JPH0521998B2 - - Google Patents
Info
- Publication number
- JPH0521998B2 JPH0521998B2 JP18559483A JP18559483A JPH0521998B2 JP H0521998 B2 JPH0521998 B2 JP H0521998B2 JP 18559483 A JP18559483 A JP 18559483A JP 18559483 A JP18559483 A JP 18559483A JP H0521998 B2 JPH0521998 B2 JP H0521998B2
- Authority
- JP
- Japan
- Prior art keywords
- gold
- bath
- alloy
- thiourea
- crystal structure
- 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
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 229910001020 Au alloy Inorganic materials 0.000 claims description 15
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 15
- 239000010931 gold Substances 0.000 claims description 15
- 229910052737 gold Inorganic materials 0.000 claims description 15
- 239000003353 gold alloy Substances 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 239000002932 luster Substances 0.000 description 6
- 238000005498 polishing Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910017944 Ag—Cu Inorganic materials 0.000 description 1
- 229910017390 Au—Fe Inorganic materials 0.000 description 1
- 229910017398 Au—Ni Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910002528 Cu-Pd Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- 229910004042 HAuCl4 Inorganic materials 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- -1 gold plates Chemical compound 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Description
【発明の詳細な説明】
本発明は装飾品の製造方法、特に金又は金合金
からなる装飾品の表面に結晶組織の模様を作成す
る装飾品の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of manufacturing an ornament, and more particularly to a method of manufacturing an ornament that creates a pattern of crystal structure on the surface of an ornament made of gold or a gold alloy.
従来、金又は金合金からなる装飾品、たとえば
金地金板，指輪，ブレスレツト，ペンダント，腕
時計側及び枠，めがねフレーム，ネツクレス，タ
イ止め，カフスボタン等の加工品の結晶組織模様
を出すには、加工品を焼鈍した後シアン浴や酸化
クロム浴で電解研磨するのが一般的であつた。シ
アン浴としてはH2O−KCN系浴やH2O−KCN−
K2CO3−HAuCl4系の浴を、酸化クロム浴として
はH2O−CH3COOH−Cr2O3系の浴をそれぞれ用
いていた。 Conventionally, in order to produce the crystal structure pattern of ornaments made of gold or gold alloys, such as gold plates, rings, bracelets, pendants, wristwatch sides and frames, eyeglass frames, necklaces, ties, cufflinks, etc., It was common to electropolish the workpiece in a cyan bath or chromium oxide bath after annealing it. Cyan baths include H 2 O−KCN baths and H 2 O−KCN−
A K2CO3 - HAuCl4 bath was used, and a H2O - CH3COOH - Cr2O3 bath was used as the chromium oxide bath.
しかしながら、いずれの浴もシアンとかクロム
とかの有害物質を含むため極めて危険であり、ま
た浴が老朽化した場合、特殊な設備により排水処
理しなければならないという欠点を有していた。 However, both baths are extremely dangerous because they contain harmful substances such as cyanide and chromium, and when the baths become obsolete, they have the disadvantage that they must be treated with special equipment.
他方、これらの有害物質を含まない電解研磨浴
としてH2O−HCl浴などがあるが、かえつて表面
光沢を失わせ、切角焼鈍して作つた結晶組織面を
消してしまうので装飾品としては好ましくない。
そこで、結晶組織面をさらにはつきりと浮き出さ
せ、かつ表面光沢の失わない電解研磨浴の出現が
強く望まれ、金又は金合金の結晶組織模様を有す
る装飾品の製造方法の早期確立が強く望まれてい
た。 On the other hand, there are electrolytic polishing baths that do not contain these harmful substances, such as H 2 O-HCl baths, but they lose surface luster and erase the crystal structure planes created by annealing, so they are not used as decorative items. is not desirable.
Therefore, there is a strong desire for the development of an electrolytic polishing bath that can bring out the crystallographic planes even more sharply without losing the surface luster, and it is highly desirable to quickly establish a method for producing ornaments with crystallographic patterns of gold or gold alloys. It was wanted.
本発明は上記要求に応えんがためになされたも
のである。 The present invention has been made to meet the above requirements.
本発明は、金又は金合金からなる加工品を焼鈍
した後チオ尿素と硫酸と水よりなる浴で電解研磨
して金又は金合金の結晶組織模様を有するように
したことを特徴とする装飾品の製造方法、特にチ
オ尿素５〜200ｇ／，硫酸１〜100ml／，のこ
り水からなることを特徴とする電解研磨浴を用い
た装飾品の製造方法である。 The present invention is a decorative article characterized in that a processed article made of gold or a gold alloy is annealed and then electrolytically polished in a bath consisting of thiourea, sulfuric acid, and water to have a crystal structure pattern of gold or a gold alloy. This is a method for producing ornaments using an electrolytic polishing bath characterized by containing 5 to 200 g of thiourea, 1 to 100 ml of sulfuric acid, and residual water.
本発明の製造方法において、金又は金合金から
なる加工品を用いるのは金又は金合金が黄金色の
色をもつているからである。金合金としては、
Au−Ag−Cu合金やこの合金にZn，Niなどを添
加したもの、Au−Ni−Cu−Zn系合金、Au−Ag
−Pd系合金、Au−Fe合金、Au−Ni合金、Au−
Cu−Pd系合金などがある。また、金又は金合金
からなる加工品を焼鈍するのは、装飾品の表面に
結晶組織面を作るためである。加工品の加工組織
面のままでは、いくら電解研磨しても結晶組織模
様はえられず、無光沢面や鏡面光沢面などがえら
れるだけである。適当な温度と時間で焼鈍すれ
ば、結晶が粒界に沿つて析出して所望の大きさの
結晶組織面をつくることができる。このときの雰
囲気は真空中であつても大気中であつてもよく、
また酸化性、環元性，中性のいずれであつてもよ
い。本発明において、塩化物とリン酸と水よりな
る浴で電解研磨するのは、表面光沢をもたせたま
ま結晶組織面を結晶組織模様に浮き出させるため
であ。硫酸と水だけからなる浴では金や金合金が
光沢面をもつように電解エツチングされない。こ
のためチオ尿素を用いる。本発明における電解方
法としては、交流電圧，直流電圧，交直併用，パ
ルス電圧などがある。 In the manufacturing method of the present invention, a processed product made of gold or a gold alloy is used because gold or a gold alloy has a golden color. As a gold alloy,
Au-Ag-Cu alloy, this alloy with Zn, Ni, etc. added, Au-Ni-Cu-Zn alloy, Au-Ag
-Pd alloy, Au-Fe alloy, Au-Ni alloy, Au-
Examples include Cu-Pd alloys. Further, the reason why a workpiece made of gold or a gold alloy is annealed is to create a crystalline structure plane on the surface of the decorative item. If the textured surface of the processed product remains unchanged, no matter how much electrolytic polishing is performed, a crystalline structure pattern cannot be obtained, and only a matte surface or a mirror-like glossy surface can be obtained. By annealing at an appropriate temperature and time, crystals can precipitate along the grain boundaries to create a crystal structure plane of a desired size. The atmosphere at this time may be in a vacuum or in the air,
It may also be oxidizing, cyclic, or neutral. In the present invention, the reason why electrolytic polishing is performed in a bath consisting of chloride, phosphoric acid, and water is to make the crystal structure surface stand out in a crystal structure pattern while maintaining surface gloss. A bath consisting only of sulfuric acid and water will not electrolytically etch gold or gold alloys to a shiny surface. For this purpose, thiourea is used. The electrolysis method in the present invention includes alternating current voltage, direct current voltage, combination of alternating current and direct current, pulsed voltage, and the like.
本発明の浴において、チオ尿素の範囲を５〜
200ｇ／と限つたのは５ｇ／以下では金又は
金合金を溶解するチオ尿素の量が少なすぎて浴寿
命を早めるからであり、200ｇ／以上ではチオ
尿素の量が多く溶解する力が強くなりすぎ、金又
は金合金の表面の光沢を失わせてしまうからであ
る。また、硫酸の範囲を１〜100ml／に限つた
のは、１ml／以下では浴を安定させる力が弱く
金又は金合金の表面の光沢を失わせてしまい、
100ml／以上では硫酸の作用が強くなりすぎム
ラが生じやすくなり実用的でない。特に200ml／
以上では光沢がなくなつて装飾品としては使用
できない。 In the bath of the present invention, the range of thiourea is from 5 to
The reason why it is limited to 200g/ is because if it is less than 5g/, the amount of thiourea that dissolves gold or gold alloy will be too small and the bath life will be shortened, whereas if it is more than 200g/, the amount of thiourea will be too large and the dissolving power will be too strong. This is because the surface of gold or gold alloy loses its luster. In addition, the range of sulfuric acid was limited to 1 to 100 ml/ml, because if it is less than 1 ml/ml, the ability to stabilize the bath is weak and the surface of gold or gold alloy loses its luster.
If it exceeds 100 ml, the action of sulfuric acid becomes too strong and unevenness tends to occur, making it impractical. Especially 200ml/
If this is the case, it will lose its luster and cannot be used as a decorative item.
以下、実施例と従来例について説明する。 Examples and conventional examples will be described below.
〔実施例 １〕
幅10mm×長さ50mm×厚さ0.5mmの圧延加工され
た金板を600℃×30分間大気中で焼鈍した。この
焼鈍品を半分だけチオ尿素50ｇ／，硫酸６ml／
，のこり水の浴に浸漬し、P.C5A／ｄm2，50℃
で20秒電解研磨したところ7.2μ（0g035）エツチン
グされ光沢面の強い約１mm前後の結晶組織が現わ
れた。[Example 1] A rolled metal plate with a width of 10 mm, a length of 50 mm, and a thickness of 0.5 mm was annealed in the air at 600°C for 30 minutes. Half of this annealed product is thiourea 50g/, sulfuric acid 6ml/
, immersed in a bath of residual water, P.C5A/dm 2 , 50℃
When it was electrolytically polished for 20 seconds, it was etched to 7.2μ (0g035) and a highly glossy crystalline structure of about 1mm appeared.
〔実施例 ２〕
実施例１と同一形状のAu−12.5％Ag−12.5％
Cu合金板を800℃×10分間大気中で焼鈍した。こ
の焼鈍品を半分だけチオ尿素20ｇ／，硫酸20
ml／，のこり水の60℃の浴に浸漬し、3.5A／
ｄm2通電２秒，休止0.5秒で60秒電解研磨したと
ころ2.4μ（0g023）エツチングされ光沢面の強い約
１mm前後の結晶組織が現われた。[Example 2] Au-12.5%Ag-12.5% with the same shape as Example 1
The Cu alloy plate was annealed in air at 800°C for 10 minutes. Half of this annealed product is thiourea 20g/, sulfuric acid 20g
ml/, immersed in a 60℃ bath of residual water, 3.5A/
Electrolytic polishing was performed for 60 seconds with 2 seconds of dm2 current and 0.5 seconds of rest, and a 2.4 μ (0g023) etching was obtained, revealing a crystalline structure approximately 1 mm in size with a highly glossy surface.
実施例１と同様な焼鈍品を半分だけ塩酸200
ml／，リン酸200ml／，のこり水の浴に浸漬
し、P.C500A／ｄm220秒間電解研磨したところ
4.7μ（0g045）エツチングされたものの光沢がなく
結晶組織はみられなかつた。
Half of the same annealed product as in Example 1 was heated with 200% hydrochloric acid.
ml/, phosphoric acid 200ml/, immersed in a bath of residual water and electrolytically polished with P.C500A/dm 2 for 20 seconds.
Although it was etched by 4.7μ (0g045), it had no luster and no crystalline structure was observed.
以上詳述したように本発明の製造方法によれ
ば、装飾品の表面に光沢のある結晶組織模様が得
られるため新規な装飾品としての価値を提供する
ことができるという効果がある。また、シアンや
クロム酸などの有害物が含まれておらず、他の重
金属元素を含まないので、浴が老朽化したときで
も回収が容易で、かつ排水も公害上の問題がな
い。 As described in detail above, according to the manufacturing method of the present invention, a shiny crystal structure pattern can be obtained on the surface of the decorative article, so that it is effective in providing value as a novel decorative article. Furthermore, since it does not contain harmful substances such as cyanide or chromic acid, and does not contain other heavy metal elements, it is easy to recover even when the bath becomes obsolete, and there are no pollution problems with drainage.
Claims (1)
オ尿素５〜200ｇ／、硫酸１〜100ml／、のこ
り水よりなる浴で電解研磨して金又は金合金の結
晶組織模様を有するようにしたことを特徴とする
装飾品の製造方法。1. A processed product made of gold or gold alloy is annealed and then electrolytically polished in a bath consisting of 5 to 200 g of thiourea, 1 to 100 ml of sulfuric acid, and residual water to give it a crystal structure pattern of gold or gold alloy. A method of manufacturing a decorative article characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18559483A JPS6077999A (en) | 1983-10-04 | 1983-10-04 | Manufacture of ornament |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18559483A JPS6077999A (en) | 1983-10-04 | 1983-10-04 | Manufacture of ornament |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6077999A JPS6077999A (en) | 1985-05-02 |
| JPH0521998B2 true JPH0521998B2 (en) | 1993-03-26 |
Family
ID=16173529
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18559483A Granted JPS6077999A (en) | 1983-10-04 | 1983-10-04 | Manufacture of ornament |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6077999A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7153411B2 (en) * | 2003-12-30 | 2006-12-26 | Boston Scientific Scimed, Inc. | Method for cleaning and polishing metallic alloys and articles cleaned or polished thereby |
| JP2005290444A (en) * | 2004-03-31 | 2005-10-20 | Electroplating Eng Of Japan Co | Golden electrolytic stripping liquid and electrolytic stripping method using the same |
-
1983
- 1983-10-04 JP JP18559483A patent/JPS6077999A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6077999A (en) | 1985-05-02 |
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