JPH0431010B2 - - Google Patents
Info
- Publication number
- JPH0431010B2 JPH0431010B2 JP62279334A JP27933487A JPH0431010B2 JP H0431010 B2 JPH0431010 B2 JP H0431010B2 JP 62279334 A JP62279334 A JP 62279334A JP 27933487 A JP27933487 A JP 27933487A JP H0431010 B2 JPH0431010 B2 JP H0431010B2
- Authority
- JP
- Japan
- Prior art keywords
- palladium
- alloys
- alloy
- platinum
- weight
- 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.)
- Expired - Lifetime
Links
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 229910045601 alloy Inorganic materials 0.000 claims description 12
- 239000000956 alloy Substances 0.000 claims description 12
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 229910001252 Pd alloy Inorganic materials 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 229910001020 Au alloy Inorganic materials 0.000 description 3
- 229910001260 Pt alloy Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003353 gold alloy Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 210000004243 sweat Anatomy 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 229910000923 precious metal alloy Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
Landscapes
- Air Conditioning Control Device (AREA)
- Adornments (AREA)
Description
＜産業上の利用分野＞
開示技術は、時計枠としての利用は勿論のこ
と、時計バンド、指輪、ネツクレス等の装身具類
等の装飾用材料として使用することが出来るプラ
チナ、シルバー色を有した装飾用のパラジウム合
金の技術分野に属する。
＜従来の技術＞
当業者に周知の如く、従来白色系の時計枠や時
計バンド、更には、指輪、ネツクレス等の装身具
類に用いる装飾用合金には貴金属系の合金として
金合金、銀合金、白金合金がある。
＜発明が解決しようとする課題＞
而して、これらの装飾用金属材料は次述する如
くいづれもメリツト、デメリツトが相半ばして重
複している。
例えば、金合金、白金合金においては時計用材
料の場合、機能性、更には、装飾品的価値の点で
良い面があるが、反面コスト高になるデメリツト
に加えて地金費の変動による価格的影響も大き
く、時計材料としての新しさにも乏しい不具合も
ある。
又、銀合金においては独特の暖かみのある銀白
色の色調を有するという優れた点があるが、強度
が不充分な点と耐硫化性に劣るという実用上の難
点がある。
＜発明の目的＞
この出願の発明の目的は上述従来技術に基づく
時計枠等の装身具類の装飾用の合金類の有する良
い点、好ましくない点が二律背反的に具備する問
題点を解決すべき技術的課題とし、良好な合金特
性を生かしながらも、パラジウムでは再現が困難
であるプラチナ、シルバー色調を有し、更には、
時計用等の構造材料としての機能を充分に発揮出
来るような機械的強度、及び、加工性を有し、更
に、使用上の充分な耐蝕性を有するようにして実
用品インテリヤ等の製造産業における金属加工技
術の利用分野に益する優れた装飾用パラジウム合
金を提供せんとするものである。
＜課題を解決するための手段・作用＞
上述目的に沿い先述特許請求の範囲を要旨とす
るこの出願の発明の構成は前述課題を解決するた
めに、時計枠は時計バンド、指輪、ネツクレス等
の装身具類等の装飾品に用いられるパラジウム50
〜95％、モリブデン５〜50％として基本的特性を
備えるようにし、更に、かかる基合金に対し白金
１〜10％、バナジウム0.5〜５％、ホウ素0.1〜１
％の重量比元素を必要に応じ添加して色調調整が
可能であり、高い強度と耐蝕性を有するようにし
た技術的手段を講じたものである。
＜発明の背景＞
次に、この出願の発明の定性的、定量的背景に
ついて述べると、主成分となるパラジウムは酸類
によつて合金の化学変化を受け難くし、空気中で
酸化され難い特性を具備させるものであり、かか
る安定化に与る要素として機能させるためにはそ
の重量比については50％以上が必要であり、95％
を越えると、例えば、時計ケースとして必要な強
度を持たせるに至らなくなり、更に、色調調整も
難しくなる。
したがつて、最適重量は実験等によつてこの50
〜95％の範囲が好ましいものである。
モリブデンについては根本的にパラジウム独特
のくすんだ白色系色調を打ち消して所謂プラチ
ナ、シルバー色に近づけることが可能であり、こ
れには重量比で５％未満では効果がなく、50％を
越えた含有状態では脆化を招来して素材自体、更
には、時計枠の打ち抜き加工も困難となることか
ら５〜50％が最適重量比範囲とされる。
そして、バナジウムに関してはベースのパラジ
ウムのガス吸蔵性が高いことは良く知られている
が、水素においては体積比で350〜850倍も吸収す
るといわれており、バナジウムは脱水素材として
効果があり、その最適範囲は実験的に0.5％未満
では効果なく、５％を越えると脆化を招くため、
0.5〜５％の範囲とするものである。
ホウ素については金属酸化物の溶解除去、結晶
粒構成物の安定化が図れ、その範囲は0.1％未満
では効果なく、１％を越えると脆化を招くため、
0.1〜１％の範囲とするものである。
次に、白金については材料の機械的強度アツプ
に役立ち、耐変色性にも効果あり、更には、切削
研磨性を向上させることが出来る。
そして、その最適範囲はそれぞれ１％未満では
効果なく、10％を越えると材料コストが高くな
り、目的に外れるため、１〜10％の範囲とする。
次に、この出願の発明の実施例を説明すれば以
下の通りである。
まず、この出願の発明の実施例の合金と公知例
の合金の試料を示すと表の通りである。
尚、各試料の合金は予めパラジウム、モリブデ
ンをアーク溶解し、それを母合金として各素材を
各々周知の高周波加熱溶解炉にて1800℃の溶解温
度中30分間溶解し、t10×W50×L100mmの形状に
鋳造後、冷間圧延ロールにて所定の形状に圧延加
工することが可能となつたものである。
<Industrial Application Field> The disclosed technology can be used not only as a watch frame, but also as a decorative material for accessories such as watch bands, rings, and net dress. Belongs to the technical field of palladium alloys. <Prior Art> As is well known to those skilled in the art, ornamental alloys used for conventional white watch frames and watch bands, as well as accessories such as rings and net necklaces, include gold alloys, silver alloys, and precious metal alloys. There is a platinum alloy. <Problems to be Solved by the Invention> As described below, all of these decorative metal materials have overlapping advantages and disadvantages. For example, gold alloys and platinum alloys have advantages in terms of functionality and ornamental value when used as watch materials, but on the other hand, they have the disadvantage of high costs, as well as price fluctuations due to fluctuations in metal costs. There are also defects that have a large impact on the market, and are not new enough as a watch material. Furthermore, although silver alloys have the advantage of having a unique warm silvery white color tone, they have practical disadvantages of insufficient strength and poor sulfidation resistance. <Objective of the Invention> The object of the invention of this application is to provide a technology to solve the problems that the alloys for decoration of accessories such as watch frames based on the above-mentioned prior art have contradictory advantages and disadvantages. Although it takes advantage of good alloy properties, it has platinum and silver tones that are difficult to reproduce with palladium.
It has sufficient mechanical strength and workability to function as a structural material for watches, etc., and has sufficient corrosion resistance during use, making it suitable for use in the manufacturing industry of practical interior goods, etc. The object of the present invention is to provide an excellent decorative palladium alloy that is useful in the field of metal processing technology. <Means/effects for solving the problem> In order to solve the above-mentioned problem, the structure of the invention of this application, which is based on the above-mentioned claims in accordance with the above-mentioned object, is to solve the above-mentioned problem. Palladium 50 used in ornaments such as jewelry
-95%, molybdenum 5-50%, and furthermore, based on the base alloy, platinum 1-10%, vanadium 0.5-5%, boron 0.1-1
It is possible to adjust the color tone by adding % weight ratio elements as necessary, and technical measures have been taken to ensure high strength and corrosion resistance. <Background of the Invention> Next, to explain the qualitative and quantitative background of the invention of this application, palladium, which is the main component, has the property of making the alloy less susceptible to chemical changes due to acids and being less likely to be oxidized in the air. In order to function as an element contributing to such stabilization, the weight ratio must be 50% or more, and 95%
If it exceeds, for example, it will not have the strength necessary for a watch case, and furthermore, it will be difficult to adjust the color tone. Therefore, the optimum weight is determined by experiment etc.
A range of 95% is preferred. Regarding molybdenum, it is fundamentally possible to cancel out the dull white color tone unique to palladium and make it closer to the so-called platinum or silver color. In this state, the material itself becomes brittle, making it difficult to punch out the material itself, and even the watch frame. Therefore, the optimum weight ratio range is 5 to 50%. As for vanadium, it is well known that palladium, the base material, has a high gas absorption property, but it is said that it absorbs 350 to 850 times more hydrogen by volume, making vanadium effective as a dehydration material. Experimentally, the optimum range is less than 0.5%, which is ineffective, and more than 5%, which causes embrittlement.
The content should be in the range of 0.5 to 5%. Regarding boron, it is possible to dissolve and remove metal oxides and stabilize crystal grain components, and if it is less than 0.1%, it is ineffective, and if it exceeds 1%, it will cause embrittlement.
The content should be in the range of 0.1 to 1%. Next, platinum is useful for increasing the mechanical strength of the material, has an effect on discoloration resistance, and can further improve cutting and polishing properties. The optimum range is set to be in the range of 1 to 10%, because if it is less than 1%, there will be no effect, and if it exceeds 10%, the material cost will increase and the purpose will not be met. Next, embodiments of the invention of this application will be described as follows. First, samples of alloys according to embodiments of the invention of this application and alloys of known examples are shown in the table below. In addition, the alloy of each sample was made by arc melting palladium and molybdenum in advance, and using it as a master alloy, each material was melted in a well-known high frequency heating melting furnace for 30 minutes at a melting temperature of 1800℃, and the size of the alloy was 100mm x 50mm x 100mm. After being cast into a shape, it is possible to roll it into a predetermined shape using cold rolling rolls.
【表】【table】
【表】
次に、上述の如くして得た各試料の加工材を加
工率50％材として用い必要枚数切断し、硬さ、引
張り試験、人工汗による変色試験、鏡面色差測定
を行つた。
そして、それらの試験結果は表に示す通りで
ある。[Table] Next, the processed materials of each sample obtained as described above were used as materials with a processing rate of 50%, and the necessary number of sheets were cut, and hardness, tensile tests, discoloration tests due to artificial sweat, and specular color difference measurements were performed. The test results are shown in the table.
【表】
尚、
硬さ試験：マイクロビツカース硬さ計にて荷重
200ｇ荷重時間30秒の条件で測定。
引張り強さ
測定試験：引張り試験片（JIS6号試験片）を引張
り速度100mm／minでテンシロン引
張り試験機を用い引張り強さを測
定。
変色試験：50±２℃の恒温箱中にて24hr下記の配
合比の人工汗に浸漬し、変色度合を
調査。
塩 化 物 0.648〜0.987％
硫 化 物 0.006〜0.0025％
尿 素 0.086〜0.173％
アンモニア 0.010〜0.018％
サツカロース 0.006〜0.022％
乳 酸 0.034〜0.107％
蒸 留 水 残
色差測定：金属色のように正反射光が着色する物
体の色を測る鏡面反射色彩計で90％
白金−パラジウム合金との色差を測
定。
Ｌ（明度）
116（Ｙ／Yn）1/3−16
Ｙ／Yn＞
0.008856
ａ（色度）
500［（Ｘ／Xn）1/3−（Ｙ／Yn）
１／３］
ｂ（色度）
200［（Ｙ／Yn）1/3−（Ｚ／Zn）
１／３］
ΔEab 総合的色調の差
上述の試験データでも分る通り、この出願の発
明の実施例の装飾用パラジウム合金は、充分な硬
さと機械的強度を有し、しかも、耐蝕性が良く、
プラチナ、シルバー色調との差においても著しく
良好であることが分る。
尚、この出願の発明の実施態様は上述実施例以
外の態様も採用可能であることは勿論のことであ
る。
＜発明の効果＞
以上、この出願の発明によれば、時計枠や時計
バンド、指輪、ネツクレス等の装身具類の材料と
しての装飾用パラジウム合金は貴金属の良い点を
充分に有しながらも、硬さや機械的強度が充分で
あるために、製品の保形性が良く、装身具として
の機能を充分に果し、又、耐蝕性に秀れているた
めに、装身具としての機能的特性を経時的にも充
分有することが出来るという優れた効果が奏され
る。
又、プラチナ、シルバー色調においても満足す
るものであり、そのうえ、装身具類として金合
金、白金合金の価格程は高くならず、しかも、価
格変動に影響される度合が少く、安定した供給を
保つことが出来るという効果が奏される。
このような機械的特性を耐蝕性と共に有した色
調調整機能も良好であり、価格的にも安定したこ
とから、装身具類等の装飾品の製造供給は勿論の
こと、使用の面においても安定した信頼が得られ
るという優れた効果が奏される。[Table] In addition, hardness test: Load using a Micro Bitskers hardness meter
Measured under the condition of 200g load time 30 seconds. Tensile strength measurement test: Measure the tensile strength of a tensile test piece (JIS No. 6 test piece) using a Tensilon tensile tester at a tensile speed of 100 mm/min. Discoloration test: The degree of discoloration was investigated by immersing it in artificial sweat with the following mixing ratio for 24 hours in a constant temperature box at 50±2℃. Chloride 0.648-0.987% Sulfide 0.006-0.0025% Urea 0.086-0.173% Ammonia 0.010-0.018% Sucrose 0.006-0.022% Lactic acid 0.034-0.107% Distilled water Residual color difference measurement: Positive as metal color reflection 90% with a specular colorimeter that measures the color of objects colored by light
Measures the color difference with platinum-palladium alloy. L (lightness) 116 (Y/Yn) 1/3 -16 Y/Yn＞
0.008856 a (chromaticity) 500 [(X/Xn) 1/3 - (Y/Yn)
1/3] b (chromaticity) 200 [(Y/Yn) 1/3 - (Z/Zn)
1/3] ΔEab Overall color tone difference As can be seen from the above test data, the decorative palladium alloy of the embodiment of the invention of this application has sufficient hardness and mechanical strength, and has good corrosion resistance. ,
It can be seen that the difference in color tone from platinum and silver is also significantly better. It goes without saying that aspects other than the above-mentioned embodiments can also be adopted as the embodiments of the invention of this application. <Effects of the Invention> As described above, according to the invention of this application, a palladium alloy for decoration as a material for accessories such as watch frames, watch bands, rings, and net necklaces has all the advantages of precious metals, but is not hard. Since the sheath has sufficient mechanical strength, the product retains its shape well and functions well as an accessory, and has excellent corrosion resistance, so it retains its functional properties as an accessory over time. The excellent effect of being able to have a sufficient amount of water is achieved. In addition, the platinum and silver tones are satisfactory, and in addition, the price for jewelry is not as high as that of gold alloys and platinum alloys, and it is less affected by price fluctuations, ensuring a stable supply. The effect of being able to do this is achieved. It has such mechanical properties as well as corrosion resistance, has a good color tone adjustment function, and is stable in price, so it is not only suitable for manufacturing and supplying decorative items such as jewelry, but also for stable use. This has the excellent effect of gaining trust.
Claims (1)
５〜50％から成ることを特徴とする装飾用パラジ
ウム合金。 ２ 重量比でパラジウム50〜95％及びモリブデン
５〜50％から成る基合金にバナジウムを0.5〜５
％の重量比元素で添加して色調調整と強度をアツ
プしたことを特徴とする装飾用パラジウム合金。 ３ 重量比でパラジウム50〜95％及びモリブデン
５〜50％から成る基合金にバナジウムを0.5〜５
％、ホウ素0.1〜１％及び白金１〜10％の重量比
元素で添加して色調調整と強度をアツプしたこと
を特徴とする装飾用パラジウム合金。[Claims] 1. A decorative palladium alloy comprising 50 to 95% palladium and 5 to 50% molybdenum by weight. 2 Add 0.5 to 5% vanadium to a base alloy consisting of 50 to 95% palladium and 5 to 50% molybdenum by weight.
A decorative palladium alloy characterized by adding elements at a weight ratio of % to improve color tone adjustment and strength. 3 Add 0.5 to 5% vanadium to a base alloy consisting of 50 to 95% palladium and 5 to 50% molybdenum by weight.
%, boron 0.1-1%, and platinum 1-10% by weight elements to improve color tone adjustment and strength.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27933487A JPH01123037A (en) | 1987-11-06 | 1987-11-06 | Palladium alloy for ornamentation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27933487A JPH01123037A (en) | 1987-11-06 | 1987-11-06 | Palladium alloy for ornamentation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01123037A JPH01123037A (en) | 1989-05-16 |
| JPH0431010B2 true JPH0431010B2 (en) | 1992-05-25 |
Family
ID=17609731
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27933487A Granted JPH01123037A (en) | 1987-11-06 | 1987-11-06 | Palladium alloy for ornamentation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01123037A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62279335A (en) * | 1986-05-28 | 1987-12-04 | Konica Corp | Silver halide photographic sensitive material having improved stability of coloring matter image |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6436737A (en) * | 1987-08-03 | 1989-02-07 | Ishifuku Metal Ind | Palladium alloy for accessory |
-
1987
- 1987-11-06 JP JP27933487A patent/JPH01123037A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62279335A (en) * | 1986-05-28 | 1987-12-04 | Konica Corp | Silver halide photographic sensitive material having improved stability of coloring matter image |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01123037A (en) | 1989-05-16 |
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