JPH08157990A - Silver-colored sintered compact and its production - Google Patents
Silver-colored sintered compact and its productionInfo
- Publication number
- JPH08157990A JPH08157990A JP29638294A JP29638294A JPH08157990A JP H08157990 A JPH08157990 A JP H08157990A JP 29638294 A JP29638294 A JP 29638294A JP 29638294 A JP29638294 A JP 29638294A JP H08157990 A JPH08157990 A JP H08157990A
- Authority
- JP
- Japan
- Prior art keywords
- sintered body
- silver
- phase
- weight
- titanium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、装飾部品，工具，摺動
部材，産業用刃物，印鑑，メガネフレーム，食器類，シ
ューズのピンやゴルフクラブ等のスポーツ用品等に用い
られる銀色焼結体およびその製造方法に関するものであ
り、特に、釣具部品や時計用外装部品，ネクタイピン，
ブレスレット，ピアス，イヤリング等の装飾用部材とし
て、高強度，高硬度，耐チッピング性，耐食性に優れ、
かつ優れた装飾性を備える銀色焼結体およびその製造方
法に関するものである。BACKGROUND OF THE INVENTION The present invention relates to a silver-colored sintered body used for decorative parts, tools, sliding members, industrial blades, stamps, eyeglass frames, tableware, shoe pins, sports equipment such as golf clubs, and the like. And a method of manufacturing the same, particularly, fishing tackle parts, exterior parts for watches, tie pins,
As a decorative member for bracelets, earrings, earrings, etc., it has excellent strength, hardness, chipping resistance and corrosion resistance.
The present invention also relates to a silver-colored sintered body having excellent decorativeness and a method for manufacturing the same.
【０００２】[0002]
【従来技術】従来、時計用外装部品等の装飾部品に要求
される特性は、耐食性に富み、耐スクラッチ性が高く、
さらに金属光沢が長く持続することが要求されている。
そして、このような装飾部品に最適な金属光沢を有する
材料として、ステンレスや金属の炭化物、例えばＷＣや
ＴｉＣをＮｉやＣｏ等の金属で結合させた焼結合金が用
いられていた。2. Description of the Related Art Conventionally, decorative properties such as exterior parts for watches are rich in corrosion resistance and high in scratch resistance.
Furthermore, it is required that the metallic luster lasts for a long time.
Then, as a material having an optimum metallic luster for such a decorative part, a sintered alloy in which a carbide of stainless steel or a metal, for example, WC or TiC is bonded with a metal such as Ni or Co has been used.
【０００３】しかしながら、ステンレスは耐食性に優れ
ているものの、硬度が低いために傷が付きやすく、一
方、ＷＣやＴｉＣを主成分としＮｉやＣｏ等の金属元素
で結合した焼結合金では、焼結体自体の硬度の問題はな
いものの、人間の汗や海水に対する耐食性が低いという
欠点があった。However, although stainless steel is excellent in corrosion resistance, it is easily scratched due to its low hardness. On the other hand, a sintered alloy composed mainly of WC or TiC and combined with a metal element such as Ni or Co is sintered. Although there is no problem with the hardness of the body itself, it has the drawback of low corrosion resistance to human sweat and seawater.
【０００４】これに対して最近では、チタンのホウ化物
であるＴｉＢ2 の高硬度，耐食性等の特性を用いたＴｉ
Ｂ2 系焼結体が開発され、実用化されている（例えば特
開昭５８ー２７９７５号公報、特開昭６１ー２７０２６
５号公報、特開平５ー２９４７３９号公報）。これらの
ＴｉＢ2 系焼結体は、その抗折強度が８００〜１０００
ＭＰａ、ビッカース硬度が１８〜２４ＧＰａ、破壊靱性
値が４〜７ＭＰａ・ｍ1/2 であり、優れた耐食性を示し
ている。On the other hand, recently, Ti using the characteristics of TiB 2 , which is a boride of titanium, such as high hardness and corrosion resistance.
B 2 type sintered bodies have been developed and put into practical use (for example, JP-A-58-27975 and JP-A-61-27026).
No. 5, JP-A-5-294739). These TiB 2 system sintered bodies have a bending strength of 800 to 1000.
MPa, Vickers hardness is 18 to 24 GPa, and fracture toughness value is 4 to 7 MPa · m 1/2 , which shows excellent corrosion resistance.
【０００５】[0005]
【発明が解決しようとする問題点】しかし、上記のよう
なＴｉＢ2 系焼結体では、１６００〜２０００℃の高温
で焼結する必要があり、焼結性が低いという問題があっ
た。However, the TiB 2 system sintered body as described above has a problem that it is necessary to sinter at a high temperature of 1600 to 2000 ° C. and the sinterability is low.
【０００６】本発明の銀色焼結体では、ＴｉＢ2 系焼結
体とほぼ同等の高硬度，耐食性等の優れた特性を有する
とともに、１３００〜１６００℃の低温で焼成すること
ができる銀色焼結体およびその製造方法を提供すること
を目的とする。The silver-colored sintered body of the present invention has excellent characteristics such as high hardness and corrosion resistance which are almost the same as those of the TiB 2 system sintered body, and can be sintered at a low temperature of 1300 to 1600 ° C. It is an object to provide a body and a method for producing the body.
【０００７】[0007]
【課題を解決するための手段】本発明者は、上記問題を
解決するために鋭意検討した結果、原料としては、Ｔｉ
Ｂ2 系焼結体とほぼ同様の原料を用い、結晶相としてＴ
ｉＣおよびＴｉＢ相を主として生成させることにより、
ＴｉＢ2 系焼結体とほぼ同等の特性を有するとともに、
１３００〜１６００℃の低温で焼成することができるこ
とを知見し、本発明に至った。また、ホウ化チタンのう
ち少なくとも一部が針状結晶として存在することによ
り、焼結体の靱性を向上できることを知見し、本発明に
至った。As a result of intensive studies for solving the above problems, the present inventor found that Ti was used as a raw material.
A material similar to that of the B 2 system sintered body is used, and T is used as a crystal phase.
By primarily forming the iC and TiB phases,
It has almost the same characteristics as the TiB 2 system sintered body,
The present inventors have found that they can be fired at a low temperature of 1300 to 1600 ° C, and have reached the present invention. Further, they have found that the presence of at least a part of titanium boride as acicular crystals can improve the toughness of the sintered body, and have reached the present invention.
【０００８】即ち、本発明の銀色焼結体は、少なくとも
チタン, 炭素, ホウ素を主たる構成元素とし、三成分基
準でチタンが全量中８０〜９５重量％、ホウ素が全量中
３〜１２重量％、炭素が全量中２〜８重量％からなる銀
色焼結体であって、該焼結体中にＴｉＣ相およびＴｉＢ
相が存在するものである。ここで、ＴｉＢ相の一部が針
状結晶であることが望ましい。That is, the silver-colored sintered body of the present invention contains at least titanium, carbon and boron as main constituent elements, and based on the three components, titanium is 80 to 95% by weight in the total amount, and boron is 3 to 12% by weight in the total amount. A silver-colored sintered body containing carbon in an amount of 2 to 8% by weight, the TiC phase and the TiB in the sintered body
There are phases. Here, it is desirable that a part of the TiB phase is a needle crystal.
【０００９】さらに、本発明の銀色焼結体は、例えば、
チタンの粉末、チタンの炭化物粉末およびチタンのホウ
化物粉末を混合したものを所定形状に成形し、これを非
酸化性雰囲気下において１３００〜１６００℃で焼成す
ることにより得られる。Further, the silver-colored sintered body of the present invention is, for example,
It is obtained by molding a mixture of titanium powder, titanium carbide powder and titanium boride powder into a predetermined shape, and calcining the mixture in a non-oxidizing atmosphere at 1300 to 1600 ° C.
【００１０】ここで、上記のように元素量を限定した理
由について説明する。Here, the reason why the amount of elements is limited as described above will be explained.
【００１１】先ず、チタンを全量中８０〜９５重量％と
したのは、チタンが８０重量％よりも少なくなると焼結
性が低下するとともに焼結体の強度が低下するためであ
り、９５重量％を越えると硬質相としてのＴｉＣ相とＴ
ｉＢ相が共存できなくなり、焼結体の硬度が低くなるた
めである。チタンは全量中８５〜９０重量％含有するこ
とが望ましい。焼結体中にチタンは一部が金属として存
在していても良い。金属として存在する量は４０重量％
以下が望ましく、特には、３０重量％以下が望ましい。First, the reason why the total amount of titanium is 80 to 95% by weight is that when the amount of titanium is less than 80% by weight, the sinterability is lowered and the strength of the sintered body is lowered. If it exceeds, the TiC phase and T as a hard phase
This is because the iB phase cannot coexist and the hardness of the sintered body becomes low. It is desirable that titanium is contained in an amount of 85 to 90% by weight based on the total amount. Part of titanium may be present as a metal in the sintered body. The amount present as metal is 40% by weight
The following is desirable, and particularly 30 wt% or less is desirable.
【００１２】ホウ素を全量中３〜１２重量％としたの
は、ホウ素が３重量％よりも少なくなると硬質相として
のＴｉＢが存在せず、硬度が低くなるためである。一
方、１２重量％よりも多くなると二ホウ化物のＴｉＢ2
の生成が多くなり、焼成温度が高くなるからである。ホ
ウ素の量は全量中４〜９重量％であることが望ましい。The amount of boron is set to 3 to 12% by weight in the total amount because if the amount of boron is less than 3% by weight, TiB as a hard phase does not exist and the hardness becomes low. On the other hand, if the amount exceeds 12% by weight, the diboride TiB 2
Is increased, and the firing temperature is increased. The amount of boron is preferably 4 to 9% by weight based on the total amount.
【００１３】炭素を全量中２〜８重量％としたのは、炭
素が２重量％よりも少ないと硬質相としてのＴｉＣが存
在せず、硬度が低くなるためである。一方、８重量％よ
りも多くなると焼結体中に炭素が残留し、焼結性が低下
するためである。炭素は全量中、３〜６重量％であるこ
とが望ましい。The reason why the carbon content is 2 to 8% by weight is that if the carbon content is less than 2% by weight, TiC does not exist as a hard phase and the hardness is lowered. On the other hand, when the content is more than 8% by weight, carbon remains in the sintered body and the sinterability is deteriorated. Carbon is preferably 3 to 6% by weight in the total amount.
【００１４】また、本発明の銀色焼結体では、焼結体中
にＴｉＣ相およびＴｉＢ相が存在するものであるが、Ｔ
ｉＢ相の一部が針状結晶であることが望ましい。これ
は、ＴｉＢ粒子の一部を針状結晶とすることにより、焼
結体の靱性を大幅に向上することができるからである。In the silver-colored sintered body of the present invention, the TiC phase and the TiB phase are present in the sintered body.
It is desirable that a part of the iB phase is acicular crystals. This is because the toughness of the sintered body can be significantly improved by making a part of the TiB particles into needle crystals.
【００１５】針状結晶とは、直径の大きい柱状も含まれ
る意味であり、ＴｉＢ粒子のアスペクト比（長径／短
径）は１．５〜１０であることが望ましく、短径が０．
５〜２０μｍであることが望ましい。これは、ＴｉＢ粒
子を上記のようなサイズとすることにより靱性の向上効
果が大きくなるからであり、前記範囲を越える場合には
焼結体の密度が低く、緻密化しなくなる傾向があるため
である。ＴｉＢ粒子は異方性を有する粒子であり、これ
により針状結晶となると考えられる。The acicular crystals mean that they also include columns having a large diameter, and the TiB particles preferably have an aspect ratio (major axis / minor axis) of 1.5 to 10 and a minor axis of 0.
The thickness is preferably 5 to 20 μm. This is because the effect of improving the toughness is enhanced by making the TiB particles the size as described above, and if the TiB particles exceed the above range, the density of the sintered body tends to be low and the densification tends not to occur. . TiB particles are particles having anisotropy and are considered to be acicular crystals.
【００１６】また、ＴｉＢの針状結晶は、ＴｉＢ相の一
部に存在していれば良い。針状結晶の存在量は、全Ｔｉ
Ｂ粒子に対して２０％以上であることが、靱性向上のた
めには望ましい。ＴｉＢ相のすべてが針状結晶であって
も良い。Further, the needle-like crystal of TiB may be present in a part of the TiB phase. The abundance of needle crystals is
20% or more of the B particles is desirable for improving the toughness. All of the TiB phase may be needle crystals.
【００１７】また、本発明の銀色焼結体は、少なくとも
チタン, 炭素, ホウ素を主たる構成元素とし、三成分基
準でチタンが全量中８０〜９５重量％、ホウ素が全量中
３〜１２重量％、炭素が全量中２〜８重量％からなる主
成分１００重量部に対して、周期律表第４ａ，５ａ，６
ａ族元素（Ｔｉを除く）を０．５〜２０．０重量部の割
合で存在させた銀色焼結体であって、該焼結体中にＴｉ
Ｃ相およびＴｉＢ相が存在するものである。ＴｉＢ相の
一部が針状結晶であることが望ましい。Further, the silver-colored sintered body of the present invention contains at least titanium, carbon and boron as main constituent elements, and based on three components, titanium is 80 to 95% by weight in the total amount, and boron is 3 to 12% by weight in the total amount. 100 parts by weight of the main component of carbon, which is 2 to 8% by weight, is included in the periodic table 4a, 5a, 6
A silver-colored sintered body in which a group a element (excluding Ti) is present in a proportion of 0.5 to 20.0 parts by weight, wherein Ti is contained in the sintered body.
The C phase and the TiB phase are present. It is desirable that a part of the TiB phase is acicular crystals.
【００１８】チタン, 炭素, ホウ素量の限定理由は上記
した通りである。そして、チタン，ホウ素，炭素からな
る主成分に対して、周期律表第４ａ，５ａ，６ａ族元素
（Ｔｉを除く）を存在させたのは、これらの周期律表第
４ａ，５ａ，６ａ族元素を含有させることにより、抗折
強度，ビッカース硬度，破壊靱性等の機械的特性をさら
に向上することができるからである。また、その量を
０．５〜２０．０重量部としたのは、０．５重量部より
も少ない場合には、上記機械的特性を向上する効果が小
さく、２０．０重量部よりも多い場合には焼結性が低下
し、強度が低下するからである。周期律表第４ａ，５
ａ，６ａ族元素は、２〜１６重量部存在させることが望
ましい。これらの周期律表第４ａ，５ａ，６ａ族元素
は、殆どがＴｉＢ相またはＴｉＣ相中に固溶し、特性を
向上する。The reasons for limiting the amounts of titanium, carbon and boron are as described above. The elements of groups 4a, 5a, and 6a of the periodic table (excluding Ti) were allowed to exist with respect to the main component composed of titanium, boron, and carbon because the elements of groups 4a, 5a, and 6a of the periodic table were present. This is because the inclusion of the element can further improve mechanical properties such as transverse rupture strength, Vickers hardness, and fracture toughness. Further, the amount is 0.5 to 20.0 parts by weight, when the amount is less than 0.5 parts by weight, the effect of improving the mechanical properties is small, and the amount is more than 20.0 parts by weight. This is because in this case, the sinterability is lowered and the strength is lowered. Periodic Table 4a, 5
It is desirable that the a and 6a group elements are present in an amount of 2 to 16 parts by weight. Most of these Group 4a, 5a, and 6a elements of the periodic table are dissolved in the TiB phase or the TiC phase to improve the characteristics.
【００１９】最も望ましい組成としては、チタンが全量
中８５〜９０重量％、ホウ素が全量中４〜９重量％、炭
素が全量中３〜６重量％とし、主としてＴｉＣ相および
ＴｉＢ相が存在し、これらからなる主成分１００重量部
に対して、さらに周期律表第４ａ，５ａ，６ａ族元素
（Ｔｉを除く）を２〜１６重量部含有するものである。The most desirable composition is titanium in an amount of 85 to 90% by weight, boron in an amount of 4 to 9% by weight, carbon in an amount of 3 to 6% by weight, and TiC phase and TiB phase are mainly present. 2 to 16 parts by weight of elements of groups 4a, 5a and 6a (excluding Ti) of the periodic table are further contained with respect to 100 parts by weight of the main components composed of these.
【００２０】そして、ＴｉＢ相の一部が針状結晶である
ことが望ましい。It is desirable that a part of the TiB phase is a needle crystal.
【００２１】焼結体中には、主として、ＴｉＣ相および
ＴｉＢ相が存在しており、これらの粒界に、金属チタ
ン，周期律表第４ａ，５ａ，６ａ族元素が存在していて
も良い。また、ＴｉＣ相およびＴｉＢ相に周期律表第４
ａ，５ａ，６ａ族元素が固溶していても良い。The TiC phase and the TiB phase are mainly present in the sintered body, and metallic titanium and elements of Groups 4a, 5a and 6a of the periodic table may be present in the grain boundaries of these. . In addition, the periodic table 4
The a, 5a, and 6a group elements may be in solid solution.
【００２２】周期律表第４ａ族元素としては、Ｚｒ，Ｈ
ｆがあり、周期律表第５ａ族元素としては、Ｖ，Ｎｂ，
Ｔａがあり、周期律表第６ａ族元素としてはＣｒ，Ｍ
ｏ，Ｗがある。添加物としてはＭｏ，Ｔａ，Ｗが最も望
ましい。さらに、本発明の銀色焼結体を装飾部品として
用いる場合には、周期律表第４ａ，５ａ，６ａ族元素と
しては、Ｖ，Ｚｒ，Ｎｂ，Ｍｏ，Ｈｆ，Ｔａ，Ｗである
ことが望ましく、さらに、アレルギーを防止するために
は、焼結体中に、アレルギー源となる金属不純物（Ａ
ｌ，Ｃｒ，Ｍｎ，Ｆｅ，Ｃｏ，Ｎｉ，Ｃｕ，Ｚｎ，Ｒ
ｈ，Ｐｄ，Ｃｄ，Ｓｎ，Ｓｂ）の含有量が０．３重量％
以下であることが望ましい。Zr, H are the elements of Group 4a of the periodic table.
f, and elements of Group 5a of the periodic table are V, Nb,
There is Ta, and as elements of Group 6a of the Periodic Table, Cr, M
There are o and W. Mo, Ta, and W are the most desirable additives. Furthermore, when the silver-colored sintered body of the present invention is used as a decorative component, the elements of Groups 4a, 5a and 6a of the periodic table are preferably V, Zr, Nb, Mo, Hf, Ta and W. In addition, in order to prevent allergies, metal impurities (A
1, Cr, Mn, Fe, Co, Ni, Cu, Zn, R
h, Pd, Cd, Sn, Sb) content is 0.3% by weight
The following is desirable.
【００２３】本発明の銀色焼結体は、例えば、原料粉末
としてチタン粉末およびチタンの炭化物粉末およびチタ
ンのホウ化物粉末を混合したものを、あるいはこれに周
期律表第４ａ，５ａ，６ａ族元素、またはこれらの炭化
物，ホウ化物の１種以上を混合したものを混合粉砕し、
バインダーを所定量添加し、所定圧力で所望形状に加圧
成形し、これを非酸化性雰囲気下において所定温度で焼
成することにより得られる。The silver-colored sintered body of the present invention is, for example, a mixture of titanium powder, titanium carbide powder, and titanium boride powder as raw material powder, or a mixture thereof with a group 4a, 5a, or 6a element of the periodic table. , Or a mixture of one or more of these carbides and borides is mixed and ground,
It is obtained by adding a predetermined amount of a binder, press-molding it into a desired shape at a predetermined pressure, and firing this at a predetermined temperature in a non-oxidizing atmosphere.
【００２４】好適には、例えば、粒径が０．５〜３．０
μｍのチタンの炭化物およびホウ化物と、粒径が５〜２
５０μｍのチタン粉末と、所望により粒径１．０〜１
０．０μｍの周期律表第４ａ，５ａ，６ａ族元素の金属
またはこれらの炭化物、窒化物、ホウ化物粉末を秤量混
合し、これをアセトン等の有機溶媒中、混合粉砕した
後、有機バインダーを加え、所望形状に成形する。そし
て、成形体を非酸化性雰囲気下において所定温度で脱バ
インダーした後、真空加熱炉において所定温度で真空焼
成を行うことにより得られる。Suitably, for example, the particle size is 0.5 to 3.0.
Titanium carbide and boride having a particle size of 5 to 2
Titanium powder of 50 μm and, if desired, particle size of 1.0 to 1
Metals of elements of groups 4a, 5a and 6a of the periodic table of 0.0 μm or their carbides, nitrides and boride powders are weighed and mixed, and this is mixed and ground in an organic solvent such as acetone, and then an organic binder is added. In addition, it is formed into a desired shape. Then, the molded body is debindered at a predetermined temperature in a non-oxidizing atmosphere and then vacuum-baked at a predetermined temperature in a vacuum heating furnace.
【００２５】ここで、チタンのホウ化物としては、Ｔｉ
Ｂ2 とＴｉＢのいずれも用いることができる。原料とし
てＴｉＢ2 を用いる場合には、このＴｉＢ2 と金属Ｔｉ
が１３００〜１６００℃で反応してＴｉＢが生成され
る。Here, as the boride of titanium, Ti is
Both B 2 and TiB can be used. When TiB 2 is used as a raw material, TiB 2 and metallic Ti
Reacts at 1300 to 1600 ° C to produce TiB.
【００２６】焼成方法としては真空度が１０-1〜１０-5
torrの雰囲気や各種雰囲気において減圧または無加圧に
て、温度１３００〜１６００℃で焼成する。周期律表第
４ａ，５ａ，６ａ族元素の金属またはこれらの炭化物、
窒化物、ホウ化物を添加する場合には、非酸化性雰囲気
下、熱間静水圧焼成（ＨＩＰ）において、１００〜２０
００気圧下で１２００〜１４００℃で焼成することが望
ましい。焼成時間は試料の大きさにもよるが通常０．５
〜５時間である。そして焼成後、焼結体の表面をダイヤ
モンドペースト等により鏡面研磨することにより、光沢
のある銀色が出現する。As a firing method, the degree of vacuum is 10 -1 to 10 -5.
Firing is performed at a temperature of 1300 to 1600 ° C. under reduced pressure or no pressure in a torr atmosphere or various atmospheres. Metals of Group 4a, 5a, 6a group elements or their carbides,
When a nitride or boride is added, it is 100 to 20 in hot isostatic pressing (HIP) in a non-oxidizing atmosphere.
It is desirable to bake at 1200 to 1400 ° C. under 00 atm. The firing time is usually 0.5, although it depends on the size of the sample.
~ 5 hours. Then, after firing, the surface of the sintered body is mirror-polished with diamond paste or the like, whereby a glossy silver color appears.
【００２７】本発明の銀色焼結体では、本発明の組成範
囲を満足する限り、不純物やその他の化合物、金属が少
量含有しても特性上影響はない。In the silver-colored sintered body of the present invention, as long as the composition range of the present invention is satisfied, a small amount of impurities, other compounds, and metals will not affect the characteristics.
【００２８】[0028]
【作用】本発明の銀色焼結体では、焼結体中のＴｉＣ相
が銀色の色彩付与に寄与し、ＴｉＢ相が抗折強度，ビッ
カース硬度，破壊靱性等の機械的特性向上に寄与する。In the silver-colored sintered body of the present invention, the TiC phase in the sintered body contributes to imparting a silver color, and the TiB phase contributes to improvement in mechanical properties such as bending strength, Vickers hardness and fracture toughness.
【００２９】そして、本発明では、焼結体が主としてＴ
ｉＣ相とＴｉＢ相により構成されているため光沢のある
銀色を有し、優れた抗折強度，ビッカース硬度，破壊靱
性を得ることができるとともに、１３００〜１６００℃
の低温で焼成することができる。In the present invention, the sintered body is mainly T
Since it is composed of iC phase and TiB phase, it has a glossy silver color, and it is possible to obtain excellent bending strength, Vickers hardness, and fracture toughness, as well as 1300 to 1600 ° C.
Can be fired at low temperature.
【００３０】さらに、ＴｉＢ相の一部が針状結晶として
存在することにより破壊靭性がさらに向上する。また、
周期律表第４ａ，５ａ，６ａ族元素を含有せしめること
により、抗折強度，ビッカース硬度，破壊靱性等の機械
的特性をさらに向上することができる。Further, the fracture toughness is further improved by the existence of a part of the TiB phase as needle crystals. Also,
By including elements of Groups 4a, 5a and 6a of the periodic table, mechanical properties such as bending strength, Vickers hardness and fracture toughness can be further improved.
【００３１】このような銀色焼結体は、例えば、時計ケ
ース，時計バンド，ネックレス，ブレスレット等の装飾
用やハサミ，刃物，釣具等に利用することができるとと
もに、その他の工具や機械部品等に用いることができ
る。Such a silver-colored sintered body can be used, for example, for decoration of watch cases, watch bands, necklaces, bracelets, scissors, blades, fishing tackles, and other tools and machine parts. Can be used.
【００３２】[0032]
実施例１ 原料粉末として平均粒径１．１μｍのＴｉＣおよびＴｉ
Ｂ2 、粒径４０μｍのＴｉ粉末を用い、これらを表１の
割合となるように秤量混合し、これをアセトン等の有機
溶媒中、約６８時間混合粉砕した後、パラフィンを６重
量％加え、２．０ｔｏｎ／ｃｍ2 で所望形状に加圧成形
する。成形されたものを非酸化性雰囲気下において所定
温度で脱バインダーした後、真空度１０-3ｔｏｒｒの真
空加熱炉において温度１４５０℃で真空焼成を１時間行
った。焼成は、組成変化が生じないように雰囲気を調節
して行った。Example 1 TiC and Ti having an average particle size of 1.1 μm as raw material powder
B 2 and Ti powder having a particle size of 40 μm were used, and these were weighed and mixed in the proportions shown in Table 1, mixed and pulverized in an organic solvent such as acetone for about 68 hours, and added with 6% by weight of paraffin. Press-molded into a desired shape at 2.0 ton / cm 2 . The molded product was debindered at a predetermined temperature in a non-oxidizing atmosphere, and then vacuum-baked at a temperature of 1450 ° C. for 1 hour in a vacuum heating furnace having a vacuum degree of 10 −3 torr. The firing was performed by adjusting the atmosphere so that the composition did not change.
【００３３】[0033]
【表１】 [Table 1]
【００３４】このようにして得られた最終焼結体をＸ線
回折測定で結晶相を同定した結果、本発明品は、いずれ
も主としてＴｉＣ相とＴｉＢ相が存在していることを確
認した。また、最終焼結体の分析をＩＣＰ発光分光分析
等により行い、その結果を表１に示した。As a result of identifying the crystal phase of the final sintered body thus obtained by X-ray diffraction measurement, it was confirmed that TiC phase and TiB phase were mainly present in all the products of the present invention. The final sintered body was analyzed by ICP emission spectroscopy and the results are shown in Table 1.
【００３５】この表１において、金属チタンの有無は、
Ｘ線回折測定とＳＥＭによる組織観察のいずれでも金属
チタンの存在を確認できた場合を○、Ｘ線回折測定では
確認できないがＳＥＭによる組織観察では確認できる場
合を△、Ｘ線回折測定でもＳＥＭによる組織観察でも確
認できない場合を×とした。ＳＥＭによる組織図を図１
に示す。図１において、符号１はＴｉＣ相を示し、２は
ＴｉＢ相を示す。また、ＳＥＭによる組織観察によりＴ
ｉＢ粒子のアスペクト比の平均値を求めた。In Table 1, the presence or absence of metallic titanium is
When the presence of metallic titanium can be confirmed by both X-ray diffraction measurement and SEM structure observation, ◯, when it is not confirmed by X-ray diffraction measurement but can be confirmed by SEM structure observation, Δ, even by X-ray diffraction measurement by SEM The case where it could not be confirmed by tissue observation was marked with x. Figure 1 shows the organization chart by SEM
Shown in In FIG. 1, reference numeral 1 indicates a TiC phase, and 2 indicates a TiB phase. In addition, by observing the structure by SEM, T
The average value of the aspect ratio of the iB particles was obtained.
【００３６】そして、焼結体を平面研削および鏡面研磨
し、この後、抗折強度、ビッカース硬度（Ｈｖ）、破壊
靭性値および耐食性を試験し、目視により焼結体の色彩
を確認した。抗折強度の測定はＪＩＳＲ１６０１の３点
曲げ試験法に従い、ビッカース硬度の測定はＪＩＳＺ２
２４４試験法に従った。また、破壊靭性値はＩＦ法によ
り求めた。Then, the sintered body was surface-ground and mirror-polished, and then the bending strength, Vickers hardness (Hv), fracture toughness value and corrosion resistance were tested, and the color of the sintered body was visually confirmed. The bending strength is measured according to JIS R1601 three-point bending test method, and the Vickers hardness is measured according to JIS Z2.
244 test method was followed. The fracture toughness value was obtained by the IF method.
【００３７】耐食性試験は、ＩＳＯ（国際標準化機構）
規格に則した人工汗（ｐＨ４．７）を腐食液として使用
し、温度３７℃±２℃に保持した人工汗中に、鏡面研磨
した試料の下半分を２４時間浸し、浸した後の試料の研
磨面の状態を観察することにより行った。研摩面が腐食
していない場合を○、研摩面が少し腐食している場合を
△とした。また、目視によりいずれの試料も光沢のある
銀色が出現することを確認した。これらの結果を表２に
示す。The corrosion resistance test is performed by ISO (International Organization for Standardization)
Using artificial sweat (pH 4.7) conforming to the standard as a corrosive liquid, the lower half of the mirror-polished sample was immersed in artificial sweat maintained at a temperature of 37 ° C ± 2 ° C for 24 hours, and the sample after immersion It was performed by observing the state of the polished surface. The case where the polished surface was not corroded was marked with ◯, and the case where the polished surface was slightly corroded was marked with ∆. In addition, it was visually confirmed that a glossy silver color appeared in all the samples. Table 2 shows the results.
【００３８】[0038]
【表２】 [Table 2]
【００３９】これらの表１および表２から、本発明の試
料では、抗折強度が７００〜１０００ＭＰａ、ビッカー
ス硬度が１０．０〜１３．５ＧＰａ、破壊靱性値が５．
０〜６．８ＭＰａ・ｍ1/2 であり、耐食性が良好である
ことが判る。From these Tables 1 and 2, the samples of the present invention have a flexural strength of 700 to 1000 MPa, a Vickers hardness of 10.0 to 13.5 GPa and a fracture toughness value of 5.
It is 0 to 6.8 MPa · m 1/2 , which shows that the corrosion resistance is good.
【００４０】実施例２ 原料粉末として平均粒径１．１μｍのＴｉＣおよびＴｉ
Ｂ2 、粒径４０μｍのＴｉ粉末、平均粒径１．０μｍの
周期律表第４ａ，５ａ，６ａ族元素、またはそれらの炭
化物あるいは硼化物を用い、これらを最終焼結体の各金
属量が表３の割合になるように秤量混合し、これをアセ
トン等の有機溶媒中、約６８時間混合粉砕した後、パラ
フィンを６重量％加え、２．０ｔｏｎ／ｃｍ2 で所望形
状に加圧成形する。成形されたものを非酸化性雰囲気下
において４００℃で脱バインダーした後、真空度１０-3
ｔｏｒｒの真空加熱炉において温度１４５０℃で真空焼
成を１時間行った。さらに、アルゴン雰囲気において１
３００℃１時間の条件で熱間静水圧焼成（ＨＩＰ）を行
った。このようにして得られた最終焼結体の結晶相およ
び金属元素の分析，並びにアスペクト比の測定を、上記
実施例１と同様に行った。その結果を表３に示す。Example 2 TiC and Ti having an average particle size of 1.1 μm as raw material powders
B2, Ti powder having a particle size of 40 μm, elements of Groups 4a, 5a and 6a of the periodic table having an average particle size of 1.0 μm, or their carbides or borides are used. The mixture is weighed and mixed in a ratio of 3 and mixed and pulverized in an organic solvent such as acetone for about 68 hours, 6% by weight of paraffin is added, and the mixture is pressure-molded into a desired shape at 2.0 ton / cm 2 . The molded product is debindered at 400 ° C. in a non-oxidizing atmosphere, and then the vacuum degree is 10 −3.
Vacuum firing was performed for 1 hour at a temperature of 1450 ° C. in a vacuum heating furnace of torr. Furthermore, 1 in an argon atmosphere
Hot isostatic pressing (HIP) was performed under the conditions of 300 ° C. for 1 hour. The analysis of the crystal phase and the metal element of the final sintered body thus obtained, and the measurement of the aspect ratio were performed in the same manner as in Example 1 above. Table 3 shows the results.
【００４１】[0041]
【表３】 [Table 3]
【００４２】そして、焼結体を平面研削および鏡面研磨
し、この後、上記実施例１と同様に、アスペクト比，抗
折強度，ビッカース硬度（Ｈｖ），破壊靭性値，耐食性
を試験し、また、目視により焼結体の色彩を確認した。
目視による観察の結果、いずれの試料も光沢のある銀色
が出現することを確認した。これらの結果を表４に示
す。Then, the sintered body was subjected to surface grinding and mirror polishing, and thereafter, the aspect ratio, bending strength, Vickers hardness (Hv), fracture toughness value and corrosion resistance were tested in the same manner as in Example 1 above. The color of the sintered body was visually confirmed.
As a result of visual observation, it was confirmed that a glossy silver color appeared in all the samples. The results are shown in Table 4.
【００４３】[0043]
【表４】 [Table 4]
【００４４】これらの表３および表４より、焼結体中に
周期律表第４ａ，５ａ，６ａ族元素が添加されることに
より、特に、抗折強度やビッカース硬度が向上している
ことが判る。From these Tables 3 and 4, it is found that the addition of the elements of Groups 4a, 5a and 6a of the Periodic Table to the sintered body improves the bending strength and Vickers hardness in particular. I understand.
【００４５】[0045]
【発明の効果】以上詳述したように本発明の銀色焼結体
によれば、実用上何等支障のない強度および硬度を有す
るとともに、耐チッピング性、耐食性に優れ、また、焼
結性の向上により銀色の鏡面が容易に現出し、これによ
り、長期間にわたり腐食や傷が発生しない銀色装飾品と
して、例えば、時計ケース、時計バンド、ネックレス、
ブレスレット、ボタン等の装飾品やパターや釣具、刃物
等に利用することができる。本発明の銀色焼結体は、装
飾品以外の摺動部材や食器類、スポーツ用品などに用い
ることもできる。As described in detail above, according to the silver-colored sintered body of the present invention, it has strength and hardness that do not cause any problems in practical use, is excellent in chipping resistance and corrosion resistance, and has improved sinterability. The silver-colored mirror surface can be easily revealed by this, and as a silver-colored accessory that does not cause corrosion or scratches for a long period of time, for example, a watch case, a watch band, a necklace,
It can be used for ornaments such as bracelets and buttons, putters, fishing tackle, and blades. The silver-colored sintered body of the present invention can also be used for sliding members other than ornaments, tableware, sports equipment and the like.
【図１】ＳＥＭによる組織図を示す。FIG. 1 shows a structural chart by SEM.
１・・・ＴｉＣ相 ２・・・ＴｉＢ相 1 ... TiC phase 2 ... TiB phase
Claims (5)
構成元素とし、三成分基準でチタンが全量中８０〜９５
重量％、ホウ素が全量中３〜１２重量％、炭素が全量中
２〜８重量％からなる銀色焼結体であって、該焼結体中
にＴｉＣ相およびＴｉＢ相が存在することを特徴とする
銀色焼結体。1. At least titanium, carbon, and boron are the main constituent elements, and titanium is 80 to 95 out of the total amount on the basis of three components.
% Of boron, 3-12% by weight of boron in total, and 2-8% by weight of carbon in total, characterized in that a TiC phase and a TiB phase are present in the sintered body. A silver-colored sintered body.
徴とする請求項１記載の銀色焼結体。2. The silver-colored sintered body according to claim 1, wherein a part of the TiB phase is a needle crystal.
構成元素とし、三成分基準でチタンが全量中８０〜９５
重量％、ホウ素が全量中３〜１２重量％、炭素が全量中
２〜８重量％からなる主成分１００重量部に対して、周
期律表第４ａ，５ａ，６ａ族元素（Ｔｉを除く）を０．
５〜２０．０重量部の割合で存在させた銀色焼結体であ
って、該焼結体中にＴｉＣ相およびＴｉＢ相が存在する
ことを特徴とする銀色焼結体。3. At least titanium, carbon, and boron are the main constituent elements, and titanium is 80 to 95 out of the total amount on the basis of three components.
% Of boron, 3 to 12% by weight of total amount, and 2 to 8% by weight of carbon in total of 100 parts by weight of main components, elements of Groups 4a, 5a, and 6a of the periodic table (excluding Ti) are added. 0.
A silver-colored sintered body which is present in an amount of 5 to 20.0 parts by weight, wherein a TiC phase and a TiB phase are present in the sintered body.
徴とする請求項３記載の銀色焼結体。4. The silver-colored sintered body according to claim 3, wherein a part of the TiB phase is acicular crystals.
チタンのホウ化物粉末を混合したものを所定形状に成形
し、これを非酸化性雰囲気下において１３００〜１６０
０℃で焼成することを特徴とする銀色焼結体の製造方
法。5. A mixture of titanium powder, titanium carbide powder, and titanium boride powder is molded into a predetermined shape, and this is molded in a non-oxidizing atmosphere at 1300 to 160.
A method for producing a silver-colored sintered body, which comprises firing at 0 ° C.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29638294A JP3255811B2 (en) | 1994-09-29 | 1994-11-30 | Silver sintered body and method for producing the same |
| CH01850/95A CH690129A5 (en) | 1994-09-29 | 1995-06-22 | Silver-colored, sintered product, and process for its preparation. |
| DE19523531A DE19523531B4 (en) | 1994-09-29 | 1995-06-28 | Silver-colored sintered product and process for its production |
| FR9510021A FR2725197B1 (en) | 1994-09-29 | 1995-08-23 | SILVER-COLORED SINTERED PRODUCT AND PROCESS FOR MAKING SAME |
| KR1019950026573A KR100385208B1 (en) | 1994-09-29 | 1995-08-25 | Silver Sintered Product and Manufacturing Method Thereof |
| US08/878,582 US6171989B1 (en) | 1994-09-29 | 1997-06-19 | Silver-colored sintered product and method of producing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23486794 | 1994-09-29 | ||
| JP6-234867 | 1994-09-29 | ||
| JP29638294A JP3255811B2 (en) | 1994-09-29 | 1994-11-30 | Silver sintered body and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08157990A true JPH08157990A (en) | 1996-06-18 |
| JP3255811B2 JP3255811B2 (en) | 2002-02-12 |
Family
ID=26531808
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29638294A Expired - Fee Related JP3255811B2 (en) | 1994-09-29 | 1994-11-30 | Silver sintered body and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3255811B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006137667A (en) * | 2004-11-12 | 2006-06-01 | General Electric Co <Ge> | Article having titanium-base matrix wherein titanium boride superfine particles are dispersed |
| JP2007143956A (en) * | 2005-11-29 | 2007-06-14 | Kyocera Corp | Cutting tool |
| US10100386B2 (en) | 2002-06-14 | 2018-10-16 | General Electric Company | Method for preparing a metallic article having an other additive constituent, without any melting |
-
1994
- 1994-11-30 JP JP29638294A patent/JP3255811B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10100386B2 (en) | 2002-06-14 | 2018-10-16 | General Electric Company | Method for preparing a metallic article having an other additive constituent, without any melting |
| JP2006137667A (en) * | 2004-11-12 | 2006-06-01 | General Electric Co <Ge> | Article having titanium-base matrix wherein titanium boride superfine particles are dispersed |
| US8562714B2 (en) | 2004-11-12 | 2013-10-22 | General Electric Company | Article having a dispersion of ultrafine titanium boride particles in a titanium-base matrix |
| US10604452B2 (en) | 2004-11-12 | 2020-03-31 | General Electric Company | Article having a dispersion of ultrafine titanium boride particles in a titanium-base matrix |
| JP2007143956A (en) * | 2005-11-29 | 2007-06-14 | Kyocera Corp | Cutting tool |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3255811B2 (en) | 2002-02-12 |
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