EP3592875B1 - Elements de chambres a vide en alliage d'aluminium stables a haute temperature - Google Patents

Elements de chambres a vide en alliage d'aluminium stables a haute temperature Download PDF

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EP3592875B1
EP3592875B1 EP18714563.6A EP18714563A EP3592875B1 EP 3592875 B1 EP3592875 B1 EP 3592875B1 EP 18714563 A EP18714563 A EP 18714563A EP 3592875 B1 EP3592875 B1 EP 3592875B1
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thickness
weight
temperature
plate
solution
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EP3592875C0 (fr
EP3592875A1 (fr
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Guillaume DELGRANGE
Christophe CHABRIOL
Romain-Fabrice BERNES
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Constellium Issoire SAS
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
    • C22C21/08—Alloys based on aluminium with magnesium as the next major constituent with silicon
    • 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
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C22F1/05—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys of the Al-Si-Mg type, i.e. containing silicon and magnesium in approximately equal proportions
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/02—Alloys based on aluminium with silicon as the next major constituent
    • 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
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C22F1/043—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with silicon as the next major constituent
    • 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
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C22F1/047—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with magnesium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing

Definitions

  • the invention relates to aluminum alloy products intended to be used as elements of vacuum chambers in particular for the manufacture of integrated electronic circuits based on semiconductors, flat display screens as well as photovoltaic panels and their manufacturing process.
  • Vacuum chamber elements for the manufacture of integrated electronic circuits based on semiconductors, flat display screens as well as photovoltaic panels, can typically be obtained from aluminum alloy sheets.
  • Vacuum chamber elements are elements intended for the manufacture of vacuum chamber structures and vacuum chamber internal components including vacuum chamber bodies, valve bodies, flanges, connection elements, elements sealing, passages, diffusers, electrodes. They are notably obtained by machining and surface treatment of aluminum alloy sheets.
  • aluminum alloy sheets must have certain properties.
  • the sheets must first of all have satisfactory mechanical characteristics to produce by machining parts having the desired dimensions and rigidity so as to be able to reach, without deformation, a vacuum generally of the level at least of the average vacuum (10 - 3 - 10 -5 Torr ).
  • the desired breaking strength (R m ) is generally at least 260 MPa and even more if possible.
  • sheets intended to be machined in mass must have homogeneous properties in thickness and present a low density of stored elastic energy coming from residual stresses.
  • the vacuum chamber elements are subjected to high temperatures and it is important that their resistance to deformation by creep at high temperatures is significant.
  • the level of porosity of the sheets must also be low enough to reach high vacuum if necessary (10 -6 - 10 -8 Torr).
  • the gases used in vacuum chambers are frequently very corrosive and in order to avoid the risk of pollution of silicon wafers or liquid crystal devices by particles or substances coming from the elements of vacuum chambers and/or frequent replacement of these elements, it It is important to protect the surfaces of the vacuum chamber elements.
  • Aluminum turns out to be an advantageous material from this point of view because it is possible to carry out a surface treatment generating an oxide layer resistant to reactive gases. This surface treatment includes an anodization step and the oxide layer obtained is generally called an anodic layer.
  • the term “corrosion resistance” is more particularly understood to mean the resistance of anodized aluminum to corrosive gases used in vacuum chambers and to the corresponding tests.
  • the protection provided by the anodic layer is affected by numerous factors linked in particular to the microstructure of the sheet (grain size and shape, phase precipitation, porosity) and it is always desirable to improve this parameter.
  • Corrosion resistance is notably assessed by the so-called “bubble test” which consists of measuring the duration of the appearance of hydrogen bubbles on the surface of the anodized product upon contact with a diluted hydrochloric acid solution. The durations known in the state of the art are of the order of tens of minutes to a few hours.
  • the aluminum sheets and/or the surface treatment carried out can be improved.
  • the patent US 6,713,188 (Applied Materials Inc.) describes an alloy suitable for the manufacture of chambers for manufacturing semiconductors of composition (in % by weight) Si: 0.4 - 0.8; Cu: 0.15-0.30; Fe: 0.001 - 0.20; Mn 0.001 - 0.14; Zn 0.001 - 0.15; Cr: 0.04 - 0.28; Ti 0.001 - 0.06; Mg: 0.8 - 1.2.
  • the parts are obtained by extrusion or machining to the desired shape.
  • the composition allows control of the size of the impurity particles which improves the performance of the anodic layer.
  • the patent US 7,033,447 claims an alloy suitable for the manufacture of chambers for manufacturing semiconductors of composition (in % by weight) Mg: 3.5 - 4.0; Cu: 0.02 - 0.07; Mn: 0.005 - 0.015; Zn 0.08 - 0.16; Cr 0.02 - 0.07; Ti: 0 - 0.02; If ⁇ 0.03; Fe ⁇ 0.03.
  • the parts are anodized in a solution comprising 10% to 20% by weight of sulfuric acid, 0.5 to 3% by weight of oxalic acid at a temperature of 7 to 21°C.
  • the best bubble test result is 20 hours.
  • the patent US 6,686,053 claims an alloy having improved corrosion resistance, in which the anodic oxide comprises a barrier layer and a porous layer and in which at least part of the layer is altered to boehmite and/or pseudo-boehmite.
  • the best result obtained in the bubble test is around 10 hours.
  • the patent application US 2010/0018617 (Kobe Steel, Ltd.) describes an alloy of composition (in % by weight) Mg: 0.1 - 2.0; If: 0.1 - 2.0; Mn: 0.1 - 2.0; Fe, Cr, and Cu ⁇ 0.03, the alloy being homogenized at a temperature of more than 550 °C down to 600 °C or less.
  • Patent applications US 2001/019777 And JP2001 220637 (Kobe Steel ) describe an alloy for chambers comprising (in % by weight) Si: 0.1 - 2.0, Mg: 0.1 - 3.5, Cu: 0.02 - 4.0 and impurities, the Cr content being less than 0.04%.
  • These documents disclose in particular products obtained by carrying out a hot rolling step before being dissolved.
  • the patent US 6,066,392 (Kobe Steel ) describes an aluminum material having an anodic oxidation film with improved corrosion resistance, in which cracks are not generated even in high temperature thermal cycles and corrosive environments.
  • the patent US 7,005,194 (Kobe Steel ) describes an improved surface treatment process for vacuum chamber elements in which the anodized film is composed of a porous layer and a non-porous layer whose structure is at least partly boehmite or pseudo -boehmite.
  • the patent application WO2014/060660 (Constellium France) relates to a vacuum chamber element obtained by machining and surface treatment of a sheet of thickness at least equal to 10 mm in aluminum alloy of composition, in % by weight, Si: 0.4 - 0.7; Mg: 0.4 - 0.7; Ti 0.01 - ⁇ 0.15, Fe ⁇ 0.25; Cu ⁇ 0.04; Mn ⁇ 0.4; Cr 0.01 - ⁇ 0.1; Zn ⁇ 0.04; other elements ⁇ 0.05 each and ⁇ 0.15 in total, remains aluminum.
  • a first object of the invention is a vacuum chamber element obtained by machining and surface treatment of a sheet of thickness at least equal to 10 mm in aluminum alloy of composition, in % by weight, Si: 0 .4 - 0.7; Mg: 0.4 - 1.0; the ratio in % by weight Mg/Si being less than 1.8; Ti: 0.01 - 0.15, Fe 0.08 - 0.25; Cu ⁇ 0.35; Mn ⁇ 0.4; Cr: ⁇ 0.25; Zn ⁇ 0.04; other elements ⁇ 0.05 each and ⁇ 0.15 in total, remains aluminum, characterized in that the grain size of said sheet is such that the average linear intercept length l , measured in the L/TC plane measured according to the ASTM E112 standard, is at least equal to 350 ⁇ m between surface and 1 ⁇ 2 thickness.
  • the static mechanical characteristics in other words the breaking strength Rm, the conventional yield strength at 0.2% elongation Rp0.2 and the elongation at break A%, are determined by a tensile test according to standard ISO 6892-1, the sampling and direction of the test being defined by standard EN 485-1. Hardness is measured according to EN ISO 6506.
  • Grain sizes are measured according to ASTM E112.
  • the average grain sizes are measured in the L/TC plane according to the intercept method of the standard (ASTM E112-96 ⁇ 16.3).
  • the average linear intercept length is measured in the longitudinal direction l l (0°) and the transverse direction l l (90°) .
  • ⁇ L ⁇ L 90 ° max L ⁇ L 90 ° S , 1 2 EP , 1 4 EP ⁇ min L ⁇ L 90 ° S , 1 2 EP , 1 4 EP / mev L ⁇ L 90 ° S , 1 2 EP , 1 4 EP in which S: means Surface, 1 ⁇ 2 Ep means mid-thickness and 1 ⁇ 4 Ep means quarter-thickness.
  • surface grain size we mean in the context of the present invention the grain size measured after machining making it possible to remove 2 mm in the direction of the thickness.
  • the breakdown voltage is measured according to EN ISO 2376:2010.
  • vacuum chamber elements have very advantageous properties in terms of resistance to creep deformation at high temperatures, while also having advantageous properties in terms of corrosion resistance, uniformity of properties and of machinability, are obtained for a specific 6xxx series aluminum alloy whose grain size is high and homogeneous in thickness compared to products known according to the state of the art.
  • a method of manufacturing a vacuum chamber element comprising steps making it possible to obtain the grain size according to the invention has also been invented.
  • composition of the aluminum alloy sheets making it possible to obtain the vacuum chamber elements according to the invention is in % by weight, Si: 0.4 - 0.7; Mg: 0.4 - 1.0; the ratio in % by weight Mg/Si being less than 1.8; Ti: 0.01 - 0.15, Fe 0.08 - 0.25; Cu ⁇ 0.35; Mn ⁇ 0.4; Cr: ⁇ 0.25; Zn ⁇ 0.04; other elements ⁇ 0.05 each and ⁇ 0.15 in total, remains aluminum.
  • Magnesium and silicon are the major addition elements in the alloy products according to the invention. Their content has been precisely chosen so as to achieve sufficient mechanical properties, in particular a breaking strength in the TL direction of at least 260 MPa and/or an elastic limit in the TL direction of at least 200 MPa and also a homogeneous granular structure in the thickness.
  • the silicon content is between 0.4 and 0.7% by weight and preferably between 0.5% and 0.6% by weight.
  • the magnesium content is between 0.4 and 1.0% by weight.
  • the minimum magnesium content is 0.5% by weight.
  • the maximum magnesium content is 0.7% by weight and more preferably 0.6% by weight.
  • the magnesium content is 0.4 to 0.7% by weight and preferably 0.5 to 0.6% by weight.
  • the preferred contents of silicon and/or magnesium make it possible in particular to achieve, both on the surface and at mid-thickness, durations of appearance of hydrogen bubbles in the bubble test that are particularly remarkable for the products according to the invention.
  • the ratio in % by weight Mg/Si must remain less than 1.8 and preferably less than 1.5. The present inventors have in fact observed that if this ratio is too high, the resistance to creep deformation at high temperature decreases. The present inventors believe that a Mg content too high in solid solution could affect the resistance to creep deformation at high temperatures.
  • the present inventors have found that surprisingly too little iron affects the resistance to creep deformation at high temperatures.
  • the minimum iron content is 0.08% by weight and preferably 0.10% by weight. Too much iron can have a detrimental effect on the properties of the anodic oxide layer.
  • the iron content is at most 0.25% by weight and preferably at most 0.20% by weight. In an advantageous embodiment of the invention, the iron content is 0.10 to 0.20% by weight.
  • the copper content is therefore less than 0.35% by weight.
  • a high copper content can degrade the properties of the protective oxide layer and/or contaminate the products manufactured in the vacuum chambers.
  • the copper content is less than 0.05% by weight, preferably less than 0.02% by weight and preferably less than 0.01% by weight.
  • the titanium content is less than 0.15% by weight.
  • the addition of a small quantity of titanium has a favorable effect on the granular structure and its homogeneity, thus the titanium content is at least 0.01% by weight.
  • the titanium content is 0.01 to 0.1% by weight and preferably 0.01 to 0.05% by weight.
  • the titanium content is at least 0.02% by weight and preferably at least 0.03% by weight.
  • the chromium content is less than 0.25% by weight.
  • the addition of a small amount of chromium can have a favorable effect on the granular structure, so the chromium content is preferably at least 0.01% by weight.
  • the chromium content is 0.01 to 0.04% by weight and preferably 0.01 to 0.03% by weight.
  • the simultaneous addition of chromium and titanium is advantageous because it makes it possible in particular to improve the granular structure and in particular to reduce the anisotropy index of the grains.
  • the manganese content is less than 0.4% by weight, preferably less than 0.04% by weight and preferably less than 0.02% by weight.
  • the zinc content is less than 0.04% by weight, preferably less than 0.02% by weight and preferably less than 0.001% by weight.
  • the aluminum alloy sheets according to the invention have a thickness of at least 10 mm.
  • the aluminum alloy sheets according to the invention have a thickness of between 20 and 110 mm and preferably between 30 and 90 mm.
  • the aluminum alloy sheets according to the invention have a thickness of at least 50 mm and preferably at least 60 mm.
  • the sheets according to the invention have a grain size such as the average linear intercept length l , measured in the L/TC plane according to the ASTM E112 standard, is at least equal to 350 ⁇ m between surface and 1 ⁇ 2 thickness, and preferably at least equal to 400 ⁇ m between surface and 1 ⁇ 2 thickness, which contributes to obtaining resistance to high temperature creep deformation.
  • the grain size is particularly homogeneous in the thickness, and the sheet is such that the variation in the thickness of the average linear intercept length in the plane L/TC in the transverse direction, called l l (90°) according to ASTM E112, is less than 30% and preferably less than 20%.
  • the grain size variation is calculated by taking the difference between the maximum value and the minimum value at 1 ⁇ 2 thickness, 1 ⁇ 4 thickness and area and dividing by the average of the values at 1 ⁇ 2 thickness, 1 ⁇ 4 thickness and area.
  • the average linear intercept length measured in the L/TC plane according to ASTM E112 in the transverse direction l l (90°) is at least equal to 200 ⁇ m and preferably at least equal to 230 ⁇ m between surface and 1 ⁇ 2 thickness.
  • the sheets according to the invention have resistance to creep deformation at high temperatures.
  • the creep deformation under a stress of 5 MPa at 420°C is after 10 hours at most 0.40% and preferably at most 0.27%.
  • the sheets according to the invention are suitable for machining.
  • the stored elastic energy density Wt,t the measurement of which is described in Example 1, for the sheets according to the invention whose thickness is between 20 and 80 mm is advantageously less than 0.2 kJ/ m 3 .
  • Homogenization is advantageous; it is preferably carried out at a temperature between 540°C and 600°C. Preferably the homogenization time is at least 4 hours.
  • the plate When homogenization is carried out, the plate can be cooled after homogenization then reheated before hot rolling or directly rolled after homogenization without intermediate cooling.
  • Hot rolling conditions are important to obtain the desired microstructure, in particular to improve the corrosion resistance of the products.
  • the rolling plate is maintained at a temperature above 400°C throughout hot rolling.
  • the temperature of the metal is at least 450°C during hot rolling.
  • the sheets according to the invention are rolled to a thickness of at least 10 mm.
  • a solution treatment of the sheet is then carried out, optionally preceded by a cold work hardening operation, and it is quenched. Quenching can be carried out in particular by spraying or by immersion.
  • the solution is preferably carried out at a temperature between 540°C and 600°C.
  • Preferably the solution duration is at least 15 min, the duration being adapted according to the thickness of the products.
  • the sheet thus put into solution is then relieved by controlled traction with a permanent elongation of 1 to 5%.
  • the sheet thus pulled is then tempered.
  • the tempering temperature is advantageously between 150°C and 190°C.
  • the duration of income is typically between 5 hours and 30 hours.
  • a peak income is produced to achieve a maximum elastic limit and/or a T651 state.
  • an additional cold deformation of at least 3% is carried out and an annealing treatment at a temperature of at least 500 °C, the annealing treatment being able to be carried out before or after the machining or surface treatment steps. .
  • the steps of rolling and/or solution and/or additional cold deformation and annealing are adapted.
  • the rolling temperature is maintained at a temperature above 500°C and preferably above 525°C during all the rolling stages.
  • the natural logarithm of the Zener-Hollomon parameter Z defined by equation (1), ln Z is between 21 and 25 and preferably between 21.5 and 24.5 for the majority passes and preferably for all of the passes carried out during hot rolling.
  • Z ⁇ ⁇ e Q / RT
  • ⁇ is the average strain rate in the thickness expressed in s -1
  • Q is the activation energy of 156 kJ/mol
  • R is the ideal gas constant 8.31 JK -1 mol -1
  • T is the rolling temperature expressed in Kelvin.
  • the last rolling pass is advantageously such that L/H is at least 0.6 where H is the thickness at the rolling mill inlet and L is the contact length in the rolling mill.
  • the solution duration and/or temperature are modified relative to the solution duration and/or temperature necessary to dissolve the alloy elements, so as to obtain a grain enlargement.
  • the duration used is at least double and/or the temperature is at least 10°C higher than the duration and/or the solution temperature necessary to dissolve the alloy elements.
  • the solution is preceded by a cold work hardening operation by rolling or traction with a deformation of at least 4% and preferably at least 7%.
  • an additional cold deformation of at least 3% is carried out after the tempering step and an annealing treatment at a temperature of at least 500°C, and preferably at least 525°C. C, the annealing treatment can be carried out before or after the machining or surface treatment steps.
  • the four embodiments can be combined to obtain the grain size according to the invention.
  • a vacuum chamber element is obtained by machining and surface treatment of a sheet with a thickness of at least 10 mm according to the invention.
  • the surface treatment preferably comprises an anodizing treatment to obtain an anodic layer whose thickness is typically between 20 and 80 ⁇ m.
  • the surface treatment preferably comprises degreasing and/or pickling before anodizing with known products, typically alkaline products.
  • Degreasing and/or stripping may include a neutralization operation, particularly in the case of alkaline stripping, typically with an acidic product such as nitric acid, and/or at least one rinsing step.
  • Anodizing is carried out using an acid solution. It is advantageous for the surface treatment to include, after anodization, hydration (also called “sealing”) of the anodic layer thus obtained.
  • anodizing is carried out at a temperature between 10 and 30°C with a solution comprising 100 to 300 g/l of sulfuric acid and 10 to 30 g/l of acid. oxalic acid and 5 to 30 g/l of at least one polyol and advantageously the product thus anodized is hydrated in deionized water at a temperature of at least 98°C preferably for a period of at least approximately 1 hour.
  • the aqueous solution used for the anodization of this advantageous surface treatment does not contain titanium salt.
  • the presence of at least one polyol in the anodizing solution also contributes to improving the corrosion resistance of the anodic layers.
  • Ethylene glycol, propylene glycol or preferably glycerol are advantageous polyols.
  • Anodizing is preferably carried out with a current density of between 1 and 5 A/dm 2 .
  • the anodizing duration is determined so as to achieve the desired anodic layer thickness.
  • a hydration step (also called sealing) of the anodic layer.
  • the hydration is carried out in deionized water at a temperature of at least 98°C, preferably for a period of at least approximately 1 hour.
  • the present inventors have observed that it is particularly advantageous to carry out the hydration subsequent to anodization in two stages in deionized water, a first stage lasting at least 10 min at a temperature of 20 to 70°C and a second stage lasting at least approximately 1 hour at a temperature of at least 98°C.
  • an anti-powder additive derived from triazine such as Anodal-SH1 ® is added to the deionized water used for the second stage of hydration.
  • the vacuum chamber elements treated with the advantageous surface treatment process and obtained from sheets whose thickness is between 20 and 80 mm easily reach at mid-thickness a duration of appearance of hydrogen bubbles in a 5% hydrochloric acid solution (“bubble test”) for at least around 400 min and preferably at least 750 min and even at least around 900 min, at least for the part corresponding to the surface of prison.
  • the vacuum chamber elements obtained from an alloy sheet according to the invention whose thickness is between 60 and 80 mm and with the advantageous surface treatment process can achieve a duration on the surface of the sheet appearance of hydrogen bubbles in a 5% hydrochloric acid solution for at least 500 min and preferably at least 900 min at mid-thickness.
  • the preferred products according to the invention whose Mg content is between 0.4 and 0.7% by weight, the Si content is between 0.4 and 0.7% by weight and the Cu content is lower at 0.05% by weight reach at mid-thickness a duration of appearance of hydrogen bubbles in a 5% hydrochloric acid solution (“bubble test”) of at least at least 750 min and a creep deformation under a stress of 5 MPa at 420 °C is after 10 hours at most 0.27%.
  • vacuum chamber elements according to the invention in vacuum chambers is particularly advantageous because their properties are very homogeneous and moreover, particularly for the anodized elements with the advantageous surface treatment process, the corrosion resistance is high, which makes it possible to avoid pollution of products manufactured in the rooms such as, for example, microprocessors or panels for flat screens.
  • Table 1 composition of alloys (% by weight) Alloy If Fe Cu Mn Mg Cr Ti Mg/Si A (Invention) 0.6 0.23 0.30 0.12 1.0 0.20 0.06 1.7 B (Reference) 0.6 0.23 0.29 0.12 1.2 0.20 0.07 2.0 C (Reference) 0.4 0.24 0.29 0.12 1.0 0.19 0.06 2.5 D (Reference) 0.6 0.07 0.29 0.12 1.0 0.20 0.06 1.7 E (Reference) 0.6 0.06 0.29 ⁇ 0.01 1.0 0.30 0.06 1.7
  • the plates were homogenized at a temperature of 560°C for 2 hours, hot rolled to a thickness of 16 mm at a temperature of at least 400°C.
  • the sheets thus obtained were put in solution for 2 hours at a temperature of 575 ° C (A, D, E), 545°C (C) or 570°C (B) adapted to their composition, quenched and tensile.
  • the sheets obtained underwent an appropriate tempering to reach a T651 state.
  • the duration and temperature of the solution were intended to obtain a grain size such as the average linear intercept length in the L/TC plane measured according to the ASTM standard.
  • E112, named l or at least equal to 350 ⁇ m between surface and 1 ⁇ 2 thickness.
  • the micrograph obtained for sheet A, representative of all the sheets, is presented on the Figure 1 .
  • Sheet A has undergone machining and surface treatment.
  • the product is degreased, pickled using an alkaline solution, then neutralized with a nitric acid solution before undergoing anodizing at a temperature of approximately 20°C in a sulpho-oxalic bath (sulfuric acid 160 g/l + oxalic acid 20g/l + 15 g/l glycerol).
  • a hydration treatment of the anodic layer is carried out in two stages: 20 min at 50 °C in deionized water then approximately 80 min in boiling deionized water in the presence of a derived anti-powder additive. of triazine Anodal-SH1 ® .
  • the anodic layer obtained had a thickness of approximately 50 ⁇ m.
  • the anodic layer obtained was characterized by the following tests.
  • the breakdown voltage characterizes the voltage at which a first electric current passes through the anodic layer.
  • the measurement method is described in standard EN ISO 2376:2010. The value obtained was 2.6 kV.
  • the “bubble test” is a corrosion test which makes it possible to characterize the quality of the anodic layer by measuring the duration of appearance of the first bubbles in a hydrochloric acid solution.
  • a flat surface of 20 mm in diameter of the sample is brought into contact at room temperature with a 5% solution by mass of HCl.
  • the characteristic duration is the duration from which a continuous flow of gas bubbles originating from at least one discrete point on the surface of the anodized aluminum is visible. The result obtained was 450 minutes.
  • alloy sheets of composition as indicated in Table 3 and of thickness 280 mm were prepared by homogenization and hot rolling at a temperature above 400 ° C.
  • Table 3 - alloy composition (% by weight) Alloy If Fe Cu Mn Mg Cr Ti Mg/Si F 0.56 0.13 0.011 0.016 0.54 0.021 0.018 1
  • the plates were homogenized at a temperature of 595°C for 12 hours.
  • Plate G was hot rolled to a thickness of 64 mm at a temperature of at least 530 °C and maintaining the Zener - Hollomon parameter for each rolling pass such that ln Z is between 22 and 24 ,5.
  • the H plate was hot rolled to a thickness of 64 mm at a temperature of between 480 and 500 °C, the Zener - Hollomon parameter being such that ln Z was greater than 26 for the majority of passes rolling.
  • the sheets thus obtained were put in solution for 4 hours at a temperature of 535 °C and tensile by 3%.
  • product G according to the invention has a larger grain size than product H and is also more homogeneous in thickness.
  • This method mainly applies to plates whose length and width are significantly greater than the thickness and for which the residual stress state can reasonably be considered to be biaxial with its two main components in the directions L and T ( ie no residual stress in the S direction) and such that the level of residual stresses varies only in the S direction.
  • This method is based on measuring the deformation of two full-thickness rectangular bars which are cut from the plate along directions L and TL. These bars are machined downward in the S direction step by step, and at each step the deflection is measured, as well as the thickness of the machined bar.
  • the width of the bar was 30 mm.
  • the bar must be long enough to avoid any edge effect on the measurements.
  • a length of 400 mm was used.
  • Measurements are taken after each machining pass.
  • the bar is removed from the vice, and a stabilization time is observed before the deformation measurement is carried out, so as to obtain a uniform temperature in the bar after machining.
  • the thickness h(i) of each bar and the deflection f(i) of each bar are collected.
  • the stress profile in the thickness for the direction L is given in the figure 5 .
  • the total measured energy W tot was 0.18 kJ/m 3 for sample G and 0.17 kJ/m 3 for sample H.
  • the products have undergone machining and surface treatment.
  • the product is degreased, pickled using an alkaline solution, then neutralized with a nitric acid solution before undergoing anodizing at a temperature of approximately 20°C in a sulpho-oxalic bath (sulfuric acid 160 g/l + oxalic acid 20g/l + 15 g/l glycerol).
  • a hydration treatment of the anodic layer is carried out in two stages: 20 min at 50 °C in deionized water then approximately 80 min in boiling deionized water in the presence of a derived anti-powder additive. of triazine Anodal-SH1 ® .
  • the anodic layer obtained had a thickness of approximately 50 ⁇ m.
  • the anodic layers were characterized by the following tests.
  • the breakdown voltage characterizes the voltage at which a first electric current passes through the anodic layer.
  • the measurement method is described in standard EN ISO 2376:2010. The values are indicated in absolute value after direct current (DC) measurement.
  • the “bubble test” is a corrosion test which makes it possible to characterize the quality of the anodic layer by measuring the duration of appearance of the first bubbles in a hydrochloric acid solution.
  • a flat surface of 20 mm in diameter of the sample is brought into contact at room temperature with a 5% solution by mass of HCl.
  • the characteristic duration is the duration from which a continuous flow of gas bubbles originating from at least one discrete point on the surface of the anodized aluminum is visible.
  • the product according to the invention has excellent properties after surface treatment.

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  • Crystallography & Structural Chemistry (AREA)
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  • Laminated Bodies (AREA)
  • Physical Vapour Deposition (AREA)
  • Powder Metallurgy (AREA)
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EP18714563.6A 2017-03-10 2018-03-01 Elements de chambres a vide en alliage d'aluminium stables a haute temperature Active EP3592875B1 (fr)

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FR1751981A FR3063740B1 (fr) 2017-03-10 2017-03-10 Elements de chambres a vide en alliage d’aluminium stables a haute temperature
PCT/FR2018/050481 WO2018162823A1 (fr) 2017-03-10 2018-03-01 Elements de chambres a vide en alliage d'aluminium stables a haute temperature

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US11203801B2 (en) 2019-03-13 2021-12-21 Novelis Inc. Age-hardenable and highly formable aluminum alloys and methods of making the same
CN110129633B (zh) * 2019-05-23 2020-06-05 江苏亨通电力特种导线有限公司 家具用铝合金铆钉线及其制备方法
FR3101641B1 (fr) 2019-10-04 2022-01-21 Constellium Issoire Tôles de précision en alliage d’aluminium
CN111041294B9 (zh) * 2019-12-31 2021-03-12 辽宁忠旺集团有限公司 具有高长期热稳定性的6系低合金成分及其制备方法
PT3922743T (pt) * 2020-06-10 2024-08-22 Novelis Koblenz Gmbh Método de fabrico de uma chapa de liga de alumínio para elementos da câmara de vácuo
CN113234972A (zh) * 2021-04-30 2021-08-10 广东坚美铝型材厂（集团）有限公司 一种铝合金建筑模板及其制备方法
CN113684400A (zh) * 2021-08-22 2021-11-23 山东华建铝业科技有限公司 一种高性能光伏铝合金边框及其生产工艺
FR3136242B1 (fr) 2022-06-01 2024-05-03 Constellium Valais Tôles pour éléments de chambres à vide en alliage d’aluminium

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EP0792951B1 (en) 1994-11-16 2001-09-26 Kabushiki Kaisha Kobe Seiko Sho Vacuum chamber made of aluminum or its alloys
JPH11140690A (ja) 1997-11-14 1999-05-25 Kobe Steel Ltd 耐熱割れ性および耐食性に優れたＡｌ材料
JP3997009B2 (ja) * 1998-10-07 2007-10-24 株式会社神戸製鋼所 高速動部品用アルミニウム合金鍛造材
JP3919996B2 (ja) 2000-02-04 2007-05-30 株式会社神戸製鋼所 プラズマ処理装置用アルミニウム合金、プラズマ処理装置用アルミニウム合金部材およびプラズマ処理装置
US6521046B2 (en) 2000-02-04 2003-02-18 Kabushiki Kaisha Kobe Seiko Sho Chamber material made of Al alloy and heater block
JP2003034894A (ja) 2001-07-25 2003-02-07 Kobe Steel Ltd 耐腐食性に優れたＡｌ合金部材
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JP2004225113A (ja) 2003-01-23 2004-08-12 Kobe Steel Ltd 耐腐食性及び耐プラズマ性に優れたＡｌ合金部材
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JP5064935B2 (ja) 2007-08-22 2012-10-31 株式会社神戸製鋼所 耐久性と低汚染性を兼備した陽極酸化処理アルミニウム合金
FR2955336B1 (fr) 2010-01-20 2013-02-15 Alcan Rhenalu Procede de fabrication de produits en alliage 6xxx pour chambre a vide
FR2996857B1 (fr) * 2012-10-17 2015-02-27 Constellium France Elements de chambres a vide en alliage d'aluminium

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FR3063740B1 (fr) 2019-03-15
SG11201907957YA (en) 2019-11-28
CN110402296B (zh) 2021-04-20
EP3592875C0 (fr) 2024-05-01
US11248280B2 (en) 2022-02-15
TW201840864A (zh) 2018-11-16
WO2018162823A1 (fr) 2018-09-13
JP2020510761A (ja) 2020-04-09
US20210130933A1 (en) 2021-05-06
KR102584052B1 (ko) 2023-09-27
EP3592875A1 (fr) 2020-01-15
CN110402296A (zh) 2019-11-01
KR20190126851A (ko) 2019-11-12

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