KR20170028027A - Method for producing titanium nitride using titanium scrap - Google Patents
Method for producing titanium nitride using titanium scrap Download PDFInfo
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- KR20170028027A KR20170028027A KR1020150124786A KR20150124786A KR20170028027A KR 20170028027 A KR20170028027 A KR 20170028027A KR 1020150124786 A KR1020150124786 A KR 1020150124786A KR 20150124786 A KR20150124786 A KR 20150124786A KR 20170028027 A KR20170028027 A KR 20170028027A
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0637—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with metals not specified in groups C01B21/0607 - C01B21/0635, other than aluminium, titanium, zirconium or hafnium
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- C01G23/00—Compounds of titanium
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- C—CHEMISTRY; METALLURGY
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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Abstract
The present invention relates to a method for producing titanium nitride, and more particularly, to a method for preparing titanium nitride, Hydrogenation of the Ti scrap; A step of powdering the hydrogenated TiH 2 ; TiH 2 A dehydrogenation step of the powder; And a TiN forming step; To a process for producing titanium nitride. The present invention can provide TiN powder of high quality using Ti scrap.
Description
The present invention relates to a method for producing titanium nitride using Ti scrap.
TiN has high melting point (2950 ℃), excellent oxidation resistance, chemical stability, excellent hardness and abrasion resistance, and excellent lubricity due to low friction coefficient, so that it can be used as a coating material for cutting tool, Widely used.
It has various applications ranging from excellent thermal conductivity, excellent infrared absorption ability and ultraviolet shielding ability of 80% or more to application to semiconductor components. For example, it has a gate electrode of metal-oxide-semiconductor transistors, a Schottky barrier diode , Optical elements, barrier layers in connection and connection metallization, and the like.
Cutting tools made of TiN powder and Ni binder are being developed as substitutes for WC + Co binder products occupying more than 5% of cutting tools. In these new tools, TIN can be used as a binder instead of expensive Co as a substitute for WC, which is relatively expensive. It is much more attractive in terms of cost, low sintering temperature and 3 ~ 5 times longer lifetime have.
TiN is produced by a direct nitriding method in which a Ti metal powder is heated at about 1200 ° C in a nitrogen or ammonia gas, or a reductive nitriding method in which a mixed powder of a metal oxide (TiO 2 ) and carbon is heated in a nitrogen or ammonia gas . The direct nitriding process is relatively simple because the process is relatively simple and can be synthesized under relatively low nitrogen pressure. However, there is a disadvantage in that a long time is required in the synthesis process. In the reduction nitriding process, There is a disadvantage that the purity drops.
The present invention provides an economical method of providing high-purity TiN, and is a process for producing TiN from a pure Ti scrap which is abandoned in large quantities in an industrial field where production and processing of Ti weld pipe, pipe, .
Disclosure of Invention Technical Problem [8] The present invention has been made to solve the above problems, and it relates to a method for producing titanium nitride which recycles Ti scrap to produce high functional and high purity TiN powder in a batch process.
The problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood from the following description.
One aspect of the present invention relates to a method of manufacturing a Ti scrap; Hydrogen scrambling the Ti scrap; A step of powdering the hydrogenated TiH 2 ; Dehydrogenating the powdered hydrogenated Ti; And a TiN forming step; ≪ / RTI >
According to an embodiment of the present invention, the hydrogenation step may be carried out in a pure hydrogen atmosphere at 400 ° C to 700 ° C for 10 minutes to 4 hours.
According to one embodiment of the present invention, the hydrogen partial pressure in the hydrogenation step may be from 1 torr to 10 atm.
According to an embodiment of the present invention, the dehydrogenation step may be performed in a vacuum atmosphere at 450 ° C. to 800 ° C. for 30 minutes to 4 hours.
According to one embodiment of the present invention, the vacuum in the dehydrogenation step may be carried out at 10 -3 to 10 -4 torr.
According to an embodiment of the present invention, the TiN forming step may be performed in a nitrogen atmosphere at 800 ° C to 1200 ° C for 1 hour to 6 hours.
According to an embodiment of the present invention, the nitrogen in the TiN formation step may be supplied at a flow rate of 500 ml / min to 1000 ml / min.
The present invention can provide TiN powder of high added value at an economical cost by recycling Ti scraps discarded in industrial wastes.
According to the present invention, the soft Ti scrap is powdered through a hydrogenation process, and then the deformation of the metal material is recovered through dehydrogenation, thereby proceeding the nitriding. Thus, TiN powder having a fine particle size and a high purity can be obtained .
Figure 1 illustrates, by way of example, a process flow diagram of a method of making titanium nitride, according to one embodiment of the present invention.
Figure 2 shows an X-ray diffraction (XRD) pattern of hydrogenated titanium scrap according to an embodiment of the present invention.
Figure 3 shows the XRD pattern of dehydrated Ti according to an embodiment of the present invention.
FIG. 4 shows a scanning electron microscope (SEM) image of dehydrated Ti according to an embodiment of the present invention.
Figure 5 shows the XRD pattern of TiN produced according to an embodiment of the present invention.
6 shows an SEM image and powder appearance of TiN produced according to an embodiment of the present invention.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description of the present invention, detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear. Also, terminologies used herein are terms used to properly represent preferred embodiments of the present invention, which may vary depending on the user, intent of the operator, or custom in the field to which the present invention belongs. Therefore, the definitions of these terms should be based on the contents throughout this specification.
The present invention relates to a method for producing titanium nitride, and it is possible to recycle titanium scrap and produce high-performance titanium nitride in a batch process.
Referring to FIG. 1, a method of manufacturing titanium nitride according to an embodiment of the present invention will be described with reference to FIG. 1. Referring to FIG. 1, pulverization step of the Ti hydride Chemistry step (S2), a hydrogen compound of scrap Chemistry TiH 2 (S3), TiH 2 A dehydrogenation step (S4) of powder, and a TiN formation step (S5).
The preparation step (S1) of the Ti scrap is a step of pretreating the Ti scrap for the hydrogenation process.
According to one embodiment of the present invention, step S1 includes collecting the Ti scrap at an industrial site and cleaning it, for example, after collecting the Ti scrap generated in the manufacturing and processing of the Ti pipe, Alternatively, the Ti scrap may be added to the mixture of the solvent and the cleanser and then washed at room temperature, or at 30 ° C to 60 ° C for 10 minutes to 50 hours, preferably 30 minutes to 48 hours. The washing may be performed by stirring and / or ultrasonic waves. The solvent can be appropriately selected in consideration of impurities of the Ti scrap generated during processing such as cutting oil. For example, water, acetone, ethanol and the like can be used as the solvent. The cleaning agent may be an anionic surfactant; Cationic surfactants; Or a non-ionic surfactant. After washing, it can be dried at room temperature or below 100 ° C.
The hydrogenation step (S2) of the Ti scrap is a step of hydrogenating the Ti scrap prepared in step (S1) to obtain TiH 2 . In step S2, TiH 2 having high brittleness can be formed to solve the problem of Ti scrap which is difficult to be powdered by a mechanical method owing to high ductility, and pulverization can be made by a mechanical method such as ball milling.
According to one embodiment of the present invention, step S2 may be carried out in a pure hydrogen atmosphere at 400 占 폚 to 700 占 폚 for 10 minutes to 4 hours, preferably for a holding time of 1 hour to 2 hours. If the hydrogen atmosphere is contained within the temperature and / or time range in the hydrogen atmosphere, the hydrogenation heat treatment can be performed well. The atmosphere may be maintained at a gas partial pressure of from 1 torr to 10 atm, preferably from 1 atm to 2 atm.
The steps of a powdered hydrogen compound Chemistry TiH 2 (S3) is a step of pulverizing a hydride stylized TiH 2 obtained in the step (S2) by mechanical means. In step S3, a powdered TiH 2 powder having a fine particle size and a homogeneity can be obtained.
According to one embodiment of the present invention, step S3 is performed using mechanical milling and at a speed of 100 rpm to 300 rpm, preferably 100 rpm to 200 rpm, for 24 hours to 80 hours, preferably 40 hours To < RTI ID = 0.0 > 65 < / RTI > If it is contained within the above-mentioned speed and / or time range, the homogeneity of the particle size can be excellent or a powder having a fine particle size of 3 탆 or less can be obtained.
TiH 2 A dehydrogenation step (S4) of the powder, TiH 2 obtained in the step (S3) And dehydrogenating the powder to obtain a Ti powder. Step S3 is a step of dehydration to recover the Ti characteristics and increase the reactivity between Ti and nitrogen, so that nitrogenization can be sufficiently performed.
According to one embodiment of the present invention, step S4 is performed at a temperature of 450 ° C to 800 ° C, preferably 600 ° C to 700 ° C, more preferably 650 ° C at a vacuum of 10 -3 to 10 -4 torr, Deg.] C to 670 [deg.] C for 30 minutes to 4 hours, preferably 1 hour to 3 hours, more preferably 2 hours to 3 hours. When the degree of vacuum is contained within the range of the temperature, the temperature, and / or the time, sufficient dehydrogenation is performed and the occurrence of agglomeration between the powders can be prevented.
The TiN forming step S5 is a step of nitrating the dehydrogenated Ti powder obtained in the step S4 to obtain TiN.
According to one embodiment of the present invention, step S5 is performed at a temperature of 800 占 폚, while flowing nitrogen gas at a flow rate of 500 ml / min to 1000 ml / min, preferably 750 ml / min to 850 ml / Nitration of the Ti powder can be effected for a holding time of from 1 to 6 hours, preferably from 2 to 4 hours at a temperature of from 1,200 to 1,200, preferably from 1000 to 1,200, more preferably from 1050 to 1100 have. When the temperature is within the range of the flow rate, the temperature and the holding time, sufficient nitrogenization is achieved and TiN of high purity can be obtained.
The TiN powder produced by the production method of the present invention may have a particle size of 10 μm or less, preferably 5 μm or less, more preferably 3 μm or less.
According to an embodiment of the present invention, a post-treatment process such as a refining process for removing impurities such as Ca and the like, a surface treatment of TiN powder for various application fields, etc. is further performed using deoxidation treatment of TiN powder or the like However, this application is not specifically mentioned.
It will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Preparation of titanium scrap
The titanium scrap generated in the manufacture of the titanium tube was collected and washed in a washing solution of a kitchen detergent and water (1:10 weight ratio) for 48 hours, then rinsed with water and air-dried. Next, after washing in acetone for 24 hours, it was immersed in ethanol, washed with an ultrasonic washing machine for 30 minutes, and air-dried.
Example One
(One) Ti Scrap Hydrogenation
The washed titanium scrap was placed in an electric furnace and heat-treated at 630 ° C for 2 hours in a hydrogen atmosphere (1 atm) to produce TiH 2 . Exhibited the XRD pattern Preparation of TiH 2 (D / MAX-2200 / PC, Rigagu) is 2, can also be confirmed that Looking to Figure 2, consistent with the peak of the TiH 2 in the XRD pattern.
(2) Hydrogenated Scrap Powdered
Using zirconium balls of 3 mm and 11 mm in diameter, the hydrogenated titanium scrap was subjected to dry ball milling for 24 hours, 48 hours, 60 hours, and 72 hours, respectively, at a rate of 140 rpm. After ball milling, powder was sieved through a sieve. The powder produced by the ball milling time was dispersed by applying ultrasonic waves to the ethanol solvent, and the change in particle size was measured and shown in Table 1.
Table 1 shows that when the 24 h ball milling is performed, the Mode Size, which is the largest size, is 6.23 μm, the mean size is 6.12 μm and the homogeneity is the best. When the ball milling time becomes longer, the Mean size and Mode size And the grain size of the powder was the smallest at a Mode Size of 1.85 mu m and a Mean Size of 3.42 mu m when the ball was milled by 60 h. In addition, the particle size of the powder is expected to decrease when the milling time is further increased, but it increases again at 72 h. This is because the micronized particles agglomerate with each other as the milling proceeds.
(3) TiH 2 Dehydration of powder
The hydrogenated scrap pulverized at 60 h was put in a vacuum furnace, maintained at a vacuum of 10 -4 torr, and maintained at 650 ° C for 3 hours to conduct dehydrogenation. The XRD pattern and SEM image of the dehydrogenated powder are shown in FIG. 3 and FIG. Referring to FIG. 3, it can be seen that the XRD pattern coincides with the peak of Ti. Referring to FIG. 4, it can be confirmed that the powder has a polygonal shape, has a particle size in the range of 3 μm to 6 μm, .
(4) Ti Nitrogenization
800 ml / min, and the dehydrogenated powders were subjected to nitrogenization at 850 ° C, 1050 ° C, and 1150 ° C for 2 hours in a tubular nitrogen atmosphere. The XRD pattern and SEM image of the nitrated powder are shown in FIG. 5 and FIG. Referring to FIG. 5, it can be seen that the powder nitrided at 850 ° C in the XRD pattern contains a mixture of Ti peaks, and it can be confirmed that the XRD pattern of the powder nitrided at 1050 ° C and 1100 ° C coincides with the TiN peak .
6, the SEM image (a) and the apparent image (b) relate to a powder nitrided at 1050 ° C., and while retaining a polygonal shape similar to that of the dehydrogenated powder of FIG. 6, Size and fine powders of 3 탆 or less are mixed and powder having an average particle size of 3.2 탆 is confirmed, and it can be confirmed that the color of the powder is a blackish brown color with metal.
The TiN powder nitrided at 1050 ° C was 3418 ppm in terms of the oxygen content (O / H / N analyzer, ELTRA GmbH, ONH-2000M, test method JIS H 1620: 1995) and the Fe content (Test Method KS D 2527: 2003, ICP analysis) was 0.09 wt%, and the purity was measured as 97%.
Comparative Example One
Without dehydration of the hydrogenated Ti scrap, dehydrogenation was carried out under the same conditions as in Example 1, and then the gas was nitrogenated at 800 ml / min and 1050 ° C for 2 hours. The XRD pattern and the SEM image of the obtained powder were confirmed, and it was confirmed that the XRD patterns contained TiH 2 , TiH, Ti and the like in addition to TiN, and the SEM image confirmed that the particles 15 μm or more were agglomerated strongly .
Comparative Example 2
Without dehydrogenation of the hydrogenated scrap, the gasification was carried out under the same conditions as in Example 1 at 800 ml / min of gas and 1050 ° C for 2 hours. The XRD pattern and the SEM image of the obtained powder were confirmed. As a result, it was confirmed that the XRD patterns contained TiN, TiH 2, and other peaks in addition to the TiN peak, which means that the nitrogenization was not uniform. A size and powder shape similar to that of Example 1 can be identified in the SEM image.
The present invention promotes nitrogenization through Ti scrap hydrogenation, pulverization, and dehydrogenation, so that TiN scrap can be used to provide uniform and high purity TiN.
Claims (5)
Hydrogenation of the Ti scrap;
A step of powdering the hydrogenated TiH 2 ;
TiH 2 A dehydrogenation step of the powder; And
TiN forming step;
≪ / RTI >
Wherein the hydrogenation step is carried out in a pure hydrogen atmosphere at 400 ° C to 700 ° C for 10 minutes to 4 hours.
Wherein the dehydrogenating step is carried out in a vacuum atmosphere at 450 캜 to 800 캜 for 30 minutes to 4 hours.
Wherein the TiN forming step is performed in a nitrogen atmosphere at 800 to 1200 DEG C for 1 to 6 hours.
Wherein the nitrogen in the TiN formation step is supplied at a flow rate of 500 ml / min to 1000 ml / min.
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| KR1020150124786A KR20170028027A (en) | 2015-09-03 | 2015-09-03 | Method for producing titanium nitride using titanium scrap |
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| KR1020150124786A KR20170028027A (en) | 2015-09-03 | 2015-09-03 | Method for producing titanium nitride using titanium scrap |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20210127479A (en) * | 2020-04-14 | 2021-10-22 | (주)동아특수금속 | Ferro-Titanium Manufacturing Process Using Ti Scraps |
| KR20230062492A (en) * | 2020-11-16 | 2023-05-09 | (주)동아특수금속 | Casting of ferro-titanium using continuous melting technology through temperature control |
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2015
- 2015-09-03 KR KR1020150124786A patent/KR20170028027A/en not_active Application Discontinuation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20210127479A (en) * | 2020-04-14 | 2021-10-22 | (주)동아특수금속 | Ferro-Titanium Manufacturing Process Using Ti Scraps |
| KR20230062492A (en) * | 2020-11-16 | 2023-05-09 | (주)동아특수금속 | Casting of ferro-titanium using continuous melting technology through temperature control |
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