.
The invention will now be illustrated by the following examples.
Example 1
An electroless nickel plating composition was made up in water as follows:
Ni2+ (as nickel sulphate) Lactic acid (80% w/v) CH3C00 Na.3H20 Sod. hypophosphite Pb2+ (as lead acetate) 3-((aminoimmunomethyl)thio) 1propane sulphonic acid NaOH approx Na saccharin pH 6.2 g/1 30.0 ml/l 24.0 g/1 30.0 g/1 1. 3 ng/1 2. 0 mg/1 3.6 g/1 1. 5 g/1 4.8 8 A steel panel was plated in the above composition f or 35 minutes at pH 4. 9 and at a temperature of 890C.
Example 2
The nickel-plated steel panel resulting from Example 1 was treated in a solution of the following formulation:
Cr03 H3P04 (85%) H2S04 (98%) g/1 2 0 Tnl/ 1 2 ml/l under periodic reverse current conditions, as described generally in EP-A- 0094127, but using the following specific parameters:
Anodic time Cathodic time Current density Temperature 0.8 seconds 0.2 seconds 0.25 ASD 20-220C The electrolytic treatment continued for 30 minutes An excellent uniform black deposit was obtained.
Example 3
Steel panels were plated as described in Example 1. During plating, nickel was added, together with appropriate extra amounts of hypophosphite and stabiliser, to bring the ingredients back to their original concentrations. Further lactic acid was added so as to prevent precipitation of nickel orthophosphite which is an unavoidable by-product of the process.
9 After 1, 2, 3, 4 and 5 metal turnovers, a steel panel was subjected to the conversion process described in Example 2. In each case, an excellent uniform black deposit was obtained.
comparison Example A steel panel was plated with electroless nickel in a composition as described in Example 1, except that the sodium saccharin was omitted. After 1 metal turnover, the steel panel was extracted and subjected to the conversion process described in Example 2. High current density areas of the converted nickel deposit were dark green, medium current density areas were black with some iridescence, and low current density areas were iridescent and dark; a satisfactory black deposit was not obtained.
Claims (22)
1. An electroless nickel plating composition which comprises saccharin.
2. A composition as claimed in claim 1, wherein nickel is present in an amount of from 1 to 25 g/1.
3. A composition as claimed in claim 1 or 2, comprising a reducing agent present in an amount of from 5 to 50 g/1.
4. A composition as claimed in claim 3, wherein the reducing agent is sodium hypophosphite.
5. A composition as claimed in any one of claims 1 to 4, comprising a complexor for the nickel ions present in an amount of from 5 to 50 g/1.
6. A composition as claimed in claim 5, wherein the complexor comprises lactic acid.
7. A composition as claimed in any one of claims 1 to 6, wherein the saccharin is present in an amount of at least 0.7 g/1.
8. A composition as claimed in any one of claims 1 to 7, wherein the saccharin is present in an amount up to 2 g/1.
9. A composition as claimed in any one of claims 1 to 8, which comprises from 5 to 40 g/1 of buffer.
c X 11
10. A composition as claimed in claim 9, wherein the buffer comprises acetic acid.
11. A composition as claimed in any one of claims 1 to 10, which comprises one or more stabilisers.
12. A process for preparing a black electroless nickel deposit, the process comprising contacting a substrate for the deposit with an electroless nickel plating composition comprising saccharin and forming a conversion layer comprising chromium.
13. A process as claimed in claim 12, wherein the conversion layer comprises phosphorus and optionally sulphur.
14. A process as claimed in claim 13, wherein the conversion layer comprises a hydrated basic chromium phosphate which comprises the components CrP04 and Cr(OH)3, wherein Cr2(S04)3 may be present and in which the weight ratio CR:P:S = l:(0.2 to 1.5):(0 to 0.5).
15. A process as claimed in claim 12, 13, or 14, wherein the conversion layer is formed by treatment in a conversion composition with periodically reversed current.
16. A process as claimed in claim 15, wherein the frequency of current reversal is from 0.5 to 25 Hz.
17. A process as claimed in any one of claims 12 to 16, wherein the ratio of the time for which the electroless nickel plated article is the cathode and 12 the time for which it is the anode for a given current Cycle (tcat/ tan) is from 0.1 to 0.8.
18. A process as claimed in any one of claims 12 to 17, wherein the conversion layer is formed by contact with a conversion composition comprising nitrate ions.
19. A process as claimed in claim 18, wherein nitrate ions are present in an amount as is provided by from 5 to 10 ml/l nitric acid (65%).
20. A process as claimed in any one of claims 12 to 19 wherein conversion takes place by contact with a composition comprising from 2 to 20 g/1 Cr03.
21. A process as claimed in any one of claims 12 to 20 wherein conversion takes place by contact with a composition comprising phosphate ions in an amount as is provided by from 2 to 40 ml/l concentrated phosphoric acid.
22. A process as claimed in any one of claims 12 to 21 wherein conversion takes place by contact with a composition comprising sulphate ions in an amount as is provided by from 0.1 to 5 ml/l concentrated sulphuric acid.
Published 1990 at The Patent Office. State House, 6671 High Holborn, LondonWC1R4TP.Further copies maybe obtainedfrom. The Patent=ceSales Branch. St Mary Cray, Orpington. Kent BR5 3RD. Printed by Multiplex techmques ltd. St Mary Cray. Kent, Con. 187
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8904435A GB2231063A (en) | 1989-02-27 | 1989-02-27 | Electroless plating composition containing saccharin |
| NL9000308A NL9000308A (en) | 1989-02-27 | 1990-02-09 | MIXTURE AND METHOD FOR MANUFACTURING METAL DEPOSITS. |
| DE4005088A DE4005088A1 (en) | 1989-02-27 | 1990-02-17 | PLATING COMPOSITION AND METHOD |
| ES9000522A ES2021949A6 (en) | 1989-02-27 | 1990-02-21 | Electroless plating composition containing saccharin |
| IT47670A IT1240776B (en) | 1989-02-27 | 1990-02-23 | NICKEL PLATING COMPOSITION AND PROCEDURE TO PREPARE AND EXECUTE IT. |
| BE9000202A BE1003583A5 (en) | 1989-02-27 | 1990-02-23 | Coating composition and method of using a metal. |
| JP2047102A JPH0317277A (en) | 1989-02-27 | 1990-02-27 | Formation of plating composition and black electroless nickel-plating membrane |
| CH609/90A CH680449A5 (en) | 1989-02-27 | 1990-02-27 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8904435A GB2231063A (en) | 1989-02-27 | 1989-02-27 | Electroless plating composition containing saccharin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB8904435D0 GB8904435D0 (en) | 1989-04-12 |
| GB2231063A true GB2231063A (en) | 1990-11-07 |
Family
ID=10652386
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8904435A Withdrawn GB2231063A (en) | 1989-02-27 | 1989-02-27 | Electroless plating composition containing saccharin |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPH0317277A (en) |
| BE (1) | BE1003583A5 (en) |
| CH (1) | CH680449A5 (en) |
| DE (1) | DE4005088A1 (en) |
| ES (1) | ES2021949A6 (en) |
| GB (1) | GB2231063A (en) |
| IT (1) | IT1240776B (en) |
| NL (1) | NL9000308A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7846503B2 (en) | 2002-10-04 | 2010-12-07 | Enthone Inc. | Process and electrolytes for deposition of metal layers |
| US8962070B2 (en) | 2009-07-03 | 2015-02-24 | Enthone Inc. | Method for the deposition of a metal layer comprising a beta-amino acid |
| CN111850534A (en) * | 2020-06-16 | 2020-10-30 | 中国石油天然气集团有限公司 | Martensite stainless steel oil pipe low-stress pre-passivation film and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4705776B2 (en) * | 2004-12-17 | 2011-06-22 | 日本カニゼン株式会社 | Method for forming electroless nickel plating film having phosphate coating and film for forming the same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1059003A (en) * | 1964-02-03 | 1967-02-15 | Harshaw Chem Corp | Substituted saccharins |
| JPS4885434A (en) * | 1972-02-18 | 1973-11-13 | ||
| GB1390451A (en) * | 1971-03-09 | 1975-04-16 | Hoechst Ag | Manufacture of metallized shaped bodies of macromolecular material |
| GB1481564A (en) * | 1974-04-01 | 1977-08-03 | Oxy Metal Industries Corp | Electrodeposition of bright nickel-iron deposits |
| GB1553503A (en) * | 1976-05-14 | 1979-09-26 | Oxy Metal Industries Corp | Electrodeposition of bright nickel-iron deposits |
| GB2043693A (en) * | 1979-02-12 | 1980-10-08 | Oxy Metal Industries Corp | Electroplating bath and process for producing bright nickel iron electro-deposits |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3088846A (en) * | 1962-01-24 | 1963-05-07 | Gen Am Transport | Processes of treating nickel-phosphorus alloy coatings and the resulting modified coatings |
| US3586524A (en) * | 1969-07-10 | 1971-06-22 | Shell Oil Co | Consolidation of formations by electroless metal plating process |
| NL8201849A (en) * | 1982-05-06 | 1983-12-01 | Philips Nv | ARTICLE WITH A NICKEL-PHOSPHORUS ALLOY COAT AND CONVERSION COAT. |
| JPS6075583A (en) * | 1983-09-29 | 1985-04-27 | Komatsu Ltd | Electroless plating method of ultra abrasive |
| JPS60248882A (en) * | 1984-05-24 | 1985-12-09 | Aisin Seiki Co Ltd | Electroless plating bath for plating high-phosphorus nickel alloy |
| CA1274754A (en) * | 1985-09-06 | 1990-10-02 | Gary A. Reghi | Passivation process and composition for zinc-aluminum alloys |
-
1989
- 1989-02-27 GB GB8904435A patent/GB2231063A/en not_active Withdrawn
-
1990
- 1990-02-09 NL NL9000308A patent/NL9000308A/en not_active Application Discontinuation
- 1990-02-17 DE DE4005088A patent/DE4005088A1/en active Granted
- 1990-02-21 ES ES9000522A patent/ES2021949A6/en not_active Expired - Lifetime
- 1990-02-23 BE BE9000202A patent/BE1003583A5/en not_active IP Right Cessation
- 1990-02-23 IT IT47670A patent/IT1240776B/en active IP Right Grant
- 1990-02-27 JP JP2047102A patent/JPH0317277A/en active Pending
- 1990-02-27 CH CH609/90A patent/CH680449A5/de not_active IP Right Cessation
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1059003A (en) * | 1964-02-03 | 1967-02-15 | Harshaw Chem Corp | Substituted saccharins |
| GB1390451A (en) * | 1971-03-09 | 1975-04-16 | Hoechst Ag | Manufacture of metallized shaped bodies of macromolecular material |
| JPS4885434A (en) * | 1972-02-18 | 1973-11-13 | ||
| GB1481564A (en) * | 1974-04-01 | 1977-08-03 | Oxy Metal Industries Corp | Electrodeposition of bright nickel-iron deposits |
| GB1553503A (en) * | 1976-05-14 | 1979-09-26 | Oxy Metal Industries Corp | Electrodeposition of bright nickel-iron deposits |
| GB2043693A (en) * | 1979-02-12 | 1980-10-08 | Oxy Metal Industries Corp | Electroplating bath and process for producing bright nickel iron electro-deposits |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7846503B2 (en) | 2002-10-04 | 2010-12-07 | Enthone Inc. | Process and electrolytes for deposition of metal layers |
| US8962070B2 (en) | 2009-07-03 | 2015-02-24 | Enthone Inc. | Method for the deposition of a metal layer comprising a beta-amino acid |
| US9249513B2 (en) | 2009-07-03 | 2016-02-02 | Enthone Inc. | Beta-amino acid comprising plating formulation |
| CN111850534A (en) * | 2020-06-16 | 2020-10-30 | 中国石油天然气集团有限公司 | Martensite stainless steel oil pipe low-stress pre-passivation film and preparation method thereof |
| CN111850534B (en) * | 2020-06-16 | 2022-03-01 | 中国石油天然气集团有限公司 | Martensite stainless steel oil pipe low-stress pre-passivation film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8904435D0 (en) | 1989-04-12 |
| DE4005088A1 (en) | 1990-08-30 |
| NL9000308A (en) | 1990-09-17 |
| JPH0317277A (en) | 1991-01-25 |
| IT9047670A0 (en) | 1990-02-23 |
| BE1003583A5 (en) | 1992-04-28 |
| ES2021949A6 (en) | 1991-11-16 |
| CH680449A5 (en) | 1992-08-31 |
| IT1240776B (en) | 1993-12-17 |
| IT9047670A1 (en) | 1990-08-28 |
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| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |