JPH0543966A - Golden sintered alloy - Google Patents
Golden sintered alloyInfo
- Publication number
- JPH0543966A JPH0543966A JP3200339A JP20033991A JPH0543966A JP H0543966 A JPH0543966 A JP H0543966A JP 3200339 A JP3200339 A JP 3200339A JP 20033991 A JP20033991 A JP 20033991A JP H0543966 A JPH0543966 A JP H0543966A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- sintered alloy
- golden
- metal
- carbon
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、例えば、装飾用に使用
される金色を呈する金色焼結合金に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gold-colored sintered alloy having a gold color used for decoration, for example.
【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、これに
より、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, for example, as a gold-colored material used for decoration, pure gold, alloys of these metals, various metals such as brass, or metal plated with gold has been used. All of them have a low hardness, and as a result, they are liable to be scratched or cracked on the surface due to contact with a hard substance.
【０００３】そこで、最近においては、上記のような欠
点を解決すべく、金属の窒化物、例えば、窒化チタン等
をＮｉ，Ｃｏ等の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, in recent years, in order to solve the above-mentioned drawbacks, a metal-nitride, for example, a gold-colored sintered alloy in which titanium nitride or the like is bonded with a metal such as Ni or Co has come to be used. (See Japanese Patent Publication No. 2-58335).
【０００４】ところで、上記のような金色焼結合金は一
般に焼結性が悪いために、このような焼結性を改善すべ
く、周期律表第４ａ，５ａ，６ａ族元素の炭化物や炭窒
化物等の各種の添加物を添加して焼成する必要があっ
た。By the way, since the above-mentioned gold-colored sintered alloys generally have poor sinterability, in order to improve such sinterability, carbides and carbonitrides of elements of Groups 4a, 5a and 6a of the periodic table are improved. It was necessary to add various additives such as a product and calcinate.
【０００５】[0005]
【発明が解決しようとする問題点】しかしながら、これ
らの各種添加物の添加により、焼結体本来の黄金色から
色調が著しく変化するという問題があった。特に、焼結
性の改善に良好である周期律表第４ａ，５ａ族元素の炭
化物および炭窒化物の添加においては、焼結体の色調が
赤銅色に変化してしまい鮮明で良好な金色の呈色が得ら
れないという問題があった。However, there has been a problem that the addition of these various additives causes a marked change in color tone from the original golden color of the sintered body. In particular, in the addition of carbides and carbonitrides of elements of Groups 4a and 5a of the Periodic Table, which are good for improving the sinterability, the color tone of the sintered body changed to red copper color, and a clear and good gold color was obtained. There was a problem that no color was obtained.
【０００６】また、これらの添加物の添加量が増えるほ
ど、焼結体の切削加工時に脱粒が顕著になるとともに、
焼結体中のボイド（空孔）も増加し、これにより、強度
や硬度が低下したり、研磨しても鏡面が得られ難いとい
う問題があった。さらに、添加物の増加に伴い、例え
ば、人間の汗や海水に対する耐食性が低下するようにな
るという問題もあった。さらに、耐チッピング性に劣
り、装飾加工時に脱粒等が発生しやすく、シャープエッ
ジ加工が困難であるという問題があった。[0006] Further, as the amount of these additives added increases, shedding becomes more noticeable during cutting of the sintered body, and
There are also problems that voids (holes) in the sintered body are increased, which lowers the strength and hardness, and makes it difficult to obtain a mirror surface even after polishing. Further, there has been a problem that, as the amount of the additive increases, for example, human's corrosion resistance to sweat and seawater is reduced. Further, there is a problem in that chipping resistance is poor, particle breakage or the like is likely to occur during decoration processing, and sharp edge processing is difficult.
【０００７】[0007]
【問題点を解決するための手段】本発明者等は鮮明で良
好な金色の色調を有し、かつ、強度および硬度が高くて
耐食性に優れ、さらに耐チッピング性に優れており、シ
ャープエッジ加工を容易に行うことができる良好な金色
焼結合金を得るべく、種々の検討を重ねた結果、非金属
元素に対する炭素の割合を一定以下とし、かつ、結合金
属としての各種添加物の添加量を所定量に制限するとと
もに、焼結体中に所定量でクロムを存在させ、さらに、
焼結体中の平均結晶粒径を所定値以下に制限すると上記
のような効果を得ることができることを突き止めた。The inventors of the present invention have a sharp and good gold color tone, high strength and hardness, excellent corrosion resistance, excellent chipping resistance, and sharp edge processing. In order to obtain a good gold-colored sintered alloy that can be easily carried out, as a result of various studies, the ratio of carbon to non-metallic elements was kept below a certain level, and the addition amount of various additives as binding metals was adjusted. In addition to limiting the amount to a predetermined amount, a predetermined amount of chromium is present in the sintered body, and further,
It was found that the above effects can be obtained by limiting the average crystal grain size in the sintered body to a predetermined value or less.
【０００８】即ち、本発明の金色焼結合金は、チタンが
全量中５５〜７５重量％、鉄族金属および少なくともク
ロムを含む周期律表第６ａ族元素が全量中３〜２９重量
％、残部が非金属元素である炭素，窒素により構成され
るとともに、前記非金属元素に対する炭素の割合が１０
重量％以下であり、かつ、チタンを除く金属元素中にお
けるクロムの占める割合が４０重量％以上であり、さら
に、平均結晶粒径が３μｍ以下としてなるものである。
ここで、鉄族金属にはＮｉをはじめＦｅ，Ｃｏがあり、
周期律表第６ａ族元素にはＣｒ，Ｍｏ，Ｗがあり、非金
属元素としては炭素や窒素等がある。That is, in the gold-colored sintered alloy of the present invention, titanium is 55 to 75% by weight in total amount, iron group metal and Group 6a element containing at least chromium are 3 to 29% by weight in total amount, and the balance is It is composed of non-metal elements such as carbon and nitrogen, and the ratio of carbon to the non-metal elements is 10
The content of chromium is less than or equal to 50% by weight, the proportion of chromium in the metal elements other than titanium is equal to or greater than 40% by weight, and the average crystal grain size is equal to or less than 3 μm.
Here, the iron group metals include Ni and Fe and Co,
Cr, Mo, and W are among the elements of Group 6a of the periodic table, and carbon, nitrogen, and the like are among the nonmetallic elements.
【０００９】そして、Ｔｉを全量中５５〜７５重量％と
したのは、５５重量％よりも少なくなると金色の色調が
薄くなり、７５重量％を超えると焼結性が低下し、強度
が低下するからである。この量は６０〜７５重量％であ
ることが望ましい。尚、Ｔｉは焼結体中において、主に
ＴｉＮやＴｉＣＮとして存在し硬質相を形成する。The reason why Ti is 55 to 75% by weight based on the whole amount is that if it is less than 55% by weight, the color tone of the golden color becomes light, and if it exceeds 75% by weight, the sinterability is lowered and the strength is lowered. Because. This amount is preferably 60 to 75% by weight. Incidentally, Ti mainly exists as TiN or TiCN in the sintered body and forms a hard phase.
【００１０】さらに、鉄族金属および周期律表第６ａ族
元素を全量中３〜２９重量％としたのは、これらの量を
３重量％未満とすると焼結が困難となる傾向にあるから
であり、また、焼結体の強度が低下するからである。一
方、２９重量％よりも多いと、焼結体の硬度の低下が顕
著になるとともに耐食性が低下するからである。尚、鉄
族金属および周期律表第６ａ族元素量は５〜２９重量％
であることが望ましい。Further, the iron group metal and the Group 6a element of the periodic table are set to 3 to 29% by weight in the total amount, because if the amount is less than 3% by weight, sintering tends to be difficult. This is because the strength of the sintered body decreases. On the other hand, when it is more than 29% by weight, the hardness of the sintered body is remarkably lowered and the corrosion resistance is lowered. The amount of iron group metal and Group 6a element of the periodic table is 5 to 29% by weight.
Is desirable.
【００１１】また、非金属元素に対する炭素の割合を１
０重量％以下としたのは、１０重量％よりも多いと、色
調的には本来の黄金色から赤みが強くなり、炭素比率の
増加に伴い赤銅色から灰褐色へと変化するようになる。
従って、鮮明で良好な金色の色調を保持するためには、
非金属元素に対する炭素の割合を１０重量％以下にする
必要があるからである。特に、非金属元素の炭素の割合
は８重量％以下にすることが望ましい。Further, the ratio of carbon to the non-metal element is 1
The reason why the amount is 0% by weight or less is that if the amount is more than 10% by weight, the original golden color becomes reddish and the reddish copper color changes to grayish brown as the carbon ratio increases.
Therefore, in order to maintain a clear and good golden tone,
This is because the ratio of carbon to the non-metal element needs to be 10% by weight or less. In particular, it is desirable that the proportion of carbon, which is a nonmetallic element, be 8% by weight or less.
【００１２】さらに、チタンを除く金属元素中における
クロムの占める割合を４０重量％以上としたのは、４０
重量％未満とすると、焼結体中にボイドが発生し易くな
り、研削，研磨等の加工時に脱粒が著しく発生し、強度
が低下するようになり、また耐食性も低下するからであ
る。一方、焼結体中の結合金属に対するＣｒの割合が４
０重量％以上であると焼結性が向上し、上記のような問
題が生じないからである。これは、Ｃｒの添加により、
硬質相と結合相との濡れ性が改善されるからと考えられ
る。Further, the proportion of chromium in the metallic elements other than titanium is set to 40% by weight or more.
When the content is less than wt%, voids are apt to occur in the sintered body, graining occurs remarkably during processing such as grinding and polishing, the strength is lowered, and the corrosion resistance is also lowered. On the other hand, the ratio of Cr to the binder metal in the sintered body is 4
This is because if it is 0% by weight or more, the sinterability is improved and the above problems do not occur. This is due to the addition of Cr
It is considered that the wettability between the hard phase and the binder phase is improved.
【００１３】また、金色焼結合金の平均結晶粒径を３μ
ｍ以下としたのは、３μｍよりも大きくするとクラック
の伸展が著しくなり、研削加工時に大きなチッピングが
発生し、シャープエッジ加工ができなくなるからであ
る。一方、平均結晶粒径が３μｍ以下であるとシャープ
エッジ加工を容易に行うことができるようになる。これ
は、セラミックは脆性材料であるため衝撃力に弱く、ク
ラックが発生し易いが、平均結晶粒径を３μｍ以下とす
ると、研削加工時等で粒子に応力が作用した場合、粒子
１個当たりに作用する応力が小さくなるため脱粒等が発
生しにくくなるからと考えられる。尚、残部には少量の
不可避不純物が含有されている。The average grain size of the gold-colored sintered alloy is 3 μm.
The reason why it is set to m or less is that when it is larger than 3 μm, crack extension becomes remarkable, large chipping occurs during grinding, and sharp edge processing cannot be performed. On the other hand, when the average crystal grain size is 3 μm or less, sharp edge processing can be easily performed. This is because ceramic is a brittle material, so it is weak against impact and easily cracks. However, when the average crystal grain size is 3 μm or less, when stress acts on particles during grinding, etc. It is considered that this is because the stress acting on the surface becomes small, so that shedding or the like is less likely to occur. The balance contains a small amount of unavoidable impurities.
【００１４】そして、本発明の金色焼結合金は、原料粉
末として、Ｔｉの窒化物および炭窒化物粉末にＮｉ等の
鉄族金属および周期律表第６ａ族金属元素を混合したも
のを、アセトン等の有機溶媒中、所定時間混合粉砕した
後、バインダーを所定量加え、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
脱バインダーした後、所定温度で焼成を行うことにより
得られる。例えば、粒径が０．５〜３．０μｍのＴｉの
窒化物および炭窒化物と、鉄族金属として粒径０．１〜
１．０μｍのＮｉやＣｏと、Ｃｒを含む周期律表第６ａ
族元素として粒径１．０〜１０．０μｍのＷＣやＣｒ3
Ｃ2 等の各粉末を秤量混合し、これをアセトン等の有機
溶媒中、約２０〜１００時間混合粉砕した後、プレス成
形，射出成形，押出成形等により所望形状に成形する。
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、真空加熱炉において所定温度で真
空焼成することにより得られる。尚、このとき、Ｗ，Ｃ
ｒは原料粉末として炭化物として添加し、焼成する過程
において金属Ｃｒ，金属Ｗとして結合金属中に固溶した
り、ＴｉＮやＴｉＣＮ中に固溶し、ＷＣやＣｒ3 Ｃ2 の
形では存在していない。The raw material powder of the gold-colored sintered alloy of the present invention is a mixture of a Ti nitride and carbonitride powder mixed with an iron group metal such as Ni and a metal element of Group 6a of the periodic table. After mixing and pulverizing in an organic solvent such as for a predetermined time, add a predetermined amount of binder, press-mold into a desired shape at a predetermined pressure, debinder this at a predetermined temperature in a non-oxidizing atmosphere, and then bake at a predetermined temperature It is obtained by performing. For example, Ti nitride and carbonitride having a particle size of 0.5 to 3.0 μm, and a particle size of 0.1 to 0.1 as an iron group metal.
Periodic table 6a containing Ni and Co of 1.0 μm and Cr
WC or Cr 3 having a particle size of 1.0 to 10.0 μm as a group element
Powders such as C 2 are weighed and mixed, and this is mixed and pulverized in an organic solvent such as acetone for about 20 to 100 hours, and then molded into a desired shape by press molding, injection molding, extrusion molding or the like.
It is obtained by debinding the molded product at a predetermined temperature in a non-oxidizing atmosphere, and then vacuum-baking it at a predetermined temperature in a vacuum heating furnace. At this time, W, C
r is present in the form of WC or Cr 3 C 2 because it is added as a carbide as a raw material powder and dissolved in the binding metal as metal Cr and metal W in the process of firing or in TiN or TiCN. Absent.
【００１５】焼成方法としては真空度が１０-1〜１０-4
torrの雰囲気や、各種雰囲気中において減圧または無加
圧にて、温度１３００〜１８００℃で焼成する。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、光沢のある金色
が出現する。このようにして得られた金色焼結合金は、
例えば、時計ケース，時計バンド，ネックレス，ブロー
チ，記念メダル，ボタン等の装飾用やハサミ，刃物，釣
り具等に利用することができる。As a firing method, the degree of vacuum is 10 -1 to 10 -4.
Firing is performed at a temperature of 1300 to 1800 ° C. under reduced pressure or no pressure in a torr atmosphere or various atmospheres. The firing time is usually 0.5 to 5 hours, depending on the size of the sample. Then, after firing, the surface of the sintered body is mirror-polished with diamond paste or the like, whereby a glossy gold color appears. The gold-colored sintered alloy thus obtained is
For example, it can be used for decoration of watch cases, watch bands, necklaces, broaches, commemorative medals, buttons, scissors, blades, fishing tackle, and the like.
【００１６】[0016]
【実施例】原料粉末として粒径１．２μｍのＴｉＮ，粒
径１．５μｍのＴｉＣＮ，粒径７．０μｍのＣｒ
3 Ｃ2 ，粒径９．０μｍのＷＣ，粒径３．０μｍのＮ
ｉ，粒径４．０μｍのＣｏの各粉末を用い、これらを最
終焼結体の各金属量が表１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４〜５重量％加え、１．５ton/
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１０-2torr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。このようにして得られた最
終焼結体の分析を、ＩＣＰ発光分光分析等により行な
い、その結果を表１に示す。Example As a raw material powder, TiN having a particle size of 1.2 μm, TiCN having a particle size of 1.5 μm, and Cr having a particle size of 7.0 μm
3 C 2 , particle size 9.0 μm WC, particle size 3.0 μm N
i, Co powders having a particle size of 4.0 μm were used, and these were weighed and mixed so that the respective metal contents of the final sintered body were in the ratios shown in Table 1, and the powders were mixed in an organic solvent such as acetone for about 68 hours. After mixing and pulverizing, add paraffin in an amount of 4-5% by weight, and add 1.5 ton /
It is pressed into a desired shape with cm 2 . After debinding the molded product at a predetermined temperature in a non-oxidizing atmosphere,
Temperature 1450 ° C in a vacuum furnace with a vacuum of 10 -2 torr
Vacuum firing was carried out for 1 hour. The final sintered body thus obtained was analyzed by ICP emission spectroscopy and the results are shown in Table 1.
【００１７】[0017]
【表１】 [Table 1]
【００１８】そして、焼結体を平面研削および鏡面研磨
し、この後、試料の色調，抗折強度，ビッカース硬度
（Ｈｖ），気孔率および平均結晶粒径，耐チッピング性
および耐食性を試験した。抗折強度の測定は、ＪＩＳＲ
１６０１の３点曲げ試験法に従い、ビッカース硬度の測
定はＪＩＳＺ２２４４試験法に従い、気孔率においては
アルキメデス法に従った。そして、耐食性試験について
は、ＩＳＯ（国際標準化機構）規格に則した人工汗（ｐ
Ｈ4.7)を腐食液として使用し、温度４０℃±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況を観察することに
より行った。平均結晶粒径は焼結体中のＳ．Ｅ．Ｍ写真
より算出した、また、耐チッピング性は、鏡面研磨した
試料をクリープ研削した時の最大チッピング幅で示し
た。これらの結果を表２に示す。Then, the sintered body was subjected to surface grinding and mirror polishing, and thereafter, the color tone, bending strength, Vickers hardness (Hv), porosity and average crystal grain size, chipping resistance and corrosion resistance of the sample were tested. The bending strength is measured by JISR
According to the 1601 three-point bending test method, the Vickers hardness was measured according to the JISZ2244 test method, and the porosity was measured according to the Archimedes method. And for the corrosion resistance test, artificial sweat (p
H4.7) is used as a corrosive liquid, and the lower half of the mirror-polished sample is immersed in artificial sweat kept at a temperature of 40 ° C ± 2 ° C for 24 hours, and the condition of the polished surface of the sample after immersion is observed. I went by. The average crystal grain size is the S. E. The chipping resistance calculated from the M photograph was shown by the maximum chipping width when creep grinding was performed on the mirror-polished sample. The results are shown in Table 2.
【００１９】[0019]
【表２】 [Table 2]
【００２０】表１，表２において、＊印を付した試料番
号のものは、本発明の範囲外のものを示している。ま
た、表２における気孔率については、○印は５％未満の
高緻密体、×印は５％より大きい低緻密体であることを
示す。また、耐食性試験の結果については、○印は変色
および腐食が全くなく、×印は変色に加え、腐食も認め
られたことを示す。耐チッピング性については、○印は
シャープエッジ加工として良好なもの、×印はチッピン
グが多発してシャープエッジ加工不能なものを示す。In Tables 1 and 2, the sample numbers marked with * indicate those outside the scope of the present invention. Regarding the porosity in Table 2, ◯ indicates a high-density body of less than 5%, and x indicates a low-density body of more than 5%. Regarding the results of the corrosion resistance test, the mark "○" indicates no discoloration and corrosion, and the mark "x" indicates that not only discoloration but also corrosion was observed. Regarding chipping resistance, ◯ indicates good sharp edge processing, and x indicates chipping that is impossible and sharp edge processing is not possible.
【００２１】これらの表１及び表２より、本発明の請求
の範囲内の試料Ｎo,２〜７及び９については、気孔率，
抗折強度，ビッカース硬度，耐食性，耐チッピング性に
ついて非常に優れており、優美な黄金色を有することが
判る。From these Tables 1 and 2, the porosities of the samples No. 2 to 7 and 9 within the claims of the present invention are
It has excellent bending strength, Vickers hardness, corrosion resistance, and chipping resistance, and is known to have an elegant golden color.
【００２２】[0022]
【発明の効果】以上詳述した通り、本発明によれば、使
用上何ら支障のない硬度および強度を有するとともに、
耐食性に優れ、また，焼結性の著しい向上により優美な
黄金色の鏡面が容易に現出し、さらに、製作上必要なシ
ャープエッジ加工を容易に行うことができ、その結果、
長期にわたり腐食やキズが発生しない美しい色調の金色
焼結合金として、例えば、時計ケース，時計バンド，ネ
ックレス，ブローチ，記念メダル，ボタン等の装飾用や
刃物，釣り具等に利用することができる。As described above in detail, according to the present invention, the hardness and the strength are not hindered in use, and
It has excellent corrosion resistance, and the sinterability has been significantly improved to create a beautiful golden mirror surface. Furthermore, the sharp edge processing required for manufacturing can be easily performed.
As a gold-colored sintered alloy having a beautiful color tone that does not cause corrosion or scratches for a long period of time, it can be used, for example, for decoration of watch cases, watch bands, necklaces, broaches, commemorative medals, buttons and the like, blades, fishing tackle and the like.
Claims (1)
属および少なくともクロムを含む周期律表第６ａ族元素
が全量中３〜２９重量％、残部が非金属元素である炭
素，窒素により構成され、前記非金属元素に対する炭素
の割合が１０重量％以下、チタンを除く金属元素中にお
けるクロムの占める割合が４０重量％以上であり、か
つ、平均結晶粒径が３μｍ以下であることを特徴とする
金色焼結合金。1. A total of 55 to 75% by weight of titanium, 3 to 29% by weight of the group 6a element of the periodic table containing an iron group metal and at least chromium, and the balance of carbon and nitrogen which are non-metal elements. The ratio of carbon to the non-metal element is 10% by weight or less, the ratio of chromium in the metal elements other than titanium is 40% by weight or more, and the average crystal grain size is 3 μm or less. And a golden sintered alloy.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3200339A JPH0543966A (en) | 1991-08-09 | 1991-08-09 | Golden sintered alloy |
| EP92110770A EP0520465B1 (en) | 1991-06-27 | 1992-06-26 | Sintered alloy of golden color |
| DE1992616156 DE69216156T2 (en) | 1991-06-27 | 1992-06-26 | Gold-colored sintered alloy |
| KR1019920011202A KR100239844B1 (en) | 1991-06-27 | 1992-06-26 | Sintered alloy of golden color |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3200339A JPH0543966A (en) | 1991-08-09 | 1991-08-09 | Golden sintered alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0543966A true JPH0543966A (en) | 1993-02-23 |
Family
ID=16422649
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3200339A Pending JPH0543966A (en) | 1991-06-27 | 1991-08-09 | Golden sintered alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0543966A (en) |
-
1991
- 1991-08-09 JP JP3200339A patent/JPH0543966A/en active Pending
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