KR20110075192A - Method for manufacturing titanum-contaning powder material having titanum containing phase by using titanum oxide - Google Patents

Abstract

PURPOSE: A method for manufacturing titanium included metallic phase powder from titanium oxide is provided to manufacture the titanium included metallic phase powder for reducing and thermally treating by uniformly ball-milling more than one kind of powder. CONSTITUTION: Oxide certainly includes titanium oxide powder and carbon-powder. Oxide comprises one of Fe, Ni, Co, Al, Mn, Cr, V And Fe. The compound powder, in which oxide is selectively added, is ball-milled. The ball-milled compound powder is uniformly mixed(S100). The ball-milled compound powder is reduced and processed under the vacuum atmosphere or argon atmosphere(S200). The compound powder, reduced and heat-processed, is made to be titanium included metallic phase.

Description

Method for manufacturing titanum-contaning powder material having titanum containing phase by using titanum oxide}

1 is a process flow chart showing a method for producing a powder containing a metal phase containing titanium from titanium oxide according to the present invention.

Figure 2 is a graph showing the X-ray diffraction test results of the powder prepared according to Comparative Example 1.

Figure 3 is a graph showing the X-ray diffraction test results of the powder prepared according to Comparative Example 2.

Figure 4 is a graph showing the X-ray diffraction test results of the powder prepared according to Comparative Example 3.

Figure 5 is a graph showing the X-ray diffraction test results of the powder prepared according to Example 1 of the present invention.

Figure 6 is a graph showing the results of the X-ray diffraction test of the powder prepared according to Example 2 of the present invention.

Explanation of symbols on the main parts of the drawings

S100. Powder mixing step S200. Reduction heat treatment step

The present invention is titanium oxide After ball milling the mixed powder including powder and carbon powder, and optionally adding one of Fe, Ni, Co, Al, Mn, Cr, V, Fe, or an oxide containing any one of these, vacuum It relates to a method for producing a powder containing a metal phase containing titanium by reducing heat treatment in the atmosphere or argon atmosphere.

Powder materials containing a metal phase containing titanium (Ti) include FeTi-based hydrogen storage materials (FeTi, FeTi with Al or Mn partially added), Ti-Cr-based hydrogen storage materials (Ti-Cr-V, Ti-Cr -V-Fe, etc.), NiTi-based shape memory alloys (Ni-Ti, Ni-Ti-Cu), and the like.

Here, the metal phase containing titanium (Ti) is a solid solution containing Ti component such as Ti phase, FeTi phase, FeTi ₂ phase, Ti-Cr solid solution phase, Ti-Cr-V solid solution phase, NiTi-based intermetallic compound phase, or the like. The alloying elements added, referring to the compound, may be partially dissolved in these phases.

These solid solutions or compounds contain titanium as the main component and titanium is an expensive metal. In general, these materials are manufactured by melting and casting titanium and additive alloying materials together, or by pulverizing the cast alloy when powder is required.

On the other hand, in the case of manufacturing by powder metallurgy, expensive titanium (Ti) powder and powders of alloy components to be added may be manufactured by high energy milling. However, there is an uneconomical disadvantage because expensive titanium is included as an initial material to produce a powder containing titanium by the conventional method.

The object of the present invention is to solve the above problems, inexpensive titanium oxide A powder and a carbon powder which is a reducing agent must be included and at least one powder of Fe, Ni, Co, Al, Mn, Cr, V, Fe oxide, Ni oxide, Co oxide, Al oxide, Mn oxide, Cr oxide, and V oxide It is to provide a method for producing a powder containing a metal phase containing titanium (Ti) by mixing and reducing heat treatment in a vacuum atmosphere or argon atmosphere.

Method for producing a powder containing a metal phase containing titanium from the titanium oxide according to the present invention, titanium oxide A powder and carbon powder must be included, and the powder mixed with Fe, Ni, Co, Al, Mn, Cr, V, Fe, or an oxide containing any one of them selectively added is uniformly mixed by ball milling And a reduction heat treatment step of forming a powder containing a metal phase containing titanium by reducing heat treatment of the powder milling step and the ball milled mixed powder in a vacuum atmosphere or argon atmosphere.

The powder mixing step is characterized in that the particle diameter of the mixed powder has a size of less than 150㎛.

The reduction heat treatment step is characterized in that the mixture powder is charged into the graphite mold and the graphite punch is inserted and then heated by energization and then cooled.

In the reduction heat treatment step, the mixed powder is heated in a temperature range of 1250 to 1500 ℃.

In the reduction heat treatment step, the reduced mixed powder is cooled after the heat treatment temperature is maintained for a predetermined time.

According to the present invention as described above, inexpensive titanium oxide The powder may be mixed with carbon to reduce heat treatment, thereby producing a powder containing a titanium-containing metal phase.

Hereinafter, a method of manufacturing a powder containing a metal phase containing titanium from titanium oxide according to the present invention will be described with reference to FIG. 1.

1 is a process flow chart showing a method for producing a powder containing a titanium-containing metal phase from a titanium oxide according to the present invention.

As shown in the drawing, the method for producing a powder according to the present invention is titanium oxide. Must include powder and carbon powder and ball mill one or more of Fe, Ni, Co, Al, Mn, Cr, V, Fe oxide, Ni oxide, Co oxide, Al oxide, Mn oxide, Cr oxide, V oxide Powder mixing step (S100) to form a mixed powder, and a reduction heat treatment step (S200) of reducing heat treatment of the mixed powder in a vacuum atmosphere or an argon atmosphere, wherein the powder prepared according to the above method contains titanium. Metal phases are included.

The powder mixing step (S100) is titanium oxide in the ball milling vessel The powder and the carbon powder are necessarily charged, and an oxide containing any one of Fe, Ni, Co, Al, Mn, Cr, V, Fe, or any of these is optionally added.

The mixed powder mixed in this configuration is finely ground by ball milling and uniformly mixed.

For example, when manufacturing a FeTi-based hydrogen storage material, titanium oxide powder and carbon powder must be charged and at least one of Fe powder and Fe oxide is added as an additive element.

In the case of manufacturing a FeTi-based hydrogen storage material containing a part of manganese (Mn), titanium oxide powder and carbon powder must be charged, and as an additive element, at least one of Fe powder and Fe oxide, among Mn powder and Mn oxide 1 or more types will be added.

In the case of producing a Ti-Cr-V-based hydrogen storage material, titanium oxide powder and carbon powder must be charged and at least one of Cr powder and Cr oxide, and at least one of V powder and V oxide is added as an additive element. Done.

Finally, when manufacturing the NiTi-based shape memory alloy powder, titanium oxide powder and carbon powder must be charged and at least one of Ni powder and Ni oxide powder is added as an additive element.

According to the use of the powder to be prepared according to the present invention as described above, the remaining components except for the titanium oxide powder and the carbon powder may be optionally included.

In addition, the ball milled powder mixed in the powder mixing step (S100) is configured to have a particle diameter of 150 μm or less by selecting using a size having a size of 100 mesh.

That is, when the particle diameter of the mixed powder exceeds 150㎛, since the reduction reaction of oxides by carbon is insufficient during the reduction heat treatment step, titanium oxide is likely to remain, so that the mixed powder mixed and pulverized after ball milling Silver is preferably configured to have a particle size of 150㎛ or less.

After the powder mixing step (S100), a reduction heat treatment step (S200) is performed. The reduction heat treatment step (S200) is a process for reducing the mixed powder by heat treatment in a vacuum or inert atmosphere, and is heated within a temperature range of 1250 to 1500 ℃.

That is, if the reduction heat treatment temperature is less than 1250 ℃, the reduction reaction of the titanium oxide does not occur sufficiently, and if it exceeds 1500 ℃, the power consumption accordingly increases not only economically, but also the reduced metal powder may evaporate Not desirable

 Hereinafter, with reference to the accompanying Figures 2 to 4 looks at the experimental results of the comparative example.

2 to 4 are graphs showing the X-ray diffraction test results of the powder prepared according to Comparative Examples 1 to 3.

Comparative Example 1

After reduction by the carbon _{TiFe 0 .85 Mn 0 .15 (Ti46.233} % by weight, 45.813% by weight of Fe, Mn 7.954% by weight) so that the final target composition.

TiO ₂ 50.054% by weight, C 15.048% by weight, Fe 29.735% by weight, and Mn 5.163% by weight were loaded into a ball milling vessel made of stainless steel.

That is, charged with TiO ₂ 25.027g, nano carbon black 7.524g, Fe 14.868g, Mn 2.582g, hexane 100cc in the ball milling container and ball milling for 24 hours, dried and passed through 100 mesh blade of less than 150㎛ A powder having a particle size was obtained.

As a result of X-ray diffraction test of the milled mixed powder, titanium oxide phase, carbon phase, Fe phase and Mn phase were detected.

Comparative Example 2

After carbon was reduced with a _{Ti 0 .32 Cr 0 .43 V 0} .25 {Ti 36.985%, Cr 40.147%, V 22.868% ( % by weight)} for the purpose of the composition.

Preparation of TiO ₂ + V ₂ O ₅ + Cr ₂ O ₃ + C mixed powder is 7.077g TiO ₂ + 9.374 g V ₂ O ₅ + 6.731 g Cr ₂ O ₃ + 6.818 g C (23.591 wt% ₂ , 31.245 wt% V ₂ O ₅ , 22.438 wt% Cr ₂ O ₃ , 22.726 wt% C) A mixed powder was prepared by ball milling.

After the ball milled mixed powder was dried to obtain a mixed powder having a particle size of less than 150㎛ passed through 100 mesh.

The XRD results of the ball milled powders were determined by TiO ₂ , V ₂ O ₅ , Cr ₂ O ₃ It consists of oxide phases.

Comparative Example 3

Mixed powder having a particle size of 150 μm or less obtained through the procedure of Comparative Example 1 (TiO ₂ 50.054 wt%, C 15.048 wt%, Fe 29.735 wt%, Mn 5.163 wt%) Charge 10 g into a graphite mold having an inner diameter of 20 mm, insert a graphite punch, and energize it. 1230 ° C. at 25 ° C. per minute in a vacuum atmosphere. Heated to maintain for 10 minutes and then cooled.

As a result of the X-ray diffraction test of the reduced heat-treated powder, titanium oxide phase, carbon phase, and Fe phase were detected, and thus the loaded titanium oxide was not reduced.

Hereinafter, the experimental results according to the preferred embodiment of the present invention will be described with reference to FIGS. 5 and 6.

Example 1

Mixed powder having a particle size of 150 μm or less obtained through the process of Comparative Example 1 (TiO ₂ 50.054% by weight, C 15.048% by weight, Fe 29.735% by weight, Mn 5.163% by weight) Charge 10 g into a graphite mold having an inner diameter of 20 mm, insert a graphite punch, and energize it to obtain a temperature of 1300 ° C. at 25 ° C. per minute in a vacuum atmosphere. Heated to 3 minutes and then cooled.

As a result of the X-ray diffraction test of the reduced heat-treated powder, a titanium powder containing FeTi phase, FeTi ₂ phase, and Ti phase were detected to obtain a reduced powder.

[Example 2]

10 g of a mixed powder having a particle size of 150 μm or less obtained through the process of Comparative Example 2 (23.591 wt% TiO ₂ , 31.245 wt% V ₂ O ₅ , 22.438 wt% Cr ₂ O ₃ , 22.726 wt% C) It was charged into a 20 mm graphite mold, a graphite punch was inserted, energized, heated to 1300 ° C. at a temperature increase rate of 25 ° C. per minute in a vacuum atmosphere, and maintained for 3 minutes, followed by cooling.

As a result of the X-ray diffraction test of the powder subjected to reduction heat treatment, a Ti phase, a Ti-Cr-V alloy phase, a Cr phase, and a V phase were obtained to obtain a reduced powder.

Example 3

Mixed powder having a particle size of 150 μm or less obtained through the process of Comparative Example 1 (TiO₂ 50.054 wt%, C 15.048 wt%, Fe 29.735 wt%, Mn 5.163 wt%) Charge 10 g into a graphite mold having an inner diameter of 20 mm, insert a graphite punch, and energize it. It heated to ℃, it hold | maintained for 3 minutes, and cooled.

As a result of the X-ray diffraction test of the powder subjected to reduction heat treatment, a Ti phase in which ellipsoid was dissolved and a Cr phase in which ellipsoid was dissolved were obtained, thereby obtaining a reduced powder.

Example 4

10 g of a mixed powder having a particle size of 150 μm or less obtained through the process of Comparative Example 2 (23.591 wt% TiO ₂ , 31.245 wt% V ₂ O ₅ , 22.438 wt% Cr ₂ O ₃ , 22.726 wt% C) It was charged into a 20 mm graphite mold and inserted into a graphite punch, and energized, and heated to 1500 ° C. at a temperature rising rate of 25 ° C. per minute in a vacuum atmosphere for 3 minutes, and cooled.

As a result of the X-ray diffraction test of the reduced heat-treated powder, a Ti phase in which ellipsoids were dissolved and a Cr phase in which ellipses were dissolved were obtained, thereby obtaining a reduced powder.

The scope of the present invention is not limited to the above-exemplified embodiments, and many other modifications based on the present invention may be made by those skilled in the art within the above technical scope.

In the present invention, titanium oxide Must include powder and carbon powder and ball mill one or more of Fe, Ni, Co, Al, Mn, Cr, V, Fe oxide, Ni oxide, Co oxide, Al oxide, Mn oxide, Cr oxide, V oxide To reduce heat treatment to uniformly mixed powder can be produced a powder containing a metal phase containing Ti.

Thus, low cost titanium oxide By reducing the powder in a simple process there is an advantage that the production of a powder material containing titanium.

Claims (5)

Titanium oxide A powder and carbon powder must be included, and the powder mixed with Fe, Ni, Co, Al, Mn, Cr, V, Fe, or an oxide containing any one of them selectively added by ball milling to uniformly mix Powder mixing step, The ball milled mixed powder is subjected to a reduction heat treatment step of reducing heat treatment in a vacuum atmosphere or in an argon atmosphere to form a powder containing a titanium-containing metal phase. How to manufacture. The method of claim 1, wherein the powder mixing step is a process for producing a powder containing titanium from titanium oxide, characterized in that the particle diameter of the mixed powder has a size of less than 150㎛. The method of claim 1, wherein the reducing heat treatment step, Charging the mixed powder into a graphite mold, inserting a graphite punch, and then heating and energizing the graphite powder, thereby producing a powder containing a titanium-containing metal phase from titanium oxide. The method of claim 3, wherein in the reducing heat treatment step, The mixed powder is a method for producing a powder containing a metal phase containing titanium, characterized in that heated in the temperature range of 1250 to 1500 ℃. The method of claim 4, wherein in the reducing heat treatment step, The reduced mixed powder is cooled after the heat treatment temperature is maintained for a predetermined time to produce a powder containing a titanium containing metal phase.

Images