EP3140438B1 - 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 Download PDF

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Publication number
EP3140438B1
EP3140438B1 EP15726512.5A EP15726512A EP3140438B1 EP 3140438 B1 EP3140438 B1 EP 3140438B1 EP 15726512 A EP15726512 A EP 15726512A EP 3140438 B1 EP3140438 B1 EP 3140438B1
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EP
European Patent Office
Prior art keywords
zinc
voltage
pores
time interval
workpiece
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EP15726512.5A
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German (de)
English (en)
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EP3140438A1 (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
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Christian Albrechts Universitaet Kiel
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    • 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. But in addition to the cost of the primer usually additional work steps are 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.
  • trenches, pores or local elevations on the workpiece surface can be structures which can be penetrated, filled or surrounded by a flowable polymer or lacquer, so that the subsequently curing polymer or lacquer film is fixed as a result of mechanical anchoring.
  • PTFE polytetrafluoroethylene
  • 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 also 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 on finished parts - galvanizing with coating thicknesses in the range 50-150 micrometers - as well as on endless steel strips - strip galvanizing with coating thicknesses up to about 20 micrometers - applied. 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, whereby 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 object is achieved by providing a galvanized workpiece, which has polycrystalline zinc with particle sizes greater than 20 micrometers, at least on parts of the workpiece surface, characterized by irregularly distributed, penetrating into the zinc grains, different diameter, conical pores.
  • the subclaims are directed to advantageous embodiments of the galvanized workpiece and to a method for its production.
  • 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.
  • etching conditions can be found in which, firstly, the pore etching speed along a crystal axis differs approximately ten times from the etching speeds along a crystal axis - this can be termed the "fast etching direction" of the zinc grain secondly, crystal defects such as grain boundaries and dislocation nests are not preferentially etched.
  • the prior art knows deep, largely constant diameter in the micrometer range having channel-like or conical pores, for example, of monocrystalline semiconductors, in particular 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 fast etching direction is a property of the zinc grain, but can also be affected by the etching electrolyte. However, it is not readily foreseeable in any of the zinc grains which direction the fast etching direction will face.
  • zinc grains with different orientations and thus also a different direction of the rapid etching direction with respect to the workpiece surface form.
  • adjacent zinc grains have quite different crystal orientations in the finished zinc layer. Therefore, the fast etch directions with respect to the workpiece surface at quite different angles are also with respect to the surface of the workpiece. In particular, 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 of wide and deep as well as at the same time interspersed by less wide and less deep pores.
  • the depth to diameter ratio - also: aspect ratio - exceeds the value of 3
  • the pores penetrate so deeply into the grain, which is a part of the pore space of the zinc grain wall on which the pores attach, hidden.
  • 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. This is certainly the case with larger aspect ratios, preferably greater than about 10.
  • Hidden pore space undercuts the workpiece surface, thereby providing greater resistance to peeling, e.g. a polymer film, which is applied in liquid form to the galvanized workpiece, also penetrates into the pore space and then cured.
  • 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 in particular sets forces which are suitable for displacing the covering layer on the surface to be of 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.
  • 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 subsequent second time interval, the time period from the beginning of the first to the end of the second time interval being the period of the periodic square voltage.
  • the nucleation of the pores should preferably be done by applying a third voltage once for a third time interval before applying the periodic square wave 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. be achieved by extending the second time interval compared to the first time interval. In the case of large zinc grains, preferential etching of the grain boundaries plays a negligible role.
  • the specific etching parameters must be adapted and optimized to the specific zinc etch incident, but this is within the skill of the artisan and given him as necessary experimentation to find a favorable Is to expect working point. Usually, such tests are only to be carried out once for series production.
  • Fig. 1 shows the achieved pore structure.
  • Fig. 1 a It can be seen that the pores have been formed in a random distribution and with different pore diameters. Since all pores should become deeper and wider at the same time as the etch time increases, it can be assumed 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, shows Fig. 1 a) also a random distribution of pore density along the surface. Closely adjacent pores do not inevitably grow together, but can certainly interfere with each other in their broadening, as can be seen from the excerpt from the enlargement Fig. 1 b) can suspect. 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 in the metal. That is, on each free zinc metal surface quickly forms an oxide layer is inevitable and not further problematic. However, 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 cover layers.
  • the conical pores at any point should not traverse the entire thickness of the zinc coating, because this would both weaken the anti-corrosion effect of the zinc layer and possibly lead to the replacement of the galvanizing of the workpiece.
  • FIG. 2 a A look at the sectional sketch in Fig. 2 a) are intended to illustrate the particularly favorable effect of the generated pore structure for the anchoring of cover layers.
  • the workpiece 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 crystallites.
  • the sketch represents a cross section to the galvanized workpiece surface. In the individual crystallites are each juxtaposed several parallel pores (recesses) etched into it. The pore shape is different in each crystallite, resulting in pores in all directions along the galvanized surface. In every crystallite the Fig. 2 a) there is covered pore space.
  • the real pore structure of a zinc workpiece is in Fig. 2b ) shown in supervision. 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 crystallites with respect to the surface of the zinc workpiece.
  • FIG. 2c Figure 3 shows the photograph of an actual vertical section through the porous zinc foil described above.
  • This image is unexpectedly difficult to interpret, because you can barely make out the expected pore channels. This is due to the simple fact that it is very difficult to make the cut exactly along the fast etching direction of any zinc grain because it can not be determined beforehand.
  • monolithic semiconductors which typically cleave along certain planes, which afford a nice view of the etching geometry, are in Fig. 2c) at most difficult to identify small areas with pore walls of the etched pores in the image plane. Their parallel growth is, however, recognizable by the section.

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  • 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)

Claims (9)

  1. Pièce d'oeuvre zinguée qui présente, au moins sur des parties de la surface de la pièce d'oeuvre, du zinc polycristallin présentant des grosseurs de grain supérieures à 20 micromètres, caractérisée par des pores coniques répartis irrégulièrement, pénétrant dans les parois des grains de zinc et présentant des diamètres différents.
  2. Pièce d'oeuvre selon la revendication 1, caractérisée en ce que les pores, à l'intérieur d'un même grain de zinc, s'étendent parallèlement.
  3. Pièce d'oeuvre selon l'une des revendications précédentes, caractérisée en ce que les pores présentent un rapport profondeur sur diamètre d'au moins 3, de préférence d'au moins 10.
  4. Pièce d'oeuvre selon l'une des revendications précédentes, caractérisée en ce que les pores à la surface de la pièce d'oeuvre présentent des diamètres compris dans l'intervalle entre 100 nanomètres et 15 micromètres, de préférence dans l'intervalle entre 1 micromètre et 5 micromètres.
  5. Pièce d'oeuvre selon l'une des revendications précédentes, caractérisée en ce qu'au moins une partie de l'espace du pore gravé chimiquement dans les grains de zinc est couverte par les parois de grains de zinc formant la surface de la pièce d'oeuvre.
  6. Procédé pour fabriquer une pièce d'oeuvre zinguée selon l'une des revendications précédentes, caractérisé par une gravure électrochimique de la surface zinguée de la pièce d'oeuvre dans un électrolyte aqueux contenant du chlorure de potassium à une température prédéfinie avec application d'une tension rectangulaire périodique.
  7. Procédé selon la revendication 6, caractérisé en ce qu'une première tension est appliquée pendant un premier intervalle de temps et une deuxième tension est appliquée pendant un deuxième intervalle de temps situé immédiatement après, le laps de temps entre le début du premier intervalle de temps et la fin du deuxième intervalle de temps est la durée de la période de la tension rectangulaire périodique.
  8. Procédé selon l'une des revendications 6 ou 7, caractérisé en ce que la nucléation des pores est réalisée par application unique d'une troisième tension pendant un troisième intervalle de temps avant l'application de la tension rectangulaire périodique.
  9. Procédé selon l'une des revendications 6 à 8, caractérisé en ce que l'électrolyte contient 0,1 mol/litre de chlorure de potassium, la température prédéfinie est choisie autour de 50 °C, et la première tension est fixée à 0 V, la durée du premier intervalle de temps à 4,6 s, la deuxième tension à - 1 V, la durée du deuxième intervalle de temps à 0,8 s, la troisième tension à 0,5 V et la durée du troisième intervalle de temps à 1 s.
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 EP3140438A1 (fr) 2017-03-15
EP3140438B1 true EP3140438B1 (fr) 2018-06-06

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

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

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102018109531A1 (de) 2018-04-20 2019-10-24 Christian-Albrechts-Universität Zu Kiel Klebe-Fügevorrichtung sowie Klebe-Fügeverfahren für eine metallische Oberfläche
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

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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

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DE102014106276A1 (de) 2015-11-12
EP3140438A1 (fr) 2017-03-15
WO2015169278A1 (fr) 2015-11-12

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