JP4773399B2 - Quantitative analysis method for tin or tin alloy plating layer - Google Patents
Quantitative analysis method for tin or tin alloy plating layer Download PDFInfo
- Publication number
- JP4773399B2 JP4773399B2 JP2007132681A JP2007132681A JP4773399B2 JP 4773399 B2 JP4773399 B2 JP 4773399B2 JP 2007132681 A JP2007132681 A JP 2007132681A JP 2007132681 A JP2007132681 A JP 2007132681A JP 4773399 B2 JP4773399 B2 JP 4773399B2
- Authority
- JP
- Japan
- Prior art keywords
- tin
- plating layer
- plating
- copper
- brass
- 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.)
- Active
Links
- 238000007747 plating Methods 0.000 title claims description 76
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims description 33
- 238000004445 quantitative analysis Methods 0.000 title claims description 13
- 238000000034 method Methods 0.000 title claims description 12
- 229910001128 Sn alloy Inorganic materials 0.000 title claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 28
- 229910052802 copper Inorganic materials 0.000 claims description 28
- 239000010949 copper Substances 0.000 claims description 28
- 229910001369 Brass Inorganic materials 0.000 claims description 25
- 239000010951 brass Substances 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 12
- 229910052796 boron Inorganic materials 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 150000001639 boron compounds Chemical class 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 description 16
- 239000011133 lead Substances 0.000 description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 12
- 229910052804 chromium Inorganic materials 0.000 description 12
- 239000011651 chromium Substances 0.000 description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 11
- 229910052793 cadmium Inorganic materials 0.000 description 11
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 11
- 229910052725 zinc Inorganic materials 0.000 description 11
- 239000011701 zinc Substances 0.000 description 11
- 238000004090 dissolution Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000011002 quantification Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- -1 iron ions Chemical class 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000383 hazardous chemical Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- GCYHRYNSUGLLMA-UHFFFAOYSA-N 2-prop-2-enoxyethanol Chemical compound OCCOCC=C GCYHRYNSUGLLMA-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- WVMHLYQJPRXKLC-UHFFFAOYSA-N borane;n,n-dimethylmethanamine Chemical compound B.CN(C)C WVMHLYQJPRXKLC-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- VEWFZHAHZPVQES-UHFFFAOYSA-N boron;n,n-diethylethanamine Chemical compound [B].CCN(CC)CC VEWFZHAHZPVQES-UHFFFAOYSA-N 0.000 description 1
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/20—Metals
- G01N33/202—Constituents thereof
- G01N33/2028—Metallic constituents
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/20—Metals
- G01N33/208—Coatings, e.g. platings
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Pathology (AREA)
- Immunology (AREA)
- General Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Analytical Chemistry (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Investigating And Analyzing Materials By Characteristic Methods (AREA)
- Sampling And Sample Adjustment (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- ing And Chemical Polishing (AREA)
- Chemically Coating (AREA)
Description
本発明は、銅または黄銅からなる基材に、スズまたはスズ合金からなるめっき層（以下、「スズめっき層」ともいう）を形成してなる試料における前記めっき層を定量分析する方法に関する。 The present invention relates to a method for quantitatively analyzing the plating layer in a sample formed by forming a plating layer made of tin or a tin alloy (hereinafter also referred to as “tin plating layer”) on a base material made of copper or brass.
電気機器や電子機器の電極や端子として銅や黄銅が広く使用されており、耐食性の向上や、接触抵抗の低減、挿入力の低減等の目的でスズめっき層で被覆されることが多い。しかし、スズめっき層には、鉛やカドミウム、クロム等の環境負荷物質が混入していることがあり、それらの含有量を定量する必要がある。 Copper and brass are widely used as electrodes and terminals of electrical and electronic devices, and are often coated with a tin plating layer for the purpose of improving corrosion resistance, reducing contact resistance, and reducing insertion force. However, environmental impact substances such as lead, cadmium, and chromium may be mixed in the tin plating layer, and it is necessary to quantify their contents.
スズめっき層の定量分析方法としては、簡便であることから、試料をめっき剥離液に浸漬してスズめっき層を溶解し、溶解分を含有するめっき剥離液について、ＩＰＣ−ＡＥＳ法等により定量することが主流になっている（例えば、非特許文献１参照）。 As a quantitative analysis method for the tin plating layer, since it is simple, the sample is immersed in the plating stripper to dissolve the tin plating layer, and the plating stripper containing the dissolved content is quantified by the IPC-AES method or the like. Has become mainstream (see, for example, Non-Patent Document 1).
めっき剥離液は、めっき層だけを選択的に溶解する必要があるが、基材の種類によっては、少なからず基材も溶解している。そのため、基材側にも測定対象の金属成分が含まれていると、その分を定量値から差し引く必要がある。しかし、測定精度を高めるためにめっき層の溶解量を多くしようとすると、基材の溶解量も多くなるため、測定対象の金属成分が基材側に多く含まれていると、めっき層における測定対象の金属成分の定量値がマイナスになることがあり、定量できない。 The plating stripper needs to selectively dissolve only the plating layer, but depending on the type of base material, the base material is also dissolved. Therefore, if the metal component to be measured is also included on the substrate side, it is necessary to subtract that amount from the quantitative value. However, if the amount of dissolution of the plating layer is increased in order to increase the measurement accuracy, the amount of dissolution of the substrate also increases. The quantitative value of the target metal component may be negative and cannot be quantitatively determined.
非特許文献１に記載の定量方法では、めっき剥離液としてホウ酸、フッ化水素酸、硝酸の混酸を用いることで、基材をできるだけ溶解しない工夫がなされているが、この混酸は銅系材料を溶解する。また、希硫酸系のめっき剥離液も知られているが、純銅は溶解しないものの、黄銅や鉄系材料を溶解する。 In the quantification method described in Non-Patent Document 1, there is devised that the base material is not dissolved as much as possible by using a mixed acid of boric acid, hydrofluoric acid, and nitric acid as a plating stripping solution. Dissolve. A dilute sulfuric acid-based plating stripper is also known, but does not dissolve pure copper, but dissolves brass and iron-based materials.
その他、金属イオンを含有するめっき剥離液も知られている。例えば、鉄イオンを含有するめっき剥離液が知られているが、定量下限値が高く、分析結果を示すスペクトルが良好ではない。また、クロムイオンを含有するめっき剥離液も知られているが、クロムの定量はできず、またＰｂ：２２０．３５３ｎｍに干渉があるため鉛の測定にも不適である。 In addition, plating stripping solutions containing metal ions are also known. For example, although a plating stripper containing iron ions is known, the lower limit of quantification is high, and the spectrum indicating the analysis result is not good. Also, a plating stripping solution containing chromium ions is known, but chromium cannot be quantified, and Pb: 220.353 nm interferes with it, which is not suitable for lead measurement.
このように、従来のめっき剥離液は銅系材料を溶解しやすく、銅や黄銅を基材とするスズめっき層には不適である。 Thus, the conventional plating stripper easily dissolves the copper-based material and is not suitable for a tin plating layer based on copper or brass.
そこで本発明は、銅や黄銅からなる基材にスズめっき層を形成した試料について、スズめっき層をより正確に定量する方法を提供することを目的とする。 Then, this invention aims at providing the method of quantifying a tin plating layer more correctly about the sample which formed the tin plating layer in the base material which consists of copper or brass.
上記課題を解決するために、請求項１に記載された発明は、銅または黄銅からなる基材に、スズまたはスズ合金からなるめっき層を形成してなる試料、もしくは金属製の基材に、銅または黄銅からなる下地層を介して、スズまたはスズ合金からなるめっき層を形成してなる試料における前記めっき層の定量分析方法であって、ホウフッ化水素酸をホウ素元素換算で１．６質量％、ホウ素化合物をホウ素元素換算で０．２質量％以下、チオ尿素を１質量％以下の割合で含む水溶液からなるめっき剥離液を前記試料に接触させて前記めっき層を溶解し、溶解分を含有する前記めっき剥離液について定量することを特徴とするスズまたはスズ合金めっき層の定量分析方法である。 In order to solve the above-mentioned problem, the invention described in claim 1 is directed to a base material made of copper or brass, a sample formed with a plating layer made of tin or a tin alloy, or a metal base material, A method for quantitative analysis of a plating layer in a sample formed by forming a plating layer made of tin or a tin alloy through an underlayer made of copper or brass, wherein borofluoric acid is converted to 1.6 mass in terms of boron element %, A plating stripping solution composed of an aqueous solution containing 0.2% by mass or less of a boron compound in terms of boron element and 1% by mass or less of thiourea is brought into contact with the sample to dissolve the plating layer. It is the quantitative analysis method of the tin or tin alloy plating layer characterized by quantifying about the said plating peeling liquid to contain.
本発明のスズまたはスズ合金めっき層の定量分析方法で用いるホウ素系の特定組成のめっき剥離剤は、実質的にスズめっき層のみを選択的に溶解することができるため、めっき層の定量を正確に行なうことができる。 Boron-based plating stripping agent used in the method for quantitative analysis of tin or tin alloy plating layers of the present invention can selectively dissolve only the tin plating layer, so accurate determination of the plating layer is possible. Can be done.
以下、本発明に関して詳細に説明する、 Hereinafter, the present invention will be described in detail.
本発明の定量方法は、基本的には従来と同様に、スズめっき層が形成された試料をめっき剥離液に浸漬してスズめっき層を溶解し、溶解分を含有するめっき剥離液を定量するが、その際、下記に示すホウ素系の特定組成のめっき剥離液を用いる。 In the quantitative determination method of the present invention, basically, as in the conventional case, the sample on which the tin plating layer is formed is immersed in the plating stripper to dissolve the tin plating layer, and the plating stripper containing the dissolved content is quantified. However, at that time, a plating stripping solution having a boron-based specific composition shown below is used.
めっき剥離液は、ホウフッ化水素酸をホウ素元素換算で１．６質量％、ホウ素化合物をホウ素元素換算で０．２質量％以下、チオ尿素を１質量％以下の割合で含む水溶液である。ホウ素化合物としては水素化ホウ素カリウム、水素化ホウ素ナトリウム等の水素化ホウ素化合物、ジメチルアミンボラン、トリメチルアミンボラン、トリエチルアミンボラン等のアミンボラン化合物、ヒドラジン等が挙げられる。各成分とも含有量が下限値を下回るとスズめっき層を溶解し難くなり、上限値を上回ると銅や黄銅を溶解するようになる。また、めっき剥離液には、その他にも、例えば、安定剤としてエチレングリコールモノアリルエーテル、エチレングリコールモノブチルエーテル等のグルコールエーテル類等を１〜１０質量％の割合で含有してもよい。 The plating stripper is an aqueous solution containing 1.6% by mass of borofluoric acid in terms of boron element, 0.2% by mass or less of boron compound in terms of boron element, and 1% by mass or less of thiourea. Examples of the boron compound include borohydride compounds such as potassium borohydride and sodium borohydride, amine borane compounds such as dimethylamine borane, trimethylamine borane and triethylamine borane, and hydrazine. When the content of each component is lower than the lower limit value, it becomes difficult to dissolve the tin plating layer, and when it exceeds the upper limit value, copper and brass are dissolved. In addition, the plating stripper may contain, for example, glycol ethers such as ethylene glycol monoallyl ether and ethylene glycol monobutyl ether in a proportion of 1 to 10% by mass as a stabilizer.
測定精度を高めるためにはスズめっき層の溶出量が多いほど好ましいため、めっき剥離液との接触は、基材が露出するまで行なう。尚、基材の露出は、目視により十分可能である。 In order to increase the measurement accuracy, it is preferable that the elution amount of the tin plating layer is larger. Therefore, the contact with the plating stripper is performed until the substrate is exposed. It should be noted that the substrate can be sufficiently exposed by visual observation.
そして、スズめっき層の溶解分を含有するめっき剥離液について、定量分析を行なう。定量分析は、簡便で、高精度の定量ができる等の理由から、ＩＣＰ−ＡＥＳ（誘導結合プラズマ発光分光分析法）を行なうことが好ましい。本発明では、特にスズめっき層中の環境負荷物質である鉛、カドミウム、クロムの定量を目的とするが、ＩＣＰ−ＡＥＳによりこれらを高精度で測定することができる。 Then, a quantitative analysis is performed on the plating stripping solution containing the dissolved content of the tin plating layer. Quantitative analysis is preferably performed by ICP-AES (inductively coupled plasma emission spectroscopy) for reasons such as simple and highly accurate quantification. The purpose of the present invention is to determine lead, cadmium, and chromium, which are environmentally hazardous substances, in the tin plating layer, and these can be measured with high accuracy by ICP-AES.
本発明で用いる上記のめっき剥離液は、銅、並びに黄銅成分である亜鉛を、測定に影響を与えるレベルまで溶解せず、実質的にスズめっき層のみを溶解する。従って、測定値をそのままスズめっき層における含有量と見做して問題ない。しかし、後述する実施例１のように、銅や亜鉛の測定値を試料量から差し引いて新たな試料量とし、鉛やカドミウム、クロム等の各成分の含有量を補正することでより、高精度の定量ができる。 The plating stripping solution used in the present invention does not dissolve copper and zinc, which is a brass component, to a level that affects measurement, but substantially dissolves only the tin plating layer. Therefore, there is no problem when the measured value is regarded as the content in the tin plating layer as it is. However, as in Example 1 to be described later, the measured value of copper or zinc is subtracted from the sample amount to obtain a new sample amount, and by correcting the content of each component such as lead, cadmium, chromium, etc., high accuracy Can be quantified.
また、同じく環境負荷物質である水銀を定量する場合には、ＣＶ−ＡＡＳ（冷蒸気還元気化原子吸光法）を行なうことが好ましい。 Similarly, when quantifying mercury, which is an environmentally hazardous substance, it is preferable to perform CV-AAS (cold vapor reduction vaporization atomic absorption spectrometry).
尚、本発明で用いるめっき剥離液は銅及び黄銅を溶解しないため、試料は、銅や黄銅からなる基材にスズめっき層が形成されたものの他に、銅や黄銅以外の金属製基材で、銅や黄銅を下地層としてその上にスズめっき層を形成したものであってもよい。 In addition, since the plating stripper used in the present invention does not dissolve copper and brass, the sample is made of a metal base material other than copper or brass, in addition to a tin plating layer formed on a base material made of copper or brass. In addition, a tin plating layer may be formed thereon using copper or brass as a base layer.
（実施例１）
黄銅製基材に銅下地めっき、スズめっき層を形成した試料を、メルテックス株式会社製めっき剥離液「エンストリップＴＬ−１０５」（ホウフッ化水素酸をホウ素元素換算で１．６質量％、ホウ素化合物をホウ素元素換算で０．２質量％以下、チオ尿素を１質量％以下、安定化剤含有、残部水）に浸漬した。黄銅製基材が露出した時点で試料を取り出し、浸漬前との重量差を求めたところ、試料量は０．０１３１５ｇであった。
Example 1
A sample in which a copper base plating and a tin plating layer are formed on a brass base material is used as a plating stripping solution “Enstrip TL-105” (1.6% by mass of boron borofluoride in terms of boron element, boron The compound was immersed in 0.2% by mass or less in terms of boron element, 1% by mass or less of thiourea, containing a stabilizer, and the balance water). When the brass substrate was exposed, the sample was taken out and the weight difference from before immersion was determined. The sample amount was 0.01315 g.
次いで、スズめっき層を溶解した後のめっき剥離液についてＩＣＰ−ＡＥＳにて定量分析を行ない、銅、亜鉛、鉛、カドミウム及びクロムの含有量を求めた。結果を表１に示すが、銅及び亜鉛の含有量は僅かであり、黄銅製基材の溶解が抑えられていることがわかる。 Next, the plating stripping solution after dissolving the tin plating layer was quantitatively analyzed by ICP-AES, and the contents of copper, zinc, lead, cadmium and chromium were determined. Although a result is shown in Table 1, content of copper and zinc is slight and it turns out that melt | dissolution of the base material made from brass is suppressed.
上記の測定値を基に、銅と亜鉛の各量を上記試料量から差し引いて真の試料量（０．０１２１１ｇ）とし、下記の如くスズめっき層における鉛、カドミウム及びクロムの各含有量を求めた。
鉛 ：３．３／０．０１２１１＝２７６．３ｐｐｍ
カドミウム：０．０５９１８／０．０１２１１＝４．９ｐｐｍ
クロム ：０．２９０６２／０．０１２１１＝２４．０ｐｐｍ
Based on the above measured values, subtract the copper and zinc amounts from the sample amount to obtain the true sample amount (0.01211 g), and determine the lead, cadmium and chromium contents in the tin plating layer as follows. It was.
Lead: 3.3 / 0.01211 = 276.3ppm
Cadmium: 0.05918 / 0.01211 = 4.9ppm
Chromium: 0.29062 / 0.01211 = 24.0ppm
（実施例２〜７）
黄銅製基材に、銅下地めっき、組成の異なるスズめっき層を形成した試料Ａ〜Ｆを用意し、実施例１で用いたメルテックス株式会社製めっき剥離液「エンストリップＴＬ−１０５」に浸漬した。黄銅製平板が露出した時点で試料を取り出し、めっき剥離液についてＩＣＰ−ＡＥＳにて定量分析を行ない、銅、亜鉛、鉛、カドミウム及びクロムの含有量を求めた。尚、ここでは実施例１のような銅及び亜鉛量を差し引く補正は行なっていない。結果を表２に示すが、銅及び亜鉛の含有量が少なく、黄銅製基材の溶解が少ないことがわかる。
(Examples 2 to 7)
Samples A to F in which a copper base plating and tin plating layers having different compositions were formed on a brass substrate were prepared and immersed in the plating stripper “Enstrip TL-105” manufactured by Meltex Co., Ltd. used in Example 1. did. When the brass flat plate was exposed, the sample was taken out, and the plating stripper was subjected to quantitative analysis with ICP-AES to determine the contents of copper, zinc, lead, cadmium and chromium. Here, correction for subtracting the amounts of copper and zinc as in Example 1 is not performed. Although a result is shown in Table 2, it turns out that there is little content of copper and zinc and there is little melt | dissolution of the base material made from brass.
（比較例１〜４）
めっき剥離液として、何れも硝酸と塩酸との混合液からなり、混合比の異なる混酸Ａ〜Ｄを用い、それぞれに黄銅製基材にスズめっき層を形成した同一の試料を浸漬した。黄銅製平板が露出した時点で試料を取り出し、めっき剥離液についてＩＣＰ−ＡＥＳにて定量分析を行ない、銅、亜鉛、鉛、カドミウム及びクロムの含有量を求めた。また、黄銅製基材について、蛍光Ｘ線により銅及び亜鉛の含有量を測定し、ＩＣＰ−ＡＥＳにより銅、亜鉛、鉛、カドミウム及びクロムの含有量を測定した。そして、黄銅製基材中の各成分の含有割合を基に、めっき剥離液中の各成分の含有量を補正した。鉛、カドミウム及びクロムについて表３に示すが、鉛、カドミウム及びクロムの含有量がマイナスとなる場合が多く、混酸系のめっき剥離液は黄銅製基材を溶解し、スズめっき層の定量には使用できないことがわかる。
(Comparative Examples 1-4)
As the plating stripping solution, mixed acids A to D, each consisting of a mixed solution of nitric acid and hydrochloric acid, having different mixing ratios, were immersed in the same sample in which a tin plating layer was formed on a brass substrate. When the brass flat plate was exposed, the sample was taken out, and the plating stripper was subjected to quantitative analysis with ICP-AES to determine the contents of copper, zinc, lead, cadmium and chromium. Moreover, about the brass-made base material, content of copper and zinc was measured with the fluorescent X ray, and content of copper, zinc, lead, cadmium, and chromium was measured by ICP-AES. And based on the content rate of each component in the base material made from brass, content of each component in plating stripping solution was correct | amended. Lead, cadmium, and chromium are shown in Table 3, but the lead, cadmium, and chromium contents are often negative, and the mixed acid plating stripper dissolves the brass substrate, and the quantification of the tin plating layer It turns out that it cannot be used.
Claims (1)
ホウフッ化水素酸をホウ素元素換算で１．６質量％、ホウ素化合物をホウ素元素換算で０．２質量％以下、チオ尿素を１質量％以下の割合で含む水溶液からなるめっき剥離液を前記試料に接触させて前記めっき層を溶解し、溶解分を含有する前記めっき剥離液について定量することを特徴とするスズまたはスズ合金めっき層の定量分析方法。 Sample made by forming a plating layer made of tin or tin alloy on a substrate made of copper or brass, or plating made of tin or tin alloy on a metal substrate through an underlayer made of copper or brass A method for quantitative analysis of the plating layer in a sample formed by forming a layer,
A plating stripping solution composed of an aqueous solution containing 1.6% by mass of borofluoric acid in terms of boron element, 0.2% by mass or less of boron compound in terms of boron element, and 1% by mass or less of thiourea is used as the sample. A method for quantitative analysis of a tin or tin alloy plating layer, wherein the plating layer is dissolved by contact and the plating stripping solution containing the dissolved content is quantified.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007132681A JP4773399B2 (en) | 2007-05-18 | 2007-05-18 | Quantitative analysis method for tin or tin alloy plating layer |
| PCT/JP2008/059026 WO2008143170A1 (en) | 2007-05-18 | 2008-05-16 | Method for quantitative analysis of tin or tin alloy plating layer |
| CN2008800163980A CN101680826B (en) | 2007-05-18 | 2008-05-16 | Method for quantitative analysis of tin or tin alloy plating layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007132681A JP4773399B2 (en) | 2007-05-18 | 2007-05-18 | Quantitative analysis method for tin or tin alloy plating layer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2008286672A JP2008286672A (en) | 2008-11-27 |
| JP4773399B2 true JP4773399B2 (en) | 2011-09-14 |
Family
ID=40031872
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007132681A Active JP4773399B2 (en) | 2007-05-18 | 2007-05-18 | Quantitative analysis method for tin or tin alloy plating layer |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP4773399B2 (en) |
| CN (1) | CN101680826B (en) |
| WO (1) | WO2008143170A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009014525A (en) * | 2007-07-05 | 2009-01-22 | Yazaki Corp | Method of quantitatively analyzing mercury in tin or tin alloy plating layer |
| JP5046963B2 (en) * | 2008-01-10 | 2012-10-10 | 矢崎総業株式会社 | Hazardous metal analysis method for silver plating layer |
| US8616077B2 (en) * | 2009-08-05 | 2013-12-31 | United Technologies Corporation | Non-destructive inspection method for metallic alloys |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5051154A (en) * | 1988-08-23 | 1991-09-24 | Shipley Company Inc. | Additive for acid-copper electroplating baths to increase throwing power |
| EP1097618B1 (en) * | 1998-07-01 | 2003-03-26 | FRY'S METALS, INC. d/b/a ALPHA METALS, INC. | Post-treatment for copper on printed circuit boards |
| JP3055554B2 (en) * | 1999-08-02 | 2000-06-26 | ヤマハ株式会社 | Operation instruction device |
| JP2002194574A (en) * | 2000-12-25 | 2002-07-10 | Mitsubishi Gas Chem Co Inc | Peeling liquid for coating of tin or tin alloy |
| JP3909035B2 (en) * | 2003-04-09 | 2007-04-25 | 三井金属鉱業株式会社 | Plating pretreatment liquid and plating pretreatment method |
| JP4273266B2 (en) * | 2005-03-23 | 2009-06-03 | 石原薬品株式会社 | Dissolving current suppression type tin alloy electroplating method |
-
2007
- 2007-05-18 JP JP2007132681A patent/JP4773399B2/en active Active
-
2008
- 2008-05-16 WO PCT/JP2008/059026 patent/WO2008143170A1/en active Application Filing
- 2008-05-16 CN CN2008800163980A patent/CN101680826B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008286672A (en) | 2008-11-27 |
| WO2008143170A1 (en) | 2008-11-27 |
| CN101680826B (en) | 2012-07-04 |
| CN101680826A (en) | 2010-03-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5305498B2 (en) | Quantitative analysis method for nickel or nickel alloy plating layer | |
| JP4773399B2 (en) | Quantitative analysis method for tin or tin alloy plating layer | |
| Zhang et al. | Corrosion inhibition of ammonium molybdate for AA6061 alloy in NaCl solution and its synergistic effect with calcium gluconate | |
| Lahem et al. | Synergistic improvement of inhibitive activity of dicarboxylates in preventing mild steel corrosion in neutral aqueous solution | |
| CN106770512A (en) | The assay method of fluohydric acid content in a kind of nitric hydrofluoric acid type Acidwash solution | |
| CN101140271B (en) | Galvanizing plate layered detecting method | |
| Wang et al. | A new method for preventing corrosion failure: Thiourea and Hexamethylenetetramine as inhibitor for copper | |
| Chiba et al. | Synergistic effects of Cl− and Cu2+ ions on corrosion of pure Al and Al alloys in aqueous solutions at 363 K | |
| Bastidas et al. | Kinetic study of formate compounds developed on copper in the presence of formic acid vapor | |
| Jotanović et al. | Comparison of x-ray fluorescent analysis and cupellation method for determination of gold in gold jewellery alloy | |
| Tashdjian et al. | Preparation of Silver Nanoparticles‐Based Sensors for the Electrochemical Detection of Thiourea in Leaching Solutions of Waste Electrical and Electronic Equipment | |
| JP2010256215A (en) | Stripper and quantitative analysis method for tin or tin alloy plated layer | |
| Liu et al. | Gold immersion deposition on electroless nickel substrates: Deposition process and influence factor analysis | |
| JP4104454B2 (en) | Etching solution | |
| JP2008224423A (en) | Plating film separation method and analysis method of plating film separated thereby | |
| CN108760654A (en) | Method for rapidly determining content of lead element in tin plate coating | |
| JP2009014525A (en) | Method of quantitatively analyzing mercury in tin or tin alloy plating layer | |
| JP7056498B2 (en) | Method for quantifying amide sulfuric acid | |
| Ibrahim et al. | Newly Developed Nano Sensitive Carbon Paste Electrode Modified with Silver Sulphadiazine and Zinc Oxide for Voltammetric Determination of Loperamide Hydrochloride in Pharmaceutical Formulation and in Human Plasma | |
| Matschat et al. | High purity metals as primary calibration materials for elemental analysis-their importance and their certification | |
| Mu et al. | The effect of nonmetallic element P in electroless Ni‐P coating on the passivation process during chemical conversion treatment | |
| JP4314224B2 (en) | Method for quantitative analysis of hexavalent chromium in chromate film | |
| KR102218457B1 (en) | Liquefaction reagent composition for plating layer of nickel plated steel sheet, and analyzing method of plating layer of nickel plated steel sheet using thereof | |
| JP2014185932A (en) | Simple evaluation method for concentration of organic substance in solution containing metallic salt | |
| Guśpiel et al. | KInEtIcs of corrosIon procEss In H2so4 and Hno3 aquEous solutIons of lEad frEE sn-ag-cu soldEr alloys |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20100325 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20110614 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20110623 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140701 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4773399 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |