High purity manganese and method for producing same

Abstract

High purity manganese having a purity of 3N (99.9%) or more, wherein number of non-metal inclusions with a size of 0.5 μm or more is 50000 or less per 1 g of the high purity manganese. A method for producing high purity manganese, wherein refining is performed using a raw material (secondary raw material) obtained by acid-washing a manganese raw material (primary raw material) so that the produced high purity manganese has a purity of 3N (99.9%) or more, and number of non-metal inclusions with a size of 0.5 μm or more is 50000 or less per 1 g of the high purity manganese. The present invention provides a method for producing high purity metal manganese from commercially available manganese, and aims to obtain high purity metal manganese having a low LPC.

Claims

1. A method for producing a high purity manganese, comprising a refining process performed by the steps of: acid-washing a manganese primary raw material having a purity of 2N or higher to remove contaminants and a layer of oxides from a surface thereof to obtain a secondary raw material; leaching manganese with an acid from the secondary raw material to produce an acid leachate such that an amount of 1% or more of the secondary raw material remains undissolved within the acid leachate after said leaching step; performing electrolysis using the acid leachate as an electrolytic solution on a cathode side of the electrolysis to obtain a manganese deposit; and melting the manganese deposit in an inert atmosphere of a reduced pressure of 0.01 to 750 torr to eliminate impurities as slag and to obtain a cast ingot of high purity manganese having a purity of 3N (99.9%) or higher and containing a dispersion of foreign substances of non-metal inclusions with a size of 0.5 μm or larger in a number of 50000 or less per 1 g of the high purity manganese.

2. The method according to claim 1, wherein, during said melting step, a deoxidizing agent having a stronger active potency than Mn is added to the manganese deposit and wherein the slag is concentrated on an upper part of the ingot.

3. The method according to claim 2, wherein the deoxidizing agent is La, Ca or Mg.

4. The method according to claim 1, further comprising the step of washing the manganese deposit with diluted nitric acid.

5. The method for producing high purity manganese according to claim 1, wherein the amount of the secondary raw material remaining undissolved in the acid leachate is 1 to 50%.

6. The method according to claim 5, wherein, during said melting step, a deoxidizing agent having a stronger active potency than Mn is added to the manganese deposit and wherein the slag is concentrated on an upper part of the ingot.

7. The method according to claim 6, wherein the deoxidizing agent is La, Ca or Mg.

8. The method according to claim 6, further comprising the step of washing the manganese deposit with diluted nitric acid.

Description

DETAILED DESCRIPTION

(1) Embodiments of the present invention are now explained in detail.

(2) With the method for producing high purity manganese according to the present invention, it was discovered that a commercially available manganese raw material having a purity of 2N level has numerous impurities and foreign substances deposited thereon, and the acid washing of the surface of the manganese raw material is effective for reducing impurities and non-metal inclusions. Any method may be used so as long as it is possible to eliminate the surface deposits and oxidized surface layer on the raw material manganese. As the acid, used may be nitric acid, sulfuric acid, hydrochloric acid or a mixed acid thereof.

(3) Moreover, with the method for producing high purity manganese according to the present invention, since MnS, MnO, MnC and foreign substances (non-metal inclusions such as SiO.sub.2) remain on the surface of a commercially available manganese raw material having a purity level of 2N, the manganese raw material is acid-washed to eliminate these impurities. While the manganese raw material is subsequently dissolved in acid, the dissolution is performed so that 1 to 50% of raw material manganese will remain, and more preferably so that 10 to 30% of raw material manganese will remain.

(4) When raw material manganese is caused to remain in the solution as described above, the productivity will deteriorate by that much and, therefore, is not normally implemented (not noticed). Nevertheless, it was discovered that, by causing raw material manganese to remain in the solution as described above, it is possible to effectively reduce foreign substances, which are non-metal inclusions with a size of 0.5 μm or more.

(5) The reason for this has been discovered to be a phenomenon where the impurities, which are nobler than the manganese in the solution, are adsorbed to the remaining manganese and eliminated. Moreover, the remaining manganese functions as a filter, and eliminates the foreign substances. When the remaining manganese is less than 1%, the foregoing refining effect is not yielded. In the foregoing case, metal manganese may be newly added. Similarly effects can thereby be exhibited.

(6) Since the productivity will not be considerably affected so as long as the remaining raw material manganese is 50% or less, the preferred range of the remaining raw material manganese is 1 to 50%. The productivity is considerably affected if the remaining raw material manganese exceeds 50%.

(7) Nevertheless, the present invention does not deny causing the manganese content to remain beyond 50%, and such residual amount of manganese may be adopted as needed. The greater the residual amount of manganese, the higher the refining effect.

(8) High purity manganese is obtained from this solution via electrolysis. In addition, it is possible to produce high purity Mn by melting the manganese under reduced pressure in an inert atmosphere and eliminating impurities as slag. The expression “under mildly reduced pressure in an inert atmosphere” refers to an atmosphere of argon, helium or the like having a level of 0.01 to 750 torr. It is more effective to add La, Ca, Mg or the like to the melting manganese as a deoxidizing agent, which has stronger deoxidizing activity than Mn. With this melting and succeeding casting, impurities are condensed into a top part of the cast ingot to form slag, which can be removed from the ingot.

(9) A commercially available Mn raw material is acid-washed and the manganese is acid-leached as described above. By performing electrolysis using the resultant leachate as an electrolytic solution and melting the resultant cathode-deposited manganese, it is possible to produce manganese having a purity of 4N (99.99%) or more.

(10) Moreover, based on the foregoing processes, it is possible to cause the number of foreign substances, which are non-metal inclusions with a size of 0.5 μm or more, to be 50000 or less per 1 g of the high purity manganese. Note that these non-metal inclusions can be measured as an insoluble residual particle count (LPC).

(11) In other words, it is possible to produce manganese in which the number of foreign substances with a size of 0.5 μm or more is 50000 or less per 1 g of the high purity manganese based on the insoluble residual particle count (LPC), and further possible to produce manganese in which the number of foreign substances (non-metal inclusions) with a size of 0.5 μm or more is 10000 or less per 1 g of the high purity manganese based on the insoluble residual particle count (LPC).

(12) The insoluble residual particle count (LPC) is a parameter that is valued as one of the methods for evaluating the metal raw material for electronic devices, and refers to the insoluble residual particle count that is detected upon dissolving metal in acid, and extremely favorable correlation is acknowledged between such LPC value and electronic material quality; specifically, between such LPC value and the defect ratio of sputter deposition, including the generation of particles upon sputtering a sputtering target.

(13) Note that the insoluble residual particle count is abbreviated as “LPC” because a Liquid Particle Counter (LPC) is used for measuring the insoluble residual particle count (LPC).

(14) To specifically explain this measurement method, 5 g of a sample is collected, slowly dissolved in 200 cc of acid so that the inclusions do not dissolve therein, and further diluted with ultrapure water up to 500 cc, and 10 cc is extracted therefrom to measure with the Liquid Particle Counter. For example, if the number of inclusions is 1000 inclusions/cc, since 0.1 g of the sample is measured in 10 cc, the number of inclusions will be 10000 inclusions/g.

EXAMPLES

(15) The present invention is now explained with reference to the following Examples and Comparative Examples. However, these Examples and Comparative Examples are described for facilitating the understanding of the invention, and the present invention shall not be limited to these Examples or Comparative Examples.

Example 1

(16) Commercially available manganese having a purity of 2N (99%) was used as the starting raw material.

(17) The manganese raw material was washed in a nitric acid solution. In addition, while the manganese is leached in hydrochloric acid, such leaching was performed by causing 1% of the raw material manganese (metal) to remain in the solution. Electrolysis was performed by placing this solution on the cathode side. When the manganese obtained from the foregoing electrolysis was melted at 1300° C. at 500 torr in an Ar atmosphere, the yield of the normal part was 73%.

(18) Subsequently, 5 g of Mn was dissolved in hydrochloric acid, diluted with ultrapure water up to 500 cc, and 10 cc was extracted therefrom and measured. Consequently, the number of non-metal inclusions (foreign substances) per 1 g of the manganese was 49800. The purity level was 3N.

Example 2

(19) Manganese (primary raw material) having a purity of 2N (99%) was used as the starting raw material.

(20) The manganese raw material was washed in a sulfuric acid solution. In addition, while the manganese is leached in hydrochloric acid, such leaching was performed by causing 50% of the raw material manganese (metal) to remain in the solution.

(21) Electrolysis was performed by placing this solution on the cathode side, Subsequently, the obtained manganese was melted at 1280° C. under a reduced pressure of 1 torr in an Ar gas atmosphere. Consequently, slag was condensed at the upper part of the ingot.

(22) The yield of the normal part was 82%. Consequently, the number of non-metal inclusions (foreign substances) per 1 g of the manganese was 9500. The purity level was 4N.

Example 3

(23) The 3N manganese obtained in Example 1 was used as the starting raw material, this was used as the anode to perform electrolysis in a hydrochloric acid solution, and electrolytic Mn having a purity level of 4N was thereby produced.

(24) In addition, since foreign substances still remained on the electrodeposited surface, the electrodeposited surface was washed in diluted nitric acid to eliminate impurities and the like, and the manganese was thereafter melted at 10 torr in an Ar atmosphere with a molten metal holding time of 30 minutes. Based on this melting, it was possible to eliminate the slag portion formed at the upper part of the ingot, and obtain high purity Mn of 5N (99.999%).

(25) This product was able to satisfy the conditions of the present invention. Consequently, the number of non-metal inclusions (foreign substances) per 1 g of the manganese was 5900.

Example 4

(26) Commercially available manganese (primary raw material) having a purity of 2N (99%) was used as the starting raw material. The manganese raw material was washed in a diluted sulfuric acid solution.

(27) Subsequently, the manganese raw material was acid-leached so as to cause approximately 20% of raw material manganese (metal) to remain in the solution. Subsequently, electrolysis was performed using a sulfuric acid solution as the solution of the anode, and the acid-leached solution as the solution of the cathode. The electrolytic manganese was melted at 1280° C. under a reduced pressure of 20 torr in an Ar gas atmosphere. Here, Mg was added in order to efficiently extract oxygen. Consequently, slag was condensed at the upper part of the ingot.

(28) The yield of the normal part was 82%. Consequently, the number of non-metal inclusions (foreign substances) per 1 g of the manganese was 5300. The purity level was 3N.

(29) The Comparative Examples are now explained.

Comparative Example 1

(30) The raw material was the same as Example 1, and the commercially available manganese was directly melted at 1300° C. under mildly reduced pressure of several torr. Consequently, a large amount of slag was generated, and the yield was 38%. The LPC of the produced manganese was 121000, and extremely high. The purity level was 2N.

Comparative Example 2

(31) The raw material was the same as Example 1, and the entire amount of manganese was leached in a sulfuric acid solution without acid-washing the manganese. The solution was electrolyzed to obtain electrolytic manganese. The manganese was directly melted at 1300° C. under mildly reduced pressure of approximately 10 torr. Consequently, a large amount of slag was generated, and the yield was 51%. The LPC of the produced manganese was 52100, and extremely high. The purity level was 2N5.

(32) According to the present invention, it is possible to achieve the following effects.

(33) (1) At the stage of the raw material, it is possible to obtain high purity metal manganese with few non-metal inclusions; that is, number of foreign substances with a size of 0.5 μm or more is 50000 or less per 1 g of the high purity manganese (number of foreign substances with a size of 0.5 μm or more, as the insoluble residual particle count (LPC), is 50000 or less per 1 g of the high purity manganese).
(2) High purity manganese can be produced with a general-purpose furnace without using a special device, and high purity manganese can be obtained at a lower cost and higher yield in comparison to the conventional distillation method.

(34) Since the significant effects described in (1) and (2) can be obtained, the present invention is useful as: metal manganese for use as a wiring material, an electronic component material of a magnetic material (magnetic head) or the like, and a semiconductor component material; and a metal manganese thin film, and is particularly useful as high purity manganese for use as a sputtering target material for forming a manganese-containing thin film.