WO2008029979A1 - Procédé de réparation de la piqûration et des fissures des métaux ou alliages par dépôt électrophorétique de nanoparticules - Google Patents

Procédé de réparation de la piqûration et des fissures des métaux ou alliages par dépôt électrophorétique de nanoparticules Download PDF

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Publication number
WO2008029979A1
WO2008029979A1 PCT/KR2007/001029 KR2007001029W WO2008029979A1 WO 2008029979 A1 WO2008029979 A1 WO 2008029979A1 KR 2007001029 W KR2007001029 W KR 2007001029W WO 2008029979 A1 WO2008029979 A1 WO 2008029979A1
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WIPO (PCT)
Prior art keywords
metal
alloy
pitted
nano
poly
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PCT/KR2007/001029
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English (en)
Inventor
Chang-Kyu Rhee
Min-Ku Lee
Gyoung-Ja Lee
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Korea Atomic Energy Research Institute
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Publication of WO2008029979A1 publication Critical patent/WO2008029979A1/fr

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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
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/22—Servicing or operating apparatus or multistep processes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/02—Electrophoretic coating characterised by the process with inorganic material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
    • 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
    • C25D5/67—Electroplating to repair workpiece

Definitions

  • the present invention relates to a method of repairing pitting damage or cracks in metals or alloys using an electrophoretic deposition process.
  • the parts When using machine parts containing various metals or alloys, the parts may be corroded or damaged under a variety of natural environmental conditions, such as rain and snow, corrosive environments, or the operating conditions of the parts used, undesirably generating pitting damage or cracks in the parts. Further, the pitting damage or cracks thus generated cause the lifetime of the parts to be shortened and hasten the time for replacement with new parts. A consequence of the earlier part replacement time is the problem of increasing costs for maintenance and repair of apparatuses composed of the parts. In particular, in the case where parts, for example, heat exchangers, various condensers, heat transfer tubes of instrumental coolers, or various pipes, are used under poor operating conditions, they need to be maintained and repaired in proper time.
  • Korean Patent No. 266881 discloses a process for conducting surface- alloying on plated metal or alloy substrates or surface-repairing of damaged metal or alloy substrates using a laser beam, comprising forming a film or coat having a desired alloy composition on a metal or alloy substrate through wet plating, electroplating, or other processes and then melting the surface of the substrate using a laser beam to thereby form an alloy layer.
  • Korean Patent No. 270193 discloses a heat tube repair method and corresponding apparatus for a large heat exchanger, the method comprising steps of fitting a sleeve for explosive expansion to the position where the heat tube is damaged; explosive expanding the sleeve for explosive expansion at the above position; removing the expanded residue and disposing a laser sleeving head at the above position; and applying a laser beam to the inner surface of the sleeve in a circumferential direction using the laser sleeving head, therefore welding the low- melting-point brazing metal of the outer surface of the sleeve to the heat tube.
  • Korean Patent No. 425950 discloses a method of repairing an oil storage tank for preventing the leakage of oil due to corrosion, in which a strip having a predetermined width is continuously brought into contact with the inner surface of a corroded oil storage tank and the joint therebetween is welded to thus manufacture a double-walled oil storage tank, thereby completely repairing the oil storage tank.
  • an electrophoretic deposition process is a combination of techniques of electrophoresis and deposition.
  • the electrophoretic deposition process is a technique in which particles are induced to aggregate and thus deposited at predetermined positions by controlling the movement of charged particles by appropriately combining direct current and alternating current.
  • the above- mentioned conventional techniques do not describe a method of repairing parts by intensively depositing a nano-metal colloid in a partially cracked region using an electrophoretic deposition process.
  • an object of the present invention is to provide a method of repairing pitting damage or cracks in metals or alloys using an electrophoretic deposition process, which can rapidly repair localized damage or corrosion pits occurring in the surface of a metal or alloy substrate, and can also form a repaired structure that is closely continuous and dense, without a change in the microstructure of the metal around the damage or pits, thus exhibiting superior mechanical strength of the repaired structure.
  • the invention provides to a method of repairing pits or cracks in metals or alloys using an electrophoretic deposition process.
  • the repair method is advantageous because it has a short process time period, can be performed at low temperatures to thus have no influence on the microstructure of the metal around the pits or cracks, and can form a continuous and dense bond to assure superior mechanical strength of the repaired structure than when using conventional repair methods.
  • the repair method of the present invention is expected to be effectively applied to techniques for repairing various kinds of metals or alloys having diverse pits or cracks.
  • FIG. 1 schematically illustrates the aggregation of nano-metal colloid particles using an electrophoretic deposition process
  • FIG. 2 illustrates the (a) potentiodynamic polarization curve of Ni metal plate with a scan rate of 0.5 mV s in aqueous 0.1 M NaCl solution and (b) potentiostatic anodic current transient obtained from Ni metal plate at the applied anodic potential of 0.9 V (vs. Ag/ AgCl) in aqueous 0.1 M NaCl solution;
  • FIG. 3 illustrates SEM micrographs of pit morphology on the surface of Ni metal plate subjected to a constant electric field of 20 VCt for (a) 0 sec, (b) 120 sec and (c) 1200 sec, respectively, in Ni-dispersed solution;
  • FIG. 4 illustrates SEM micrographs of pit morphology on the surface of Ni metal plate subjected to a constant electric field of 100 VCt for (a) 0 sec, (b) 90 sec and (c) 180 sec, respectively, in Ni-dispersed solution;
  • FIG. 5 illustrates binary SEM images transformed from the digitized SEM images of pitted Ni metal specimens (a) A, (b) B, (c) C and (d) D.
  • Specimens A, B, C and D were made just after the fresh Ni metal plates were subjected to a constant anodic potential of 0.9, 0.8, 0.7 and 0.6 V (vs. Ag/ AgCl) above the pitting potential, respectively, for 60 sec;
  • FIG. 6 illustrates the dependence of perimeter P and area A obtained from the binary SEM images of pitted Ni metal specimens (a) A, (b) B, (c) C and (d) D and
  • FIG. 7 illustrates the plots of (a) electrophoretic current Ip versus applied electric field E experimentally determined from pitted Ni metal specimen A and (b) electrophoretic current Ip versus surface fractal dimension (d F,surf ) for pitted Ni metal specimens A (O), B( ⁇ ), C(D) and D(V) under applied electric field E of 20 YU. Best Mode for Carrying Out the Invention
  • the present invention provides a method of repairing pitting damage or cracks in metals or alloys using an electrophoretic deposition process, comprising (a) preparing nano-powder particles of a metal or alloy that is the same as the metal or alloy having the pitted or cracked region; (b) adding the nano-powder particles of the metal or alloy in (a) to an organic solvent containing a dispersant, to thus prepare a stabilized colloidal dispersion; (c) immersing the metal or alloy having the pitted or cracked region in the stabilized colloidal dispersion in (b); and (d) applying an electrical field to the metal or alloy having the pitted or cracked region via electrophoretic deposition to concentrate current density on the pitted or cracked region of the metal or alloy such that the nano-powder particles of the metal or alloy having surface charges are intensively deposited in the pitted or cracked region of the metal or alloy, thereby forming a uniform layer.
  • the repair method using an electrophoretic deposition process functions to repair the cracked or pitted surface region of structural parts using electrophoresis, that is, using the electrohydrodynamic flow of colloidal metal or alloy particles having surface charges through the application of an electrical potential to metal or alloy powder, having a particle size set on the nano-scale through a nano- technique, dispersed in an appropriate dispersion medium. Further, based on an electrochemical principle in which current is selectively increased in a cracked region, as is apparent from FIG. 1, current density is concentrated on the pitted or cracked region in order to enable the selective coating and/or repair of the cracked region.
  • (a) is a step of preparing nano-power particles of a metal or alloy that is the same as a metal or alloy having a pitted or cracked region.
  • the nano-powder particles of the metal or alloy in (a) may be prepared through levitation-gas condensation.
  • levitation-gas condensation is a technique well- known in the art, in which a base material is heated and evaporated through high- frequency induction heating to thus produce powder, which is then condensed with an inert gas, for example, nitrogen or argon, thereby preparing nano-powder, but the present invention is not limited thereof.
  • any metal ion or alloy thereof may be used, examples of which include, but are not limited to, metals such as Ni, Zn, Fe, W, and Sn, alloys thereof, and alloys based thereon.
  • the nano-powder particles of the metal or alloy may be prepared to a size ranging from 10 nm to 40 nm. This is because, within the above size range, it is easy to disperse the particles in a colloidal solution and also to aggregate the particles using an electrical field to thus efficiently repair the pitted or cracked region.
  • the nano-colloid prepared using the nano-powder particles of the metal or alloy may have a size ranging from 10 to 100 nm. If the size of the prepared nano-colloid is less than 10 nm, the ability to aggregate the nano-metal colloid in the locally damaged or corroded region using the current density generated by the predetermined electrical field may be deteriorated. On the other hand, if the size exceeds 100 nm, the nano- metal colloid may be easily precipitated in the dispersion medium due to its weight.
  • (b) is a step of adding the nano-powder particles of the metal or alloy in (a) to an organic solvent containing a dispersant, thus preparing a stabilized colloidal dispersion.
  • Examples of the organic solvent include C1-C5 alcohols
  • examples of the dispersant include, but are not limited to, polyvinylpyrrolidone, polyacrylamide, poly- acrylonitrile, polyethyleneimine, polyglycine, polyacrylic acid, polymethacrylic acid, poly(3-hydroxybutyric acid), poly-L-leucine, poly-L-methionine, poly-L-proline, poly- L-serine, poly-L-tyrosine, poly(vinylbenzenesulfonic acid), poly(vinylsulfonic acid), etc.
  • the dispersant is polyvinylpyrrolidone and the organic solvent is a C1-C5 lower alcohol.
  • (c) is a step of immersing the metal or alloy having the pitted or cracked region in the stabilized colloidal dispersion in (b).
  • the stabilized colloidal dispersion in which the metal or alloy having the pitted or cracked region is immersed, may be used as an electrolytic solution for the efficient flow of an electrical field in a subsequent step (d).
  • (d) is a step of applying an electrical field to the metal or alloy having the pitted or cracked region via electrophoretic deposition to concentrate the current density on the pitted or cracked region of the metal or alloy such that the nano-powder particles of the metal or alloy having surface charges are intensively deposited in the pitted or cracked region of the metal or alloy, thereby forming a uniform layer.
  • the electrical field may be used at 10-120 YU for 100- 1 ,500 sec. If the electrical field is less than 10 YU, it is difficult for the nano-metal colloid to have sufficient current density at the damaged or corroded region, and thus the nano-metal or alloy colloid is not efficiently induced to aggregate. On the other hand, if the electrical field exceeds 120 VtJ, the nano-metal or alloy colloid does not further aggregate, despite the application of the above electrical field.
  • the electrophoretic deposition process may be performed, for example, using an Ni or Ni alloy having a pitted or cracked region as a working electrode, a platinum electrode as a counter electrode, and a colloidal dispersion having Ni nano-powder particles dispersed therein as an electrolyte.
  • the electrophoretic deposition for the pitted or cracked region of the metal or alloy may be realized through lyosphere distortion.
  • a lyosphere distortion phenomenon in the particles of a double layer consisting of a van der Waals attractive component and an osmotic pressure component, polarization is decreased and thus van der Waals attraction dominates, whereby polarization induced between the particles leads to aggregation of the particles.
  • a heat treatment step may be further included. Through such heat treatment, mechanical strength may be additionally increased.
  • Ni metal plate having a locally damaged or corroded region in the surface
  • Ni metal plate having the locally damaged or corroded region was connected with a anode and Pt plate was connected with an cathode for electrophoretic deposition.
  • Ni metal plate which was immersed in the nano-nickel colloid, was treated with a predetermined electrical field of 20 Vtf using a PE 1649 DC power supply, available from Philips, Belgium, for 120 sec and 1200 sec, respectively, in order to subject it to electrophoretic deposition.
  • Ni metal plate was immersed in a 0.1 M NaCl solution at a potential of 0.9 V
  • the pitting process is categorized into the two stages: a decrease in anodic current density up to time necessary for pit embryo formation tpit, i.e., the first stage of passivation, an increase in anodic current density after tpit, i.e., the second stage of pit formation and growth.
  • the fall of current density in the first stage indicates the thickening of oxide film due to the repassivation process on the bare surface.
  • the increase in current density in the second stage is attributable to the film breakdown caused by the formation and growth of the stable pits.
  • d F.surf The surface fractal dimension characterizes the surface ir- regularity: the larger the value of d F,surf is, the more irregular and the rougher becomes the surface.
  • d 2 and 3 mean a perfectly flat surface and a very rough
  • Fig. 5(a-d) present the binary SEM images transformed from the digitized SEM images of pitted Ni metal specimens A, B, C and D, respectively.
  • the white portions that look bright are considered to be the pit of the specimen and dark portions are regarded as the outer surfaces of the specimen.
  • F.surf specimens were determined by using perimeter-area method.
  • the perimeter- area method is based upon the fact that the intersection of a plane with a self-affine fractal surface generates self-similar lakes. It is well known that area A and perimeter P of the self-similar lakes relate to their
  • Fig. 6(a-d) demonstrates on a logarithmic scale the dependence of perimeter P on area A of the pit obtained from the binary SEM images of specimens A, B, C and D, respectively, given in Fig. 5. For all the specimens, one can find clearly a linear relationship between log P and log A. From the slopes of the linear regions in Fig. 6(a-d), the values of d were estimated from Eqs. 1 and 2 to be 2.324, 2.264, 2.216
  • the deposition rate correspondingly becomes higher but the surface of the repaired pit consists of more agglomerates of Ni nano-particles. While, for smaller E, the deposition rate is correspondingly lower but the repaired pit exhibits a smoother surface with less agglomerates of Ni nano-particles. As a result, it is strongly suggested that the applied electric field is an important external parameter in controlling the electrophoretic deposition rate and the surface property of the repaired pit.
  • Fig. 7(b) demonstrates the plot of electrophoretic current I p against the d F,surf for four kinds of pitted specimens A (O), B( ⁇ ), C(D) and D(V) during electrophoretic deposition under E of 20 Vtf.
  • the value of I was determined by taking the current
  • the present invention provides a method of repairing pitting damage or cracks in metals or alloys using an electrophoretic deposition process.
  • the repair method of the present invention is advantageous because it has a short process time period, may be performed at low temperatures to thus have no influence on the microstructure of the metal around the pitting damage or cracks, and can form a continuous and dense bond to realize superior mechanical strength of the repaired structure. Consequently, the repair method of the invention can be efficiently used in repair techniques of various kinds of metal or alloy having diverse pits or cracks, therefore being industrially applicable.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

La présente invention concerne un procédé de réparation de la piqûration et des fissures des métaux ou alliages par dépôt électrophorétique de nanoparticules. Ce procédé comporte plus particulièrement les opérations suivantes. (a) On commence par préparer des particules de nano-poudre de métal ou d'alliage de même nature que le métal ou l'alliage piqué ou fissuré. (b) On ajoute les particules de nano-poudre du métal ou de l'alliage de (a) à un solvant organique contenant un dispersant, ce qui donne une dispersion colloïdale stabilisée. (c) On plonge le métal ou l'alliage piqué ou fissuré dans la dispersion colloïdale stabilisée de (b). Enfin, (d) on applique un champ électrique au métal ou à l'alliage piqué ou fissuré par l'intermédiaire d'un dépôt électrophorétique de façon à concentrer la densité de courant sur les zones piquées ou fissurées du métal ou de l'alliage, si bien que les particules de nano-poudre de métal ou d'alliage présentent des charges superficielles intensément déposées dans les zones piquées ou fissurées du métal ou de l'alliage, formant ainsi une couche uniforme. Par comparaison aux procédés conventionnels de réparation, le procédé de réparation de l'invention présente l'avantage de demander peu de temps de traitement, de pouvoir se faire à basses températures, de n'avoir aucune influence sur le métal autour des piqûres ou des fissures, et de pouvoir donner des liaisons continues et denses, ce qui confère à la structure réparée une résistance mécanique supérieure.
PCT/KR2007/001029 2006-09-09 2007-02-28 Procédé de réparation de la piqûration et des fissures des métaux ou alliages par dépôt électrophorétique de nanoparticules WO2008029979A1 (fr)

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KR1020060087101A KR100753909B1 (ko) 2006-09-09 2006-09-09 전기영동 보수기술을 이용한 금속 또는 합금의 결함 또는 균열 보수 방법
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Cited By (4)

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Publication number Priority date Publication date Assignee Title
CN104820002A (zh) * 2015-04-16 2015-08-05 山东大学 基于电化学检测装置的淬硬钢加工白层检测方法
WO2015114227A1 (fr) * 2014-01-29 2015-08-06 Snecma Procede de reparation localisee d'une barriere thermique endommagee
CN107604396A (zh) * 2017-10-30 2018-01-19 苏州阿罗米科技有限公司 一种水溶剂自修复压铸铝合金防腐处理的方法
CN116120487A (zh) * 2022-11-29 2023-05-16 广州工程技术职业学院 可碱性溶液分解的纳米颗粒、可自愈的聚丙烯酸盐复合材料及制备方法

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US6071051A (en) * 1991-08-28 2000-06-06 Louise A. Rollins Casting repair apparatus and method
US6605160B2 (en) * 2000-08-21 2003-08-12 Robert Frank Hoskin Repair of coatings and surfaces using reactive metals coating processes
US7094450B2 (en) * 2003-04-30 2006-08-22 General Electric Company Method for applying or repairing thermal barrier coatings

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JP3601572B2 (ja) 1996-07-17 2004-12-15 株式会社神戸製鋼所 耐久性に優れた連続鋳造用鋳型及びその製造方法
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US6071051A (en) * 1991-08-28 2000-06-06 Louise A. Rollins Casting repair apparatus and method
US5925228A (en) * 1997-01-09 1999-07-20 Sandia Corporation Electrophoretically active sol-gel processes to backfill, seal, and/or densify porous, flawed, and/or cracked coatings on electrically conductive material
US6605160B2 (en) * 2000-08-21 2003-08-12 Robert Frank Hoskin Repair of coatings and surfaces using reactive metals coating processes
US7094450B2 (en) * 2003-04-30 2006-08-22 General Electric Company Method for applying or repairing thermal barrier coatings

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015114227A1 (fr) * 2014-01-29 2015-08-06 Snecma Procede de reparation localisee d'une barriere thermique endommagee
US9840914B2 (en) 2014-01-29 2017-12-12 Safran Aircraft Engines Method for localised repair of a damaged thermal barrier
RU2678347C2 (ru) * 2014-01-29 2019-01-28 Сафран Эркрафт Энджинз Способ локального ремонта поврежденного теплового барьера
EP3789518A1 (fr) * 2014-01-29 2021-03-10 Safran Aircraft Engines Procede de reparation localisee d'une barriere thermique endommagee
CN104820002A (zh) * 2015-04-16 2015-08-05 山东大学 基于电化学检测装置的淬硬钢加工白层检测方法
CN107604396A (zh) * 2017-10-30 2018-01-19 苏州阿罗米科技有限公司 一种水溶剂自修复压铸铝合金防腐处理的方法
CN116120487A (zh) * 2022-11-29 2023-05-16 广州工程技术职业学院 可碱性溶液分解的纳米颗粒、可自愈的聚丙烯酸盐复合材料及制备方法

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