EP3140438A1 - Pièce zinguée dotée d'une meilleure adhérence pour les couches de recouvrement - Google Patents

Pièce zinguée dotée d'une meilleure adhérence pour les couches de recouvrement

Info

Publication number
EP3140438A1
EP3140438A1 EP15726512.5A EP15726512A EP3140438A1 EP 3140438 A1 EP3140438 A1 EP 3140438A1 EP 15726512 A EP15726512 A EP 15726512A EP 3140438 A1 EP3140438 A1 EP 3140438A1
Authority
EP
European Patent Office
Prior art keywords
zinc
voltage
pores
workpiece
time interval
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.)
Granted
Application number
EP15726512.5A
Other languages
German (de)
English (en)
Other versions
EP3140438B1 (fr
Inventor
Mark-Daniel GERNGROSS
Jürgen CARSTENSEN
Rainer Adelung
Helmut FÖLL
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Christian Albrechts Universitaet Kiel
Original Assignee
Christian Albrechts Universitaet Kiel
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Christian Albrechts Universitaet Kiel filed Critical Christian Albrechts Universitaet Kiel
Publication of EP3140438A1 publication Critical patent/EP3140438A1/fr
Application granted granted Critical
Publication of EP3140438B1 publication Critical patent/EP3140438B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/02—Etching

Definitions

  • the invention relates to a galvanized workpiece having polycrystalline zinc at least on parts of the workpiece surface.
  • the invention further relates to a method for producing a galvanized workpiece with improved adhesion for cover layers.
  • the protective passivation layer has the disadvantage of reduced adhesion to polymers, paints or other metallic films to be applied as a cover layers on a galvanized workpiece surface.
  • Adhesion can be improved by providing adhesion promoting chemicals, either as a separate interlayer or as a component of the overcoat to be applied.
  • adhesion promoting chemicals either as a separate interlayer or as a component of the overcoat to be applied.
  • additional steps are usually required and the coating result is not always satisfactory. For example, delamination may occur over time when the thermal expansion coefficients of the workpiece and the paint are very different and the painted workpiece is subject to high temperature variations. It is generally known that a roughening of the metallic workpiece surface can be helpful in improving the adhesion of cover layers.
  • trenches, pores or local elevations on the workpiece surface can be structures which can be penetrated, filled or enclosed by a flowable polymer or lacquer, so that the subsequently curing polymer or lacquer film is fixed as a result of mechanical anchoring
  • a flowable polymer or lacquer so that the subsequently curing polymer or lacquer film is fixed as a result of mechanical anchoring
  • PTFE polytetrafluoroethylene
  • DE 181 1264 A1 (1968) reveals how a metallic piston of a cryogenic expansion device is coated with PTFE by electrochemically etching a large number of holes or grooves in a chromium layer initially deposited on the piston, so that the subsequently applied PTFE is at least these wells filled and mechanically anchored.
  • DE 1811264 A1 is concerned with a functional coating which is intended to reduce the friction of the piston and to prevent its tilting in the cylinder.
  • the etched chromium layer plays the role of a bonding agent.
  • contiguous network patterns of grooves are to be produced, as can be seen in FIGS. 6 and 7 of the document. It may be assumed that the deposited chromium layer is polycrystalline and that the grooves form by etching along the grain boundaries.
  • Intergranular etching of metal surfaces to improve the adhesion of polymers is also the subject of DE 601 28 364 T2, which moreover proposes an immersion plating step.
  • the galvanizing of a workpiece can be done by galvanic deposition, flame spraying or by dip coating in a molten zinc - also: hot dip galvanizing.
  • Dip coating is the most widely used industrial process for corrosion protection of steel. He will both Fierigieiie - piece galvanizing with coating thicknesses in the range 50-150 microns - as well as on endless steel belts - strip galvanizing with coating thicknesses up to about 20 micrometers - used. Strip-galvanized steel sheets are generally still cut after cutting, punched and formed, whereby the coating is damaged in places. It is therefore common to provide such galvanized workpieces with other cover layers, not least also to restore the corrosion protection.
  • galvanized workpiece is also used for such workpieces that attain their final shape only after being coated with zinc. It is only important that at least parts of their surface have a zinc layer.
  • the coating is a polycrystalline zinc layer on the workpiece surface, and the zinc crystallites can reach particle sizes of millimeters to centimeters.
  • the etching of depressions along the grain boundaries does not provide sufficient space for a robust anchoring of cover layers on the galvanized workpiece with very large particle sizes.
  • the invention therefore has the task of improving the adhesion of outer layers on galvanized workpieces.
  • the object is achieved by providing a galvanized workpiece which has at least on parts of the workpiece surface polycrystalline zinc with particle sizes greater than 20 microns, characterized by irregularly distributed, penetrating into the zinc grains, different diameter, conical pores.
  • a conical pore in the sense of the present invention is a pore whose pore diameter at the pore approach - on the workpiece surface - assumes a maximum and decreases monotonically towards the pore tip - in the interior of the zinc layer.
  • the pore diameter never increases with the etching depth, but it decreases or at best remains piecewise constant.
  • the structures according to the invention are not created by intergranular etching, but by etching into the zinc crystallites, including zinc grains.
  • the pores penetrate into the zinc grains and penetrate into the interior of the zinc grains.
  • the prior art knows deep, largely constant diameter in the micrometer range, kanai shame or conical pores, for example, monocrystalline semiconductors, especially silicon wafers. These so-called macropores can penetrate almost the entire wafer if, for example, they are electrochemically etched in n-type silicon from one wafer side, while the other wafer side is illuminated. The illumination serves to provide sufficient free charge carriers at the pore tips. By contrast, the pore walls are hardly etched because there are no free charge carriers available there. The pore wall stability is therefore most likely to be found in semiconductors and also not along arbitrary crystal axes.
  • the rapid etch directions with respect to the workpiece surface are also at different angles with respect to the surface of the workpiece.
  • the fast etching direction is almost never perpendicular to the workpiece surface.
  • the pore structure of the galvanized workpiece according to the invention thus typically comprises side by side in a random arrangement in the wall of the same zinc grain penetrating, parallel, conical pores, of which typically only a few are directed perpendicular to the workpiece surface.
  • the diameter of the pores which has its maximum at the pore approach and should preferably be in the interval between 100 nanometers and 15 microns, more preferably between 1 and 5 microns, varies along the wall of each individual zinc grain, ie each grain is both broad and deep as well as at the same time interspersed by less wide and less deep pores.
  • the pores penetrate into the grain so deeply that part of the pore space is obscured by the zinc grain wall where the pores are located.
  • the pore tip is no longer visible from the surface of the workpiece formed by the zinc grain walls because the pore has grown obliquely.
  • larger aspect ratios preferably greater than about 10.
  • the proportion of hidden pore space increases. Concealed pore space undercuts the workpiece surface and thus offers a greater resistance to the removal of, for example, a polymer film which is applied in liquid form to the galvanized workpiece, also penetrates into the pore space and then hardens.
  • the direction in which the pores undercut the workpiece surface varies from zinc grain to zinc grain.
  • a covering layer which is toothed with the zinc layer locally in different directions along the surface of the material opposes, in particular, forces which are suitable for displacing the covering layer on the surface to a greater resistance.
  • temperature-induced expansion changes of the workpiece relative to the cover layer at many points of the workpiece surface lead to increased adhesion of the cover layer, namely where the locally acting forces press the cover layer deeper into the hidden pore space.
  • the cover layer has barbs in practice, and these have local directions along the entire workpiece surface in each case in a direction dependent on the zinc grain present there.
  • FIG. 1 electron micrographs of a porous zinc foil in the
  • FIG. 2 a) Schematically vertical section through the porous Zinkfoüe, b)
  • the pore etching takes place in an electrochemical etching cell with a potassium chloride-containing, aqueous electrolyte.
  • the temperature is controlled and kept constant by a thermostat.
  • a square wave voltage is applied between the zinc layer and the electrode in the electrolyte, i. a temporal voltage curve, which is described by a rectangular function.
  • the square-wave voltage is periodic and preferably has a predetermined number of periods.
  • a first voltage is applied for a first time interval and a second voltage for an immediately following second ZestintervaM, wherein the time period from the beginning of the first to the end of the second time interval, the period of the periodic square wave voltage.
  • nucleation of the pores should preferably be done by applying a third voltage once for a third time interval before applying the periodic square voltage.
  • a polycrystalline, rolled, 100 micron thick zinc foil (Zn content 99.95%) is etched.
  • the electrolyte contains 0.1 mol / liter of potassium chloride.
  • the temperature is chosen to be 50 ° C.
  • the first voltage is 0 V
  • the length of the first time interval is 4.6 s
  • the second voltage is -1 V
  • the length of the second time interval is 0.8 s
  • the third voltage is 0.5 V
  • the length of the second third time interval has been determined to be 1 s.
  • the total etching time is 10 min.
  • the etching parameters must be adjusted so as to suppress preferential etching of the grain boundaries. This can e.g. can be achieved by extending the second time interval compared to the first time interval, in the case of large zinc grains preferential grain boundary concentration plays a negligible role.
  • Fig. 1 shows the obtained pore structure. From Fig. 1 a) it can be seen that the pores have been formed in random distribution and with different sized pore diameters. Since all pores should become deeper and wider at the same time with increasing etching time, one can assume that not all visible pores are nucleated at the same time, ie during the third time interval, but some may only be nucleated during any period of the subsequent square wave. However, Fig. 1 a) also shows a random distribution of the pore density along the surface. Closely adjacent pores do not inevitably grow together, but may well interfere with each other in their broadening, as can be assumed also on the basis of the enlarged detail in Fig. 1 b), in Fig.
  • the steps are subsequently simply wet-chemical with a weak acid, e.g. Citric acid, dissolve. They do not consist of zinc oxide, but of zinc metal, which is oxidized on its surface - by ambient air.
  • a weak acid e.g. Citric acid
  • They do not consist of zinc oxide, but of zinc metal, which is oxidized on its surface - by ambient air.
  • This is a useful distinguishing feature of the prior art. Namely, it is well known to etch in zinc surfaces by first oxidizing the zinc and then etching into the semiconductor zinc oxide. The zinc oxide can then be completely or partially removed with a weak acid, for example corresponding steps on the pore walls,
  • the etching is carried out directly into the metal, that an oxide layer forms rapidly on each free zinc metal surface inevitable and not further problematic.
  • through-oxidation of the zinc layer to a predetermined depth to propel the pores to that depth does not occur. It would also be counterproductive to practically remove zinc plating for this purpose.
  • pore depths of between about 3 and 50 microns appear sufficient to provide good anchorage of overcoat layers.
  • the conical pores should not traverse the entire thickness of the zinc coating at any point, since this would both weaken the anticorrosive effect of the zinc layer and possibly lead to detachment of the galvanizing from the workpiece.
  • a look at the sectional sketch in FIG. 2 a) is intended to illustrate the particularly favorable effect of the pore structure produced for the anchoring of cover layers.
  • At the bottom (black) is the workpiece with a layer of zinc arranged on top of it, which here is very much made up of three zinc crystals.
  • the sketch represents a cross-section to the galvanized workpiece surface. In each of the individual crystallites, a plurality of juxtaposed, parallel pores (recesses) are etched into each. The pore shape is oriented differently in each crystallite, so that along the galvanized surface pore courses in all possible directions, in each crystallite of Fig. 2 a) there is a hidden pore space.
  • the real pore structure of a zinc workpiece is shown in plan view in FIG. 2b). You can see many individual areas parallel to each other grown pores. The orientation of the pores with respect to the surface of the zinc workpiece is very different in adjacent regions depending on the orientation of the zinc crystals with respect to the surface of the zinc workpiece.
  • Fig. 2 (c) shows the recording of an actual vertical section through the porous zinc foil described above. This picture is unexpectedly difficult to interpret, because you can barely make out the expected pore pie. This is because of the simple fact that it is very difficult to make the cut exactly along the fast etch direction of any zinc grain because it can not be previously determined, unlike typical monolithic semiconductor fissile that can be split along certain planes allow the ⁇ tzgeometrie are in Fig. 2 c) at best with difficulty small areas with pore walls of the etched pores in the image plane to identify, but their parallel growth is recognizable by the section.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

L'invention concerne une pièce zinguée, qui présente, au moins sur des parties de la surface de la pièce, du zinc polycristallin présentant des grosseurs de grain supérieures à 20 µm, caractérisée par des pores coniques, répartis irrégulièrement, pénétrant dans les parois des grains de zinc, présentant des diamètres différents. En outre, l'invention concerne un procédé pour la production d'une pièce zinguée selon l'invention, caractérisée par une gravure électrochimique de la surface zinguée de la pièce dans un électrolyte aqueux contenant du chlorure de potassium à une température définie au préalable avec application d'une tension carrée périodique.
EP15726512.5A 2014-05-06 2015-04-08 Pièce zinguée dotée d'une meilleure adhérence pour les couches de recouvrement Active EP3140438B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102014106276.0A DE102014106276A1 (de) 2014-05-06 2014-05-06 Verzinktes Werkstück mit verbesserter Haftung für Deckschichten
PCT/DE2015/100150 WO2015169278A1 (fr) 2014-05-06 2015-04-08 Pièce zinguée dotée d'une meilleure adhérence pour les couches de recouvrement

Publications (2)

Publication Number Publication Date
EP3140438A1 true EP3140438A1 (fr) 2017-03-15
EP3140438B1 EP3140438B1 (fr) 2018-06-06

Family

ID=53276677

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15726512.5A Active EP3140438B1 (fr) 2014-05-06 2015-04-08 Pièce zinguée dotée d'une meilleure adhérence pour les couches de recouvrement

Country Status (3)

Country Link
EP (1) EP3140438B1 (fr)
DE (1) DE102014106276A1 (fr)
WO (1) WO2015169278A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019201395A1 (fr) 2018-04-20 2019-10-24 Christian-Albrechts-Universität Zu Kiel Dispositif d'assemblage par collage et procédé d'assemblage par collage d'une surface métallique

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102485014B1 (ko) * 2020-12-18 2023-01-04 주식회사 포스코 밀착성이 우수한 복합 강판 및 이의 제조방법
DE102024111115A1 (de) 2024-04-19 2025-10-23 Christian-Albrechts-Universität zu Kiel, Körperschaft des öffentlichen Rechts Gepulstes anodisches ätz-herstellungsverfahren von verzahnungsstrukturen auf oberflächen von kupfer und/oder kupferlegierungen, kupfer und/oder kupferlegierungen

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE370195C (de) * 1921-10-09 1923-02-28 Elek Scher Zuender G M B H Fab Verfahren, Metalle und duenne Metallbleche oder -folien, insbesondere solche aus Kupfer oder Zink, auf Faserstoffen klebfaehig zu machen
GB1202337A (en) 1967-11-27 1970-08-12 Tokyo Shibaura Electric Co A method of coating a metal body with a plastics material and a metal body coated with a plastics material
JPS5443463B2 (fr) * 1972-07-18 1979-12-20
US6506314B1 (en) 2000-07-27 2003-01-14 Atotech Deutschland Gmbh Adhesion of polymeric materials to metal surfaces
DE202006013555U1 (de) * 2006-09-01 2006-12-21 Zeschky Galvanik Gmbh & Co. Kg Schwenklager für Automobil-Vorderradaufhängungen

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019201395A1 (fr) 2018-04-20 2019-10-24 Christian-Albrechts-Universität Zu Kiel Dispositif d'assemblage par collage et procédé d'assemblage par collage d'une surface métallique
DE102018109531A1 (de) 2018-04-20 2019-10-24 Christian-Albrechts-Universität Zu Kiel Klebe-Fügevorrichtung sowie Klebe-Fügeverfahren für eine metallische Oberfläche
US12049708B2 (en) 2018-04-20 2024-07-30 Nascit Gmbh Adhesive joining device and adhesive joining method for a metal surface

Also Published As

Publication number Publication date
EP3140438B1 (fr) 2018-06-06
DE102014106276A1 (de) 2015-11-12
WO2015169278A1 (fr) 2015-11-12

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