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    • 专利摘要:
    Process and plant for continuous chromium-plating of metal bars, tubular elements and the like, in which the bar to be chrome-plated is advanced rapidly in a chromium-free device without a chromium-plating tank comprising several chromium-plated tubular-torx anode cells, in the which is made to flow a high current density electrolytic solution, to form a multilayer chromium deposit on the bar while the bar advances through the cell anodes themselves, and in which the device is characterized by the feeding of the electrolytic solution with an axially distributed flow and circulation of the electrolyte in turbulent mode, controlled through the chromium-plated anode, said plant further comprising several stations for cooling the bar by means of jets of liquid with a cryoscopic thermal jump. The seal of the bathroom is guaranteed by plastic gaskets reinforced by harmonic steel springs. The system is characterized by the fact that it is built with materials (titanium) and techniques suitable for the use of trivalent chromium in place of hexavalent chromium according to REACH directives. The plant produces a closed cycle with low energy consumption, due to the exceptional faradic yield.
    公开号:CH710741A2
    申请号:CH00371/15
    申请日:2015-03-17
    公开日:2016-08-15
    发明作者:Angelini Giorgio
    申请人:Acrom S A；
    IPC主号:
    专利说明:

    [0001] The present invention relates to the deposition of thick hard chromium on elongated metal pieces such as bars, by electrolytic deposition of trivalent chromium instead of hexavalent chromium.
    [0002] More particularly, the present invention relates to a continuous chromium-plating process with forced circulation, in turbulent motion, of an electrolytic solution of trivalent chromium, inside annular anodes while the metal pieces are made to advance inside of them.
    [0003] Chrome plating is a chrome coating on an iron or steel product to protect it from corrosion, giving it a high resistance to abrasion thanks to the high hardness of the electro-deposited chrome.
    [0004] These chromium plating properties depend essentially on the number of "micro-cracks" in a given distance. In general, a structure with a high density of cracks is desirable as it tends to have less stress, greater lubricating power, good wear resistance and better corrosion resistance.
    [0005] Furthermore, the non-correspondence of the slits provides greater protection against corrosion, and a lower permeability of the fill, because the probability of correspondence of micro slits between each layer of chromium tends to zero.
    [0006] To obtain the non-correspondence of the cracks and a lower permeability of the deposit s i resort to the deposition of more overlapping deposits or multilayer chrome plating.
    [0007] Currently the multilayer chrome plating of metal bars is carried out by means of various continuous processes which use hexavalent chromium.
    [0008] Said processes can be of the static type where the electrolytic solution is placed in a tank in which the pieces to be chromed are immersed, or of the dynamic type where the continuous circulation of the electrolytic solution within one or more is provided more annular anodes in which the bars to be chromated which act as cathodes are continuously passed.
    [0009] An example of the latter type of process is reported in patent application MI 98 A 002 595, which provides for the use in series of particular perforated anodes through which the electrolytic solution is fed, axially with respect to the bar forward, dynamically and with non-turbulent motions. In this patent application it is said that thanks to this type of power supply and this type of electrodes, it is possible to use a current density of around 300 Ampere / dm <2>.
    [0010] The anode used in the aforementioned implant is of the annular type, drilled along the crown with three series of holes that determine, intentionally, a surrounding environment (electrolytic solution) calm.
    [0011] However tests carried out by the Applicant have shown that it is only the first anode to work at such high current densities, while in the second and third anodes the galvanic process is not activated at the indicated current densities, except for lower current densities , from 300 to 70 Ampere / dm <2>.
    [0012] The Applicant has in fact found that if a current density of at least 300 Ampere / dm <2> is used on all three anodes, made of lead as in other processes using hexavalent chromium, and operating in a cell of plating in lead, after only one month of work there is the deformation of the anode due to the strong heat generated by the high current density, with the risk of short circuits between the anode and cathode (bar), while to work simultaneously with the three anodes in series it is necessary to use a low current density equal to 50 Ampere / dm <2>: this obviously involves a considerable productive disadvantage in that lower current densities imply low speed of advancement of the bar through the chromium-plated anode in order to have a certain deposit thickness, thus slowing down the working speed. The production difference between the use of an anode instead of three anodes, as you can imagine, involves a reduction in the industrial efficiency of 66%.
    [0013] Furthermore, the process described in the aforementioned patent application, as indeed the other known processes, is based on the use of an electrolytic solution of hexavalent chromium which, if on the one hand determines good chromium-plating results, on the other represents a considerable environmental pollutant.
    [0014] In the field of continuous chromium plating, the need to find a hard chromium deposition process which is efficient from the point of view of industrial productivity and which at the same time eliminates the use of hexavalent chromium so as to have a high environmental sustainability.
    [0015] In particular, many national legislations (REACH and EPA) established 2017 as a deadline within which to ban chromium trioxide, even if the legislators could grant an extension of the use for a certain time against significant fiscal and imposing fiscal impositions volume reductions.
    [0016] Trivalent chromium is currently used in some decorative chromium-plating processes where the deposition of thin chromium films (<1 micron) is expected, while to date, as far as is known to the Applicant, it has not been possible to make hard chrome deposits (thickness around 50–60 microns) of quality.
    [0017] The object of the present invention is to overcome, at least in part, the disadvantages of the prior art by providing a process and a plant capable of operating with high current densities, high industrial productivity but low environmental impact.
    [0018] This and other objects are achieved by the plant according to the invention having the characteristics listed in the appended independent claim 1.
    [0019] Advantageous embodiments of the invention appear from the dependent claims.
    [0020] One object of the present invention relates to the use, to obtain thick hard chromium deposits on elongated metal pieces such as bars, of an electrolytic solution of Cr for the electrolytic deposition of chromium, circulating forcibly in turbulent regime in at least one platinate, highly perforated or microperforated titanium anode such as a mesh or a micro-perforated net, in place of lead-perforated anodes. With "titanioplatinato" here we intend to identify any type of platinatura that can be made on titanium, including platinatura with Niobium or other noble metals.
    [0021] The Applicant has found that the aforementioned replacement of the drilled anodes in lead with those in highly perforated platinum titanium allows all three anodes of a plant such as that of MI 98 A 002 595 to work, even at a current density of at least 300 Ampere / dm <2>.
    [0022] Furthermore, on platinized titanium anodes the spontaneous oxidation of Cr <3+> does not take place: it is in fact known that in conventional processes based on hexavalent chromium, the anode consists of lead or its alloys with Sn or Sb , in addition to oxidizing anodically to lead dioxide (polluting mud), it determines the oxidation to chromic acid (Cr <6+>) of the Cr <3+> ions produced at the cathode, which is necessary to maintain the Cr <3 ions +> within certain values to obtain an optimal deposit.
    [0023] In practice it is envisaged to use a bath based on trivalent chromium and fluorine catalysts in combination with insoluble anodes, capable of maintaining an electrode potential which prevents the oxidation of Cr <3> <+>.
    [0024] Furthermore, in the processes known as that of MI 98 A 002 595, when anodes with small dimensions are consequently used having a small area, if the anodic current density becomes large, the trivalent chromium reoxidation takes place at low current efficiency. so that the amount of Cr <3+> in the electrolyte gradually increases by oxidation, compromising the optimal deposit. This happens because the anode is covered with a layer of lead dioxide: if this film does not form, a layer of lead chromate appears in its place, which has the characteristic of not allowing re-oxidation of trivalent chromium.
    [0025] Platinized titanium anodes offer a number of advantages, including reducing the environmental impact (Pb is toxic), excellent work possibilities with high current densities and therefore high penetrating power.
    [0026] In fact, since the platinised titanium anodes can withstand much higher current densities than the known lead anodes, it is possible to work with high current densities necessary to obtain a greater penetrating power of the chrome plating baths.
    [0027] Furthermore, since the anodes in platinum titanium do not alter in the geometric form at high current densities, unlike the known anodes in lead, the cathode / node distance does not vary, thus allowing to reduce the anode / cathode space without problems of short circuit, thus causing a greater uniformity of deposit.
    [0028] With the baths containing fluorine catalysts, a better use of niobium platinized anodes has occurred.
    [0029] A further advantage of the use of platinised titanium anodes lies in the fact that the greater surface density of holes due to their being in micro-perforated or knitted, allows a greater expulsion of hydrogen, which is produced in large quantities when operating at high current density, thus not requiring the dehydrogenation phase normally envisaged.
    [0030] The high production of hydrogen in the chromium-plating process is due to the secondary reaction to the cathode, which also causes the production of a solution aerosol which causes an absorption of hydrogen both in the deposit and in the base metal, producing tensioning in the chromed products which therefore require a supplementary dehydrogenation process (steel decarburization), no longer necessary in the present process according to the invention.
    [0031] Furthermore, the expulsion of hydrogen is further facilitated by the fact that the use of the aforementioned platinised titanium anode is preferably provided in combination with the circulation in a turbulent regime of the electrolytic solution based on Chromium (III).
    [0032] In fact, since strong current densities determine an immediate rise in the temperature of the bath on which the efficiency and the deposition rate depend, it is clear how important the control of the bath temperature is: the Applicant has found that, contrary to what stated in MI 98 A 002 595, a circulation with strong whirling motions of the solution inside the perforated electrode contributes to a regular deposition of chromium thanks to the turbulent motion of the electrolytic solution which generates an effective cooling for the increase of the heat exchange, with the consequent decrease and regulation of the temperature.
    [0033] The tests carried out by the Applicant, operating with a current density of 250 A / dm <2>, have shown that a circulation speed of the electrolyte of 5 m / s is adequate, even if a circulation speed of the electrolyte of at least about 2 m / s can be used, at a temperature of 50 ° C.
    [0034] The aforementioned speeds are about six times higher than those obtained in conventional or traditional apparatus which limit the use of currents with a density of 50 A / dm <2> against 300 A / dm <2> of the new technique.
    [0035] The Applicant has found that the performances mentioned in the patent MI 98 A 002 595 cannot be reached due to the failure to control the temperature: in fact the "train" of bars on which the in-line current is applied overheats due to the Joule effect and, the cooling exclusively by air is insufficient to quickly dissipate the heat so as to reach a temperature of about 50 ° C, except for an unacceptable drop in the performance of the system.
    [0036] Furthermore the forced circulation of the electrolyte favors the reduction of the anode-cathode distance, thanks to the rapid cooling operated, which consequently determines the lowering of the omnic resistance in the interface.
    [0037] Without wishing to be bound by any theory, it is likely that turbulent motion causes an intense bombardment of the coating in the growth phase due to collisions of chromium ions or process vapors: this bombardment would seem to undermine the not perfectly adhered molecules from the coating and mechanically compact the coating as a whole, favoring the formation of adherent and defect-free coatings.
    [0038] As a suitable solution based on trivalent chromium, suitable for the replacement of those based on hexavalent chromium, it is possible to mention, for example, a solution containing 300 g / l of Cr <+3> catalytic fluoride, for example a solution of 300g / l of Cr <+3> to which catalyst is added to the sodium fluoroaluminate (Na3AIF6 - cryolite) in the concentration of about 1.5% by weight over small amounts of salts such as strontium sulfate (SrS04) and fluosilicate of potassium. These salts, which act as catalysts, have a solubility in chromic acid such as to provide a concentration of sulfuric and hydrofluoric ions corresponding to the ideal one for the deposition of chromium. It must be kept in mind that the solubility of these salts is a function of the temperature and the concentration of the chromic acid: these two parameters can vary in a defined interval but sufficiently wide for a successful electrodeposition. Due to these characteristics, these self-regulating baths are called SRHR (self regulating high speed). All this is not binding for the purposes of the present invention and therefore other baths based on chromium (III) can be used.
    [0039] It should be noted that in order to maintain the correct concentration of trivalent chromium (III) in the electrolyte formed at the cathode, and overcome the inability of the platinized titanium anodes to reoxidize the trivalent chromium due to their low anodic potential , one or more sacrificial anodes in lead tin antimony (Pb-Sn-Sb) have been provided upstream of the chromium-plating cells, flanked by an independent rectifier which operates with low current (50 A / dm <2>) to allow the chemical precipitation of hydroxide ions that allows the dissolution of the sacrificial anode in Pb due to the application of the electric current, while the adsorption of lead peroxide occurs in situ. The application of the body, in fact, generates the formation of hydroxide ions at the sacrificial anode and the development of hydrogen gas at the cathode.
    [0040] The hydroxide ions activate the anodic oxidation process of lead dioxide and excite the platinized titanium anodes placed downstream, favoring electrolysis. A small amount of lead added to the electrolyte is deposited on the platinized titanium anode as lead peroxide (Pb02) and the latter catalyzes the oxidation of Cr <3> <+> to chromic acid.
    [0041] In fact the application of high density electric current to the sacrificial anode allows its dissolution (Pb + 2H20 → Pb02 + 4H + + 4e).
    [0042] It should be noted that for each current density there is an optimal temperature for chromium deposition: at high temperatures, increasing the current density produces an increase in hardness, while at low temperatures increasing the current density it diminishes considerably.
    [0043] Example of electrolysis conditions which have allowed to obtain deposits of hard chromium at a good quality thickness, using anodes in platinum titanium, turbulent motion and trivalent chromium, are preferably the following:<tb> bath temperature <SEP> 50–60 ° C<tb> current density from <SEP> 200 to ≤ 500 A / dm <2>;<tb> electrolyte circulation speed <SEP> m / s
    [0044] In particular, the maximum hardness that can be obtained for all current values with a solution containing 300 g / 1 of Cr <3+> and catalysts is obtained at T = 50 ° C. At a temperature of 55 ° C, the hardness is equally high for all current density values.
    [0045] Further characteristics of the invention will become clearer from the detailed description which follows, referring to a purely exemplary and therefore non-limiting embodiment thereof, illustrated in the annexed drawings, in which:<tb> Fig. 1 <SEP> is a schematic view of the whole of the chromium plating plant in shortening of the present invention;fig. 2 <SEP> shows the gasket foreseen in the system of fig. 1, shown respectively in a front view (a), in vertical section (b) and in perspective (c) mounted in the plant;fig. 3 <SEP> shows an enlarged view of a first embodiment of an anode structure according to the invention;fig. 4 <SEP> is an enlarged section along the line 4–4 of fig. 3;fig. 5 <SEP> is a schematic view, in vertical section (on the right), of the sealing system foreseen in correspondence of the inlet and outlet openings of the bars of the plant of fig. 1;fig. 6 <SEP> is an enlarged schematic view of the degreasing section of the bars of the plant of fig. 1;fig. 7 <SEP> is a longitudinal section showing a first realization of a joint connecting the bars to be chromed;fig. 8 <SEP> is a longitudinal section showing a second embodiment of a joint connecting the bars to be chromed;fig. 9 <SEP> is a partially interrupted perspective view of a second embodiment of an anode according to the invention;fig. 10 <SEP> is a partially interrupted perspective view of a third embodiment of an anode according to the invention.
    [0046] With reference to fig. 1 the characteristics of the procedure and of the equipment (plant) according to the invention will now be described.
    [0047] As shown in said figure, the plant mainly comprises a chromium-plating chamber 30, which may have a sloping or flat bottom, in which the electrolytic solution is collected which comes out of chromium-plated anodes, for example three, inside the chamber same and generally indicated with the reference number 17, to be conveyed by means of the pipe 36 to a storage tank 29 containing a quantity of electrolytic solution sufficient to allow the feeding and the continuous replacement of the electrolyte to the anodes 17 of the chromium-plating apparatus .
    [0048] The electrolyte contained in the storage tank 29 is kept at a constant temperature, suitable for chrome plating, which is felt by a thermometer T1 which controls a heat exchanger 29, which intervenes to maintain the electrolyte in the tank 29 at the selected temperature. The chamber 30 on one or more side walls is provided with a large window closed by a sheet of transparent material, to view the entire chrome plating process of the bars; appropriate jets of water keep the windows clean from any electrolyte splashes.
    [0049] The electrolyte initially contained in the tank 29 is advantageously composed of a solution based on Cr (III) containing 300g / l of Cr <+> <3> catalytic with fluoride: it is understood that also other solutions based on of Cr (III) can be used in the present plant and process, for example TriChrome <®> Plus of Atotech or Tristar <®> of Coventya.
    [0050] Each anode 17 is fed by the electrolyte solution, by means of a respective pump 31 with delivery pipe 37, while an auxiliary pump 28 with separate piping allows to feed the electrolytic solution to a sacrificial anode 16, in lead antimony tin, arranged at input of said chromium-plating chamber 30, upstream of the chromium-plating anodes 17, to cause by the same electrolytic solution an anodic activation (electrolytic activation not to be confused with the inversion of current used in the known processes) of the bar 27 which will trigger the adhesion of chromium to the bar itself during the electrolytic deposition process through the anodes 17, as explained below.
    [0051] Said sacrificial anode 16 is advantageously realized with a ring structure in Pb having axial holes on the inner crown.
    [0052] The chrome-plating chamber 30, in correspondence with its inlet wall 26 and, respectively, its outlet wall bars 33, is also provided with ntercaps for cooling the bars by means of jets of water with cryoscopic lowering from a cryogenic plant, and a cavity with activation jets with moist and acid air.
    [0053] In particular, a front space 12 for cooling by means of water with a cryoscopic lowering is provided, a gap 13 in which there are arranged humid and acid air jets for preparation to electrolysis, at room temperature, and two rear gaps. 19 and 20 with cooling jets respectively with water (coming from a cryogenic system) and with air.
    [0054] The various jets of water and air are suitable for cooling the bar 27 both on the inlet side and on the outlet side of the chromium-plating chamber 30, keeping it at a predetermined temperature suitable for chromium-plating, for example at a temperature between 50 and 55 ° C, preventing the bar 27 from overheating too much due to the Joule effect originating from the current flowing in the bar itself.
    [0055] Upstream of the chromium-plating tank 30, the apparatus comprises a roller conveyor 24 for supporting the bars, schematically indicated, by which the bars 27, suitably connected to each other by means of intermediate joints 70, which will be illustrated in detail below, they are made to advance and at the same time rotate on themselves to improve the homogeneity of the chrome deposit on the bar which advances through the chromium-plated anodes 17.
    [0056] At the roller conveyor 24 a device 10 is provided for connecting the bar to the negative pole (cathode contact) of a DC electric power source, consisting of current-carrying grippers moved by an advancement, rotation and electrical connection unit, the which work with the 1 mechanical concept of the "Passo del Pellegrino" in which the simultaneous translation of all the pieces operates at a fixed pitch and, during the movement of the bar, an electrical contact also works when the other, who is in motion, detaches .
    [0057] Subsequently a degreasing tank 15 is provided, described later with reference to fig. 6, and a rinsing tank with water 14 to remove all traces of solvent and / or degreasing surfactant before the bar enters the chromium plating chamber 30.
    [0058] The advancement movement of the cathode clamps 10 is impressed by a rack and pinion system: the pinion receives the motion, by electromagnetic coupling and pulleys, from the transmission shaft used for the movement of the rotation. The transmission shaft is controlled by a three-phase asynchronous motor powered by a frequency converter unit. The current is transmitted to the bars to be chromed by means of the copper clamps connected to a manifold on which the current is carried by means of copper stockings fixed to the manifold. The clamp closing pressure is regulated by a pneumatic cylinder.
    [0059] The advantage of this system is represented by the fact that it is able to withstand currents higher than 70 A / dm <2> while the known sliding contact, such as for example the one described in the patent MI 98 A 002 595, does not withstand density of currents higher than 70 A dm <2>: in fact with higher densities, for example 300 Ndm <2>, an electric arc is formed caused by a connection touches and does not touch, which causes the welding of the copper brushes (sliding contact) with the steel bar 27 totally compromising the product.
    [0060] The Applicant has found that a connection with copper clamps that work with the mechanical concept of the "Passo ciel Pellegrino", and with the precautions indicated above, avoids sparking, dispersion, surface damage and is mainly capable of operating with high current density due to the fact that at least one contact is fixed while the other moves, and the contact connected in DC never strips.
    [0061] With the reference number 11, in fig. 1, there have also been indicated some jets of air cooling the bar in correspondence with the rotating contact 10.
    [0062] A section 90 (fig. 1, 5) is provided upstream of the interspace 12 of the chromium-plating chamber 30 for the in-line surface treatment of the bar 27, arranged in a cavity, with a grid for protection: said treatment surface is carried out by means of a circular thrust bearing with a mechanical arm and PVC orbiting tools (peripheral speed 30m / sec) containing an abrasive (3M Scotch-Brite abrasive <TM>) and drip feed for electropolishing. Such a superficial treatment provides the mechanical surface dressing by means of the abrasive, with an antioxidant function using Triethanolamine 85% (C6H15NO3) dissolved in 0.1% water.
    [0063] The advantage of this system is represented by the fact that the bar 27 is activated (prepared) outside the chromium-plating line with a method that is respectful of the environment, leaving the sacrificial anode 16 with the mere triggering function for electrolysis of the anodes in platinum titanium 17 places downstream, in the anode tanks.
    [0064] Downstream of the chromium-plating chamber 30, immediately after the exit for the bars, a washing device 21 is provided with water jets from a cryogenic plant, a second electrical connection device 23, as well as a second roller conveyor 34 suitable for supporting chromed bars at the outlet, allowing them to be unscrewed or disengaged for the introduction of each chromed bar 27 in a cryogenic cooling station 35 sufficient time to cool the bars to a temperature of around 50-70 ° C, suitable for subsequent finishing treatments.
    [0065] It should be noted that according to Ohm's law for a current I at whose heads there is a potential difference equal to V we have an electric power P = V * I which is transformed into heat (Joule effect): unrelatedness of the electrical contacts 23 and 10 on the single line of each bar train are unloaded approx. 5 000 A with 7 Volts in DC (total 10 000 A) which, due to resistance, generate heat such as to bring the outer surface (bark) of the bar to a temperature much higher than 100 ° C depending on the diameter treated.
    [0066] Since the temperature of the bar must be limited, a maximum of 50 ° C due to the necessity of the galvanic process that we recall occurs at 55 ° C (further air-cooled stations are located at points 11 and 22), the use of cooled water cryogenically lowers the rate of deterioration that increases with temperature, resulting in a more efficient and faster cooling compared to air.
    [0067] With reference to figs 1, 2 and 5 will describe further characteristics of the chroming chamber 30 and of the apparatus according to the invention.
    [0068] As shown, the chamber 30 is totally sealed by peripheral walls such as to avoid the escape of the vapors and of the electrolytic solution: in this regard the chromium-plating chamber 30 is connected to a suction apparatus 18 by means of a pipe leading to the Smoke collection scrubber which recycles chromium electrolyte, contained in saturated vapors, in the tank 29.
    [0069] The chrome plating chamber 30 has, in addition to a bottom wall 32, a front wall 26 and a rear wall (exit) 33 provided with wide openings, axially aligned for the passage of the bars 27. Similar openings are formed in positions axially aligned in the front walls of the gaps 12, 13, 19 and 20.
    [0070] Each of the passage openings of the bars, in the walls of the interspaces and of the chamber 30, as shown in fig. 5, is provided with a suitable sealing means in the form of a flexible gasket 25, designed to allow the passage of the bars 27, guaranteeing a sufficient seal to prevent the chromium-plating liquid from escaping to the outside.
    [0071] Since the apparatus must be suitable for treating bars of different diameters, the seals 25 fig. 2, as shown in the example of fig. 5, are positioned in a removable gasket-holder assembly 41, held by an outer flange 42 which is integral with the walls of the chamber 30 and functional to the interspaces 12, 13 and 19,20 (the holes illustrated in Fig. 5 schematically illustrate holes through which the jets of water / air come out).
    [0072] In this way it is possible to remove the gasket body 41 together with the respective gaskets 25, replacing it with a new gasket pack arranged for the passage and sealing of a bar of different diameter. Each «gasket pack» allows you to work with ten different diameters.
    [0073] The sealing gasket shown in fig. 2 is made of PVC plastic, and is suitably reinforced by radial elastic means, for example harmonic steel springs, incorporated in the gasket itself, and suitably shaped to fit different sections of the bars to be chromed.
    [0074] In particular, the gasket 25 consists of two sheets of soft PVC pressed and welded together, between which the radial elastic reinforcing means 102, 102 ́ are fixed, in the form of steel for bending springs, differently combined and oriented towards the central opening.
    [0075] Each gasket 25 also has flexible sealing fins, defined by slits directed substantially in a radial direction, whose inner edges of the fins delimit the bar passage, which is smaller than the section of the bars themselves.
    [0076] In practice, the pack of gaskets 25 constitutes a sealing device suitable for continuous chrome-plated tanks of bars or the like.
    [0077] The said gaskets are located in correspondence with the openings for the passage of the bars on the walls of the chromium-plated tank.
    [0078] These gaskets 25 are therefore placed as a sealing element for the cells / anode both inlet and outlet, containing the turbulent flow of the electrolyte.
    [0079] The advantage of this gasket system, inserted by the Applicant, is represented by the fact that not only the electrolyte but also the solution saturated fumes are perfectly retained, without spills in the working environment. The "damper" seal used in art such as the one described in MI 98 A 002 595 does not completely seal the chrome plating tank, creating environmental problems.
    [0080] With reference now to figs 3, 4, 9 we will describe in greater detail the characteristics of the chromium-plated anode according to the present invention.
    [0081] As can be seen from the above figures; the chromium-plated anode structure, generally indicated with the reference number 17, comprises a tubular element 45 which extends longitudinally in the direction of sliding of the bars 27.
    [0082] The tubular element 45 of the chromium-plated anode is made of platinated titanium (further indicated also with Ti PI), where generally the standard thickness of platinum is 5 microns, while platinum thicknesses of 20 microns are reported where the anode is stressed.
    [0083] Said tubular element 45 is provided, in the lower wall, with a plurality of holes 46 for entering the electrolytic solution, distributed uniformly over the entire length of the chromium-plated anode.
    [0084] Correspondingly, the upper wall of the tubular element 45 has in turn a plurality of holes 47 for the escape of the electrolytic solution, distributed uniformly over the entire length of the chromium-plated anode.
    [0085] Even if in the figure the number of holes 46, 47 is contained, in reality the holes 46 and 47 are distributed in such a way, and in such number, as to result in a tubular element preferably microperforated or meshed (mesh) as illustrated in fig. 9
    [0086] The annular element 45 of the chromium-plated anode, in its lower part, is surrounded by a chamber 48 for distributing the flow of electrolyte and for pressure equalization, connected to one of the pumps 31 of the tank 29, by means of the pipe 37, the chamber 48 consists of sheets of titanium, similar to the tubular element 45, connected to the copper bars 49 with positive polarity which conduct current to the anode itself.
    [0087] More particularly, in the example shown, the tubular element 45 is supported by two lateral septa 50 which separate the lower closed chamber 48 which distributes the electrolytic solution to the inlet openings 46 of the electrolytic solution in the tubular element 45 of the chromium-plated anode, towards an upper chamber 51, opened upwardly provided on one of its walls with an overflow hole 52 for the formation of a sufficient chromium-plated liquid head above the tubular element itself.
    [0088] While the upper chamber 51 serves to collect the electrolytic solution which emerges from the upper holes 47 of the tubular element 45 to then discharge it by overflow through the overflow hole 52 on the bottom of the chrome-plating chamber 30, the lower chamber 48 constitutes a sort of "plenum" or a pressurized chamber, which allows a homogeneous distribution of the electrolytic solution to the inlet holes 46, thus ensuring that the electrolytic solution maintains a direct flow for the entire length of the anode homogeneous from the bottom upwards, transversely to the anode itself, that is to say directed substantially in a direction orthogonal to the sliding direction of the bar 27, wrapping two opposite sides of the bar. A tile-shaped deflector 53 is placed inside the chamber 48 to divert the incoming flow and avoid the creation of preferential flows, while a T2 thermometer controls the temperature of the electrolyte flowing through the anode.
    [0089] The pressure inside the chamber 48 for distributing the electrolytic solution, the number and the dimensions of the inlet holes 46 and the outlet holes 47, may vary from case to case, suitably calculated so as to have an inlet turbulent of the electrolytic solution and consequently a homogeneous distribution thereof inside the tubular element 45. The flow from the bottom to the top of the electrolyte, in the direction in which the hydrogen bubbles may develop due to the electrolytic chroming process, is however such as to facilitate the entrainment and the escape of the bubbles themselves through the numerous upper holes 47 (greater density of holes with respect to the known anodes).
    [0090] The platinized titanium anode can also be made in a star-shaped torx (fig. 10) as an alternative to the tubular, without departing from the scope of the present invention.
    [0091] In this case the anode consists of a titanium support in the form of expanded metal, with a titanium frame filled with «2» DIN 3.7035 grade.
    [0092] In practice the anode used in the aforementioned implant is of the annular type, highly perforated along the crown so as to ensure that said anode is crossed by a turbulent flow of the electrolytic solution.
    [0093] Regarding the materials of the plant, all the circuitry, the structure of the anode cell, in addition to the tank, are in titanium: this guarantees greater safety even in the case of the use of high overpressures or high vacuum values.
    [0094] It should be noted instead that in systems that use hexavalent chromium, lead cells, lead anodes, fiberglass and PVC pipes and tanks are used with working pressures close to atmospheric pressure.
    [0095] We shall now describe the continuous chromium-plating process according to the invention, which can be implemented by means of the apparatus described above.
    [0096] The bars 27 which must be chromed, are connected mechanically and electrically in succession to each other, for example by means of intermediate joints that can be screwed into corresponding threaded holes made at the opposite ends of the bars 27 (Figs. 7-8) in this way the bars they can be advanced towards the chromium-plating apparatus, also imparting to them a rotation about their longitudinal axis, with a predetermined translation and rotation speed depending on the dimensions and / or diameter of the same bars to be chromed.
    [0097] Thus the bars, as they advance at a constant speed, pass through the cathode contact 10, then through the degreasing station 15 where they are struck by a jet of detergent liquid, for example water containing a surfactant, preferably a degreasing solution LHC / 3 (Low Heat Cleaner 3), then pass through the washing tank 14.
    [0098] The degreasing solution to be used must contain a percentage of LHC / 3 of between 3% and 8%, while the bath arrives to be exhausted when it contains 10% concentration LHC / 3. The separation of the oil from the surfactants takes place by acid breaking, bringing the pH of the residual surfactants, which are biodegradable, between 6.5 and 8.5.
    [0099] The degreasing station 15 generally consists of a tank in insulated AISI 304 stainless steel, with a total capacity of 2 000 liters. A spillway is foreseen that is able to continuously remove the floating sludge from the surface of the degreasing solution. In addition, a filter is provided for separating the degreasing means from the solution. Resistances (not shown in the figure), with a power of 6 kW, are provided to heat the degreasing solution up to the 80 ° C working temperature, adjusted by means of a thermostat, while connected cooling coils 67 are also provided at the cryogenic station.
    [0100] The washing station 14 is equipped with four 60 ° blade opening nozzles, placed every 90 ° on a circumference with a diameter such as to cover the entire production range with two bar rinsing tanks, each fitted with a pump float for level control, powered upstream.
    [0101] In particular, as shown in fig. 6, the degreasing station 15 is preferably constituted by a closed tank 60 containing at the bottom an amount of degreasing solution 61 which by means of a pump 62 and a pipe 63 is continuously fed to a spray head 64 placed above the bar 27. The bar 27 enters and exits from the degreasing tank 60 through appropriate openings formed on the two side walls in positions axially aligned with the openings for the passage of the bar in the chromium-plating chamber 30, providing suitable sealing gaskets 65 and 66 (Fig. 6) which they can be identical to the gaskets 25 or they can be conventional gaskets made for example from felt.
    [0102] As previously stated, since the bar 27 must be thermally conditioned to prevent excessive overheating due to the current circulating in the bar itself, in order to keep it at a temperature suitable for the chromium-plating phase, before the degreasing station 15 jets are provided. cooling air 11.
    [0103] Moreover, if the temperature of the degreasing liquid 61 increases, exceeding a value considered dangerous, inside the degreasing tank 60, immersed in the liquid 61, a suitable cooling coil 67 is provided in which a cooling fluid, for example water from a source of fluids 68 (piping from the cryogenic station), providing suitable means, for example a thermal probe for controlling the temperature of the fluid 61.
    [0104] After the degreasing station 15, the bar 27 is passed through the washing tank 14 where the bar is struck by jets of water which completely clean it before the surface treatment 90 carried out by means of a mechanical surface dressing ( with 3MScotch-Brite <TM> abrasive, having an antioxidant function using 85% Triethanolamine (C6H15NO3). This treatment, external to the tank 30, can be defined as chemical-physical etching (it emphasizes chemical-physical and non-electrolytic activation) which differs from the electrolytic one generally performed by current inversion (anodic attack for 30–120 sec with the bar which acts as an anode instead of a cathode). All the resulting liquids (at room temperature) are recycled in the chrome tank.
    [0105] It should be noted that the polarity inversion in conventional Cr (VI) -based chromium plating baths in the long run involves the contamination of the electrolyte which causes a drop in current efficiency, due to a reduction in the conductivity of the bathroom, and the deterioration of the deposit characteristics.
    [0106] In the present process, on the other hand, the surface roughening of the steel of the bar to create the conditions of good adherence (etching) is advantageously obtained without resorting to the inversion of polarity on the bar 27.
    [0107] Continuing its movement, the bar 27 is subjected, after the cryogenic cooling by means of water placed in the interspace 12, to a surface preparation with moist and acid air carried out inside the interspace 13.
    [0108] Subsequently, inside the chromium-plating chamber 30, the bar 27 is first struck by a jet of electrolytic solution fed by the pump 28 to the annular sacrificial anode 16 with axial holes, made of a less noble material (lead) than the anodes in platinum titanium which improves a cathodic protection and favors the priming of electrolysis to the following anodes 17 in platinized titanium.
    [0109] Furthermore, this finely divided jet of electrolytic solution which hits the bar 27, due to the previous chemical-physical etching 90 and the pressure of the jet itself, causes a surface activation of the bar necessary to allow a firm anchoring of the first layer of chrome when it is deposited inside the anode or the first anode 17 of the apparatus.
    [0110] Since the nature of the material of the bar may vary, and since the treatment of surface corrosion, as well as the chemical nature of the electrolytic solution may also depend on other factors, such as the temperature of the liquid itself and the impact pressure of the various jets against the surface of the bar to be chromed, suitable means must be provided to vary the pressure and / or flow rate of the liquid supplied by the pump 28, as well as to maintain adequately controlled temperature conditions.
    [0111] After the surface activation zone, the bar enters the anode 17 or in the first of a series of anodes 17, in each of which a layer of chromium having a predetermined thickness depending on the parameters of the process is deposited due to the electrogalvanic effect of chromium plating and in particular of the linear speed of advancement of the bar 27, the ratio between the diameter of the bar itself and the internal diameter of the tubular element 45 of the chromium anode, as well as the surface density of current supplied to the bar by the anode same.
    [0112] In this regard, in order to be able to operate with high current densities, including for example between 150 and 500 A / dm <2> or higher, and in order to maintain at the same time high bar sliding speeds, for example between 10 and 30 meters / hour, it is advisable for the inner diameter of the tubular element 45 to be slightly greater than the external diameter of the bar 27, for example greater by about 5-20%, since excessive distances between bar and anode are negative for the chrome plating process .
    [0113] A reduced distance between the surface of the bar 27 and the tubular element of the chromium-plated anode 45, besides allowing to work with higher amperages and with higher speeds of sliding of the bar, allows a more regular deposition of chrome thanks to the the fact that the electrolytic solution flow is distributed homogeneously over the entire length of the chromium anode maintaining a bottom-up direction; the cooling effect of the bars, obtained in a controlled manner by adjusting or varying the flow rate of the electrolytic solution, by means of a variable displacement feed pump 31, finally allows to improve the chrome-plating conditions and the productivity.
    [0114] Since the pressure of the electrolytic solution inside the compensation chamber (electrolyte input) 46 is far greater than the atmospheric pressure, a turbulent circulation of the electrolytic solution is obtained inside the chromium anode; which causes a regular chrome deposit.
    [0115] The electrolytic solution which comes out of the tubular element 45 through the holes 47, collects in the overflow chamber 51 from which it overflows through the hole (too full) 52 gathering on the bottom of the chromium plating chamber 30 to return again into the tank of storage 29.
    [0116] After the anode or the complex of chromium-plated anodes 17, the bar 27, continuing to slide forward, enters the rear hollow space 19, where it is hit by jets of water which, in addition to keeping the bar cooled , cause the separation of the veil of electrolytic solution the remaining adherent to the bar itself.
    [0117] At the exit of the interspace 19 the bar is passed through an interspace 20 for cooling with air, then dried.
    [0118] The bar 27 moves forward and enters the cooling station 21 by means of a jet of water from a cryogenic system through an annular sprayer, then it is dried by air jets 22, before entering the contact station 23 and further cooled with air 22, then the device 23 (cathode contact) in parallel with the device 10 which connects the bar to the negative pole (cathode contact) of a DC electric power source, constituted as said by current carrying grippers moved by an advancement group.
    [0119] The bar then advances on the exit roller conveyor 34 from which it is then unloaded laterally into the cooling bed 35.
    [0120] In the general scheme of fig. 1 the use of three chromium-plating electrodes 17 in succession between them has been shown: however the number of electrodes could also vary with respect to what is shown. The use of three electrodes of a length of about 33 cm in general proves to be advantageous, since it reduces the risks of contact with the bars 27 caused by a possible bending of the bar itself. Therefore, depending on the number of anodes used, it will be possible to obtain, in a single step, the deposition of one or more superimposed layers of chromium, the thickness of which will depend substantially on the temperature conditions, on the flow rate of the electrolytic solution passing through the anode or each anode, as well as the internal diameter of the tubular element of the anode itself. Therefore, depending on the requirements of use, the apparatus can be arranged to vary the temperature and flow of the electrolyte in each anode, for example by adjusting the flow rate of the pumps 31 so as to vary the cooling and chrome-plating conditions of the bar.
    [0121] The possibility of performing continuous multi-layer chromium-plating, by means of a single passage, according to the present invention is extremely important since the micro-cracks which may occur in the deposition of a chrome layer are closed and covered by the chromium deposit following; furthermore, this possibility drastically reduces the processing times since it is no longer necessary to carry out subsequent steps for the same bar through a chromium-plating apparatus, as it is still necessary with the apparatuses of the known type to obtain greater chromium-plating thicknesses.
    [0122] Furthermore, the present invention has, with respect to conventional equipment, the advantage of maintaining extremely low amounts of electrolytic solution in circulation, of the order of a few tens of liters per minute, against the thousands of liters of electrolytic solution required in the equipment conventional chrome plating. In this way substantial energy savings and extremely low process costs are achieved.
    [0123] From what has been said and shown in the accompanying drawings, it will therefore be understood that a highly versatile method and plant for continuous chromium-plating of metal bars, tubular and similar elements has been provided, which uses an original anode structure able to allow a precise control of the chrome plating conditions, for the controlled deposition of one or more layers of chromium plating on the same bar while it advances through the anode and / or the anodes themselves. The possibility of controlling the cooling conditions of the bar within each anode, or therefore the chrome plating conditions by means of a controlled circulation and a longitudinal distribution of the electrolytic solution while it flows transversely from the bottom upwards in each chromium-plated anode, allows they also operate with very high current densities, however higher than those possible with conventional systems, thus increasing productivity.
    [0124] In this regard, considering the high current densities made possible with the method and apparatus according to the invention, with values that can vary from 150 to 500 A per dm <2> of surface to be chromed, according to another aspect of the invention a particular mechanical and electrical connection joint between adjacent bars has been provided, suitable to allow an electrical contact on a wide surface and the passage of high current chromium density; the joint in question also makes it possible to compensate for any flatness defects in the facing of the bars to be connected. In this way the problems associated with the overheating of the conventional joints are eliminated or greatly reduced, which sometimes caused fusion problems and its consequent welding to the ends of the bars to be chromed.
    [0125] According to the present invention, in order to mechanically and electrically connect two bars to be chromed, an intermediate joint of deformable metallic material is therefore used, comprising contact surfaces with the ends of the bars, made of deformable metallic material, for example copper, aluminum or other suitable metallic material having a lower degree of hardness than that of the same bars to be chromed.
    [0126] The joint is substantially constituted by a cylindrical core, having the same diameter as the bars to be chromed, provided at its ends with suitable connecting means which can be engaged and disengaged by rotation, to corresponding connection means, provided or formed at the opposite ends of the splicing bars.
    [0127] The connection means can be of any suitable type; the possible embodiment of the joint is shown in the example of fig. 7
    [0128] In fig. 7 shows the joint 70 according to the invention for connecting two bars to be chromed 27 ́ and 27 ́ ́. The joint 70 comprises a central core 71 having the same diameter or the transverse dimensions of the bars 27 ́ and 27 ́ ́, from which protrude two threaded pins 72,73 with opposite right and left threads, suitable for screwing into corresponding threaded holes 74 , 75 axially formed in the opposite ends of the two bars 27 ́ and 27 ́ ́.
    [0129] a respective washer 77, 78 made of copper, aluminum or other deformable metal material was interposed between the central core 71 of the joint and the opposite ends of the two bars 27 ́ and 27 ́ ́ to facilitate adaptation and electrical contact between the surfaces: however, the presence of these washers is not binding for the purposes of the present invention.
    [0130] Since the bars 27 ́ and 27 ́ may have wanted to present facing or flatness errors at their ends, which with conventional connection systems would cause them to make contact in limited areas through which they would pass a too high current density, such as to cause a strong localized overheating and a fusion welding of the ends in contact with the same bars, according to the present invention a joint is used comprising a central core 71 made of soft material, having a hardness lower than that of the steel bars to be chromed, for example in copper, aluminum or other material suitable both to conduct the electric current and to undergo a partial plastic deformation by compression during the tightening of the joint, so as to come intimately in contact and to adapt against the extreme surface of the two bars to be joined .
    [0131] In order to facilitate screwing and the final tightening, it is possible to provide in the central core 71 the formation of grooves (cutter) 76 for engagement with a tightening wrench. Other solutions are obviously possible to achieve the same result.
    [0132] In fig. 7 shows a screw connection between the central core and the ends of the bars to be connected; however, other solutions are possible, providing other mechanical and electrical attack systems.
    [0133] In the case in which the bars to be connected were of small diameter, for example from 6 to 60 mm, it is preferable to use as a connecting joint a single threaded pin 72 of fig. 8 with opposite right and left threads, suitable for screwing into the corresponding threaded holes 74 and 75, formed axially in the opposite ends of the two bars 27 ́ and 27 ́ ́, similarly to what described in relation to fig. 7
    [0134] The advantages of the present invention are considerable, in particular:greater environmental safety due to the use of Cr <3> <+> instead of Cr <6> <+>;controlled containment of the parasitic reaction from hydrogen and complete environmental safety, with elimination of discharges and disposal of process residues;higher current yield (faradic yield) due to higher current density;lower energy costs thanks to greater faradic efficiency and higher carryover speed;higher deposit quality due to the control of the fill morphology in the absence of steel fragility attributable to hydrogen entrapment, promoter control of constant and homogeneous production quality and better resistance to corrosion;lower anode-cathode distance and therefore low ohmic resistance to the interface thanks to the forced circulation in turbulent regime.
    [0135] The present invention is not limited to the particular embodiments previously described and illustrated in the annexed drawings, but numerous modifications of detail may be made to it, within the reach of the person skilled in the art, without thereby departing from the scope of the invention. itself, as defined in the appended claims.
    权利要求:
    Claims (13)
    [1]
    1. System for continuous chromium-plating of metal bars (27), tubular elements and the like, comprising:- a chromium plating chamber (30) having inlet and outlet openings of said bars axially aligned in the direction of movement of said bars;- means (24) for advancing said bars through said chromium-plating chamber (30);- one or more chrome-plated tubular anodes (17), preferably at least three, axially aligned with the path of the bars to be chromed, each of said anodes (17) having a plurality of holes on the surface, and placed in said chromium-plating chamber (30 );- a sacrificial anode (16) with holes for axial jets;- means (28, 31) for forcibly circulating an electrolytic chrome-plating solution (37, 28) inside said tubular anodes (17) and said annular sacrificial anode with axial jets (16) ;- a storage tank (29) containing said electrolytic solution (37, 28 ́),characterized in that said electrolytic solution contained in said tank is a solution based on trivalent chromium, eat least said means (31) for circulating said electrolytic chrome-plating solution inside chosen anodes (17) arranged in said chromium plating chamber (30) are suitable for circulating a suitable solution in a turbulent regime,said chromium-plated anodes (17) being made of platinated titanium, said sacrificial anode (16), made of lead or its alloys with Sn or Sb, being arranged at the entrance of said chromium-plating chamber (30).
    [2]
    2. Plant according to claim 1 wherein said anodes in platinated titanium (17) contained in said chromium-plating chamber (30) are three, each fed independently by respective means of circulation (31) of said electrolytic solution.
    [3]
    3. Plant according to claim 1 or 2 in which the sacrificial anode (16) is fed independently from said platinated anodes (17) by half-respective circulation means (28) of said electrolytic solution.
    [4]
    4. Plant according to any one of the preceding claims, wherein said circulation means (28) and / or said circulation means (31) of said electrolytic solution are in the form of a variable-flow pump.
    [5]
    5. Plant according to any one of the preceding claims, in which cooling cavities (12, 19, 20) of the bars by means of water jets with lowering are provided upstream of the sacrificial anode (16) and downstream of the chromium-plating chamber (30) cryoscopic, and an interspace (13) with activation jets with moist and acid air is provided adjacent to said cooling interspace (12).
    [6]
    6. Plant according to any one of the preceding claims, wherein said sacrificial anode (16) is in the shape of a ring and has a plurality of holes axially distributed on the inner crown.
    [7]
    7. Plant according to any one of the preceding claims, wherein said anodes in platinum titanium (17) have a surface distribution of holes (47) that is absolutely greater than that of the sacrificial anode (16).
    [8]
    8. Apparatus according to any one of the preceding claims, in which said anodes in platinated titanium (17) are made of mesh, and are provided with a circular, oval or stellar torx cross section.
    [9]
    9. Plant according to any one of the preceding claims, in which the said chromium plating chamber (30), the said cooling interspaces (12,19,20) and the said acid-etched activation interspace (13) are connected to a suction apparatus (18) by piping.
    [10]
    10. Plant according to any one of the preceding claims, in which in axially aligned positions in the front walls of said chrome-plating chamber (30), of said cooling interspaces (12, 19, 20) and of said acid-etched activation interspace (13), at the inlet and outlet of the bars, sealing elements are provided comprising at least one flexible gasket (25) reinforced by radial elastic means.
    [11]
    11. Sealing device (25) for continuous chrome-plated tanks of bars or the like, comprising sealing gaskets in correspondence of openings for the passage of the bars on the walls (26; 33) of the chromium-plating tank (30), characterized in that each gasket (25) consisting of two plates (101) made of soft plastic material welded together, has a central opening and flexible sealing fins, defined by slits directed substantially in a radial direction, whose inner edges of the fins delimit the bar passage , of smaller size than the cross-section of the bars themselves, and in that each gasket (25) comprises elastic reinforcement means in the form of bending springs oriented towards said central opening.
    [12]
    12. Process for the continuous chrome-plating of metal bars (27), tubular elements and the like, comprising the advancement of a bar to be chromed through at least one tubular and perforated chromium-plated anode (17) as defined in the preceding claims, wherein flowing an electrolytic solution, characterized in that said chromating anode (17) is fed with said electrolytic solution circulating in turbulent regime, said electrolytic solution being based on trivalent chromium instead of hexavalent.
    [13]
    13. Plant according to any one of the preceding claims, in which the bars to be chromed are mechanically and electrically connected to each other by means of an intermediate joint (70) or threaded pins (72) which extend axially to be screwed into threaded holes (74) in the opposite ends of the bars to be joined, said intermediate joint or threaded pins being made of conductive metal, for example copper.
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    同族专利:
    公开号 | 公开日
    US20180016688A1|2018-01-18|
    WO2016120700A3|2017-06-29|
    CN107250441A|2017-10-13|
    MX2017009794A|2018-06-07|
    WO2016120700A2|2016-08-04|
    US10760173B2|2020-09-01|
    KR20170107494A|2017-09-25|
    EP3172360A2|2017-05-31|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
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    CN110438537B|2019-08-09|2021-10-01|常州大学|High-flux heat exchange tube and preparation method and application thereof|
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    法律状态:
    2017-05-31| NV| New agent|Representative=s name: ING. ALESSANDRO GALASSI C/O PGA S.P.A., MILANO, CH |
    2018-02-15| AZW| Rejection (application)|
    优先权:
    申请号 | 申请日 | 专利标题
    ITMI20150128|2015-01-30|
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