JP2014235815A - Method for manufacturing aluminum compact, method for analyzing aluminum, and aluminum plating system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a method for manufacturing an aluminum compact preventing generation of defective products, specifically brittle products and thereby capable of achieving stabilization of quality; a method for analyzing aluminum capable of being used for the method for manufacturing an aluminum compact; and an aluminum plating system capable of being used for the method for manufacturing an aluminum compact.SOLUTION: A method for manufacturing an aluminum compact includes a plating step of plating aluminum on a substrate and a step of removing the substrate after plating. The plating step includes: an analyzing step of quantifying aluminum carbide in aluminum having been plated on the substrate, using an RIR method by means of an X-ray diffraction (XRD); and a plating solution adjustment step of adjusting the composition of a plating solution on the basis of the content of the aluminum carbide having been quantified. A method for analyzing aluminum can be used for the method for manufacturing an aluminum compact. An aluminum plating system can be used for the method for manufacturing an aluminum compact.

Description

  The present invention relates to a method for producing an aluminum molded body such as an aluminum porous body, an aluminum wire, and an aluminum foil (film), an aluminum analysis method used in the production method, and an aluminum plating system that can be used in the production method. .

  Aluminum (Al) is excellent in electrical conductivity, corrosion resistance, thermal conductivity, light weight, and the like, and is widely used as an electrode material for power storage devices such as capacitors and lithium ion batteries. As a specific example, a positive electrode material in which an active material is applied to the surface of an aluminum foil is used for a positive electrode of a lithium ion battery.

  In recent years, in order to improve the utilization rate of the active material per unit area, it has been proposed to use a porous aluminum body having a three-dimensional network structure instead of an aluminum foil (for example, Patent Document 1). Such an aluminum porous body is produced by applying an aluminum coating to a resin porous body having continuous pores such as urethane foam by plating and then decomposing and removing the resin porous body by heat treatment.

In the above aluminum plating, a plating solution made of a molten salt is generally used. Examples of the molten salt include ionic liquids containing alkyl imidazolium chlorides such as AlCl ₃ and ethyl methyl imidazolium chloride (EMIC). Various additives are added to the plating solution to improve the quality of the product. For example, phenanthroline or the like is added to improve quality such as smoothness and strength. That is, with only an ionic liquid composed of AlCl ₃ and alkylimidazolium chloride, plating tends not to form a film but to form aggregates of particles, resulting in a rocky and brittle aluminum porous body, but phenanthroline should be added. As a result, the gloss is increased and a smooth and porous aluminum porous body is obtained.

  On the other hand, when the phenanthroline in the plating solution is excessive, the gloss of the aluminum porous body of the product is further increased and the product tends to become brittle. Therefore, by preparing an appearance limit sample for plating and comparing the generated plating with the appearance limit sample, the concentration of phenanthroline in the plating solution is controlled so that the generated plating does not become rocky and does not have excessive luster. doing.

JP 2011-222483 A

  However, this management method is a management method that adjusts the plating conditions (such as the amount of phenanthroline) when the obtained plating deviates from the standard of the appearance limit sample, and thus cannot be adjusted quickly. As a result, generation of defective products, particularly fragile products cannot be sufficiently prevented. That is, in general, aluminum plating is performed continuously for a long time by a so-called roll-to-roll method while passing a long substrate through a plating solution. Good product is generated. Moreover, since contrast with the appearance limit sample is not a quantitative management method, it has been difficult to manage so that a product of a certain quality can be stably obtained.

  The problem to be solved by the present invention is to enable quick adjustment of plating conditions (phenanthroline amount, etc.), to prevent generation of defective products, particularly brittle products, and to stably obtain products of constant quality. It is providing the manufacturing method of an aluminum molded object.

  Another object of the present invention is to provide an aluminum analysis method capable of quickly and quantitatively analyzing impurities contained in an aluminum molded body in order to realize the method for producing the aluminum molded body.

  Furthermore, the present invention provides a plating system for continuously plating aluminum on a long substrate, which can sufficiently prevent generation of defective products, particularly fragile products, and can stabilize quality. Is also an issue.

As a result of intensive studies, the inventor has determined that the brittleness of the porous aluminum body of the product is because aluminum carbide (aluminum carbide: Al ₄ C ₃ ) derived from phenanthroline in the plating solution removes a substrate such as urethane. Due to grain boundary precipitation inside the aluminum skeleton during heat treatment, by suppressing the formation of aluminum carbide inside the aluminum skeleton, it is possible to prevent the generation of brittle porous bodies,
The content of aluminum carbide in the aluminum skeleton can be measured by X-ray diffraction (XRD), and furthermore, an RIR method for quantifying based on the Reference Intensity Ratio (RIR value) can be applied to this measurement. We found that rapid measurement is possible by applying the method.

  Then, by applying this analytical method to the plating process, the content of aluminum carbide in the porous aluminum body can be quickly quantified, and based on the results, the plating conditions, particularly the concentration of phenanthroline in the plating solution, can be quickly determined. I found out that it can be adjusted. Furthermore, the adjustment found that the formation of aluminum carbide inside the aluminum skeleton can be suppressed, the occurrence of brittleness can be prevented and the quality can be stabilized, and the first to third aspects of the invention comprising the following configurations have been completed. It came to do.

The first aspect is
A method for producing an aluminum molded body having a plating step of depositing aluminum on a substrate in a plating solution,
The plating step is
An analysis step of quantifying aluminum carbide contained in the aluminum electrodeposited on the substrate using an RIR method by X-ray diffraction;
A plating solution adjusting step of adjusting the composition of the plating solution based on a value obtained by quantifying the aluminum carbide.

The second aspect is
In this aluminum analysis method, aluminum carbide in aluminum is quantified by X-ray diffraction (XRD) using the RIR method.

The third aspect is
An aluminum plating system for continuously depositing aluminum on a long substrate,
A plating bath containing a plating solution using a molten salt of aluminum, a temperature control device for controlling the temperature of the plating solution to a predetermined temperature, and
A transport device for passing the substrate through the plating solution at a predetermined speed;
A power supply unit for energizing a predetermined amount of aluminum to be deposited on the substrate being transported in the plating solution;
An aluminum analysis unit that quantifies aluminum carbide in electrodeposited aluminum using an RIR method by X-ray diffraction (XRD), and adjustment of the composition of the plating solution based on the determination result by the analysis unit Is an aluminum plating system.

According to the first aspect, it is possible to provide a method for manufacturing an aluminum molded body that can sufficiently prevent generation of defective products, particularly brittle products, and can stabilize the quality of the products.
According to the second aspect, it is possible to provide an aluminum analysis method for quickly quantitatively analyzing aluminum carbide contained in an aluminum molded body.
According to the aluminum plating system of the third aspect, the generation of defective products, particularly brittle products, can be sufficiently prevented, and the aluminum plated products can be continuously supplied while stabilizing the quality.

It is a figure explaining 1 process of the manufacturing method of the aluminum molded object of a 1st aspect. It is a figure explaining 1 process of the manufacturing method of the aluminum molded object of a 1st aspect. It is a figure explaining 1 process of the manufacturing method of the aluminum molded object of a 1st aspect. It is an XRD chart by the wide angle measurement of an example of an aluminum porous body. 3 is an XRD chart of an example of an aluminum porous body with 2θ ranging from 30 ° to 33 °. It is a XRD chart of 2 an example of the range of 37 degrees-40 degrees of an example of an aluminum porous body. It is a schematic diagram which shows an example of the plating system of the aluminum of a 3rd aspect.

The first aspect is as follows.
A method for producing an aluminum molded body having a plating step of depositing aluminum on a substrate in a plating solution,
The plating step is
An analysis step of quantifying aluminum carbide contained in the aluminum electrodeposited on the substrate using an RIR method by X-ray diffraction;
A plating solution adjusting step of adjusting the composition of the plating solution based on a value obtained by quantifying the aluminum carbide.

  The aluminum molded body is produced by quantifying aluminum carbide in aluminum electrodeposited (plated) on a substrate by X-ray diffraction (XRD) using the RIR method, and based on the measured value, a plating solution. The composition is adjusted. Aluminum carbide in aluminum can be quantified by X-ray diffraction (XRD), but the quantification can be performed quickly by using the RIR method. Therefore, by quickly adjusting the composition of the plating solution based on the measured values, it is possible to sufficiently prevent the generation of defective products, particularly brittle products, and stabilize the product quality in the production of aluminum molded bodies. Can do.

Examples of the aluminum molded body include an aluminum porous body, an aluminum wire, and an aluminum foil (film). Therefore, in the present application, the first aspect described above,
A method for producing an aluminum molded body in which the aluminum molded body is an aluminum porous body; a method for producing an aluminum molded body in which the aluminum molded body is an aluminum wire;
And the manufacturing method of the aluminum molded object whose said aluminum molded object is aluminum foil is also provided.

  Since an aluminum porous body, an aluminum wire, and an aluminum foil are thin films or thin molded bodies, they are molded bodies suitable for production by electrodeposition (plating). Further, these molded products often require quality such as sufficient strength stably. Therefore, by applying the invention of the first aspect to the production of these molded articles, a molded article having sufficient strength can be stably obtained, so that the effects of the invention can be exhibited remarkably.

The second aspect includes
In this aluminum analysis method, aluminum carbide in aluminum is quantified by X-ray diffraction (XRD) using the RIR method.

  As described above, aluminum carbide in aluminum can be quickly and accurately quantified by using the RIR method by X-ray diffraction (XRD). Therefore, by using this aluminum analysis method in an aluminum production process, production conditions can be quickly prepared so that excellent quality aluminum can be obtained, and excellent quality aluminum can be stably obtained. It becomes possible.

  Here, the analysis using the RIR method by X-ray diffraction (XRD) is to measure the X-ray diffraction of aluminum, and in the obtained diffraction spectrum, diffraction peaks corresponding to each crystal lattice of aluminum and impurities in the aluminum A predetermined peak (preferably the strongest peak or a plurality of strong peaks) is selected from the diffraction peaks corresponding to each crystal lattice of (aluminum carbide, etc.), and the diffraction line intensity of impurities relative to the diffraction line intensity of aluminum. This is a method for quantitatively analyzing the amount of impurities in aluminum based on the ratio. Although the intensity of X-ray diffraction lines differs between aluminum and its impurities (such as aluminum carbide) even if the content is the same mass, the intensity of the diffraction line corresponding to the same mass is different for each peak of aluminum and each impurity. The impurity content is calculated from the intensity ratio of diffraction lines corresponding to the same mass and the intensity ratio of diffraction lines obtained by measurement.

  As the diffraction peak used for calculating the intensity ratio of diffraction lines, it is preferable to select the 111 diffraction line which is the strongest peak for aluminum, and the integrated intensity of the spectrum in the range corresponding to the 111 diffraction line, specifically Specifically, it is preferable to calculate the intensity ratio based on the integrated intensity in the range of 2θ in X-ray diffraction of 37 to 40 °. For aluminum carbide, the content is usually small and the intensity of the diffraction line is small, so the 101 diffraction line, 012 diffraction line, and 009 diffraction line with relatively high strength are selected and these diffraction lines are selected. It is preferable to calculate the intensity ratio based on the integrated intensity of the spectrum in the range corresponding to the line, specifically, the integrated intensity in the range where 2θ in X-ray diffraction is 30 to 33 °. Therefore, in the present application, in the second aspect, the RIR method is based on the ratio of the integrated intensity in the range of 2θ of 37 to 40 ° and the integrated intensity in the range of 2θ of 30 to 33 ° in X-ray diffraction. Also provided are methods for analyzing aluminum performed in

In the third aspect,
An aluminum plating system for continuously depositing aluminum on a long substrate,
A plating bath containing a plating solution using a molten salt of aluminum, a temperature control device for controlling the temperature of the plating solution to a predetermined temperature, and
A transport device for passing the substrate through the plating solution at a predetermined speed;
A power supply unit for energizing a predetermined amount of aluminum to be deposited on the substrate being transported in the plating solution;
An aluminum analysis unit that quantifies aluminum carbide in electrodeposited aluminum using an RIR method by X-ray diffraction (XRD), and adjustment of the composition of the plating solution based on the determination result by the analysis unit Is an aluminum plating system.

  As described above, the amount of aluminum carbide in the aluminum plating greatly affects the quality of the aluminum plating, but in the plating system of the third aspect, the amount of aluminum carbide in the aluminum plating is determined by X-ray diffraction (XRD). Quantification is performed using the RIR method (that is, according to the second aspect of the present invention), and the composition of the plating solution is rapidly adjusted to a suitable composition based on the result. Therefore, according to this plating system, generation | occurrence | production of inferior goods, especially a brittle product can fully be prevented, and the plating product of the stable quality can be supplied continuously. Therefore, for example, it can be suitably applied to the production of an aluminum porous body used for an electrode material of an electricity storage device.

  Next, the embodiment of the present invention will be described more specifically with reference to the drawings and the like. However, this embodiment does not limit the scope of the present invention.

1. Production of Aluminum Molded Body (Aluminum Porous Body) First, an example of production of an aluminum porous body to which the method for producing an aluminum molded body according to the first aspect can be applied will be described with reference to FIGS.

  FIG. 1A is an enlarged schematic view schematically showing an enlarged part of a cross section of a foamed resin molded body serving as a base of an aluminum porous body. In the figure, 1a represents a resin constituting the base body 1 made of a foamed resin molded body. However, as shown in the figure, the resin 1a forms bubbles, and the foamed resin molded body to be the base body 1 has continuous air holes. It has a three-dimensional network structure. In the production of the aluminum porous body, aluminum is electrodeposited on the substrate 1 having the three-dimensional network structure to form a plating layer.

  FIG. 1B is an enlarged schematic view schematically showing a state in which the aluminum plating layer 2 is formed on the surface of the substrate 1 (resin 1a). When the substrate 1 is removed by heat treatment or the like after the formation of the plating layer 2, the aluminum porous body 3 made of the aluminum plating layer 2 is obtained. FIG. 1C is an enlarged schematic view schematically showing a part of a cross section of the aluminum porous body 3 manufactured in this way. Hereinafter, it demonstrates for every process.

(1) Base 1
The substrate 1 is a foamed resin molded body having a three-dimensional network structure and continuous pores (continuous vent holes). The shape, cell diameter, porosity, and the like are not particularly limited, and are selected according to the use of the product. As the substrate 1, a foamed resin molded body such as polyurethane, melamine, polypropylene, and polyethylene is preferably used. For example, a foamed urethane resin molded article having a porosity of 80 to 98% and a cell diameter of 50 to 500 μm is suitable for manufacturing electrode materials for power storage devices such as capacitors and lithium ion batteries. Moreover, a nonwoven fabric etc. can also be used.

(2) Aluminum plating step Since the base body 1 made of a foamed resin molded body does not have conductivity, it cannot be electrodeposited (electrolytic plating) on its surface as it is. Therefore, in order to perform electrodeposition (electrolytic plating) of aluminum, the surface of the substrate 1 is subjected to a conductive treatment. The treatment method is not particularly limited as long as the treatment can provide a conductive layer on the surface of the foamed resin. Examples thereof include electroless plating of a conductive metal such as nickel, vapor deposition and sputtering of aluminum, and application of a conductive paint containing conductive particles such as carbon.

  After the conductive treatment, aluminum electrodeposition (electrolytic plating) is performed to form an aluminum plating layer 2 on the substrate 1. Specifically, the substrate 1 is used as a cathode and aluminum is used as an anode, and a direct current voltage is applied in a molten salt to conduct electricity. As the anode aluminum, for example, aluminum having a purity of 99.0% can be used.

  A molten salt is used for the plating solution. Examples of the molten salt include an organic molten salt that is a eutectic salt of an organic halide and an aluminum halide, an inorganic molten salt that is a eutectic salt of an alkali metal halide and an aluminum halide, and the like. Use of an organic molten salt (ionic liquid) that melts at a relatively low temperature is preferable because electroplating can be performed without decomposing the foamed resin molded body of the substrate 1.

  As the organic halide constituting the organic molten salt, an imidazolium salt, a pyridinium salt, or the like can be used. Specifically, ethylmethylimidazolium chloride (EMIC) or butylpyridinium chloride (BPC) is preferably used. Of these, a salt containing an imidazolium cation having an alkyl group at the 1,3-position (1-ethyl-3-methylimidazolium chloride or the like) is preferably used.

As the molten salt, an organic molten salt (AlCl ₃ + EMIC molten salt) composed of aluminum chloride and 1-ethyl-3-methylimidazolium chloride is particularly preferably used because it is highly stable and difficult to decompose. Further, a eutectic molten salt in which a salt selected from the group consisting of aluminum chloride and lithium chloride (LiCl), potassium chloride (KCl) and sodium chloride (NaCl) is mixed to lower the melting point is preferable.

In the case of using AlCl ₃ + EMIC molten salt, a plating solution having an AlCl ₃ : EMIC molar ratio of 2: 1 is preferably used because the concentration of Al ₂ Cl ₇ ⁻ contributing to plating is maximized. Further, in order to form a smooth film-like aluminum plating layer 2, an organic additive such as xylene, benzene, toluene, 1,10-phenanthroline (phenanthroline) may be added to the plating solution. In particular, when aluminum plating is performed on the substrate 1 made of a porous resin body having a three-dimensional network structure, an aluminum plating layer having a uniform thickness is obtained by adding phenanthroline to the plating solution so that the aluminum skeleton is not easily broken. 2 is preferable.

On the other hand, when the organic additive such as phenanthroline in the plating solution is excessive, the amount of the organic additive taken into the aluminum plating layer 2 increases. Then, when the heat treatment is performed to remove the substrate 1, in the process of aluminum carbide (Al 4 _{C 3)} is grain boundary precipitation, resulting aluminum layer 2 becomes fragile. For example, when the organic additive is phenanthroline, the preferable concentration range in the plating solution is 0.25 to 7 g / L.

(3) Adjustment of plating conditions As described above, in order to stably obtain an aluminum plating layer 2 of excellent quality, it is necessary to keep the plating conditions such as the amount of the organic additive in the plating solution within a suitable range. As desired, the plating conditions are managed and adjusted. In the present embodiment, as described later in “2. Determination of aluminum carbide in the aluminum plating layer”, the content of aluminum carbide in the aluminum plating layer 2 is determined by XRD using the RIR method (that is, the second Quantitative analysis (by the analysis method of the embodiment) enables rapid quantification. As a result of the rapid determination, the suitability of the concentration of the organic additive can be quickly determined and managed and adjusted, and the aluminum plating layer 2 having excellent quality can be stably obtained.

  As a method of adjusting the concentration of the organic additive, if the organic additive is excessive, adsorption removal using an adsorbent such as activated carbon that consumes the organic additive by plating on a dummy material called empty electrolysis The method of doing etc. can be mentioned. On the other hand, when the amount is insufficient, the concentration of the organic additive can be maintained within a suitable concentration range by replenishing the organic additive.

  When an organic molten salt is used for the plating solution, the temperature of the plating solution is preferably 10 ° C to 60 ° C, more preferably 25 ° C to 45 ° C. The lower the temperature, the narrower the current density range that can be plated, and the more difficult it is to deposit aluminum on the entire surface of the porous body. On the other hand, at a high temperature exceeding 60 ° C., a problem that the shape of the base resin is impaired tends to occur. Further, when moisture or oxygen is mixed in the molten salt, the molten salt deteriorates. Therefore, it is preferable to perform the electrodeposition of aluminum in a dry atmosphere with an inert gas such as nitrogen or argon and an outdoor temperature of −30 ° C. or lower.

(4) Substrate removal Depending on the application, it is used as it is as a composite of the base 1 made of a foamed resin molded product and an aluminum plating. Usually, however, the base 1 is removed and aluminum without resin due to restrictions on the use environment. A porous body is produced. Examples of the method for removing the substrate 1 include a method of heating to a temperature at which the substrate 1 is decomposed and removing it by heat treatment. Specifically, a method of removing the substrate 1 by thermal decomposition in a molten salt so that aluminum is not oxidized can be mentioned.

  That is, the substrate 1 on which the aluminum plating layer 2 is formed is immersed in a molten salt and heated to a temperature at which the foamed resin molded body is decomposed while applying a negative potential (potential lower than the standard electrode potential of aluminum) to the aluminum layer. . By decomposing and removing the resin, a porous aluminum body 3 as shown in FIG. 1C is obtained.

  The heating temperature is appropriately selected according to the type of the foamed resin molded body. For example, when the material of the substrate 1 is urethane, the temperature is preferably 500 ° C. or higher and 600 ° C. or lower.

  The method for producing an aluminum molded body has been described above by taking the aluminum porous body as an example. By changing the shape of the substrate 1 to another shape, the aluminum wire and the aluminum foil can be obtained in the same manner as in the case of the aluminum porous body. (Membrane) etc. can be manufactured. That is, in the case of manufacturing an aluminum wire, a linear substrate is used, and in the case of manufacturing an aluminum foil (film), a film-shaped substrate is used, and aluminum plating is performed on the substrate by the same method as in the case of the aluminum porous body. By applying and removing the substrate after forming the plating, an aluminum wire and an aluminum foil (film) can be manufactured.

2. Next, a method for quantifying aluminum carbide (Al ₄ C ₃ ) in the aluminum plating layer will be described. Quantification is performed using the RIR method by X-ray diffraction (XRD) as described above. In the RIR method, 111 diffraction lines are preferably selected for aluminum, and three diffraction lines 101, 012 and 009 are preferably selected for Al ₄ C ₃ .

For each diffraction line of aluminum and Al ₄ C ₃ , when the RIR value (I / Ic: the substance and corundum (Al ₂ O ₃ ) is mixed at a mass ratio of 1: 1, the intensity of each diffraction line of the substance (The ratio of the intensity Ic of the I and corundum diffraction lines), and these values are known on the ICDD card. Therefore, if the content of aluminum or Al ₄ C ₃ in each aluminum plating layer is Wi, the peak intensity of each diffraction line is Ii, and the RIR value of the diffraction line is Ri, the following relational expression is established. .
Wi ∝ Ii / Ri

Therefore, X-ray diffraction (XRD) was performed on aluminum, and the intensity of the diffraction line of aluminum (111 diffraction line) and the diffraction line of Al ₄ C ₃ (101, 012, 009) in the obtained diffraction spectrum. The amount of Al ₄ C ₃ contained in the aluminum can be calculated from the intensity ratio of the diffraction lines.

  Since the 111 diffraction line of aluminum is the strongest peak, it is selected for calculation of the intensity ratio. This diffraction line has a peak when 2θ of X-ray diffraction (XRD) is around 38.6 °, but in order to make the calculation of the intensity ratio more accurate, the integration of the spectrum between 2θ and 37 ° to 40 °. Intensity is used to calculate the intensity ratio.

Since Al ₄ C ₃ is a trace amount, its diffraction line intensity is very weak compared to that of aluminum. Accordingly, among the diffraction lines of Al ₄ C ₃ , _three diffraction lines 101, 012, and 009 having relatively high intensity and peaks at close positions are selected for calculation of the intensity ratio. Specifically, the integrated intensity of the spectrum in which 2θ, in which three diffraction lines 101, 012 and 009 exist, is between 30 ° and 33 ° is used for calculation of the intensity ratio. Further, in order to accurately measure the weak peak intensity (diffraction intensity), it is preferable to measure over a longer time than in the case of aluminum. Thus, the X-ray diffraction (XRD) measurement range need only be between 2θ between 30 ° and 33 ° and between 37 ° and 40 °. Rapid quantification is possible by limiting the measurement range.

2 to 4 show specific examples of X-ray diffraction (XRD) spectra of a porous aluminum body (manufactured by Sumitomo Electric: Aluminum Celmet). FIG. 2 is an XRD chart (X-ray diffraction spectrum) of wide angle measurement. The horizontal axis in FIG. 2 is the diffraction angle (2θ), and the vertical axis is the diffraction intensity (cps: count / second). This wide-angle measurement was performed using Cu-Ka line as the X-ray, and measurement conditions: 2θ = 10 ° to 80 °, step width = 0.03 °, and Time / step = 1 s. Since Al ₄ C ₃ is a very small amount, the diffraction line is small as shown in FIG.

In FIG. 4, the range of 2θ is narrowed to 30 ° to 33 ° where Al ₄ C ₃ 101, 012 and 009 diffraction lines exist, and Time / step = 40 s and the measurement time (integrated time) for each step. It is the XRD chart (X-ray diffraction spectrum) measured by lengthening. From this measurement result, an integrated intensity of 2θ of 30 ° to 33 ° is obtained and set as Al ₄ C ₃ integrated intensity (peak intensity).

FIG. 3 shows a case where 2θ in which 111 diffraction lines of aluminum exist is in the range of 37 ° to 40 °, and Time / step = 5 s and the measurement time for each step is set to 1/8 of the above Al ₄ C _3. Is an XRD chart (X-ray diffraction spectrum). From this measurement result, the integrated intensity of 2θ of 37 ° to 40 ° is obtained and set as the aluminum integrated intensity (peak intensity).

Next, calculation of the quantitative value (content) of Al ₄ C _{3 in} aluminum performed based on the aluminum integrated intensity and Al ₄ C ₃ integrated intensity obtained above will be described. First, an aluminum diffraction line correction value and an Al ₄ C ₃ diffraction line correction value are calculated by the following equations.

Aluminum diffraction line correction value = aluminum integrated intensity × 8 / 4.3
(Here, 4.3 is the RIR value of the 111 diffraction line of aluminum described in the ICDD card. 8 is the measurement time correction value. That is, the measurement time for each step of aluminum is Al ₄ C _3. (It is multiplied by 8 to correct 1/8 of.)
Al ₄ C ₃ diffraction line correction value =
Al integrated intensity × {100 / (46.5 + 97.1 + 8.3)} / 1.03
(Here, 1.03 is the RIR value of the 111 diffraction line of Al ₄ C ₃ described on the ICDD card. Also, 46.5, 97.1, and 8.3 are the ICDD card, respectively. (The relative intensity of 101, 012 and 009 diffraction lines when the intensity of the 111 diffraction lines of Al ₄ C ₃ described is 100.)

From the aluminum diffraction line correction value and the Al ₄ C ₃ diffraction line correction value thus obtained, a quantitative value (content) of Al ₄ C _{3 in} aluminum is calculated by the following formula.
Quantitative values of Al ₄ C ₃ (content) = _Al 4 _{C 3} diffraction line correction value / aluminum diffraction correction value

3. Aluminum Plating System Next, the aluminum plating system of the third aspect will be described. FIG. 5 is a schematic diagram showing an example of the aluminum plating system according to the third embodiment.

  In this aluminum plating system, a molten salt of aluminum is used as a plating solution, and is stored in a plating solution tank. In FIG. 5, 4 is a plating solution tank, and 5 is a plating solution. As the molten salt of aluminum, an organic molten salt containing an organic additive such as phenanthroline is used.

  During the plating process, the plating solution is controlled to a predetermined temperature by the temperature control device. For example, a temperature control device having a function of heating or cooling the plating solution in the plating solution tank is provided in or adjacent to the plating solution tank. Reference numeral 6 in FIG. 5 denotes a temperature control device. The temperature control device 6 is provided in the plating solution tank 4 (in the plating solution 5) and heats or cools the plating solution 5.

  In this aluminum plating system, a long substrate is passed through a plating solution in a plating solution tank, and an electric current is applied between the long substrate and the plating solution so that aluminum is continuously electroplated on the long substrate. (Electrodeposition). The long base is, for example, a strip-shaped resin molded body or a strip-shaped foamed resin molded body. However, when the base is made of a non-conductive material such as a resin, the surface is preliminarily subjected to a conductive treatment to enable energization. Yes. Reference numeral 7 in FIG. 5 denotes a long base made of a foamed urethane resin molded body having a band shape or a sheet shape, and having a surface subjected to a conductive treatment.

  The long substrate is transported at a predetermined speed by the substrate transport device and passes through the plating solution in the plating solution tank. The substrate transport device includes an unwinding device for unwinding the long substrate, a winding device for winding the aluminum-plated substrate, and a roller for passing the long substrate through the plating solution in the plating solution tank. Become. In FIG. 5, 8 is an unwinding device, 9 is a winding device, and 10 is a roller.

  Reference numeral 11 in FIG. 5 denotes a cathode which is in contact with the long base 7. Reference numeral 12 in FIG. 5 denotes an anode made of an aluminum plate, which is immersed in the plating solution 5 and arranged to face the long substrate 7 at a predetermined interval. When a voltage is applied between the cathode 11 and the anode 12 and energized, aluminum is electrodeposited on the substrate to be plated. Reference numeral 13 in FIG. 5 denotes a DC power source for applying a voltage between the cathode 11 and the anode 12. The DC power supply 13, the cathode 11, and the anode 12 constitute a power supply unit for an aluminum plating system. It is preferable that the plating bath of the aluminum plating system and its peripheral devices are disposed in a sealed space that can be in an inert and dry atmosphere.

The analysis unit of the aluminum plating system includes an XRD device and an XRD measurement data analysis device. Reference numeral 14 in FIG. 5 denotes an XRD apparatus, which is provided at a position where X-ray diffraction can be measured by irradiating X-rays on aluminum deposited on the long base 7 immediately after being taken out of the plating bath 4. It has been. The XRD data obtained by the XRD device 14 is immediately analyzed (data processing) by the analysis device 15 to calculate the Al ₄ C ₃ content in the aluminum plating layer.

The calculated Al ₄ C ₃ content is fed back to a plating condition adjusting section (not shown) such as a plating solution composition, and the plating conditions are adjusted so that excellent quality aluminum plating can be obtained. . In the adjustment unit, when it is determined that the organic additive is excessive based on the quantification result of the Al ₄ C ₃ content, for example, air electrolysis is performed, and the adsorbent is added to the plating solution to adsorb the organic additive. Etc. to reduce the concentration of the organic additive. On the other hand, when it is determined that the organic additive is insufficient, the organic additive is replenished and adjusted to a predetermined concentration.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, an Example is an illustration and does not limit the scope of the present invention.

A foamed urethane resin molded article having a thickness of 2 mm and a porosity of 98% was used as the substrate. As the plating solution, an ionic liquid containing AlCl ₃ and EMIC at a molar ratio of 2: 1 and phenanthroline at 0.5 g / L was used. After continuously performing aluminum plating, the substrate was removed by heat treatment at 600 ° C. for 30 minutes in the air to produce a porous aluminum body.

The production of the aluminum porous body under the same conditions was performed 4 times. For each product, performs a quantitative analysis of _Al 4 _{C 3} in aluminum using the RIR method by XRD, was obtained a quantitative value. The results of each round are shown in the column of quantitative values in Table 1.

  In addition, the brittleness was judged by examining whether the product collapsed when cut with scissors. Those that were easily broken when cut with scissors were considered defective, and those that did not collapse were considered good. The results of each round are shown in the column of the quality of the Al plating layer in Table 1.

The measurement conditions with the XRD apparatus were as follows.
・ X-ray used: Cu-Ka line focus ・ Excitation conditions: 45 kV, 40 mA
-Incident optical system: Mirror / slit: 1/4
・ Mask: 10mm
・ Sample stage: Open Eurelian cradle ・ Light receiving optical system: Flat collimator 0.27
Scanning method: θ-2θ scan Measurement range AlCl ₃ diffraction lines 101, 012 and 009:
2θ = 30 ° to 33 °, step width 0.04 °, integration time 40 sec,
Diffraction line of aluminum 111:
2θ = 37 ° -40 °, step width 0.04 °, integration time 5 sec,

From Table 1, it can be seen that when the quantitative value of Al ₄ C ₃ is low, it is a non-defective product, and when it is high, it is defective or slightly defective. From this result, the quantitative analysis of Al ₄ C ₃ using the RIR method by XRD makes it possible to quickly obtain data indicating the quality deterioration of the aluminum plating layer and the sign of poor quality as somewhat poor, and this quantitative analysis method can be used. It has been shown that the concentration of organic additives in the plating solution can be quickly and accurately prepared.

  As mentioned above, although this invention was demonstrated based on embodiment, this invention is not limited to the said embodiment. Various modifications can be made to the above-described embodiment within the same and equivalent scope as the present invention.

DESCRIPTION OF SYMBOLS 1 Substrate 2 Aluminum plating layer 3 Aluminum porous body 4 Plating solution tank 5 Plating solution 6 Temperature control device 7 Long substrate 8 Unwinding device 9 Winding device 10 Roller 11 Cathode 12 Anode 13 DC power supply 14 XRD device 15 Analysis device

Claims (7)

A method for producing an aluminum molded body having a plating step of depositing aluminum on a substrate in a plating solution,
The plating step is
An analysis step of quantifying aluminum carbide contained in the aluminum electrodeposited on the substrate using an RIR method by X-ray diffraction;
A plating solution adjusting step of adjusting the composition of the plating solution based on a value obtained by quantifying the aluminum carbide.   The method for producing an aluminum molded body according to claim 1, wherein the aluminum molded body is an aluminum porous body.   The method for producing an aluminum molded body according to claim 1, wherein the aluminum molded body is an aluminum wire.   The method for producing an aluminum molded body according to claim 1, wherein the aluminum molded body is an aluminum foil.   An aluminum analysis method for quantifying aluminum carbide in aluminum by X-ray diffraction (XRD) using an RIR method.   The aluminum analysis method according to claim 5, wherein the RIR method is performed based on a ratio of an integrated intensity in a range of 2θ of 37 to 40 ° in X-ray diffraction and an integrated intensity in a range of 2θ of 30 to 33 °. An aluminum plating system for continuously depositing aluminum on a long substrate,
A plating bath containing a plating solution using a molten salt of aluminum, a temperature control device for controlling the temperature of the plating solution to a predetermined temperature, and
A transport device for passing the substrate through the plating solution at a predetermined speed;
A power supply unit for energizing a predetermined amount of aluminum to be deposited on the substrate being transported in the plating solution;
An aluminum analysis unit that quantifies aluminum carbide in electrodeposited aluminum using an RIR method by X-ray diffraction (XRD), and adjustment of the composition of the plating solution based on the determination result by the analysis unit Aluminum plating system is performed.

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