Electroplating solution, preparation method thereof and method for electroplating radium

Abstract

The invention discloses an electroplating solution, a preparation method thereof and a radium electroplating method, the electroplating solution comprises barium ions, radium ions, acetate ions, sodium ions and ammonium ions, and the pH value of the electroplating solution is 4.5-6. By adopting the electroplating solution, efficient electroplating of a laser target can be realized, and the problems that barium laser cannot be electroplated, a plating layer is easy to fall off and is difficult to tolerate a high-temperature condition and the like in an electroplating treatment process are solved, so that an important target material is provided for subsequent actinide 225 irradiation laser preparation by an accelerator.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of medical isotope actinium 225 preparation, in particular, to an electroplating solution, a preparation method thereof and a method for electroplating radium. BACKGROUND

[0002] Targeted alpha therapy (TAT) is a kind of nuclear medicine treatment method based on alpha particle emitting radionuclide and tumor selective carrier molecule as a specific targeting cancer cell carrier, which is a very promising tumor treatment method. Actinium 225 (Ac-225) is one of the best choices of radionuclide in TAT due to its suitable half-life, unique decay properties, easy coordination and other characteristics.

[0003] At present, due to insufficient production capacity and a huge gap between supply and demand, the price of Ac-225 has been high for a long time. Therefore, although the potential of Ac-225 in treating advanced cancer has been confirmed by clinical trials, research work is still hindered, which seriously hinders the development of medical and health undertakings.

[0004] The nuclear reaction byproduct of the technical route for preparing Ac-225 by bombarding radium 226 (Ra-226) with a low-energy cyclotron is less, and basically no other isotopes of actinium will be produced except Ac-225, which is conducive to obtaining high-purity Ac-225, and is the most promising method for preparing medical Ac-225 at present. The biggest difficulty of this technical route is how to fix barium carbonate radium on the target for accelerator irradiation, and not to fall off during high-energy ray irradiation.

[0005] It should be noted that the above statements are only used to provide background technical information related to the present application, and do not necessarily constitute the prior art. SUMMARY

[0006] In the first aspect of the present application, an electroplating solution is provided, comprising: barium ions, radium ions, acetate ions, sodium ions and ammonium ions, and the pH of the electroplating solution is 4.5-6. In the electroplating solution, the sodium ions play a role in conducting electricity, the ammonium ions reduce the barium ions and radium ions to barium and radium, thereby forming a barium radium oxide target during electroplating, the acetate ions are weak acid ions and play a buffering role, which can maintain the system relatively stable and make the electroplating speed more appropriate; at the same time, if the pH is too low, electroplating cannot be carried out, and if the pH is too high, the electroplating speed is too fast, and when the pH is in the above range, the electroplating speed is moderate, which is conducive to efficiently, uniformly and firmly electroplating radium on the metal substrate target, and improves the problems of the barium radium in the electroplating process, such as being unable to be electroplated, the plated layer being easy to fall off and being difficult to resist high temperature conditions, thereby providing important target material for subsequent accelerator irradiation of radium to prepare actinium 225.

[0007] In addition, the electroplating solution according to the above embodiments of the present application can also have the following additional technical features:

[0008] In some embodiments of the present application, the concentration of the acetate ions is 0.72 g / L-2.88 g / L, the concentration of the sodium ions is 0.7 mg / L-2.8 mg / L, and the concentration of the ammonium ions is 2 mg / L-8 mg / L. In this way, it is conducive to maintaining the stability of the electroplating solution system and more efficient electroplating of radium.

[0009] In a second aspect of the present application, a method for preparing an electroplating solution is provided, comprising:

[0010] mixing barium radium carbonate, sodium acetate and ammonium acetate to obtain an electroplating salt;

[0011] adding the electroplating salt to water to obtain an electroplating salt solution;

[0012] adjusting the pH of the electroplating salt solution to 4.5-6 to obtain the electroplating solution.

[0013] The electroplating solution prepared by the above method is simple to operate, and the use of the electroplating solution is conducive to efficient, uniform and stable electroplating of dissolved barium radium carbonate onto a metal substrate target.

[0014] In some embodiments of the present application, the mass ratio of the ammonium acetate, the sodium acetate and the barium radium carbonate is 1000:(300-500):(1-6); in some specific examples of the present application, the mass ratio of the ammonium acetate, the sodium acetate and the barium radium carbonate is 1000:370:1.7. In this way, a stable electroplating solution formula can be obtained.

[0015] In some embodiments of the present application, the mass fraction of the electroplating salt is 1%-4% based on the total mass of the electroplating salt solution; in some specific examples of the present application, the mass fraction of the electroplating salt is 2.7%. In this way, the system of the electroplating solution is relatively stable.

[0016] In some embodiments of the present application, the mass fraction of the electroplating salt is 1%-4% based on the total mass of the electroplating solution. In this way, it is conducive to obtaining an electroplating solution with a suitable concentration, thereby improving the electroplating effect.

[0017] In some embodiments of the present application, nitric acid or hydrochloric acid is used to adjust the pH of the electroplating salt solution to 4.5-6; in some specific examples of the present application, the pH is 5. The pH of the electroplating solution in the above range is conducive to electroplating radium onto a metal substrate target, and maintains a relatively moderate electroplating speed, which is conducive to obtaining a uniform and dense plating layer.

[0018] In a third aspect of the present application, a method for electroplating radium is provided, which comprises: placing the electroplating solution of the first aspect of the present application or the electroplating solution prepared by the method of the second aspect of the present application in an electroplating bath, taking a metal substrate target as a cathode, taking platinum as an anode, and connecting a direct current for electroplating treatment. In this way, efficient electroplating of radium targets can be achieved, which is conducive to solving the problems of the inability of barium and radium to be electroplated, the easy peeling of the plating layer, and the inability to withstand high temperature conditions during the electroplating process.

[0019] In some embodiments of the present application, the metal substrate target comprises at least one of gold, silver, copper, and aluminum. In this way, the metal substrate target can be selected from a wider range, and can be used in a wider range.

[0020] In some embodiments of the present application, the electroplating treatment time is 6-7 hours. In this way, the electroplating efficiency can be improved, and a more uniform, firm, and dense radium-barium oxide target can be obtained.

[0021] In some embodiments of the present application, the voltage of the direct current is 7-10 V; in some specific examples of the present application, the voltage of the direct current is 8 V. In this way, a more uniform, firm, and dense radium-barium oxide target can be obtained. BRIEF DESCRIPTION OF DRAWINGS

[0022] The above and / or additional aspects and advantages of the present application will become apparent and be readily understood from the following description, taken in conjunction with the following drawings, in which:

[0023] Figure 1 A surface morphology diagram of the radium-barium oxide obtained in Example 1 of the present application.

[0024] Figure 2 A result diagram of the scratch test of the radium-barium oxide obtained in Example 1 of the present application. DETAILED DESCRIPTION

[0025] The embodiments of the present application are described in detail below, and examples of the embodiments are shown in the accompanying drawings, but there will be cases where unnecessary detailed descriptions are omitted. For example, there will be cases where detailed descriptions of matters known well, repeated descriptions of substantially the same structures are omitted. This is to avoid the following description from becoming unnecessarily lengthy and to facilitate understanding by those skilled in the art. In addition, the accompanying drawings and the following description are provided so that those skilled in the art can fully understand the present application, and are not intended to limit the subject matter recited in the claims.

[0026] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; the terminology used in the specification is for describing particular embodiments only and is not intended to be limiting of the application; and any parameters recited are only approximations, unless otherwise specified. Unless otherwise specified, any parameters recited are approximations.

[0027] The terms "comprising" and "having," and any variations thereof, as used in the specification and claims, are open-ended, that is, they mean "including, but not limited to," and allow for equivalents.

[0028] In the description of the application, all numbers disclosing amounts, amounts, and other such quantities are approximate. Unless otherwise specified, the exact number can vary from that indicated about 10%, or as understood by one of ordinary skill in the art to be reasonable under the circumstances.

[0029] The ranges disclosed herein are defined by the endpoints as they are presented in the specification and claims. The endpoints are included in the ranges. The ranges are inclusive of the endpoints. The ranges are also inclusive of any points or values between the endpoints. The ranges are also inclusive of any points or values that fall within the scope of the ranges. For example, if a range is indicated as 60-120 and 80-110, it is understood that the ranges 60-110 and 80-120 are also contemplated. Furthermore, if a minimum range value of 1 and 2 is indicated, and a maximum range value of 3, 4, and 5 is indicated, then the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In the present application, a numerical range "a-b" indicates a shorthand way of describing each and every number that is contained in the range, wherein a and b are both real numbers. For example, the numerical range "0-5" indicates that all real numbers between 0 and 5 have been listed herein, and "0-5" is a shorthand way of describing those numerical combinations. Additionally, when a parameter is stated to be an integer ≥ 2, it is equivalent to disclose that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0030] In the description of the application, "A and / or B" can include any one of A alone, B alone, and A and B, where A and B are used only for example, and can be any technical features connected by "and / or" in the present application.

[0031] In the present application, the order of writing each step does not mean a strict execution order and constitute any limitation to the implementation process, and the specific execution order of each step should be determined by its function and possible inherent logic. If not specifically stated, all steps of the present application can be performed in sequence or randomly, and the preferred order is sequential. For example, the method comprises steps (a) and (b), which means that the method can comprise steps (a) and (b) performed in sequence, or steps (b) and (a) performed in sequence. For example, the method also comprises step (c), which means that step (c) can be added to the method in any order, for example, the method can comprise steps (a), (b) and (c), or steps (a), (c) and (b), or steps (c), (a) and (b), etc.

[0032] If not specifically stated, all embodiments and optional embodiments of the present application can be combined to form new technical solutions.

[0033] If not specifically stated, all technical features and optional technical features of the present application can be combined to form new technical solutions.

[0034] In the technical route of preparing Ac-225 by bombarding Ra-226 in a low-energy cyclotron, the biggest difficulty is to fix barium carbonate radium on the target for accelerator irradiation, and not to fall off during high-energy ray irradiation. Electroplating is the main method to fix barium carbonate radium on the metal substrate target of the accelerator. However, due to the lack of a suitable electroplating solution formula, problems such as the inability of barium radium to be electroplated, the easy falling off of the plating layer, and the inability to withstand high temperature conditions often occur during electroplating.

[0035] In the first aspect of the present application, the present application provides an electroplating solution, comprising: barium ions, radium ions, acetate ions, sodium ions and ammonium ions, and the pH of the electroplating solution is 4.5-6. In the electroplating solution, the sodium ions serve as conductive ions, the ammonium ions reduce the barium ions and radium ions to barium and radium, thereby facilitating the formation of a barium radium oxide target during electroplating, the acetate ions are weak acid ions and have a buffering effect, which can maintain a relatively stable state of the reaction system and make the electroplating treatment speed more appropriate; at the same time, if the pH is too low, electroplating cannot be performed, if the pH is too high, the electroplating speed is too fast, and when the pH is within the above range, the electroplating speed is moderate, which is conducive to efficiently, uniformly and firmly electroplating barium and radium onto the metal substrate target, and improves the problems of the inability of barium and radium to be electroplated, the easy falling off of the plating layer, and the difficulty in withstanding high temperature conditions during the electroplating process, thereby providing important target material for subsequent accelerator irradiation of radium to prepare actinium 225.

[0036] In addition, the electroplating solution according to the above embodiments of the present application can also have the following additional technical features:

[0037] In some embodiments of the present application, the concentration of acetate ions is 0.72 g / L-2.88 g / L (such as 0.72 g / L, 0.8 g / L, 1 g / L, 1.3 g / L, 1.5 g / L, 1.8 g / L, 2 g / L, 2.4 / L or 2.88 g / L, etc.), the concentration of sodium ions is 0.7 mg / L-2.8 mg / L (such as 0.7 mg / L, 1 mg / L, 1.3 mg / L, 1.5 mg / L, 1.8 mg / L, 2 mg / L, 2.3 mg / L, 2.5 mg / L or 2.8 mg / L, etc.), and the concentration of ammonium ions is 2 mg / L-8 mg / L (such as 2 mg / L, 4 mg / L, 6 mg / L or 8 mg / L, etc.). The ion concentration in the above range is conducive to maintaining the stability of the electroplating solution system, thereby more efficiently electroplating radium.

[0038] In a second aspect of the present application, a method for preparing an electroplating solution is provided, comprising:

[0039] S1: mixing barium radium carbonate, sodium acetate and ammonium acetate to obtain an electroplating salt.

[0040] Specifically, the barium radium carbonate, sodium acetate and ammonium acetate can be mixed in a certain proportion, and the order of addition is not specifically limited, which can be selected flexibly by those skilled in the art. In addition, the form of the barium radium carbonate raw material can be a solution or a powder. When the barium radium carbonate is in a powder form, it can be first dissolved in a weak acid and then subjected to the subsequent mixing step.

[0041] In some embodiments of the present application, the mass ratio of ammonium acetate, sodium acetate and barium radium carbonate is 1000:(300-500):(1-6), for example, it can be 1000:300:1, 1000:300:3, 1000:300:6, 1000:400:1, 1000:400:6, 1000:500:1, 1000:500:3 or 1000:500:6, etc.; in some specific examples of the present application, the mass ratio of ammonium acetate, sodium acetate and barium radium carbonate is 1000:370:1.7. The mass ratio in the above range is conducive to obtaining a stable electroplating solution formula.

[0042] S2: adding the electroplating salt to water to obtain an electroplating salt solution.

[0043] In some embodiments of the present application, the mass fraction of the electroplating salt is 1%-4% based on the total mass of the electroplating salt solution, for example, it can be 1%, 2%, 3% or 4%, etc.; in some specific examples of the present application, the mass fraction of the electroplating salt is 2.7%. Thus, the system of the electroplating solution is relatively stable.

[0044] S3: adjusting the pH of the electroplating salt solution to 4.5-6 to obtain an electroplating solution.

[0045] In some embodiments of the present application, nitric acid or hydrochloric acid is used to adjust the pH of the electroplating salt solution to 4.5-6, for example, it can be 4.5, 4.8, 5, 5.2, 5.5, 5.8 or 6, etc.; in some specific examples of the present application, the pH is 5. The pH of the electroplating solution in the above range is conducive to electroplating radium onto the metal substrate target and keeping the electroplating speed moderate, which is conducive to obtaining a uniform and dense coating.

[0046] In some embodiments of the present application, the mass fraction of the electroplating salt is 1%-4% based on the total mass of the electroplating solution, for example, it can be 1%, 2%, 3% or 4%, etc. In this way, it is conducive to obtaining an electroplating solution with appropriate concentration, thereby improving the electroplating effect.

[0047] The present application prepares the electroplating solution by the above method, which is simple in operation process. Using the electroplating solution for electroplating treatment is conducive to efficiently, uniformly and stably electroplating the dissolved barium carbonate radium onto the metal substrate target.

[0048] In the third aspect of the present application, a method for electroplating radium is provided, which comprises: placing the electroplating solution of the first aspect of the present application or the electroplating solution prepared by the method of the second aspect of the present application in an electroplating cell, taking a metal substrate target as a cathode, platinum as an anode, and connecting a direct current for electroplating treatment. In this way, efficient electroplating of radium target can be achieved, which is conducive to solving the problems of the inability of barium radium to be electroplated, the easy peeling of the coating, and the inability to withstand high temperature conditions during electroplating treatment.

[0049] In some embodiments of the present application, the metal substrate target comprises at least one of gold, silver, copper and aluminum. In this way, the metal substrate target has a wider range of options and a wider range of uses.

[0050] In some embodiments of the present application, the electroplating treatment time is 6h-7h, for example, it can be 6h, 6.2h, 6.4h, 6.6h, 6.8h or 7h, etc. In this way, the electroplating efficiency can be improved, and a more uniform, firm and dense radium barium oxide target can be obtained.

[0051] In some embodiments of the present application, the voltage of the direct current is 7V-10V, for example, it can be 7V, 8V, 9V or 10V; in some specific examples of the present application, the voltage of the direct current is 8V. As an example, the voltage can be first adjusted to 5V, electroplating treatment for 5-10 minutes, then the voltage is adjusted to 6V, electroplating treatment for 5-10 minutes, then the voltage is adjusted to 7V, electroplating treatment for 5-10 minutes, and finally the voltage is adjusted to 8V, electroplating treatment for 6-7 hours. In this way, by selecting an appropriate voltage, the electroplating speed is moderate, the coating is more firm, and a more uniform, firm and dense radium barium oxide target can be obtained.

[0052] The above description of various embodiments tends to emphasize differences between the various embodiments, and the same or similar parts can be mutually referred to for brevity, which will not be repeated herein.

[0053] The scheme of the present application will be described below through specific examples. It should be noted that the following examples are only used to illustrate the present application, and should not be regarded as limiting the scope of the present application. If the specific technology or condition is not specified in the examples, it is performed according to the technology or condition described in the literature in the art or according to the product manual. If the reagent or instrument is not specified by the manufacturer, it is a conventional product that can be obtained by purchase.

[0054] Example 1

[0055] (1) Ammonium acetate, sodium acetate, barium radium carbonate were mixed in a mass ratio of 1000:370:1.7 to obtain a plating salt;

[0056] (2) The plating salt was dissolved in deionized water to obtain a plating salt solution with a salt content of 2.7%;

[0057] (3) The pH value of the plating salt solution was adjusted to 5 using nitric acid to obtain a plating solution;

[0058] (4) The plating solution was poured into a specific plating cell, with a copper-based target as the cathode and platinum gold as the anode, and a direct current of 8V was connected for plating;

[0059] (5) After plating for 6 hours, a dense and uniform radium barium oxide target was obtained.

[0060] Example 2

[0061] The difference from Example 1 is:

[0062] (3) The pH value of the plating salt solution is 4.5.

[0063] Example 3

[0064] The difference from Example 1 is:

[0065] (3) The pH value of the plating salt solution is 6.

[0066] Example 4

[0067] The difference from Example 1 is:

[0068] (1) The mass ratio of ammonium acetate, sodium acetate, barium radium carbonate is 1000:300:1.

[0069] Example 5

[0070] The difference from Example 1 is:

[0071] (1) The mass ratio of ammonium acetate, sodium acetate, and barium carbonate radium is 1000:500:6.

[0072] Example 6

[0073] The difference from Example 1 is that:

[0074] (2) The electroplating salt is dissolved in deionized water to obtain an electroplating salt solution with a salt content of 4%.

[0075] Example 7

[0076] The difference from Example 1 is that:

[0077] (2) The electroplating salt is dissolved in deionized water to obtain an electroplating salt solution with a salt content of 4%.

[0078] Example 8

[0079] The difference from Example 1 is that:

[0080] (5) The electroplating time is 7 hours.

[0081] Example 9

[0082] The difference from Example 1 is that: Direct current of 10V is connected for electroplating.

[0083] Example 10

[0084] The difference from Example 1 is that: Direct current of 7V is connected for electroplating.

[0085] Comparative Example 1

[0086] The difference from Example 1 is that: There is no ammonium acetate in the electroplating salt.

[0087] Comparative Example 2

[0088] The difference from Example 1 is that: There is no sodium acetate in the electroplating salt.

[0089] Comparative Example 3

[0090] The difference from Example 1 is that:

[0091] (3) The pH value of the electroplating salt solution is 3.

[0092] Comparative Example 4

[0093] The difference from Example 1 is that:

[0094] (3) The pH value of the electroplating salt solution is 8.

[0095] Test method:

[0096] (1) Morphology characterization:

[0097] The morphology of the plating layer after electroplating can be observed by scanning electron microscopy after magnification, and the element composition can be obtained qualitatively by spectrum analysis.

[0098] (2) Scratch test:

[0099] The scratch test can determine whether the plating layer is reliably attached to the surface of the substrate. The length of the copper substrate drawn by the scratch test can be used to quantitatively compare the adhesion ability of different samples. The greater the length, the more firmly the plating layer is attached.

[0100] From Figure 1 It can be seen that the electroplating solution of the present application is used for electroplating to obtain a dense and uniform plating layer. Figure 2 The photo of the plating layer of Example 1 after the scratch test shows that the length of the copper substrate drawn by the scratch test of Examples 1-10 (under the same force application speed and movement speed conditions) is 70 microns, 65 microns, 63 microns, 68 microns, 68 microns, 52 microns, 54 microns, 53 microns, 60 microns and 60 microns, respectively; and the length of the copper substrate drawn by the scratch test of Comparative Examples 1-4 (under the same force application speed and movement speed conditions) is 20 microns, 15 microns, 22 microns and 16 microns, respectively. This shows that the plating layer obtained by electroplating using the electroplating solution of the present application is relatively firm. Therefore, the electroplating solution of the present application can be used to efficiently electroplate the dissolved barium radium carbonate onto the copper substrate target, thereby providing important target material for subsequent accelerator irradiation of radium to prepare actinium 225.

[0101] It should be noted that the present application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are only examples, and embodiments having the same technical idea and playing the same role and effect within the scope of the technical solution of the present application are all included in the technical scope of the present application. In addition, within the scope of the main idea of the present application, various modifications that can be thought of by those skilled in the art, and other ways constructed by combining part of the components of the embodiments are also included in the scope of the present application.

Claims

1. An electroplating solution, characterized in that include: Barium ions, radium ions, acetate ions, sodium ions and ammonium ions, and the pH of the electroplating solution is 4.5-6.

2. The electroplating solution according to claim 1, wherein The concentration of the acetate ion is 0.72 g / L-2.88 g / L, the concentration of the sodium ion is 0.7 mg / L-2.8 mg / L, and the concentration of the ammonium ion is 2 mg / L-8 mg / L.

3. A method for preparing the electroplating solution according to any one of claims 1 to 2, characterized in that: include: Mix barium radium carbonate, sodium acetate, and ammonium acetate to make electroplating salt; adding the electroplating salt to water to obtain an electroplating salt solution; The pH of the electroplating salt solution is adjusted to 4.5-6 to obtain the electroplating solution.

4. The method according to claim 3, characterized in that The mass ratio of the ammonium acetate, the sodium acetate, and the barium radium carbonate is 1000:(300-500):(1-6), preferably 1000:370:1.

7.

5. The method according to claim 3 or 4, characterized in that Based on the total mass of the electroplating salt solution, the mass fraction of the electroplating salt is 1%-4%, preferably 2.7%.

6. The method according to claim 3 or 5, characterized in that Based on the total mass of the electroplating solution, the mass fraction of the electroplating salt is 1%-4%.

7. The method according to claim 3 or 4, characterized in that The pH of the electroplating salt solution is adjusted to 4.5-6 using nitric acid or hydrochloric acid, and the pH is preferably 5.

8. A method for electroplating radium, characterized in that: include: The electroplating solution according to any one of claims 1 to 2 or the electroplating solution prepared by the method according to any one of claims 3 to 7 is placed in an electroplating cell, and a metal substrate target is used as a cathode and platinum is used as an anode, and direct current is connected for electroplating.

9. The method according to claim 8, characterized in that The metal matrix target comprises at least one of gold, silver, copper and aluminum.

10. The method according to claim 8 or 9, characterized in that The electroplating treatment time is 6h-7h; and / or, The voltage of the direct current is 7V-10V, preferably 8V.

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