WO2013141422A1 - Procédé de formation de couche dure sur le titane, et alliage ayant couche dure formée par ledit procédé - Google Patents

Procédé de formation de couche dure sur le titane, et alliage ayant couche dure formée par ledit procédé Download PDF

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WO2013141422A1
WO2013141422A1 PCT/KR2012/002146 KR2012002146W WO2013141422A1 WO 2013141422 A1 WO2013141422 A1 WO 2013141422A1 KR 2012002146 W KR2012002146 W KR 2012002146W WO 2013141422 A1 WO2013141422 A1 WO 2013141422A1
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titanium
hard layer
layer
present
coating
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PCT/KR2012/002146
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English (en)
Korean (ko)
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이동근
이용태
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한국기계연구원
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Priority to US13/988,348 priority Critical patent/US20130248051A1/en
Priority to PCT/KR2012/002146 priority patent/WO2013141422A1/fr
Priority to JP2015503083A priority patent/JP2015519470A/ja
Publication of WO2013141422A1 publication Critical patent/WO2013141422A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/20—Carburising
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/02—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/24—Nitriding
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/28—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases more than one element being applied in one step
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/28—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases more than one element being applied in one step
    • C23C8/30—Carbo-nitriding
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/80—After-treatment

Definitions

  • the present invention relates to a method for forming a hard layer on the surface layer of titanium (pure titanium and titanium alloy), and more particularly, to a method for forming a hard layer having properties of continuously changing properties at low cost on the surface layer of titanium. It relates to titanium in which a hard layer is formed by the method.
  • titanium and titanium alloys are relatively lighter than other structural materials and are widely used in the military and aerospace industries where weight reduction is essential because of their high specific strength in the temperature range from cryogenic temperatures to 400 to 500 ° C.
  • titanium has excellent corrosion resistance and biocompatibility, most biomaterials to be inserted into the human body are used.
  • titanium is capable of coloring through anodization, its use has recently been expanded in civilian products requiring various color expressions.
  • the TiN film which has been actively studied among the coating materials for improving abrasion resistance, has excellent oxidation resistance, excellent surface roughness and ductility, and is beautiful in color due to its golden color, which is widely used not only for wear but also for corrosion resistance or decoration. to be.
  • TiN film has very large volume expansion (volume expansion rate of about 64%) when TiO 2 is formed through oxidation process, it forms a large compressive stress in the formed oxide layer and causes cracks in the film. Oxidation proceeds rapidly.
  • an oxynitride material containing oxygen such as TiN x O y may be used as the surface curing film.
  • the oxynitride coating material based on the ternary composition also has excellent hardness, electrical properties, abrasion resistance, and corrosion resistance similar to the TiN coating due to the chemical bonding of atoms in the lattice and the electrical structure of the oxynitride.
  • a method of forming a titanium oxynitride film having excellent properties such as TiN x O y on the surface of the titanium alloy, nitriding, carburizing, thermal spraying, physical vapor deposition (PVD) and chemical vapor deposition (CVD; Chemical Vapor Deposition) and the like.
  • PVD methods such as ion plating, cathode arc deposition, and reactive sputtering, and CVD methods using plasma are mainly considered.
  • the PVD process can be deposited at a lower temperature than the CVD process, minimizes the change of the structure at the interface between the titanium alloy surface and the coating layer, and can form a coating layer having excellent abrasion resistance, heat resistance, oxidation resistance, and corrosion resistance.
  • the adhesion between the coating layer and the titanium alloy base is weak, the coating equipment is expensive, and the formation of the coating layer takes a long time.
  • the CVD process has the advantage of easy control of the composition and coating thickness of the coating layer, but mainly due to the deposition process at a high temperature can cause a change in the structure of the coating layer and the titanium alloy in the mechanical properties and corrosion of the titanium alloy There are disadvantages that can have a bad effect.
  • the coating layer contains a lot of pores, so it is difficult to expect sufficient physical properties such as oxidation resistance, and the coating layer formed by PVD and CVD has less pores than the spray coating, but basically It is difficult to form a dense coating layer because it has considerable defects.
  • the over-layer coating is added to the processed part of the coating layer, when the thick coating layer is formed, the dimensional change before and after the coating is significant, the necessity of post-processing increases, which leads to an increase in the manufacturing cost of the component.
  • thermo-chemical treatment TCT
  • invasive elements such as oxygen, carbon and nitrogen from the surface of titanium.
  • TCT thermo-chemical treatment
  • another object of the present invention is to provide a titanium in which a hard layer in which an invasive element such as oxygen, carbon or nitrogen obtained by the above method has a concentration gradient from the surface thereof is formed.
  • the present invention provides a method for forming a hard layer on the surface layer of titanium, comprising the steps of: (a) injecting and evacuating titanium to a vacuum heat treatment apparatus to maintain an air pressure of 10 -4 torr or less; (b) a pretreatment step of heating the titanium at 730 to 800 ° C. for 10 minutes to 5 hours to remove an oxide film formed on the surface of the titanium; (c) injecting at least one gas selected from nitrogen, oxygen, and carbon into the vacuum heat treatment apparatus and heating the titanium at 740 to 950 ° C. for 30 minutes to 20 hours, thereby gradient of concentration of the gas on the surface of the titanium alloy. Curing step to form a hard layer having a; And (d) cooling the titanium.
  • the air pressure of step (a) may be 5 ⁇ 10 -5 torr or less.
  • step (b) may be performed at 740 ⁇ 780 °C.
  • step (b) may be performed for 10 minutes to 1 hour.
  • the temperature of the step (c) may be higher than the temperature of the step (b).
  • the step (c) may be performed at 740 ⁇ 850 °C.
  • step (c) may be performed for 30 minutes to 5 hours.
  • step (d) may be cooled by a step cooling method.
  • step (d) may include an aging step of maintaining for 30 minutes to 30 hours at 500 ⁇ 800 °C.
  • the step (d) by using an over-layer coating method such as CVD method or PVD method, additionally forming a coating layer for the purpose of rubbing, color expression, etc. on the surface of titanium. It may include the step.
  • an over-layer coating method such as CVD method or PVD method
  • the titanium may be pure titanium or a titanium alloy.
  • the present invention also provides titanium and its alloys with hard layers formed by the method described above and various components utilizing this technology.
  • the oxide film removal of the titanium alloy surface, the formation of the inclined coating layer, etc. can be performed in one unit, so that the process is simplified and an excellent inclined hard layer can be obtained at low cost.
  • the hard layer formed according to the present invention is because the concentration gradient is formed from the surface of the intrusion-type element from the surface of the base material is a continuous change of physical properties between the hard layer and the base material, the peeling phenomenon at the interface does not occur.
  • the hard layer formed according to the present invention is a penetration type element is introduced into the base material, there is almost no dimensional change, so that subsequent processing is not necessary after the hardening treatment and thus economical.
  • the hard layer formed according to the present invention is an intrusion type element is injected into the crystal lattice of the base material, the defects of the thermal spray coating, PVD or CVD coating layer does not occur.
  • Example 1 is a schematic view of a cured layer forming process according to Example 1 of the present invention.
  • Figure 3 is a photograph of the observation of the surface of the hard layer formed according to Examples 1, 2 and Comparative Examples of the present invention with an optical microscope.
  • Figure 4 is a photograph of the cross-section of the hard layer and the PVD coating layer formed according to Examples 1, 2 and Comparative Examples of the present invention with a scanning electron microscope.
  • Figure 5 shows the results of measuring the surface roughness of the hard layer and the PVD coating layer formed according to Examples 1, 2 and Comparative Examples of the present invention.
  • Figure 6 shows the results of measuring the friction characteristics of the hard layer formed according to Examples 1, 2 and Comparative Examples of the present invention.
  • Figure 7 shows the results of measuring the cross-sectional hardness of the hard layer formed according to Examples 1, 2 and Comparative Examples of the present invention.
  • the inventors of the present invention found that when the surface of pure titanium and titanium alloys is coated with an over-layer coating method such as thermal spray coating, PVD, or CVD, a bilayer having a significant difference in physical properties at the interface between the titanium alloy base and the coating layer is essential. It is not only difficult to prevent the hard film from being peeled off due to external force, and the dimensional change due to the overlayer coating is inevitable, resulting in inevitable subsequent processing.Inner layers such as carburizing and sedimentation are noted. Attention was paid to the (inner-layer) coating method.
  • an over-layer coating method such as thermal spray coating, PVD, or CVD
  • the present inventors studied various inner layer coating methods, and as a result, several nanometer-thick oxide films formed on the surface of titanium when maintained at a high vacuum of 10 -4 torr or more in a specific temperature range in a vacuum chamber capable of heat treatment It can be confirmed that when the temperature range and gas pressure are maintained to facilitate the penetration of invasive elements such as nitrogen, oxygen, or carbon, in a short time, a hard layer of excellent physical properties having an inclination function can be obtained even in a short time.
  • the present invention has been reached.
  • the hard layer formed according to the present invention can prevent the separation between the coating layer and the matrix surface and the occurrence of cracking due to the external influence that may occur in the existing over-layer coating, and in particular, using a multi-step thermal diffusion surface hardening process technology.
  • the surface hardening treatment can be performed continuously without separately performing processes such as removing the oxide film and suppressing the formation of the oxide film, thereby enabling economical advantageous surface hardening while having optimal physical properties.
  • the method of forming a titanium hard layer comprises the steps of: (a) adding titanium to a vacuum heat treatment apparatus and evacuating to maintain an air pressure of 10 ⁇ 4 torr or less; (b) a pretreatment step of heating the titanium at 730 to 800 ° C. for 10 minutes to 5 hours to remove an oxide film formed on the surface of the titanium; (c) after removing the oxide film, injecting at least one gas selected from nitrogen, oxygen, and carbon into the heat treatment apparatus and heating the titanium at 740 to 950 ° C. for 30 minutes to 20 hours, thereby hardening the surface of the titanium alloy. Allowing a layer to be formed; And (d) cooling the titanium.
  • 'titanium' is used in the sense containing pure titanium and titanium alloy.
  • the degree of vacuum of the heat treatment apparatus should be lower than 1 ⁇ 10 -4 torr. If the pressure is 1 ⁇ 10 -4 torr or lower, the oxide film formed on the surface of titanium in step (b) cannot be removed cleanly. It is because the effect of the hardening process to do is not enough, It is more preferable to maintain so that the atmospheric pressure of a heat processing apparatus may be 5 * 10 ⁇ -5> torr or less.
  • the oxide film removing step should be carried out at 730 ⁇ 800 °C, if less than 730 °C the removal of the oxide film is not made sufficiently, the subsequent penetration process of intrusion type gas is long, if it exceeds 800 °C microhistological And a disadvantage in mechanical properties. More preferably, it is carried out at a temperature range of 740 °C to 780 °C.
  • the removal time in the oxide film removing step is more preferably 10 minutes to 1 hour, if less than 10 minutes is not sufficient oxide film removal, more than 1 hour is disadvantageous in terms of economic cost and mechanical properties Because.
  • the curing step may be carried out continuously with the removal of the oxide film, or may be performed by a two-stage heat treatment method performed by raising the temperature above the oxide film removal temperature, which is more preferable because the two-stage heat treatment method may shorten the curing time. . That is, the surface hardening treatment time can be considerably shortened by introducing a pretreatment process before performing the hardening heat treatment with the intruded gas element.
  • the temperature of the curing step should be carried out at 740 °C or more and can be carried out up to 850 °C depending on the depth and the required hardness of the cured layer. More preferably, it is performed at 780 ° C. or higher, which is higher than the oxide film removing step.
  • the curing treatment time is preferably 30 minutes to 20 hours, but less than 30 minutes is not enough to penetrate invasive elements such as oxygen, nitrogen, carbon, etc., and if it exceeds 20 hours, the grain size grows microscopically. This is because it is disadvantageous in terms of declining mechanical properties and economic cost.
  • the gas used for the hardening treatment is an element that can easily penetrate into the titanium crystal lattice, carbon, nitrogen, oxygen gas or a mixture thereof may be used.
  • the cooling step may be a method of furnace cooling or air cooling in the heat treatment furnace, during the cooling or air cooling, at 500 ⁇ 800 °C to evenly form the structure of the hard layer to be formed and to form a thick hard layer on the surface of the hard layer It is also possible to use a step cooling method including an aging step for 30 minutes to 30 hours.
  • the surface hardening specimen used in Example 1 of the present invention used commercially pure titanium (Gr. 2 material) having a width, length, and height of 30 mm ⁇ 25 mm ⁇ 2 mm, and the chemical composition of Gr.2 material suggested by the manufacturer. Is shown in Table 1 below.
  • the prepared titanium specimen was immersed in an acetone solution, ultrasonically cleaned and dried, and then surface hardened in the same manner as shown in FIG. 1.
  • the specimen was charged in a chamber of a gas controlled vacuum furnace (GCVF), and then decompressed to 5 ⁇ 10 ⁇ 6 torr using a vacuum pump. Subsequently, the temperature of the heat treatment furnace was raised to 750 ° C. and maintained for 30 minutes, so that the titanium oxide film having a thickness of about 10 ⁇ naturally formed on the surface of the titanium specimen could be removed by pyrolysis.
  • GCVF gas controlled vacuum furnace
  • the oxide film was removed in this manner, 100 ccm of a mixed gas of oxygen and nitrogen was injected, and the partial pressure in the chamber was adjusted so that the pressure in the chamber was maintained at 5 ⁇ 10 ⁇ 1 torr. Then, the temperature of the heat treatment furnace was raised to 800 ° C. and maintained for 3 hours to allow the injected oxygen and nitrogen elements to penetrate into the interior from the surface of the titanium specimen. After the hardening treatment was completed as described above, the titanium specimen was cooled by air cooling or furnace cooling.
  • a TiN coating layer was formed by PVD.
  • the PVD coating layer was formed using a Ti target in a nitrogen gas atmosphere at 150 ° C. for 10 minutes, and the thickness of the PVD coating layer formed was 2.1 ⁇ m.
  • Example 2 of the present invention after the specimen pretreatment and curing treatment under the same conditions using the same specimen as in Example 1 of the present invention, as shown in Figure 2, in the cooling step, homogenization of the microstructure and In order to maximize the strength and increase the thickness of the surface hard layer, an aging treatment held at 700 ° C. for 1 hour is performed, and then the hard layer is removed by air cooling (ie, step cooling). Formed.
  • the TiN coating layer was formed by PVD in order to lower the roughness of the titanium surface and to realize uniform color.
  • the PVD coating layer was formed using a Ti target in a nitrogen gas atmosphere at 150 ° C. for 10 minutes as in Example 1, and the thickness of the formed PVD coating layer was 2.1 ⁇ m.
  • Comparative Example is a TiN coating layer formed on the surface of the titanium specimen prepared in the same manner as Example 1 of the present invention by using a PVD method, the TiN coating layer is formed by using a Ti target in a nitrogen gas atmosphere at 150 °C for 10 minutes At this time, the thickness of the TiN coating layer formed was 3.4 ⁇ m.
  • the surface shape, cross-sectional shape, cross-sectional hardness, surface roughness, surface wear characteristics, and the like of the surface hard layer formed as described above were analyzed.
  • the shape of the surface was observed through an optical microscope, and the shape of the cross section was observed by a scanning electron microscope.
  • the surface roughness was measured by fixing the scan length to 9000 ⁇ m using a surface profiler (Model TENCOR P-11).
  • wear characteristics were measured using a ball on disk wear tester (J &L; Model JLTB-02 tribometer). At this time, as a counterpart, a stainless steel ball having a diameter of 1 mm was used. The friction coefficient of each specimen was measured under friction conditions of rotation radius 3mm, rotation speed 100rpm and load 1N, and the friction behavior was observed.
  • the cross-sectional hardness measured the cross-sectional hardness of the hard layer after cutting and grinding the specimen to the inclined surface. At this time, the hardness was measured from the surface of the specimen toward the matrix center while maintaining the load at 100 g for 10 seconds using a micro-Vickers hardness tester (FUTURE-TECH; Model FM-700).
  • FIG 3 is a photograph of the surface of the titanium specimen in which the hard layer was formed according to Examples 1, 2 and Comparative Examples of the present invention by an optical microscope.
  • the cross-sectional shape of the three surface-hardened specimens was observed using a scanning electron microscope.
  • the cross section was polished to an inclined surface and the diffusion hard layer was observed in FIG. 4. As shown in Figure 4, all three specimens can confirm the coating layer interface.
  • the entire surface hard layer is formed to have a thick surface hard layer of about 84 ⁇ m, including a TiN thin film layer of about 2.1 ⁇ m formed by PVD.
  • the thickest surface hard layer is formed to have a thickness of about 99 ⁇ m, including both the TiN thin film layer formed by PVD and the hard layer formed by the TCT process. .
  • the diffusion of the invasive element is promoted, and the boundary of the diffusion layer is changed obliquely, thereby preventing the thin film separation phenomenon during the abrasion test. For this reason, as shown below, the specimen according to Example 2 of the present invention exhibits the best surface friction characteristics (FIG. 6C).
  • the hard layer formed according to Example 2 Ra has a value of 0.14 ⁇ m.
  • the surface roughness is similar without significant change compared to the case where the surface hardening treatment is not performed. It can be seen that is almost similar to the comparative example in which PVD was formed directly on the titanium base material. That is, it can be seen that even if the titanium base material, or its hardening treatment or hardening treatment, the aging treatment does not significantly affect the surface roughness of the final PVD coating layer.
  • Figure 6 shows the surface friction coefficient measured by the wear test
  • Figure 6a is a comparative example
  • Figure 6b is a wear test result of the specimen formed with a cured layer by Example 1
  • Figure 6c is Example 2.
  • the friction coefficient values of the three specimens showed a significant difference in the initial change within about 3,000 cycles, and the specimen according to the comparative example reached the average friction coefficient value before 50 revolutions, unlike the specimens according to Examples 1 and 2. Shows a sharp increase.
  • the specimen according to Example 1 reached the average friction coefficient value only after reaching 500 rotations, and exhibited excellent wear resistance compared to the comparative example.
  • the specimen according to Example 2 had up to about 2,500 rotations. It has the best wear resistance with low coefficient of friction.
  • the PVD TiN layer formed by the proportional example causes the TiN layer to easily separate and fall off at the beginning of the abrasion test due to the distinct characteristic difference (i.e. hardness difference) formed between the base material and the TiN layer. It is.
  • the average coefficient of friction of CP Ti (Gr. 2), the base material of the three specimens used to analyze the wear characteristics, was about 0.7, and all three specimens showed relatively lower coefficients of friction than the untreated specimens. It is judged that the coating layer is not completely removed even up to 20,000 times due to the small load of 1N, and it is possible to obtain a certain effect of increasing the surface hardness only by physical vapor deposition. It can be seen that the wear characteristics can be obtained.
  • the surface hardness of three specimens was measured to investigate the effect of nitride on the surface of pure titanium matrix and the effect of surface treatment conditions on the specimens.
  • CP Ti Ge (Gr. 2)
  • the Vickers hardness was about 167 Hv
  • Comparative Example 373 Hv, Example 1 441 Hv, Example 2 was measured at 489 Hv, respectively. That is, it can be seen that the surface hardness increases considerably due to the formation of the hard film regardless of the method of surface hardening treatment.
  • Figure 7 shows the results of measuring the hardness change according to the cross-sectional depth from the surface of the specimens according to Comparative Example, Example 1 and Example 2 using Vickers hardness measurement.
  • the cross-sectional hardness is measured from the surface of the specimen toward the center of the matrix.
  • the cross-sectional hardness of the outermost surface portion is about 340 Hv of the specimen according to the comparative example, while the specimen according to Example 1 is 450 Hv, and the specimen according to Example 2 is 500 Hv or more, three times higher than known. The value is shown.
  • the hard layer of the specimen according to the comparative example has a thickness within a few micrometers, and after the surface hard layer, a sudden sudden decrease in hardness up to about 160 Hv, which is the standard hardness value of CP Ti, is observed.
  • the hardness decreases continuously as the depth increases from the surface.
  • the hardness value is higher than the known hardness value even at a depth of about 80 ⁇ m.
  • a hardness value higher than the known hardness value was maintained up to about 100 ⁇ m.
  • the hardness distribution results of the inclined functional hard layer is initially due to the higher internal hardness and thicker inclined functional hard layer formed in the specimen according to Example 2 when compared with the friction characteristics (Fig. 6).
  • the coefficient of friction rises the slowest and reaches more than 2,500 times, which coincides with the convergence tendency to reach the average coefficient of friction other than the hard layer.
  • the hard layer forming method according to the present invention enables formation of a hard layer having excellent physical properties in a short time as compared with the conventional hard layer forming method.

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  • Engineering & Computer Science (AREA)
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  • Chemical Vapour Deposition (AREA)

Abstract

La présente invention concerne un procédé de formation à faible coût d'une couche dure présentant d'excellentes propriétés à gradient fonctionnel sur la surface du titane. Ledit procédé consiste à : a) insérer le titane dans un dispositif de traitement thermique, en ventilant ledit titane, et à maintenir la pression de l'air entre 10 et 4 torr ou moins ; b) prétraiter le titane par chauffage à une température variant entre 730 et 800°C pendant 10 minutes à 5 heures et retirer le film d'oxyde formé sur la surface du titane ; injecter un ou plusieurs gaz choisis parmi l'azote, l'oxygène et le carbone dans le dispositif de traitement thermique et chauffer le titane à une température variant entre 740 et 950°C pendant 30 minutes à 20 heures, ce qui permet de former la couche dure présentant une densité neuf fois supérieure à celle du gaz sur la surface de l'alliage ; et d) refroidir le titane.
PCT/KR2012/002146 2012-03-23 2012-03-23 Procédé de formation de couche dure sur le titane, et alliage ayant couche dure formée par ledit procédé WO2013141422A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US13/988,348 US20130248051A1 (en) 2012-03-23 2012-03-23 Method of forming rigid layer on titanium and titanium alloy having rigid layer formed by the same
PCT/KR2012/002146 WO2013141422A1 (fr) 2012-03-23 2012-03-23 Procédé de formation de couche dure sur le titane, et alliage ayant couche dure formée par ledit procédé
JP2015503083A JP2015519470A (ja) 2012-03-23 2012-03-23 チタンに硬質層を形成する方法及びこれにより形成された硬質層を有するチタン合金

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PCT/KR2012/002146 WO2013141422A1 (fr) 2012-03-23 2012-03-23 Procédé de formation de couche dure sur le titane, et alliage ayant couche dure formée par ledit procédé

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Families Citing this family (1)

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Publication number Priority date Publication date Assignee Title
CN106244981B (zh) * 2016-08-29 2018-09-14 华南理工大学 一种气门热锻模强化处理方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05331617A (ja) * 1991-12-13 1993-12-14 Toyota Motor Corp チタン系合金部材の表面処理法
JP2001081544A (ja) * 1999-09-13 2001-03-27 Citizen Watch Co Ltd チタン、あるいはチタン合金製食器およびその表面処理方法
JP2001301400A (ja) * 2000-04-19 2001-10-31 Citizen Watch Co Ltd 硬質装飾被膜を有する基材及びその製造方法
KR100773886B1 (ko) * 2006-05-11 2007-11-06 부산대학교 산학협력단 타이타늄-몰리브덴-실리콘-질소계 경질 코팅막

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5633487A (en) * 1979-08-22 1981-04-03 Hitachi Ltd Removing method for oxidized film of titanium or titanium alloy
JPH04200557A (ja) * 1990-11-30 1992-07-21 Koki Bussan Kk 生体用インプラント材料
JPH08296064A (ja) * 1995-04-24 1996-11-12 Sumitomo Metal Mining Co Ltd 耐酸化性・耐摩耗性被膜付き物品
JPH10280126A (ja) * 1997-04-08 1998-10-20 Citizen Watch Co Ltd 表面硬化チタン材料およびチタン材料の表面硬化方法ならびにその製品

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05331617A (ja) * 1991-12-13 1993-12-14 Toyota Motor Corp チタン系合金部材の表面処理法
JP2001081544A (ja) * 1999-09-13 2001-03-27 Citizen Watch Co Ltd チタン、あるいはチタン合金製食器およびその表面処理方法
JP2001301400A (ja) * 2000-04-19 2001-10-31 Citizen Watch Co Ltd 硬質装飾被膜を有する基材及びその製造方法
KR100773886B1 (ko) * 2006-05-11 2007-11-06 부산대학교 산학협력단 타이타늄-몰리브덴-실리콘-질소계 경질 코팅막

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JEONG, HYEON GYEONG ET AL.: "Improvement of Surface Properties of CP-Titanium by Thermo-Chemical Treatment (TCT) Process", KOREAN JOURNAL OF METALS AND MATERIALS, vol. 49, no. 9, 25 September 2011 (2011-09-25), pages 692 - 698 *

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