WO2011107199A2 - Verfahren zur herstellung von nickelband - Google Patents
Verfahren zur herstellung von nickelband Download PDFInfo
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- WO2011107199A2 WO2011107199A2 PCT/EP2011/000509 EP2011000509W WO2011107199A2 WO 2011107199 A2 WO2011107199 A2 WO 2011107199A2 EP 2011000509 W EP2011000509 W EP 2011000509W WO 2011107199 A2 WO2011107199 A2 WO 2011107199A2
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- sheets
- welding
- nickel
- strip
- hot rolling
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/4902—Electromagnet, transformer or inductor
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/4902—Electromagnet, transformer or inductor
- Y10T29/49071—Electromagnet, transformer or inductor by winding or coiling
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/4902—Electromagnet, transformer or inductor
- Y10T29/49073—Electromagnet, transformer or inductor by assembling coil and core
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49117—Conductor or circuit manufacturing
- Y10T29/49124—On flat or curved insulated base, e.g., printed circuit, etc.
- Y10T29/4913—Assembling to base an electrical component, e.g., capacitor, etc.
- Y10T29/49133—Assembling to base an electrical component, e.g., capacitor, etc. with component orienting
- Y10T29/49135—Assembling to base an electrical component, e.g., capacitor, etc. with component orienting and shaping, e.g., cutting or bending, etc.
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49117—Conductor or circuit manufacturing
- Y10T29/49169—Assembling electrical component directly to terminal or elongated conductor
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49117—Conductor or circuit manufacturing
- Y10T29/49204—Contact or terminal manufacturing
Definitions
- the invention relates to the production of strips of Nickelkathodenblechen, and indeed of a plurality of substantially entire cathode sheets, wherein preferably the differences in thickness within sheets and between different sheets are compensated by hot rolling, without that by the heating before hot rolling and hot rolling itself a no longer reducible to nickel oxide layer and irreversible grain boundary corrosion and internal corrosion arises.
- nickel is mentioned in this description in the general part or the part of the exemplary embodiment, cobalt is also disclosed as being an alternative metal to the person skilled in the art in the same way. All of the aspects essential to the invention described here also apply to cobalt.
- Nickel strips are mainly produced by fusion metallurgy. In order to limit non-metallic oxidic impurities, the VIM process is melted and poured off, remelted to eliminate porosity in the ESU or VAR process. Surface cracks caused by the high shrinkage of nickel must be removed by grinding; the removal is about 6 to 9 mm.
- Hot rolling usually begins at temperatures of about 1,150 ° C to 1,250 ° C. Hot rolling not only produces a surface oxide layer, it also causes grain boundary corrosion. The thickness of the oxide layer and the near-surface layer affected by grain boundary corrosion depends on the degree of purity of the material, the exposure time and the processing temperature. These layers (on both sides of the strip) have a total layer thickness of about 50 ⁇ on. Oxides are only slightly deformable. If the layers affected by oxidation were not completely removed, oxides rolled into films during the subsequent cold rolling would lead to holes in the strip and ribbon tears. Rolled oxides lead to surface defects. Border damage caused by grain boundary corrosion leads to irreparable strength losses.
- cathode sheets should first be cut into strips "in a cold process" (column 2 Z.44), the strips optionally joined at the transverse side and the strip produced in this way further processed restoring only the initial dimensions.)
- the patent does not claim to provide a method for producing a metal strip from substantially completely sintered cathode sheets, but claims to provide a method for producing a metal strip formed from strips which in turn constitute chopped cathode sheets.
- the strip-wise cutting of entire cathode sheets is a feature of claim 1 of said patent
- the advantage of the method is that thickness variations in the related starting material occur only to the extent that they exist in a sheet rather than between different sheets.
- Thickness deviations within cathode sheets and between different sheets are not even mentioned in DE 2905508 incidentally; the method description therefore does not explicitly address the problems of producing a strip of constant thickness. This is not necessary if, for example, elongated anode plates to be produced, where it does not depend on dimensional accuracy.
- DE 2905508 also does not mention cold rolling with recoil applied by reels. Rather, even after the connection of reduced by rollers and then split sheets and frontally joined sheets still spoken of "bars" and the coiling described as a separate step after rolling ("then", Sp. 4 Z. 7).
- DE 2905508 is therefore a sheet metal, not a strip rolling process in which rolling with coiler pulleys is an integral part.
- the reason for dispensing with hoists when rolling is due to the fact that in DE 2905508 no method for producing a pore-free weld is specified, but pores reduce the effective cross-section and lead to tearing of the strip in the case of coiler trains.
- the weight of the units which can be generated is limited by the length of the roller tables before and after the rolling stand ("up to 2 t weight", column 4 Z 8).
- the given procedures (eg degree of reduction> 75%, preferably> 96%) serve to avoid the blistering that occurs during annealing after cold rolling. It is also avoided that the sheets separate during cold rolling.
- a particular advantage is stated that large generating units can be achieved by stacking the sheets. In contrast to rolling single sheets, hot rolling from blocks is a very productive process. After hot rolling, however, up to 5% of the area of each opposing metal sheets should not be connected. The unconnected areas therefore increase linearly with the number of stacked sheets. Sheets with unconnected areas are not marketable.
- the hot rolling step results in the entire strip being scaled with a porous oxide layer and deep grain boundary corrosion occurring. Surface corrosion of the individual sheets in the stack, however, should be avoided. Blasting, grinding or pickling of the surface are required to remove the resulting oxide layer.
- WO2006024526 (EP1784273, DE102004042481; Stuth) describes a method for arranging and connecting cathode sheets before hot or cold rolling. In this case, a hot deformation should be avoided, provided that the material oxidized and the oxide layers are difficult to eliminate. The harmfulness of H and S is described, limitations on the analysis of the starting material are not quantified.
- Targeted thickness matching by hot rolling is a technique that solves a problem that only occurs with cathode sheets.
- the thickness of the cathode sheets can not be influenced in contrast to the melt-metallurgical production of slabs. Their thickness depends on their position in the tank house, the flow at this position and the proximity to the inflows of the electrolyte rich in metal ions.
- nickel cathode sheets have the following characteristics:
- the sheets To make strip from sheets, the sheets must be joined at one edge. In particular, when the joint is to be rolled, the abutting edges must not have any projections, incursions or gaps.
- the aim of the proposed method is to use hot rolls to equalize the thicknesses within and between different nickel cathode sheets, wherein in the band by the heating and hot rolling neither embrittlement, internal oxidation, nor grain boundary corrosion should occur and on the band at most a thin substantially single-layer dense oxide layer arises, which can be converted by reducing annealing in firmly adhering to the body pure nickel. It should be avoided that the hot rolling mill must be encapsulated to prevent air access. The sheets must also be weldable prior to their connection, whether this occurs before or after hot rolling.
- the oxide layer formed during heating and hot rolling should still be plastically deformable in such a way that after hot rolling and joining or the strip produced from the sheets, the sheets can be recharged after hot rolling without the oxide layer flaking off.
- Entire cathode sheets are understood to mean sheets which are produced in the electrolysis, the hangers (loops) may already be separated.
- substantially whole cathode sheets are meant those which are entire cathode sheets except for the edge regions.
- the edge regions are characterized in that their surface thickness decreases or on the contrary rises sharply (namely where the hangers were welded to the sheet, the remains thereof after cutting off the protruding parts, they remain on the sheet.)
- These edge portions are separated after hot rolling, and sheets divided into strips do not fall under the term “substantially whole cathode sheets”.
- “Ribbon” is understood to mean a flat body which is produced by welding the at least substantially entire cathode sheets together on the edge side in the metal industry.
- strip is used in various compositions in the metal industry (strip rolling mill, strip steel) provide very different dimensions, there are no a priori fixed longitudinal and transverse sides, the strips made of sheets can have a width between about 500 mm and several meters, the latter in particular when the sheets joined only after hot rolling with their long sides The dimensions are illustrative only, without her concluding the bandwidths achievable by the method.
- the term “single-layer / single-layer” hot rolling is intended to clarify that the method does not refer to layered and thus fixed hot-rolled sheets.
- Two-layer nickel oxide layers have a ratio of about 50:50.
- a "substantially single-layer oxide layer” should also comprise a two-layer oxide layer if the relation of the two layers is ⁇ 10:> 90.
- a thin oxide layer is understood to mean a layer which does not exceed a thickness of approximately 10 ⁇ m when heated to 1.00 ° C. and has a holding time of 800 seconds.
- the oxide layer thickness after hot rolling was 2 ⁇ in the described application example.
- the thickest part of the sheet is considered sheet thickness, ignoring the warts.
- Welding gases are considered to be "free from” other gas additives if they contain the minor constituents contained in industrially produced standard mixtures, which are to be considered as cylinder gases, as well as 100% of an element, for example argon 100% Minor components and harmless:
- pure nickel and “high purity nickel” is meant nickel having a purity of> 99.94 wt.%.
- the achievement of the object is to limit the permissible trace elements in the already clean cathode plates so or deliberately degrade that when heated before hot rolling and hot rolling itself
- the morphology of the oxide layer develops in such a way that
- a resulting oxide layer can be converted by reduction annealing in pure nickel.
- the adhesion of the oxide layer on the base material and possibly the adhesion between different oxide layers is important. The layers must not flake off during heating and cooling.
- Nickel depending on the degree of purity in general and the concentration of trace elements in particular, can form a single-layer or two-layer oxide layer. With regard to the goal of eliminating the resulting oxide layer by reducing annealing, a two-layer oxide layer is undesirable. Oxidation of various grades of nickel can cause internal corrosion and grain boundary corrosion to a great extent. The number of oxide layers, on the one hand, and the occurrence of grain boundary corrosion and internal corrosion, on the other hand, are not unambiguously related: there are compositions which, upon oxidation, develop a two-layer oxide but have no grain boundary corrosion. However, very pure laboratory-grade nickel with a purity level of> 99.997% develops a single-layer oxide layer on heating and no grain boundary corrosion or internal corrosion.
- Electrolytically produced cathode sheets which only achieve the analytical values of ASTM B 39-79 (Reapproved 2004), despite their - compared to melt-metallurgically produced material - significantly higher degree of purity a two-layer oxide layer and in addition to grain boundary corrosion and internal corrosion. Sandblasting, pickling or grinding are gem. the prior art, even after the hot rolling of cathode nickel, so particularly pure nickel, required (US
- Gases and gas-forming elements which, when heated, possibly only caused by a chemical reaction, form gases, expand and subsequently either form bubbles in the material due to the gas pressure or loosen the grain structure or cause voids, in particular at the grain boundaries. This is true for C.
- Si can form on nickel a surface film and with other segregationfreudigen ele- ments, namely Mn and Al, on the metal a glassy film of manganese silicate Mn 3 Si 8 Al 3 . This happens when heating in a humid atmosphere.
- Mg, Mn, Ti, Al, Cr, Zn, Fe, Si and Sn are Mg, Mn, Ti, Al, Cr, Zn, Fe, Si and Sn.
- Claim 1 refers expressly to the trace elements before hot rolling, not before heating.
- the limiting analysis values therefore need not be complied with by the manufacturers of the cathode sheets with respect to these elements, which, however, does not preclude their use for the proposed method from the outset.
- the formation of a - especially dense - oxide layer prevents contamination by annealing can be eliminated. Therefore, these elements must, if they exceed the limits mentioned in claims 1 and 2, if necessary, be removed before the oxidation.
- C When nickel is heated in air, C oxidizes preferentially to nickel. C segregates to the grain boundaries, where it reacts with penetrating oxygen in near-surface areas and forms vacancies. C segregates at high temperatures, e.g. the hot rolling temperature of 1,100 ° C, also to the surface and is incorporated into the oxide layer. It reacts with diffusing oxygen at the metal - metal oxide interface, leaving voids behind. The formation of blisters on the surface during annealing of nickel at temperatures of> 760 ° C is also attributed to C.
- the reaction with oxygen produces CO and CO2.
- the gas pressure can make the material brittle by loosening the grain boundaries and rupture or break off an already formed oxide layer. The tape must then be sanded or pickled.
- the C content can be reduced by annealing in vacuo. Tests have shown that by annealing in vacuum at 700 ° C for one hour, the C content can be reduced from 20 to 5 ppm. Especially effective is the oxidation of C by annealing in wet hydrogen.
- the O liberated from the water combines with the surface C and does not penetrate the material, unlike annealing in air, because O, which does not combine with C, combines with H.
- the reaction of C with O produces a concentration gradient in the material that causes C to diffuse to the surface where it combines with O to form CO. As a result of this process, the entire metal body is depleted of C without any grain boundary widening due to gas formation in the metal body. If C is to be degraded by annealing in wet hydrogen, the contents of Mn, Al and Si must be so low that these elements do not form a glassy film of manganese silicate Mn 3 Si 8 Al 3 .
- Sulfur is soluble in nickel up to 50 ppm. At levels beyond that, it precipitates as nickel sulfide at the grain boundaries.
- the sulfur content may at most be 1/10 of this value. This is due to the fact that at annealing temperatures of around 750 ° C, sulfur diffuses to the surface and - several orders of magnitude faster - segregates at the grain boundaries and moves from there to the surface. As a result, the forming oxide layers are infiltrated. Since sulfides occupy a larger volume than the equivalent amount of metal, voltages at the phase boundary Me- tall / oxide layer, which favor a flaking of the oxide layer. The tape would then have to be ground.
- the sulfur content must be reduced by high-temperature annealing in dry hydrogen. The sulfur diffuses to the surface and evaporates there or reacts with hydrogen.
- an oxide layer prevents impurities from being removed by annealing, but rather collects in the oxide layer or at the interface between metal and oxide layer. Therefore, the high temperature anneal must be performed before the surface oxidizes.
- Si oxidizes preferentially to nickel and forms SiO 2 .
- the Si content is not high enough that a closed SiO 2 intermediate layer could form.
- SiO 2 can form islands under the NiO layer. Due to the different coefficients of expansion of SiO 2 and NiO, the cooling of the material after heating may cause the NiO layer to flake off in places.
- Si oxides can not be reduced by annealing in dry hydrogen; they would be rolled into the metal if the layer in which the oxide is enriched would not be removed after hot rolling. The Si content must therefore be strictly limited - to ⁇ 15 wt ppm.
- the manganese content must therefore be limited to ⁇ 14 ppm.
- the magnesium content should therefore be limited to ⁇ 11 ppm.
- NiAl alloys form a protective Al 2 O 3 layer firmly adhering to the main body, which makes the material resistant to high temperatures, even at cyclic temperature control.
- the Al content in electrolytically obtained nickel is too low to allow the formation of a closed Al 2 O 3 layer.
- Al 2 O 3 in the matrix is formed by selective oxidation due to the high oxygen affinity of the aluminum.
- Nickel ions continue to diffuse outwards where a NiO layer forms.
- AI therefore tends to create stratification.
- Alumina is very hard; it deforms when Not rolling and can lead to the formation of holes during rolling of films.
- Al oxides can not be reduced by annealing in dry hydrogen; they would be rolled into the metal if the layer in which the oxide is enriched would not be removed after hot rolling.
- the Al content must therefore be strictly limited to ⁇ 7 wt. Ppm. titanium
- Titanium migrates to the surface and is preferentially oxidized to T1O2. It can not be reduced by conventional heat treatment measures. The titanium content must therefore be limited to ⁇ 25 wt. Ppm.
- cobalt behaves like nickel.
- the content of cobalt therefore need not be limited.
- Cobalt is still much more expensive than nickel. It is therefore separated during nickel extraction and recovered separately.
- the contents of nickel cathode sheets on cobalt are therefore i.d.R. below 60 ppm. In test material but also 200 ppm have been found.
- chrome Chromium has a higher oxygen affinity than nickel. Nevertheless, initially formed due to the higher reaction rate during oxidation in air at a temperature of 1 000 0 C initially a NiO layer. Upon continued heating, chromium contained in nickel diffuses toward the surface.
- the chromium activity depends on the concentration in the alloy. At up to 7 at.% Chromium in the nickel, the scale constant increases much more than with all other metallic trace elements; higher-value metal ions, eg Cr 34 cations, are incorporated into the NiO layer. If only traces of chromium are contained in the nickel, the chromium activity is reduced. Chromium is harmless up to levels of 100 ppm.
- the chromium content in the investigated cathode sheets was ⁇ 5 ppm. At these chromium contents, no continuous chromium oxide layer is formed. A restriction of the chromium content is unnecessary.
- iron is similar to chromium. Also Fe oxidizes before Ni. It is therefore surprising that even high Fe contents can be tolerated.
- Iron oxides can be decomposed by annealing in dry hydrogen. Such annealing to reduce the nickel oxide is part of the process anyway. Iron oxides are up to 200 ppm without detrimental effect on the proposed process. The iron contents in the investigated cathode sheets were between> 5 and ⁇ 200 ppm. A restriction is therefore unnecessary.
- Hydrogen has proven to be exceptionally harmful in fusion welding. It causes Badausgianfe, which lead to irregular welds, and triggers microporosity of the weld.
- H must be reduced to a residual content of ⁇ 0.1 wt.ppm before fusion welding.
- This can be done by a heat treatment (from mere days of heating to 250 ° C to annealing in vacuo or under inert gas).
- Calculated is atomic hydrogen from a 6 mm thick sheet at an annealing temperature of 1,100 ° C after about 4 min. outgassed. It has been found that the heating in the continuous furnace at 1,100 ° C with a cycle time of 800 seconds before hot rolling is sufficient to reduce the hydrogen content so far that can be welded easily after hot rolling. Cracking could not be detected by a radius of 4 mm in a 90 ° bend test.
- the prescribed procedure means that the hydrogen content does not have to be restricted. If the sheets are joined by hot welding prior to hot rolling, it is advisable to pre-expel the hydrogen by heat treatment.
- the content of nitrogen is relevant because nitrogen present in the material can lead to pore formation during fusion welding. In cathode sheets, per gas analysis ⁇ 2 wt. ppm nitrogen detected. This amount of nitrogen is harmless when welding.
- the top layer is foamy and completely reduced; she sticks well on the
- the advantages of hot rolling can be used, in particular the mass balance in the width, without having to accept its disadvantages, such as the need to grind or pickle after hot rolling.
- Advantages of the method are further that the production on existing industrial plants can be done without their controls need to be adjusted.
- a sorting of the sheets by thickness is unnecessary, since all sheets after hot rolling are the same thickness.
- the constant thickness, particularly when the sheets are still being tempered after hot rolling, also facilitates welding of the sheets into a strip because alignment of the heights of the sheets is not required and no wedge-shaped transition is made between the welded sheets to accommodate different thicknesses must become.
- Another object of the present invention is the use of the strip produced by the above process steps as a starter sheet for the production of cathode sheets.
- the present invention furthermore relates to the use of the optionally divided strip or sheet produced according to the above method steps as a starting material for the production of wire, in particular a welding wire with a nickel content of at least 99.94% and starter sheets for the production of cathode sheets.
- Another object of the present invention is a starter sheet, obtained by any of the method steps described above.
- Another object of the present invention is a wire, in particular
- Welding wire obtainable from longitudinally, transversely and / or in a pattern-divided sheet or strip and / or non-dimensionally finished end pieces and / or side strips separated before or after hot rolling according to any one of the method steps described above.
- the sheet metal parts intended for the production of wire are cut into strips with a rectangular cross section, which may also be curved (cf., Fig. 6) and welded on the front side, preferably by butt welding.
- the protruding weld edges are deburred, e.g. by deburring, and then processed by rolling or drawing into wire.
- Fig. 2 a metallographic cut with a view from the transverse direction of the tape with reproduction of the oxide layer
- Fig. 3 a hot rolled material polished to show internal corrosion
- Fig. 4 a subjected to a 24 h oxidation material, 50 times enlarged
- Fig. 5 The material of FIG. 4, which is then subjected to reduction, 500 times enlarged
- Fig. 6 an example of the cutting of a separated Walzunge to raw material for wire
- Application example Production of tape from cathode plates with limited analysis
- the selected 12 to 15 mm thick stock had the following analysis before hot rolling:
- the material is usually delivered on pallets with a weight of about 1 t with handles.
- the handles are cut off.
- the individual sheets were 1280 mm long, 720 mm wide and 12 to 15 mm thick.
- Electrolytically produced sheets have so-called warts (nodules) on the surface. Since these warts are firmly connected to the base plate and cone-shaped, it has not been found necessary to grind the entire sheets. Some particularly prominent warts (from about 6 mm height to the base of the wart) have been sanded off.
- the material is under the stress of the deposition process; It can therefore be recrystallized by vacuum annealing or annealing under inert gas even without any previous deformation.
- an annealing time of 1 hour is sufficient at a temperature of 700 ° C.
- 800 seconds were annealed at 1,100 ° C.
- a previous heat treatment for the degradation of certain trace elements was not performed.
- Usual annealing temperatures of about 900 to 1,290 ° C.
- the cathode sheets were hot rolled in a heat to uniformly 6 mm, d. H. they have been reduced by 50 to 60%.
- the required in claim 3 minimum reduction can be secured by the delivery of the rolls or the pass schedule and check compliance with the requirements by mounted in the mill stand thickness gauges.
- the hot rolling of strips is a very cost effective process, at least cheaper than a reduction in thickness by cold rolling.
- the total thickness reduction of bands is therefore advantageously split between hot and cold rolls so that by hot rolling already as thin as possible bands, e.g. ⁇ 4 mm thick, produced and only the remaining reduction by cold rolling is made. This corresponds to the examples given in US Pat. No. 3,722,073 (hot strip thickness: 3.175 mm, section 5 No. 56 and section 6 No. 24).
- the hot rolling of sheets is a relatively expensive process compared to cold rolling of strips, so that one will limit the thickness reduction by hot rolling on the maximum workable through the available cold rolling unit thickness. These were in the present case 6 mm.
- the hot rolling started at a temperature of about 1070 ° C.
- Nickel is usually rolled at temperatures of 875 ° C to 1250 ° C. This includes the temperature range mentioned in US Pat. No. 3,722,073.
- the different thickness of the starting material leads during rolling under ⁇ different sheet widths.
- the narrowest sheet determines the dimensions of the strip to be produced; wider latitudes lead to scrap metal.
- the microstructure is completely recrystallized after hot rolling (see Fig. 1).
- the mean grain diameter is 62 ⁇ .
- Grain size was determined by the line-cut method using a metallographic cut with grain boundary etch.
- the grain size determined according to ASTM E112 is 5.4.
- the average thickness of the oxide layer is about 2 ⁇ ; it was determined by means of a metallographic cut with a view from the transverse direction of the strip (see Fig. 2).
- the oxide layer is only one layer. Internal corrosion or grain boundary corrosion could not be detected.
- Fig. 3 shows hot rolled material polished to show internal corrosion.
- the pearl-like second phase which is visible in the figure, can be identified as a preparation contamination due to depth-of-field studies.
- the determined macrohardness according to Vickers is 98 HV10, the measured microhardness according to Vickers averaged 103 HV0.2.
- the sheets were after hot rolling straightened and cut in the hot rolling mill with a pair of scissors to a uniform width; The rolls were separated.
- edges must be removed by separation processes, in particular cutting, chipping, removal and disassembly, so that after an alignment of the sheets at any point a gap occurs that exceeds 2 mm, preferably 1 mm.
- a rectangular blank of the sheets is useful for scrap avoidance; but it is also possible to cut the sheets to be joined with a corresponding angle or wavy, if only the sheets before welding with clash with technical zero gap.
- the weld then becomes longer than with rectangular blank; thus the load capacity of the weld increases. But it also increases the scrap rate. The generation of a long weld was not required in the example.
- a chamfer of 30 ° was milled, whereby a line was milled exactly at an angle of 90 ° to a longitudinal edge, which served the later alignment of the sheets.
- a chamfer can also be planed or cut through a water jet cutting machine equipped with a 3D head.
- the sheets were aligned after milling with technical zero gap and welded in two layers in the TIG process with pure nickel wire.
- work has been done with inlet and outlet pieces.
- a pilot tape is welded.
- the resulting by welding tape is wound on a plate by plate.
- the high-purity and therefore relatively soft nickel can also be added by friction stir welding (FSW).
- FSW friction stir welding
- welding speeds of about 100 mm / min are achieved at a speed of the tool of about 1200 U / min and a spindle force (z-axis) of about 9 KN.
- a preheating of the material and the use of forming gas have been found to be unnecessary.
- the use of the expensive pure nickel welding wire required for TIG welding is eliminated.
- PCBN polycrystalline cubic boron nitride
- the degree of purity of the material is not impaired during welding.
- the welds produced are sufficiently strong and free of pores that they can be rolled over and the strip can be cold-rolled with a full drawstring.
- the nickel tape could be recharged without the oxide layer breaking or flaking off.
- the coil produced by welding from sheet metal had a weight of 9 t, including 4 m long pilot belts made of structural steel.
- the final gauge rolled strip must be free of inclusions. At least in these cases, it is necessary to free the strip produced by hot rolling from the oxides, which are otherwise rolled during cold rolling in the material and there lead to non-metallic inclusions, which do not join the deformation of the strip due to their hardness. In the production of films or thermoforming, the material can then tear.
- the H 2 / H 2 O ratio required for the reduction of NiO by hydrogen can be determined from the Ellingham diagram. For example, when annealing nickel at 1,160 ° C, an H2 H2O ratio of at least 10 -2 is required.
- the reduction of the surface oxide layer by annealing in hydrogen results in a sponge-like surface structure.
- the first pass is at a reduced speed of about 30 to 50 m / min. driven to level the welds. Otherwise, the material may be rolled like molten metallurgically produced nickel.
- the annealing temperature to be used depends on the grain size of the starting material, the strip thickness and the degree of cold rolling. Pure nickel can be deformed by up to approx. 97% without intermediate annealing. After a reduction by 88%, the recrystallization is sufficient for annealing temperatures of 200 ° C. for an annealing time of 2 hours.
- the starting material used according to the invention with limited values of trace elements prevents blistering during annealing even under 100% hydrogen and annealing temperatures of> 760 ° C., ie the conditions below those According to US 3,722,073 bubble formation occurs in the material.
- the described method thus increases the degrees of freedom in the selection of the annealing atmospheres and the annealing temperatures.
- US 3,722,073 attempts the desired objectives by high reduction in hot rolling (depending on temperature: 75% to 92%, preferably 96% or more) and as low (Sp 2 Z. 31) and particularly advantageous (Sp 4 Z. 63) estimated annealing temperatures of 510 to 650 ° C.
- Sp 2 Z. 31 estimated annealing temperatures of 510 to 650 ° C.
- the annealing temperature may be well below the lower limit given in US 3,722,073.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Metal Rolling (AREA)
- Pressure Welding/Diffusion-Bonding (AREA)
- Arc Welding In General (AREA)
- Heat Treatment Of Sheet Steel (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP11710667.4A EP2542359B1 (de) | 2010-03-05 | 2011-02-04 | Verfahren zur herstellung von nickelband |
RU2012130398/02A RU2561629C2 (ru) | 2010-03-05 | 2011-02-04 | Способ получения никелевой полосы |
JP2012556395A JP5850864B2 (ja) | 2010-03-05 | 2011-02-04 | ニッケル帯状物の製造法 |
KR1020127020048A KR101752022B1 (ko) | 2010-03-05 | 2011-02-04 | 니켈 스트립 제조 방법 |
CN201180011365.9A CN102917812B (zh) | 2010-03-05 | 2011-02-04 | 用于制备镍带的方法 |
US13/521,296 US9003641B2 (en) | 2010-03-05 | 2011-02-04 | Method for producing a nickel strip |
CA2791546A CA2791546C (en) | 2010-03-05 | 2011-02-04 | Method of making nickel strip |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102010010536.8A DE102010010536B4 (de) | 2010-03-05 | 2010-03-05 | Verfahren zur Herstellung von Nickelband |
DE102010010536.8 | 2010-03-05 |
Publications (2)
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WO2011107199A2 true WO2011107199A2 (de) | 2011-09-09 |
WO2011107199A3 WO2011107199A3 (de) | 2012-09-20 |
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Application Number | Title | Priority Date | Filing Date |
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PCT/EP2011/000509 WO2011107199A2 (de) | 2010-03-05 | 2011-02-04 | Verfahren zur herstellung von nickelband |
Country Status (9)
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---|---|
US (1) | US9003641B2 (de) |
EP (1) | EP2542359B1 (de) |
JP (1) | JP5850864B2 (de) |
KR (1) | KR101752022B1 (de) |
CN (1) | CN102917812B (de) |
CA (1) | CA2791546C (de) |
DE (1) | DE102010010536B4 (de) |
RU (1) | RU2561629C2 (de) |
WO (1) | WO2011107199A2 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023222359A1 (de) | 2022-05-18 | 2023-11-23 | Evonik Oxeno Gmbh & Co. Kg | Verfahren zur aufreinigung von kohlenwasserstoffströmen inklusive heterogen und homogen katalysierter reaktionen |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9114356B2 (en) * | 2012-09-20 | 2015-08-25 | Clean Air Group, Inc. | Fiberglass dielectric barrier ionization discharge device |
CN103618060A (zh) * | 2013-12-04 | 2014-03-05 | 郑真勇 | 连续镍带及其处理方法 |
JP6201192B2 (ja) * | 2014-06-17 | 2017-09-27 | 住友金属鉱山株式会社 | ニッケルの軟化処理方法及びニッケルの切断方法 |
RU2620218C2 (ru) * | 2014-12-18 | 2017-05-23 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Московский государственный университет имени М.В. Ломоносова" (МГУ) | Способ создания износостойкого приповерхностного слоя в кобальтсодержащем материале |
CN106337156B (zh) * | 2015-07-15 | 2018-10-19 | 中国钢铁股份有限公司 | 耐蚀高镍合金的制造方法 |
CN107252820B (zh) * | 2017-05-26 | 2019-03-08 | 金川集团股份有限公司 | 一种高纯镍板带材的制备方法 |
CN108246803A (zh) * | 2017-12-29 | 2018-07-06 | 江苏圣珀新材料科技有限公司 | 一种应用于镍基合金带料的轧制方法 |
RU2686705C1 (ru) * | 2018-05-18 | 2019-04-30 | Общество с ограниченной ответственностью "Лаборатория специальной металлургии" (ООО "Ласмет") | Способ производства металлопродукции из металлического кобальта |
RU2694098C1 (ru) * | 2018-08-15 | 2019-07-09 | Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" (ФГУП "ВИАМ") | Способ получения полуфабрикатов из высокопрочных никелевых сплавов |
CN112275796B (zh) * | 2020-09-03 | 2023-03-24 | 太原钢铁(集团)有限公司 | 提升镍基合金线材轧制表面质量的方法 |
CN115889454B (zh) * | 2022-05-09 | 2024-01-30 | 湖南湘投金天钛金属股份有限公司 | 一种纯镍热轧带卷及其制备方法 |
CN114888529A (zh) * | 2022-05-10 | 2022-08-12 | 安徽恒均粉末冶金科技股份有限公司 | 一种新能源动力电池极耳用镍带的制备工艺 |
CN115074650A (zh) * | 2022-08-01 | 2022-09-20 | 江苏以豪合金有限公司 | 一种高纯镍丝的制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1131037A (en) | 1913-12-26 | 1915-03-09 | Cary Mfg Co | Method of making bands from sheet metal. |
US3722073A (en) | 1971-10-01 | 1973-03-27 | Int Nickel Co | Production of products directly from nickel cathodes |
DE2905508A1 (de) | 1979-02-14 | 1980-08-21 | Hurdelbrink Montamet | Verfahren zur herstellung von nickelhalbzeugprodukten |
WO2006024526A2 (de) | 2004-09-02 | 2006-03-09 | Theodor Stuth | Verfahren zur herstellung von metallbändern |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SU286793A1 (ru) * | 1969-08-08 | 1975-08-25 | Ордена Ленина физико-технический институт им.А.Ф.Иоффе | Способ изготовлени игольчатых холодных эмиттеров |
JPS571579A (en) * | 1980-06-03 | 1982-01-06 | Kobe Steel Ltd | Welding method for pure nickel |
FR2657624B1 (fr) * | 1990-01-26 | 1992-04-24 | Saint Louis Inst | Procede pour la fabrication de plaques en metal ductile et ses applications. |
US5675209A (en) * | 1995-06-19 | 1997-10-07 | Hoskins Manufacturing Company | Electrode material for a spark plug |
JP4240367B2 (ja) * | 2003-03-14 | 2009-03-18 | 日立金属株式会社 | ニッケル材料 |
JP3741311B2 (ja) * | 2003-03-19 | 2006-02-01 | 日立金属株式会社 | リチウムイオン二次電池のリード用ニッケル材料帯の製造方法 |
CN100462194C (zh) * | 2005-07-20 | 2009-02-18 | 林榆滨 | 一种镍带制造方法 |
JP4264901B2 (ja) * | 2005-09-09 | 2009-05-20 | 日立金属株式会社 | ハンダ付け性に優れたニッケル材料帯の製造方法 |
JP5152897B2 (ja) * | 2006-11-21 | 2013-02-27 | タツタ電線株式会社 | 銅ボンディングワイヤ |
US20100215981A1 (en) * | 2009-02-20 | 2010-08-26 | Nucor Corporation | Hot rolled thin cast strip product and method for making the same |
-
2010
- 2010-03-05 DE DE102010010536.8A patent/DE102010010536B4/de active Active
-
2011
- 2011-02-04 EP EP11710667.4A patent/EP2542359B1/de active Active
- 2011-02-04 US US13/521,296 patent/US9003641B2/en active Active
- 2011-02-04 CN CN201180011365.9A patent/CN102917812B/zh active Active
- 2011-02-04 RU RU2012130398/02A patent/RU2561629C2/ru active
- 2011-02-04 WO PCT/EP2011/000509 patent/WO2011107199A2/de active Application Filing
- 2011-02-04 KR KR1020127020048A patent/KR101752022B1/ko active IP Right Grant
- 2011-02-04 CA CA2791546A patent/CA2791546C/en active Active
- 2011-02-04 JP JP2012556395A patent/JP5850864B2/ja active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1131037A (en) | 1913-12-26 | 1915-03-09 | Cary Mfg Co | Method of making bands from sheet metal. |
US3722073A (en) | 1971-10-01 | 1973-03-27 | Int Nickel Co | Production of products directly from nickel cathodes |
DE2905508A1 (de) | 1979-02-14 | 1980-08-21 | Hurdelbrink Montamet | Verfahren zur herstellung von nickelhalbzeugprodukten |
WO2006024526A2 (de) | 2004-09-02 | 2006-03-09 | Theodor Stuth | Verfahren zur herstellung von metallbändern |
DE102004042481A1 (de) | 2004-09-02 | 2006-03-23 | Stuth, Theodor, Dipl.-Kaufm. | Verfahren zur Herstellung von Metallbändern hoher Reinheit aus Kathodenblechen |
EP1784273A2 (de) | 2004-09-02 | 2007-05-16 | Theodor Stuth | Verfahren zur herstellung von metallb[ndern |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023222359A1 (de) | 2022-05-18 | 2023-11-23 | Evonik Oxeno Gmbh & Co. Kg | Verfahren zur aufreinigung von kohlenwasserstoffströmen inklusive heterogen und homogen katalysierter reaktionen |
Also Published As
Publication number | Publication date |
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US20120311859A1 (en) | 2012-12-13 |
RU2561629C2 (ru) | 2015-08-27 |
KR101752022B1 (ko) | 2017-06-28 |
CN102917812B (zh) | 2015-08-19 |
EP2542359B1 (de) | 2014-08-27 |
DE102010010536A1 (de) | 2011-09-08 |
WO2011107199A3 (de) | 2012-09-20 |
CN102917812A (zh) | 2013-02-06 |
US9003641B2 (en) | 2015-04-14 |
EP2542359A2 (de) | 2013-01-09 |
CA2791546C (en) | 2017-08-22 |
JP5850864B2 (ja) | 2016-02-03 |
CA2791546A1 (en) | 2011-09-09 |
DE102010010536B4 (de) | 2017-01-05 |
KR20130043081A (ko) | 2013-04-29 |
RU2012130398A (ru) | 2014-03-10 |
JP2013522456A (ja) | 2013-06-13 |
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