WO2002097171A2 - Installation de traitement de surface de produits finis metalliques, en particulier d'aluminium, au moyen d'un effet plasma produit dans la couche helmotz d'un solvant dielectrique, transforme en conducteur par sa solution avec un acide dans une cellule electrochimique - Google Patents

Installation de traitement de surface de produits finis metalliques, en particulier d'aluminium, au moyen d'un effet plasma produit dans la couche helmotz d'un solvant dielectrique, transforme en conducteur par sa solution avec un acide dans une cellule electrochimique Download PDF

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Publication number
WO2002097171A2
WO2002097171A2 PCT/EP2002/005841 EP0205841W WO02097171A2 WO 2002097171 A2 WO2002097171 A2 WO 2002097171A2 EP 0205841 W EP0205841 W EP 0205841W WO 02097171 A2 WO02097171 A2 WO 02097171A2
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WO
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Prior art keywords
plant
surface treatment
metals according
previous
metals
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Application number
PCT/EP2002/005841
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English (en)
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WO2002097171A3 (fr
Inventor
Ines Urbani
Original Assignee
Ines Urbani
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Publication date
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Priority to AU2002312948A priority Critical patent/AU2002312948A1/en
Publication of WO2002097171A2 publication Critical patent/WO2002097171A2/fr
Publication of WO2002097171A3 publication Critical patent/WO2002097171A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/026—Anodisation with spark discharge
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/005—Apparatus specially adapted for electrolytic conversion coating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • C25D17/12—Shape or form

Definitions

  • the present invention relates to a plant for the use of a process for the surface treatment of aluminum or other metallic materials for making them resistant to the attack of atmospheric agents and for making their surface suitable for the anchorage of polymeric organic resin paints, or treatable with anodic oxidation.
  • These modifications on the metal surface called conversion layers normally have a protective nature and are formed either chemically or electrochemically.
  • the new technology proposed by the invention is capable of substituting traditional treatment baths without producing effluents which are harmful for the environment; it is economically advantageous, as it offers the possibility of substituting the different successive treatment phases, used in the present state of the art, with a single treatment.
  • the tanks have significant dimensions and volumes due to the length of the aluminum draw pieces to be treated (about eight meters) .
  • the volume, and therefore the quantities of the various chemical solutions introduced into the tanks depends on the total number of draw pieces treated contemporaneously in order to reduce the overall operating times per unit and consequently the industrial costs per production unit-time.
  • the properties of the chemical products and their combinations must be kept constant over a period of time.
  • the constancy of the baths quality is obtained by 5 its continual replacement, or by its partial or total substitution.
  • These quality integration processes of the baths are effected by means of complex systems connected to suitable process and composition analysis equipment which drives discharge and charging pumps and which ex- 10 tract from reserves of fresh solutions or chemical products.
  • the application of the invention is oriented towards the surface treatment of metals, in particular aluminum draw pieces for casings, in order to protect the surface from corrosion 20 and make it suitable for the anchorage of organic resin paints such as powder resins for electrostatic painting.
  • the treatment is normally carried out on the same line. 25.
  • the treatment plant can consist of a certain number of tanks containing appropriate baths for the horizontal type, or a tunnel subdivided into sections, for the vertical plant, in which the draw pieces are treated in the various sections with the spraying pressure, by means of pumps, of the various solutions through particular nozzles .
  • the treatment, for horizontal-type plants, is effected in tanks by the immersion of groups of rods hung on suspended tray conveyors, namely on particular frames, to which draw pieces are hung or baskets where the rods are placed at random: in the former case, as the rods are situated on frames suitable for effecting the painting, they are subsequently and automatically loaded onto the line itself; in the latter case, they must be manually assembled onto the frames of the painting line.
  • the vertical treatment carried out in a considerably long tunnel, takes place on line, with the outgoing draw pieces ready for the final painting after phospho- chromating or chromate treatment, analogous to that car- ried out for the horizontal painting.
  • the pre-established objectives of the invention are substantially: a) Surface treatment of a metal to make it resistant to oxidation attacks due to atmospheric agents . b) Surface preparation thereof to obtain surface anchorages for the organic resins with which it is painted. c) Reduction of the solutions for the treatment. d) Reduction in the number of tanks or abolition of the tunnel. e) A more compact plant. f) Lack of toxic residues in the baths. g) Simple use due to the control of the properties of a single solution. h) Reduction in the operating costs of the plant.
  • a non-limiting example, according to the invention, is to apply the invention for surface treatment to an electrostatic powder painting plant of aluminum draw pieces.
  • Table 1 figures 1 to 3, example of the formation process of conductive cavities inside a dielectric liquid under the force of an electric field, and the generation of plasma in the same cavities.
  • Table 2 figure 4, a cross-section view of the invention (treatment tank), applied to a vertical painting plant.
  • Table 3 figures 5 and 6, a cross-section view of the treatment tank, explaining the effects due to the current passing through the electrodes.
  • Table 4 figures 7 and 8, functioning views of the cell in two successive phases.
  • Table 5 figures 9 and 10 cross-section view of the tank with the upward and downward movement of the frames carrying the draw pieces .
  • Table 6 figures 11, 12, 13, example and applicative pro- cedure of the invention in a horizontal painting plant.
  • Table 1 figure 14, plan view of a normal vertical treatment and painting plant.
  • Table 8 figure 15, plan view of a painting plant in which the invention is applied for comparison with the traditional plant of Table 7.
  • the plant and process of the invention have the object of advantageously reducing both the times and number of treatment tanks or, in our case, the complete substitution of the tunnel, exploiting a particular electrolytic cell where aluminum draw pieces are situated at the anode and the cathode is made of an inert material.
  • a galvanic cell As it is known in electrochemistry, a galvanic cell, Table 1, figure 1, filled with a dielectric solvent, which is in a low percentage solution with a conductor liquid, causes a stratified arrangement (27) of the molecules of the dielectric solvent itself, also called Hel- motz layer, from the name of the scientist who studied the properties.
  • This layer is defined as a polarizable virtual electrode, if it does not allow any charge transfer through the interface layer between the metal (37) which forms another electrode and the solution (31) contained in the cell.
  • the interface between the polari- zable solution (27) and the metal of the electrode (37) functions as the dielectric of a condenser.
  • the charge on the two metallic armatures is due to an excess or lack of electrons, whereas the charge of the solution is due to an excess of anions and cations near the surface itself of the electrodes .
  • the whole arrangement of electric charges and ori- ented dipoles, existing at the dielectric interface (27) between solution and metal, can be compared to a double layer of charges: the first, the polarizable dielectric layer (27) , the second, made up of free charges (28), (29) in the solution (31) .
  • the layer nearest to the metal (37) is made up of molecules of the dielectric solvent and sometimes of other chemical species such as ions or molecules absorbed by the solvent itself.
  • a virtual dielectric electrode (27) made up of polarized dipoles
  • a further objective of the invention is therefore to allow this physical effect to be applied to a surface treatment process of a metal, advantageously exploiting firstly the confinement of the conduction current as plasma through the micro-cavities and subsequently the normal physico-chemical processes which take place in an electrochemical cell.
  • the ionic species in the solute and free electrons therein subject to the electric field established in the electrodes acquire energy very rapidly and transfer it to other species present in the solute by means of collisions.
  • the density of the solute would imply an average short free run, from the electric charges, before a col- lision to discharge energy.
  • the electric field has extremely high values: for example in the case of 100 Angstrom it can have a value of 100 million volts for each volt of external electromotive force established, in the non-conductive dielectric.
  • the acceleration as a result of the electric charges from the electric field in this interface, compels a large quantity of charges to passage within the time unit and consequently guarantee a high conduction current of this plasma (consisting of ions, radicals and electrons) confined in the micro-channels.
  • the various species present in the discharge interact with the surface of the target electrode. These reactions depend on the energy distribution of this plasma. Typical reactions are dissociation of molecules absorbed, expulsion of atoms from the surface of the electrode.
  • the surface of the electrode can absorb neutral species by means of chemical bonds with the substrate.
  • the formation of the plasma also gives rise to the formation of atoms and radicals capable of chemically interacting with the surface to form volatile products.
  • the vari- ous ionic species present in the solution can interact with the surface of the electrode by electrolytic effect.
  • oxygen molecules are capable of removing organic substances from aluminum by means of oxi- dation due to the gas ions forming, in turn, volatile compounds such as carbon monoxide, carbon dioxide, water. This type of effect also induces the growth of layers of oxide on the metal surface, anti-corrosion and anchorage layers, activating it and increasing its wet- tability.
  • FIG 4 the aluminum draw pieces (15) are hung on a frame device (19), known device with a frame shape, used for the treatment of draw pieces and their painting, by means of a low resistivity hook (14), connected to the frame itself.
  • the cell (1), Table 2, figure (4) has a depth higher than the length of the draw pieces to be treated, whose length is 6.5-7 me- ters with a width suitable for forming a volume in order to contain the treatment solution necessary for the process.
  • the cell from a constructive point of view, is almost totally englobed in the floor of the area where the treatment is to be effected, complicated upward move- ments of the draw pieces along the painting line can be avoided.
  • a partial detecting system of the overall transverse surface of the draw pieces consisting of an emitter (12) and a receiver (13), which, by indicating the occlusion surface due to the draw pieces (15), are capable of driving the extraction or immersion of the electrode, cathode (3) , in order to supply, with its surface immersed, the necessary current density per square decimeter of the anodes surface in order to guarantee the uniformity of the process changing the exposed surf ce .
  • shield electrodes Underneath the electrodes (3), separated by an insulating septum (4), there are other electrodes (5) called shield electrodes, which can be connected either to the mass line of the generator (30) or to the active line by means of a high impedance connection, in order to have an electric voltage thereon equal to that of the cathodes (3), other draw piece guide devices (6).
  • the cell When the cell has been filled to a suitable level (2) with the solution selected, for example a solution of de ineralized water and phosphoric acid, it can be initially heated, by means of the electric resistance (17) immersed therein, to help the reachment of an initial temperature of the solution for increasing the Joule effect due, as previously described, to the pressure of the electric field in the dielectric layer.
  • the solution selected for example a solution of de ineralized water and phosphoric acid
  • the heating of the solution thus allows the pressure of the electric field to be advantageously lowered, i.e. the electric voltage supplied to the electrodes (3) and (15) by means of the electromotive force generator (30) to start the formation of the channels of plasma.
  • the suction hoods (18) are activated by means of the fans (10) to eliminate the dispersion of vapours which are formed during the process.
  • the process is applied progressively, during immersion, on a reduced surface zone of the anode (15) and the dispersion current in the bath itself is limited.
  • the electrodes (3) are selected with a minimum surface directed towards the anode and therefore, as is known in physics, with an intense quantity of electric charge per surface unit, with the same voltage applied.
  • electrodes (5) have been advantageously added, which are symmetrical with re- spect to the anodes (15), Table 2, figure 4. If these are connected to the same electric pole as the anodes (15) , they will deviate part of the cathode current to themselves thus preventing surface dispersion along the same immersed anodes (15) .
  • the deviation effect of the current lines (26) of the new electrodes (5) is schematically represented in Table 3, figure 6.
  • the process and plant of the invention allow a surface anodic oxidation of 3-4 microns to be effected, always operating in the same tank, with rapid times compatible with the velocity, in metres per minute, of the draw pieces towards the painting zone.
  • Table 4 illustrates the final configuration of the process with the draw pieces (15) completely immersed in the electrolyte of the cell (1) , with the uniform passage of the current between the electrodes represented by the crossed area (24) , to obtain an increase in the surface oxidation with open oxide pores for anchorage of the paint.
  • the frame is lifted and the washing water sprays (9) can start functioning, when necessary, Table 2, figure 4 for rinsing any possible acid residues remaining on the surface of the aluminum, in our case only phosphates, as phosphoric acid is used in the solution.
  • figure 9 shows a constructive possibility of the moving system of the frames (19) , hung onto the rail of the aerial conveyor (41) , for being immersed or extracted from the tank (1), where the number of the various devices refer to Table 2, figure 4.
  • the conveyor must move the frames across the painting plant, passing them through the various process phases: loading zone of the draw pieces onto the frames, pre- treatment tunnel, drying tunnel, electrostatic powder painting compartment, passage in the paint polymerization oven, unloading zone of the end-product.
  • figure 9 illustrates an arm (40), moved by a motor (42) which, advancing, de- taches the frame from the rail (41) , positioning it in the centre of the treatment tank (1) .
  • the motor (39) by descending along a rack (43) , subsequently moves the arm (40) supporting the frame with the draw pieces (15) inside the tank, the final position illustrated in figure 10 of the same table.
  • Table 6 briefly examines the case of the application of the invention to a horizontal painting plant, where with the necessary geometrical change positions of the specified elements in the cell
  • Table 6 schematically represents, in section, the electrolytic cell (60), object of the invention, in which the above process is analogously effected.
  • Two traditional ascending and descending mechanisms (79) and (75) consisting of two extendable arms (55) , running along the racks (80), can take and remove the frame (58) from the rail of the conveyor (41) .
  • a descending command is given to the mechanisms so that the frame carrying the aluminum draw pieces to be treated is immersed in the cell (60) in the position rep- resented by figure 11: i.e. with an inclination of about ten degrees.
  • Two trolleys (56) run symmetrically on the upper longer edges (57) of the tank (60) . (In the view, only the trolley behind the frame carrying the draw pieces, is represented) .
  • These trolleys (56) in turn, carry the electrodes (62), (63), (66) which, instead of being perpendicular with respect to the frame contained therein, are inclined towards the running direction of the trolley and fixed at the lower part to an insulating support (64) .
  • the electrode (63) acts as a cathode, whereas the electrodes (62), (64) act as a shield as described above .
  • the plate (61) represents the electrode for effecting an anodic oxidation at the end of the first plasma effect process for the surface treatment of aluminum draw pieces.
  • FIG. 12 schematically represents the situation in which a draw piece (73), in section, between the cathodes (63) is surrounded by the formation of gas bubbles (68), (69), (70).
  • the bubbles (69), (70), generated on the lateral sides of the draw piece rise towards the surface of the solution (59), whereas the bubbles (68), generated in the cavities of the draw piece, can remain inside.
  • the draw pieces (73) are slanted so that the bubbles (74) can run inside, fol- lowing the direction of the arrows (71), exit from the ends (76) and rise to the surface as bubbles (72) .
  • Figure 11 represents the overall effect of the formation of gas bubbles (77), (78) on the surface of the draw pieces (67), hung onto the frame (58).
  • the negative interference of these bubbles on the process of the invention is evident.
  • This problem can be solved by a simple geometrical repositioning of the electrodes (62), (63), (66): as can be seen from the same figure 11, the inclination of the group of electrodes (62), (63), (66), is advantageous as the gas bubbles generated on the surface of the draw piece situated lower down, do not interfere with the operating surface of the subsequent draw piece.
  • Table 6 in fact, the columns of bub- bles (78), (77), generated on two adjacent draw pieces are separate. As can be seen from the figure, the column (78) generated on the lowest draw piece, does not interfere with the operating zone of the cathodes of that immediately above.
  • Tables 7 and 8 show the constructive differences and advantages with respect to the space occupied by the two painting plants: Table 7 is a traditional plant using phosphocro- mating as pretreatment, Table 8 is a plant which uses the invention for the process described on line.
  • the two plants are drawn with the same scale, the parts common to both such as the drying tunnel and polym- erization oven are of the same size.
  • the pretreatment zone in the tunnel (48), figure 11.
  • the recovery tanks (49) of the treatment liquids blocks of pumps (50) for pumping the baths to the sprayers (51) , to effect the treatment, inside the tunnel (48) .
  • the drying oven (46) painting boot (54) with powder recovery cyclones (52) and subsequently the polymerization oven (45) .
  • the plant proposes, initially, a limited loading zone (53) of the draw pieces to the conveyor (41), Table 8, figure 15.
  • the treatment only consists of the tank (1), with the ascending and descending system composed of the arms (40) which move as described along a rack (43) , of the single integration tank of the baths (49) , of the same drying oven (46), of the same painting compartment (54), of the polymerization oven (45) and of the reduced un- loading zone (44) .

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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)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Catalysts (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

Dans le domaine industriel du traitement de surface de métaux, ladite surface doit être préparée au moyen de processus physico-chimiques, de façon à être résistante à la corrosion induite par des agents ou des processus atmosphériques activés par des effets électrolytiques. Cette surface doit également être préparée de façon que des finitions particulières, telles que des peintures, présentent un très bon accrochage. Ces processus sont notamment orientés vers des produits finis en aluminium. Dans ce domaine, il est nécessaire de mettre au point de nouveaux systèmes permettant de simplifier et de réduire les coûts des processus complexes mis en oeuvre et d'améliorer la protection de la surface par rapport à la corrosion. La présente invention concerne une cellule électrochimique simple et unique, qui sert de substitut aux systèmes actuels. Dans cette cellule électrochimique, un plasma gazeux servant à la préparation de surface requise du métal est produit dans un solvant diélectrique et une légère oxydation anodique à pores ouverts permettant à la fois une protection anticorrosion et un accrochage de peintures polymères a également lieu dans cette même cellule électrochimique.
PCT/EP2002/005841 2001-05-30 2002-05-28 Installation de traitement de surface de produits finis metalliques, en particulier d'aluminium, au moyen d'un effet plasma produit dans la couche helmotz d'un solvant dielectrique, transforme en conducteur par sa solution avec un acide dans une cellule electrochimique WO2002097171A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002312948A AU2002312948A1 (en) 2001-05-30 2002-05-28 Plant for the surface treatment of metallic end-products, in particular aluminum, by means of a plasma effect generated in the so-called helmotz layer of a dielectric solvent, changed into a conductor by its solution with an acid in an electrochemical cell

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT2001MI001141 IT1325556B (it) 2001-05-30 2001-05-30 Impianto per il trattamento superficiale di manufatti metallici, in particolare di alluminio, per mezzo di un effetto plasma generato nel co
ITMI2001A001141 2001-05-30

Publications (2)

Publication Number Publication Date
WO2002097171A2 true WO2002097171A2 (fr) 2002-12-05
WO2002097171A3 WO2002097171A3 (fr) 2005-08-04

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AU (1) AU2002312948A1 (fr)
IT (1) IT1325556B (fr)
WO (1) WO2002097171A2 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD151331A1 (de) * 1980-06-03 1981-10-14 Peter Kurze Verfahren zur herstellung modifizierter oxidschichten
JPH03162600A (ja) * 1989-11-21 1991-07-12 Arumetsuku:Kk アルミ型材の縦吊り表面処理設備
JPH05263288A (ja) * 1992-03-18 1993-10-12 Fujitsu Ltd 電気めっき方法
JPH07228992A (ja) * 1994-02-15 1995-08-29 Casio Comput Co Ltd メッキ方法およびその装置
DE19539866A1 (de) * 1995-10-26 1997-04-30 Lea Ronal Gmbh Vorrichtung zur chemischen oder elektrolytischen Oberflächenbehandlung plattenförmiger Gegenstände
JPH09157897A (ja) * 1995-12-01 1997-06-17 Casio Comput Co Ltd 電気メッキ方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5481134A (en) * 1977-12-12 1979-06-28 Fuji Photo Film Co Ltd Anodic oxidation device

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD151331A1 (de) * 1980-06-03 1981-10-14 Peter Kurze Verfahren zur herstellung modifizierter oxidschichten
JPH03162600A (ja) * 1989-11-21 1991-07-12 Arumetsuku:Kk アルミ型材の縦吊り表面処理設備
JPH05263288A (ja) * 1992-03-18 1993-10-12 Fujitsu Ltd 電気めっき方法
JPH07228992A (ja) * 1994-02-15 1995-08-29 Casio Comput Co Ltd メッキ方法およびその装置
DE19539866A1 (de) * 1995-10-26 1997-04-30 Lea Ronal Gmbh Vorrichtung zur chemischen oder elektrolytischen Oberflächenbehandlung plattenförmiger Gegenstände
JPH09157897A (ja) * 1995-12-01 1997-06-17 Casio Comput Co Ltd 電気メッキ方法

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch, Week 197932 Derwent Publications Ltd., London, GB; Class M11, AN 1979-58877B XP002329754 -& JP 54 081134 A (FUJI PHOTO FILM CO LTD) 28 June 1979 (1979-06-28) *
PATENT ABSTRACTS OF JAPAN vol. 015, no. 398 (C-0874), 9 October 1991 (1991-10-09) & JP 03 162600 A (ARUMETSUKU:KK), 12 July 1991 (1991-07-12) *
PATENT ABSTRACTS OF JAPAN vol. 018, no. 040 (C-1155), 21 January 1994 (1994-01-21) & JP 05 263288 A (FUJITSU LTD), 12 October 1993 (1993-10-12) *
PATENT ABSTRACTS OF JAPAN vol. 1995, no. 11, 26 December 1995 (1995-12-26) -& JP 07 228992 A (CASIO COMPUT CO LTD), 29 August 1995 (1995-08-29) *
PATENT ABSTRACTS OF JAPAN vol. 1997, no. 10, 31 October 1997 (1997-10-31) & JP 09 157897 A (CASIO COMPUT CO LTD), 17 June 1997 (1997-06-17) *

Also Published As

Publication number Publication date
WO2002097171A3 (fr) 2005-08-04
ITMI20011141A1 (it) 2002-11-30
IT1325556B (it) 2004-12-13
AU2002312948A1 (en) 2002-12-09
AU2002312948A8 (en) 2005-11-17
ITMI20011141A0 (it) 2001-05-30

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