WO2017077122A1

WO2017077122A1 - Treatment device for pickling and phosphating metal parts, and treatment method, and treatment plant for coating the metal parts

Info

Publication number: WO2017077122A1
Application number: PCT/EP2016/076869
Authority: WO
Inventors: Joachim SCHÖNBERG
Original assignee: Retomax Ag
Priority date: 2015-11-05
Filing date: 2016-11-07
Publication date: 2017-05-11
Also published as: CN108291309A; DE102015014323A1; HK1257124A1; EP3371342A1; EP3371342B1

Abstract

The invention relates to a treatment device (1) for the single-stage treatment of a metal object (2) to be treated, wherein the treatment comprises at least the pickling and the phosphating of the object (2) to be treated, wherein the treatment device (1) comprises at least the following apparatuses: a treatment container (4) for holding the object (2) to be treated and for holding a flowable treatment substance (6), a pumping apparatus (10) for circulating at least a portion of the treatment substance (6), wherein the treatment substance (6) flows around at least part of the object (2) to be treated, in particular the entire object (2) to be treated, wherein the treatment substance (6) is a phosphorus- or phosphate-containing solution, in particular phosphoric acid, wherein the phosphorus- or phosphate-containing solution consists of water, in particular deionized water, and of a reaction substance, and the reaction substance consists of phosphorus or of a phosphate and of at least one additional substance that improves the treatment effect, in particular one or more inhibitors, wherein the fraction of the phosphorus or the phosphate in the reaction substance is between 75 vol% and 94 vol% and preferably between 80 vol% and 90 vol% and especially preferably between 83 vol% and 88 vol%, wherein the reaction substance has no fractions of hydrochloric acid and sulfuric acid and preferably also no fractions of fluorine, chlorine, bromine, iodine, lead, mercury, and selenium and wherein the reaction substance is mixed with water at a specified ratio, wherein the specified ratio lies between a lower limit and an upper limit, wherein the lower limit is defined by a mixture at a ratio of 1 kg of reaction substance to 4 liters of water and the upper limit is defined by a mixture of 1 kg of reaction substance to 12 liters of water, and in particular the mixture has a ratio of 1 kg of reaction substance to 6 liters of water.

Description

Treatment device for pickling and phosphating of metal parts and treatment methods and treatment plant for coating the metal parts

The present invention relates according to claim 1 to a treatment apparatus for single-stage treatment of articles, according to claim 9 on a treatment plant according to claim 10 to a treatment method for at least pickling and phosphating a metallic treatment article and according to claim 15 on a metallic body.

Previous treatment systems for phosphating objects require a variety of steps, in particular 7 steps, and for this purpose have a variety of different baths. The object is first inserted into a first bath, in which a first liquid is provided for degreasing the article. After degreasing, the article must be pumped out of the first bath and into a second bath. In the second bath, a rinsing liquid is provided for rinsing the article. After rinsing, the article is conveyed to a third bath. The third bath is filled with a hydrochloric acid / sulfuric acid mixture. After the hydrochloric acid / sulfuric acid treatment, the article is successively conveyed into two further baths each filled with a rinsing liquid for rinsing the article. Furthermore, the article is conveyed after the last rinse in a bath for passivation. After passivation, the article is phosphated and then conveyed to another location for drying. In such a system, the highly toxic and environmentally harmful chemicals in the degreasing baths and in the treatment baths must be completely changed after about 6 to 8 weeks of production time, because the chemicals are worn out after this time and sludge must be removed from the baths. This means a shutdown of the system and high replacement and disposal costs.

It can be seen that the systems known from the prior art, on the one hand, require a great deal of space, since they have to provide six different baths and, on the other hand, require a great many different chemical substances in large quantities. Furthermore, conveying the articles from one bath to the next requires a great deal of time, corresponding transport systems and operating personnel. Furthermore, the chemicals used are toxic or harmful to the environment, for example, sulfuric acids and hydrochloric acids are used, which either expensive security measures must be carried out or l There is a high risk for the personnel and the environment as well as the mostly steel hall construction.

Furthermore, a hydrogen embrittlement of the treated workpieces or treatment objects should be prevented. Hydrogen embrittlement usually occurs through the penetration and incorporation of hydrogen into a metal grid and can result in material fatigue. Hydrogen embrittlement occurs when the metal surface, either through hydrogen corrosion or another chemical reaction in metal processing involving hydrogen, produces atomic hydrogen, which binds to the material more quickly than it does at the material surface diffusible H ₂ molecules zusammenfügt together. Part of the hydrogen is stored in the metal grid or accumulates at defects or at the grain boundary. Depending on the load of the respective object, eg by the initiation of tensile and / or load voltages, there is a risk of material failure.

It is therefore an object of the present invention to provide a treatment device and a treatment method, wherein at least one disadvantage, and preferably several, and particularly preferably all, of the abovementioned disadvantages of the treatment systems known from the prior art for phosphating objects are avoided by the treatment device according to the invention and the treatment method according to the invention should. Particularly preferably, the surface finish of a treatment article treated according to the invention is to be improved.

The aforementioned object is achieved according to a first aspect of the invention by a treatment device for preferably single-stage treatment of a metallic treatment article, the treatment comprising at least the pickling and the phosphating of the treatment article. The treatment device according to the invention, in particular a bath installation, preferably comprises a treatment container for receiving the treatment object and for receiving a flowable treatment substance, and a pumping device for exchanging at least a portion of the treatment substance, wherein at least a part of the treatment object, in particular the entire treatment object, of the treatment substance is flowed around, wherein the treatment substance is a phosphorus or phosphate-containing solution, in particular phosphoric acid, wherein the phosphorus or 76869 phosphate-containing solution for a water and on the other consists of a reaction substance, wherein the reaction substance of phosphorus or a phosphate and preferably at least one additional

Treatment effect improving substance, in particular having one or more inhibitors, and water, in particular deionized water, wherein the proportion of the phosphorus or phosphate to the reaction substance between 75% vol. and 94% vol., and is preferably between 80% vol. and 90% vol. and more preferably between 83% vol. and 88% vol. and most preferably between 84% vol. and 87% vol., such as 85% vol. or 86% vol., and the treatment effect improving substance, in particular one or more inhibitors, preferably in an amount of 0.1 vol. % to 2.5 vol. % preferably between 0.2 vol.% and 2 vol. % and more preferably between 0.5 vol. % and 1, 5 vol. % of the reaction substance is present. The of 100% vol. lacking further portions are preferably formed by water, in particular demineralized water. Preferably, the reaction substance has no proportions of hydrochloric acid and sulfuric acid and further preferably does not contain any proportions of fluorine, chlorine, bromine, iodine, lead, mercury and selenium. Furthermore, the reaction substance is preferably mixed with water, in particular in a predetermined ratio, wherein the predetermined ratio between a lower limit and an upper limit, wherein the lower limit is defined by a mixture in a ratio of 1kg reaction substance to 3 liters of water and the upper limit by a Mixture of 1 kg of reaction substance to 12 liters of water is defined, in particular, the mixture is present in a ratio of 1 kg of reaction substance to 6 liters of water.

The reaction substance is thus preferably mixed with water in a ratio of 1 kg of reaction substance to 3 liters of water and 1 kg of reaction substance to 9 liters of water, in particular in a ratio of 1 kg of reaction substance to 5 liters of water and 1 kg reaction substance to 7 liters of water mixed with water, in particular in a ratio of exactly or substantially 1 kg of reaction substance to 5.5 liters of water or in a ratio of exactly or substantially 1 kg of reaction substance to 5.8 liters of water or in a ratio of exactly or substantially 1 kg of reaction substance to 6, 2 liters of water or mixed in a ratio of exactly or substantially kg of reaction substance to 6.5 liters of water.

This solution is advantageous since, for a further coating, in particular a coating or powder coating, an advantageous protective layer or primer layer is produced on the article to be treated and / or an advantageous cleaning of the article to be treated takes place. Furthermore, the protective layer prevents, for example, the material of the treatment article from being oxidized, as a result of which a substance can be oxidized by means of the protective layer Device according to the invention treated treatment object can be exposed to the air much longer than an untreated article.

According to a further preferred embodiment of the present invention, a swirling device is provided for swirling impurities depositing in the treatment substance, in particular solid particles, wherein the swirling device has at least one provision device and a fluid line element with a plurality of outlet openings for supplying a fluidizing fluid to the treatment substance the Verwirbelungsfluid by the supply device to the fluid line element with a pressure of more than 2bar, in particular with more than 3bar or more than 4bar or more than 5bar or more than 6bar or more than 7bar or with up to 10bar or with up to 15bar or with up to 20bar, can be fed.

This embodiment is advantageous because no toxic or environmentally harmful chemicals are used. Furthermore, the treatment substance does not have to be exchanged and disposed of every 6-8 weeks, since the treatment device according to the invention provides a system structure in which the used chemistry is constantly cleaned. By evaporation and carryover resulting losses of the treatment substance can be replenished by the addition of water and the reaction substance, whereby it is possible that the required number of changes of the treatment substance per year to less than 4 changes, especially to 2 or to less than 2 changes, to 1 or to less than 1 change, is reducible. Preferably, the treatment substance is replaced only when there is a predetermined concentration of dissolved iron in the treatment substance, wherein an exchange preferably takes place only at a dissolved iron concentration of more than 2%. Furthermore, by the inventive solution contaminants or impurities, especially sludge and / or metal or rust particles, prevented from depositing and / or removed from accumulations formed by deposits. The accumulations can be separated again by the swirling device, whereby the impurities can again be kept as suspended matter in the treatment substance. As suspended matter, the impurities can then be discharged out of the receiving space by supplying portions of the treatment substance to the filter device.

According to a further preferred embodiment of the present invention, the fluid line element forms a plurality of line sections which can be decoupled from one another at least functionally or fluidically by means of valve devices, at least the Majority of the line sections are arranged in the region of the bottom of the treatment tank. In this case, any portion of the treatment container which is arranged or formed closer to the bottom than to the opening formed on the upper side of the treatment container is to be regarded as the region of the bottom. However, it is also conceivable that the fluid conduit element is formed as a component of the soil or in the soil and thus may be formed in sections or completely below the surface of the soil directed to the receiving space. Preferably, the fluid conduit element is at least partially formed less than 50cm, preferably less than 30cm and more preferably less than 10cm spaced from the bottom of the receiving space. The outlet openings or individual outlet openings or the plurality of outlet openings or a minority of the outlet openings are preferably oriented downward, ie oriented in the direction of the floor or oriented to the side, ie in the direction of a wall or side wall of the receiving space, at a fluid line element arranged above the floor, or upwards, ie in the direction of the introduction opening of the receiving space, through which the treatment objects can be introduced into the receiving space. It is also conceivable that the outlet openings of different pipes are directed in different directions. It is also conceivable that each outlet section or pipe or on individual line sections or pipes first outlet openings are provided, which are oriented in a first direction, and second outlet openings are provided which are oriented in a second direction, wherein the first direction and the second Direction preferably by at least 10 ° and preferably at least 20 ° and more preferably at least 45 ° or at least 60 ° or at least 90 ° or at least 120 ° or at least 150 ° or up to 180 ° are oriented differently from each other. In addition, it is conceivable that third outlet openings are provided, which are oriented to the first outlet openings at an angle which is different from the angle between the first outlet openings and the second outlet openings. Similarly, this may be true for fourth outlet openings and / or fifth outlet openings, etc. This embodiment is advantageous since the introduction of the fluidizing fluid or of the functional fluid or of the fluid, in particular air, can be directed in such a way that the turbulences generated by the turbulence fluid effectively dissolve the deposits.

According to a further preferred embodiment of the present invention, the line sections are formed by tubes, in particular made of copper, aluminum, iron and / or stainless steel, in particular with a tube diameter between 2mm and 12mm and preferably in a tube diameter between 3mm and 9mm and more preferably in one Pipe diameter between 4mm and 6mm, wherein the tubes are coupled to the bottom of the treatment container or arranged thereon, wherein the Tubes are connected to each other by means of at least one distribution unit, and wherein each valve device as a shut-off valve, in particular as Absperrmagnetventil is formed. The outlet openings are preferably designed as holes, in particular bores, and preferably have a diameter between 0.5 mm and 8 mm, preferably a diameter between 1, 5 mm and 6 mm and particularly preferably a diameter between 2.5 mm and 4 mm, in particular exactly or substantially 3 mm , on.

According to a further preferred embodiment of the present invention, the provision device is designed to provide a gas which is under at least 2 bar pressure, in particular air. In the case in which the gas is air, the air preferably consists of ambient air from the environment of the device according to the invention. This embodiment is advantageous because ambient air is available free of charge and, due to its low density, moves automatically through the treatment substance or moves out of the movement substance itself. As it traverses the treatment substance, the air causes a local displacement of the treatment substance, causing it to move, which could result in turbulence.

A filter device for filtering the treatment substance is provided according to a further preferred embodiment of the present invention, wherein filtering removes impurities from the treatment substance which have accumulated in the treatment substance. In addition, a control device for operating the filter device and the swirling device is preferably provided. Particularly preferably, the filter device and the swirling device can be operated at least temporarily as a function of one another.

This embodiment is advantageous because the interaction of the swirling device with the filter device allows the impurities to be very efficiently removed from the treatment substance.

According to a further preferred embodiment of the present invention, the operation of the swirling device comprises, at least at times, the provision of the fluid and the activation of the valve device, wherein the valve devices can be actuated according to predetermined courses, in particular at programmed time intervals. It is thus possible for individual, several, the plurality or all valve devices of the line element or individual line sections to be switched in such a way that fluid is supplied to the treatment substance through all the outlet openings which are fluidically connected to the opened valve devices for a preferably predetermined period of time. However, it is also conceivable that one or more valve devices switched in succession, in particular pulsating switched. The individual valve devices are particularly preferably controlled, however, by means of a predetermined program and / or a preferably adjustable interval circuit and / or as a function of status data of the treatment substance detected by means of sensor device. In this case, the swirling device is particularly preferably activated and / or deactivated as a result of the sensor data. In this case, the sensor data may have, for example, data relating to the proportion of impurities in the bottom region of the device and / or in one or individual regions of the treatment container. Additionally or alternatively, it is conceivable that the swirling device can be activated and / or deactivated manually and / or by means of a remote control.

In addition, the reaction substance particularly preferably contains no fractions of hydrochloric acid and sulfuric acid. This is advantageous because a very simple treatment of treatment objects is possible by the present invention. Essentially, the articles of treatment need only be dipped in the treatment substance, the treatment substance must act and dry after removal of the article of treatment from the bath. In particular, a protective layer is formed after drying on the treatment objects by the high-purity phosphorus or the high-purity phosphate, so that they are protected over a longer period, in particular several weeks before further Ausbefall, this being without the required according to the prior art Passivation and subsequent phosphating takes place, and wherein in particular the resulting protective layer is far superior to the phosphating according to the prior art. This solution is also advantageous because the treatment substance is incombustible, the use of the treatment substance does not exceed the MAK values (maximum workplace concentration) and no corrosive vapors are caused, which means that no extraction is required.

Another advantage of the present invention is that the treatment effect enhancement substance (s) used provides significant protection of the material and does not compromise weldability.

Yet another advantage is the versatility of the present invention. It can be used eg for pretreatment and post-treatment in hardening shops or it can be used to remove the oxide layer on aluminum. Furthermore, they can be avoided during the galvanic reworking of castings efflorescence. The Savings in putty in the casting skin removal is therefore considerable. Furthermore, eg hydraulic pipes and pipelines can be pickled directly on construction sites in a single operation, without a rinsing and neutralization would be required.

In addition to the pickling and phosphating of the treatment article, the treatment device according to the invention preferably also preferably effects the degreasing and / or derusting and / or descaling and / or preserving and / or descaling of the treatment article.

As treatment objects can preferably be treated purely by way of example: metal parts, such as aluminum parts, iron parts, cast iron parts, wire, steel parts, copper parts or parts of alloys, polymer parts, such as plastic parts or rubber parts, etc., especially vehicle frames, pipes, machine parts, turbocharger parts, housing, car parts , Hydraulic parts, cast steel parts, turbine parts.

Insofar as nothing different arises from the subject matter of this invention, the percentages with regard to the invention apply as volume percent. In addition, it should be noted that the percentages and temperatures in ° C with respect to the invention refer to the ambient pressure or normal pressure, if nothing different arises from the subject of the invention, and further, the information in ° C accordingly for Kelvin be valid. However, those skilled in the art are not going to further explain the physical units of the invention with respect to the overall disclosure of the invention, but if one physical parameter should be modified, it will be apparent to those skilled in the art that the resulting changes in the other physical Adjust sizes accordingly, without departing from the scope of the invention.

Advantageous embodiments of the invention will become apparent from the dependent claims, wherein a tempering is provided for tempering the vorhaltbaren in the action container treatment substance, wherein by means of the temperature control means, the temperature of the treatment substance is defined adjustable.

The preferred temperature of the treating substance is preferably higher than O'C, especially higher than or equal to 5 ° C, higher than or equal to 10 ° C, higher than or equal to 15 ° C, higher or equal to 17 ° C, greater than or equal to 20 ° C, greater than or equal to 25 ^e C, greater than or equal to 30 ° C, greater than or equal to 35 ° C, greater than or equal to 37'C, greater than or equal to 40 ° C, preferably between 20 ° C and 60 ° C and more preferably between 30 ° and 50 ° C. Preferably, the temperature of the treatment substance is a heating of the treatment substance, but it is also conceivable that the temperature represents a cooling. Furthermore, it is conceivable that the treatment substance can be temporarily heated and temporarily cooled by the tempering device. The tempering device is preferably designed as an electrical heating device, electrical cooling device and / or as a heat exchanger system. Depending on the temperature of the treatment substance, the work flow can be controlled. For example, when degreasing rust, the acceleration factor can be 20: 20Cx6. This means that the subject of the treatment can be made stainless with a 20 ° C treatment lasting 2 hours or with a treatment at 40 ° C lasting 20 minutes.

A particularly preferred operating temperature range is 35X to 45 ^e C, this temperature range is advantageous, since an extraction is not necessary because no corrosive - or harmful harmful vapors arise. However, it is conceivable that a suction is provided if, for example, the working space is extremely low or if the working space is not to be ventilated.

The phosphorus-containing and phosphate-containing solution preferably consists of fully descaled water and the reaction substance, the proportion of reaction substance to the proportion of deionized water being between 1: 4 and 1: 7, the proportion of reaction substance to the proportion of deionized water being preferred 1: 6, when the reaction substance is in a solid state or wherein the proportion of reaction substance to the proportion of deionized water is preferably 1: 5, when the reaction substance is in a liquid state.

According to a further advantageous embodiment of the invention, the reaction substance further has no proportions of fluorine, chlorine, bromine, iodine, lead, mercury and selenium, so that the device according to the invention works without harmful or environmentally harmful substances or substances.

The pumping device is preferably designed as a circulating pump and preferably causes a circulation of the treatment substance within the treatment container. It is However, alternatively or additionally conceivable that a pumping device is provided for generating a Wehrströmung. One or more nozzles are preferably coupled to the pumping device, through which the treatment substance is dispensed, in particular, into treatment containers, in particular for bath circulation.

The treatment container is preferably executable in any size. Particularly preferably, the treatment tank has an inside, i. on the side in contact with the treatment substance, a material or a mixture of materials which is not attacked by the treatment substance. Preferred materials here include, among others, stainless steel, GVP, PVC. However, it is also conceivable that not only the surface of the treatment container in contact with the treatment substance consists of such a material, but also that additional elements of the treatment container, in particular the entire treatment container, consists of such a material or material mixture.

According to a preferred embodiment of the present invention, a filter device is provided for filtering the treatment substance, wherein filtering removes impurities from the treatment substance which accumulate in the treatment substance. This embodiment is advantageous because the treatment substance in the treatment tank can be continuously or sequentially cleaned or processed.

According to another preferred embodiment of the present invention is the

Treatment container coupled to at least two receiving spaces, wherein a first

Receiving space a preferably formed below the treatment tank

Buffer receiving space for receiving a certain amount of the treatment substance, and wherein a second receiving space a preferably laterally of the

Treatment tank is formed Temperierungsraum, the

Tempering device is at least partially disposed in the Temperierungsraum.

The first recording space or buffer space may be e.g. to hold a desired

Serving volume of the treatment substance. Furthermore, it is conceivable that the first

Reception room or the buffer space for receiving or depositing sediments is used. The sediments may be e.g. Parts or particles that are different from the

Remove treatment items during treatment. The Temperierungsraum is preferably arranged laterally next to the treatment tank, as this is a very good

Accessibility to the temperature control can be created. Further, however, is Alternatively, also conceivable that the temperature control device in the first receiving space or in the buffer space, ie below the treatment container, is formed or arranged. This embodiment is advantageous in that the individual portions of the treatment substance can reach different functional areas or receiving spaces and the main receiving space, without damage to devices formed or arranged in one or more receiving areas, such as the tempering device, being possible by collision with the subject of treatment ,

The treatment container is separated in accordance with yet another preferred embodiment of the present invention by a wall of a collecting space for collecting treatment substance flowing over the wall, wherein the treatment substance collected in the collecting space by means of a conveyor, in particular by means of the pumping device, via a feed line into the treatment vessel is recoverable. This embodiment is advantageous since the particles accumulating on the surface of the treatment substance and detached from the treatment object and / or foam forming on the surface of the treatment substance and / or other material concentrations can be diverted out of the treatment tank and can preferably be fed to the filter device.

The pumping device and the filter device according to a further preferred embodiment of the present invention form a component of the delivery line and the conveyed treatment substance is preferably conveyed by or by means of the pumping device through the filter device. This embodiment is advantageous because, by means of this arrangement, the pumping device effects the delivery of the treatment substance through the filter device and at least partially a circulation of the treatment substance in the treatment container.

The or a delivery line is designed according to a further preferred embodiment of the present invention such that preferably by the back in the

Treatment tank promoted treatment substance, a weir flow for discharging a part of the treatment substance out of the treatment tank and into the

Collection space is generated in it. This embodiment is advantageous because by means of preferably a pumping device, the delivery of the treatment substance through the filter device, at least partially a circulation of the treatment substance in the

Treatment tank and the creation of a Wehrströmung is effected. According to a further preferred embodiment of the present invention, a metering device is provided for adjusting the composition of the treatment substance, wherein the treatment substance consists of a mixture of several components. Preferably, the metering device is indirectly coupled to one or more sensor devices directly or via a control device, the sensor devices preferably monitoring or analyzing the composition of the treatment substance and / or monitoring the volume or the remaining quantity or the filling level in the treatment container existing treatment substance allows or allow.

In particular, the metering device compensates losses by adding the appropriate amount of treatment substance lost, in particular evaporation and / or immersion losses are bleached out. The addition of the components which form the treatment substance, in particular of deionized water, the reaction substance and the treatment effect improving substance, is preferably carried out by the metering device. The addition of the components forming the treatment substance is preferably carried out in a fixed ratio, in particular in the ratio in which the individual components are also provided in the treatment container or in some other fixed ratio. Furthermore, it is conceivable that the treatment substance to be added is already added in the form of a finished mixture or finished solution.

The sensor device may preferably be used as a device for performing a titration, i. be designed for concentration determination. However, it is also conceivable that the metering and introduction of substances into the treatment substance is effected partially, temporarily or always manually.

According to a further preferred embodiment of the present invention, the proportion of reaction substance to the proportion of deionized water is between 1: 4 and 1: 7, wherein the proportion of reaction substance to the proportion of deionized water is preferably 1: 6, if the reaction substance in a solid state is mixed with the deionized water, or wherein the proportion of the reaction substance to the proportion of deionized water is preferably 1: 5, when the reaction substance is mixed in a liquid state with the deionized water. Preferably, the losses are also replaced in a fixed ratio of several substances. The preferred substance / s is / are here thus flowable, in particular liquid, or solid reaction substance / s, which is preferably mixed with a diluent, such as water, especially desalted or distilled water or fully demineralized water (deionised water) , Preferred mixing ratios between the reaction substance and the diluting substance, in particular demineralized water, are furthermore for example 1: 2; 1: 3. 1: 4; 1: 5; 1: 5.5; 1: 6; 1: 6.5; 1: 7.5; 1: 8; 1: 8.5; 1: 9.

Preferably, automatically or manually, depending on values generated by the sensors, an admixture of a mixture or solution of one or more additional substances, in particular one or more liquids, in particular demineralized water, and / or one or more preferably soluble additives to the treatment substance takes place. It is also conceivable for an additional substance, in particular for pickling degreasing and / or defoaming, to be added to the treatment substance. Preferably, the additional substance with about 0.5% to 10%, in particular with 1% to 5%, of the volume of the treatment substance of the treatment substance is buried. The use of demineralized water is preferred in this case, as this substantially or consistent surface quality is obtained on the treatment objects.

The use of a pickling remover is advantageous because by adding it to the treating substance, contaminants such as light fatty deposits, debris, oil, coal and graphite can be removed in the same operation.

The treatment substance is according to a particularly preferred embodiment of the present invention, a phosphorus or phosphate-containing solution, in particular phosphoric acid, wherein the phosphorus content or the phosphate content of the solution is preferably highly pure, i. a purity of more than 75%, in particular more than 75%. 80%, 82%. 85% and preferably of exactly or substantially 86%, which is by volume. Due to the purity of the phosphorus content or the phosphate content of the treatment substance according to the invention, it has almost no impurities, so that a corresponding protective layer is formed on the treatment object.

The pH of the reaction substance is preferably substantially 1, the density of the reaction substance is at a temperature of 20 ° C, preferably at 1, 8 and the Flash point of the reaction substance is preferably 280 ° C or preferably higher than 280 ° C.

In the case of treatment articles comprising aluminum or made of aluminum, the treatment substance preferably comprises deionized water and, in addition to the demineralized water, it prefers a reaction substance in an amount of 1-10%, especially 3-5%, of the amount of VE -Wassers. At a bath temperature of 40 ° C to 45 ° C, i. when the treating substance is at a temperature of 40 ° C to 45 ° C, the exposure time, i. the time that the treatment object is exposed in the treatment container of the treatment substance, preferably 0.5 min. To 20 min., And more preferably 1 min. To 10 min. The reaction substance here preferably consists of phosphoric acid, water, especially deionized water (ie demineralized water) and inhibitors.

According to a further preferred embodiment of the present invention, the treatment substance has an additive substance for pickling degreasing or such an additive substance is added to a treatment substance, wherein the etching agent additive preferably comprises an aqueous solution of nonionic biodegradable surfactants and inhibitors, in particular but-2-in-1 , 4-diol, and wherein the pickle degreaser additive is added with a volume of 0.5% to 7% of the volume of the phosphorus- or phosphate-containing solution or the treatment substance.

According to a further preferred embodiment of the present invention, the treatment substance has an additional substance for defoaming, the defoamer additive preferably having triisobutyl phosphate and the defoamer addition of the treatment substance having a volume of from 0.01% to 5%, in particular with a volume of 0.1%. to 1%, the volume of the phosphorus- or phosphate-containing solution or the treatment substance or with a volume of 0.01% to 5%, in particular with a volume of 0.1% to 1%, of the volume of the offset with the pickle degreaser phosphorus - or phosphate-containing solution or the treatment substance is added.

According to a further preferred embodiment of the present invention, a control device is provided, wherein the control device controls the tempering device such that the treatment substance to a Target temperature or a target temperature profile is tempered and / or wherein the control means controls the pumping means such that the treatment substance is conveyed with a target flow rate or a Zielströmungscharakteristik, and / or the control means controls the filter means such that the filtered portion of the treatment substance has a target purity, and / or the control device controls the metering device such that a target composition of the treatment substance is adjustable.

Furthermore, it is conceivable that according to a further embodiment or several further embodiments, the treatment device one or more ölabscheide system / s, ultrasonic system / s, high-pressure system / s, turning and lifting device / s and / or Vollentkalktes-water supply system / e has.

In accordance with a further preferred embodiment of the present invention, a degreasing bath, in particular for degreasing the articles of treatment with unusually high fat content, may be provided, in particular upstream of the treatment tank. This embodiment is advantageous in that the treatment substance in the degreasing bath may preferably be heated to a temperature higher than the preferable operating temperature of the treatment substance in the treatment tank. Preferably, the temperature in the degreasing bath is greater than 50 ° C. in particular greater than 52 ° C. and particularly preferably greater than or equal to 60 ° C. This embodiment is advantageous since only highly oiled or greased treatment objects can be introduced into a degreasing bath which is suitably tempered for degreasing In addition, the formation of water vapor in the region of the treatment container of the treatment device according to the invention can preferably be prevented if the temperature of the treatment substance is below a threshold temperature, in particular below 52 ° C. , is or is not heated above this threshold temperature.

The invention further relates to a treatment method for at least pickling and

Phosphating a, especially metallic, treatment object. The method according to the invention preferably comprises the steps of providing a

A treatment container for receiving at least one treatment article and for receiving a flowable treatment substance, wherein no further

Treatment tank is used for degreasing and phosphating, the introduction of the Treating substance into the treatment container and introducing the treatment object into the treatment container at least partially filled treatment container for contacting the treatment object with the treatment substance, wherein the contact between the treatment substance and the treatment object at least a pickling and phosphating the treatment object is effected, wherein the Treatment substance is a phosphorus or phosphate-containing solution, in particular phosphoric acid, wherein the phosphorus or phosphate-containing solution consists of a vollentkalktem water and on the other hand of a reaction substance, wherein the reaction substance of phosphorus or a phosphate and water, in particular deionized water, and preferably an additional treatment effect improving substance, wherein the proportion of the phosphorus or the phosphate to the reaction substance is at least 75%, wherein the proportion of the phosphorus or the Pho sphats on the reaction substance between 75% vol. and 94% vol., and is preferably between 80% vol. and 90% vol. and more preferably between 83% vol. and 88% vol. is. In particular, the reaction substance preferably contains no fractions of hydrochloric acid and sulfuric acid.

The treatment method according to the invention is advantageous because a closed circuit is created which does not require a rinsing process and thus does not require conveying the article into a sink. Furthermore, the method according to the invention is highly advantageous since, in particular in comparison with mechanical treatment methods, it enables a very thorough, gentle and rapid treatment of the subject of the treatment. This solution is also advantageous because the treatment substance is incombustible, the use of the treatment substance does not exceed the MAK values (maximum workplace concentration) and no corrosive vapors are caused, which means that no extraction is required.

The method according to the invention preferably further comprises the steps of removing the treatment object from the treatment tank, swirling impurities transferred to the treatment substance by the treatment article by means of a swirling device, wherein a swirling fluid is supplied to the treatment substance by the swirling device for swirling the contaminations, supplying the swirled Contaminating treatment substance to a filter device, filtering out the impurities from the treatment substance fractions, which are supplied to the filter device, re-introduction of the treatment article in the processing container with the treatment substance at least partially filled treatment container for contacting the treatment object with the filtered treatment substance or introducing a another treatment object in the treatment container at least partially filled treatment container for contacting the treatment object with the filtered treatment substance.

According to a further preferred embodiment of the present invention, a control device for operating the filter device and / or the swirling device is provided. An operation of the filter device preferably takes place at least temporarily as a function of an operation of the swirling device or wherein an operation of the swirling device takes place at least temporarily as a function of an operation of the filter device. The operation of the swirling device preferably comprises, at least temporarily, the provision of the fluid or swirling fluid and the actuation of the valve device. Preferably, the valve devices are controlled according to predetermined courses, in particular at programmed time intervals. This solution is advantageous because the impurities can be filtered out of the treatment substance very quickly or effectively.

Preferably, the treatment articles remain more than 5 minutes, in particular more than 10 minutes and preferably between 20 minutes and 120 minutes, in particular between 30 minutes and 90 minutes, together with the treatment substance in the treatment container.

The process according to the invention particularly preferably has the effect that the treatment object is exposed to the treatment substance such that degreasing and / or descaling and / or preserving and / or decalcifying of the treatment object takes place in addition to the pickling and phosphating.

According to a further preferred embodiment of the present invention, a non-porous protective layer is produced on the surface of the treatment article by means of the treatment substance, in particular by means of the reaction substance, with prevention of hydrogen embrittlement, the protective layer having a thickness of at least 2 μm and preferably of at least 3 μm. In particular, the nonporous protective layer protects the subject of the treatment from oxygen and water, so that rusting is effectively prevented. The protective layer, in particular a phosphate layer, in particular an iron phosphate layer, preferably results from the treatment method according to the invention, in particular after a drying time of 3 hours to 48 hours, in particular from 6 hours to 24 hours, in the ambient air or after a drying time of approx 5 minutes to 60 minutes, in particular of about 20 minutes, in an oven at 70 ° C to 150 ° C, in particular at about or 100 ° C, on the material surface of the object to be treated (in particular of iron or normal steel). The resulting protective layer is preferably between 2 m and 10 μιτι, in particular more than or exactly 3 μπι, 4 μητι or 5 μιη, thick. Particularly preferably, the protective layer has a thickness of 2 μπι to 10 μηη and preferably from 3 μηι to 8 μηι and more preferably from 4 μηι to 6 μιτι on. The protective layer preferably has no or essentially no pores and is therefore particularly preferably pore-free. Furthermore, the protective layer is elastic and particularly preferably adapts to temperature fluctuations of -60 ° C. to 750 ° C. and more preferably from -40 ° C. to 680 ° C., without flaking off, the protective layer preferably having a high flexural capability, in particular from to to 180 ° or more than 180 ° (eg iron bars). In this case, the protective layer can be an excellent basis for a further treatment, in particular a color treatment, which, for example, can follow the process of the invention. The protective layer preferably reacts neutrally and does not enter into any chemical connections with hydraulic fluids. Further extremely important advantages of the method according to the invention are that no rusting of the treatment objects takes place through the protective layer and, during pickling, material removal of preferably less than 10 g / m 2, in particular less than 5 g / m 2, and particularly preferably less than or equal to 2.24 g / sqm is done.

Furthermore, the treatment method according to the invention preferably also has the step of tempering the treatment substance which can be pre-stored in the treatment container and / or the step of generating a flow of at least part of the treatment substance, wherein at least a part of the treatment object is flowed around by the treatment substance.

According to a further preferred embodiment of the present invention, a tempering of the treatment substance vorhaltbaren in the treatment container by means of a temperature control device, wherein the temperature of the treatment substance is set defined by means of the temperature control device, and wherein by means of a pumping means, a flow for moving at least a portion of the treatment substance at least a part of the treatment object is flowed around by the treatment substance.

By means of a filter device, the treatment substance is filtered according to a further preferred embodiment of the present invention, wherein filtering removes impurities from the treatment substance which have accumulated in the treatment substance.

The treatment container is separated according to a further preferred embodiment of the present invention by a wall of a collecting space for collecting treatment substance flowing over a wall, wherein the treatment substance collected in the collecting space by means of a conveyor, in particular by means of the pumping device, fed back via a feed line in the treatment vessel becomes.

According to a further preferred embodiment of the treatment method according to the invention, the pump device and the filter device form part of the delivery line and the conveyed treatment substance is conveyed by the pump device through the filter device.

According to a further preferred embodiment of the treatment method according to the invention, the delivery line is designed in such a way that through the treatment substance conveyed back into the treatment container, a weir flow is generated for discharging a part of the treatment substance out of the treatment container and into the collection space.

According to a further preferred embodiment of the treatment method according to the invention, the composition of the treatment substance is controlled by means of a metering device, wherein the treatment substance consists of a mixture of several components.

According to a further preferred embodiment of the present invention, the treating substance is an additive for pickling degreasing and / or an additive substance for defoaming, the pickling agent additive preferably a aqueous solution of non-ionic biodegradable surfactants and inhibitors, in particular but-2-yn-1, 4-diol, and wherein the pickle degreaser additive with a volume of 0.5% to 7% of the volume of the phosphorus or phosphate-containing solution or the defoamer additive preferably comprises triisobutyl phosphate and wherein the defoamer additive of the treatment substance is in a volume of 0.1% to 1% of the volume of the phosphorus or phosphate-containing solution or in a volume of 0.1% to 1% by volume the phosphoric or phosphate-containing solution or treatment substance added with the pickling degreaser additive is added.

In accordance with a further preferred embodiment of the present invention, the temperature control device is controlled by means of a control device such that the treatment substance is heated to a target temperature or a target temperature profile and / or the pump device is controlled by the control device in such a way that the treatment substance is conveyed with a target flow velocity or a target flow characteristic and / or by means of the control device, the filter device is controlled so that the filtered portion of the treatment substance has a target purity, and / or by means of the control device, the metering device is controlled such that a target composition of the treatment substance is adjustable and / or by means of the control device is the Swirling device, in particular the supply device and / or the valve devices, in particular of the fluid line element and / or the supply device, controlled such that a turbulence or Aufwirbelung present in the treatment substance, in particular settled, impurities, in particular solid particles, such as metal particles, in particular rust particles, takes place.

The present invention is preferably also solved by a treatment plant.

Preferably, the treatment plant according to the invention comprises at least one or more of those mentioned above or below

Treatment devices, in particular one or more according to any one of claims 1 to 8 for forming a protective layer formed on the subject of the treatment

Treatment device, wherein the protective layer preferably has a thickness of 1 pm to 10 pm, and preferably from 3 pm to 8 pm or preferably from 2 pm to 4 pm, and at least one further surface treatment device for treating the

Protective layer of the subject of the treatment. Is preferred by the

Surface treatment device coated the protective layer, in particular painted or powder coated. Therefore, particularly preferably in the

Surface treatment device to a painting, at least for 9 is formed in sections coating the subject of the treatment, or a powder coating device, which is preferably formed for at least partially powder coating the subject of the treatment. Furthermore, a transport device for transporting the treatment object treated by means of the treatment device, in particular according to one of claims 1 to 8, to the surface treatment device is preferably provided. The powder coating can also be done by applying a powder coating.

Furthermore, the present invention also relates to a metallic object, in particular a metallic component, such as a frame, in particular a vehicle frame, or carrier element or connecting means or cladding element, or a metallic device, such as a container. The metallic object preferably has at least one metallic component, in particular a metallic surface component. Preferably, the metallic portion is provided with a phosphor or phosphate containing protective layer, the protective layer being e.g. a thickness of 1 pm to 10 pm and preferably from 3 pm to 8 pm or preferably from 2 pm to 4 pm. Particularly preferably, the protective layer is complete in volume, majority or substantially free of pores. The protective layer is preferably coated, in particular painted or powder-coated. The protective layer was preferably produced by means of a previously mentioned or subsequently mentioned and described treatment device, in particular according to one of claims 1 to 9, or the protective layer was preferably produced by a method mentioned above or below, in particular a method according to one of claims 10 to 14, or Protective layer and the coating produced on the protective layer was produced by means of a treatment plant, in particular according to claim 9.

The use of the words "substantially" preferably defines a deviation in the range of 1% -30%, in particular of 1% -20%, in particular of 1% -10, in all cases in which these words are used in the context of the present invention %, in particular from 1% -5%, in particular from 1% -2%, of the definition that would be given without the use of these words.

Individual or all illustrations of the figures described below are preferably to be regarded as construction drawings, ie the dimensions, proportions, functional relationships and / or arrangements resulting from the figure or figures preferably correspond exactly or preferably substantially to those of the device according to the invention or of the product according to the invention , Further advantages, objects and features of the present invention will be explained with reference to the following description of appended drawings, in which exemplary treatment devices according to the invention are shown. Elements of the devices and methods according to the invention, which in the figures at least substantially coincide with regard to their function, may hereby be identified by the same reference symbols, these components or elements not having to be numbered or explained in all figures. The invention will be described purely by way of example with reference to the accompanying drawings.

It shows:

1 shows a first illustration of a treatment device according to the invention in a passive state;

FIG. 2 shows a second illustration of a treatment device according to the invention in an active state; FIG.

Fig. 3 is a perspective view of another invention

Treatment device;

Fig. 4 is a perspective view of yet another invention

Treatment device;

5 shows a further perspective illustration of the treatment device according to the invention shown in FIG. 4;

FIG. 6 shows a detailed perspective view of part of the treatment device according to the invention shown in FIGS. 4 and 5; FIG.

FIG. 7 shows a first plan view of the treatment device according to the invention shown in FIGS. 4 to 6; FIG.

8 shows a second plan view of the treatment device according to the invention shown in FIGS. 4 to 6; a perspective view of substantially the bottom of the treatment device according to the invention shown in Figures 4 to 8; a first schematic side view of the treatment device according to the invention shown in Figures 4 to 9; a second schematic side view of the treatment device according to the invention shown in Figures 4 to 9; a scanning electron micrograph of a steel sheet, which has been treated by the method according to the invention; an enlarged view of the scanning electron micrograph of Figure 1 1, an example of a swirling device, as preferably according to the present invention preferably provided in a treatment vessel according to one of the figures 1 to 10, the known from FIG. 13, purely exemplary known swirling means is purely exemplary in arranged a treatment container, a side view of a device according to the invention with a vortex preferably arranged therein; a treatment plant according to the invention with a treatment device for pickling and phosphating and a surface treatment device; three differently configured samples after a salt spray test; three more differently configured samples after a salt spray test. In Fig. 1, a treatment device 1 according to the invention is shown. The treatment device 1 is used for treatment, in particular for degreasing, pickling, phosphating, descaling, preserving and de-rusting, one or more articles to be treated 2. The article 2 to be treated is preferably introduced from above into a treatment container 4 of the treatment device 1. The treatment container 4 is preferably at least partially and particularly preferably completely filled with a treatment substance 6. Furthermore, a tempering device 8 for tempering, in particular for heating, the treatment substance 6 is preferably provided. Furthermore, at least one pump device 10 is preferably provided for circulating the treatment substance 6 and / or for creating a weir flow 20 and / or for reclaiming treatment substance 6 that has emerged from the treatment container 4 back into the treatment container 4. The treatment container 6 is separated by a wall 12 of a collecting space 14. Due to the flow created in the treatment tank 4, treatment liquid 6 exits the treatment tank 4 via the wall 12 and thus enters the catchment space 14. However, it is also conceivable that the treatment substance or liquid 6 can be introduced into the treatment area 2 by introducing the treatment object 2 Treatment chamber 4 undergoes such a displacement that a part of the treatment substance 6 emerges from the treatment container 4 via the wall 12. The reference numeral 16 denotes a delivery line, by means of which the treatment substance 6 discharged from the treatment tank 4 is conveyed back into the treatment tank 4. In the region of the delivery line 16 or in the delivery line 16 or as part of the delivery line 16, a filter device 18 for filtering or processing the treatment substance 6 is preferably arranged. It is conceivable here that the pumping device 10 or a further pumping device (not shown) is arranged or formed in the course of the delivery line 16. Furthermore, a pumping filter device can be provided which either replaces a pumping device and / or a filter device or can be designed in addition thereto. It can also be seen from the illustration that the treatment container 4 preferably has at least one main receiving space 22, a first secondary receiving space 24 and a second secondary receiving space 26. The individual receiving spaces 22, 24, 26 are in this case, for example, by grids 27, in particular in each case a grid, separated from each other. The grille 27 prevents the object of treatment 2 from entering one of the secondary receiving spaces 24, 26. The reference numeral 28 denotes a nozzle, by means of which a flow of the treatment substance 6 can be generated. FIG. 2 shows the representation known from FIG. 1, the treatment object 2 being arranged in the treatment container 4 in accordance with this illustration and thus being in contact with the treatment substance 6.

FIG. 3 shows a further embodiment variant of a treatment device 1 according to the invention, in particular for wire coil treatment. The treatment device 1 shown in FIG. 3 has, by way of example, a receiving bag 40, which preferably carries a plurality of wire coils 39 to be treated. The receiving bag 40 is arranged on a delivery parts 41, wherein preferably a plurality of receiving bag 40 and several delivery points 41 are provided. Furthermore, the treatment device 1 preferably has a plurality of, in particular 2, 3, 4, 5, 6, 7, 8, or more, treatment baths 42. In a treatment bath 42 are preferably, in particular at the same time, a plurality, in particular 2, 3, 4, 5, 6, 7, 8, 9 or more, wire coils 39 at the same time introduced for treatment. The reference numeral 43 denotes a preferably purely optional device, namely a fixing bath. It is conceivable here that a plurality of wire coils 39, in particular 2, 3, 4, 5, 6, 7, 8 or more, can be introduced at the same time into a fixing bath 43. Furthermore, it is conceivable that a plurality of fixing baths 43 are provided. The treated wire coils 39 can be arranged at a removal point 44 for removal. The treated wire coils 39 are preferably conveyed to the respective removal point 44 with a transport device 45, in particular a dolly or a rail-guided gantry crane. Furthermore, several devices for supplying, regulating and controlling the treatment device 1 are preferably provided. Thus, the illustrated embodiment, for example, a pressure belt filter device 46, a metering device 47, a VE water treatment device 48, a control device 49, another pressure belt filter device 50, a storage tank for treatment tank 51 and a plurality of side channel compressor 52, in particular 8 pieces on. The metering device 47 is preferably automated and particularly preferably has a buffer tank with a volume of preferably more than 5m ³ , more preferably more than 10m ³ and most preferably more or exactly 20m ³ .

4 shows a perspective view of a treatment apparatus 1 according to the invention. The treatment apparatus 1 is preferably L-shaped, ie it comprises a treatment tank 4, wherein the treatment tank 4 has a first interior portion which extends at right angles to a second interior portion. Preferably, an interior portion is longer than the other interior portion, which is also conceivable that the interior parts are the same length or are substantially the same length. The illustrated design allows eg curved Elements, like pipes. To treat carriers, panels, etc. The treatment container 4 preferably has at least or exactly one wall 12, wherein an area into which the treatment objects to be treated are introduced is separated from a collecting space 14 by the wall 12. The collecting space 14 is preferably used for collecting over the wall 12 from the treatment chamber exiting treatment substance.

The reference numeral 10 denotes a pumping device, in particular for generating a flow within the treatment substance to be introduced into the treatment space. The reference numeral 18 denotes a filter device 18 for filtering or treating the treatment substance.

A flow of the treating substance is by means of nozzles 28a, 28b and 29a. 29b, 29c (see Fig. 5) causes, from which the pumped by means of the pumping device 10 treatment substance is pumped into the treatment chamber.

The housing 61 surrounds or houses the nozzles 29a-29c. Preferably, three rows with 2 nozzles 28a, 28b and three rows with three nozzles 29a, 29b, 29c are provided, wherein it is also conceivable that exactly or at least one nozzle 28 and / or 29 is provided. Particularly preferably, the nozzles 28 are inclined to the nozzles 29 aligned, in particular aligned at right angles.

The reference numeral 60 designates a main suction line, by means of which the treatment substance is discharged from the treatment space via outlets 57a-57g (see FIG. The discharged treatment substance is preferably processed by means of the filter device 18 and conveyed by means of the pumping device 10 via the nozzles 28 and 29 back into the treatment space.

The treatment apparatus 1 may preferably be dimensioned such that a footprint of 5100 mm × 3800 mm is required. Preferably, the treatment device 1 comprises a bath volume of substantially, up to. at least or exactly 14m ³ . The useful volume of the treatment device 1 according to the invention is preferably 3400 mm × 3000 mm × 1500 mm and the height of the overflow to the upper edge is preferably 200 mm.

FIG. 5 shows a further view of the aforementioned embodiment of the treatment apparatus 1 according to the invention. It can be seen from this illustration that the nozzles 29a-29c or the 3x3 nozzle arrangement are preferably located in a pocket 61 in FIG 6869 a wall of the treatment container 4 is housed in order not to disturb the useful surface or not to affect. Preferably, the nozzles 28a-28b are also housed in a pocket in another wall of the treatment tank 4, preferably not to disturb the useful surface or not to affect. The pockets 61 are preferably provided with a not shown ramming protection to avoid damaging the internals.

Furthermore, a further filter device 19 is shown, wherein the further filter device 19 is preferably designed as a coarse filter. Particularly preferably, the treatment substance to be treated is first aspirated from the treatment container, then fed to the further filter device 19, then passed through the pump 10, then passed through the filter device 18, which may be preferably designed as a bag filter, and then back via the nozzles 28, 29 conveyed into the treatment tank.

Furthermore, the illustration shows that the bottom of the treatment container 4 with respect to the horizontal inclined surface portions 53, 54, 55, 56 has. Preferably, the surface portions 53-54 and 55-56 are each arranged such that they form a linear contact area with each other in the region of a low point considered with respect to a vertical direction. The contact region is preferably at a level below a contact region between the outer wall of the container extending in the vertical direction and the respective surface portion or bottom portion 53, 54. The surface portions or base portions 53, 54 and 55, 56 thus preferably form channels through which the treatment substance and dirt particles are directed to one or more outlets. The surface portions 53-56 are preferably oriented with an inclination of 2 ° to 25 ° and more preferably with an inclination of 6 ° to 15 ° and most preferably with an inclination of substantially or exactly 10 ° with respect to the horizontal.

The reference numeral 8 denotes a preferably provided temperature control device. The tempering device 8 preferably has 8 electrical heating elements, in particular 2 KW. The heating elements are preferably also accommodated in the pocket 61 in the wall in order not to disturb or impair the preferably required effective area. The design of the heating power of the temperature control device may preferably be based on a Wessling system (20m ³ = 20KW heating power).

Fig. 6 shows in particular a detailed representation of the pocket 61, in which the nozzles 29a-29c and the temperature control device 8 are preferably arranged. 7 shows the first portion of a channel 62 resulting from the mutually inclined base portions 53, 54 and 55, 56 of the treatment container 4 and the resulting second portion 63 of the channel. The channel preferably also extends into the collecting space 14. Particularly preferably, in the gutter or in the region of the gutter outlets 57a-57f, in particular a plurality of outlets, are provided for discharging or for aspirating the treatment substance out of the treatment space. Furthermore, at least one outlet 57g for discharging or aspirating the treatment substance out of the collecting space 14 is preferably provided in the collecting space 14. The outlets 57a-57g are preferably in fluid communication with the main suction line 61 via connecting lines.

Not shown is a grid, which preferably aligned horizontally or perpendicular to the side walls of the treatment container 4 aligned the bottom 53, 54, 55. 56 of the treatment space superimposed, wherein the grate is spaced from the ground. in particular more than 20 mm and preferably more than 50 mm and more preferably more than 100 mm, wherein the grid is particularly preferably at most 500 mm from the bottom of the treatment container spaced. The grille preferably performs the function of spacing a treatment object introduced into the treatment room from the floor of the treatment room, whereby particles detached from the treated treatment objects can accumulate below the treatment object and so extraction of these particles is always possible.

Fig. 8 shows the main suction line 60 and a part of the connection pipes 58a-58g through which the outlets 57a-57g are connected to the main suction pipe 60. The total suction line preferably consisting of at least the connection tubes 58a-58g and the main line 60 is preferably designed to be removable. This is particularly advantageous for a cleaning of the individual parts of the Gesamtabsaugleitung.

9 shows a perspective view of the underside of the treatment apparatus 1 according to the invention. This illustration can be taken in particular from the connection pipes 58a-58g connected to the outlets and the main suction line.

FIGS. 10a and 10b show different side views of the treatment device 1 according to the invention shown in FIGS. 4 to 9. Figures 1 1 and 12 each show a steel sheet, which has been treated by the method according to the invention, and thereby results in a closed surface structure consisting of deposited on the steel sheet phosphorus. The scanning electron micrographs have been created by the Fraunhofer Institute with the specifics mentioned in the figures:

IFAM GEMINI

Resolution 10 pm

EHT = 10.00 kV

WD = 12.3 mm

Signal A = SE2

Signal B = InLens

Signal = 0.5000

As can be seen from the resolution of less than 10 pm, although the structure in the photograph is somewhat photographically shaped in relief, it is clear to the person skilled in the art that a smooth and closed surface structure has resulted from the deposited phosphorus on the steel sheet , This closed surface structure of phosphorus has resulted from the use of the ultrapure phosphor and can be used for further processing with lacquer or a powder coating without further pretreatment. This is particularly advantageous in that the deposited phosphor layers attach to the steel sheet without clearance, and as a result, the steel sheet is very rust resistant. In addition, the steel sheet thus treated with the deposited phosphor layers can be directly used for painting or powder coating. In salt spray tests, excellent results could be achieved with steel sheets having phosphorus deposited by the process according to the invention. Furthermore, the treated steel sheet with the protective phosphor layer could be stored for months without powder coating or painting due to the method according to the invention, which has not resulted in re-rusting in dry rooms.

13 shows a schematic illustration of an example of a turbulizer 70 in a plan view. The swirling device 70 may in this case be formed as a fixed component of a treatment container 4 or be detachably connected to such a treatment container 4. The swirling device 70 preferably comprises a fluid line element 74, which preferably comprises one or more line sections 80a-80e is formed. The individual line sections 80a-80e can in this case be formed by lines, in particular hoses or pipes. Preferably, each line section 80a-80e has a multiplicity of outlet openings 76, through which a fluidizing fluid, which can be supplied to the fluid line element 74 via a fluid supply device 72, can exit or escape from the fluid line element 74 again. The individual line sections (preferably tubes) are particularly preferably connected or coupled to a distributor device 84. Each line section 80a-80e is preferably connected or coupled to a valve device 78, in particular a magnetic shut-off valve. Preferably, the valve devices 78 are each arranged in the fluid flow direction of the fluidization element guided by the fluidizing fluid between the distributor device 84 and the first outlet device 76. Furthermore, it is conceivable that a plurality of line sections 80a-80e are coupled to a common valve device 78 or a common valve device 78, in particular a shut-off valve, such as a magnetic shut-off valve, is provided for several line sections. A control device 86 and / or pulse generator device 86 is preferably connected to the distributor device 84. The control device 86 in this case preferably causes the opening and / or closing of one, several, plurality, or all of the valve devices 78, in particular shut-off valves 78. The control device 86 preferably has a control valve device through which a fluid communication channel, by means of the control device 86 Verwirbelungsfluid is supplied, interrupted, limited or can be opened. The fluid communication channel is, preferably formed on the one hand by the distributor unit 84 with the adjoining line sections 80a-80e and on the other hand by a line connection 73, in particular a hose communicating with a fluid supply device 72 communicating. Alternatively, however, the fluid supply device 72 may also be connected directly to the control device 86 and / or the distributor unit 84. The fluid supply device 72 is preferably a pressure fluid port of a compressed fluid source, such as a compressed gas port of a compressed gas source, in particular a compressed air connection of a compressed air source. This may be, for example, a compressor and / or a pressurized storage.

In FIG. 14, the swirling device 70 known from FIG. 13 and described purely by way of example is arranged in a treatment container 4 and thereby exemplarily forms the device according to the invention. The treatment container 4 is bounded in this case in the longitudinal direction on the one hand by the Wehrwandung 12 and on the other hand by the rear wall 92. In the width direction, the treatment tank bounded on the one hand by the first side wall 90 and on the other hand by the second side wall 91. The bottom 82 of the treatment container 4 preferably has a discharge mouth 85, through which the treatment substance can be discharged from the main receiving space, in particular can be diverted or pumped off. The Abiaufmündung 85 is preferably connected to the filter device 18 such that the discharged via the Abiaufmündung 85 treatment substance is supplied to the filter device or can be fed. On the other hand, the weir wall 12 delimits the collecting space 14 into which the impurities stirred up by the swirling device 70 can be guided, with the treatment substance passing over the weir wall 12, over the discharge outlet 83 to the filter device 18 for filtering. Thus, pipes, in particular made of stainless steel, with a preferred diameter of between 4 mm and 6 mm, are preferably permanently installed on the tank bottom of the treatment plant. These tubes are preferably combined via a distributor unit. Particularly preferably, each tube is provided with a shut-off valve, wherein it is alternatively conceivable that only the distributor unit is provided with a valve device, in particular a shut-off valve, such as a magnetic shut-off valve, so that individual partial areas or the entire area can be acted upon in the bath. That is, as needed, the fluidizing fluid can be selectively supplied to one or more tubes, whereby special flows or turbulences can be generated in the treatment substance. About the fluid line element or the piping is preferably during the downtime of the treatment plant or the device according to the invention the fluidizing fluid under pressure, in particular compressed air, embedded in the bath or the treatment substance and thus the still stored on the ground dirt whirled, so that he in can distribute the liquid or the treatment substance. The admission, in particular blowing, of the fluidizing fluid, in particular of the compressed air, is preferably controlled by a time-switching valve and / or a control device 86 and can take place uniformly or pulsatingly, permanently or at programmed time intervals or as a function of detected sensor measurement data. Preferably, during the blowing of the fluid and more preferably up to 3 hours after or up to two hours after or until 1 hour after or more than 3 hours after that, the filter device 18 or the installed filter system preferably runs with and removes the fluidized up dirt from the treatment substance.

Fig. 15 shows schematically the ascending fluidizing fluid, in particular the ascending air bubbles 88. Through the air bubbles 88 exiting through the outlet ports 76, the treatment substance is fluidized. Furthermore, impurities, in particular sludge, from the bottom region of the invention are produced together with the air bubbles Device stirred up and promoted up to the Wehrströmung. Furthermore, FIG. 15 shows a conduit 75 purely as an alternative to the conduit 73. The conduit 75 may in this case be coupled to the treatment vessel 4 such that portions of the treatment substance can be removed from the treatment vessel 4. The treatment substance fractions removed by means of the line 75 are then preferably supplied to the swirling device 70 by means of a pumping device (not shown). The swirling fluid delivered by the swirling device 70 in this case to the treatment substance provided in the treatment container for swirling the treatment substance provided in the treatment container is thus the proportion of the treatment substance removed via the line 75. The line 75 may in this case be connected, for example, to the treatment substance removal means or the opening or mouth or suction opening 85.

FIG. 16 shows a purely exemplary and schematic structure of the treatment installation 100 according to the invention. According to this representation, one or more of the treatment facilities 1, as e.g. is known from the preceding figures, be provided. Furthermore, one or more surface treatment devices 94 for surface treatment of the treatment object 2 previously treated by the treatment device 1 can be further treated. Preferably, a further treatment of at least a portion of the surface of the treatment article 2 and more preferably at least the majority of the surface of the treatment article 2, and most preferably of substantially or exactly the entire surface of the treatment article 2, is performed. The surface treatment device 94 is preferred for coating the treatment article 2 educated. Preferably, the surface treatment device 94 applies or produces one or more layers of material on the surface of the treatment article 2. The surface treatment device 94 preferably effects a powder coating and / or a coating of the treatment object. Preference here may be given as varnish, e.g. a 2K HS one coat paint can be used.

It is also conceivable that in the transport path 96 between the treatment device 1 and the surface treatment device 94, a drying device (not shown) is provided or designed for drying the treatment object 2. Additionally or alternatively, it is conceivable that after the surface treatment device 94 or as part of the surface treatment device, a drying device (not shown) is provided or formed. It is also conceivable that the step Powder coating is to be understood as the application of a powder coating. In the case of the application of a powder coating, a primer is preferably produced or applied to the subject of treatment prior to the application of the powder coating by the surface treatment device 94 or by an upstream device, in particular by means of cathodic dip painting.

Figures 17a-c show schematically test results as recorded in a salt spray test. All surfaces are provided with a 2K HS one-coat paint. Fig. 17a shows the surface of a normal steel after a 600 hour salt spray test. The degree of blast according to ISO 4628-2 is mOgO, the infiltration at the score is 18mm, the degree of rust according to ISO 4628-03 is Ri 0 and the delamination at the scribe is 21 mm. Fig. 17b shows the surface of a normal phosphated steel after a 600 hour salt spray test. The degree of blasting according to ISO 4628-2 is mOgO, the infiltration at the scribe is 17mm, the rust degree according to ISO 4628-03 is Ri 0 and the delamination at the scribe is 25-28 mm.

Fig. 17c shows the surface of a steel pretreated according to the present invention after a 1000 hour salt spray test. The degree of blistering according to ISO 4628-2 is mOgO, the infiltration at the score is 6mm, the degree of rust according to ISO 4628-03 is Ri 0 and the delamination at the score is 4-6 mm.

It is thus recognized that many 2K HS systems based on polyesters in salt spray resistance have great problems with undercutting at the scribe. When the present invention is applied, there are massive improvements in this phenomenon.

Figs. 18a-c schematically show differently treated surfaces each exposed to a salt spray test for 1008 hours. The metal body shown in FIG. 18a was phosphated by a method known in the art, then a cathodic dip was applied, and finally the metal body was coated with a powder paint. The infiltration at the Ritz is 2mm. There is no blistering or rusting on the surface. The delamination on the Ritz, tested with fabric adhesive tape, is 3mm. The metal body shown in FIG. 18b was pretreated with the treatment device according to the invention, then a cathodic dip coating was applied and finally the metal body was coated with a powder coating. The infiltration at the Ritz is 1 mm. There is no blistering or rusting on the surface. The delamination on the Ritz, tested with fabric adhesive tape, is 2mm. The metal body shown in FIG. 18c was pretreated with the treatment device according to the invention and then the metal body was coated with a powder coating. The infiltration at the Ritz is 5mm. There is no blistering or rusting on the surface. The softening on the Ritz, tested with fabric adhesive tape, is 5mm.

In FIGS. 17a-c and 18a-c, the reference numerals 11 and 12 respectively indicate two mutually different indicator locations which have been analyzed to determine the indicated measured values.

The present invention can thus relate to a treatment device 1 for single-stage treatment of a metallic object 2, the treatment comprising at least the pickling and the phosphating of the article 2, wherein the treatment device 1 comprises at least the following devices: a treatment container 4 for receiving the metal object Treatment article 2 and for receiving a flowable treatment substance 6, and a pumping device 10 for exchanging at least a portion of the treatment substance 6, wherein at least a part of the treatment article 2, in particular the entire treatment article 2, is flowed around by the treatment substance 6, wherein the treatment substance 6 a phosphoric or phosphate-containing solution, in particular phosphoric acid, is, wherein the phosphorus or phosphate-containing solution consists of a water and on the other hand from a reaction substance, wherein the reaction substance from Phosphorus or a phosphate and an additional treatment effect improving substance, wherein the proportion of the phosphorus or the phosphate to the reaction substance preferably at least 75% vol. is, wherein the reaction substance in particular has no proportions of hydrochloric acid and sulfuric acid.

The present invention preferably relates to a treatment device 1 for single-stage treatment of a metallic treatment article 2, wherein the treatment comprises at least the pickling and the phosphating of the treatment article 2, wherein the treatment device 1 comprises at least the following devices: a treatment container 4 for receiving the treatment article 2 and for receiving a flowable treatment substance 6, a pumping device 10 for circulating at least a portion of the treatment substance 6, wherein at least a part of the treatment object 2, in particular the entire treatment object 2, is flowed around by the treatment substance 6, wherein the treatment substance 6 a phosphorus or phosphate-containing Solution, in particular phosphoric acid, wherein the phosphorus or phosphate-containing solution consists of a water and on the other hand of a reaction substance, and a swirling device 70 for stirring up in the treatment substance depositing impurities, in particular solid particles, wherein the swirling device 70 at least one supply device 72 and a fluid conduit member 74 having a plurality of outlet ports 76 for supplying a fluidizing fluid to the treatment substance 6, wherein the fluidizing fluid is supplied by the supply means 72 to the fluid conduit member 74 with a pressure of more than 2bar.

The present invention particularly preferably relates to a treatment device 1 for single-stage treatment of a metallic treatment article 2, wherein the treatment comprises at least pickling and phosphating of the treatment article 2: Preferably, the treatment device 1 according to the invention comprises at least the following devices: a treatment container 4 for receiving a pumping device 10 for circulating at least a portion of the treatment substance 6, wherein at least a part of the treatment object 2, in particular the entire treatment object 2, is circulated by the treatment substance 6, wherein the treatment substance 6 a phosphoric or phosphate-containing solution, in particular phosphoric acid, is, wherein the phosphorus or phosphate-containing solution for a water, especially deionized water, and on the other from a Reactio Substance consists. Preferably, the reaction substance consists of phosphorus or a phosphate and at least one additional treatment effect improving substance, in particular having one or more inhibitors. The proportion of the phosphorus or the phosphate in the reaction substance is preferably between 75% vol. and 94% vol. and preferably between 80% vol. and 90% vol. and more preferably between 83% vol. and 88% vol. The reaction substance preferably has no proportions of hydrochloric acid and sulfuric acid and further preferably does not contain any amounts of fluorine, chlorine, bromine, iodine, lead, mercury and selenium and is preferably in a ratio of 1kg reaction substance to 4 liters of water and 1 kg reaction substance to 12 liters of water mixed with water, in particular in a ratio of 1 kg of reaction substance to 6 liters mixed with water. LIST OF REFERENCE NUMBERS

Treatment device 48 VE water treatment device Subject of treatment

49 control device

treatment tank

50 Further pressure belt filter device Treatment substance

51 storage tank

tempering

52 side channel blower

pumping device

53 First inclined ground wall

54 Second sloping soil retention area

55 Third inclined soil share

56 Fourth inclined bottom section Filter device

57 outlet

Further filter device

58 connection pipe

weir flow

60 main suction line

Main reception space

61 bag with nozzles

First secondary room

62 First part of the channel

Second side room

63 Second part of the channel

grid

70 swirling device

jet

72 Supply device wire coil

73 line

Treatment device for

Treatment of wire 74 Fluid line element Delivery point 76 Outlet openings Treatment bath 78 Valve device Fixing bath 80 Line sections / pipes Removal point 80a First line section Transport device 80b Second line section Pressure belt filter device 80c Third line section Metering device 80d Fourth line section 80e fifth line section 90 side wall

82 floor 92 rear wall

84 distributor unit 94 surface treatment device

86 control unit

96 Transport route

84 Abiaufmündung in the collection area

100 treatment plant

86 Abiaufmündung in

Main receiving space 11 first indicator place

88 ascending fluid (preferably 12 second indicator air)

Claims

claims

A treatment device (1) for treating a metallic object for treatment (2), the treatment comprising at least pickling and phosphating the subject (2), the treatment device (1) comprising at least the following: a treatment container (4) for Receiving the treatment object (2) and receiving a flowable treatment substance (6), pumping means (10) for circulating at least a portion of the treatment substance (6), at least part of the treatment object (2), in particular the entire treatment object (2) , is circulated by the treatment substance (6), wherein the treatment substance (6) is a phosphorus- or phosphate-containing solution, in particular phosphoric acid, wherein the phosphorus- or phosphate-containing solution on the one hand of water, especially deionized water, and on the other hand from a Reaction substance consists, and the reaction substance of phosphorus or a Pho sphat and at least one additional treatment effect improving substance, in particular having one or more inhibitors, wherein the proportion of the phosphorus or the phosphate in the reaction substance is between 75% vol. and 94% vol., and is preferably between 80% vol. and 90% vol. and more preferably between 83% vol. and 88% vol. wherein the reaction substance has no proportions of hydrochloric acid and sulfuric acid, and preferably further no proportions of fluorine, chlorine, bromine, iodine, lead, mercury and selenium, and wherein the reaction substance is mixed with water in a predetermined ratio, wherein the predetermined ratio is between a lower limit and an upper limit, the lower limit is defined by a mixture in a ratio of 1kg reaction substance to 3 liters of water and the upper limit by a mixture of 1kg Reaction substance is defined to 12 liters of water, in particular, the mixture is present in a ratio of 1kg reaction substance to 6 liters of water.

2. Treatment device according to one of the preceding claims, characterized in that a swirling device (70) for swirling up in the treatment substance depositing impurities, in particular solid particles, is provided, wherein the swirling device (70) at least one supply device (72) and a fluid line element ( 74) having a plurality of outlet openings (76) for supplying a fluidizing fluid to the treatment substance (6), said fluidizing fluid being deliverable by said providing means (72) to said fluid conduit member (74) at a pressure greater than 2 bar, said fluid conduit member (74 ) forms a plurality by means of valve devices (78) from each other decoupled line sections (80), wherein at least the majority of the line sections (80) in the region of the bottom (82) of the treatment container (4) are arranged.

3. A treatment device according to claim 2, characterized in that the line sections are formed by tubes (80), in particular with a diameter between 2mm and 12mm and preferably in a diameter between 3mm and 9mm and more preferably in a diameter between 4mm and 6mm, wherein the tubes (80) are coupled to or disposed on the bottom (82) of the treatment container (4), the tubes (80) being interconnected by at least one distributor unit (84), and each valve means (78) being a shut-off valve , in particular as a shut-off solenoid valve, and the provision device (72) is designed to provide a gas which is under at least 2 bar pressure, in particular air.

4. Treatment device (1) according to one of the preceding claims, characterized in that a filter device (18) for filtering the treatment substance (6) is provided, wherein by filtering impurities from the treatment substance (6) are removed, resulting in the treatment substance (6) have enriched, and a control device for operating the filter device and / or the swirling device is provided, wherein the filter device and the swirling device are at least temporarily operable in dependence on each other.

5. Treatment device (1) according to one of the preceding claims 2 to 4, characterized in that the operation of the swirling device at least temporarily comprises the provision of the fluid and the control of the valve device, wherein the valve means according to predetermined courses, in particular at programmed intervals, are controllable.

Treatment device (1) according to one of the preceding claims, characterized in that the treatment container (4) is separated by a wall (12) from a collecting space (14) for collecting treatment substance (6) flowing over the wall (12) in the receiving chamber (4) in the receiving space (14) trapped treatment substance (6) by means of a feed line (16), wherein the pump means (10) and the filter means (18) form a part of the delivery line (16) and the conveyed treatment substance (6) from the pumping device (10) through the filter device (18) is conveyed through, wherein the conveying line (16) is designed such that by the back into the treatment tank (4) funded treatment substance (6) a weir flow (20) for Discharging part of the treatment substance (6) out of the treatment container (4) and into the collecting space (14).

Treatment device (1) according to one of the preceding claims, characterized in that the treatment substance (6) an additive substance for defoaming is added, wherein the defoamer additive preferably triisobutyl phosphate and wherein the defoamer additive of the treatment substance (6) with a volume of 0.01% to 5% , in particular with 0.2%, of the volume of the phosphorus- or phosphate-containing solution or with a volume of 0.01% to 5%, in particular 0.2%, of the volume of the phosphoric- or phosphate-containing solution added with the pickling-degreaser additive and / or an additive substance for pickling-degreasing is added to the treatment substance (6) Pickle Filler Additive preferably comprises an aqueous solution of non-ionic biodegradable surfactants and inhibitors, in particular but-2-yn-1,4-diol, and wherein the pickle degreaser additive has a volume of from 0.5% to 7%, especially from 1% to 5% %, of the volume of the phosphorus or phosphate-containing solution is added.

8. Treatment device (1) according to one of the preceding claims, characterized in that the treatment container (4) such a main receiving space (22) into which the treatment object (2) can be introduced and at least one first side receiving space (24), wherein the main receiving space (22) and the first auxiliary receiving space (24) are connected to one another in such a way that the treatment substance (6) can flow out of the main receiving space (22) into the first secondary receiving space (24) and from the first secondary receiving space (24). out into the main receiving space (22), wherein the main receiving space (22) and the first side receiving space (24) are delimited from each other such that penetration of the subject of treatment (2) into the first sub receiving space (24) is at least partially and preferably completely prevented and wherein the main receiving space (22) is also coupled to a second secondary receiving space (26), wherein the first sub-receiving space (24) is a buffer receiving space formed below the main receiving space (22) for receiving a predetermined amount of treating substance (6), and wherein the second sub-receiving space (26) is a tempering space preferably formed laterally of the main receiving space (22) the temperature control device (8) is arranged at least partially in the second secondary receiving space (26).

9. treatment plant, comprising at least one or more treatment devices according to one of claims 1 to 8 for producing a protective layer on the treatment article, wherein the protective layer has a thickness of 1 pm to 10 pm, and preferably from 3 pm to 8 pm or preferably from 2 pm to 4 pm, and at least one further surface treatment device for treating the protective layer of the treatment article, wherein the protective layer is coated, in particular painted or powder-coated by the surface treatment device, wherein the surface treatment device is designed as a painting device for at least partially coating the treatment object or as a powder coating device at least in sections powder coating of the subject of the treatment is formed, and wherein preferably a transport device for transporting by means of the treatment device according to one of the claims 1-8 treated article of treatment to the surface treatment device.

0. Treatment method for processing, in particular metallic, subject of treatment (2), comprising at least the steps:

Providing a treatment container (4) for receiving at least one treatment object (2) and for receiving a flowable treatment substance (6),

Introducing the treatment substance (6) into the treatment container (4), wherein no further treatment container is used for pickling and phosphating, and

Introducing the treatment object (2) into the treatment container (4) at least partially filled with the treatment substance (6) for bringing the treatment object (2) into contact with the treatment substance (6), the contact between the treatment substance (6) and the treatment object (2) at least one cleaning, in particular a degreasing, and phosphating the treatment object (2) is effected, wherein the treatment substance (6) is a phosphorus or phosphate-containing solution, in particular phosphoric acid, wherein the phosphorus or phosphate-containing solution on the one hand from water and on the other hand consists of a reaction substance, wherein the reaction substance of phosphorus or a phosphate and water, wherein the proportion of the phosphorus or phosphate to the reaction substance between 75% vol. and 94% vol., and is preferably between 80% vol. and 90% vol. and more preferably between 83% vol. and 88% vol. is, wherein the reaction substance has no proportions of hydrochloric acid and sulfuric acid, and in a ratio of 1kg of reaction substance to 4 liters of water and 1kg of reaction substance to 12 liters of water mixed with water. especially in a ratio of 1 kg of reaction substance to 6 liters is mixed with water.

1 1. A method according to claim 10, characterized in that the treatment substance is heated to a temperature between 35 ° C and 70 ° C, in particular to a temperature between 40 ° C and 60 ° C, and the treatment subject between 15 minutes and 90 minutes , in particular between 30 minutes and 60 minutes is immersed in the treatment substance.

12. The method of claim 10 or 11, further comprising the steps of:

Removing the subject of treatment from the treatment container,

Drying of the treatment article, in particular by means of a drying oven,

Treating a protective layer produced by the previously performed treatment by means of a surface treatment device, wherein the protective layer is painted or powder-coated by means of the surface treatment device.

13. The method according to any one of claims 10 to 12, further comprising the step:

Adding an additive substance for pickling degreasing to the treatment substance (6), wherein the pickle degreaser additive preferably comprises an aqueous solution of nonionic biodegradable surfactants and inhibitors, in particular but-2-yn-1,4-diol, and wherein the pickle degreaser additive has a volume of 0.5% to 7%, in particular 1% to 5%, of the volume of treatment substance (6) is added. and / or the step:

Adding an additional substance for defoaming to the treatment substance (6), wherein the defoamer additive comprises triisobutyl phosphate and wherein the defoamer additive of the treatment substance (6) has a volume of 0.01% to 5%, in particular 0.2%, of the volume of the treatment substance (6) 6) or with a volume of 0.01% to 5%, in particular 0.2% by volume of the treatment substance (6) added with the pickle degreaser additive.

14. The method according to any one of claims 10 to 13, further comprising the steps:

Removing the subject of treatment from the treatment container,

Agitating impurities transferred to the treating substance by the treatment article by means of a swirling device, wherein, for swirling the impurities, a fluidizing fluid is supplied to the treating substance through the swirling device,

Supplying the treatment substance provided with the fluidized impurities to a filter device,

Filtering out impurities from the treatment substance fractions fed to the filter device, Reintroducing the treatment object (2) into the treatment container (4) at least partially filled with the treatment substance (6) for contacting the treatment object (2) with the filtered treatment substance (6) or

Introducing a further treatment object into the treatment container (4) at least partially filled with the treatment substance (6) for bringing the treatment object (2) into contact with the filtered treatment substance (6), characterized in that a control device for operating the filter device and / or the Whirling device is provided, wherein an operation of the filter device is at least temporarily in response to an operation of the swirling device or wherein an operation of the swirling at least temporarily in response to an operation of the filter device takes place wherein the operation of the swirling at least temporarily includes the provision of fluidizing fluid and the control of the valve device , wherein the valve devices are controlled according to predetermined courses, in particular at programmed intervals.

15. Metallic object, in particular metallic component, such as a frame, in particular a vehicle frame, or carrier element or connecting means or cladding element, or metallic device, such as a container, at least comprising a metallic portion, wherein the metallic portion provided with a phosphor or phosphate-containing protective layer is wherein the protective layer has a thickness of 1 pm to 10 pm and preferably from 3 μm to 8 μm or preferably from 2 μm to 4 μm, and wherein the protective layer is nonporous and wherein the protective layer is coated, in particular painted or powder-coated, and wherein the protective layer was produced by means of a treatment device according to one of claims 1 to 9 or the protective layer was produced by a method according to one of claims 10 to 14 or the protective layer and the coating produced on the protective layer were produced by means of a treatment plant according to claim 9.