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EP0739995B1 - Verwendung einer Zn-Ni-Legierung zur Herstellung eines Zn-Ni-Legierungsfeuergalvanisierungsbads - Google Patents

Verwendung einer Zn-Ni-Legierung zur Herstellung eines Zn-Ni-Legierungsfeuergalvanisierungsbads Download PDF

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Publication number
EP0739995B1
EP0739995B1 EP96111036A EP96111036A EP0739995B1 EP 0739995 B1 EP0739995 B1 EP 0739995B1 EP 96111036 A EP96111036 A EP 96111036A EP 96111036 A EP96111036 A EP 96111036A EP 0739995 B1 EP0739995 B1 EP 0739995B1
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Prior art keywords
alloy
temperature
bath
flux
melt
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EP96111036A
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English (en)
French (fr)
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EP0739995A1 (de
Inventor
Hiroshi Tasaki
Eiji Nishimura
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Nippon Mining Holdings Inc
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Nippon Mining and Metals Co Ltd
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Priority to DE1992626713 priority Critical patent/DE69226713T2/de
Priority claimed from EP92115844A external-priority patent/EP0587933B1/de
Publication of EP0739995A1 publication Critical patent/EP0739995A1/de
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/12—Process control or regulation
    • C25D21/14—Controlled addition of electrolyte components

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  • the present invention is related to the use of a Zn-Ni alloy for simultaneously dissolving Zn and Ni into a Zn-Ni hot-dip galvanizing bath. Furthermore, the present invention is related to a method for producing a Zn-Ni alloy.
  • Japanese Unexamined Patent Publication No. 60-248855 discloses a Zn-Ni alloy with 3% or less of Ni used for preparation of a hot-dip galvanizing bath. It is described that a Zn-Ni alloy with a higher Ni content causes vigorous vaporization of Zn as the Zn-Ni alloy is dissolved, and more Ni is transferred into dross than when Zn-Ni alloy with less than 3% of Ni is dissolved. Incidentally, the zinc metal is melted and then Ni is added to the molten Zn so as to provide an alloy having a predetermined composition.
  • Zn-Ni alloy with 2 wt% or less of Ni has a melting point of approximately 600°C. Such Zn-Ni alloy can therefore be melted without relying on a flux. However, since the melting point is greatly raised when the Ni content is higher than 2 wt% according to a phase diagram, the melting temperature of Zn-Ni alloy exceeds the temperature where vigorous vaporization of Zn occurs. It is therefore extremely difficult to produce a Zn-Ni alloy by melting. More specifically, when the surface temperature of Zn-Ni bath exceeds 750°C, the Zn vigorously vaporizes and is oxidized. As a result, an igniting and combusting phenomenon occurs. In addition, bumping phenomenon of the Zn-Ni bath may occur. For the reasons described above, it is recognized that production of Zn-high Ni alloy is difficult by Method (1).
  • Method (2) also, a high temperature is necessary for producing a Zn-Ni alloy. In addition, since nickel chloride, which is expensive, is used in Method (2), this Method is not advisable.
  • Object of the present invention is to provide the use of Ni-Zn alloy for preparation of hot dip galvanizing plating bath, so that: for a short period of time, a bath having desired Ni content can be made up or replenished with Ni due to a high Ni content of the alloy; and virtually all of the Zn-Ni alloy can be melted in the hot-dip galvanizing bath.
  • a Zn-Ni alloy for supplying Ni and Zn into a hot-dip galvanizing bath, said alloy having a composition containing from 4 to 50% by weight of Ni, the balance being essentially Zn, and being produced by using a flux consisting of a fused-salt former for forming a salt having a melting temperature of 700°C or less and Na 2 B 4 O 7 , and occasionally further containing Na 2 CO 3 .
  • the Zn-Ni alloy to be used for the preparation of the hot-dip galvanizing bath advantageously contains from 10 to 30% of Ni.
  • a method for producing a Zn-Ni alloy having a high Ni content which method can solve the operational problems of Zn vaporization and oxidation reaction, and which can avoid the bumping of the Zn-Ni alloy bath, and exhibit improved dissolving characteristics in the hot-dip galvanizing bath while generating only a small amount of dross when melting in the hot-dip galvanizing bath.
  • said alloy has a composition containing from 2 to 50% by weight of Ni, the balance being essentially Zn, and is melted by using a flux consisting of a fused salt-former for forming a salt having a melting temperature of 700°C or less and Na 2 B 4 O 7 , and optionally further containing Na 2 CO 3 .
  • Purest zinc electric zinc (99.99% Zn) or distilled zinc (98.5% Zn) can be used as the zinc metal.
  • Ni metal having 99.5% or more of Ni-purity can be used.
  • the Zn-Ni alloy to be used in the present invention must have a maximum Ni content of 50% by weight, because a high-grade material having a Ni content greater than 50% is difficult to produce by melting due to its high melting point. In addition, when the Ni content is high, the surface area of Ni, which is left after the preferential solution of Zn, is so decreased that the dissolving speed of Ni is lowered.
  • the Zn-Ni alloy to be used in the present invention must contain at least 2% of Ni, because a Zn-Ni alloy having a lower grade of Ni is not practical for the dissolving preparation of an electroplating bath, which usually has a Ni concentration of from 25 to 100g/l.
  • a preferred composition of Zn-Ni alloy used for the preparation of a bath for Zn-Ni electroplating is from 10 to 30% of Ni, the balance being Zn.
  • a Zn-Ni alloy having a composition containing from 4 to 50% by weight of Ni, the balance being essentially Zn is preliminarily melted by using a flux consisting of a fused-salt former for forming a salt having a melting temperature of 700°C or less and Na 2 B 4 O 7 and optionally further containing Na 2 CO 3 , and, the so-produced alloy is then dissolved in the molten bath.
  • the so-produced Zn-Ni alloy has a high Ni content, contains Ni uniformly distributed therein, and has a melting point which is virtually the same that is given in a phrase diagram.
  • This alloy can therefore be melted at such temperature while not incurring the disadvantages of the Zn-Ni alloy produced by the conventional method. Even if the Zn-Ni alloy having the inventive composition could be produced by the conventional method, at the sacrifice of yield, Ni, which has a high melting point, greatly segregates, so that much of Ni is left as undissolved residue when such alloy is dissolved. Since the present invention does not involve such disadvantages, addition of Ni to the molten bath is very easy.
  • Particle size of the alloy to be used in the present invention is not at all limited but is practically 20mm or less. When the particle size is too small, the alloy floats on the surface of plating bath.
  • the particle size is preferably 1mm or more.
  • the method involves a discovery that a certain composition of flux can prevent, during melting production of a Zn-Ni alloy having 2wt% or more at high temperature, oxidation of the Zn-Ni alloy on its surface and zinc vaporization, as well as ignition and combustion of the zinc-nickel bath.
  • the flux consists, as described above, of a fused-salt former having a melting point of 700°C or less, and Na 2 B 4 O 7 .
  • Na 2 CO 3 can optionally be added.
  • NaCl and KCl can be used as the fused-salt former having a melting point of 700°C or less.
  • the NaCl content is preferably from 30 to 70% by weight, because the melting point of the NaCl-KCl is 700°C or less, ignition of the vaporizing Zn can be prevented, and advantageous fluxing effects are attained for melting the Zn-Ni alloy.
  • Proportion of Na 2 B 4 O 7 and Na 2 CO 3 is preferably from 10-100 wt% and 90-0 wt%, because the binary Na 2 B 4 O 7 -Na 2 CO 3 melts at a temperature of 800°C or more and easily absorbs such oxides as ZnO and NiO.
  • the NaCl-KCl composition is preferably contained in the flux at a content of from 3 to 20 wt%, because the ignition of vaporizing Zn can thoroughly be prevented during the temperature elevation of the zinc metal.
  • the fused-salt former having a melting point of 700°C or less, e.g., NaCl and KCl, first melts at approximately 650°C, and covers the surface of the molten bath to shield it from contact with air. Neither vaporization of Zn resulting in Zn loss nor ignition and combustion of the Zn vapor therefore occur.
  • the fused-salt former having a melting point of 700°C or less e.g., NaCl and KCl, does not absorb therein such oxides as ZnO and NiO slightly formed on the surface of Zn-Ni bath. These oxides therefore are present as solids in the interface between the fused salt and the molten alloy.
  • the flux consists only of NaCl and KCl
  • amount of the oxides is so increased that it becomes difficult for the flux in molten state to cover the surface of Zn-Ni bath.
  • Such flux exhibits no longer has effect of shielding the molten alloy from contact with air.
  • Zn then actively vaporizes, leading to ignition and burning of Zn.
  • the temperature of the metal bath, which is covered with NaCl-KCl one of the components of the flux according to the present invention, is further heated to approximately 800°C, then the Na 2 B 4 O 7 or Na 2 B 4 O 7 and Na 2 CO 3 is caused to melt.
  • Such oxides as ZnO and NiO are absorbed in or dissolve in the resultant Na 2 B 4 O 7 or Na 2 B 4 O 7 and Na 2 CO 3 fused salt.
  • the surface of the Zn-Ni alloy melt is covered by the fused salt of NaCl-KCl and the fused salt of Na 2 B 4 O 7 -Na 2 CO 3 .
  • These fused salts stably cover the surface of the Zn-Ni alloy melt up to a temperature of approximately 1300°C. Their vapor pressure is so low as not to incur loss of the fused salts.
  • the oxides of Zn and Ni formed due to high-temperature oxidation are absorbed by the flux, while the vaporization of metallic Zn is suppressed.
  • the alloy melt is protected from contact with air, so that neither ignition nor combustion of the alloy melt occurs. Since the above merits are attained, it is possible to stably produce Zn alloy having a high Ni content under high temperature.
  • the Ni content is preferably from 2 to 50 wt%, because at a Ni content less than 2% the alloy has such low melting point that it can be produced by any method other than the present invention, and at a Ni content more than 50%, the melting point is so high as to make production by the present method impossible.
  • Nickel is added to the Zn bath until the predetermined Ni grade is attained.
  • Ni grade of the Zn bath is gradually increased, and the temperature of the alloy melt is elevated with the increase in the Ni content.
  • the alloy bath suddenly becomes higher than the boiling point of Zn, i.e., 906°C, when the Ni metal reacts with zinc metal and hence imparts heat to the melt due to exothermic reaction of alloying. As a result, bumping arises. This then leads to ignition and combustion of Zn.
  • the temperature of the bath is raised in accordance with the increase in Ni content.
  • the melting temperature can be raised up to 1100°C, which exceeds the boiling point of Zn.
  • Figure 1 illustrates the melting speed in the various dissolving methods.
  • NaCl (50g), KCl (50g), Na 2 B 4 O 6 (250g) and Na 2 CO 3 (650g) were mixed in a mortar to provide a flux.
  • the flux weighing in approximately 100g was dispersed on the surface of molten Zn bath, when temperature of this bath was elevated to approximately 450°C.
  • the temperature of the molten bath was further enhanced.
  • the mixed salts of NaCl and KCl were first melted and covered the surface of molten Zn bath. At this stage the mixed salts of Na 2 B 4 O 7 and Na 2 CO 3 were in half molten state.
  • the so-produced Zn-50% Ni alloy melt was cast into a mold, and the cast alloy was produced.
  • the cast product was crushed by a vibrating mill. As a result, crushed product having particle diameter of under 325 mesh (43 ⁇ m) was obtained. The Ni content of the cast product was 49.9%. The balance was Zn.
  • a Zn-13 wt% Ni alloy was produced by melting 3kg of Zn and 448g of Ni. In the present example, the melting temperature was elevated, while adding Ni into the Zn melt, as in Example 1 until the melt temperature of 950°C, which exceeded the boiling point of Zn, was finally obtained.
  • the Zn-13 wt% Ni alloy could be cast into the same shape as a mold.
  • alloy shot having an optional size could be produced by dropping the melt of this alloy into water.
  • the particle size of under 325 mesh (43 ⁇ m) could be obtained by crushing.
  • the Ni content of the cast product was 12.85 wt%, the balance being Zn.
  • a Zn-4 wt% Ni alloy was produced by melting 3kg of Zn and 125g of Ni.
  • the melting temperature was elevated as in Example 1, while adding Ni into the Zn melt, until the melt temperature of 850°C, which was directly below the boiling point of Zn, was obtained.
  • the Zn-4 wt% Ni alloy could be cast into a mold.
  • alloy shot having an optional size could be produced by dropping the melt of this alloy into water.
  • the Ni content of the cast product was 4 wt%, the balance being Zn.
  • the Zn-Ni alloys melted in Examples 1-3 were atomized by the same atomizing method of Zn.
  • the particle size became 1mm or less.
  • a Zn-13 wt% Ni alloy was produced by the same method as in Example 1 except for the flux, whose composition was 13.3 wt% NaCl, 16.7 wt% of KCl, and 70 wt% of Na 2 B 4 O 7 (melting point approximately 700°C). Ni could be uniformly alloyed.
  • KCl and NaCl were weighed at 50g, respectively, and were mixed in a mortar. It was intended in this example to melt a Zn-4 wt% Ni alloy. When the melt temperature of this alloy was elevated to 450°C, 100g of this flux was dispersed on the surface of melt. When melt temperature was elevated to approximately 650°C, then the flux covered the surface of melt. Melt temperature was further elevated to approximately 800°C. The flux could not absorb Zn oxide and Ni oxide, which were formed by partial oxidation of Zn and Ni during the temperature rise. The solid ZnO and NiO were therefore mixed in the flux melt. Since the alloy melt could not be thoroughly covered by the flux melt, Zn was actively vaporized and then ignited. Vigorous combustion of Zn thus occurred. Melting of a Zn-4 wt% Ni alloy was therefore not successful because of the phenomena as described above.
  • Zn-15 wt% Ni alloy was melted by the method of Example 1 and was then crushed and sieved to provide the grain size as given in Table 1.
  • a sample 13.3g in weight was taken from this alloy and was dissolved together with the zinc metal (purest zinc - 99.99wt% of Zn) in an amount of 986.7g by the mixing or stirring method given in Table 1.
  • the melting temperature was 460 o C ⁇ 10 o C.
  • the flux used was NH 4 Cl. This NH 4 CL flux and Zn-15%wt Ni alloy was mixed in a proportion of 1:0.5, except for Nos. 6 and 7 in Table 1 in which the proportion was 1:0.2. Dissolving Result of Zn-0.2%Ni Nos.
  • the asterisked* Nos. are comparative runs, in which the dissolving time is short. It is clear that the charged materials in the size range of from 10 to 20mm could be completely dissolved by means of stirring. Charged materials with the particle size of 44 microns or less could be completely dissolved even in dissolving time of 10 minutes.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Automation & Control Theory (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Coating With Molten Metal (AREA)

Claims (3)

  1. Verwendung einer Zn-Ni-Legierung zur Bereitstellung von Ni und Zn in einem Feuergalvanisierungsbad, dadurch gekennzeichnet, daß besagte Legierung eine Zusammensetzung hat, die 4 bis 50 Gewichtsprozent Ni enthält und deren Rest im wesentlichen Zn ist, und durch Verwendung eines Flußmittels, daß aus einem Salzschmelzenbildner, der ein Salz, das eine Schmelztemperatur von 700 °C oder weniger hat, bildet, und aus Na2B4O7 besteht, hergestellt wird.
  2. Die Verwendung einer Zn-Ni-Legierung gemäß Anspruch 1., dadurch gekennzeichnet, daß das Flußmittel weiterhin Na2CO3 enthält.
  3. Die Verwendung einer Zn-Ni-Legierung gemäß Anspruch 1. und 2., dadurch gekennzeichnet, daß der Nickelgehalt 10 bis 30 Gewichtsprozent ist.
EP96111036A 1992-09-16 1992-09-16 Verwendung einer Zn-Ni-Legierung zur Herstellung eines Zn-Ni-Legierungsfeuergalvanisierungsbads Expired - Lifetime EP0739995B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE1992626713 DE69226713T2 (de) 1992-09-16 1992-09-16 Verwendung einer Zn-Ni-Legierung zur Herstellung eines Zn-Ni-Legierungsfeuergalvanisierungsbads

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP92115844A EP0587933B1 (de) 1992-09-15 1992-09-16 Verwendung einer Zn-Ni-Legierung zur Herstellung eines Zn-Ni-Legierungsgalvanisierbads sowie Herstellungsverfahren für eine Zn-Ni-Legierung

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EP92115844.0 Division 1992-09-16

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EP0739995B1 true EP0739995B1 (de) 1998-08-19

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1270289B (de) * 1966-10-15 1968-06-12 Luigi Vellani Verfahren zur Herstellung von Vorlegierungen fuer das Erschmelzen nickelhaltiger Weissgoldlegierungen
US3420754A (en) * 1965-03-12 1969-01-07 Pittsburgh Steel Co Electroplating a ductile zinc-nickel alloy onto strip steel
DE3816419C1 (de) * 1988-05-13 1989-04-06 Rasselstein Ag, 5450 Neuwied, De
JPH01275799A (ja) * 1988-04-28 1989-11-06 Furukawa Electric Co Ltd:The 電気ＺｎメッキにおけるＺｎイオンの供給方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02282435A (ja) * 1989-04-21 1990-11-20 Sumitomo Metal Mining Co Ltd ニッケルを含有した亜鉛母合金の製造方法
JPH0379732A (ja) * 1989-08-23 1991-04-04 Sumitomo Metal Mining Co Ltd 溶融Ｚｎめっき浴の成分調整用Ｚｎ―Ｎｉ母合金の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3420754A (en) * 1965-03-12 1969-01-07 Pittsburgh Steel Co Electroplating a ductile zinc-nickel alloy onto strip steel
DE1270289B (de) * 1966-10-15 1968-06-12 Luigi Vellani Verfahren zur Herstellung von Vorlegierungen fuer das Erschmelzen nickelhaltiger Weissgoldlegierungen
JPH01275799A (ja) * 1988-04-28 1989-11-06 Furukawa Electric Co Ltd:The 電気ＺｎメッキにおけるＺｎイオンの供給方法
DE3816419C1 (de) * 1988-05-13 1989-04-06 Rasselstein Ag, 5450 Neuwied, De

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 014, no. 043 (C - 681)<3986> 26 January 1990 (1990-01-26) *

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EP0739995A1 (de) 1996-10-30
DE69223616T2 (de) 1998-04-30
DE69223616D1 (de) 1998-01-29

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