JP3255738B2 - Golden sintered alloy and method for producing the same - Google Patents
Golden sintered alloy and method for producing the sameInfo
- Publication number
- JP3255738B2 JP3255738B2 JP33058792A JP33058792A JP3255738B2 JP 3255738 B2 JP3255738 B2 JP 3255738B2 JP 33058792 A JP33058792 A JP 33058792A JP 33058792 A JP33058792 A JP 33058792A JP 3255738 B2 JP3255738 B2 JP 3255738B2
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- Japan
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- boron
- weight
- titanium
- sintered alloy
- titanium nitride
- Prior art date
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、例えば、美しい色調の
金色装飾用部材，耐摩耗部材として、壁材，時計部材，
ブローチ，ネックレス，メダル，ボタン，釣具等に使用
される高硬度金色焼結合金およびその製造方法に関す
る。BACKGROUND OF THE INVENTION The present invention relates to, for example, a wall decoration, a clock member,
The present invention relates to a high-hardness golden sintered alloy used for broaches, necklaces, medals, buttons, fishing gear, and the like, and a method for producing the same.
【０００２】[0002]
【従来技術】従来、例えば、装飾用に使用される金色を
呈する材料としては、純金やこれらの合金、黄銅等の各
種金属、または、金属表面に金メッキを施したものが使
用されていたが、これらはいずれも硬度が低く、硬質物
質との接触により表面に傷が生じ易く、或いは割れ等が
発生するという欠点があった。2. Description of the Related Art Conventionally, as a gold-colored material used for decoration, for example, various metals such as pure gold, their alloys, brass, and the like, or a metal-plated metal has been used. All of these have the drawback that the hardness is low and the surface is easily scratched by contact with a hard substance, or cracks or the like occur.
【０００３】このような欠点を解決するため、従来で
は、高硬度で耐酸化性に優れ、かつ美麗な金色の発色が
得られる窒化チタンが使用されていた。しかしながら、
窒化チタンを単味焼結体として得るためには、２３００
℃以上の高温で、しかも特殊な方法で焼結させる必要が
あった。また、得られた焼結体は抗折強度が低く脆いと
いう欠点があった。[0003] In order to solve such disadvantages, conventionally, titanium nitride which has high hardness, excellent oxidation resistance and obtains a beautiful golden color has been used. However,
In order to obtain titanium nitride as a simple sintered body, 2300
It was necessary to perform sintering at a high temperature of at least ℃ and a special method. In addition, the obtained sintered body had a drawback that the bending strength was low and brittle.
【０００４】そこで、最近においては、窒化チタンをＮ
ｉ，Ｃｏ等の鉄族金属で結合させた金色焼結合金が用い
られるようになってきている（特公平２−５８３３５号
公報等参照）。Therefore, recently, titanium nitride has been
Gold sintered alloys bonded with iron group metals such as i and Co have been used (see Japanese Patent Publication No. 2-58335).
【０００５】[0005]
【発明が解決しようとする問題点】しかしながら、窒化
チタンに鉄族金属からなる焼結助剤を添加すると、焼結
体中の金属成分の腐食の進行により、例えば、海水や汗
などのため変色し、装飾部材の呈色が損なわれるという
問題があった。しかも、前記焼結助剤は窒化チタンとの
濡れ性が悪く、結晶および粒界の全般にわたり、多くの
空隙が現れ、鏡面研磨しても鮮やかな鏡面が出現しない
という欠点があった。However, when a sintering aid composed of an iron group metal is added to titanium nitride, the discoloration due to, for example, seawater or sweat, due to the progress of corrosion of metal components in the sintered body. However, there is a problem that the coloration of the decorative member is impaired. In addition, the sintering aid has poor wettability with titanium nitride, has many voids throughout the crystal and grain boundaries, and does not have a bright mirror surface even after mirror polishing.
【０００６】さらに、窒化チタンに鉄族金属や他の耐食
助剤等を添加して焼結して得られる焼結合金は、いずれ
もビッカース硬度ＨV が１５００ｋｇ／ｍｍ2 以下のも
のであり、近年における各種セラミック製品や高硬度コ
ーティング製品の普及により、耐摩耗性，耐キズ性とい
う面で必ずしも充分な硬度を有しているとは言えない状
況となってきている。Furthermore, sintered alloy obtained by sintering with the addition of iron group metal or other corrosion-resistant aids such as titanium nitride is any one Vickers hardness H V of 1500 kg / mm 2 or less, With the spread of various ceramic products and high-hardness coating products in recent years, it has become impossible to say that they have sufficient hardness in terms of wear resistance and scratch resistance.
【０００７】[0007]
【問題点を解決するための手段】本発明者は、上記の問
題点について検討を重ねた結果、窒化チタンに硼化チタ
ンおよびボロン金属を添加して焼結させると、窒化チタ
ン本来の高硬度を低下させずに、充分に高い強度および
優れた耐酸化性，耐食性を有する金色焼結合金を得るこ
とができることを知見し、本発明に至った。The inventors of the present invention have studied the above problems, and found that when titanium boride and boron metal are added to sintering and sintering, the original high hardness of titanium nitride is obtained. It has been found that a gold-colored sintered alloy having sufficiently high strength and excellent oxidation resistance and corrosion resistance can be obtained without lowering the temperature, and the present invention has been accomplished.
【０００８】即ち、本発明の金色焼結合金は、チタン，
窒素，ボロンを構成元素とし、チタン６０〜７３重量
％、窒素１３〜１８重量％、ボロン１０〜３０重量％の
組成からなる金色焼結合金であって、該合金中に結晶相
として窒化チタンと硼化チタンが存在し、結合相として
ボロンが存在するとともに、上記結晶相の平均結晶粒径
が４μｍ以下のものである。このような金色焼結合金
は、窒化チタンに、硼化チタンを１〜８重量％とボロン
を６〜４０重量％添加した混合粉末を焼結することによ
り得られる。That is, the golden sintered alloy of the present invention comprises titanium,
A golden sintered alloy having a composition of 60 to 73% by weight of titanium, 13 to 18% by weight of nitrogen, and 10 to 30% by weight of boron with nitrogen and boron as constituent elements. Titanium boride is present, boron is present as a binder phase, and the average crystal grain size of the crystal phase is 4 μm or less. Such a golden sintered alloy is obtained by sintering a mixed powder obtained by adding 1 to 8% by weight of titanium boride and 6 to 40% by weight of boron to titanium nitride.
【０００９】ここで、全体組成をチタン６０〜７３重量
％、窒素１３〜１８重量％、ボロン１０〜３０重量％か
ら構成したのは、チタンが６０重量％よりも少ないと色
調が暗くなり、７３重量％よりも多くなると硬度が低下
するからである。また、窒素が１３重量％よりも少ない
と金色の色調がくすみ、１８重量％よりも多いと光沢が
乏しくなるからである。さらに、ボロンが１０重量％よ
りも少ないと硬度が低下し、３０重量％よりも多くなる
と色調および耐食性が悪くなるからである。Here, the total composition is composed of 60 to 73% by weight of titanium, 13 to 18% by weight of nitrogen and 10 to 30% by weight of boron. If the amount is more than the weight%, the hardness is reduced. If the nitrogen content is less than 13% by weight, the golden color tone becomes dull, and if the nitrogen content is more than 18% by weight, the gloss becomes poor. Further, if the content of boron is less than 10% by weight, the hardness is reduced, and if the content is more than 30% by weight, the color tone and the corrosion resistance are deteriorated.
【００１０】また、焼結合金中の平均結晶粒径を４μｍ
以下としたのは、４μｍよりも大きいと、焼結合金の強
度および硬度が低下するとともに、耐食性が低下するか
らである。平均結晶粒径は３μｍ以下が望ましい。この
ような平均結晶粒径は、原料粉末を３μｍ以下に粉砕
し、かつ、窒化チタンに、硼化チタンを１〜８重量％
と、ボロンを６〜４０重量％添加して、適性温度下にお
いて焼成することにより制御することができる。The average grain size of the sintered alloy is 4 μm.
The reason for this is that if it is larger than 4 μm, the strength and hardness of the sintered alloy will decrease and the corrosion resistance will decrease. The average crystal grain size is desirably 3 μm or less. Such an average crystal grain size is obtained by pulverizing the raw material powder to 3 μm or less, and adding titanium boride to titanium nitride by 1 to 8% by weight.
And 6 to 40% by weight of boron, followed by firing at an appropriate temperature.
【００１１】また、窒化チタンに硼化チタンを１〜８重
量％を含有させて焼成したのは、硼化チタンが１重量％
よりも少ないと焼結性が著しく低下し、８重量％よりも
多いと焼結中に硼素が分解して結晶中に空隙等の欠陥の
発生が著しくなり、強度が低下するとともに鏡面状態が
悪くなるからである。窒化チタンに含有される硼化チタ
ンは、特に３〜７．５重量％の割合で配合することが望
ましい。The reason why the titanium nitride containing 1 to 8% by weight of titanium boride and calcined is that titanium boride is 1% by weight.
If it is less than 8 wt%, sinterability will be remarkably reduced, and if it is more than 8 wt%, boron will be decomposed during sintering and defects such as voids will be remarkably generated in the crystal, and the strength will be reduced and the mirror surface state will be poor Because it becomes. It is desirable that the titanium boride contained in the titanium nitride is blended at a ratio of 3 to 7.5% by weight.
【００１２】また、窒化チタンに添加されるボロンを６
〜４０重量％添加して焼成したのは、６重量％よりも少
ないとビッカース硬度が低下し、４０重量％よりも多い
と、金色の色調が薄暗くなるからである。ボロンは８〜
２５重量％の範囲で配合することが望ましい。Further, boron added to titanium nitride is 6
The reason for baking with addition of ４０40% by weight is that if it is less than 6% by weight, the Vickers hardness decreases, and if it is more than 40% by weight, the golden color tone becomes dark. Boron is 8 ~
It is desirable to mix in a range of 25% by weight.
【００１３】本発明の金色焼結合金は、窒化チタンに、
硼化チタンを１〜８重量％と、ボロンを６〜４０重量％
添加した混合粉末を焼結することにより得られるが、窒
化チタンの原料粉末、硼化チタンの原料粉末の平均粒径
はいずれも４μｍ以下であれば良く、焼結性の活性化の
点から特に３μｍ以下が好ましい。[0013] The golden sintered alloy of the present invention comprises
1 to 8% by weight of titanium boride and 6 to 40% by weight of boron
It is obtained by sintering the added mixed powder, and the average particle diameter of the raw material powder of titanium nitride and the raw material powder of titanium boride may be 4 μm or less, especially from the viewpoint of sintering activation. It is preferably 3 μm or less.
【００１４】ボロンは、アモルファスボロンおよび結晶
化ボロンのいずれでも良いが、特に焼成性および反応性
の活性化の点からアモルファスボロンが特に好ましい。The boron may be either amorphous boron or crystallized boron, but amorphous boron is particularly preferred from the viewpoint of sinterability and activation of reactivity.
【００１５】このボロンの粒径については４μｍ以下で
あれば良く、特に分散および活性化の点から２μｍ以下
が好ましい。The particle size of boron is preferably 4 μm or less, and particularly preferably 2 μm or less from the viewpoint of dispersion and activation.
【００１６】尚、原料組成と焼結体組成が理論上一致し
ないのは、焼成中に硼化チタンやボロンの一部が飛散す
るからである。The reason why the composition of the raw material and the composition of the sintered body do not match in theory is that part of titanium boride or boron is scattered during firing.
【００１７】また、本発明の金色焼結合金の構造は、窒
化チタンと硼化チタンの分散粒子相にボロンが結合相と
して存在し、このボロンが窒化チタンと硼化チタンの濡
れ性を向上し、硼化チタンの分解を抑制していると考え
られる。In the structure of the golden sintered alloy of the present invention, boron is present as a binder phase in the dispersed particle phase of titanium nitride and titanium boride, and this boron improves the wettability of titanium nitride and titanium boride. It is considered that the decomposition of titanium boride is suppressed.
【００１８】本発明の金色焼結合金の製造方法を具体的
に説明すると、窒化チタンの原料粉末に硼化チタンの原
料粉末およびボロン原料粉末を上述した割合で添加し、
均一に混合した後、この混合粉末を、公知の成形方法、
例えば、プレス成形により加圧成形し、焼成する。焼成
は窒素，アルゴン等の非酸化性雰囲気または真空雰囲気
（真空度１０-2〜１０-5ｔｏｒｒ）において１９００〜
２２００Ｋの温度範囲で０．５〜３時間行う。この焼結
の過程においてボロンや窒素がガスとして分解蒸発す
る。このため、焼結体組成が前述した組成となるよう
に、原料組成および焼成時間等を制御する必要がある。
これにより高強度，耐酸化性，耐食性にすぐれた高硬度
金色焼結合金を得ることができる。The method for producing a golden sintered alloy according to the present invention will be described in detail. A titanium boride raw material powder and a boron raw material powder are added to a titanium nitride raw material powder in the above-described ratios.
After uniform mixing, the mixed powder is formed by a known molding method,
For example, pressure molding is performed by press molding and firing is performed. The sintering is performed in a non-oxidizing atmosphere such as nitrogen or argon or in a vacuum atmosphere (vacuum degree: 10 −2 to 10 −5 torr) at 1900 to
Perform for 0.5 to 3 hours at a temperature range of 2200K. During this sintering process, boron and nitrogen are decomposed and evaporated as gas. Therefore, it is necessary to control the raw material composition, the firing time, and the like so that the composition of the sintered body becomes the above-described composition.
As a result, a high-hardness golden sintered alloy having high strength, oxidation resistance, and corrosion resistance can be obtained.
【００１９】[0019]
【作用】本発明によれば、窒化チタン本来の高硬度を低
下させずに、充分に高い強度および優れた耐酸化性，耐
食性を有する金色焼結合金を得ることが可能となる。According to the present invention, a gold sintered alloy having sufficiently high strength and excellent oxidation resistance and corrosion resistance can be obtained without lowering the inherent high hardness of titanium nitride.
【００２０】これは、窒化チタンにボロンを添加するこ
とにより、ボロンが窒化チタン粒子の表面を均一に包み
込み、高硬度粒子を形成するとともに、硼化チタンとの
濡れ性を向上するからである。This is because, by adding boron to titanium nitride, boron uniformly wraps around the surface of the titanium nitride particles, forms high hardness particles, and improves wettability with titanium boride.
【００２１】[0021]
【実施例】以下、本発明を次の例で説明する。The present invention will be described below with reference to the following examples.
【００２２】窒化チタン（ＴｉＮ）粉末，硼化チタン
（ＴｉＢ2 ）粉末，アモルファス状のボロン（ａ−Ｂ）
粉末を表１に示す量比で配合し６８時間混合粉砕した。Titanium nitride (TiN) powder, titanium boride (TiB2) powder, amorphous boron (a-B)
The powders were blended at the ratios shown in Table 1 and mixed and ground for 68 hours.
【００２３】これを乾燥後、パラフィンを４重量％添加
し、１．５ｔｏｎ／ｃｍ2 の圧力で加圧成形し、脱バイ
ンダー後、１０-3ｔｏｒｒの真空中において２０５０Ｋ
で１時間焼成した。After drying, 4% by weight of paraffin was added, the mixture was molded under pressure at a pressure of 1.5 ton / cm 2 , and after removing the binder, it was subjected to 2050K in a vacuum of 10 -3 torr.
For 1 hour.
【００２４】[0024]
【表１】 [Table 1]
【００２５】得られた焼結合金の表面を研削した後、抗
折強度を測定した。また、鏡面研磨した後、その色調、
ビッカース硬度、焼結体の平均結晶粒径および鏡面の耐
食性を測定した。また、焼結体を粉砕してその焼結体組
成を測定した。抗折強度はＪＩＳＲ１６０１の３点曲げ
試験法に従い、ビッカース硬度の測定はＪＩＳＺ２２４
４試験法に従った。また、平均結晶粒径はＳＥＭ写真に
より算出した。さらに、耐食試験については、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、これに試料を浸すという耐汗試験、およ
び塩水（４ｗｔ％／ｖｏｌ）を霧状にして吹きかけると
いう塩水噴霧試験（ＪＩＳＺ２３７１）を行った。そし
て、焼結体組成はＩＣＰ発光分光分析およびＬＥＣＯ社
製窒素ガスの熱伝導度検出器にて、チタン，ボロン，窒
素の定量分析を行った。After grinding the surface of the obtained sintered alloy, the transverse rupture strength was measured. Also, after mirror polishing, the color tone,
The Vickers hardness, the average crystal grain size of the sintered body, and the corrosion resistance of the mirror surface were measured. Further, the sintered body was pulverized and the composition of the sintered body was measured. The flexural strength was measured according to the JISR1601 three-point bending test method, and the Vickers hardness was measured according to JISZ224.
Four test methods were followed. The average crystal grain size was calculated from an SEM photograph. Further, regarding the corrosion resistance test, ISO
(International Organization for Standardization) Artificial sweat in accordance with the standard (PH 4.7)
Was used as a corrosive liquid, and a sample was immersed in a perspiration test, and a salt water spray test (JISZ2371) in which salt water (4 wt% / vol) was sprayed in a mist state was performed. The composition of the sintered body was subjected to ICP emission spectroscopy and quantitative analysis of titanium, boron and nitrogen by a thermal conductivity detector of nitrogen gas manufactured by LECO.
【００２６】これらの結果を表１に示す。The results are shown in Table 1.
【００２７】表１において、耐食性試験の結果について
は、耐汗試験および塩水噴霧試験とも、変色および腐食
が全くなく、色調劣化の全くないものを○、これとは逆
に変色または腐食が認められ、徐々に色調が劣化し、装
飾部材として不適であるものを×とした。In Table 1, regarding the results of the corrosion resistance test, in both the sweat resistance test and the salt spray test, no discoloration and no corrosion and no color tone deterioration were observed. On the contrary, discoloration or corrosion was observed. Those which gradually deteriorated in color tone and were unsuitable as decorative members were evaluated as x.
【００２８】表１より明らかなように、試料４，５，
６，７，１１の金色焼結合金は耐食性に優れ、装飾用途
上、何ら支障のない優れた硬度および強度を示してい
る。また、その焼結合金を研磨すると鮮やかな金色の鏡
面が現出し、著しく優れた金色装飾部材となることがわ
かった。As apparent from Table 1, samples 4, 5,
The 6, 7, and 11 golden sintered alloys have excellent corrosion resistance and exhibit excellent hardness and strength without any hindrance in decorative applications. In addition, it was found that when the sintered alloy was polished, a bright gold mirror surface appeared, resulting in an extremely excellent gold decorative member.
【００２９】一方、試料１，２，３，８，１０，１３で
は強度に劣り、試料１，２，８，１０，１４では耐食性
に劣り、それぞれ光沢に乏しい金色および暗い金色とな
り、いずれも金色装飾部材として不適であった。さら
に、試料２，９，１５では硬度が充分に高いものとは言
えないものであった。On the other hand, Samples 1, 2, 3, 8, 10, and 13 were inferior in strength, while Samples 1, 2, 8, 10, and 14 were inferior in corrosion resistance, each having poor gloss and dark gold. It was not suitable as a decorative member. Further, in Samples 2, 9, and 15, the hardness was not sufficiently high.
【００３０】[0030]
【発明の効果】以上記述したように、本発明の金色焼結
合金およびその製造方法では、窒化チタン本来の高硬度
を低下させずに、充分に高い強度および優れた耐酸化
性，耐食性を有する金色焼結合金を得ることができ、装
飾用途上および耐摩耗用途上、何ら支障のない硬度およ
び強度を有するとともに、従来の金色焼結合金と比較し
て耐食性が向上し、かつ鮮やかな黄金色の鏡面が現出
し、その結果、長期に渡り腐食やキズが発生しない美し
い色調の金色装飾用部材および耐摩耗部材として、壁
材，時計部材，ブローチ，ネックレス，メダル，ボタ
ン，釣具等に好適に用いることができる。As described above, the golden sintered alloy of the present invention and the method for producing the same have sufficiently high strength and excellent oxidation resistance and corrosion resistance without lowering the inherent high hardness of titanium nitride. A gold-colored sintered alloy can be obtained, which has no problem in hardness and strength for decorative and wear-resistant applications, and has improved corrosion resistance compared to conventional gold-colored sintered alloys, and has a bright golden color Mirror surface appears, and as a result, it is suitable for wall materials, clock members, brooches, necklaces, medals, buttons, fishing gear, etc. Can be used.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C04B 35/58 101 C04B 35/58 105 C22C 1/04 C22C 1/05 C22C 29/00 - 29/18 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. 7 , DB name) C04B 35/58 101 C04B 35/58 105 C22C 1/04 C22C 1/05 C22C 29/00-29/18
Claims (2)
タン６０〜７３重量％、窒素１３〜１８重量％、ボロン
１０〜３０重量％の組成からなる金色焼結合金であっ
て、該合金中に結晶相として窒化チタンと硼化チタンが
存在し、結合相としてボロンが存在するとともに、上記
結晶相の平均結晶粒径が４μｍ以下であることを特徴と
する金色焼結合金。1. Titanium, nitrogen and boron as constituent elements, 60 to 73 % by weight of titanium, 13 to 18 % by weight of nitrogen, boron
A gold sintered alloy consisting of 10 to 30% by weight of the composition, together with the present titanium nitride and titanium boride as a crystal phase in the alloy, boron is present as a binder phase, the <br/> crystalline phase Wherein the average grain size is 4 μm or less.
と、ボロンを６〜４０重量％添加した混合粉末を焼結す
ることを特徴とする請求項１記載の金色焼結合金の製造
方法。2. A titanium nitride containing 1 to 8% by weight of titanium boride.
When manufacturing method of gold sintered alloy according to claim 1, wherein sintering a mixed powder prepared by adding boron 6 to 40 wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33058792A JP3255738B2 (en) | 1992-12-10 | 1992-12-10 | Golden sintered alloy and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33058792A JP3255738B2 (en) | 1992-12-10 | 1992-12-10 | Golden sintered alloy and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06172889A JPH06172889A (en) | 1994-06-21 |
| JP3255738B2 true JP3255738B2 (en) | 2002-02-12 |
Family
ID=18234323
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33058792A Expired - Fee Related JP3255738B2 (en) | 1992-12-10 | 1992-12-10 | Golden sintered alloy and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3255738B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009119481A1 (en) * | 2008-03-24 | 2009-10-01 | 京セラ株式会社 | Ceramic for decorative part and decorative part comprising the same |
| JP2011093725A (en) * | 2009-10-28 | 2011-05-12 | Kyocera Corp | Ceramics for ornamental piece, and ornamental piece |
| US8790438B2 (en) * | 2009-12-29 | 2014-07-29 | Nokia Corporation | Colored metal |
-
1992
- 1992-12-10 JP JP33058792A patent/JP3255738B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06172889A (en) | 1994-06-21 |
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