Highly dense tungsten alloy and method for manufacturing the same

Abstract

The application discloses a kind of high-density tungsten alloys, the high-density tungsten alloy is tungsten powder, nano zirconium oxide, nano Sc powder composite modifier, yttrium oxide modified shell polysaccharide composite coupling agent liquid is prepared according to weight ratio (19-21):1:(2-5):(14-16) modification preparation.The tungsten alloy of the application is mainly tungsten powder, nano zirconium oxide, by adding nano Sc powder composite modifier is matched and improved, by yttrium oxide modified shell polysaccharide composite coupling agent liquid treatment optimization, the interface between raw materials is enhanced, the strength, toughness of product is improved, raw materials are matched and combined mutually, strength, toughness is coordinated and improved, with excellent improvement efficiency.

Description

Technical Field

[0001] This invention relates to the field of tungsten alloy technology, specifically to a high-density tungsten alloy and its preparation method. Background Technology

[0002] Tungsten alloys are alloys composed of tungsten as the base material and other elements. Among metals, tungsten has the highest melting point, excellent high-temperature strength and creep resistance, as well as good thermal conductivity, electrical conductivity, and electron emission properties. It also has a high specific gravity. In addition to being widely used in the manufacture of cemented carbides and as an alloying additive, tungsten and its alloys are widely used in the electronics and electric light source industries. They are also used in aerospace, casting, and weaponry sectors to make rocket nozzles, die-casting molds, armor-piercing projectile cores, contacts, heating elements, and heat shields.

[0003] Existing tungsten alloys suffer from a mismatch between strength and toughness, making it difficult to achieve a synergistic improvement. Therefore, this invention provides a high-density tungsten alloy and its preparation method. Summary of the Invention

[0004] In view of the deficiencies of the prior art, the purpose of this invention is to provide a high-density tungsten alloy and its preparation method, so as to solve the problems mentioned in the background art.

[0005] The present invention solves the technical problem by adopting the following technical solution:

[0006] This invention provides a high-density tungsten alloy, which is prepared by mixing tungsten powder, nano-zirconia, nano-Sc powder composite modifier, and yttrium oxide modified chitosan composite coupling agent in a weight ratio of (19-21):1:(2-5):(14-16).

[0007] Preferably, the particle size of the tungsten powder is 0.5-1.0 μm.

[0008] Preferably, the modification method of the nano-Sc powder composite modifier is as follows:

[0009] S01: Add Sc powder to 3-6 times the amount of hydrochloric acid solution, then add 2-5% sodium dodecyl sulfate and 1-5% sodium oxalate of the total amount of Sc powder, stir evenly to obtain Sc powder treatment solution;

[0010] S02: Add Si powder to 2-3 times the amount of sodium alginate solution and stir evenly. Then add 5-10% sodium phenolsulfonate and 1-5% pentadecylphenol of the total amount of Si powder and stir thoroughly to obtain Si powder preparation solution.

[0011] S03: The Si powder preparation solution and Sc powder treatment solution are stirred and reacted at a weight ratio of 1:7. After stirring, the mixture is washed with water and dried to obtain the nano-Sc powder composite modifier.

[0012] Preferably, the hydrochloric acid solution has a mass fraction of 5-10%; the sodium alginate solution has a mass fraction of 10-20%.

[0013] Preferably, the stirring speed of the stirring reaction treatment is 500-1000 r / min, the stirring time is 20-30 min, and the stirring temperature is 55-65℃.

[0014] Preferably, the preparation method of the yttrium oxide-modified chitosan composite coupling agent solution is as follows:

[0015] S11: Add yttrium oxide to 20-30 parts of deionized water and stir well. Then add phosphate buffer solution to adjust the pH to 5.0. Then add 2-5 parts of silane coupling agent and stir well.

[0016] S12: Add chitosan to 2-3 times the volume of sulfuric acid aqueous solution, then add stearic acid at 2-5% of the total amount of chitosan, and stir thoroughly;

[0017] S13: Mix the products of S12 and S11 at a weight ratio of 2:6 until fully stirred to obtain a yttrium oxide-modified chitosan composite coupling agent solution.

[0018] Preferably, the pH value of the phosphate buffer solution is 5.0-6.0.

[0019] Preferably, the silane coupling agent is coupling agent KH560; the mass fraction of the sulfuric acid aqueous solution is 10-20%.

[0020] This invention provides a method for preparing a high-density tungsten alloy, comprising the following steps: tungsten powder, nano-zirconia, and nano-Sc powder composite modifier raw materials are sequentially stirred and mixed thoroughly, then added to a yttrium oxide-modified chitosan composite coupling agent solution for stirring and modification, finally washed with water and dried, added to a mold for pressing and molding, with a pressing pressure of 20-30 MPa and a pressing time of 5-10 min. After pressing, hot-pressing and sintering is carried out at 1310-1320℃ for 1-2 h at a sintering pressure of 3-4 MPa. After sintering, the tungsten alloy of this invention is obtained.

[0021] Preferably, the stirring speed for the stirring modification is 550-650 r / min, and the stirring time is 20-30 min.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] This invention relates to a tungsten alloy using tungsten powder and nano-zirconia as the main agents. It is further improved by adding nano-Sc powder composite modifier and by optimizing the liquid treatment with yttrium oxide-modified chitosan composite coupling agent. This enhances the interfacial properties between the raw materials and improves the strength and toughness of the product. The synergistic combination of the raw materials results in coordinated improvement of strength and toughness, exhibiting excellent improvement efficiency. Detailed Implementation

[0024] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to specific examples. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0025] This embodiment describes a high-density tungsten alloy, which is prepared by mixing tungsten powder, nano-zirconia, nano-Sc powder composite modifier, and yttrium oxide modified chitosan composite coupling agent in a weight ratio of (19-21):1:(2-5):(14-16).

[0026] The tungsten powder in this embodiment has a particle size of 0.5-1.0 μm.

[0027] The modification method of the nano-Sc powder composite modifier in this embodiment is as follows:

[0028] S01: Add Sc powder to 3-6 times the amount of hydrochloric acid solution, then add 2-5% sodium dodecyl sulfate and 1-5% sodium oxalate of the total amount of Sc powder, stir evenly to obtain Sc powder treatment solution;

[0029] S02: Add Si powder to 2-3 times the amount of sodium alginate solution and stir evenly. Then add 5-10% sodium phenolsulfonate and 1-5% pentadecylphenol of the total amount of Si powder and stir thoroughly to obtain Si powder preparation solution.

[0030] S03: The Si powder preparation solution and Sc powder treatment solution are stirred and reacted at a weight ratio of 1:7. After stirring, the mixture is washed with water and dried to obtain the nano-Sc powder composite modifier.

[0031] In this embodiment, the hydrochloric acid solution has a mass fraction of 5-10%, and the sodium alginate solution has a mass fraction of 10-20%.

[0032] In this embodiment, the stirring speed for the stirring reaction process is 500-1000 r / min, the stirring time is 20-30 min, and the stirring temperature is 55-65℃.

[0033] The preparation method of the yttrium oxide modified chitosan composite coupling agent solution in this embodiment is as follows:

[0034] S11: Add yttrium oxide to 20-30 parts of deionized water and stir well. Then add phosphate buffer solution to adjust the pH to 5.0. Then add 2-5 parts of silane coupling agent and stir well.

[0035] S12: Add chitosan to 2-3 times the volume of sulfuric acid aqueous solution, then add stearic acid at 2-5% of the total amount of chitosan, and stir thoroughly;

[0036] S13: Mix the products of S12 and S11 at a weight ratio of 2:6 until fully stirred to obtain a yttrium oxide-modified chitosan composite coupling agent solution.

[0037] The pH value of the phosphate buffer solution in this embodiment is 5.0-6.0.

[0038] In this embodiment, the silane coupling agent is coupling agent KH560; the mass fraction of the sulfuric acid aqueous solution is 10-20%.

[0039] The preparation method of a high-density tungsten alloy according to this embodiment includes the following steps: tungsten powder, nano-zirconia, and nano-Sc powder composite modifier raw materials are stirred and mixed in sequence until fully mixed. Then, the mixture is added to a yttrium oxide-modified chitosan composite coupling agent solution and stirred for modification. Finally, the mixture is washed with water, dried, and then pressed into a mold for molding. The pressing pressure is 20-30 MPa, and the pressing time is 5-10 min. After pressing, the mixture is hot-pressed and sintered at 1310-1320℃ for 1-2 h at a sintering pressure of 3-4 MPa. After sintering, the tungsten alloy of this invention is obtained.

[0040] In this embodiment, the stirring speed for the stirring modification is 550-650 r / min, and the stirring time is 20-30 min.

[0041] Example 1.

[0042] This embodiment describes a high-density tungsten alloy, which is prepared by mixing tungsten powder, nano-zirconia, nano-Sc powder composite modifier, yttrium oxide modified synergistic chitosan composite coupling agent liquid in a weight ratio of 19:1:2:14.

[0043] The tungsten powder in this embodiment has a particle size of 0.5 μm.

[0044] The modification method of the nano-Sc powder composite modifier in this embodiment is as follows:

[0045] S01: Add Sc powder to 3 times the amount of hydrochloric acid solution, then add 2% sodium dodecyl sulfate and 1% sodium oxalate of the total amount of Sc powder, stir evenly to obtain Sc powder treatment solution;

[0046] S02: Add Si powder to twice the amount of sodium alginate solution and stir evenly. Then add 5% sodium phenolsulfonate and 1% pentadecylphenol of the total Si powder and stir thoroughly to obtain Si powder preparation solution.

[0047] S03: The Si powder preparation solution and Sc powder treatment solution are stirred and reacted at a weight ratio of 1:7. After stirring, the mixture is washed with water and dried to obtain the nano-Sc powder composite modifier.

[0048] In this embodiment, the hydrochloric acid solution has a mass fraction of 5%, and the sodium alginate solution has a mass fraction of 10%.

[0049] In this embodiment, the stirring speed for the stirring reaction process is 500 r / min, the stirring time is 20 min, and the stirring temperature is 55℃.

[0050] The preparation method of the yttrium oxide modified chitosan composite coupling agent solution in this embodiment is as follows:

[0051] S11: Add yttrium oxide to 20 parts of deionized water and stir well. Then add phosphate buffer solution to adjust the pH to 5.0. Then add 2 parts of silane coupling agent and stir well.

[0052] S12: Add chitosan to a sulfuric acid aqueous solution of 2 times its volume, then add stearic acid at 2% of the total amount of chitosan, and stir thoroughly;

[0053] S13: Mix the products of S12 and S11 at a weight ratio of 2:6 until fully stirred to obtain a yttrium oxide-modified chitosan composite coupling agent solution.

[0054] The pH value of the phosphate buffer solution in this embodiment is 5.0.

[0055] In this embodiment, the silane coupling agent is coupling agent KH560; the mass fraction of the sulfuric acid aqueous solution is 10%.

[0056] The preparation method of a high-density tungsten alloy according to this embodiment includes the following steps: tungsten powder, nano-zirconia, and nano-Sc powder composite modifier raw materials are stirred and mixed in sequence until fully mixed. Then, the mixture is added to a yttrium oxide-modified chitosan composite coupling agent solution and stirred for modification. Finally, the mixture is washed with water, dried, and then pressed into a mold. The pressing pressure is 20 MPa, and the pressing time is 5 min. After pressing, the mixture is hot-pressed and sintered at 1310℃ for 1 h at a sintering pressure of 3 MPa. After sintering, the tungsten alloy of this invention is obtained.

[0057] In this embodiment, the stirring speed for the stirring modification is 550 r / min, and the stirring time is 20 min.

[0058] Example 2.

[0059] This embodiment describes a high-density tungsten alloy, which is prepared by mixing tungsten powder, nano-zirconia, nano-Sc powder composite modifier, yttrium oxide modified synergistic chitosan composite coupling agent liquid in a weight ratio of 21:1:5:16.

[0060] The tungsten powder in this embodiment has a particle size of 1.0 μm.

[0061] The modification method of the nano-Sc powder composite modifier in this embodiment is as follows:

[0062] S01: Add Sc powder to 6 times the amount of hydrochloric acid solution, then add 5% sodium dodecyl sulfate and 5% sodium oxalate of the total amount of Sc powder, stir evenly to obtain Sc powder treatment solution;

[0063] S02: Add Si powder to 3 times the amount of sodium alginate solution and stir evenly. Then add 10% sodium phenolsulfonate and 5% pentadecylphenol of the total amount of Si powder and stir thoroughly to obtain Si powder preparation solution.

[0064] S03: The Si powder preparation solution and Sc powder treatment solution are stirred and reacted at a weight ratio of 1:7. After stirring, the mixture is washed with water and dried to obtain the nano-Sc powder composite modifier.

[0065] In this embodiment, the hydrochloric acid solution has a mass fraction of 10%; the sodium alginate solution has a mass fraction of 10-20%.

[0066] In this embodiment, the stirring speed for the stirring reaction process is 1000 r / min, the stirring time is 30 min, and the stirring temperature is 65℃.

[0067] The preparation method of the yttrium oxide modified chitosan composite coupling agent solution in this embodiment is as follows:

[0068] S11: Add yttrium oxide to 20 parts of deionized water and stir well. Then add phosphate buffer solution to adjust the pH to 5.0. Then add 2 parts of silane coupling agent and stir well.

[0069] S12: Add chitosan to a sulfuric acid aqueous solution of 2 times its volume, then add stearic acid at 2% of the total amount of chitosan, and stir thoroughly;

[0070] S13: Mix the products of S12 and S11 at a weight ratio of 2:6 until fully stirred to obtain a yttrium oxide-modified chitosan composite coupling agent solution.

[0071] The pH value of the phosphate buffer solution in this embodiment is 5.0.

[0072] In this embodiment, the silane coupling agent is coupling agent KH560; the mass fraction of the sulfuric acid aqueous solution is 10%.

[0073] The preparation method of a high-density tungsten alloy according to this embodiment includes the following steps: tungsten powder, nano-zirconia, and nano-Sc powder composite modifier raw materials are stirred and mixed in sequence until fully mixed. Then, the mixture is added to a yttrium oxide-modified chitosan composite coupling agent solution and stirred for modification. Finally, the mixture is washed with water, dried, and then pressed into a mold. The pressing pressure is 20 MPa, and the pressing time is 5 min. After pressing, the mixture is hot-pressed and sintered at 1310℃ for 1 h at a sintering pressure of 3 MPa. After sintering, the tungsten alloy of this invention is obtained.

[0074] In this embodiment, the stirring speed for the stirring modification is 550 r / min, and the stirring time is 20 min.

[0075] Example 3.

[0076] This embodiment describes a high-density tungsten alloy, which is prepared by mixing tungsten powder, nano-zirconia, nano-Sc powder composite modifier, yttrium oxide modified synergistic chitosan composite coupling agent liquid in a weight ratio of 20:1:3.5:15.

[0077] The tungsten powder in this embodiment has a particle size of 0.75 μm.

[0078] The modification method of the nano-Sc powder composite modifier in this embodiment is as follows:

[0079] S01: Add Sc powder to 4.5 times the amount of hydrochloric acid solution, then add 3.5% sodium dodecyl sulfate and 3% sodium oxalate of the total amount of Sc powder, stir evenly to obtain Sc powder treatment solution;

[0080] S02: Add Si powder to 2.5 times the amount of sodium alginate solution and stir evenly. Then add 7.5% sodium phenolsulfonate and 3% pentadecylphenol of the total amount of Si powder and stir thoroughly to obtain Si powder preparation solution.

[0081] S03: The Si powder preparation solution and Sc powder treatment solution are stirred and reacted at a weight ratio of 1:7. After stirring, the mixture is washed with water and dried to obtain the nano-Sc powder composite modifier.

[0082] In this embodiment, the hydrochloric acid solution has a mass fraction of 7.5%; the sodium alginate solution has a mass fraction of 10-20%.

[0083] In this embodiment, the stirring speed for the stirring reaction process is 750 r / min, the stirring time is 25 min, and the stirring temperature is 60℃.

[0084] The preparation method of the yttrium oxide modified chitosan composite coupling agent solution in this embodiment is as follows:

[0085] S11: Add yttrium oxide to 25 parts of deionized water and stir well. Then add phosphate buffer solution to adjust the pH to 5.0. Then add 3.5 parts of silane coupling agent and stir well.

[0086] S12: Add chitosan to 2.5 times the amount of sulfuric acid aqueous solution, then add stearic acid at 3.5% of the total amount of chitosan, and stir thoroughly;

[0087] S13: Mix the products of S12 and S11 at a weight ratio of 2:6 until fully stirred to obtain a yttrium oxide-modified chitosan composite coupling agent solution.

[0088] The pH value of the phosphate buffer solution in this embodiment is 5.5.

[0089] In this embodiment, the silane coupling agent is coupling agent KH560; the mass fraction of the sulfuric acid aqueous solution is 15%.

[0090] The preparation method of a high-density tungsten alloy according to this embodiment includes the following steps: tungsten powder, nano-zirconia, and nano-Sc powder composite modifier raw materials are stirred and mixed in sequence until fully mixed. Then, the mixture is added to a yttrium oxide-modified chitosan composite coupling agent solution and stirred for modification. Finally, the mixture is washed with water, dried, and then pressed into a mold. The pressing pressure is 25 MPa, and the pressing time is 7.5 min. After pressing, the mixture is hot-pressed and sintered at 1315℃ for 1.5 h at a sintering pressure of 3.5 MPa. After sintering, the tungsten alloy of this invention is obtained.

[0091] In this embodiment, the stirring speed for the stirring modification is 600 r / min, and the stirring time is 25 min.

[0092] Comparative Example 1.

[0093] Unlike Example 3, no nano-Sc powder composite modifier was added.

[0094] Comparative Example 2.

[0095] The modification method of the nano-Sc powder composite modifier is different from that of Example 3; no Si powder preparation solution was added.

[0096] Comparative Example 3.

[0097] Unlike Example 3, the Si powder preparation solution in the preparation method of the nano-Sc powder composite modifier uses Si powder.

[0098] Comparative Example 4.

[0099] Unlike Example 3, the yttrium oxide modified chitosan composite coupling agent solution did not contain the S12 product.

[0100] Comparative Example 5.

[0101] Unlike Example 3, no phosphate buffer solution was added in the preparation of the yttrium oxide modified chitosan composite coupling agent solution.

[0102] The product performance tests for Examples 1-3 and Comparative Examples 1-5 are as follows:

[0103]

[0104] As can be seen from Examples 1-3 and Comparative Examples 1-5, the product of Example 3 of the present invention has excellent tensile strength, elongation and density, and the performance of the product is improved in a coordinated manner.

[0105] As can be seen from Comparative Examples 1-3, without the addition of nano-Sc powder composite modifier, the performance of the product deteriorates significantly. At the same time, the performance of the product varies depending on the modification method of the nano-Sc powder composite modifier.

[0106] The preparation of the nano-Sc powder composite modifier has unique characteristics, and the improvement effect of this invention is the most significant compared to other technologies.

[0107] As can be seen from Comparative Examples 4-5, the performance of the yttrium oxide-modified chitosan composite coupling agent solution without the addition of S12 product and without the addition of phosphate buffer solution during preparation both showed a deterioration trend. Furthermore, the improvement effect of the yttrium oxide-modified chitosan composite coupling agent solution was not as significant as that of the present invention.

[0108] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0109] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A high-density tungsten alloy, characterized in that, The high-density tungsten alloy is prepared by mixing tungsten powder, nano-zirconia, nano-Sc powder composite modifier, and yttrium oxide modified chitosan composite coupling agent in a weight ratio of (19-21):1:(2-5):(14-16). The modification method of the nano-Sc powder composite modifier is as follows: S01: Add Sc powder to 3-6 times the amount of hydrochloric acid solution, then add 2-5% sodium dodecyl sulfate and 1-5% sodium oxalate of the total amount of Sc powder, stir evenly to obtain Sc powder treatment solution; S02: Add Si powder to 2-3 times the amount of sodium alginate solution and stir evenly. Then add 5-10% sodium phenolsulfonate and 1-5% pentadecylphenol of the total amount of Si powder and stir thoroughly to obtain Si powder preparation solution. S03: Si powder preparation solution and Sc powder treatment solution are stirred and reacted at a weight ratio of 1:

7. After stirring, the mixture is washed with water and dried to obtain nano-Sc powder composite modifier. The preparation method of the yttrium oxide modified chitosan composite coupling agent solution is as follows: S11: Add yttrium oxide to 20-30 parts of deionized water and stir well. Then add phosphate buffer solution to adjust the pH to 5.

0. Then add 2-5 parts of silane coupling agent and stir well. S12: Add chitosan to 2-3 times the volume of sulfuric acid aqueous solution, then add stearic acid at 2-5% of the total amount of chitosan, and stir thoroughly; S13: Mix the products of S12 and S11 at a weight ratio of 2:6 until fully stirred to obtain a yttrium oxide modified chitosan composite coupling agent solution; The preparation method of high-density tungsten alloy includes the following steps: tungsten powder, nano-zirconia, and nano-Sc powder composite modifier raw materials are stirred and mixed in sequence until fully mixed. Then, the mixture is added to a yttrium oxide-modified chitosan composite coupling agent solution and stirred for modification. Finally, the mixture is washed with water, dried, and then pressed into a mold. The pressing pressure is 20-30 MPa, and the pressing time is 5-10 min. After pressing, the mixture is hot-pressed and sintered at 1310-1320℃ for 1-2 h at a sintering pressure of 3-4 MPa. After sintering, the tungsten alloy is obtained.

2. The high-density tungsten alloy according to claim 1, characterized in that, The tungsten powder has a particle size of 0.5-1.0 μm.

3. The high-density tungsten alloy according to claim 1, characterized in that, The hydrochloric acid solution has a mass fraction of 5-10%; the sodium alginate solution has a mass fraction of 10-20%.

4. The high-density tungsten alloy according to claim 1, characterized in that, The stirring speed for the stirring reaction treatment is 500-1000 r / min, the stirring time is 20-30 min, and the stirring temperature is 55-65℃.

5. The high-density tungsten alloy according to claim 1, characterized in that, The pH value of the phosphate buffer solution is 5.0-6.

0.

6. The high-density tungsten alloy according to claim 1, characterized in that, The silane coupling agent is coupling agent KH560; the mass fraction of the sulfuric acid aqueous solution is 10-20%.

7. The method for preparing a high-density tungsten alloy according to claim 1, characterized in that, The stirring speed for the stirring modification is 550-650 r / min, and the stirring time is 20-30 min.

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