CN106493363A - Titanium sintered body and ornament - Google Patents

Titanium sintered body and ornament Download PDF

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Publication number
CN106493363A
CN106493363A CN201610806098.9A CN201610806098A CN106493363A CN 106493363 A CN106493363 A CN 106493363A CN 201610806098 A CN201610806098 A CN 201610806098A CN 106493363 A CN106493363 A CN 106493363A
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China
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phases
sintered body
titanium
titanium sintered
less
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CN201610806098.9A
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CN106493363B (en
Inventor
川崎琢
中村英文
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Seiko Epson Corp
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Seiko Epson Corp
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Priority claimed from JP2016107641A external-priority patent/JP6884994B2/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F5/10—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of articles with cavities or holes, not otherwise provided for in the preceding subgroups
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B37/00—Cases
    • G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C27/00—Making jewellery or other personal adornments
    • A44C27/001—Materials for manufacturing jewellery
    • A44C27/002—Metallic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1003—Use of special medium during sintering, e.g. sintering aid
    • B22F3/1007—Atmosphere
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B22F3/15—Hot isostatic pressing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
    • B22F3/225—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip by injection molding
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/045—Alloys based on refractory metals
    • C22C1/0458—Alloys based on titanium, zirconium or hafnium

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Powder Metallurgy (AREA)

Abstract

The present invention provides the titanium sintered body and ornament of the specularity that can remain good for a long time.Titanium sintered body (1) is characterised by, including：Used as crystalline structure α phases (2) and β phases (3), the mean diameter of α phases (2) is less than more than 3 μm 30 μm in cross section, and the area occupation ratio shared by α phases (2) is less than more than 70% 99.8% in cross section.In addition, it is less than more than 13 that titanium sintered body (1) is preferably the average aspect ratio of the α phases (2) in section.In addition, titanium sintered body (1) is preferably with titanium as main constituent and including α phases stabilizing element and β phase stabilizing elements.

Description

Titanium sintered body and ornament
Technical field
The present invention relates to titanium sintered body and ornament.
Background technology
The mechanical strength of titanium alloy, excellent corrosion resistance, therefore in the fields such as airborne vehicle, space development, chemical plant Using the titanium alloy.In addition, recently, the characteristic of compatible, low Young's moduluss of organism of effectively utilizes titanium alloy etc., and constantly It is applied to the exterior member of wrist-watch, sports goods and spring as ornament, golf clubs as frame Deng.
In addition, in such application, by adopting powder metallurgic method, can easy to manufacture be close to the shape of net shape Titanium sintered body.Thereby, it is possible to omitting secondary operations, reducing processing capacity, efficient part production can be carried out.
However, the titanium sintered body manufactured by powder metallurgic method easily reflects the characteristic of material powder, it is difficult to improve surface Flatness.Therefore, the specularity of titanium sintered body is easily reduced, so as to become apparent technical problem.
In this regard, proposing the trial of the specularity for improving the titanium sintered body manufactured by powder metallurgic method.
For example, the decoration titanium alloy with following feature Patent Document 1 discloses：Include to press in press-powder shaping The mixing that the iron powder of weight ratio meter 0.1%～1.0%, 0.1%～4.0% molybdenum powder and remainder are made up of titanium powder After powder, it is sintered with 1200 DEG C～1350 DEG C.Then, the titanium alloy of acquisition includes the two-phase structure of alpha+beta, obtains outside wrist-watch Specularity required by dress part etc..
However, the titanium alloy described in patent documentation 1 includes ferrum outside titanium, therefore resistance to ag(e)ing is poor.Therefore, growing In the case that phase is exposed to harsh environment, surface produces deterioration, as a result, causing the reduction of specularity.
Prior art literature
Patent documentation
Patent documentation 1：Japanese Unexamined Patent Publication 8-92674 publication
Content of the invention
It is an object of the invention to, there is provided the titanium sintered body and ornament of good specularity can be maintained for a long time.
Above-mentioned purpose is realized by following present invention.
The present invention titanium sintered body be characterised by, including：
As the α phases and β phases of crystalline structure,
The mean diameter of the α phases is less than more than 3 μm 30 μm in cross section,
Area occupation ratio shared by the α phases is less than more than 70% 99.8% in cross section.
Thus, the titanium sintered body of the specularity that can remain good for a long time is obtained.
In the titanium sintered body of the present invention, preferably, the average aspect ratio of the α phases is less than more than 13 in cross section.
Thus, as the amount of grinding when attrition process is implemented to titanium sintered body is difficult to produce anisotropy, therefore grinding It is difficult to produce on flour milling concavo-convex.Therefore, it is possible to further improve the flatness of abradant surface, the excellent titanium of specularity is particularly obtained Sintered body.
In the titanium sintered body of the present invention, preferably, in the X-ray diffraction spectra obtained by X-ray diffraction method, it is based on The peak value of the reflex strength of the planar orientation (110) of the β phases is the peak of the reflex strength of the planar orientation (100) based on the α phases Less than more than the 3% 60% of value.
Thus, characteristic that the characteristic that α phases have had with β phases will not be buried respectively and which is significantly changed.As a result, special The titanium sintered body of high specularity Huo get not maintained for a long time.
In the titanium sintered body of the present invention, preferably, the titanium sintered body is with titanium as main constituent and including α phases stabilisation unit Element and β phase stabilizing elements.
Thus, even if the manufacturing condition of titanium sintered body, use condition change, it is also possible to have as crystallization group in the lump The α phases that knits and β phases, therefore form the excellent material of resistance to ag(e)ing.As a result, titanium sintered body has the spy that α phases are in the lump The characteristic that property with β phases is in, particularly mechanical property are excellent.
In the titanium sintered body of the present invention, preferably, the relative density of the titanium sintered body is more than 99%.
Thus, when the surface to titanium sintered body is ground, especially good specularity is shown.
The ornament of the present invention preferably includes the titanium sintered body of the present invention.
Thus, good specularity is maintained for a long time, as a result, acquisition can maintain excellent cosmetic look for a long time Ornament.
Description of the drawings
Fig. 1 is the electron microscopic mirror image of the embodiment of the titanium sintered body for representing the present invention.
Fig. 2 is the figure of a part for the electron microscopic mirror image shown in schematic representation Fig. 1.
Fig. 3 is the axonometric chart of the watchcase of the embodiment for representing the ornament for being suitable for the present invention.
Fig. 4 is partial cross section's axonometric chart of the bezel, cluster of the embodiment for representing the ornament for being suitable for the present invention.
Fig. 5 is the X-ray diffraction spectra of the titanium sintered body acquisition for embodiment 1.
Fig. 6 is the electron microscopic mirror image in the section of the titanium sintered body of comparative example 2.
Fig. 7 is the electron microscopic mirror image in the section of the titanium melting material of reference example 1.
Symbol description
1st, titanium sintered body；2nd, α phases；3rd, β phases；11st, watchcase；12nd, bezel, cluster；112nd, housing main body；114th, band installation portion.
Specific embodiment
Hereinafter, the titanium sintered body and ornament of the present invention are carried out specifically based on desirable embodiments shown in the drawings Bright.
Titanium sintered body
First, the embodiment of the titanium sintered body of the present invention is illustrated.
Fig. 1 is the electron microscopic mirror image of the embodiment of the titanium sintered body for representing the present invention, and Fig. 2 is schematic representation Fig. 1 The figure of a part for shown electron microscopic mirror image.Additionally, Fig. 1 is the figure for cutting section for shooting titanium sintered body, Fig. 1's The band of the dark color that upper end edge or so extends is the region in the outside of titanium sintered body.
The titanium sintered body of present embodiment is manufactured by such as powder metallurgic method.That is, in the titanium sintered body, closed by making titanium The particle at bronze end is sintered each other and is constituted.
More particularly, as shown in Fig. 2 in titanium sintered body 1, including the α phases 2 as crystalline structure and β phases 3.Wherein, α Phase 2 refers to that constituting its crystal structure is mainly the region (titanium α phases) that six side's closest packings (hcp) are constructed.On the other hand, β phases 3 Refer to that constituting its crystal structure is mainly the region (titanium β phases) that body-centered cubic lattic (bcc) is constructed.Additionally, in FIG, α phases 2 are revealed as the region relatively in light color, and β phases 3 are revealed as relatively in dark region.
With regard to α phases 2, relatively hardness is relatively low and ductility is abundant, therefore especially contribute to realize intensity under high temperature, The excellent titanium sintered body 1 of deformation resistance.On the other hand, with regard to β phases 3, relatively hardness is higher, easily produces plastic deformation, because This contributes to realizing as entirety and the titanium sintered body 1 of tenacity excellent.
In the section of titanium sintered body 1, preferably its overwhelming majority is occupied by such α phases 2 and β phases 3.α phases 2 and β phases 3 Total occupation rate (area occupation ratio) is not particularly limited, but preferably more than 95%, more preferably more than 98%.Such titanium burns In knot body 1, α phases 2 and β phases 3 are characteristically formed and are dominated, and therefore reflect the lot of advantages that titanium has.
Additionally, total occupation rate of α phases 2 and β phases 3 is in the following way trying to achieve：For example pass through ultramicroscope, light The section of the observation titanium such as microscope sintered body 1 is learned, is distinguished based on the difference of the different colour generation according to crystal structure, contrast Crystalline phase, and measured area.
In addition, as the crystalline structure beyond α phases 2, β phases 3, such as enumerating ω phases, γ equal.
In addition, titanium sintered body 1 is as described above comprising α phases 2 and β phases 3, and the mean diameter of α phases 2 is more than 3 μm 30 μ Below m, also, the occupation rate (area occupation ratio) shared by α phases 2 is less than more than 70% 99.8%.
The α phases 2 of such titanium sintered body 1 are small, also, become leading due to α phases 2, therefore on the basis of intensity height It is rich in the uniformity of attrition process.Therefore, in attrition process, it is difficult to which generation is concavo-convex with the difference of hardness of β phases 3 based on α phases 2, The flatness of abradant surface can be improved.In addition, the α phases 2 that dominance is present are difficult to produce dislocation, therefore, it is difficult to because of grinding Generation is modified, also, corrosion resistance is higher, hence helps to the smooth state after long-term maintenance grinding.In other words, due to carrying High abrasion resistance, therefore, it is possible to suppress scraping of abradant surface etc., maintains abradant surface for a long time well.On the other hand, with 2 phase of α phases Than and the easy generation plastic deformation as described above of the less β phases 3 of amount, therefore promote the 2 mutual slip of α phases.Therefore, exist In the case of applying stress during attrition process, the stress can be also relaxed in β phases 3.As a result, can suppress produce with residual A problem that reduction of the flatness for staying stress associated.In other words, obtaining to carry out the abrasiveness of good grinding, therefore The high abradant surface of specularity can be readily available.
Additionally, if the mean diameter of α phases 2 is less than the lower limit, the particle diameter of α phases 2 becomes too small, therefore, it is difficult to carrying out Appropriate grinding, and the α phases 2 of path are easily impacted to the reflection of light, it is possible to make the specularity of abradant surface.Except this it Outward, due to cannot fully improve the occupation rate of α phases 2, it is therefore possible to the mechanical strength of titanium sintered body 1 fully cannot be improved.Separately On the one hand, if the mean diameter of α phases 2 exceedes the higher limit, α phases 2 easily become needle-like shape.If becoming needle-like shape, Then the fatigue strength of titanium sintered body 1 is easily reduced, it is difficult to maintain high specularity for a long time.Wear resistance reduction is additionally, since, therefore Abradant surface becomes easily scraping, it is possible to become to be difficult to long-term maintenance abradant surface well.In addition to that it is possible to make mainly to come Reduce from the mechanical strength of α phases 2.
If in addition, the area occupation ratio shared by α phases 2 is less than the lower limit, correspondingly increasing the area shared by β phases 3.Thus, β Phase 3 contributes to the degree increase of the reflection of light, and the specularity of abradant surface reduces.On the other hand, if the area occupation ratio shared by α phases 2 is high In the higher limit, the amount of β phases 3 is correspondingly reduced.Thus, the stress produced between α phases 2 for mitigation is damaged β phases 3 function, it is therefore possible to together reducing the flatness of abradant surface with residual stress.
In addition, the mean diameter of α phases 2 is preferably less than more than 5 μm 25 μm, more preferably less than more than 7 μm 20 μm.
Additionally, the mean diameter of α phases 2 is determined in the following way.First, using electron microscope observation titanium sintered body 1 Section, randomly choose the α phases 2 of more than 100 as in the observation for obtaining.Next, calculating the α selected as in observation The area of phase 2, obtains with the diameter of a circle with the area identical area.The particle diameter that the circle that so obtains is considered as the α phases 2 (diameter of equivalent circle), obtains the meansigma methodss of the α phases 2 for more than 100.Using the meansigma methodss as α phases 2 mean diameter.
In addition, the area occupation ratio shared by α phases 2 is preferably less than more than 75% 99%, more preferably less than more than 80% 98%.
Additionally, the area occupation ratio shared by α phases 2 is measured in the following way.First, titanium is observed using ultramicroscope The section of sintered body 1, calculates the area of the observation picture for obtaining.Next, obtaining the conjunction of the area of the α phases 2 for being revealed in observation picture Meter.Then, by total area divided by observation picture of the area of the α phases 2 that obtains.Its solution becomes the area occupation ratio shared by α phases 2.
On the other hand, in the case where α phases 2 are area occupation ratio as described above, the area occupation ratio of β phases 3 diminishes in contrast.Tool For body, the area occupation ratio of β phases 3 is preferably less than more than 0.2% 30% Zuo You, more preferably less than more than 1% 25% Zuo You, enters One step is preferably less than more than 2% 20% Zuo You.β phases 3 easily produce plastic deformation as described above, therefore promote α phases 2 each other Slip.Therefore, existed with the ratio in the scope by making β phases 3, thus when being ground to titanium sintered body 1, It is prevented from resistance when grinding to significantly increase.As a result, the flatness of abradant surface further can be improved, mirror is obtained in that Face property is high and in the excellent titanium sintered body 1 of the aspect of appearance looks elegant.
The constituent material of such titanium sintered body 1 is titanium monomer or titanium-base alloy.
Titanium-base alloy is the alloy with titanium as main constituent, be outside titanium (Ti) for example comprising carbon (C), nitrogen (N), oxygen (O), Aluminum (Al), vanadium (V), niobium (Nb), zirconium (Zr), tantalum (Ta), molybdenum (Mo), chromium (Cr), manganese (Mn), cobalt (Co), ferrum (Fe), silicon (Si), The alloy of the elements such as gallium (Ga), stannum (Sn), barium (Ba), nickel (Ni), sulfur (S).
Wherein, the titanium-base alloy of present embodiment preferably comprises α phases stabilizing element with β phase stabilizing elements.Thus, close In titanium sintered body 1, even if its manufacturing condition, use condition change, it is also possible to have the α phases 2 as crystalline structure in the lump With β phases 3, therefore become the excellent material of resistance to ag(e)ing.Therefore, titanium sintered body 1 becomes the characteristic and β that there is α phases 2 to be in the lump The material of the characteristic that phase 3 is in, especially mechanical property is excellent.
Wherein, as α phase stabilizing elements, for example, aluminum, gallium, stannum, carbon, nitrogen, oxygen etc. are enumerated, be applied in combination in these Plant or two or more.On the other hand, as β phase stabilizing elements, for example, molybdenum, niobium, tantalum, vanadium, ferrum etc. is enumerated, this is applied in combination More than the one or two kinds of in a little.
As the concrete composition of titanium-base alloy, enumerate in JIS H 4600：Be defined as in 2012 60 kinds, 60E kinds, 61 kinds or The titanium alloy of person's 61F kinds.Specifically, Ti-6Al-4V, Ti-6Al-4V ELI, Ti-3Al-2.5V etc. are enumerated.Additionally, enumerating Ti-6Al-6V-2Sn, Ti-6Al-2Sn-4Zr-2Mo-0.08Si, Ti-6Al- of aerospace material specification (AMS) defined 2Sn-4Zr-6Mo etc..In addition, enumerating Ti-5Al-2.5Fe, the Ti- for the specification defined that the International Organization for Stand (ISO) is formulated 6Al-7Nb etc..In addition, enumerating Ti-13Zr-13Ta, Ti-6Al-2Nb-1Ta, Ti-15Zr-4Nb-4Ta, Ti-5Al-3Mo-4Zr Deng.
Additionally, the statement constituted with regard to above-mentioned alloy, records the big composition of concentration successively from a left side, before element Numeral be used for representing the concentration of the element with quality %.For example, Ti-6Al-4V represents the Al comprising 6 mass % and 4 mass % V and remainder is Ti and impurity.Additionally, impurity be with specify ratio (such as impurity add up to 0.40 mass % with Under) element being inevitably mixed into or the element for intentionally adding.
In addition, the scope of the main matter of above-mentioned alloy composition is as described below.
In Ti-6Al-4V alloys, with more than 5.5 mass % 6.75 mass % Al included below, more than 3.5 mass % 4.5 mass % V included below, remainder are Ti and impurity.As impurity, for example allow below with Fe as 0.4 mass %, It is below 0.05 mass %, the ratio that H is below 0.015 mass %, C is below 0.08 mass % that O is below 0.2 mass %, N Include above-mentioned element respectively.Further, it is allowed to be respectively below 0.10 mass %, add up to 0.40 mass % with other elements Following ratio includes above-mentioned other elements respectively.
In Ti-6Al-4V ELI alloys, with more than 5.5 mass % 6.5 mass % Al included below, with 3.5 mass % with Upper 4.5 mass % V included below, remainder are Ti and impurity.As impurity, for example allow with Fe as 0.25 mass % with Under, O be 0.13 mass % below, N be 0.03 mass % below, H be 0.0125 mass % below, C be 0.08 mass % below Ratio respectively include above-mentioned element.Further, it is allowed to be respectively below 0.10 mass %, add up to 0.40 with other elements Ratio below quality % includes above-mentioned other elements respectively.
With regard to Ti-3Al-2.5V alloys, it is allowed to more than 2.5 mass % 3.5 mass % Al included below, with 1.6 matter Amount 3.4 mass % of more than % V included below, as desired with more than 0.05 mass % 0.20 mass % S included below, according to Need to add up at least one in 0.70 mass % of more than 0.05 mass % La, Ce, Pr and Nd included below, remainder It is divided into Ti and impurity.As impurity, for example allow below with Fe as 0.30 mass %, O be 0.25 mass % below, N be Below 0.05 mass %, H is below 0.015 mass %, C is below 0.10 mass % ratio include above-mentioned element respectively.Enter One step, it is allowed to include other elements to add up to the ratio of below 0.40 mass %.
In Ti-5Al-2.5Fe alloys, it is allowed to more than 4.5 mass % 5.5 mass % Al included below, with 2 mass % with Upper 3 mass % Fe included below, remainder are Ti and impurity.As impurity, for example allow below with O as 0.2 mass %, The ratio that N is below 0.05 mass %, H is below 0.013 mass %, C is below 0.08 mass % includes above-mentioned element respectively. Further, it is allowed to include other elements to add up to the ratio of below 0.40 mass %.
In Ti-6Al-7Nb alloys, with more than 5.5 mass % 6.5 mass % Al included below, more than 6.5 mass % 7.5 mass % Nb included below, remainder are Ti and impurity.As impurity, for example allow with Ta as 0.50 mass % with Under, Fe be 0.25 mass % below, O be 0.20 mass % below, N be 0.05 mass % below, H be 0.009 mass % below, C is that the ratio of below 0.08 mass % includes above-mentioned element respectively.Further, it is allowed to add up to the ratio of below 0.40 mass % Example includes other elements.Additionally, the cytotoxicity of Ti-6Al-7Nb alloys is especially low compared with other alloy species, therefore In the case where titanium sintered body 1 to be applied to organism adaptation purposes, it is useful especially.
In addition, with regard to the composition contained by titanium sintered body 1, can pass through with such as JIS H 1632-1 (2014)～JIS H Method on the basis of the titanium-ICP ICP Atomic Emission Spectrophotometer methods of 1632-3 (2014) defined is analyzed.
In addition, titanium sintered body 1 can also include the particle with titanium oxide as main constituent and (below, omitting and being referred to as " titanium oxide grain Son ".).The Titanium particles pass through to disperse in titanium sintered body 1, it is believed that can share to the Titanium applying as matrix Stress.Therefore, by comprising Titanium particles, realizing the raising of the mechanical strength in 1 entirety of titanium sintered body.In addition, titanium oxide Harder than Titanium, therefore disperseed by making Titanium particles, can further improve the wear resistance of titanium sintered body 1.Thus, by Scraping in abradant surface etc. is suppressed, and maintains abradant surface well therefore, it is possible to long-term.
Additionally, the particle with titanium oxide as main constituent is referred to for example shown by fluorescent x-ary analysis or electron probe It is in titanium and oxygen that differential analyzer carries out the component analyses of the particle for becoming object and analyzed as being the element for containing up to Side, next more containing element for the opposing party particle.
The mean diameter of Titanium particles is not particularly limited, preferably less than more than 0.5 μm 20 μm, more preferably 1 μm Above less than 15 μm, more preferably less than more than 2 μm 10 μm.If the mean diameter of Titanium particles is in the scope Interior, then will not the mechanical property such as the toughness of larger infringement titanium sintered body 1, tensile strength, it is possible to increase wear resistance.That is, if oxygen The mean diameter for changing titanium particle is less than the lower limit, it is likely that reduce Titanium particles because of the containing ratio of Titanium particles The effect of sharing of the stress for being played.If in addition, the mean diameter of Titanium particles is higher than the higher limit, it is likely that because of oxygen Change the containing ratio of titanium particle and make Titanium particles become the starting point of crackle, so as to reduce mechanical strength.
In addition, the crystal structure of Titanium particles can be arbitrary in rutile-type, Detitanium-ore-type and brookite type Person, it is also possible to mix multiple types.
Additionally, the mean diameter of Titanium particles is measured in the following way.First, seen using ultramicroscope The section of titanium sintered body 1 is examined, in the Titanium particles that the observation for obtaining randomly chooses more than 100 as in.Now, can be by scheming Surface analysis of the contrast of picture and oxygen etc. is determining whetheing there is Titanium particles.Next, calculating the oxygen selected as in observation Change the area of titanium particle, obtain with the diameter of a circle with its area identical area.The circle that so obtains is considered as the oxidation The particle diameter (diameter of equivalent circle) of titanium particle, obtains the meansigma methodss of the Titanium particles for more than 100.The meansigma methodss become oxygen Change the mean diameter of titanium particle.
In addition, the α phases 2 of present embodiment are preferably shaped to not needle-like shape but wait square or with which as base Accurate shape.By with such shape, the reduction of the fatigue strength of titanium sintered body 1 as described above, can be suppressed.Which is tied Fruit is to obtain the titanium sintered body 1 that can maintain high specularity for a long time.
Specifically, in the section of titanium sintered body 1, the average aspect ratio of α phases 2 is preferably less than more than 13, more preferably For less than more than 1 2.5.By making the average aspect ratio of α phases 2 in the scope, suppress the fatigue strength of titanium sintered body 1 with And the reduction of hardness.Therefore, obtain as the useful titanium sintered body 1 of structural member.In addition, by by average aspect ratio adjust to In the scope, the amount of grinding when attrition process is implemented to titanium sintered body 1 is difficult to produce anisotropy, therefore on abradant surface It is difficult to produce concavo-convex.As a result, the flatness of abradant surface further can be improved, particularly obtain the excellent titanium of specularity and burn Knot body 1.In other words, if amount of grinding easily produces anisotropy, it is likely that also produce anisotropy in the reflection of light, make mirror Face property, taste reduce.
Additionally, the average aspect ratio of α phases 2 is determined in the following way.First, using electron microscope observation titanium sintered body 1 section, in the α phases 2 that the observation for obtaining randomly chooses more than 100 as in.Select next, determining as in observation Most long axle on the direction orthogonal with the major axis is further defined as short axle by the major axis of α phases 2.Next, by major axis/short Axle is calculated as aspect ratio.Then, aspect ratio of the average needle to the α phases 2 of more than 100, is set to average aspect ratio.
In addition, in the titanium sintered body 1 of present embodiment, the particle diameter of α phases 2 is more neat.Therefore, wait square or with Outside shape on the basis of which, also realize making particle diameter neat, it is possible to increase the fatigue strength of titanium sintered body 1, and keep for a long time High specularity.
If the transverse axis with the particle diameter of α phases 2 as drawing area, with the quantity of α phases 2 corresponding with the particle diameter as drawing area The longitudinal axis and draw the measurement result of particle diameter, then obtain the particle size distribution of α phases 2.In the particle size distribution, will be individual from path side Several build up as overall 16% when particle diameter be set to D16, by overall for the build up as of the number from path side 84% When particle diameter be set to D84.Now, standard deviation S D of particle size distribution is obtained by following formula.
SD=(D84-D16)/2
Standard deviation S D that so obtains becomes the benchmark of the dispersion of distribution of particle size distribution.Then, in present embodiment In titanium sintered body 1, standard deviation S D of the particle size distribution of α phases 2 is preferably less than 5, more preferably less than 3, more preferably 2 Below.The particle size distribution of titanium sintered body 1 of standard deviation S D of the particle size distribution of α phases 2 in the scope is very narrow, makes The particle diameter of α phases 2 is neat enough.With regard to the titanium sintered body 1, particularly fatigue strength is higher, and can maintain Gao Jing for a long time Face property.
In addition, titanium sintered body 1 is used for the crystal structure based on X-ray diffraction method parsing, the X-ray diffraction spectra of acquirement The peak value of the peak value comprising the reflex strength with α phases as cause and the reflex strength with β phases as cause.
Here, reflex strength of the X-ray diffraction spectra for obtaining particularly preferably comprising the planar orientation (100) based on titanium α phases Peak value, the peak value of the reflex strength of planar orientation (110) based on titanium β phases.On its basis, the planar orientation based on titanium β phases (110) peak value (value of summit) of reflex strength is preferably based on the peak value of the reflex strength of the planar orientation (100) of titanium α phases Less than more than the 3% 60% of (value of summit), more preferably less than more than 5% 50%, more preferably more than 10% 40% Below.Thus, characteristic that the characteristic that described α phases 2 have had with β phases 3 will not be buried respectively and which is significantly changed.Its result It is to obtain the titanium sintered body 1 that particularly can maintain high specularity for a long time.
Additionally, in the peak value of the reflex strength caused by the planar orientation (100) of titanium α phases, 2 θ are near 35.3 °.Another Aspect, in the peak value of the reflex strength of the planar orientation (110) based on titanium β phases, 2 θ are near 39.5 °.
In addition, as the x-ray source of X-ray diffraction device, using Cu-K alpha rays, tube voltage is set to 30kV, by pipe electricity Stream is set to 20mA.
In addition, the relative density of titanium sintered body 1 is preferably more than 99%, more preferably more than 99.5%.Burnt by making titanium The relative density of knot body 1 obtains, in the scope, the titanium sintering for showing especially good specularity when surface is ground Body 1.That is, relative density as by adopting, is difficult to produce emptying aperture in titanium sintered body 1.Therefore, it is possible to suppress because of the sky Hole and hinder light reflect.
Additionally, the relative density of titanium sintered body 1 is with JIS Z 2501：The density of the sintered metal materials of 2000 defineds The dry density determined on the basis of test method.
In addition, the Vickers hardness (HV) of titanium sintered body 1 is not particularly limited, but preferably more than 300, more preferably 350 Above less than 600.The titanium sintered body 1 with such hardness is difficult to form scraping etc. on surface.Therefore, even if obtaining for example Can also suppress in the case of being used as the constituent materials such as ornament because of the titanium sintered body 1 of the infringement aesthetic feeling such as scraping.
The Vickers hardness (HV) of titanium sintered body 1 is determined at the surface of titanium sintered body 1, and assay method is based on JIS Z 2244：Vickers hardness test-the test method of 2009 defineds.Additionally, the test force of tabletting is set to 9.8N (1kgf), will examination The retention time for testing power is set to 15 seconds.Then, the meansigma methodss of the measurement result at 10 are set to the Vickers hardness on surface.
Such titanium sintered body 1 can be applied to various uses, be not particularly limited, be particularly useful as ornament Constituent material.
Ornament
Next, the embodiment to the ornament of the present invention is illustrated.
As the ornament of the present invention, for example, enumerate watchcase (main body, inner lid, the main body monolithic shell integrated with inner lid Deng), watchband is (including bracelet, band-bracelet charging crane etc..), bezel, cluster (such as rotation bezel, cluster etc.), table is (such as twist-lock Formula table etc.), button, glass edge, calibration loop, panel board, table exterior member, glasses (such as spectacle-frame as pad Frame), tiepin, cuff snap-fastener, ring, necklace, bracelet, foot chain, brooch, ear pendant, earrings, haberdashery as ear nail, Spoon, fork, chopsticks, knife, butter knife, feeder, lighter or body as its shell, golf clubs as bottle opener (for example mobile phone, smart mobile phone, current guideboard terminal, mobile model are calculated to educate articles for use, label, panel, trophy and housing The housing of machine, music player, video camera, shaver etc.) as equipment exterior member etc..These ornaments are respectively provided with excellent Different cosmetic look.Titanium sintered body 1 is used by the constituent material as these ornaments, can be to the surface of ornament Give excellent specularity.Thus, the ornament of the cosmetic look that can remain excellent for a long time is obtained.
Fig. 3 be represent be suitable for the present invention ornament embodiment watchcase axonometric chart, Fig. 4 be represent applicable this Partial cross section's axonometric chart of the bezel, cluster of the embodiment of bright ornament.
Watchcase 11 shown in Fig. 3 possesses housing main body 112 and is protrusively provided from housing main body 112 and is used for installing The band installation portion 114 of watchband.Such watchcase 11 can build container in the lump with glass plate (not shown), inner lid.In the container Interior, receive pointer (not shown), dial plate etc..Thus, container protection pointer etc. exempts to be affected by, and pair when count Cosmetic look affect greatly.
Bezel, cluster 12 shown in Fig. 4 is annular in shape, and is assemblied in watchcase, can rotate as desired relative to watchcase.To table During shell assembling bezel, cluster 12, bezel, cluster 12 is located at the outside of watchcase, and therefore bezel, cluster 12 can affect the cosmetic look of table.
In addition, such watchcase 11, bezel, cluster 12 are used in the state of human body is assemblied in, therefore often easily cause and scrape Wipe.Therefore, titanium sintered body 1 is used by the constituent material as such ornament, it is possible to obtain the specularity on surface is high And the excellent ornament of cosmetic look.In addition, the specularity can be maintained for a long time.
The manufacture method of titanium sintered body
Next, illustrating to the method for manufacturing titanium sintered body 1.
The manufacture method of titanium sintered body 1 has [1] mixing titanium alloy powder and organic bond and obtains the work of mixing thing Sequence, [2] shape mixing thing by powder metallurgic method, obtains the operation of formed body, [3] carries out defat and is taken off to formed body The operation of fat body, [4] are fired and obtain the operation of sintered body, [5] and implement hip treatment to sintered body to defat body The operation of (HIP process).Hereinafter, each operation is described successively.
[1] compounding procedure
First, by become the raw material of titanium sintered body 1 titanium monomer powders or titanium alloy powder (below, omission is referred to as " titanium alloy powder ".) kneaded with organic bond in the lump, obtain mixing thing.
The mean diameter of titanium alloy powder is not particularly limited, preferably less than more than 1 μm 50 μm, more preferably 5 μm with Upper less than 40 μm.
In addition, the powder (pre-alloyed powder) that titanium alloy powder can be the particle being only made up of single alloy to be constituted, It can also be the mixed-powder (premixing powder) for mixing the multiple particles for mutually constituting different.Feelings in premixing powder Condition, each particle can be only comprising a kind of particle of element, or the particle comprising multiple element, as long as premixed powder Last entirety meets ratio of components as described above.
The containing ratio of the organic bond in mixing thing and the correspondingly appropriate settings such as molding condition, the shape of shaping, excellent Elect below 20 mass % of more than 2 overall mass % of mixing thing left and right as, more than more preferably 5 mass % 10 mass % are with bottom left Right.By the containing ratio of organic bond is set in the scope, make mixing thing that there is good mobility.Thus, carry The fillibility of mixing thing during high shaping, obtains the sintering of the shape (near-net-shape) closer to the shape for eventually serving as purpose Body.
As organic bond, for example, enumerate the polyolefin such as polyethylene, polypropylene, vinyl-vinyl acetate copolymer, gather The styrene resin of the acrylic resins such as methyl methacrylate, polybutyl methacrylate, polystyrene etc., polychlorostyrene second The polyester such as alkene, Vingon, polyamide, polyethylene terephthalate, polybutylene terephthalate (PBT), polyethers, poly- The various resins such as vinyl alcohol, polyvinylpyrrolidone or their copolymer, various pomades, paraffin, higher fatty acids (example： Stearic acid), higher alcohol, high-grade aliphatic ester, the various organic bonds such as higher fatty acid amides, can be by these organics The use mixed above of one or two kinds of in agent.
In addition, in mixing thing, it is also possible to be added with plasticizer as desired.As the plasticizer, for example, enumerate neighbour Phthalic acid ester (example：DOP, DEP, DBP), ethanedioic acid ester, trimellitate, SA ester etc., can be by these plasticizers One or two kinds of use mixed above.
And, in mixing thing, outside titanium alloy powder, organic bond, plasticizer, for example can add as needed Plus the various additives such as lubricant, antioxidant, defat accelerator, interfacial agent.
Additionally, compounding conditions because the alloy composition of the titanium alloy powder that uses, particle diameter, the composition of organic bond and All many conditions such as use level of these materials and different, if enumerating one example, melting temperature can be set to more than 50 DEG C 200 Left and right below left and right below DEG C, more than 15 points 210 points of mixing time.
In addition, mixing thing carries out particle (fritter) change as desired.The particle diameter of particlized be, for example, more than 1mm 15mm with Lower left and right.
In addition it is also possible to according to manufacturing process described later, manufacture prilling powder rather than mixing thing.
[2] forming process
Next, shaping mixing thing and manufacturing formed body.
As manufacturing process, it is not particularly limited, for example, press-powder shaping (compression molding) method, metal powder injection molded (MIM：Metal Injection Molding) the various forming processes such as method, extrusion molding method.Wherein, from can manufacture near net into From the viewpoint of the sintered body of shape is such, metal powder injection molded method is preferably used.
In addition, molding condition in the case of press-powder forming process composition, particle diameter because of the titanium alloy powder that uses, organic viscous All many conditions such as use level of the composition of mixture and these materials and different, but forming pressure be preferably more than 200MPa Below 1000MPa (2t/cm2Above 10t/cm2Left and right below).
In addition, the molding condition in the case of titanium alloy powder is still different because of all many conditions, but preferably make material temperature It is more than 50MPa below 500MPa (0.5t/cm to spend for less than more than 80 DEG C 210 DEG C Zuo You, injection pressure2Above 5t/cm2With Under) left and right.
In addition, the molding condition in the case of extrusion molding method is still different because of all many conditions, but preferably material temperature It is more than 50MPa below 500MPa (0.5t/cm to spend for less than more than 80 DEG C 210 DEG C Zuo You, extrusion pressure2Above 5t/cm2With Under) left and right.
The formed body for so obtaining becomes the mutual gap of particle in titanium alloy powder and is similarly distributed organic bond State.
Additionally, the geomery of the formed body for making is the shaping in being contemplated to following degreasing process and ablating work procedure The amount of contraction of body and determine.
In addition, as needed, it is also possible to implement the machinings such as cutting, grinding, cut-out relative to formed body.Formed body Hardness is than relatively low, and compares and be rich in plasticity, therefore, it is possible to prevent the shape deterioration of formed body, and easily implement machinery plus Work.According to such machining, the titanium sintered body 1 of final size high precision can be easily obtained.
[3] degreasing process
Next, implementing ungrease treatment (unsticking mixture process) to the formed body for obtaining, defat body is obtained.
Specifically, decompose organic bond by thermoforming body, from formed body remove organic bond to A few part, and complete ungrease treatment.
As the ungrease treatment, for example, enumerate the method for thermoforming body, make formed body be exposed to the gas for decomposing binding agent Method of body etc..
In the case of the method using thermoforming body, the heating condition of formed body because organic bond composition, match somebody with somebody Resultant and slightly different, but preferably below more than 100 DEG C 750 DEG C of temperature × less than 20 hours more than 0.1 hour Zuo You, more excellent Elect less than 15 hours less than more than 150 DEG C 600 DEG C × more than 0.5 hour Zuo You as.Must thereby, it is possible to sinter formed body The defat of formed body is sufficiently carried out and.As a result, can be reliably prevented remained in the inside of defat body in a large number organic Adhesive ingredients.
In addition, environment during thermoforming body is not particularly limited, reducibility gas environment, nitrogen as hydrogen is enumerated Oxidizing gas environment as non-reactive gas ambient, air as gas, argon or these environment are reduced pressure and Into reduced pressure atmosphere etc..
On the other hand, as the gas for decomposing binding agent, for example, ozone etc. is enumerated.
Additionally, such degreasing process is divided into the different multiple processes (step) of degreasing condition carry out, thus, it is possible to more fast Fast ground and the organic bond for not making formed body decompose remainingly, remove in formed body.
In addition, as needed, it is also possible to implement the machinings such as cutting, grinding, cut-out relative to defat body.Due to defat The hardness of body is than relatively low, and compares and be rich in plasticity, therefore, it is possible to prevent the shape deterioration of defat body, and easily implements Machining.According to such machining, the titanium sintered body 1 of final size high precision can be more easily obtained.
[4] ablating work procedure
Next, the defat body for obtaining being fired in baking furnace and obtaining sintered body.That is, in the particle of titanium alloy powder Mutual interface produces diffusion, completes to sinter.As a result, obtaining titanium sintered body 1.
Firing temperature is different because of the composition of titanium alloy powder, particle diameter etc., is set to more than 900 DEG C as an example Less than 1400 DEG C left and right.Additionally, it is preferred that being less than more than 1050 DEG C 1300 DEG C Zuo You.
In addition, will be set to the firing time less than 20 hours more than 0.2 hour, 6 hours more than 1 hour are preferably set to bottom left Right.
Additionally, in ablating work procedure, it is also possible to make firing temperature, firing environmental change described later in midway.
In addition, environment when firing is not particularly limited, but the situation in the notable oxidation for considering to prevent metal dust Under, preferably use non-reactive gas ambient as reducibility gas environment, argon as hydrogen or these environment are entered Reduced pressure atmosphere of row decompression etc..
Additionally, in the case of by titanium alloy powder manufacture titanium sintered body 1, is formed because of firing condition etc. sometimes α phases 2 and Both β phases 3.Particularly, in the case of including described β phase stabilizing elements in titanium alloy powder, can be more reliably Form β phases 3.
On the other hand, by making various manufacturing condition optimizations, the ratio shared by α phases 2 in titanium sintered body 1 can be adjusted Example, the area occupation ratio i.e. in the section of titanium sintered body 1 shared by α phases 2.For example, due to the ratio of the β phases 3 when firing temperature increases Increase, in the way of the ratio of β phases 3 is accommodated in the range of purpose, therefore adjust firing temperature, and when considering by firing Between long caused crystalline structure hypertrophyization and set the firing time.
Thus, in the case where titanium sintered body 1 is manufactured using the titanium alloy powder for being for example practically free of β phases 3, according to The composition of titanium alloy powder, as firing temperature is higher, the ratio of β phases 3 is higher, therefore so that the area occupation ratio of α phases 2 is accommodated in Mode in the scope adjusts firing temperature, and sintering is not enough, oversintering will not cause because of the adjustment of firing temperature Mode set the firing time.
In addition, in the case where the mean diameter of α phases 2 is in the scope, as the area occupation ratio of α phases 2 increases, illustrating The shape of α phases 2 such as is close at the square trend.This is because, being reduced by the ratio for making β phases 3, the probability adjacent one another are of α phases 2 increases Height, α phases 2 are disturbed each other, thus hinder incorgruous particle growth.
[5] HIP operations
Alternatively, it is also possible to relative to the sintered body for so obtaining, further implement HIP process (hip treatment) etc.. Hereby it is achieved that the further densification of sintered body, is obtained in that the more excellent ornament of mechanical property.
As the condition of HIP process, for example make temperature for less than more than 850 DEG C 1200 DEG C, the time 10 little for more than 1 hour When below left and right.
In addition, plus-pressure is preferably more than 50MPa, is more preferably more than 100MPa below 500MPa.
In addition, as needed, it is also possible to further implement annealing, solution treatment to the sintered body for obtaining, at timeliness Reason, heat treatment, cold work etc..
Additionally, as needed, it is also possible to implement milled processed to the titanium sintered body 1 for obtaining.As milled processed, there is no spy Do not limit, for example, enumerate electrolytic polishing, half grinding, dry grinding, chemical grinding, cylinder grinding, sandblasting etc..By implementing these Milled processed, can further give metallic luster to the surface of titanium sintered body 1, so as to improve specularity.
More than, the titanium sintered body and ornament of the present invention are illustrated based on preferable embodiment, but this Bright it is not limited to this.
For example, the purposes of titanium sintered body is not limited to ornament, or various structural members etc..As the formations Part, for example, enumerate automotive part, bicycle use part, rolling stock part, ship part, component parts for aircraft, space Cosmos conveyer (such as rocket etc.) conveying equipment part, personal computer part, mobile telephone terminal as part With electronic equipment part, refrigerator, washing machine, electrical equipment part, working machine as refrigeration and heating machine as part Mechanical part as tool, semiconductor- fabricating device, atomic power station, heat power station, water-power plant, oil plant, Spare unit, operation utensil, artificial bone, artificial joint, artificial tooth, artificial tooth root, tooth is set as chemical system device Armarium etc. as row correction part.
Additionally, the organism compatibility of titanium sintered body is higher, artificial bone, dental metal is therefore particularly useful as Part.Wherein, as long as dental metal parts temporarily or semi-permanently metal parts of indwelling in the oral cavity, then do not have spy Do not limit, for example, enumerate the metal frames such as inlay, corona, bridge, metal dental bed, artificial tooth, implant, abutment, fixture, helical member Frame.
Embodiment
Next, the specific embodiment of the explanation present invention.
1. the manufacture of titanium sintered body
(embodiment 1)
1 ＞ of ＜ first, prepare the Ti-6Al-4V alloy powders of 23 μm of mean diameter manufactured by gas atomization.
Next, prepare the mixture (organic bond) of polypropylene and pomade, so that material powder and organic bond Mass ratio be 9：1 mode is weighed, and obtains titanium sintered body manufacture constituent.
Next, being kneaded with constituent to the titanium sintered body manufacture for obtaining using kneading machine, complex is obtained.So Afterwards, complex is processed as particle.
2 ＞ of ＜ are next, using the particle for obtaining, being formed by molding condition shown below, producing shaping Body.
＜ molding condition ＞
Manufacturing process：Metal powder injection molded method
Material temperature：150℃
Injection pressure：11MPa(110kgf/cm2)
3 ＞ of ＜ are next, implement ungrease treatment, acquisition relative to the formed body for obtaining according to degreasing condition shown below Defat body.
＜ degreasing condition ＞
Skimming temp：520℃
Degreasing time：5 hours
Defat environment：Nitrogen environment
4 ＞ of ＜ next, fire the defat body of acquisition according to firing condition shown below.Sintering is so produced Body.
＜ firing condition ＞
Firing temperature：1100℃
Firing time：5 hours
Fire environment：Ar gas environment
Ambient pressure：Atmospheric pressure (100kPa)
5 ＞ of ＜ are next, implement HIP process according to treatment conditions shown below to the sintered body for obtaining.Consequently, it is possible to Acquisition becomes the bar-shaped titanium sintered body of diameter 5mm × length 100mm.
＜ HIP treatment conditions ＞
Treatment temperature：900℃
Process time：3 hours
Processing pressure：1480kgf/cm2(145MPa)
6 ＞ of ＜ are next, the titanium sintered body of cut-out acquisition, implements half milled processed to cutting section.
Next, using electron microscope observation abradant surface, being obtained shared by mean diameter, α phases and the β phases of α phases respectively Area occupation ratio and α phases average aspect ratio.Its result is shown in table 1.
(embodiment 2～6)
So that area occupation ratio and α phases shared by the mean diameter of α phases, α phases and β phases average aspect ratio respectively into Beyond the mode of the value shown in table 1 changes manufacturing condition, titanium sintered body is obtained respectively same as Example 1ly.
(comparative example 1～3)
So that area occupation ratio and α phases shared by the mean diameter of α phases, α phases and β phases average aspect ratio respectively into Beyond the mode of the value shown in table 1 changes manufacturing condition, titanium sintered body is obtained respectively same as Example 1ly.
(reference example 1)
First, prepare the melting material of Ti-6Al-4V alloys.
Next, the melting material that cut-out is obtained, implements half milled processed to section.
Next, abradant surface is observed using ultramicroscope, obtain mean diameter, α phases and the β phases institute of α phases respectively The area occupation ratio for accounting for and the average aspect ratio of α phases.Its result is shown in table 1.
(embodiment 7)
Beyond the Ti-3Al-2.5V alloy powders that replacement Ti-6Al-4V alloy powders use 23 μm of mean diameter, with Embodiment 1 obtains titanium sintered body in the same manner.
Then, the titanium sintered body that cut-out is obtained, implements half milled processed to cutting section.
Next, using electron microscope observation abradant surface, being obtained shared by mean diameter, α phases and the β phases of α phases respectively Area occupation ratio and α phases average aspect ratio.Its result is shown in table 2.
(embodiment 8～12)
So that the average aspect ratio of area occupation ratio and α phases shared by the mean diameter of α phases, α phases and β phases is respectively table The mode of the value shown in 2 is changed beyond manufacturing condition, obtains titanium sintered body respectively same as Example 7ly.
(comparative example 4～6)
So that the average aspect ratio of area occupation ratio and α phases shared by the mean diameter of α phases, α phases and β phases is respectively table The mode of the value shown in 2 is changed beyond manufacturing condition, obtains titanium sintered body respectively same as Example 7ly.
(reference example 2)
First, prepare the melting material of Ti-3Al-2.5V.
Next, the melting material that cut-out is obtained, implements half milled processed to section.
Next, abradant surface is observed using ultramicroscope, obtain mean diameter, α phases and the β phases institute of α phases respectively The area occupation ratio for accounting for and the average aspect ratio of α phases.Its result is shown in table 2.
(embodiment 13)
Beyond the Ti-6Al-7Nb alloy powders that replacement Ti-6Al-4V alloy powders use 25 μm of mean diameter, with Embodiment 1 obtains titanium sintered body in the same manner.Then, the titanium sintered body that cut-out is obtained, implements half milled processed to cutting section.
Next, abradant surface is observed using ultramicroscope, obtain mean diameter, α phases and the β phases institute of α phases respectively The area occupation ratio for accounting for and the average aspect ratio of α phases.Its result is shown in table 3.
(embodiment 14～18)
So that the average aspect ratio of area occupation ratio and α phases shared by the mean diameter of α phases, α phases and β phases is respectively table The mode of the value shown in 3 is changed beyond manufacturing condition, obtains titanium sintered body identically with embodiment 13 respectively.
(comparative example 7～9)
So that the average aspect ratio of area occupation ratio and α phases shared by the mean diameter of α phases, α phases and β phases is respectively The mode of the value shown in table 3 is changed beyond manufacturing condition, obtains titanium sintered body identically with embodiment 13 respectively.
(reference example 3)
First, prepare the melting material of Ti-6Al-7Nb.
Next, the melting material that cut-out is obtained, implements half milled processed to cutting section.
Next, abradant surface is observed using ultramicroscope, obtain mean diameter, α phases and the β phases institute of α phases respectively The area occupation ratio for accounting for and the average aspect ratio of α phases.Its result is shown in table 3.
2. the evaluation of titanium sintered body
2.1 specularity
First, for each embodiment, each comparative example and each reference example titanium sintered body (titanium melting material), by visual observation To observe abradant surface.Then, the specularity of abradant surface is evaluated with reference to following metewand.Evaluation result is shown in table 1 ～3.
The metewand ＞ of the specularity of ＜ abradant surfaces
A：The specularity of abradant surface is very high (cosmetic look is especially good)
B：The specularity of abradant surface is slightly higher (cosmetic look is slightly good)
C：The specularity of abradant surface is lower slightly (cosmetic look is slightly unqualified)
D：The specularity of abradant surface is very low (cosmetic look is unqualified)
2.2 relative density
Next, the titanium sintered body (titanium melting material) for each embodiment, each comparative example and each reference example, is based on JIS Z 2501：The method of 2000 defineds and calculate relative density.Result of calculation is shown in table 1～3.
2.3 Vickers hardness
Next, the grinding of the titanium sintered body (titanium melting material) for each embodiment, each comparative example and each reference example Face, based on JIS Z 2244：The method of 2009 defineds and determine Vickers hardness.Measurement result is shown in table 1～3.
2.4 crystal structures based on X-ray diffraction method are parsed
Next, for the titanium sintered body of embodiment 1, by condition determination shown below, carrying out based on X-ray diffraction The crystal structure parsing of method.
The condition determination ＞ that crystal structures of the ＜ based on X-ray diffraction method is parsed
X-ray source：Cu-K alpha rays
Tube voltage：30kV
Tube current：20mA
The X-ray diffraction spectra of acquisition is shown in Fig. 5.It is clear that by Fig. 5, the titanium sintered body for embodiment 1 is obtained The X-ray diffraction spectra for obtaining includes the peak value of the reflex strength based on α phases (α-Ti) and is based on the reflex strength of β phases (β-Ti) Peak value.In this regard, by 2 θ be located at 35.3 ° near planar orientation (100) α-Ti caused by reflex strength peak value on the basis of when, Calculate the ratio of the peak value relative to the benchmark of reflex strength caused by planar orientation (110) β-Ti of 2 θ near 39.5 ° Example (peakedness ratio).In addition, the titanium sintered body (titanium melting material) in embodiment 2～18, comparative example 1～9 and reference example 1～3 In be also carried out same calculating.The result of calculation of peakedness ratio is shown in table 1～3.
2.5 wear resistance
Next, titanium melting material of titanium sintered body and each reference example for each embodiment and each comparative example etc., comments The wear resistance on its surface of valency.Specifically, first, the surface of titanium sintered body and titanium melting material is implemented at half grinding Reason.Next, for abradant surface, carrying out the abrasion carried out with the ball disk method of the fine ceramic of 1613 (2010) defineds of JIS R Wear test based on test method, determines the wear extent of discoideus sample.Additionally, condition determination is as described below.
The condition determination ＞ of ＜ specific wear amounts
The material of spherical sample：High-carbon-chromium bearing steel (SUJ2)
The size of spherical sample：Diameter 6mm
The material of discoideus sample：The melting material of the sintered body and each reference example of each embodiment and each comparative example
The size of discoideus sample：Diameter 35mm, thickness 5mm
The size of load：10N
Sliding speed：0.1m/s
Slip circular diameter：30mm
Sliding distance：50m
Then, the wear extent that the titanium melting material for reference example 1 is obtained is set to 1, is calculated for each shown in table 1 The relative value of the wear extent that the titanium sintered body of embodiment and each comparative example is obtained.
Equally, the wear extent that the titanium melting material for reference example 2 is obtained is set to 1, is calculated for each shown in table 2 The relative value of the wear extent that the titanium sintered body of embodiment and each comparative example is obtained.
And, the wear extent that the titanium melting material for reference example 3 is obtained is set to 1 similarly, is calculated for 3 institute of table The relative value of the wear extent that each embodiment that shows and the titanium sintered body of each comparative example are obtained.
Next, the relative value that evaluation calculation goes out with reference to following metewand.Evaluation result is shown in table 1～3.
The metewand ＞ of ＜ wear extenies
A：Wear extent considerably less (relative value is less than 0.5)
B：Wear extent few (relative value is more than 0.5 but less than 0.75)
C：Wear extent less slightly (relative value is more than 0.75 but less than 1)
D：Wear extent slightly many (relative value is more than 1 but less than 1.25)
E：Wear extent many (relative value is more than 1.25 but less than 1.5)
F：Wear extent very many (relative value is more than 1.5)
2.6 tensile strength
Next, titanium melting material of titanium sintered body and each reference example for each embodiment and each comparative example etc., surveys Its tensile strength fixed.Additionally, the measure of tensile strength is with the metal material stretching test side of 2241 (2011) defineds of JIS Z Carry out on the basis of method.
Then, the tensile strength that the titanium melting material for reference example 1 is obtained is set to 1, is calculated for each shown in table 1 The relative value of the tensile strength that the titanium sintered body of embodiment and each comparative example is obtained.
Equally, the tensile strength that the titanium melting material for reference example 2 is obtained is set to 1, is calculated for each shown in table 2 The relative value of the tensile strength that the titanium sintered body of embodiment and each comparative example is obtained.
And, the tensile strength that the titanium melting material for reference example 3 is obtained is set to 1 similarly, is calculated and is directed to 3 institute of table The relative value of the tensile strength that each embodiment that shows and the titanium sintered body of each comparative example are obtained.
Next, evaluating the relative value of acquisition with reference to following metewand.Evaluation result is shown in table 1～3.This Outward, for tensile strength, beyond above-mentioned test body, for SUS316L sintered bodies, ASTM F75, (Co-28%Cr-6%Mo is closed Gold) founding materialses and sintered body and α-Ti sintered bodies, be also evaluated as reference example a～d (table 1).In addition, being directed to reference example D, in addition, is carried out and described 2.1～2.3 and 2.5 identical evaluations.
The metewand ＞ of ＜ tensile strengths
A：Tensile strength very big (relative value is more than 1.09)
B：Tensile strength big (relative value is more than 1.06 but less than 1.09)
C：Tensile strength slightly larger (relative value is more than 1.3 but less than 1.06)
D：Tensile strength slightly smaller (relative value is more than 1 but less than 1.03)
E：Tensile strength little (relative value is more than 0.97 but less than 1)
F：Tensile strength very little (relative value is less than 0.97)
Norminal strain during 2.7 fracture (fracture is stretched)
Next, titanium melting material of titanium sintered body and each reference example for each embodiment and each comparative example etc., surveys Fixed its ruptures and stretches.Additionally, the measure that fracture is stretched is with the metal material stretching test side of 2241 (2011) defineds of JIS Z Carry out on the basis of method.
Next, the fracture for evaluating acquisition with reference to following metewand is stretched.Evaluation result is shown in table 1～3. Additionally, stretch for fracture, beyond above-mentioned test body, for SUS316L sintered bodies, ASTM F75 (Co-28%Cr-6%Mo Alloy) founding materialses and sintered body and α-Ti sintered bodies be also evaluated as reference example a～d (table 1).
The metewand ＞ that ＜ fractures are stretched
A：Fracture is stretched very big (more than 0.15)
B：Big (more than 0.125 but less than 0.15) is stretched in fracture
C：Slightly larger (more than 0.10 but less than 0.125) is stretched in fracture
D：Slightly smaller (more than 0.075 but less than 0.10) is stretched in fracture
E：Little (more than 0.050 but less than 0.075) is stretched in fracture
F：Very little (less than 0.050) is stretched in fracture
2.8 cell toxicity test
Next, for structures such as the titanium melting materials of titanium sintered body and each reference example by each embodiment and each comparative example Into test body, carry out cell toxicity test.Additionally, cell toxicity test is with ISO10993-5：The cell toxicant of 2009 defineds Property test on the basis of come carry out.Specifically, method is formed by bacterium colony based on contact method, by the clump count of matched group When the meansigma methodss of amount are set to 100%, the bacterium colony of the colony counts relative to matched group of the cell that directly sows to test body is obtained The ratio (colony forming efficiecy [%]) of quantity.Additionally, experimental condition is as described below.
Cell strain：V97 cells
Culture medium：MEM10 culture medium
Negative control material (negative control)：Density polyethylene film with high
Positive control material (positive control)：The 0.1% poly- ammonia containing (DDC)2Zn Ester film
Matched group (control)：The colony counts of the cell that directly sows to culture medium
Next, the colony forming efficiecy of acquisition of classifying with reference to following metewand, thus evaluates the thin of each test body Cellular toxicity.Evaluation result is shown in table 1～3.Additionally, cell toxicity test is directed to, beyond above-mentioned test body, for SUS316L sintered bodies, ASTM F75 (Co-28%Cr-6%Mo alloys) sintered bodies and α-Ti sintered bodies are also evaluated as referring to Example a, c, d (table 1).
The metewand ＞ of ＜ cytotoxicities
A：Colony forming efficiecy is more than 90%
B：Colony forming efficiecy is more than 80% but less than 90%
C：Colony forming efficiecy is less than 80%
[table 1]
[table 2]
[table 3]
It is clear that by table 1～3, the specularity of the abradant surface of the titanium sintered body of each embodiment is high.Further, since relatively close Degree and Vickers hardness are also higher respectively, it is taken as that the titanium sintered body of each embodiment can maintain high specularity for a long time.
In addition, the titanium sintered body of each embodiment is considered as in characteristic as specularity, density and hardness melting for titanium Refining material equal more than.Thus, feature and excellent as near-net-shape are produced in accordance with the invention it is possible to obtain Titanium sintered body.
Additionally, the electron microscopic mirror image in the section of the titanium sintered body of comparative example 2 is shown in Fig. 6.It will be appreciated from fig. 6 that than In compared with the titanium sintered body of example 2, assume the big shape of elongated shape, the i.e. anisotropy of α phases.
In addition, the electron microscopic mirror image in the section of the titanium melting material of reference example 1 is shown in Fig. 7.As shown in Figure 7, exist In the titanium melting material of reference example 1, assume the shape that particle diameter is smaller but anisotropy is big of α phases.

Claims (6)

1. a kind of titanium sintered body, it is characterised in that include：
As the α phases and β phases of crystalline structure,
The mean diameter of the α phases is less than more than 3 μm 30 μm in cross section,
Area occupation ratio shared by the α phases is less than more than 70% 99.8% in cross section.
2. titanium sintered body according to claim 1, it is characterised in that
The average aspect ratio of the α phases is less than more than 13 in cross section.
3. titanium sintered body according to claim 1 and 2, it is characterised in that
Reflex strength in the X-ray diffraction spectra obtained by X-ray diffraction method, based on the planar orientation (110) of the β phases Peak value is less than more than the 3% 60% of the peak value of the reflex strength of the planar orientation (100) based on the α phases.
4. titanium sintered body according to any one of claim 1 to 3, it is characterised in that
The titanium sintered body is with titanium as main constituent and including α phases stabilizing element and β phase stabilizing elements.
5. titanium sintered body according to any one of claim 1 to 4, it is characterised in that
The relative density of the titanium sintered body is more than 99%.
6. a kind of ornament, it is characterised in that include：
Titanium sintered body any one of claim 1 to 5.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109420769A (en) * 2017-08-31 2019-03-05 精工爱普生株式会社 Titanium sintered body, ornament and clock and watch
CN111032896A (en) * 2017-08-28 2020-04-17 日本制铁株式会社 Timepiece component

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11131010B2 (en) * 2016-04-14 2021-09-28 National Institute For Materials Science Titanium alloy and method of manufacturing material for timepiece exterior part
US10858524B2 (en) * 2016-11-15 2020-12-08 Disco Corporation Protective film forming resin agent and laser processing method
WO2019044858A1 (en) * 2017-08-28 2019-03-07 新日鐵住金株式会社 Titanium alloy member
WO2019209368A2 (en) 2017-10-23 2019-10-31 Arconic Inc. Titanium alloy products and methods of making the same
EP3674817A1 (en) * 2018-12-24 2020-07-01 Meco S.A. Method for manufacturing a decorative item
EP3796101A1 (en) * 2019-09-20 2021-03-24 Nivarox-FAR S.A. Hairspring for clock movement

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1318111A (en) * 1999-06-11 2001-10-17 株式会社丰田中央研究所 Titanium alloy and method for producing same
US20050163646A1 (en) * 2001-10-31 2005-07-28 Qingfa Li Method of forming articles from alloys of tin and/or titanium
CN1842508A (en) * 2003-05-21 2006-10-04 钴碳化钨硬质合金维迪亚产品有限公司及两合公司 Sintered part and the method for the production thereof
CN101530918A (en) * 2007-12-13 2009-09-16 通用汽车环球科技运作公司 Method for preparing composite component with strengthened TiB based on titanium alloy via powder metallurgy method
US20110277891A1 (en) * 2010-05-12 2011-11-17 Boehler Schmiedetechnik Gmbh & Co Kg Method for producing a component and components of a titanium-aluminum base alloy
JP2012007223A (en) * 2010-06-28 2012-01-12 Seiko Epson Corp Titanium sintered compact and method for manufacturing titanium sintered compact
US20130071283A1 (en) * 2010-05-31 2013-03-21 Toho Titanium Co., Ltd. Titanium alloy complex powder containing ceramic and process for production thereof, consolidated titanium alloy material using this powder and process for production thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3471092B2 (en) 1994-09-21 2003-11-25 セイコーインスツルメンツ株式会社 Decorative titanium alloy and its ornaments
JP5808894B2 (en) * 2010-08-20 2015-11-10 日本発條株式会社 High strength titanium alloy member and manufacturing method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1318111A (en) * 1999-06-11 2001-10-17 株式会社丰田中央研究所 Titanium alloy and method for producing same
US20050163646A1 (en) * 2001-10-31 2005-07-28 Qingfa Li Method of forming articles from alloys of tin and/or titanium
CN1842508A (en) * 2003-05-21 2006-10-04 钴碳化钨硬质合金维迪亚产品有限公司及两合公司 Sintered part and the method for the production thereof
CN101530918A (en) * 2007-12-13 2009-09-16 通用汽车环球科技运作公司 Method for preparing composite component with strengthened TiB based on titanium alloy via powder metallurgy method
US20110277891A1 (en) * 2010-05-12 2011-11-17 Boehler Schmiedetechnik Gmbh & Co Kg Method for producing a component and components of a titanium-aluminum base alloy
US20130071283A1 (en) * 2010-05-31 2013-03-21 Toho Titanium Co., Ltd. Titanium alloy complex powder containing ceramic and process for production thereof, consolidated titanium alloy material using this powder and process for production thereof
JP2012007223A (en) * 2010-06-28 2012-01-12 Seiko Epson Corp Titanium sintered compact and method for manufacturing titanium sintered compact

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111032896A (en) * 2017-08-28 2020-04-17 日本制铁株式会社 Timepiece component
CN109420769A (en) * 2017-08-31 2019-03-05 精工爱普生株式会社 Titanium sintered body, ornament and clock and watch

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