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
  • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
• • 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
  • C25D3/56—Electroplating: Baths therefor from solutions of alloys
  • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
  • C25D5/18—Electroplating using modulated, pulsed or reversing current
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
  • C25D5/60—Electroplating characterised by the structure or texture of the layers
  • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
  • C25D5/611—Smooth layers

Definitions

• An electroplating method of forming platings of nickel cobalt, nickel alloys or cobalt alloys An electroplating method of forming platings of nickel cobalt, nickel alloys or cobalt alloys.
• the present invention relates to an electroplating method of forming platings of nickel, cobalt, nickel alloys or cobalt alloys in an electrodepositing bath of the type: Watt's bath, chloride bath or a combination thereof by employing pulse plating with a periodic reverse pulse.
• Current density independence is obtained by means of the invention, whereby low internal stresses are always rendered, wherever the measure ⁇ ment thereof is made on a particular member and whichever current density is used.
• the most common electrodepositing baths for nickel electroplating are Watt's baths containing nickel sulfate, nickel chloride and usually boric acid; chloride baths containing nickel chloride and boric acid, and sulf amate baths containing nickel sulfamate, nickel chloride and usually boric acid.
• the latter baths are used for the more complicated platings and are difficult and comparatively expensive in use.
• Corresponding platings of cobalt may be formed in similar baths containing cobalt sulfate and cobalt chloride instead of the corresponding nickel salts. By adding other metal salts platings of nickel or cobalt alloys are obtained.
• pulse plating with periodic reverse pulse, i.e. alternating between a cathodic and anodic current.
• the cathodic current cycle the desired plating formation is obtained by metal deposition, while a portion of the deposited nickel is removed by dissolution in the anodic current cycle, any nodules in the plating thus being smoothed.
• the anodic load is to be less than the cathodic load. This method is e.g.
• US patent No. 2,470,775 discloses a process for electroplating nickel, cobalt and alloys thereof in an electrodepositing bath containing chlorides and sulfates of the metals.
• the plating is effected by means of reversed pulse resulting in an improved appearance (smoothness and maximum brightness) as well as in an expedited deposition.
• An anodic current density is employed of substantially the same range as the cathodic current density.
• additives are mentioned in the US patent, including naphthalene -1,5-disulfonic acid. These additives are referred to as advantageous components, however no directions are rendered in connection with these additives or elsewhere in the patent as to how the mechanical internal stresses are reduced in the platings resulting from electroplating.
• EP patent No. 0.079.642 (Veco Beheer B.V.) relates to pulse plating with nickel in an electrolytic bath of the Watt's bath type comprising butynediol or ethylene cyanohydrin as brightener.
• the deposition is preferably performed at a pulsating current without anodic cycles, but it is stated that anodic cycles, i.e. reverse pulse, can also be employed with the same result. It is, however, not possible to use long anodic pulses in a pure Watt's bath without passivating the nickel layer, whereby any further deposition is prevented.
• said patent discloses that the frequen ⁇ cies used are in a range from 100 to 10,000 Hz.
• DE published specification No. 2.218.967 discloses a bath for electrodeposition of nickel, to which bath a comparatively large amount of sulfonated naphthalene is added, such as from 0.1 mole/1 to saturation so as to reduce the internal stresses in the platings applied by electroplating and with a direct current of e.g. 30 or 60 mA/cm 2 corresponding to 3 to 6 A dm 2 .
• the internal stresses are only reduced from die undesired tensile stress range to the compressive stress range from 0 to 26,000 psi (approx. 179 MPa) by employing this bath.
• the present invention relates to an electroplating method of forming platings of nickel, cobalt, nickel or cobalt alloys in an electrodepositing bath belonging to the type of a Watt's bath, a chloride bath or a combination thereof by employing pulse plating with periodic reverse pulse, said method being characterised in tiiat the electrodepositing bath contains an additive selected among sulfonated naphthalenes.
• Sulfamate baths are more complicated (difficult and more expensive to maintain), but are generally used to reduce the stress in the platings. However, in a sulfamate bath, it is only possible to obtain platings with satisfactorily low internal mechanical stresses in case of simple geometric shapes.
• Sulfamate baths cannot be used for periodic reverse pulse deposition, sulfur alloyed anodes (2% S) being employed to prevent the sulfamate from decomposing in ammoma and sulfiiric acid (ruining the bath). If the current is reversed, the cathode coated with non-sulfur alloyed nickel or cobalt becomes an anode and the sulfamate is destroyed.
• sulfur alloyed anodes 2% S
• the cathode coated with non-sulfur alloyed nickel or cobalt becomes an anode and the sulfamate is destroyed.
• the invention renders it possible to manufacture complicated geome ⁇ tric shapes completely without or with considerably reduced internal stresses in tiie plating.
• sulfonated naphthalene is used, i.e. naphthalene sulfonated with from 1 to 8 sulfonic acid groups (- SO 3 H), prefer ⁇ ably with 2 to 5 sulfonic acid groups, most preferred 2-4 sulfonic acid groups.
• a sulfonated naphthalene product usually comprises a mixture of sulfonated naphthalenes with various degrees of sulfonation, i.e. the number of sulfonic acid groups per naphthalene residue.
• several isomeric com ⁇ pounds may be present for each degree of sulfonation.
• the used sulfonated naphthalene sulfonide has a degree of sulfonation on average corresponding to from 2 to 4.5 sulfomc acid groups per molecule, e.g. 2.5- to 3.5 sulfonic acid groups per molecule.
• a mixture of sulfonated naphthalenes is used as sulfonated naphthalene additive, said mixture according to analysis containing approximately 90% of naphthalene trisulfonic acid, preferably comprisingnaphthalene-l,3,6-trisulfonicacidandnaphthalene-l,3,7-trisulfonicacid.
• naphthalene residue in the sulfonated naphthalene additive is usually free of other substiments than sulfonic acid groups. Any other substiments may, however, be present provided that they are not detrimental to the beneficial effect of the sulfo ⁇ nated naphthalene additive on minimizing the internal stresses in the plating formed by employing pulse plating.
• the sulfonated naphthalene additive is used in the electroplating bath in the amount of 0.1 to 10 g/1, more preferred in an amount of 0.2 to 7.0 g/1 and most preferred in an amount of 1.0 to 4.0 g/1, e.g. around 3.1 g/1.
• the bath composition preferably contains 10- 500 g/1 of NiCl 2 , 0-500 g/1 of NiSO 4 and 10-100 g/1 of H 3 BO 3 , more preferable 100-400 g/1 of NiCl 2 , 0-300 g/1 of NiSO 4 and 30-50 g/1 of H 3 BO 3 and preferable 200-350 g/1 of NiCl 2 , 25- 175 g/1 of NiSO 4 and 35-45 g/1 of H 3 BO 3 , for instance about 300 g/1 of NiCl 2 , 50 g/1 of NiSO 4 and 40 g/1 of H 3 BO 3 .
• the anodic current density I A is at least 1.5 times the cathodic current density I , more preferable when I A ranges from 1.5 to 5.0 times the I ⁇ and most preferable when I A is 2 to 3 times the I ⁇ .
• the method according to the invention may be character ⁇ ised in that the pulsating current is made up of cathodic cycles, each of a duration T ⁇ of from 2.5 to 2000 msec, and at a cathodic current density I ⁇ of 0.1 to 16 A/dm 2 alternating with anodic cycles, each of a duration of from 0.5 to 80 msec, and at an anodic current density I A of 0.15 to 80 A/dm 2 .
• a more preferable embodi ⁇ ment according to the invention is obtained when among the pulse parameters the I ⁇ ranges from 2 to 8 A/dm 2 , the T ⁇ ranges from 30 to 200 msec, the I A ranges from 4 to 24 A/dm 2 and T A ranges from 10 to 40 msec.
• a particular preferred embodiment is obtained when I ⁇ is from 3 to 6 A/dm 2 , T ⁇ is from 50 to 150 msec. , I A is from 7 to 17 A/dm 2 and T A is from 15 to 30 msec, e.g. when I ⁇ is 4 A/dm 2 , T ⁇ is 100 msec, I A is 10 A/dm 2 and T A is 20 msec.
• a nickel bath containing 300 g/1 of NiCl 2 -6H 2 O and 50 g/1 of NiSO 4 *6H 2 O was admixed, and to which bath 40 g/1 of H 3 BO 3 and 3.1 g/1 of sulfonated naphthalene additive of technical grade comprising 90% naphthalene- 1, 3, 6/7-trisulf onic acid were added.
• Nickel was deposited on a steel strip fixed in a dilatometer so that the internal stresses in the deposited nickel can be measured as a contraction or a dilation of the steel strip.
• the temperamre of the bath was 50°C.
• the internal stresses were measured to be 0 MPa or less than the degree of accuracy of the apparams of approximately ⁇ 10 MPa.
• Example 2 Following the method according to Example 1 with the exception that only 1.1 g/1 of the same sulfonated naphthalene additive was used, the same result was obtained as in Example 1, i.e. that the internal stresses were to measure to 0 MPa or less than the degree of accuracy of the apparatus of approximately ⁇ 10 MPa.
• Example 2 Following the method according to Example 2 with the exception that the anodic current density I A and the cathodic current density I ⁇ was set at 1.25 A/dm 2 and 0.5 A/dm 2 respectively, the same result as in Example 1 was obtained, i.e. that the intemal stresses were measured to 0 MPa or less than the degree of accuracy of the apparams of approximately ⁇ 10 MPa.
• Example 3 Following the method according to Example 3 with the exception that the anodic current density I A and the cathodic current density I ⁇ was set at 18.75 A/dm 2 and 7.5 A/dm 2 respectively, the same result as in Example 1 was obtained, i.e. that the internal stresses were measured to 0 MPa or less than the degree of accuracy of the apparams of approximately ⁇ 10 MPa.
• Example 6 Following the method according to Example 5 with the exception that 1.1 g/1 of sulfonated naphthalene additive was used, similar stress-free cobalt platings may be expected.
• Example 2 Employing the same set-up and materials as in Example 1 , but at a direct current of 4 A/dm 2 , the intemal stresses for comparison with said Example were measured to 377 MPa.
• Example 2 Employing the same set-up and materials as in Example 2, but using a direct current of 7.5 A/dm 2 , the intemal stresses were measured to 490 MPa.

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• 1995
  • 1995-06-21 DK DK199500706A patent/DK172937B1/da not_active IP Right Cessation
• 1996
  • 1996-06-20 US US08/973,556 patent/US6036833A/en not_active Expired - Lifetime
  • 1996-06-20 ES ES96920744T patent/ES2136421T3/es not_active Expired - Lifetime
  • 1996-06-20 AU AU61884/96A patent/AU6188496A/en not_active Abandoned
  • 1996-06-20 CA CA002224382A patent/CA2224382C/en not_active Expired - Lifetime
  • 1996-06-20 WO PCT/DK1996/000270 patent/WO1997000980A1/en active IP Right Grant
  • 1996-06-20 JP JP9503524A patent/JPH11507991A/ja active Pending
  • 1996-06-20 AT AT96920744T patent/ATE184332T1/de active
  • 1996-06-20 EP EP96920744A patent/EP0835335B1/en not_active Expired - Lifetime
  • 1996-06-20 DE DE69604180T patent/DE69604180T2/de not_active Expired - Lifetime
• 1997
  • 1997-12-08 NO NO19975769A patent/NO320887B1/no not_active IP Right Cessation
• 1999
  • 1999-10-15 GR GR990402642T patent/GR3031549T3/el unknown

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