EP4058611A1 - Geregelte folienwärmebehandlung - Google Patents
Geregelte folienwärmebehandlungInfo
- Publication number
- EP4058611A1 EP4058611A1 EP20803186.4A EP20803186A EP4058611A1 EP 4058611 A1 EP4058611 A1 EP 4058611A1 EP 20803186 A EP20803186 A EP 20803186A EP 4058611 A1 EP4058611 A1 EP 4058611A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- content
- heat treatment
- furnace
- evaporation
- exhaust gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000010438 heat treatment Methods 0.000 title claims abstract description 104
- 239000011888 foil Substances 0.000 title claims abstract description 95
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 171
- 230000008569 process Effects 0.000 claims abstract description 114
- 229910052751 metal Inorganic materials 0.000 claims abstract description 76
- 239000002184 metal Substances 0.000 claims abstract description 76
- 230000003647 oxidation Effects 0.000 claims abstract description 71
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 71
- 238000001704 evaporation Methods 0.000 claims abstract description 69
- 230000008020 evaporation Effects 0.000 claims abstract description 69
- 238000005096 rolling process Methods 0.000 claims abstract description 42
- 238000004886 process control Methods 0.000 claims abstract description 21
- 230000033228 biological regulation Effects 0.000 claims abstract description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 30
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 24
- 230000001276 controlling effect Effects 0.000 claims description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 7
- 150000002894 organic compounds Chemical class 0.000 claims description 7
- 229910000838 Al alloy Inorganic materials 0.000 claims description 6
- 239000000047 product Substances 0.000 description 78
- 238000000137 annealing Methods 0.000 description 62
- 239000007789 gas Substances 0.000 description 60
- 239000010731 rolling oil Substances 0.000 description 32
- 229910052782 aluminium Inorganic materials 0.000 description 11
- 238000004140 cleaning Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 238000012545 processing Methods 0.000 description 8
- 238000005238 degreasing Methods 0.000 description 7
- 238000001953 recrystallisation Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000004804 winding Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000005068 cooling lubricant Substances 0.000 description 4
- 230000001419 dependent effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000012625 in-situ measurement Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
- C21D1/76—Adjusting the composition of the atmosphere
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B17/00—Furnaces of a kind not covered by any preceding group
- F27B17/0016—Chamber type furnaces
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D19/00—Arrangements of controlling devices
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D19/00—Arrangements of controlling devices
- F27D2019/0006—Monitoring the characteristics (composition, quantities, temperature, pressure) of at least one of the gases of the kiln atmosphere and using it as a controlling value
- F27D2019/0012—Monitoring the composition of the atmosphere or of one of their components
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D19/00—Arrangements of controlling devices
- F27D2019/0006—Monitoring the characteristics (composition, quantities, temperature, pressure) of at least one of the gases of the kiln atmosphere and using it as a controlling value
- F27D2019/0012—Monitoring the composition of the atmosphere or of one of their components
- F27D2019/0015—Monitoring the composition of the exhaust gases or of one of its components
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the invention relates to a method for the heat treatment of metal strips or foils in a heat treatment furnace, in particular for the removal of rolling residues.
- the invention further relates to a device for the heat treatment of metal strips or foils for carrying out the method according to the invention.
- Heat treatment plays a special role in the production of metal strips or foils.
- the metal products usually go through hot and cold rolling processes and, if necessary, intermediate annealing so that temperature-dependent processes in the structure of the material can be used to influence the properties of the metal products in a targeted manner.
- final annealing which is one of the most critical processes, especially in film production.
- the final annealing serves on the one hand for recrystallization or partial recrystallization, the so-called state annealing or back annealing of the metal strips and foils, with the recrystallization taking place when the recrystallization temperature of the material is exceeded.
- the finish annealing is used for thermal cleaning of the strip surfaces, in particular for so-called degreasing of rolling residues such as lubricants used in the rolling mills, for example greases, waxes and rolling oils.
- the strip surfaces In order to ensure a lubricant-free surface for further processing of the metal products and, for example, to prevent adhesion problems during subsequent forming, the strip surfaces must be thoroughly cleaned. This is done by the staggered glow phases of the Evaporation of lubricants and oily residues on the tape or film surface.
- the annealing programs used in which a. the temperature-time curve, the volume of process air exchange between the environment and the furnace chamber and the air volume for circulation in the furnace chamber are therefore always a compromise between recrystallization and degreasing requirements for the annealing process.
- the process becomes even more complex with state annealing, since partial recrystallizations react more sensitively to the annealing parameters.
- general annealing programs are generally used in the context of today's annealing processes and there are no differentiation criteria, it is not possible to react individually to the parameters of the starting material in particular.
- the process technology is also mostly poorly instrumented and actually effective parameters on the metal strip or the metal foil such as the metal temperature or the air volume are unknown and are only estimated on the basis of auxiliary variables such as a fan speed or a shutter position.
- the low-temperature long-term annealing is characterized by its tolerance to deviations in input and environmental parameters such as surface roughness, the oil content in quality and quantity, the density and humidity of the process air or the winding density in the case of metal strips or foils wound into coils This represents a quality-optimized, good-natured philosophy.
- a problem with low-temperature long-term annealing is the contamination of rolling oil with tramp oils that do not burn off at lower annealing temperatures.
- high-temperature short-term annealing is an efficient, throughput-optimized philosophy, it has a high incidence of annealing errors because it is not very tolerant of the aforementioned input and environmental conditions.
- the combination of fault-intolerant high-temperature short-term annealing, natural process fluctuations from the preliminary processes and poorly instrumented furnace technology inevitably leads to frequent inhomogeneities in the degreasing process and thus to annealing defects, which lead to poor unwinding quality, in particular to adhesions near the roll core, and to adhesion problems of the products in the subsequent processing.
- Thin metal strips or metal foils in particular react sensitively to the annealing treatments and develop tension, flow lines or even incandescent bubbles. Uncontrollable wrinkles and uneven strength properties have a negative effect on the subsequent processing steps through to the end product. In the worst case, the stresses, flow lines and incandescent bubbles can lead to cracks, rendering the metal products completely unusable.
- German patent application DE 197466733 A1 a method for determining the gas atmosphere in a heat treatment furnace is known, with which the supply of inert gas can be optimized during the heat treatment.
- a precise method for controlling a furnace atmosphere is also known from European patent application EP 2 871 248 A1.
- both documents do not deal with the avoidance of annealing errors in the annealing of strip or foil coils.
- the present invention is therefore based on the object of providing a method for the heat treatment of metal strips or foils in a heat treatment furnace, in particular for the removal of rolling residues which reliably and inexpensively high-quality metal products can be provided and the scrap portion of metal strips and foils can be reduced.
- the present invention is based on the object of proposing advantageous devices for the heat treatment of metal strips or foils, in particular for carrying out a method according to the invention.
- the above-indicated object for a method for the heat treatment of metal strips or foils in the form of strip or foil coils in a heat treatment furnace to remove rolling residues is achieved in that while the heat treatment is being carried out, the content of at least one Evaporation and / or oxidation product is determined in the furnace atmosphere and / or in the process exhaust gas and is used for process control or regulation of the heat treatment, the dynamics of the removal of rolling residues on the metal strips or foils being controlled or regulated during the heat treatment.
- the heat treatment is, for example, a final annealing of the metal strips or foils.
- Corresponding annealing can facilitate further processing such as subsequent forming steps, improve the mechanical properties of the metal products and promote dimensional stability.
- Finished annealing is carried out in particular for soft annealing and cleaning purposes.
- cleaning, in particular degreasing the surface of the rolled metal product can be freed from residues of the cooling lubricants and prepared, for example, for strip coating. Problems during further processing such as poor winding quality or adhesion problems during subsequent forming can be prevented by cleaning the product surfaces.
- the metal strips or foils are annealed in the form of a strip or foil coil in the heat treatment furnace.
- the heat treatment can also involve intermediate annealing, the aim of which, for example, is to facilitate subsequent rolling steps. Even with intermediate anneals, annealing defects can already occur, especially if the metal strips or foils are in the form of a coil and their thickness is very small.
- the elimination of rolling residues is determined by the evaporation and oxidation of the cooling lubricants that remained as residues on the surfaces of the metal products after rolling, whereby the metal temperature, the type and amount of rolling oil coating and the atmosphere in the furnace chamber, the so-called furnace atmosphere or process air , are decisive for the vapor pressure of the rolling oil to be evaporated and the oxidation of the same.
- the temperature of the metal product results among other things. from the given temperature-time curve of the annealing program, the weight and dimensions of the product, the material thickness, the degree of furnace filling, the construction type and the degree of efficiency of the furnace.
- the type and amount of the rolling oil coating result from the selection and the (variable) composition of the rolling oils used for rough rolling, double and finishing rolling, which in turn consist of base oils and additives.
- the composition of the furnace atmosphere has a major impact on the cleaning result.
- Both the composition of the furnace atmosphere and that of the process exhaust gas that is discharged from the furnace chamber are in turn dependent on a number of factors. They are i.a. a product of the stage of annealing, the process step to be carried out, the furnace filling level and the starting material to be treated.
- the conditions of the starting material for example the boiling behavior and the amount of oil coating, as well as the status of the annealing process, for example the evaporation and oxidation phase, implicitly by measuring the content of at least one evaporation and / or Oxidation product are detected in the furnace atmosphere and / or the process exhaust gas.
- Salary information generally quantifies the proportion of an individual Substance in a mixture. In the present case, this also includes, for example, concentrations which indicate the amount of a product in relation to a given volume of air. A pure determination of the amount without knowledge of the volume is also conceivable.
- a statement can be made about the dynamics of the evaporation and the oxidation of the cooling lubricants.
- the method according to the invention can in turn influence the control or regulation of the heat treatment, in particular the removal of the rolling residues can be controlled or regulated, whereby the dynamics of the evaporation and oxidation of the rolling residues, for example in strip or foil coils, can be advantageously controlled .
- a direct measurement in the furnace atmosphere can preferably provide real-time results and thus a high level of information about the contents of evaporation and / or oxidation products currently in the atmosphere. While a measurement in the process exhaust gas is particularly easy, it entails a time delay due to the inertia of the process.
- the heat treatment in particular the removal of rolling residues, can in turn be advantageously controlled or regulated.
- Process control means here that the actual value of a parameter, if it deviates from the desired setpoint, is changed by suitable process action so that the actual value approaches the setpoint and ideally reaches it. Because the drifting away from the setpoint is counteracted, the feedback is a negative feedback.
- the process control can be carried out, for example, by a PID controller. In the process control, on the other hand, there is no feedback and consequently no closed action sequence. Control is understood to mean influencing the behavior of a system, the system being controlled by the Control is brought into another state. The control or regulation can take place by influencing selected parameters, for example by reducing or increasing a value.
- the control or regulation according to the method according to the invention is characterized in that it depends on the content of at least one evaporation and / or oxidation product that is present in the furnace atmosphere and / or in the process exhaust gas, and thus depending on the conditions of the starting material as well as the status of the annealing process.
- This has the advantage that it is possible to react appropriately to variations in the process parameters mentioned, and thus the surface of a rolled metal product is reliably freed of cooling lubricant residues.
- the method according to the invention thus makes it possible to use high-temperature short-term annealing while at the same time avoiding the typical annealing defects. It thus represents a practicable, cost-effective solution for the removal of rolling residues and increases the fault tolerance of the high-temperature short-term annealing, which is highly dependent on the input conditions and process parameters.
- the metal strips or foils are preferably annealed in the form of strip or foil coils in a batch furnace.
- Batch ovens are usually not as costly to operate and purchase as continuous ovens.
- One difficulty with batch furnaces, however, is usually ensuring that the temperature is evenly distributed, for example when loading metal coils into the furnace.
- Inhomogeneities in the cleaning process usually occur primarily with strip or foil coils, since the rolling oil is oxidized and the exhaust gases are expelled via the end faces of the wound rolls.
- the heating initially takes place from the outside, the metal inside the foil coil, on the other hand, does not heat up as quickly.
- the method according to the invention a statement can be made about the speed and the uniformity of the evaporation process in the case of strip and foil coils.
- Harmonizing the gas pressure can be understood to mean, for example, an equalization of the increase in the gas pressure, that is to say a reduction in the dynamics of the evaporation during the heat treatment.
- the method according to the invention can therefore advantageously control or regulate the dynamics of the evaporation and oxidation of the rolling residues in strip and foil coils.
- the furnace atmosphere which is precisely coordinated with the aid of the method according to the invention, thus also ensures the desired results for the heat treatment of strip or foil coils and enables an increase in the fault tolerance of high-temperature short-term annealing.
- Tape and foil coils produced with the method according to the invention can be unwound, in particular, at increased speed without sticking.
- Metal foils with a thickness of 1 ⁇ m to 250 ⁇ m, preferably 1 ⁇ m to 60 ⁇ m, particularly preferably 4 ⁇ m to 20 ⁇ m, are treated with the method according to the invention.
- the production of metal foils is carried out starting from what is known as foil pre-rolled strip, usually with the process steps of pre-rolling, doubling, finishing rolling, separating, winding and finish annealing.
- the pre-rolling and finish-rolling serve to decrease the height, the doubling the joining of two strip layers for the doubled finish-rolling, the separating the separation of the finished rolled foil webs, the winding up, the provision of foil coils and the final annealing, the degreasing of the foil surfaces and the recrystallization of the material.
- the gas pressure of the evaporation and / or oxidation products in the strip or foil coil is controlled or regulated during the heat treatment, so that targeted damage to the metal strips or foils through too rapid evaporation or too rapid generation of oxidation products in the strip. or foil coil can be significantly reduced.
- the furnace temperature, the furnace temperature gradient, the process air exchange volume, the circulating volume of process air and / or the composition of the furnace atmosphere is dependent on the content of the at least one evaporation and / or oxidation product in the furnace atmosphere and / or controlled or regulated in the process exhaust gas. It was recognized that in particular the parameters temperature, temperature gradient, exchange volume and circulation volume as well as the composition of the furnace atmosphere have an influence on a particularly effective and homogeneous heat treatment of strip or foil coils. Uniform evaporation of the residues is necessary to ensure that rolling residues are uniformly removed from the product surfaces, for which a homogeneous temperature distribution is crucial.
- the temperature gradient can be adjusted accordingly with the aid of the method according to the invention.
- the circulating volume of process air can also be used to indirectly influence the uniformity of the temperature distribution in the heat treatment furnace.
- a constant distribution of the individual gas components in the furnace chamber can be achieved by controlling or regulating the circulation volume.
- Through a control or Regulation of the process air exchange volume for example in the context of convection ventilation, can also influence the furnace atmosphere.
- the dynamics of the evaporation and oxidation of the rolling residues, in particular the rolling oils, are thus controlled according to the invention, for example, by a hindering or promoting setting of the furnace temperature, the setting of the gradient of the furnace temperature and the setting of the furnace atmosphere.
- the vapor pressure of the rolling oil to be evaporated and the speed of the evaporation process are influenced by measuring and setting the furnace chamber temperature and the gradient of the furnace chamber temperature. For example, setpoint values can be assigned to the parameters to be measured. In cases in which the concentration of rolling oil and partially oxidized rolling oil or the concentration of rolling oil oxidation products in the furnace atmosphere exceeds or falls below a predefined threshold value, the furnace temperature is changed, for example held or lowered, or the gradient of the temperature rise is changed, for example reduced .
- the vapor pressure of the rolling oil to be evaporated and the speed of the evaporation process are also influenced by measuring and setting the content of already evaporated and / or oxidized rolling oil in the furnace atmosphere. If the content of rolling oil and partially oxidized rolling oil or the content of rolling oil oxidation products in the furnace atmosphere falls below, for example, a predefined threshold value, the process air exchange is changed, for example increased or reduced.
- the oxidizability of the rolling oil to be evaporated and / or evaporated and the speed of the oxidation processes are also influenced by measuring the content of already evaporated and / or oxidized rolling oil in the furnace atmosphere and by setting the oxidizing ability of the furnace atmosphere.
- the oxidation ability of the furnace atmosphere can be increased by adding process gases that weaken or reduce the oxidation, such as nitrogen or hydrogen.
- the oxidation capability of the furnace atmosphere is influenced, preferably reduced, by adding process gases that increase oxidation, such as oxygen or ozone influenced, preferably increased.
- the advantageous embodiment of the method according to the invention thus makes it possible in particular to influence the gas pressure in metal strip or metal foil coils in many ways, to harmonize it over time and thus to increase the fault tolerance of high-temperature short-term annealing.
- the cleaning process of the surface of the metal strip or the metal foil in the wound coil can be optimized through the continuous control of and the regulated influence on the temperature level and gradient and / or the composition of the furnace atmosphere.
- the furnace temperature gradient is controlled or regulated in the process control or regulation depending on the gradient of the content of the at least one evaporation and / or oxidation product in the furnace atmosphere and / or in the process exhaust gas.
- the steam pressure of the rolling oil to be evaporated and the speed of the evaporation process can also be influenced in a targeted manner. If the gradient of the content of rolling oil and partially oxidized rolling oil and / or the content of rolling oil oxidation products in the furnace atmosphere exceeds, for example, a predefined one Threshold value, the gradient of the temperature rise is adapted, for example reduced.
- the carbon content (Cges content), the content of organic compounds (Vorg content), the carbon monoxide content (CO content) and / or the carbon dioxide content (CO2- Content) in the furnace atmosphere and / or in the process exhaust gas and used for process control or regulation of the heat treatment.
- the carbon content of the furnace atmosphere and the process exhaust gas can be reliably determined in a particularly simple manner and is characteristic of evaporation and oxidation products.
- the CO and / or CO2 content represents the content of rolling oil oxidation products, while the Vorg content reflects the content of rolling oil and partially oxidized rolling oil.
- the totality of all carbon-containing substances, ie including Vorg, CO and CO2, is characterized by C tot.
- the Cges content, the Vorg content, the CO content and the C02 content in the furnace atmosphere or in the process gas are particularly critical parameters.
- the maximum carbon content Cges max, the maximum content of organic compounds Vorgmax, the maximum carbon monoxide content COmax and / or the maximum carbon dioxide content CO2 max is preferably limited in the furnace atmosphere and / or in the process exhaust gas, for example with a defined exchange volume of the furnace atmosphere or process exhaust gas volume.
- the method according to the invention allows, for example, to control the maximum evaporation rate , whereby advantageously good annealing results can be achieved, in particular incandescent bubbles can be reduced or avoided entirely.
- the carbon gradient C ge s Grad, the gradient of the content of organic compounds Vorg Grad, the carbon monoxide gradient COcrad and / or the carbon dioxide gradient CO2 Grad in the furnace atmosphere and / or in the process exhaust gas is limited. It has been shown that too high a gradient in the C ge s, Vorg, CO or C02 content in the furnace atmosphere or in the process exhaust gas indicates a sudden and strong increase in evaporation and / or oxidation products which in turn would lead to sticking and the formation of incandescent bubbles in the metal products.
- the control of the gradient thus enables control of the evaporation rate and thus, regardless of the total content of C ge s, Vorg, CO and / or CO2 in the furnace atmosphere and / or in the process exhaust gas, avoidance of incandescent defects such as incandescent bubbles.
- the pre-content is preferably measured by an FID analyzer, preferably an on-line FID analyzer, the CO content by a CO analyzer, preferably an on-line CO analyzer, the CO 2 content by a CO 2 analyzer, preferably an on-line CO 2 analyzer, and / or the C total content by an FID analyzer and a CO analyzer and optionally a CO 2 analyzer.
- F1D (flame ionization detector) analyzers are particularly suitable for monitoring for volatile carbonaceous substances. Since the detector signal of an FID analyzer is linearly proportional to the carbon content over a wide concentration range, this can be estimated without calibration, so that F1D analyzers can be used particularly well for quantification. In addition, an FID analyzer is not only fast and robust, it is also very sensitive. The determination of the carbon content can thus be carried out reliably and reliably.
- CO or C02 sensors or infrared analyzers can be used, which are characterized by particularly high precision.
- the CO 2 infrared analysis represents a particularly precise in situ measurement method.
- infrared analyzes are relatively expensive and complex, since the analyzers require regular calibrations.
- the Cges content can be measured using an FID analyzer, preferably an on-line FID analyzer, a CO analyzer, preferably an on-line CO analyzer, and a CO 2 analyzer, preferably an on-line CO 2 analyzer, be determined. Sufficient accuracy for determining the C total content can, however, be achieved by using an FID analyzer and a CO analyzer.
- the heat treatment is carried out at a temperature of 80 to 120.degree. C. or more than 200.degree. C., preferably more than 220.degree. C., particularly preferably more than 300.degree.
- annealing temperatures above 200 ° C an essentially complete elimination of rolling residues on the product surfaces can be achieved.
- the duration of the heat treatment depends, among other things, on the temperature and the mass of the material to be treated.
- the method according to the invention can remove Roll residues, for example in the case of hard-rolled foils, can be achieved without significant softening.
- Metal strips or foils are preferably treated in the form of coils.
- annealing times can be approx. 20 to 180 hours in order to achieve essentially complete removal of the rolling residues.
- the coil width depends primarily on the use of the metal strips and foils. Narrow coils have a width of 250 mm to 1000 mm, for example.
- the annealing times for narrow coils are about 80 hours at an annealing temperature of approx. 220 ° C, approx. 35 hours at a temperature of approx. 350 ° C and one at a temperature of approx. 400 ° C Glowing time of only about 20 hours.
- Wide coils can have widths of 1000 mm to 2500 mm, preferably 1300 mm to 2100 mm.
- the glow time at a temperature of approx. 220 ° C. is approx. 180 hours, at a temperature of approx. 350 ° C. approx. 80 hours and at a temperature of approx. 400 ° C. approx. 60 hours.
- Aluminum or aluminum alloy strips or foils are preferably treated.
- the material aluminum is characterized by its diverse technical uses. By adding alloying elements, aluminum strips and foils with different properties can be produced. In combination with different thermal treatments, the mechanical properties of aluminum can be optimally adapted to the respective processing and usage conditions.
- aluminum is considered a key material for the packaging industry.
- aluminum is found in many packaged product forms, such as liquid packaging, e.g. B. milk or juice cartons, omnipresent. Due to their low density, the use of aluminum tapes and foils is particularly advantageous for weight-sensitive applications. No competing material can match it A combination of formability, printability and excellent barrier properties, such as low permeability for light, oxygen and flavorings, make aluminum foil unsurpassed when it comes to protecting and maintaining complex food supply chains.
- the use of appropriately treated aluminum strips and foils for food packaging, in particular for liquid packaging is therefore particularly advantageous.
- the above-mentioned object is achieved by a device for the heat treatment of metal strips or foils in the form of a strip or foil coil for removing rolling residues according to the method according to the invention, in that the device has at least one means for determining the content at least one evaporation and / or oxidation product in the furnace atmosphere and / or in the process exhaust gas while the heat treatment is being carried out and at least one means for controlling or regulating the heat treatment depending on the content of at least one evaporation and / or oxidation product in the furnace atmosphere and / or in the process exhaust gas, which are designed in such a way that the dynamics of the removal of rolling residues on the metal strips or foils during the heat treatment can be controlled or regulated with them.
- the at least one means for controlling or regulating the heat treatment is designed in particular for controlling or regulating the heat treatment depending on the content of at least one evaporation and / or oxidation product in the furnace atmosphere and / or in the process exhaust gas.
- the device according to the invention is therefore suitable for carrying out the method according to the invention.
- the device for heat treatment is preferably a batch furnace.
- Batch ovens are usually less expensive to operate and purchase than continuous ovens and enable the heat treatment of metal strips or foils wound into coils.
- a batch furnace has a furnace body and a furnace chamber, the furnace chamber inside the Furnace body is arranged and is designed for receiving at least one tape or foil coil.
- the device according to the invention also has at least one means for determining the content of at least one evaporation and / or oxidation product in the furnace atmosphere and / or in the process exhaust gas, such as a Vorg, CO and / or CO 2 analyzer, preferably an F1D or an infrared analyzer.
- the process air inside the furnace chamber is called the furnace atmosphere.
- An exchange of process air takes place between the furnace chamber and the environment, it also being possible according to the invention to provide means for determining evaporation and / or oxidation products in the process exhaust gas.
- a PID controller for example, can be provided as a means for controlling or regulating the heat treatment.
- the device according to the invention enables the monitoring of levels of evaporation and / or oxidation products in the furnace atmosphere and / or in the process exhaust gas and a targeted influence on the process parameters of the heat treatment, for example a control or regulation of the dynamics of the removal of rolling residues on the metal strips or - foils in the coil during heat treatment.
- the gas pressure of the evaporation and / or oxidation products in the strip or foil coil can be controlled or regulated in this way during the heat treatment, so that a process-safe, efficient and reliable cleaning of the surfaces of the metal strips or foils from rolling residues is guaranteed.
- the device has at least one means for controlling or regulating the furnace temperature, the furnace temperature gradient, the process air exchange volume and / or the circulating volume of process air depending on the content of at least one evaporation and / or oxidation product in the furnace atmosphere and / or in the process exhaust.
- the device preferably has at least one means for controlling or regulating the furnace temperature gradient depending on the gradient of the content of at least one evaporation and / or oxidation product in the furnace atmosphere and / or in the process waste gas.
- a direct harmonization that is to say for example an equalization, in particular a reduction in the dynamics of the evaporation of a rolling residue in the strip or foil coil can be achieved.
- the device preferably has at least one controllable means for influencing the heat treatment.
- a controllable means for influencing the heat treatment With the aid of a heater or flap, it is possible, for example, to influence the temperature or the temperature gradient in the furnace space.
- a fan is advantageous for circulating air in the furnace chamber, while process gases, for example protective gas or reaction gas, can be supplied with the aid of a metering valve to adjust the furnace atmosphere, in particular the furnace atmosphere's ability to oxidize.
- FIG. 2 in a schematic representation an embodiment of the device according to the invention
- 3a, b show, in a schematic representation, advantageous embodiments of the method according to the invention.
- FIG. 4a, b in a diagram of test results of measurements of the
- FIG. 1 a a metal foil 1, preferably an aluminum or aluminum alloy foil, is shown which has been wound up in two layers to form a coil 2 and conventionally soft-annealed at 220 ° C. to 250 ° C. in a heat treatment furnace.
- the coil 2 has a width of 250 mm to 2500 mm, in particular approx. 1000 mm or approx. 1700 mm.
- the winding height h is 18 mm, for example, which means that the film layers shown are very close to the core 3 of the coil 2.
- a critical glow bubble 4 has formed on the film surface as a result of a conventionally carried out final annealing.
- On the inner surface of the bulb 4 scratches can be seen transversely to the direction of travel, with material having been pushed on at these points.
- the cross section of the incandescent bulb 4 in section AB is shown in detail in FIG.
- At the edge of the incandescent bubble 4 in the area X there is a compression of the material. The compression can be on the inside or on the outside of the incandescent bulb 4.
- the film 1 has flow lines which indicate a constriction of the material and can lead to a crack or breakthrough in the metal film 1.
- the aim of the method according to the invention is to avoid the formation of such incandescent bubbles and welding of the metal strips or foils, to provide high-quality metal products in a process-reliable and cost-effective manner and thereby to reduce the scrap portion of metal strips and foils. Damage to the metal surfaces in the form of impressions and scratches also leads to quality devaluations and rejects.
- film coils are rated as good if they have good running properties and have no or a significantly reduced local tendency to stick. Incandescent bubbles of acceptable form do not stick and can be slowed down without problems with increased tape tension. This also applies in particular to film layers that are located near the coil core 3, for example at a winding height of up to 12 mm or up to 18 mm.
- the problems known from the prior art can be solved with the aid of the method according to the invention for the heat treatment of metal strips or foils, in particular for the treatment of aluminum or aluminum alloy strips or foils, in the form of strip or foil coils 2 in a heat treatment furnace to remove rolling residues , solve in that the content of at least one evaporation and / or oxidation product in the furnace atmosphere and / or in the process exhaust gas is determined while the heat treatment is being carried out and is used for process control or regulation of the heat treatment, the dynamics of the removal of rolling residues on the metal strips or foils is controlled or regulated during the heat treatment.
- the method according to the invention which thus includes, for example, atmospheric control and regulation or regulation taking into account the kinetics of the evaporation and oxidation products, can ensure the flatness of the metal products and increase their quality accordingly.
- 2 shows an advantageous embodiment of a device according to the invention for the heat treatment of metal strips or foils, in particular for the removal of rolling residues, the device having at least one means 8 for determining the content of at least one evaporation and / or oxidation product in the furnace atmosphere 11 and / or in the process exhaust gas 12 while the heat treatment is being carried out and at least one means 9 for controlling or regulating the heat treatment, which are designed in such a way that they can be used to control or regulate the dynamics of the removal of rolling residues on the metal strips or foils during the heat treatment .
- the device is a heat treatment furnace 5, in particular a batch furnace, which has a furnace body 10 in addition to the furnace chamber 6, the furnace chamber 6 being arranged inside the furnace body 10 and for receiving metal strips or foils reeled into coils 2 an annealing rack (not shown here) is designed.
- the process air in the interior of the furnace chamber 6 is referred to as the furnace atmosphere 11.
- An exchange of process air takes place between the furnace chamber 6 and the environment, with process exhaust gas 12 being emitted from the furnace chamber 6.
- the heat treatment furnace 5 also has a fan 7 for circulating air in the furnace chamber 6.
- the heat treatment furnace 5 has at least one means 8 for determining the content of at least one evaporation and / or oxidation product in the furnace atmosphere 11 and / or in the process exhaust gas 12 while the heat treatment is being carried out.
- the heat treatment furnace 5 has an FID analyzer, preferably an on-line FID analyzer, for determining the Vorg content, a CO analyzer, preferably an on-line CO analyzer, for determining the CO content and / or a CO 2 analyzer, preferably an on line CO 2 analyzer, for determining the CO 2 content in the furnace atmosphere 11.
- a CO or CO2 analyzer can in particular be an infrared analyzer.
- the heat treatment furnace 5 can have at least one means 8 for determining the content of at least one evaporation and / or Have oxidation product in the process exhaust gas 12 (shown here by a dashed line).
- the heat treatment furnace 5 also has at least one means 9 for controlling or regulating the heat treatment.
- the at least one means 9 for controlling or regulating the heat treatment is designed in particular for controlling or regulating the heat treatment depending on the content of at least one evaporation and / or oxidation product in the furnace atmosphere 11 and / or in the process exhaust gas 12.
- At least one means 9 for controlling or regulating the furnace temperature, the furnace temperature gradient, the process air exchange volume and / or the circulating volume of process air depending on the content of at least one evaporation and / or oxidation product in the furnace atmosphere 11 and / or in the process exhaust gas 12 and / or at least one means 9 for controlling or regulating the furnace temperature gradient depending on the gradient of the content of at least one evaporation and / or oxidation product in the furnace atmosphere 11 and / or in the process exhaust gas 12 can be provided.
- a PID controller can be provided as the means 9 for controlling or regulating the heat treatment.
- At least one controllable means 13 for influencing the heat treatment in particular a heater, a flap, a Fan and / or a metering valve are provided.
- a heater or flap it is possible, for example, to influence the temperature or the temperature gradient in the furnace space.
- a fan is advantageous for circulating air in the furnace chamber, while process gases, for example protective gas or reaction gas, can be supplied with the aid of a metering valve to adjust the furnace atmosphere, in particular the furnace atmosphere's ability to oxidize.
- the heat treatment furnace 5 according to the invention is therefore particularly suitable for carrying out the method according to the invention.
- the heat treatment furnace 5 according to the invention can also be used to control or regulate the gas pressure of the evaporation and / or oxidation products in the strip or foil coil during the heat treatment.
- FIG. 3a shows an advantageous embodiment of the method according to the invention.
- the content G of at least one evaporation and / or oxidation product in the furnace atmosphere and / or in the process exhaust gas is determined in step A and used for process control of the heat treatment in step C in step A.
- the Vorg content in the furnace atmosphere and / or in the process exhaust gas can be determined, for example by means of an FID analyzer.
- the determination of the CO content for example using a CO analyzer, and / or the determination of the CO 2 content, for example using a CO 2 analyzer, or the determination of the Ctot content using an FID analyzer and a CO analyzer and optionally a C 02 analyzer would be conceivable.
- step B the actual value of the content of at least one evaporation and / or oxidation product Gist, for example the actual value C tot ist of the Cges content, is used for process control of the heat treatment.
- the Gist value is compared with a nominal value Gsoii. This can be done manually, for example.
- the heat treatment is controlled depending on the Gist value. For example, at least one parameter P, e.g. B. the oven temperature, lowered in the event that the Gist value is greater than the Gsoii value. In the event that the Gist value is smaller than the Gsoii value, the parameter P is increased. This can also be done the other way around.
- the furnace temperature gradient, the process air exchange volume and the circulating volume can also be set in the process control Process air and / or the composition of the furnace atmosphere depending on the content G of at least one evaporation and / or oxidation product in the furnace atmosphere and / or in the process exhaust gas, e.g. B. depending on the C total content, and / or the furnace temperature gradient depending on the gradient of the content of at least one evaporation and / or oxidation product in the furnace atmosphere and / or in the process exhaust gas, e.g. B. be controlled depending on the C ges gradient.
- FIG. 3b A further advantageous embodiment of the method according to the invention is shown in FIG. 3b.
- the content G of at least one evaporation and / or oxidation product in the furnace atmosphere and / or in the process exhaust gas is determined in step A 'and used for process control of the heat treatment in step C'.
- the V or content may for example be in the furnace atmosphere and / or in the process gas, for example by means of a FID analyzer determined, wherein the determination of the CO content, for example by means of a CO analyzer, and / or the determination of the C02 content, for example by means of a C02 analyzer, or the determination of C ges -content and a CO analyzer and C were by an FID analyzer 02 optionally conceivable.
- the actual value Gist of the content of at least one evaporation and / or oxidation product is used for process control of the heat treatment.
- the Gist value is also compared in step B 'with a setpoint value Gsoii.
- a parameter P e.g. B. the furnace temperature, regulated.
- the parameter P is lowered in the event that the Gist value is greater than the Gsoii value.
- the parameter P is increased, for example. This can also happen the other way around.
- the furnace temperature gradient can also be used in the process control Process air exchange volume, the circulation volume of process air and / or the composition of the furnace atmosphere depending on the content of at least one evaporation and / or oxidation product in the furnace atmosphere and / or in the process exhaust gas, e.g. B. depending on the C total content, and / or the furnace temperature gradient depending on the gradient of the content of at least one evaporation and / or oxidation product in the furnace atmosphere and / or in the process exhaust gas, e.g. B. be regulated depending on the C ges gradient.
- the Gist value is continuously compared with the Gsoii value and influenced by changing the parameter P in order to adjust it to the Gsoii value.
- a PID controller for example, can be used for process control.
- Fig. 4a the writing of an FI D analyzer is shown during a conventional finish annealing on an aluminum foil coil with a width of 1616 mm.
- the final annealing was carried out at a program temperature of 330 ° C for a duration of almost 72 hours.
- the diagram shows the CO content [ppm], the oven and program temperature [° C], the air volume [m 3 / h] and the fan speed [rpm] as a function of time [h].
- Content was carried out in the present case in the furnace atmosphere. This allows conclusions to be drawn about the content of evaporation and / or oxidation products in the furnace atmosphere. Alternatively, however, the CO content can also be determined in the process exhaust gas. Further alternatively or additionally, the V or can be - and / or the CO-content or the C tot content in the furnace atmosphere and / or process exhaust gas to be determined.
- the diagram shows very clearly that with conventional finish annealing, a COmax peak of 1000 ppm in the furnace atmosphere occurs after a short time.
- the CO gradient in this case was about 200 ppm / h.
- extensive tests have shown that, for example, COmax peaks of more than 220 ppm and CO gradients of more than 10 ppm / h reflect a negative annealing result. It has been shown that with an appropriate furnace atmosphere there is tension, welds and the formation of incandescent bubbles in the metal foil. In the worst case, these in turn can lead to cracks in the film when the coil is being unwound.
- the COmax content was limited to only approx.
- the COmax gradient is approx. 5.5 ppm / h.
- the program temperature was set at 220 ° C., the amount of air was kept constant at about 280 m 3 / h and the speed of rotation was kept constant at about 640 rpm. As can be seen from the graph, the formation of a pronounced CO peak during the annealing treatment could be avoided in the present case.
- the furnace temperature was controlled or regulated depending on the CO content in the furnace atmosphere. While both the furnace temperature and the CO content in the furnace atmosphere rise uniformly up to the point in time of about ten hours (cf. dashed line), the furnace temperature was lowered at the critical value of about 50 ppm of CO content.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- General Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Heat Treatment Of Strip Materials And Filament Materials (AREA)
- Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
- Furnace Details (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP19208640 | 2019-11-12 | ||
PCT/EP2020/081870 WO2021094432A1 (de) | 2019-11-12 | 2020-11-12 | Geregelte folienwärmebehandlung |
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EP20803186.4A Pending EP4058611A1 (de) | 2019-11-12 | 2020-11-12 | Geregelte folienwärmebehandlung |
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EP (1) | EP4058611A1 (de) |
JP (1) | JP7378615B2 (de) |
KR (2) | KR20240026248A (de) |
CN (1) | CN114729413B (de) |
BR (1) | BR112022007669A2 (de) |
WO (1) | WO2021094432A1 (de) |
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JPS57161036A (en) * | 1981-03-28 | 1982-10-04 | Sumitomo Metal Ind Ltd | Production of clean cold rolled steel strip |
JPS6456825A (en) * | 1987-08-27 | 1989-03-03 | Kobe Steel Ltd | Heat-treating method for pipe stock |
DE59300400D1 (de) * | 1992-04-06 | 1995-08-31 | Ebg Elektromagnet Werkstoffe | Verfahren und Vorrichtung zur Reinigung von Metallbandoberflächen durch Gasspülung in wasserstoffreichen Atmosphären. |
DE4336771A1 (de) * | 1993-10-28 | 1995-05-04 | Loi Ind Ofenanlagen | Verfahren zum Glühen von Glühgut sowie zugehöriger Glühofen |
SE507916C2 (sv) * | 1996-10-15 | 1998-07-27 | Aga Ab | Sätt och anordning för kontroll och/eller styrning av gasatmosfären i en värmebehandlingsugn |
CN101078096A (zh) * | 2006-05-25 | 2007-11-28 | 福建方明钢铁有限公司 | 一种带钢连续热镀锌的工艺方法 |
SI2067871T2 (sl) * | 2007-11-30 | 2023-01-31 | Speira Gmbh | Aluminijev trak za litografske nosilce tiskarskih plošč in njegova izdelava |
CZ301924B6 (cs) * | 2009-02-10 | 2010-08-04 | Raclavský@Milan | Technologie rafinace kovonosných odpadu s obsahem zinku v rotacní peci |
RU2465080C1 (ru) * | 2011-07-08 | 2012-10-27 | Открытое акционерное общество "Магнитогорский металлургический комбинат" | Способ производства холоднокатаных полос на четырехклетевом непрерывном стане 2500 |
JP5517382B1 (ja) * | 2012-07-04 | 2014-06-11 | 関東冶金工業株式会社 | 熱処理装置および熱処理方法 |
CN105268740A (zh) * | 2014-05-30 | 2016-01-27 | 宝山钢铁股份有限公司 | 热轧免酸洗直接还原热镀产品的生产方法 |
US11239012B2 (en) * | 2014-10-15 | 2022-02-01 | Sms Group Gmbh | Process for producing grain-oriented electrical steel strip |
CN105753066A (zh) * | 2014-12-15 | 2016-07-13 | 武丽霞 | 一种从轧钢乳化液油泥中回收氧化铁粉及废油的试验方法 |
CN109266983A (zh) * | 2018-11-29 | 2019-01-25 | 天津忠旺铝业有限公司 | 一种防止铝合金卷材退火油斑产生的方法 |
-
2020
- 2020-11-12 BR BR112022007669A patent/BR112022007669A2/pt unknown
- 2020-11-12 CN CN202080078797.0A patent/CN114729413B/zh active Active
- 2020-11-12 JP JP2022527691A patent/JP7378615B2/ja active Active
- 2020-11-12 EP EP20803186.4A patent/EP4058611A1/de active Pending
- 2020-11-12 KR KR1020247005183A patent/KR20240026248A/ko not_active Application Discontinuation
- 2020-11-12 WO PCT/EP2020/081870 patent/WO2021094432A1/de active Search and Examination
- 2020-11-12 KR KR1020227014467A patent/KR20220070517A/ko not_active IP Right Cessation
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BR112022007669A2 (pt) | 2022-08-09 |
KR20240026248A (ko) | 2024-02-27 |
CN114729413B (zh) | 2024-07-16 |
CN114729413A (zh) | 2022-07-08 |
JP2022550211A (ja) | 2022-11-30 |
KR20220070517A (ko) | 2022-05-31 |
JP7378615B2 (ja) | 2023-11-13 |
WO2021094432A1 (de) | 2021-05-20 |
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