DE102015014323A1 - Treatment device for pickling and phosphating of metal parts and treatment methods and treatment plant for coating the metal parts - Google Patents

Abstract

The present invention relates to a treatment device (1) for single-stage treatment of a metallic treatment article (2), the treatment comprising at least pickling and 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 object (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 treatment object (6) flows around the treatment object (2), the treatment substance (6) being a solution containing phosphorus or phosphate, in particular phosphoric acid, the solution containing phosphorus or phosphate being firstly water, in particular demineralized water , and on the other hand consist of a reaction substance t, and the reaction substance of phosphorus or a phosphate and at least one additional treatment effect improving substance, in particular one or more inhibitors comprising, 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. wherein the reaction substance has no proportions of hydrochloric acid and sulfuric acid and preferably also 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 between a Lower limit and an upper limit, wherein the lower limit is defined by a mixture in 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, in particular, the mixture is in a ratio of 1 kg of reaction substance to 6 liters of water before.

Description

The present invention relates according to claim 1 to a treatment apparatus for single-stage treatment of objects, 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 because z. As sulfuric acids and hydrochloric acids are used, which either expensive safety measures must be performed or there is a high risk to personnel and the environment and 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 stress of the respective object, eg. B. by the initiation of Eigenigen- 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 phosphate-containing solution consists firstly of water and on the other hand 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 one or more inhibitors, and water, in particular deionized water, consists, wherein the proportion of phosphorus or of the phosphate 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. and most preferably between 84% vol. and 87% vol., such. B. 85% vol. or 86% vol., and the treatment effect improving substance, particularly one or more inhibitors, is preferably in an amount of 0.1 vol.% to 2.5 vol.%, preferably between 0.2 vol.% and 2 vol.%, and especially 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. Further, 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 1 kg of reaction substance to 3 liters of water and the upper limit 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 between 1 kg of reaction substance to 5 liters of water and 1 kg of reaction substance to 7 liters of water with water mixed, 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 1 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, by the protective layer z. B. prevents the material of the treatment article oxidized, whereby a treated by means of the device according to the invention treatment object may be exposed to the air much longer than an untreated article.

According to another 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 supply device and a fluid line element with a plurality of outlet openings for supplying a fluidizing fluid to the treatment substance Verwirbelungsfluid by the provision device the fluid line element with a pressure of more than 2 bar, in particular more than 3 bar or more than 4 bar or more than 5 bar or more than 6 bar or more than 7 bar or with up to 10 bar or with to to 15 bar or with up to 20 bar, 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 conduit element forms a plurality of conduit sections which can be decoupled from one another at least functionally or fluidically by means of valve devices, wherein at least the majority of the conduit sections are arranged in the region of the bottom of the treatment vessel. As the area of the soil here is everyone Consider proportion of the treatment container, which is arranged or formed closer to the bottom than the opening formed on the upper side of the treatment container. 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 50 cm, preferably less than 30 cm and more preferably less than 10 cm 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 copper, aluminum, iron and / or stainless steel, in particular with a tube diameter between 2 mm and 12 mm and preferably in a tube diameter between 3 mm and 9 mm and more preferably in a pipe diameter between 4 mm and 6 mm, wherein the tubes are coupled to the bottom of the treatment container or are arranged thereon, wherein the tubes are interconnected by means of at least one distributor unit, and wherein each valve device as a shut-off valve, in particular as Absperrmagnetventil formed is. 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, especially 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 connected in such a way that fluid of the treatment substance flows through all of the outlet openings which are fluidically connected to the open valve devices for a preferably predetermined period of time is supplied. However, it is also conceivable here for one or more valve devices to be connected in succession, in particular to be pulsed. 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. The sensor data can be z. B. data regarding the proportion of impurities in the bottom region of the device and / or in one or individual areas of the treatment vessel. 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 MAK values (Maximum Workplace Concentration) and no corrosive vapors are caused, thus requiring no suction.

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. You can z. B. used for the pre- 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 on putty in the removal of casting skin is therefore considerable. Furthermore, z. As hydraulic pipes and pipes are 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 preferable temperature of the treating substance is preferably higher than 0 ° C, especially higher than or equal to 5 ° C, higher than or equal to 10 ° C, higher than or equal to 15 ° C, higher than or equal to 17 ° C, higher than or equal to 20 ° C, higher or equal to 25 ° C, higher than or equal to 30 ° C, higher than or equal to 35 ° C, higher than or equal to 37 ° C, higher than or equal to 40 ° C, preferred 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 may be 20: 20C × 6. 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 35 ° C to 45 ° C, this temperature range is advantageous because an extraction is not necessary because no corrosive or harmful to health vapors. However, it is conceivable that a suction is provided when z. B. the working space is extremely low or if the working space is not to ventilate.

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. However, it is alternatively or additionally conceivable that a pump device is provided for generating a weir flow. 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 container on the inside, d. H. 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 are in addition to other z. B .: 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 can be continuously or temporarily cleaned or treated in the treatment tank.

In accordance with a further preferred embodiment of the present invention, the treatment container is coupled to at least two receiving spaces, wherein a first receiving space is a buffer receiving space preferably formed below the processing container for receiving a certain amount of the treatment substance, and wherein a second receiving space is a temperature control space preferably formed laterally of the treatment container is, wherein the temperature control device is at least partially disposed in the Temperierungsraum. The first recording room or the buffer space can, for. B. serve to provide a desired volume of the treatment substance. Furthermore, it is conceivable that the first receiving space or the buffer space is used for receiving or depositing sediments. The sediments can hereby z. For example, particles or particles that detach from the treatment articles during the treatment. The tempering space is preferably arranged laterally next to the treatment tank, as this can provide a very good accessibility to the tempering device. Furthermore, however, it is alternatively also conceivable that the tempering device is formed or arranged in the first receiving space or in the buffer space, ie below the treatment container. This embodiment is advantageous because the individual portions of the treatment substance can reach different functional areas or receiving spaces and the main receiving space without damaging one or more of them Receiving areas trained or arranged facilities, such as the tempering, by a collision with the subject of the treatment is possible.

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.

According to a further preferred embodiment of the present invention, the pump device and the filter device form a constituent part of the delivery line, and the conveyed treatment substance is preferably conveyed through the filter device by means of or by means of the pumping device. This embodiment is advantageous because, by this arrangement, the pumping means causes the conveying of the treatment substance through the filter device and at least partially causes a circulation of the treatment substance in the treatment container.

According to a further preferred embodiment of the present invention, the delivery line or a delivery line is designed in such a way that a weir flow for discharging part of the treatment substance out of the treatment container and into the collection space can preferably be generated by the treatment substance conveyed back into the treatment container. 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 container 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 be preferably used as a device for performing a titration, i. H. 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), preferably with a diluent substance, such as. As water, especially desalinated or distilled water or fully demineralized water (deionized water), is / are mixed. Preferred mixing ratios between the reaction substance to the diluting substance, in particular deionized water, are also z. 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 produced 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 Phosphotanteil of the solution is preferably highly pure, d. H. has 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 preferably 1.8 at a temperature of 20 ° C. 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, d. H. when the treatment substance is at a temperature of 40 ° C to 45 ° C, the exposure time, i. H. 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 temperature control device such that the treatment substance is heated to a target temperature or a target temperature profile and / or wherein the control device controls the pumping device such that the treatment substance with a target flow rate or a target flow characteristic is promoted, and / or the control device controls the filter device 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 another embodiment or several further embodiments, the treatment device one or more oil separation system / s, ultrasonic system / s, high-pressure system / s, turning and lifting device / s and / or Vollentkalktes-water supply system / e has.

According to another preferred embodiment of the present invention, a Degreasing, in particular for degreasing the treatment objects provided with unusually high fat content, in particular the treatment tank upstream, be. 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. The temperature in the degreasing bath is preferably greater than 50.degree. C., in particular greater than 52.degree. C. and particularly preferably greater than or equal to 60.degree. This embodiment is advantageous since only very heavily oiled or greased treatment objects can be introduced into a degreasing bath suitable for degreasing. This has considerable energy advantages, since the temperature of the preferably 50 ° C heated to above degreasing bath preferably does not have to be permanently or only temporarily effected. Furthermore, the formation of water vapor in the region of the treatment container of the treatment device according to the invention can be prevented if the temperature of the treatment substance is below a threshold temperature, in particular below 52 ° C., or is not heated above this threshold temperature.

The invention further relates to a treatment method for at least pickling and phosphating a, in particular metallic, treatment object. The method according to the invention preferably comprises the steps of providing a treatment container for receiving at least one treatment article and receiving a flowable treatment substance, wherein no further treatment container is used for degreasing and phosphating, introducing the treatment substance into the treatment container and introducing the treatment article into the treatment container Treatment substance at least partially filled treatment container for bringing the treatment object into contact with the treatment substance, wherein the contact between the treatment substance and the treatment object causes at least irritation and phosphating of the treatment object, the treatment substance being a phosphorus- or phosphate-containing solution, in particular phosphoric acid, wherein the phosphorus or phosphate-containing solution on the one hand from fully descaled water and on the other hand from a Reaktionsssubsta nz, wherein the reaction substance of phosphorus or a phosphate and water, in particular demineralized water, and preferably an additional treatment effect improving substance, wherein the proportion of the phosphorus or phosphate to the reaction substance is at least 75%, wherein the proportion of the phosphorus or phosphate 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 MAK values (Maximum Workplace Concentration) and no corrosive vapors are caused, thus requiring no suction.

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 portions, which are supplied to the filter device, re-introduction of the treatment article in the treatment container at least partially filled treatment container for contacting the treatment object with the filtered treatment substance or introducing a further treatment article in the with the treatment substance at least partially filled B A treatment container for bringing the treatment object into contact 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. To be favoured the valve devices according to predetermined courses, in particular at programmed intervals, driven. 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 method according to the invention particularly preferably has the effect that the treatment object is exposed to the treatment substance such that, in addition to the irritation and phosphating, there is likewise a degreasing and / or descaling and / or preserving and / or descaling of the treatment object.

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 min to 60 min, in particular of about 20 min, in an oven at 70 ° C to 150 ° C, in particular at about or exactly 100 ° C, on the material surface of the treatment article (in particular of iron or mild steel). The resulting protective layer is preferably between 2 μm and 10 μm, in particular more than or exactly 3 μm, 4 μm or 5 μm, thick. The protective layer particularly preferably has a thickness of from 2 μm to 10 μm, and preferably from 3 μm to 8 μm, and particularly preferably from 4 μm to 6 μm. 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 in iron bars). The protective layer may in this case be an excellent basis for a further treatment, in particular a color treatment, which may be, for. B. can connect to the inventive method. 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 a material removal of preferably less than 10 g / qm, in particular less than 5 g / qm, and particularly preferably less than or 2 , 24 gsm.

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 treatment substance is an additive for pickling degreasing and / or an additive substance for defoaming, wherein the pickling agent additive preferably an aqueous solution of non-ionic biodegradable surfactants and inhibitors, in particular but-2-in-1, 4 -diol, and wherein the pickling fat 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 and wherein the defoamer additive preferably triisobutyl phosphate and wherein the defoamer addition of the treatment substance with a volume of 0.1% to 1% of the volume of the phosphorus- or phosphate-containing solution or with a volume of 0.1% to 1% of the volume of the treated with the pickling fuming additive phosphorus or phosphate-containing solution or the treatment substance 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. The treatment system according to the invention preferably comprises at least one or more of the treatment apparatuses mentioned above or below, in particular one or more treatment apparatuses for producing a protective coating on the subject of treatment, the protective coating preferably having a thickness of 1 .mu.m to 10 .mu.m μm and preferably from 3 μm to 8 μm or preferably from 2 μm to 4 μm, and at least one further surface treatment device for treating the protective layer of the treatment article. Preferably, the protective layer is coated by the surface treatment device, in particular painted or powder-coated. Therefore, the surface treatment device is particularly preferably a painting device, which is designed for at least partially coating the article to be treated, or a powder coating device, which is preferably designed for at least partially powder coating the article to be treated. 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, wherein the protective layer z. B. has a thickness of 1 .mu.m to 10 .mu.m and preferably from 3 .mu.m to 8 .mu.m or preferably from 2 .mu.m to 4 .mu.m. 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 treatment device mentioned and described above and below, in particular according to one of claims 1 to 9, or the protective layer was preferred with a preceding or following mentioned process, in particular a method according to any one of claims 10 to 14 or the 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 representations of the figures described below are preferably to be regarded as construction drawings, d. H. 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 a first representation of a treatment device according to the invention in a passive state;

2 a second view of a treatment device according to the invention in an active state;

3 a perspective view of another treatment device according to the invention;

4 a perspective view of a still further inventive treatment device;

5 another perspective view of in 4 shown treatment apparatus according to the invention;

6 a detailed perspective view of a part of the in the 4 and 5 shown treatment apparatus according to the invention;

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

8th a second plan view of the in the 4 to 6 shown treatment device according to the invention;

9 a perspective view of substantially the bottom of the in the 4 to 8th shown treatment apparatus according to the invention;

10a a first schematic side view of the in the 4 to 9 shown treatment apparatus according to the invention;

10b a second schematic side view of the in the 4 to 9 shown treatment apparatus according to the invention;

11 a scanning electron micrograph of a steel sheet, which has been treated by the method according to the invention;

12 an enlarged view of the scanning electron micrograph of 11 .

13 an example of a swirling device, as according to the present invention preferably in a treatment container according to one of 1 to 10 is preferably provided

14 from 13 known purely exemplary known turbulizer is arranged purely by way of example in a treatment vessel,

15 a side view of a device according to the invention with a vortex preferably arranged therein;

16 a treatment plant according to the invention with a treatment device for pickling and phosphating and a surface treatment device;

17a -C three differently configured samples after a salt spray test;

18a -C three more differently configured samples after a salt spray test.

In 1 is a treatment device according to the invention 1 shown. The treatment device 1 is used for treatment, in particular for Degreasing, staining, phosphating, descaling, preserving and de-rusting, one or more articles of treatment 2 , The subject of the treatment 2 is preferably from above into a treatment tank 4 the treatment device 1 brought in. The treatment tank 4 is preferably at least partially and particularly preferably completely with a treatment substance 6 filled. Furthermore, a temperature control device is preferred 8th for tempering, in particular for heating, the treatment substance 6 intended. Furthermore, at least one pump device is preferred 10 for circulating the treatment substance 6 and / or to create a Wehrströmung 20 and / or to return from the treatment tank 4 leaked treatment substance 6 back to the treatment tank 4 intended. The treatment tank 6 is by means of a wall 12 from a collection room 14 separated. Through the in the treatment tank 4 created flow occurs treatment fluid 6 from the treatment tank 4 over the wall 12 out and get into the collection room 14 , However, it is also conceivable that the treatment substance or liquid 6 by introducing the subject of the treatment 2 in the treatment room 4 such a displacement learns that a part of the treatment substance 6 over the wall 12 from the treatment tank 4 emerges. The reference number 16 indicates a delivery line, by means of which the from the treatment tank 4 leaked treatment substance 6 back to the treatment tank 4 is encouraged. In the area of the conveying line 16 or in the promotion line 16 or as part of the support line 16 is preferably a filter device 18 for filtering or conditioning the treatment substance 6 arranged. It is conceivable here that the pumping device 10 or another pumping device (not shown) in the course of the delivery line 16 arranged or formed. 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 tank 4 preferably at least one main receiving space 22 , a first reception room 24 and a second side room 26 having. The individual recording rooms 22 . 24 . 26 are here z. B. by grids 27 , in particular in each case a grid, separated from each other. The grid 27 prevents the subject of the treatment 2 in one of the secondary reception rooms 24 . 26 can get. The reference number 28 indicates a nozzle, by means of which a flow of the treatment substance 6 can be generated.

2 shows the off 1 known representation, wherein the subject of the treatment 2 as shown in the treatment tank 4 is arranged and thereby with the treatment substance 6 in contact.

3 shows a further embodiment variant of a treatment device according to the invention 1 , in particular for wire coil treatment. In the 3 shown treatment device 1 exemplifies a pick-up bag 40 on, preferably a plurality of wire coils to be treated 39 wearing. The pickup bag 40 is at a delivery point 41 arranged, wherein preferably a plurality of receiving sacks 40 and several delivery points 41 are provided. Furthermore, the treatment device 1 preferably several, in particular 2, 3, 4, 5, 6, 7, 8, or more, treatment baths 42 on. In a treatment bath 42 are preferred, in particular at the same time, a plurality, in particular 2, 3, 4, 5, 6, 7, 8, 9 or more, wire coils 39 introduced at the same time for treatment. The reference number 43 denotes a preferably purely optional device, namely a fixation. It is conceivable that in a fixation 43 several wire coils 39 , in particular 2, 3, 4, 5, 6, 7, 8 or more, can be introduced at the same time. It is also conceivable that several fixer 43 be provided. The treated wire coils 39 are at a removal point 44 can be arranged for transport. The treated wire coils are preferred 39 with a transport device 45 , in particular a dolly or a rail-guided gantry crane, to the respective removal point 44 promoted. Furthermore, several devices for supplying, regulating and controlling the treatment device are preferred 1 intended. Thus, the illustrated embodiment, for. B. a pressure belt filter device 46 , a metering device 47 , a VE water treatment facility 48 , a control device 49 , another pressure belt filter device 50 , a storage tank for treatment tanks 51 and several side channel blowers 52 , in particular 8 pieces, on. The metering device 47 is preferably automated and more preferably comprises a buffer tank having a volume of preferably more than 5 m ³ , more preferably more than 10 m ³ and most preferably more or exactly 20 m ³ .

4 shows a perspective view of a treatment device according to the invention 1 , The treatment device 1 is preferably L-shaped, ie it comprises a treatment container 4 , wherein the treatment tank 4 a first interior portion extending perpendicular to a second interior space portion Favor. 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 z. B. curved elements, such as pipes. To treat carriers, panels, etc. The treatment tank 4 preferably has at least or exactly one wall 12 on, being through the wall 12 an area into which the treatment objects to be treated are introduced from a collecting space 14 is disconnected. The catchment room 14 is preferably used to catch over the wall 12 from the treatment room exiting treatment substance.

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

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

The enclosure 61 encloses or feeds the nozzles 29a - 29c one. Preferred are three rows with 2 nozzles 28a . 28b and three rows with three nozzles 29a . 29b . 29c provided, it is also conceivable that exactly or at least one nozzle 28 and or 29 is provided. Particularly preferred are the nozzles 28 inclined to the nozzles 29 aligned, in particular aligned at right angles.

The reference number 60 indicates a main suction line, by means of the outlets 57a - 57g (see. 7 ) Treatment substance discharged from the treatment room, in particular aspirated, is. The discharged treatment substance is preferably by means of the filter device 18 prepared and by means of the pumping device 10 over the nozzles 28 and 29 promoted back to the treatment room.

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

5 shows a further view of the aforementioned embodiment of the treatment device according to the invention 1 , It can be seen from this illustration that the nozzles 29a - 29c or the 3 × 3 nozzle arrangement preferably in a pocket 61 in a wall of the treatment tank 4 is housed in order not to disturb the useful surface or not to affect. Also preferred are the nozzles 28a - 28b in a bag in another wall of the treatment tank 4 is housed in order not to disturb the useful surface or not to affect. The bags 61 are preferably provided with a not shown ram guard to prevent damage to the internals.

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

Furthermore, the illustration shows that the bottom of the treatment tank 4 opposite the horizontal inclined surface portions 53 . 54 . 55 . 56 having. The area proportions are preferred 53 - 54 and 55 - 56 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 area shares or ground shares 53 . 54 and 55 . 56 Thus, grooves preferably form through which the treatment substance and dirt particles are directed to one or more outlets. The area shares 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 number 8th indicates a preferably provided temperature control device. The tempering device 8th preferably has 8 electrical heating elements, in particular 2 KW on. The heating elements are preferably also in the bag 61 accommodated in the wall, so as 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 (20 m ³ = 20 KW heating power).

6 in particular, shows a detail of the bag 61 in which the nozzles 29a - 29c and the tempering device 8th are preferably arranged.

7 shows that from the mutually inclined aligned bottom portions 53 . 54 and 55 . 56 of the treatment tank 4 resulting first share of a gutter 62 and the resulting second portion 63 the gutter. The gutter preferably also extends into the collecting space 14 into it. Particularly preferred are in the gutter or in the region of the gutter outlets 57a - 57f , in particular several outlets, provided for discharging or for sucking the treatment substance out of the treatment room. Furthermore, it is preferred in the collecting space 14 at least one outlet 57g for discharging or for aspirating the treatment substance from the collecting space 14 provided out. The outlets 57a - 57g are preferably via connecting lines with the Hauptabsaugleitung 61 in a fluid connection.

Not shown is a grid, which preferably aligned horizontally or at right angles to the side walls of the treatment container 4 aligned the ground 53 . 54 . 55 . 56 superimposed on the treatment space, 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 apart, 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 extraction of these particles is always possible.

8th shows the main suction line 60 and a part of the connection pipes 58a - 58g through which the outlets 57a - 57g with the main suction line 60 are connected. The preferred at least from the connection pipes 58a - 58g and the main line 60 existing Gesamtabsaugleitung is preferably designed 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 device according to the invention 1 , This representation can be particularly connected to the outlet and the Hauptabsaugleitung connecting pipes 58a - 58g remove.

The 10a and 10b show different side views of the in the 4 to 9 shown treatment apparatus according to the invention 1 ,

The 11 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 the 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 μm
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 microns, although the structure in the photograph is designed photographically somewhat relief, but it is apparent to the expert due to the strong magnification that has resulted in a smooth and closed surface structure of 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 representation of an example of a swirling device 70 in a top view. The swirling device 70 can in this case as an integral part of a treatment container 4 be formed or detachable with such a treatment container 4 be connected. The swirling device 70 preferably comprises a fluid conduit element 74 , which preferably consists of one or more line sections 80a - 80e is trained. The individual line sections 80a - 80e can in this case by lines, especially hoses or pipes are formed. Preferably, each line section 80a - 80e a variety of outlet openings 76 through which a fluidizing fluid, via a fluid supply device 72 the Fluid conduit member 74 can be supplied from the fluid line element 74 can escape or escape again. The individual line sections (preferably tubes) are particularly preferred with a distribution device 84 connected or coupled. Preferably, each line section 80a - 80e with a valve device 78 , in particular a magnetic shut-off valve, connected or coupled. The valve devices are preferred 78 in each case in the fluid flow direction of the fluidizing fluid conducted through the fluid conduit element between the distributor device 84 and the first outlet 76 arranged. Furthermore, it is conceivable that several line sections 80a - 80e with a common valve device 78 are coupled or for several line sections a common valve device 78 , in particular a shut-off valve, such. B. a solenoid shut-off valve is provided. To the distribution device 84 is preferably a control device 86 and / or pulse generator 86 connected. The control device 86 in this case preferably causes the opening and / or closing of one, several, several, the majority or all valve devices 78 , in particular shut-off valves 78 , The control device 86 preferably comprises a control valve device, through which a fluid communication channel, by means of the control device 86 the fluidizing fluid is supplied, interrupted, limited or can be opened. The fluid communication channel is, preferably on the one hand by the distributor unit 84 with the adjoining line sections 80a - 80e formed and on the other hand by a line connection 73 , in particular a hose, which is provided with a fluid supply device 72 communicating communicates. The fluid supply device 72 However, this can alternatively also directly with the control device 86 and / or the distribution unit 84 be connected. The fluid supply device 72 is preferably a pressure fluid port of a pressure fluid source, such as. B. a compressed gas connection of a compressed gas source, in particular a compressed air connection of a compressed air source. This can be z. B. be a compressor and / or a pressurized storage.

In 14 is that out 13 known and purely exemplary described turbulizer 70 in a treatment tank 4 arranged and thereby exemplifies the inventive device. The treatment tank 4 This is in the longitudinal direction on the one hand by the Wehrwandung 12 and on the other hand by the back wall 92 limited. In the width direction of the treatment container is on the one hand by the first side wall 90 and on the other hand through the second side wall 91 limited. The floor 82 of the treatment tank 4 preferably has a drain port 85 on, through which the treatment substance from the main receiving space can be discharged, in particular derivable or pumpable, is. The drainage mouth 85 is preferred with the filter device 18 connected so that the over the drain mouth 85 discharged treatment substance of the filter device is supplied or can be supplied. The defense wall 12 On the other hand limits the catchment area 14 into the through the swirling device 70 upset impurities with the over the Wehrwandung 12 passing treatment substance via the drainage mouth 83 to the filter device 18 for filtering can be performed. Thus, pipes, in particular made of stainless steel, with a preferred diameter of between 4 mm and 6 mm are preferably 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. Ie. if necessary, the turbulence fluid can be selectively supplied to one or more tubes, whereby special flows or turbulences in the treatment substance can be generated. 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 turbulence fluid, in particular the compressed air, is preferably via a time switching valve and / or a control device 86 controlled and can be uniform or pulsating, permanently or at programmed intervals or depending on acquired sensor measurement data. Preferably, during the inflation of the fluid, and more preferably up to 3 hours thereafter or up to two hours thereafter, or up to 1 hour thereafter or more than 3 hours thereafter, the filter device runs 18 or the installed filter system preferably with and removes the fluidized dirt from the treatment substance.

15 schematically shows the ascending fluidizing fluid, in particular the rising air bubbles 88 , Through the air bubbles 88 passing through the outlet openings 76 emerge, the treatment substance is vortexed. Furthermore, impurities, in particular sludge, are stirred up with the air bubbles out of the bottom region of the device according to the invention and conveyed upwards to the weir flow. Further shows 15 purely alternative to the line 73 a line 75 , The management 75 can in this case with the treatment tank 4 be coupled, that portions of the treatment substance from the treatment tank 4 can be removed. The by means of the line 75 removed treatment substance fractions are then preferably by means of a pumping device (not shown) of the swirling device 70 fed. That through the swirling device 70 In this case, the swirling fluid delivered to the treatment substance provided in the treatment container for swirling the treatment substance provided in the treatment container is thus via the line 75 discharged portion of the treatment substance. The administration 75 can hereby z. B. with the treatment substance removal means or the opening or mouth or suction 85 be connected.

16 shows a purely exemplary and schematic structure of the treatment plant according to the invention 100 , As shown, one or more of the treatment devices 1 how they z. B. from the preceding figures, may be provided. Further, one or more surface treatment devices may be included 94 for the surface treatment of the previously by means of the treatment device 1 treated treatment article 2 be treated further. Preferably, a further treatment of at least a part of the surface of the treatment article takes place 2 and most preferably at least the majority of the surface of the subject of the treatment 2 and most preferably, substantially or precisely the entire surface of the subject of the treatment 2 , The surface treatment device 94 is hereby preferred for coating the subject of the treatment 2 educated. The surface treatment device is preferred 94 one or more layers of material on the surface of the subject of the treatment 2 applied or generated. The surface treatment device is preferred 94 causes a powder coating and / or a coating of the subject of the treatment. Preference may here z as paint. B. a 2K HS monolayer paint can be used.

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

The 17a -C show schematically test results as recorded in a salt spray test. All surfaces are provided with a 2K HS single-coat finish. 17a shows the surface of a normal steel after a 600 hour salt spray test. The bubble degree according to ISO 4628-2 here m0g0, the infiltration at the Ritz is 18 mm, the degree of rust after ISO 4628-03 Ri is 0 and the delamination at the Ritz is 21 mm. 17b shows the surface of a normal phosphated steel after a 600 hour salt spray test. The bubble degree according to ISO 4628-2 here is m0g0, the infiltration at the Ritz is 17 mm, the degree of rust after ISO 4628-03 Ri is 0 and the delamination at the scribe is 25-28 mm.

17c shows the surface of a pretreated according to the present invention steel after a 1000 hour salt spray test. The bubble degree according to ISO 4628-2 here m0g0, the infiltration at the Ritz is 6 mm, the degree of rust after ISO 4628-03 Ri is 0 and the delamination at the Ritz 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.

18a -C show schematically differently treated surfaces each exposed to a salt spray test for 1008 hours. The according to 18a The metal body shown 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 2 mm. There is no blistering or rusting on the surface. The delamination on the Ritz, tested with fabric adhesive tape, is 3 mm. The according to 18b The metal body shown 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 2 mm. The according to 18c Metal body shown was with the pretreated treatment apparatus according to the invention and then the metal body was coated with a powder coating. The infiltration at the Ritz is 5 mm. There is no blistering or rusting on the surface. The delamination on the Ritz, tested with fabric adhesive tape, is 5 mm.

In the 17a -C and 18a In each case, the reference symbols I1 and I2 indicate two indicator points which are different from one another and have been analyzed to determine the indicated measured values.

The present invention can thus be applied to a treatment device 1 for the one-step treatment of a metallic treatment object 2 wherein the treatment comprises at least pickling and phosphating the subject of the treatment 2 includes, wherein the treatment device 1 at least the following devices include: a treatment tank 4 for receiving the subject of the treatment 2 and for receiving a flowable treatment substance 6 , and a pumping device 10 for the replacement of at least a portion of the treatment substance 6 wherein at least a portion of the subject of the treatment 2 , in particular the entire subject of the treatment 2 , from the treatment substance 6 is flowed around, wherein the treatment substance 6 a phosphorus- or phosphate-containing solution, in particular phosphoric acid, wherein the phosphorus- or phosphate-containing solution consists firstly of water and on the other hand of a reaction substance, wherein the reaction substance of phosphorus or a phosphate and an additional treatment effect improving substance, wherein the proportion of phosphorus or of the phosphate on 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 the one-step treatment of a metallic treatment object 2 wherein the treatment comprises at least pickling and phosphating the subject of the treatment 2 includes, wherein the treatment device 1 at least the following devices include: a treatment container 4 for receiving the subject of the treatment 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 portion of the subject of the treatment 2 , in particular the entire subject of the treatment 2 , from the treatment substance 6 is flowed around, 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 impurities depositing in the treatment substance, in particular solid particles, wherein the turbulizer 70 at least one provisioning device 72 and a fluid conduit element 74 with a large number of outlet openings 76 for supplying a fluidizing fluid to the treating substance 6 wherein the fluidizing fluid through the providing device 72 the fluid line element 74 can be supplied with a pressure of more than 2 bar.

The present invention particularly preferably relates to a treatment device 1 for the one-step treatment of a metallic treatment object 2 wherein the treatment comprises at least pickling and phosphating the subject of the treatment 2 comprises: Preferably, the treatment device according to the invention comprises 1 at least the following facilities: a treatment tank 4 for receiving the subject of the treatment 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 portion of the subject of the treatment 2 , in particular the entire subject of the treatment 2 , from the treatment substance 6 is flowed around, wherein the treatment substance 6 a phosphorus 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 hand consists of a reaction substance. 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 proportions of fluorine, chlorine, bromine, iodine, lead, mercury and selenium, and is preferably in a ratio of 1 kg of reaction substance to 4 liters of water and 1 kg of 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

1

treatment device

2

Treating article

4

treatment tank

6

treatment substance

8th

tempering

10

pumping device

12

wall

14

staging area

16

delivery line

18

filtering device

19

Further filter device

20

weir flow

22

Main reception space

24

First secondary room

26

Second side room

27

grid

28

jet

39

wire coil

40

Treatment device for treating wire

41

delivery point

42

treating

43

fixing bath

44

removal point

45

transport means

46

Pressure belt filter device

47

metering

48

Demineralized water treatment facility

49

control device

50

Further pressure belt filter device

51

storage tank

52

Side Channel Blowers

53

First inclined ground share

54

Second inclined ground share

55

Third inclined ground share

56

Fourth inclined ground share

57

outlet

58

connecting pipe

60

Hauptabsaugleitung

61

Bag with nozzles

62

First part of the gutter

63

Second part of the gutter

70

swirling

72

Providing device

73

management

74

Fluid conduit member

76

outlet

78

valve means

80

Line sections / conduits

80a

first line section

80b

second line section

80c

third line section

80d

fourth line section

80e

fifth line section

82

ground

84

distribution unit

86

control unit

84

Drainage opening in the collection area

86

Drainage opening in the main receiving room

88

ascending fluid (preferably air)

90

Side wall

92

rear wall

94

Surface treatment facility

96

transport

100

treatment plant

I1

first indicator site

I2

second indicator site

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited non-patent literature

• ISO 4628-2 [0117]
• ISO 4628-03 [0117]
• ISO 4628-2 [0117]
• ISO 4628-03 [0117]
• ISO 4628-2 [0118]
• ISO 4628-03 [0118]

Claims (15)

Treatment device ( 1 ) for the treatment of a metallic object of treatment ( 2 ), wherein the treatment comprises at least pickling and phosphating the subject of the treatment ( 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 subject of treatment ( 2 ), of the treatment substance ( 6 ), whereby the treatment substance ( 6 ) is a phosphorus or phosphate-containing solution, in particular phosphoric acid, wherein the phosphorus- or phosphate-containing solution for a water, especially deionized water, and on the other consists of a reaction substance, and the reaction substance of phosphorus or a phosphate and at least one additional Treatment effect improving substance, in particular one or more inhibitors comprising, wherein the proportion of the phosphorus or the 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. wherein the reaction substance has no proportions of hydrochloric acid and sulfuric acid and preferably also 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 between a Lower limit and an upper limit, wherein the lower limit is defined by a mixture in a ratio of 1 kg of reaction substance to 3 liters of water and the upper limit is defined by a mixture of 1 kg of reaction substance to 12 liters of water, in particular, the mixture is in a ratio of 1 kg of reaction substance to 6 liters of water before. Treatment device according to one of the preceding claims, characterized in that a swirling device ( 70 ) is provided for stirring up impurities depositing in the treatment substance, in particular solid particles, whereby the turbulizer device ( 70 ) at least one provisioning device ( 72 ) and a fluid line element ( 74 ) with a plurality of outlet openings ( 76 ) for supplying a fluidizing fluid to the treatment substance ( 6 ), wherein the fluidizing fluid through the supply device ( 72 ) the fluid line element ( 74 ) can be supplied with a pressure of more than 2 bar, wherein the fluid line element ( 74 ) several by means of valve devices ( 78 ) can be decoupled from one another 80 ), whereby at least the majority of the line sections ( 80 ) in the area of the soil ( 82 ) of the treatment container ( 4 ) are arranged. Treatment device according to claim 2, characterized in that the line sections through pipes ( 80 ) are formed, in particular with a diameter between 2 mm and 12 mm and preferably in a diameter between 3 mm and 9 mm and particularly preferably in a diameter between 4 mm and 6 mm, wherein the tubes ( 80 ) with the ground ( 82 ) of the treatment container ( 4 ) are arranged or arranged thereon, wherein the tubes ( 80 ) by means of at least one distributor unit ( 84 ), and wherein each valve device ( 78 ) is designed as a shut-off valve, in particular as a shut-off solenoid valve, and the provision device ( 72 ) as for providing a gas under at least 2 bar pressure, in particular air, is formed. 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 ), which are present in the treatment substance ( 6 ), 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 operable at least temporarily as a function of one another. Treatment device ( 1 ) according to one of the preceding claims 2 to 4, characterized in that the operation of the swirling means at least temporarily comprises the provision of the fluid and the control of the valve means, 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 tank ( 4 ) through a wall ( 12 ) from a catchment room ( 14 ) for catching over the wall ( 12 ) flowing treatment substance ( 6 ) is separated, wherein in the collecting space ( 14 ) received treatment substance ( 6 ) by means of a delivery line ( 16 ) into the treatment tank ( 4 ), wherein the pumping device ( 10 ) and the filter device ( 18 ) a component of the support line ( 16 ) and the promoted treatment substance ( 6 ) from the pumping device ( 10 ) through the filter device ( 18 ), whereby the delivery line ( 16 ) is designed such that through the back into the treatment container ( 4 ) promoted treatment substance ( 6 ) a weir flow ( 20 ) for discharging a part of the treatment substance ( 6 ) from the treatment tank ( 4 ) and into the collection room ( 14 ) can be generated. Treatment device ( 1 ) according to one of the preceding claims, characterized in that the treatment substance ( 6 ) an additional substance is added for defoaming, wherein the defoamer additive preferably comprises triisobutyl phosphate and wherein the defoamer additive of the treatment substance ( 6 ) with a volume of 0.01% to 5%, in particular 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 the phosphoric or phosphate-containing solution added with the pickle degreaser additive and / or the treatment substance ( 6 in that the pickling-degreaser additive preferably comprises an aqueous solution of non-ionogenic biodegradable surfactants and inhibitors, in particular but-2-yn-1,4-diol, and wherein the pickling-degreaser additive has a volume of 0.5%. to 7%, in particular from 1% to 5%, of the volume of the phosphorus- or phosphate-containing solution is added. Treatment device ( 1 ) according to one of the preceding claims, characterized in that the treatment tank ( 4 ) such a main receiving space ( 22 ) into which the subject of the treatment ( 2 ) and at least one first secondary reception room ( 24 ), wherein the main receiving space ( 22 ) and the first secondary reception room ( 24 ) are connected to one another such that the treatment substance ( 6 ) on the one hand from the main reception room ( 22 ) out into the first reception room ( 24 ) and on the other hand from the first secondary reception room ( 24 ) out into the main reception room ( 22 ), the main receiving space ( 22 ) and the first secondary reception room ( 24 ) are delimited from one another in such a way that the penetration of the treatment object ( 2 ) in the first secondary reception room ( 24 ) is at least partially and preferably completely prevented and wherein the main receiving space ( 22 ) also with a second secondary reception room ( 26 ), wherein the first secondary reception space ( 24 ) below the main reception room ( 22 ) formed buffer receiving space for receiving a certain amount of treatment substance ( 6 ), and wherein the second side room ( 26 ), preferably laterally from the main receiving space ( 22 ) formed Temperierungsraum, wherein the temperature control device ( 8th ) at least partially in the second side room ( 26 ) is arranged. Treatment plant at least comprehensive One or more treatment devices according to one of claims 1 to 8 for producing a protective layer on the subject of the treatment, the protective layer having a thickness of 1 μm to 10 μm and preferably of 3 μm to 8 μm or preferably of 2 μm to 4 μm, 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 article of treatment or is designed as a powder coating device for at least partially powder coating the article to be treated, and wherein preferably a transport device is provided for transporting the treatment article treated by the treatment device according to one of claims 1 to 8 to the surface treatment device. Treatment method for processing a, in particular metallic, treatment object ( 2 ), comprising at least the steps of: providing a treatment container ( 4 ) for receiving at least one treatment article ( 2 ) and for receiving a flowable treatment substance ( 6 ), Introduction of the treatment substance ( 6 ) into the treatment tank ( 4 ), with no other Treatment container is used for pickling and phosphating, and introducing the treatment object ( 2 ) in the with the treatment substance ( 6 ) at least partially filled treatment container ( 4 ) for contacting the subject of the treatment ( 2 ) with the treatment substance ( 6 ), the contact between the treatment substance ( 6 ) and the subject of the treatment ( 2 ) at least one cleaning, in particular a degreasing, and phosphating the subject of the treatment ( 2 ), the treatment substance ( 6 ) is 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 from a reaction substance, wherein the reaction substance of phosphorus or a phosphate and water, wherein the proportion of phosphorus or of the phosphate 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. wherein the reaction substance has no proportions of hydrochloric acid and sulfuric acid and is mixed with water in a ratio of 1 kg of reaction substance to 4 liters of water and 1 kg of reaction substance to 12 liters of water, in particular in a ratio of 1 kg of reaction substance to 6 liters with water is mixed. 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 subject of the treatment between 15 minutes and 90 minutes, in particular between Immersed in the treatment substance for 30 minutes and 60 minutes. Method according to claim 10 or 11, further comprising the steps: 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 previous treatment by means of a surface treatment device, wherein the protective layer is painted or powder-coated by means of the surface treatment device. A method according to any one of claims 10 to 12, further comprising the step of adding an additive substance for pickling degreasing to the treating substance ( 6 ), wherein the pickle fatliquor preferably an aqueous solution of non-ionic biodegradable surfactants and inhibitors, in particular but-2-yn-1, 4-diol, and wherein the pickle degreaser with a volume of 0.5% to 7%, in particular of 1% to 5%, of the volume of the 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 ) with a volume of 0.01% to 5%, in particular 0.2%, of the volume of the treatment substance ( 6 ) or with a volume of 0.01% to 5%, in particular 0.2%, of the volume of the treatment substance added with the pickle degreasing additive ( 6 ) is added. A method according to any one of claims 10 to 13, further comprising the steps of: removing the subject of treatment from the treatment vessel, swirling impurities transferred to the treating substance by the subject by means of a swirling means, and for swirling the contaminants, a swirling fluid is supplied to the subject by the swirling means; Supplying the treatment substance provided with the fluidized impurities to a filter device, filtering out the impurities from the treatment substance components which are fed to the filter device, reinserting the object of treatment ( 2 ) in the with the treatment substance ( 6 ) at least partially filled treatment container ( 4 ) for contacting the subject of the treatment ( 2 ) with the filtered treatment substance ( 6 ) or introducing a further treatment article into the treatment substance ( 6 ) at least partially filled treatment container ( 4 ) for contacting the subject of the treatment ( 2 ) with the filtered treatment substance ( 6 ), characterized in that a control device for operating the filter device and / or the swirling 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 device takes place at least temporarily in response to an operation of the filter device wherein the operation of the swirling device at least at times comprises the provision of the swirling fluid and the actuation of the valve device, wherein the valve devices are actuated according to predetermined courses, in particular at programmed time intervals. 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 is provided with a phosphorus or phosphate-containing protective layer, wherein the protective layer has a thickness of 1 .mu.m to 10 .mu.m, and preferably from 3 .mu.m to 8 .mu.m, or preferably from 2 .mu.m to 4 .mu.m, 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 has been produced by means of a treatment device according to one of claims 1 to 9 or the protective layer has been 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.

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