WO2011030869A1 - マグネシウム-リチウム合金、圧延材、成型品、およびその製造方法 - Google Patents
マグネシウム-リチウム合金、圧延材、成型品、およびその製造方法 Download PDFInfo
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- WO2011030869A1 WO2011030869A1 PCT/JP2010/065655 JP2010065655W WO2011030869A1 WO 2011030869 A1 WO2011030869 A1 WO 2011030869A1 JP 2010065655 W JP2010065655 W JP 2010065655W WO 2011030869 A1 WO2011030869 A1 WO 2011030869A1
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- 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
- C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/12—Light metals
Definitions
- the present invention relates to a magnesium-lithium alloy, a rolled material, and a molded product that have excellent corrosion resistance and cold workability and have a low surface electric resistance value.
- a rolled material of AZ31 Al 3 mass%, Zn 1 mass%, remaining Mg
- the magnesium-lithium alloy containing lithium has a magnesium crystal structure of hcp structure ( ⁇ phase), but when the lithium content is 6 to 10.5% by mass, the hcp structure and bcc structure ( ⁇ phase) When the lithium content is 10.5% by mass or more, a ⁇ -phase single phase is obtained.
- the ⁇ phase slip system is limited, but the ⁇ phase has many slip systems, so the lithium content is increased and the ⁇ phase and ⁇ phase mixed phase, the ⁇ phase single phase and As it becomes, the workability in the cold improves.
- lithium is an electrochemically base element, the corrosion resistance decreases significantly as the lithium content increases.
- alloys with high Li content such as LA141 (Li 14 mass%, Al 1 mass%, balance Mg) have been developed. However, this alloy does not have sufficient corrosion resistance and its use is limited.
- Patent Document 1 discloses that a magnesium-lithium alloy containing 10.5% by mass or less of lithium and having an iron impurity concentration of 50 ppm or less has excellent corrosion resistance.
- Patent Document 2 discloses that a magnesium-lithium alloy containing 6 to 10.5% by mass of lithium and 4 to 9% by mass of zinc is excellent in strength and corrosion resistance at room temperature.
- Patent Document 3 discloses a cold-pressable magnesium-lithium alloy containing 6 to 16% by mass of lithium.
- Patent Document 4 describes that a magnesium-lithium alloy containing 10.5 to 40% by mass of lithium and having an average crystal grain size of 3 to 30 ⁇ m is excellent in strength and press workability.
- Non-Patent Document 1 describes the effects on mechanical properties, corrosion resistance, etc. due to processing and heat treatment when Al, Zn, Cu, and Ag are added to a magnesium-lithium alloy of 8% by mass and 13% by mass of lithium. Yes.
- Patent Document 4 describes a magnesium-lithium alloy having excellent strength and press workability. In the example, the tensile strength of Li containing 10.5% by mass or more is at most 131 MPa. is there.
- Patent Document 4 as a method for producing a magnesium-lithium alloy excellent in strength and press workability, an ingot of a magnesium-lithium alloy raw material is hot-rolled, followed by cold-rolling, A method for recrystallizing a magnesium-lithium alloy by heat treatment at 140-150 ° C. is described.
- the magnesium-lithium alloy as described above is considered to be used as a member constituting the housing of various electric devices such as mobile phones, notebook computers, video cameras, and digital cameras, which are expected to be lighter. ing.
- various electric devices such as mobile phones, notebook computers, video cameras, and digital cameras, which are expected to be lighter.
- it is necessary to ensure a sufficient electromagnetic shielding property or to ground the substrate, and the surface electrical resistance value of the member is required to be low.
- a magnesium-lithium alloy having a low C content has been demanded.
- JP 2000-282165 A Japanese Patent Laid-Open No. 2001-40445 Japanese Patent Laid-Open No. 9-41066 JP 11-279675 A
- An object of the present invention is to achieve a very lightweight magnesium-lithium alloy, rolled material, which has a high level of both corrosion resistance and cold workability, has a certain level of tensile strength, and has a low surface electrical resistance value.
- the object is to provide a molded product and a manufacturing method thereof.
- the magnesium-lithium alloy of the present invention (hereinafter sometimes referred to as Mg-Li alloy) has a Li content of 10.5 mass% or more and 16.0 mass% or less, and Al content of 0.50. 2% by mass or more and 1.50% by mass or less, Mg is contained in the balance, the average crystal grain size is 5 ⁇ m or more and 40 ⁇ m or less, the tensile strength is 150 MPa or more, and the pin shape is 2 mm.
- the surface electric resistance value of the ammeter when a probe having a probe (contact surface area of 3.14 mm 2 ) is pressed against the surface with a load of 240 g is 1 ⁇ or less.
- the Mg—Li alloy of the present invention for solving the above-mentioned problems contains Li of 10.5% by mass or more and 16.0% by mass or less, and Al by 0.50% by mass or more and 1.50% by mass or less.
- a cylindrical two-probe having an average crystal grain size of 5 ⁇ m or more and 40 ⁇ m or less, a Vickers hardness (HV) of 50 or more, 10 mm between pins, and a pin tip diameter of 2 mm (contact surface area of one needle)
- HV Vickers hardness
- the surface electric resistance value of the ammeter when the 3.14 mm 2 ) probe is pressed against the surface with a load of 240 g is 1 ⁇ or less.
- the manufacturing method of the Mg—Li alloy of the present invention for solving the above-mentioned problems is that Li is 10.5% by mass or more and 16.0% by mass or less, Al is 0.50% by mass or more and 1.50% by mass.
- the Mg—Li alloy of the present invention for solving the above problems is a rolled material or a molded product.
- Li is 10.5% by mass or more and 16.0% by mass or less, preferably 13.0% by mass or more and 15.0% by mass or less, Al is 0.50% by mass or more, 1.50 mass% or less is contained, and Mg is contained in the remainder.
- the crystal structure is a ⁇ -phase single phase, which is lightweight and excellent in cold workability.
- the Mg—Li alloy of the present invention further improves corrosion resistance by containing Ca in a range of 0.10% by mass to 0.50% by mass.
- Ca is contained, a compound of Mg and Ca is formed, which becomes a starting point for nucleation during recrystallization, and forms a recrystallized texture having fine crystal grains.
- Corrosion of the Mg—Li alloy proceeds selectively within the crystal grains, and the grain boundaries can prevent the progress of corrosion, and the formation of such grain boundaries can improve the corrosion resistance.
- the Mg—Li alloy of the present invention has at least one selected from Zn, Mn, Si, Zr, Ti, B, Y, a rare earth metal element having an atomic number of 57 to 71, in addition to Al and Ca described above. It can be contained in a range that does not significantly affect the corrosion resistance and cold workability. For example, when Zn is contained, the cold workability is further improved. When Mn is contained, the corrosion resistance is further improved. When Si is contained, the viscosity of the molten alloy at the time of manufacture can be lowered. Inclusion of Zr increases the strength. When Ti is contained, flame retardancy is improved.
- the strength at a high temperature is increased, but when it is contained in an amount of 1% by mass or more, the strength and the workability in the cold state are reduced.
- the rare earth metal element is contained, the elongation rate is improved and the cold workability is further improved.
- the content of these optional components is preferably 0% by mass or more and 5.00% by mass or less. If the content is large, the specific gravity increases and the characteristics of the ⁇ -phase single-phase Mg—Li alloy are impaired. Therefore, the content is preferably as small as possible.
- the Mg—Li alloy of the present invention may contain impurities such as Fe, Ni, and Cu.
- impurities such as Fe, Ni, and Cu.
- Fe is 0.005 mass% or less
- Ni is 0.005 mass% or less
- Cu is 0.005 mass% or less.
- the average crystal grain size of the Mg—Li alloy of the present invention is 5 ⁇ m or more and 40 ⁇ m or less, and the average crystal grain size is preferably 5 ⁇ m or more and 20 ⁇ m or less from the viewpoint of excellent corrosion resistance.
- the average crystal grain size is 5 ⁇ m or more, it is industrially easy to obtain the Mg—Li alloy of the present invention having a tensile strength of 150 MPa or more, or a Vickers hardness of 50 or more, and the corrosion resistance is 40 ⁇ m or less, particularly 20 ⁇ m or less. Excellent.
- the average crystal grain size can be measured by a line segment method using an observation image of an alloy cross-sectional structure with an optical microscope. Observation with an optical microscope is performed at 200 times using a sample etched with 5% ethanol nitrate. In the obtained observation image, five line segments corresponding to 600 ⁇ m that divide the image into six equal parts are drawn, and the number of grain boundaries crossing the line segments is measured. A value obtained by dividing the length of the line segment by 600 ⁇ m by the number of measured grain boundaries is calculated for each line segment, and the average value is defined as the average crystal grain size.
- the Mg—Li alloy of the present invention has a tensile strength of 150 MPa or more, or a Vickers hardness of 50 or more. These upper limits are not particularly limited, but in order not to deteriorate cold workability, the tensile strength is usually 220 MPa or less, preferably 180 MPa or less, and the Vickers hardness is usually 80 or less, preferably 70 or less.
- the tensile strength is determined by cutting out three JIS No. 5 test pieces each having a thickness of 1 mm in three directions of 0 °, 45 °, and 90 ° from arbitrarily determined directions of the plate material made of the Mg—Li alloy of the present invention.
- the tensile strength of the obtained test piece can be measured at 25 ° C. at a tensile speed of 10 mm / min. And each average value of 0 degree, 45 degrees, and 90 degrees directions is calculated, and those maximum values are made into tensile strength.
- the Vickers hardness is measured according to JIS Z 2244, arbitrarily measured at 10 points with a load of 100 g weight at 25 ° C., and the average value is taken.
- the present inventors have heretofore reported the average crystal grain size and the tensile strength or Vickers hardness of a ⁇ -phase single-phase Mg—Li alloy containing the above-mentioned amounts of Li and Al, such as LA141, which has been reported to have low corrosion resistance. Was found to significantly improve the corrosion resistance while maintaining good cold workability of the resulting alloy.
- the corrosion resistance of the Mg—Li alloy of the present invention exceeds the corrosion resistance of AZ31 not containing lithium, which is one of the causes of corrosion, which is currently industrialized as a plate material.
- the ⁇ -phase single-phase Mg—Li alloy containing Li and Al has been reported for many years, it has hardly been put into practical use due to low corrosion resistance.
- the -Li alloy has industrial utility.
- the above-described AZ31 that is put into practical use requires warm pressing at about 250 ° C., but the Mg—Li alloy of the present invention is excellent in cold workability and is equal to or higher than AZ31. Since it has corrosion resistance, it can be expected to be used in a wide range of fields.
- the mechanical strength of the ⁇ -phase single-phase Mg—Li alloy containing Al is not uniquely determined if its composition and average crystal grain size are determined.
- a cast slab is subjected to plastic strain by being performed at a specific reduction rate or higher, and then annealed in a specific temperature range to give a recrystallized texture.
- the average crystal grain size is 40 ⁇ m or less, high tensile strength and / or Vickers hardness that are not conventionally provided are imparted.
- Patent Document 4 the method was described in the above-mentioned Patent Document 4 in which the composition and the average crystal grain size were similar to those of the Mg—Li alloy of the present invention, which was similarly manufactured by hot rolling, cold rolling and heat treatment.
- the alloy of Example 6 has a low tensile strength of 127 MPa, and is very inferior in corrosion resistance and poor in practicality as described in Comparative Example 1 described later.
- the inventors of the present invention have provided a ⁇ -phase single-phase Mg-Li alloy containing Al, which has given a reduction ratio of a certain degree or more in cold plastic working such as cold rolling, in which the physical properties have been lowered in the annealing process. Then, by recrystallizing in a specific range at a high temperature that has been recognized, an average particle size not conventionally achieved in this composition is 5 ⁇ m or more, 40 ⁇ m or less, and a tensile strength of 150 MPa or more or a Vickers hardness of 50 or more. It has been found that the alloys shown can be obtained, and that such alloys can achieve high levels of corrosion resistance and cold workability, which are industrially practical.
- the Mg—Li alloy of the present invention is an ammeter when a probe having a cylindrical two-probe (pin contact surface area 3.14 mm 2 ) having a pin interval of 10 mm and a pin tip diameter of 2 mm is pressed against the surface with a load of 240 g.
- the surface electrical resistance value is 1 ⁇ or less.
- the surface electric resistance value of the ammeter when this probe is pressed with a load of 60 g can be 10 ⁇ or less, and 1 ⁇ or less when adjusted to preferable conditions.
- the load of 240g assumes the fixing force when grounding to the Mg-Li alloy by screw fixing, and the load of 60g assumes the fixing force when grounding to the surface of the Mg-Li alloy by tape fixing. is doing. Therefore, the Mg—Li alloy of the present invention can be suitably used as an electronic equipment casing component that needs to be grounded from the substrate.
- the method for producing the Mg—Li alloy of the present invention is not particularly limited as long as the Mg—Li alloy of the present invention having the above composition and physical properties can be obtained.
- the production method of the present invention shown below is mentioned.
- the production method of the present invention is an alloy raw material melt containing 10.5% by mass or more and 16.0% by mass or less of Li, 0.50% by mass or more and 1.50% by mass or less of Al, and Mg in the balance.
- the obtained alloy ingot is plastically processed cold so that the reduction ratio is 30% or more, and the plastically processed alloy is 170-250
- a step (d) of treating with a low electrical resistance treatment solution is performed.
- a step (e) of immersing in a film chemical conversion treatment liquid containing a fluorine compound and performing a film chemical conversion treatment may be included.
- step (a) for example, first, a raw material in which a metal and a master alloy containing Mg, Li, Al, and optionally the above-mentioned optional element elements such as Ca are mixed to have the above-described composition is prepared. Subsequently, the raw material can be heated and melted to obtain an alloy raw material melt, which is cast into a mold and cooled and solidified. A method of cooling and solidifying the alloy raw material melt by a continuous casting method such as a strip casting method is also preferably performed.
- the thickness of the alloy ingot (slab) obtained by the step (a) can usually be about 10 to 300 mm.
- the production method of the present invention includes a step (b) of plastically processing the alloy ingot obtained in the step (a) in a cold manner so that the reduction ratio is 30% or more.
- the plastic working can be performed by a known method such as rolling, forging, extrusion, drawing, etc., and strain is given to the alloy by this plastic working.
- the temperature at that time is usually about room temperature to 150 ° C. It is preferable to carry out at room temperature or as low a temperature as possible in order to impart a large strain.
- the rolling reduction in plastic working is preferably 40% or more, more preferably 45% or more, and most preferably 90% or more, and the upper limit is not particularly limited.
- the rolling reduction is less than 30%, in the next step (c), if annealing is performed so that the tensile strength is 150 MPa or more, or the Vickers hardness is 50 or more, the average crystal of recrystallized particles as conventionally recognized The particle size becomes large and the desired effect cannot be obtained.
- the production method of the present invention includes a step (c) of annealing a cold-formed alloy at 170 to less than 250 ° C. for 10 minutes to 12 hours, or 250 to 300 ° C. for 10 seconds to 30 minutes.
- Step (c) is a step of recrystallizing the alloy to which a strain of a certain level or more is applied in step (b).
- the annealing can be performed preferably at 190 to 240 ° C. for 30 minutes to 4 hours, or at 250 to 300 ° C. for 30 seconds to 10 minutes.
- the annealing conditions are out of the range of 170-250 ° C. for 10 minutes to 12 hours, or 250-300 ° C. for 10 seconds to 30 minutes, the corrosion resistance and cold workability deteriorate, and the intended practical use A highly functional Mg—Li alloy cannot be obtained.
- the production method of the present invention can include a step (a1) of subjecting the alloy ingot obtained in the step (a) to a homogeneous heat treatment before the step (b).
- the heat treatment in the step (a1) can usually be performed at 200 to 300 ° C. for 1 to 24 hours.
- the production method of the present invention can include a step (a2) of hot rolling the alloy ingot obtained in the step (a) or the step (a1) before the step (b).
- the hot rolling in step (a2) can usually be performed at 200 to 400 ° C.
- this Mg—Li alloy is subjected to a degreasing process, a water washing process, etc., as necessary, to remove a surface oxide layer or a segregation layer, as is also performed in a normal chemical conversion treatment.
- the degreasing step can be performed by a method such as immersing in a highly alkaline solution such as sodium hydroxide.
- a highly alkaline solution such as sodium hydroxide.
- sodium hydroxide When sodium hydroxide is used, it is preferably prepared as a highly alkaline solution having a concentration of 1 to 20% by mass.
- the immersion time in the highly alkaline solution is preferably 1 to 10 minutes. If the concentration of the sodium hydroxide aqueous solution is less than 1% by mass or the immersion time is less than 1 minute, poor appearance may occur due to insufficient degreasing. Moreover, when a sodium hydroxide aqueous solution having a concentration higher than 20% by mass is used, white powder due to residual alkali may be generated.
- FAL free alkalinity
- step (d) one or two or more mixed acids selected from inorganic acids (phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, etc.) and two metal ions (aluminum and zinc) are used. It is carried out by immersing the Mg—Li alloy in a low electrical resistance treatment solution comprising an aqueous solution to which is added. By immersing with this low electrical resistance treatment solution, an Mg—Li alloy having a low surface electrical resistance value, which has not been obtained conventionally, can be obtained. The surface electrical resistance value cannot be lowered only by adding one kind of metal of aluminum and zinc alone, and an effect can be obtained only by adding both elements.
- inorganic acids phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, etc.
- two metal ions aluminum and zinc
- the supply source of aluminum is supplied by a water-soluble aluminum salt such as aluminum nitrate, aluminum sulfate, or primary aluminum phosphate.
- the aluminum content in the treatment liquid is preferably 0.021 to 0.47 g / l, more preferably 0.085 to 0.34 g / l. By setting it as 0.021 g / l or more and 0.47 g / l or less, it becomes easy to make a surface electrical resistance value low.
- the zinc content in the treatment liquid is preferably 0.0004 to 0.029 g / l, more preferably 0.0012 to 0.013 g / l. If it is 0.0004 g / l or more, the surface electrical resistance value can be easily lowered, and if it is 0.029 g / l or less, the surface electrical resistance value can be easily lowered, and the corrosion resistance of the film is also improved. .
- the inorganic acid concentration is adjusted so that the free acidity (FA) is in the range of 9.0 to 12.0 points. If it is less than 9.0 points, care must be taken not to cause insufficient processing, poor appearance, increase in surface electrical resistance, decrease in coating adhesion, etc. If it exceeds 12.0 points, excessive treatment is required. Care must be taken not to cause rough skin, poor dimensionality, or poor corrosion resistance due to coating.
- FA free acidity
- the immersion with the low electrical resistance treatment liquid in the step (d) is preferably performed at a temperature of 35 to 70 ° C., preferably 55 to 65 ° C. If it is lower than 35 ° C, it is necessary to be careful not to cause insufficient processing, poor appearance, increase in surface electrical resistance value, decrease in coating film adhesion, etc. If it exceeds 70 ° C, rough skin due to excessive processing, poor dimensionality. Care must be taken not to cause a decrease in the corrosion resistance of the film.
- the immersion time is 0.5 to 2 minutes, more preferably 1 minute. If it is less than 0.5 minutes, care must be taken not to cause insufficient treatment, increase in surface electrical resistance, or decrease in coating adhesion, and if it exceeds 2 minutes, care should be taken not to reduce film corrosion resistance. There is a need to.
- the surface adjustment treatment is performed with an alkaline aqueous solution.
- the surface conditioning treatment with this alkaline aqueous solution can be performed by a method such as immersing in a highly alkaline solution such as sodium hydroxide as in the degreasing step.
- sodium hydroxide it is preferably prepared as a highly alkaline solution having a concentration of 5 to 30% by mass.
- the immersion time in the highly alkaline solution is preferably 0.5 to 10 minutes.
- the immersion temperature is 45 to 70 ° C.
- the concentration of the aqueous sodium hydroxide is less than 5% by mass, the immersion time is less than 0.5 minutes, or the temperature is less than 45 ° C., smut will not remain or the corrosion resistance of the film will not deteriorate. You need to be careful.
- concentration higher than 30 mass% it is necessary to be careful so that the white powder resulting from an alkali residue may not generate
- FAL free alkalinity
- step (e) of performing a film chemical conversion treatment with a film chemical conversion treatment solution containing fluoride is performed. This step (e) enhances the corrosion resistance.
- the step (e) of film conversion treatment is obtained by immersing in a treatment liquid containing fluorine.
- Fluorine in this film chemical conversion treatment liquid includes hydrofluoric acid, sodium fluoride, hydrofluoric acid, acidic sodium fluoride, acidic potassium fluoride, acidic ammonium fluoride, hydrofluoric acid and its salt, and borofluoride. It is preferably supplied from at least one selected from acids and salts thereof. This is because these compounds can be obtained as a material in which fluorine is sufficiently dissolved in an active state.
- the fluorine content in the film chemical conversion treatment liquid is preferably in the range of 3.33 to 40 g / l. More preferably, it is 8.0 to 30.0 g / l.
- the fluorine content is less than 3.33 g / l, care must be taken not to cause insufficient film adhesion or decrease in film corrosion resistance.
- the fluorine content exceeds 40 g / l, the surface electrical resistance value Care must be taken not to cause a rise or a decrease in coating film adhesion.
- the acid concentration in the film chemical conversion treatment solution is adjusted so that the free acidity (FA) is in the range of 8.0 to 12.0 points. If it is less than 8.0 points, care must be taken not to cause insufficient film adhesion or decrease in film corrosion resistance. If it exceeds 12.0 points, the surface electrical resistance value will increase, and the film adhesion will Care must be taken not to cause a decrease.
- FA free acidity
- the film chemical conversion treatment with the film chemical conversion treatment liquid can be performed by a general method that allows the treatment liquid to contact the surface of the Mg—Li alloy for a certain period of time, such as immersing the Mg—Li alloy in the film chemical conversion treatment liquid. it can.
- the film chemical conversion treatment liquid is preferably carried out at a temperature of 40 to 80 ° C., preferably about 55 to 65 ° C. This is because the chemical reaction between magnesium and lithium and fluorine can be performed quickly and satisfactorily.
- the immersion time is preferably 0.5 to 5 minutes, more preferably about 1.5 to 4.5 minutes. This is because magnesium fluoride and lithium fluoride are generated on the surface of the Mg—Li alloy and the combined action is sufficiently exhibited. If the immersion time is less than 0.5 minutes, it is necessary to be careful not to cause insufficient film adhesion, decrease in film corrosion resistance, etc. If it exceeds 5 minutes, the surface electrical resistance value will increase due to excessive treatment, Care must be taken not to cause a decrease in coating adhesion.
- the step (e) is preferably performed after the degreasing treatment, the step (d), and the surface conditioning treatment.
- a degreasing process, a process (d), a surface adjustment process, and a process (e) are each performed separately, and a water washing process is performed between each process.
- the Mg—Li alloy obtained by the method of the present invention can be kept in good corrosion resistance in the formed coating film by coating the surface thereof.
- This coating treatment can be performed after the surface conditioning treatment of the present invention as described above, followed by washing and drying.
- a coating method a primer treatment by epoxy cation electrodeposition coating, a top coating treatment by melamine resin or the like, or a general baking coating method can be used.
- the coating treatment process can be performed by a known method such as electrodeposition coating, spray coating, and dip coating.
- a known organic paint or inorganic paint is used.
- the FPF (Finger-Print-Free) process (glassy coating), which is performed with a titanium alloy, etc., is applied to form an excellent high-density film with high adhesion. it can.
- a heat treatment step may be appropriately performed before and after the surface treatment.
- the Mg—Li alloy obtained by the method of the present invention has excellent corrosion resistance and can reduce the surface electrical resistance value.
- it can be used in mobile phones, notebook computers, portable translators, video, etc. Effective use as various electrical equipment casing parts that require high electromagnetic shielding properties, such as cameras and digital cameras, or that require low surface electrical resistance to take the ground from the substrate. Can do.
- the Mg—Li alloy obtained by the method of the present invention keeps excellent corrosion resistance and surface electrical resistance value low even after the obtained rolled material is processed by pressing or the like even in the state of the rolled material. be able to.
- the Mg—Li alloy obtained by the method of the present invention may be one in which the surface treatment process after the step (c) is performed on the Mg—Li alloy in a state of a molded product after press working.
- the surface treatment step after the step (c) may be performed on the Mg—Li alloy in the state of the rolled material before processing.
- the rolled material of the present invention is made of the Mg—Li alloy of the present invention, it is excellent in corrosion resistance and cold workability. Usually, the rolled material has a thickness of about 0.01 to 5 mm.
- the rolled material of the present invention can be used for moldings such as portable audio devices, digital cameras, mobile phones, laptop computers, and other automobile parts, and automobile parts by cold pressing.
- the rolled material of the present invention is excellent in cold workability, there is no cracking or poor appearance, high dimensional accuracy can be obtained, and production efficiency of the molded product can be improved.
- the molded product of the present invention is excellent in corrosion resistance because it is made of the Mg—Li alloy of the present invention.
- the molded product of the present invention can be obtained by molding the Mg—Li alloy of the present invention by, for example, cutting, grinding, polishing, pressing or the like. Considering equipment and manufacturing costs, it is preferable to use the rolled material of the present invention and to perform cold pressing.
- the Mg—Li alloy obtained through all the steps described above is a cylindrical two probe (contact surface area 3.14 mm 2 of one needle) having a pin interval of 10 mm and a pin tip diameter of 2 mm (Mitsubishi Corporation).
- the surface electrical resistance value of the ammeter when the surface is pressed against the surface with a load of 240 g can be 1 ⁇ or less. Therefore, the Mg—Li alloy obtained by the surface treatment method of the present invention should be suitably used as an electronic equipment casing component that requires grounding from the substrate or an electronic equipment casing component that requires electromagnetic shielding properties. Can do.
- the magnesium-lithium alloy of the present invention despite containing 10.5% by mass or more of Li, corrosion resistance and workability such as cold pressing are compatible at a high level, Moreover, since it contains a large amount of Li, which has a smaller specific gravity than Mg, it is excellent in practicality and can be reduced in weight, and is a cylindrical two-probe having a pin interval of 10 mm and a pin tip diameter of 2 mm (contact surface area of 3.14 mm 2 per needle). ) When the probe is pressed against the surface with a load of 240 g, the surface electrical resistance value of the ammeter is 1 ⁇ or less. It can be used for parts.
- the alloy ingot was heat-treated at 300 ° C. for 24 hours, and the surface was cut to prepare a slab for rolling having a thickness of 50 mm.
- This slab was rolled at 350 ° C. to a plate thickness of 2 mm.
- the sheet was rolled to a plate thickness of 1 mm at a reduction rate of 50% to obtain a rolled product.
- the obtained rolled product was annealed at 230 ° C. for 1 hour to prepare a rolled material.
- the average grain size, tensile strength, and Vickers hardness of the obtained rolled material were measured according to the methods described above.
- the corrosion resistance was evaluated by a 5% salt water immersion test. Further, cold workability was evaluated by measuring a limit drawing ratio (LDR) at room temperature. The results are shown in Table 1.
- the 5% salt water immersion test consists of 3 cycles of polishing the surface and then rinsing the acetone-washed specimen for 8 hours in salt water with a sodium chloride concentration of 5% at a liquid temperature of 25 ⁇ 5 ° C. and leaving it in the atmosphere for 16 hours. Performed by doing. The evaluation was performed by converting the mass change per surface area after the test as the corrosion degree, and converting the corrosion degree of the AZ31 material tested at the same time as the comparative material as 100.
- LDR measurement conditions were as follows: punch diameter: 40 mm, die diameter: 42.5 mm, die shoulder radius: 8 mm, wrinkle holding force: 12 kN, punch shoulder radius 4 mm, lubricant: molybdenum disulfide, punch speed: 3 mm / second It was.
- Comparative Example 1 A rolled material is produced in the same manner as in test alloy 1, except that the raw material composition is Li 14.0% by mass, Al 1.00% by mass, and the balance Mg, and annealing performed at 230 ° C. for 1 hour is performed at 150 ° C. for 1 hour. And evaluated. The evaluation results are shown in Table 2.
- Test Alloys 2-16, Comparative Examples 2-11) A rolled material was produced in the same manner as the test alloy 1 except that the raw materials were mixed so that the alloy compositions shown in Tables 1 and 2 were obtained, and the production conditions shown in Tables 1 and 2 were changed. The obtained rolled material was evaluated in the same manner as the test alloy 1. Table 1 shows the results of the test alloys, and Table 2 shows the results of the comparative examples.
- Comparative Example 3 shows that the alloy composition is inferior in corrosion resistance only by not containing Al.
- Comparative Example 6 it can be seen that when only the alloy composition having a large amount of Li is outside the range specified by the production method of the present invention, the corrosion resistance is poor.
- Comparative Example 7 when only the annealing temperature is 1 hour at 130 ° C., which is lower than the range specified by the production method of the present invention, recrystallization does not occur, and the tensile strength and Vickers specified by the Mg—Li alloy of the present invention are achieved. It can be seen that even if the hardness requirement is satisfied, both the cold workability and the corrosion resistance are inferior.
- this test piece was degreased by immersing in a strong alkaline aqueous solution (manufactured by Million Chemical Co., Ltd .: 30% aqueous solution of trade name GFMG15SX) maintained at a temperature of 80 ° C. for 8 minutes.
- a strong alkaline aqueous solution manufactured by Million Chemical Co., Ltd .: 30% aqueous solution of trade name GFMG15SX
- the test piece after the degreasing treatment was washed with water and then subjected to a treatment step using a low electrical resistance treatment solution shown in Table 3.
- This low electrical resistance treatment solution was prepared by adding zinc oxide and primary aluminum phosphate to phosphoric acid and adjusting the zinc and aluminum in the treatment solution to the ratios shown in Table 3.
- test piece was surface-treated by immersing in a strong alkaline aqueous solution (manufactured by Million Chemical Co., Ltd .: 45% aqueous solution of trade name GFMG15SX) for 2 minutes after washing with water.
- a strong alkaline aqueous solution manufactured by Million Chemical Co., Ltd .: 45% aqueous solution of trade name GFMG15SX
- test piece was immersed in a film chemical conversion treatment solution composed of an aqueous ammonium fluoride solution containing the fluoride shown in Table 3 at 60 ° C. for 180 seconds after washing with water.
- This film chemical conversion treatment solution was used by adjusting the amount of fluorine in ammonium fluoride to the amount shown in Table 3.
- test pieces obtained through the water washing and drying steps were prepared for one condition, and two pieces were evaluated for surface electrical resistance and bare corrosion resistance.
- the remaining two sheets were subjected to general baking coating for magnesium alloy in the following manner.
- the undercoat was painted with an epoxy resin paint primer and baked at 150 ° C. for 20 minutes, and the overcoat was baked with an acrylic paint at 150 ° C. for 20 minutes to give a total film thickness of 40 to 50 ⁇ m.
- the coating performance evaluation was performed on the test piece subjected to this coating.
- -Surface electrical resistance value For the surface electrical resistance value, a Lorester EP2 probe A probe (manufactured by Mitsubishi Chemical Analytech Co., Ltd .: 10 mm between pins, 2.0 mm in pin tip diameter (contact surface area of 3.14 mm 2 per needle), spring pressure 240 g) is used. The surface electrical resistance value was measured by pressing a pin on the center, top and bottom of the test piece surface. The measurement was performed three times for each test piece, and the total value was obtained by measuring six times in total for two sheets.
- a Lorester EP2 probe A probe manufactured by Mitsubishi Chemical Analytech Co., Ltd .: 10 mm between pins, 2.0 mm in pin tip diameter (contact surface area of 3.14 mm 2 per needle), spring pressure 240 g
- the surface electrical resistance value was measured by pressing a pin on the center, top and bottom of the test piece surface. The measurement was performed three times for each test piece, and the total value was obtained by measuring six times in total for two sheets.
- the measured value of 240 g is measured by pressing against the surface of the test piece until the pin of the two-probe probe retracts against the spring pressure.
- the case of less than 0.0 ⁇ was indicated as “ ⁇ ”
- the case of less than 1.0 to 1000 ⁇ was indicated as “ ⁇ ”, 1000 ⁇ or more, or “ ⁇ ” when measurement was impossible even once.
- the measured value of 60 g is measured by pressing a load of 30 g on the probe tip (main body 30 g) and pressing it on the surface of the test piece.
- the case of less than 10.0 ⁇ is “ ⁇ ”
- the case of 10.0 to less than 1000 ⁇ is “ ⁇ ”, 1000 ⁇ or more, or “ ⁇ ” if measurement is impossible even once.
- the measured value of 240 g assumes the case where the ground is fixed to the surface of the member with screws, and the measured value of 60 g assumes the case where the ground is fixed to the surface of the member.
- -Bare corrosion resistance test Put the test piece into a test tank set at 35 ° C by spraying with salt water according to JIS Z 2371 (SST test), spray 5% saline solution, take out after 24 hours, wash the surface with water, and surface rust area (%)It was confirmed.
- the case of 0% was designated as “ ⁇ 5”, the case of 5% or less as “ ⁇ ”, the case of exceeding 5% and less than 30% as “ ⁇ ”, and the case of 30% or more as “X”.
- -Bare moisture resistance test- The test piece was put in a thermostatic oven with a temperature of 50 ° C. and a humidity of 90%, and taken out after 120 hours to confirm the surface rust area (%). The case of 0% was designated as “ ⁇ 5”, the case of 5% or less as “ ⁇ ”, the case of exceeding 5% and less than 30% as “ ⁇ ”, and the case of 30% or more as “X”.
- -Coating corrosion resistance test- A coated test piece was cut with a cutter knife. This was put into a test tank set at 35 ° C. by a salt spray test method (SST test) according to JIS Z 2371, sprayed with 5% saline, and taken out after 240 hours.
- a tape was applied to the dried coating film cut part and peeled off, and the one-side maximum peel width (mm) after tape peeling was measured. “ ⁇ ” for less than 2.0 mm, “ ⁇ ” for 2.0 mm to less than 3.0 mm, “ ⁇ ” for 3.0 mm to less than 6.0 mm, “ ⁇ ” for 6.0 mm or more " -Water resistance test for coating film-
- the coated test piece was placed in boiling (100 ° C.) hot water, immersed for 60 minutes, then taken out, wiped with water on the surface, and left at room temperature for 1 hour.
- the case of 0% was designated as “ ⁇ 5”, the case of 5% or less as “ ⁇ ”, the case of exceeding 5% and less than 30% as “ ⁇ ”, and the case of 30% or more as “X”.
- test piece according to the present invention has a low surface electrical resistance value, and excellent bare corrosion resistance and coating film adhesion can be obtained.
- Examples 14 to 20 The test pieces of Examples 14 to 20 were obtained in the same manner as in Example 7 except that the film chemical conversion treatment solution shown in Table 5 was used.
- the film chemical conversion treatment liquid was used by adjusting ammonium fluoride and primary aluminum phosphate so that the amounts of fluorine and aluminum shown in Table 1 were obtained.
- the surface electrical resistance value, bare corrosion resistance, and coating film performance evaluation of the obtained test piece were performed in the same manner as in the above examples.
- the magnesium-lithium alloy and the manufacturing method thereof according to the present invention can be used for various electronic equipment casings that need to be grounded.
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Abstract
Description
(試験合金1)
Li14.0質量%、Al1.00質量%、Ca0.30質量%、及び残部Mgの組成となるように配合した原材料を、加熱、溶解して合金溶融物とした。続いて、この溶融物を55mm×300mm×500mmの金型中に鋳込んで合金鋳塊を作製した。得られた合金の組成をICP分析にて測定した。結果を表1に示す。
(比較例1)
原材料の配合をLi14.0質量%、Al1.00質量%、残部Mgとし、230℃で1時間行った焼きなましを、150℃で1時間行った以外は、試験合金1と同様に圧延材を作製し、評価を行った。評価結果を表2に示す。
(試験合金2~16、比較例2~11)
表1及び表2に示す合金組成となるように原材料の配合を代え、また、表1及び表2に示す製造条件を代えた以外は、試験合金1と同様に圧延材を製造した。得られた圧延材について、評価を試験合金1と同様に行った。試験合金の結果を表1に、比較例の結果を表2示す。
(実施例1~13、比較例12~30)
被処理対象物として、試験合金16と同様の製造方法によって得られたMg-Li合金
からなる縦50mm、横50mm、厚さ1.0mmの圧延材を試験片として用意した。
-表面電気抵抗値-
表面電気抵抗値は、ロレスターEP2探針Aプローブ(株式会社三菱化学アナリテック社製:ピン間10mm、ピン先直径2.0mm(1針の接触表面積3.14mm2)、バネ圧240g)を用い、試験片表面の中央部、上部、下部に、それぞれピンを押圧して表面電気抵抗値を測定した。測定は一枚の試験片につき3回測定し、2枚で合計6回測定してその平均値を求めた。
-裸耐食性試験-
JIS Z 2371に準じた塩水噴霧試験方法(SST試験)によって、35℃に設定した試験槽に試験片を入れ、5%食塩水を噴霧して24時間後に取り出し、表面を水洗いし、表面錆面積(%)を確認した。0%の場合を「◎」、5%以下の場合を「○」、5%を超え、30%未満の場合を「△」、30%以上の場合を「×」とした。
-裸耐湿試験-
温度50℃、湿度90%の恒温恒湿器に試験片を入れ、120時間後に取り出し、表面錆面積(%)を確認した。0%の場合を「◎」、5%以下の場合を「○」、5%を超え、30%未満の場合を「△」、30%以上の場合を「×」とした。
-塗膜耐食性試験-
塗装を施した試験片にカッターナイフで切り込みを入れたものを用意した。これを、JIS Z 2371に準じた塩水噴霧試験方法(SST試験)によって、35℃に設定した試験槽に入れ、5%食塩水を噴霧して240時間後に取り出した。表面を水洗いして乾燥した後、乾燥した塗膜カット部にテープを貼って剥離し、テープ剥離後の片側最大剥離幅(mm)を測定した。2.0mm未満の場合を「◎」、2.0mm~3.0mm未満の場合を「○」、3.0mm~6.0mm未満の場合を「△」、6.0mm以上の場合を「×」とした。
-塗膜耐水性試験-
沸騰(100℃)しているお湯の中に、塗装を施した試験片を入れ、60分間浸漬後、試験片を取り出し、表面の水を拭いて常温で1時間放置した。その後、試験片の表面に1mmの碁盤目状の切り込みを入れ、その表面にテープを貼って剥離し、剥離された塗膜の面積を測定した。0%の場合を「◎」、5%以下の場合を「○」、5%を超え、30%未満の場合を「△」、30%以上の場合を「×」とした。
(実施例14~20)
表5に示す皮膜化成処理液を使用する以外は、上記実施例7と同様に処理を行って、実施例14~20の試験片を得た。
Claims (12)
- Liを10.5質量%以上、16.0質量%以下、Alを0.50質量%以上、1.50質量%以下含有し、残部にMgを含む、平均結晶粒径が5μm以上、40μm以下、引張強度が150MPa以上で、
かつピン間10mm、ピン先直径2mmの円柱状2探針(1針の接触表面積3.14mm2)のプローブを、240gの荷重で表面に押圧した時の電流計の表面電気抵抗値が1Ω以下であることを特徴とするマグネシウム-リチウム合金。 - 平均結晶粒径が5μm以上、20μm以下、引張強度が150MPa以上、180MPa以下である請求項1記載のマグネシウム-リチウム合金。
- Liを10.5質量%以上、16.0質量%以下、Alを0.50質量%以上、1.50質量%以下含有し、残部にMgを含む、平均結晶粒径が5μm以上、40μm以下、ビッカース硬度(HV)が50以上で、かつ
ピン間10mm、ピン先直径2mmの円柱状2探針(1針の接触表面積3.14mm2)のプローブを、240gの荷重で表面に押圧した時の電流計の表面電気抵抗値が1Ω以下であることを特徴とするマグネシウム-リチウム合金。 - 平均結晶粒径が5μm以上、20μm以下、ビッカース硬度(HV)が50以上、70以下である請求項3記載のマグネシウム-リチウム合金。
- Liを13.0質量%以上、15.0質量%以下含有する請求項1~4のいずれか一つに記載のマグネシウム-リチウム合金。
- Caを0.10質量%以上、0.50質量%以下含有する請求項1~5のいずれか一つに記載のマグネシウム-リチウム合金。
- Liを10.5質量%以上、16.0質量%以下、Alを0.50質量%以上、1.50質量%以下含有し、残部にMgを含む合金原料溶融物を合金鋳塊に冷却固化する工程(a)と、
得られた合金鋳塊を圧下率30%以上となるように冷間で塑性加工する工程(b)と、
塑性加工した合金を170~250℃未満で10分~12時間、もしくは250~300℃で10秒~30分で焼きなましする工程(c)と、
得られた合金の表面を、アルミニウム、および亜鉛の金属イオンを含有する無機酸の低電気抵抗処理液で処理する工程(d)とを含む請求項1または3記載のマグネシウム-リチウム合金の製造方法。 - 工程(d)の後、表面調整を行ってから、フッ素化合物を含有する皮膜化成処理液に浸漬して皮膜化成処理する工程(e)とを含む請求項7記載のマグネシウム-リチウム合金の製造方法。
- 低電気抵抗処理液には、アルミニウムとして0.021~0.47g/lと、亜鉛として0.0004~0.029g/lとが含有された請求項7または8記載のマグネシウム-リチウム合金の製造方法。
- フッ素化合物を含有する皮膜化成処理液として、3.33~40g/lの酸性フッ化アンモニウム水溶液が用いられた請求項8または9記載のマグネシウム-リチウム合金の製造方法。
- 請求項1ないし6のいずれか一つに記載のマグネシウム-リチウム合金からなる圧延材。
- 請求項1ないし6のいずれか一つに記載のマグネシウム-リチウム合金からなる成型品。
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CN102753714A (zh) | 2012-10-24 |
EP2476769A1 (en) | 2012-07-18 |
EP2476770A4 (en) | 2016-09-28 |
CN102753714B (zh) | 2015-02-18 |
TW201124541A (en) | 2011-07-16 |
US9702033B2 (en) | 2017-07-11 |
CN102741436B (zh) | 2015-04-01 |
WO2011030474A1 (ja) | 2011-03-17 |
TWI507533B (zh) | 2015-11-11 |
JP5643498B2 (ja) | 2014-12-17 |
EP2476770B1 (en) | 2017-08-23 |
US20120222784A1 (en) | 2012-09-06 |
EP2476769B1 (en) | 2017-08-23 |
US20120227868A1 (en) | 2012-09-13 |
US9708700B2 (en) | 2017-07-18 |
CN102741436A (zh) | 2012-10-17 |
JP2011058074A (ja) | 2011-03-24 |
EP2476770A1 (en) | 2012-07-18 |
EP2476769A4 (en) | 2016-09-28 |
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