JP2006265707A - Coating method for platinum - Google Patents
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本発明は、白金塗布液に関し、より詳細には電極、センサーなどの電気化学用デバイス、あるいは電子回路などに熱分解による白金被覆を行うための白金塗布液及びその製造方法に関するものである。 The present invention relates to a platinum coating solution, and more particularly to a platinum coating solution for performing platinum coating by pyrolysis on an electrochemical device such as an electrode or a sensor, or an electronic circuit, and a manufacturing method thereof.
白金被覆を形成する方法として、基板が金属であり導電性が有れば電気メッキが適用され、比較的厚い、つまり１ミクロン以上の膜厚を有する白金層が形成できる。また非導電性基板では、還元剤を加えた白金液をメッキ液として使用し、非導電性基板表面にメッキ層を形成する無電解メッキ法、またはこれらの組み合わせが使用される。またいわゆる蒸着、スパッタに代表されるPVDと呼ばれる方法も知られている。
更に基板が耐熱性である場合には、基板に白金含有液を塗布しそれを熱分解することによって白金を被覆する熱分解白金も知られている。
As a method for forming the platinum coating, electroplating is applied if the substrate is a metal and has electrical conductivity, and a platinum layer having a relatively thick film thickness of 1 micron or more can be formed. For non-conductive substrates, an electroless plating method in which a platinum solution with a reducing agent added is used as a plating solution and a plating layer is formed on the surface of the non-conductive substrate, or a combination thereof is used. Further, a method called PVD represented by so-called vapor deposition and sputtering is also known.
Furthermore, when the substrate is heat resistant, pyrolyzed platinum is also known in which platinum is coated by applying a platinum-containing liquid to the substrate and thermally decomposing it.
これらの中で、比較的安定で容易に行えるのが熱分解による白金被覆生成であり、原則として空気中で300から600℃で熱分解することによって白金被膜が得られる。この熱分解法は比較的容易に実施できしかも10ナノから10ミクロン程度の厚みまで容易に得られるという特徴が有る為、広く使われている。
この熱分解法は通常入手が容易な塩化白金酸のアルコール溶液または水溶液を塗布液として使用し、基板上に塗布し、炉中で加熱、熱分解を行うことによって白金金属の析出が可能である。しかしながら文献に紹介されるように、熱分解白金被膜では塗布白金量の少なくとも15％程度が揮散してしまうとされる。高価で希少な白金がこのような形で揮散することは大きな損失であり、この方法の最も大きな問題点である。
Among these, formation of a platinum coating by pyrolysis is relatively stable and can be easily performed. In principle, a platinum coating is obtained by pyrolysis at 300 to 600 ° C. in air. This pyrolysis method is widely used because it can be carried out relatively easily and can be easily obtained in a thickness of about 10 to 10 microns.
In this thermal decomposition method, platinum metal can be deposited by applying an alcohol solution or an aqueous solution of chloroplatinic acid, which is usually easily available, as a coating solution, applying it onto a substrate, heating it in a furnace, and performing thermal decomposition. . However, as introduced in the literature, it is assumed that at least 15% of the applied platinum amount is volatilized in the pyrolytic platinum coating. Volatilization of expensive and rare platinum in this way is a big loss and the biggest problem of this method.
このメカニズムについては種々の観測があり、その一つは液中に含まれる塩素根が熱分解と共に揮発性の白金化合物を作り熱分解過程である種の塩化物となって揮散してしまうことが提起されている。また白金は熱分解で最初酸化白金、あるいは水酸基を含む酸化白金となり、それが500℃程度に加熱されることによって空気中でも還元されて、白金金属を析出し、その時の体積変化その他で、あるいは揮散酸素、水酸基と共に白金の一部が揮散してしまうとされる。いずれにしても塗布量に対しての歩留まりが極めて悪くなるという問題点が残る。
これを防ぐために白金塗布液中に還元剤として有効に働くラベンダーオイルや丁字油などの比較的炭素数の大きい非揮発性の油状物質を共存させ、熱分解時点で還元雰囲気を作ることが行われる（特許文献１）。
特に昭４４−３４０１４号公報その他では電極の製造に当たって、白金に他の白金族金属を加えたものに丁字油を加え、エチルアルコールを溶媒として塗布液を作りこれを基板に塗布し、熱分解によって白金族金属被膜を得ることが行われている。
There are various observations about this mechanism, one of which is that chlorine radicals contained in the liquid form a volatile platinum compound with thermal decomposition and volatilize as a kind of chloride in the thermal decomposition process. Has been raised. In addition, platinum is first converted into platinum oxide or platinum oxide containing hydroxyl groups by thermal decomposition, and when it is heated to about 500 ° C, it is reduced in the air, precipitating platinum metal and changing the volume at that time, or volatilization. A part of platinum is volatilized together with oxygen and hydroxyl groups. In any case, there remains a problem that the yield with respect to the coating amount is extremely deteriorated.
In order to prevent this, a non-volatile oil with a relatively large carbon number such as lavender oil or clove oil that works effectively as a reducing agent coexists in the platinum coating solution to create a reducing atmosphere at the time of thermal decomposition. (Patent Document 1).
In particular, in Japanese Patent Application Laid-Open No. 44-34014, etc., in manufacturing electrodes, a plate oil is added to a material obtained by adding platinum to another platinum group metal, and a coating solution is prepared by using ethyl alcohol as a solvent. Obtaining a platinum group metal coating has been performed.
これにより歩留まりは良くなり、また粒の良く発達した金属被膜層が得られるが、このような油状物質の熱分解は、短時間に行うためには500℃、出来れば600℃以上の温度を必要とすること、また有機物の分解に伴い臭気の発生が起こり、液の取り扱いが必ずしも容易ではないという問題点があり、その使用は比較的限られていた。更に還元を確実に行うためには実質的に還元雰囲気である火炎中での熱分解を行う必要があり、更にその取り扱いを困難としていた。
このような液を使って熱分解メッキを行うことは現在でも行われており、電極の製造技術としてはこれの他に非特許文献１や非特許文献２示されている。
This improves the yield and provides a well-developed metal coating layer, but thermal decomposition of such oily substances requires a temperature of 500 ° C, preferably 600 ° C or higher, to be performed in a short time. In addition, there is a problem that odor is generated with the decomposition of organic substances, and handling of the liquid is not always easy, and its use is relatively limited. Furthermore, in order to reliably perform the reduction, it is necessary to perform thermal decomposition in a flame that is substantially a reducing atmosphere, and the handling thereof is further difficult.
Pyrolysis plating using such a liquid is still performed, and Non-Patent Document 1 and Non-Patent Document 2 are shown as other electrode manufacturing techniques.
また特許文献２では、塩化白金酸水溶液とプロパギルアルコールの混合液を塗布液として基材に焼結する方法が開示され、塩化白金酸の焼結後に残った塩素から還元剤を含み塩素根を含まないいわゆる有機金属の一種である樹脂酸塩を塗布液とする方法が知られている。これは市販されているが、一般にその濃度が低く、厚塗りが困難であると同時に、樹脂酸塩としては通常メルカプタンなどを使用するので、臭気の問題のあること、また完全に分解して金属を出すためには焼成温度が高くなること、更に有機揮散物質が多量であることから、どうしても多孔質になりやすいという問題点があった。
更に特許文献３では、ジニトロジアンミン白金のアルコール溶液を塗布液としてチタン基材に焼結する方法が開示されているが、還元剤、界面活性剤を使用していない為、基材と白金被覆との濡れ性が悪いという問題がある。また、これは電解用電極の中間層に白金層を用いる事を目的としている為、焼結後の金属白金の緻密さは求められておらず、また、歩留まりについての言及もない。
Furthermore, Patent Document 3 discloses a method of sintering a titanium substrate using an alcohol solution of dinitrodiammine platinum as a coating solution. However, since no reducing agent or surfactant is used, There is a problem of poor wettability. Further, since this is intended to use a platinum layer as an intermediate layer of the electrode for electrolysis, the density of the platinum metal after sintering is not required, and there is no mention of the yield.
本発明は簡単な操作で金属歩留まりをほぼ100％にでき、しかも緻密な金属白金被覆が比較的低い熱分解温度で得られ、更に得られる金属白金被覆の厚みの制御が容易な熱分解白金被膜作成用の塗布液及びその製造方法を提供することを課題とする。 The present invention can achieve a metal yield of almost 100% by a simple operation, a dense metal platinum coating can be obtained at a relatively low pyrolysis temperature, and the thickness of the resulting metal platinum coating can be easily controlled. It is an object of the present invention to provide a preparation coating liquid and a manufacturing method thereof.
本発明は実質的に塩素根を含まない非塩素系白金塩又は白金錯体の溶液、特に水溶液である白金塗布液であって、該白金塗布液中にアンモニア、アンモニウム塩、アミン及びアルコールから成る群から選択される還元剤を含むことを特徴とする。 The present invention relates to a solution of a non-chlorine platinum salt or platinum complex substantially free of chlorine radicals, particularly a platinum coating solution which is an aqueous solution, and the platinum coating solution is composed of ammonia, ammonium salt, amine and alcohol. A reducing agent selected from the group consisting of:
以下本発明を詳細に説明する。
本発明による白金塗布液は平滑にしかも容易に白金被覆が出来ること、また厚みの制御が極めて容易なこと、また塗布条件、熱分解条件によって耐食性の極めて高いものから活性なもの、更には基材材料にもとらわれないという特徴があり、電解電極のような活性を要するもの、あるいは電気接点、各種センサーのセンサー本体、それらのリード線など幅広い応用が可能である。また比較的低い温度での処理が出来、ポリイミドクラスの樹脂から１０００℃以上で使用されるセラミックスあるいは金属など、対象も極めて広いという特徴がある。メッキからセンサー、装飾その他まで多くの活用が可能である。
The present invention will be described in detail below.
The platinum coating solution according to the present invention can be coated smoothly and easily with platinum, the thickness can be controlled very easily, and the coating solution and the thermal decomposition condition can be activated from the one having extremely high corrosion resistance to the active material. It has the feature that it is not bound by the material, and it can be used in a wide range of applications such as those requiring activity such as electrolytic electrodes, electrical contacts, sensor bodies of various sensors, and lead wires thereof. In addition, it can be processed at a relatively low temperature, and is characterized by a very wide range of objects such as ceramics or metals used at 1000 ° C. or higher from polyimide class resins. Many applications are possible from plating to sensors, decorations, etc.
本発明の白金塗布液は、実質的に塩素根を含まない非塩素系白金塩又は白金錯体を含有する。塩素根とは、塩化物イオン（Ｃｌ-）、次亜塩素酸イオン（ＣｌＯ-）、亜塩素酸イオン（ＣｌＯ2 -）、塩素酸イオン（ＣｌＯ3 -）及び過塩素酸イオン（ＣｌＯ4 -）などを含む。
実質的に塩素根を含まない非塩素系白金塩又は白金錯体とは具体的にジニトロジアンミン白金［（ＮＯ2）2Ｐｔ（ＮＨ3）2、水酸化白金、硝酸白金及び亜硝酸白金などがある。
ジニトロジアンミン白金に代表されるこれらの白金化合物は従来からメッキ用などで使用されており、ジニトロジアンミン白金は白金族金属化合物の中では入手が比較的容易であり、これを白金塩として使用することが望ましい。この他には、水酸化白金も塩素根を含まないので有効であるが、この水酸化白金はまず酸化物になってから更に還元されるという特性があるために、塩化物の揮散は無いものの酸化物の還元時に揮散の起こる可能性があるので、注意が必要である。
The platinum coating solution of the present invention contains a non-chlorine platinum salt or a platinum complex substantially free of chlorine radicals. Chlorine radicals are chloride ion (Cl − ), hypochlorite ion (ClO − ), chlorite ion (ClO 2 − ), chlorate ion (ClO 3 − ) and perchlorate ion (ClO 4 −). ) Etc.
Non-chlorine platinum salts or platinum complexes substantially free of chlorine radicals include dinitrodiammine platinum [(NO 2 ) 2 Pt (NH 3 ) 2 , platinum hydroxide, platinum nitrate and platinum nitrite, etc. .
These platinum compounds typified by dinitrodiammine platinum have been used for plating, etc., and dinitrodiammine platinum is relatively easy to obtain among platinum group metal compounds and should be used as a platinum salt. Is desirable. Other than this, platinum hydroxide is also effective because it does not contain chlorine radicals. However, since this platinum hydroxide first becomes an oxide and then is further reduced, there is no volatilization of chloride. Care must be taken because volatilization may occur during oxide reduction.
本発明では、このような白金塩と、還元剤としてのアンモニア、アンモニウム塩、アミンやアルコールを組み合わせて使用する。この時にアンモニア、アンモニウムあるいはアミンを含む化合物は比較的低い温度で分解することが多く、その温度では白金塩の分解とマッチングしない可能性があるので白金を直接金属として析出させるためには白金塩又は錯体中で白金にアンモニウムあるいはアミノ基が直接結合していることが望ましく、この点からもジニトロジアンミン白金の使用が推奨される。また得られる白金塗布液中には塗布対象の基板との塗れ性を有効にするために界面活性剤が含まれていることが望ましく、この界面活性剤は熱分解温度で完全に分解してしまい、成分が揮散してしまうこと、あるいは揮発性の物質であることが好ましい。このような界面活性剤として炭素数８までの低級アルコールあるいはアンモニウム、アミン化合物などがある。これらの界面活性剤は本発明の必須成分である還元剤と重複し、還元剤の量を必要量より多くして界面活性剤として機能させても、あるいは還元剤とは別の界面活性剤を添加しても良い。界面活性剤は容易に分解することが望ましく、プロパーノールアミンを始めとするアルコキシアミンを還元剤とは別に添加することが好ましい。更に必要に応じて分散剤兼界面活性剤として低級アルコールを加えることも出来る。 In the present invention, such a platinum salt is used in combination with ammonia, ammonium salt, amine or alcohol as a reducing agent. At this time, a compound containing ammonia, ammonium or amine often decomposes at a relatively low temperature, and at that temperature, there is a possibility that it does not match with the decomposition of the platinum salt. It is desirable that an ammonium or amino group is directly bonded to platinum in the complex, and from this point of view, the use of dinitrodiammine platinum is recommended. In addition, it is desirable that the obtained platinum coating solution contains a surfactant in order to make the coatability with the substrate to be coated effective, and this surfactant is completely decomposed at the thermal decomposition temperature. The component is preferably volatilized or a volatile substance. Examples of such surfactants include lower alcohols having up to 8 carbon atoms, ammonium, and amine compounds. These surfactants overlap with the reducing agent that is an essential component of the present invention, and even if the amount of the reducing agent is larger than the required amount to function as a surfactant, or a surfactant other than the reducing agent is used. It may be added. It is desirable that the surfactant be easily decomposed, and it is preferable to add an alkoxyamine such as propanolamine separately from the reducing agent. Further, if necessary, a lower alcohol can be added as a dispersant / surfactant.
このようにして作製した実質的に塩素根を含まない非塩素系白金塩又は白金錯体と還元剤及び必要に応じて界面活性剤を有する白金塗布液は通常酸で溶解するが、その液性は中性または弱塩基性であり酸液ではないことにより腐食性もなく、取り扱いが容易であり、しかも十分な界面活性剤が含まれるので、液の塗布性がよくなり、塗布された白金塗布液が流動せずに基材表面に保持される。
本発明の白金塗布液は還元剤を含むので、還元メッキに見られる場合と異なり、基材材質にはほとんど制限がない。基材は熱分解温度以上の耐熱性を要求されるが、その耐熱性を具備すれば、金属以外、たとえば酸化物セラミックスなどの基材にも容易に前記白金塗布液を塗布し白金を析出させることができる。
The platinum coating solution prepared in this way and containing a non-chlorine platinum salt or platinum complex substantially free of chlorine radicals, a reducing agent and optionally a surfactant is usually dissolved with an acid. Since it is neutral or weakly basic and is not an acid solution, it is not corrosive, easy to handle, and contains sufficient surfactant, so that the coating property of the solution is improved and the applied platinum coating solution Is held on the substrate surface without flowing.
Since the platinum coating solution of the present invention contains a reducing agent, unlike the case seen in reduction plating, there is almost no limitation on the base material. The base material is required to have heat resistance equal to or higher than the thermal decomposition temperature. If the base material has the heat resistance, the platinum coating solution can be easily applied to a base material such as oxide ceramics other than metal to deposit platinum. be able to.
白金被覆条件は特に制限されないが、例えば前記白金塗布液を被処理物である基材に塗布し、60℃程度で半乾燥し、それを350℃から600℃程度に保持したマッフル炉中に入れて熱分解を行い、あるいは塗布後に火炎にて加熱熱分解して白金を析出させる。これを繰り返して所定の厚さにする。焼き付け時間は３分ないし１５分程度であるが、それより長くても基材の変質が起こらない限りは問題にはならない。なお加熱時の雰囲気は特に指定されず、酸化雰囲気でも良いし、中性あるいは還元雰囲気でも良い。なお加熱雰囲気中に塩素根が混入しないようにする必要がある。
このようにして焼き付けた白金は所定量の被覆を行った後に更に安定化の加熱も合わせて行うことが出来、これによって更に強固な被覆とすることが出来る。
このときに白金塗布液が塩素根を含まないため、白金の揮散がほとんどなくせること、またアンモニウム、アンモニアあるいはアミンという有効な還元剤により白金イオンが金属白金に還元される。塩素根を含まないこと及び還元剤の働きで、熱分解時には緻密な金属白金の被膜を作ることが出来、さらに極めて高い歩留まり、実質的にほぼ100%の歩留まりが達成できる。
The platinum coating conditions are not particularly limited. For example, the platinum coating solution is applied to a substrate to be processed, semi-dried at about 60 ° C., and then placed in a muffle furnace maintained at about 350 ° C. to 600 ° C. Pyrolysis is carried out, or platinum is deposited by thermal pyrolysis with a flame after coating. This is repeated until a predetermined thickness is obtained. The baking time is about 3 to 15 minutes, but even longer than that is not a problem as long as the base material does not deteriorate. The atmosphere during heating is not particularly specified, and may be an oxidizing atmosphere, or a neutral or reducing atmosphere. It is necessary to prevent chlorine roots from being mixed in the heating atmosphere.
The platinum baked in this manner can be coated with a predetermined amount of coating and then further stabilized for heating, whereby a stronger coating can be obtained.
At this time, since the platinum coating solution does not contain chlorine radicals, platinum volatilization can be almost eliminated, and platinum ions are reduced to metallic platinum by an effective reducing agent such as ammonium, ammonia or amine. Due to the absence of chlorine radicals and the action of a reducing agent, a dense platinum metal coating can be formed during pyrolysis, and an extremely high yield and substantially 100% yield can be achieved.
以上述べたように、本発明の白金塗布液を基材に塗布し、熱分解することにより金属白金の被膜を形成することが出来る。しかも塩化白金酸液による熱分解のケースと異なり白金の歩留まり率はほぼ１００％となり、更に熱分解過程に光沢のある白金被覆が得られるようになる。また白金被覆形成の操作自体は従来の方法と変わらず、また実質的には温度の幅、塗布時の歩留まりなども向上する。
このようにして得られる白金被覆は金属白金であり、その粒径は比較的大きく、従って安定である。またこのような状態にもかかわらず白金塗布液を使用して製造された製品は電極としても使用でき、その場合では化学的に安定であると共に、ある程度活性であるという特性を有し、広く使われることから安定で活性という相反する要因をカバーしている。
As described above, a platinum film can be formed by applying the platinum coating solution of the present invention to a substrate and thermally decomposing it. Moreover, unlike the case of thermal decomposition with a chloroplatinic acid solution, the yield rate of platinum is almost 100%, and further, a glossy platinum coating can be obtained in the thermal decomposition process. Further, the operation itself for forming the platinum coating is not different from the conventional method, and the temperature range, the yield during coating, and the like are substantially improved.
The platinum coating thus obtained is metallic platinum, whose particle size is relatively large and is therefore stable. In addition, a product manufactured using a platinum coating solution in spite of such a state can be used as an electrode. In that case, it has characteristics of being chemically stable and active to some extent, and is widely used. It covers the conflicting factors of stability and activity.
次に本発明を実施形態に基づいて詳細に説明するが、本発明はこれらに限定されるものではない。 Next, although this invention is demonstrated in detail based on embodiment, this invention is not limited to these.
[実施例１]
ジニトロジアンミン白金１０ｇ（白金として約６ｇ）を脱イオン水に添加し、更に界面活性剤としてnープロパノールアミンを白金量に対して５％（約０．３ｇ）となるように秤取し前記脱イオン水に加えた。この脱イオン水を温度６０℃で攪拌しながらジニトロジアンミン白金を溶解させた。最初薄い黄色の懸濁液であったが、溶解につれて透明性が増し、薄い黄色の透明液体になった。この透明液体の攪拌を続け、１５分ほどで、加熱をやめて攪拌のみ続けた。液の温度が４０℃程度になったとき、ｎ−プロピルアルコールと脱イオン水の１：１の混合液を添加し所定の濃度になるようにして白金塗布液を作製した。
蓚酸で表面を洗浄し、エッチングしたチタン板を基材とした。この基材に前記白金塗布液を塗布し、５分間乾燥した後、温度３５０℃で１０分間焼き付けた。取り出したところ白色の被覆が生成しているのが認められた。この塗布−焼成を５回繰り返したところ白色の被覆が生成しているのが認められた。なお、白金の歩留まりは重量増加から測定し、計算上は９９％以上であった。
[Example 1]
10 g of dinitrodiammine platinum (about 6 g as platinum) is added to deionized water, and n-propanolamine as a surfactant is weighed so as to be 5% (about 0.3 g) with respect to the amount of platinum. Added to ionic water. The dinitrodiammine platinum was dissolved while the deionized water was stirred at a temperature of 60 ° C. It was initially a pale yellow suspension, but became more transparent as it dissolved and became a pale yellow clear liquid. Stirring of the transparent liquid was continued. In about 15 minutes, heating was stopped and stirring was continued. When the temperature of the solution reached about 40 ° C., a 1: 1 mixture of n-propyl alcohol and deionized water was added to prepare a platinum coating solution so as to have a predetermined concentration.
The surface was washed with oxalic acid, and an etched titanium plate was used as a base material. The platinum coating solution was applied to the substrate, dried for 5 minutes, and baked at a temperature of 350 ° C. for 10 minutes. Upon removal, a white coating was observed. When this coating-firing was repeated 5 times, a white coating was observed. In addition, the yield of platinum was measured from an increase in weight and was 99% or more in calculation.
［実施例２］
界面活性剤として白金量に対して１０％のイソプロパノールアミンを用いたこと以外は、実施例１と同様にして、ジニトロジアンミン白金を脱イオン水に６０℃で溶解した。この液を溶解後室温まで冷却し、ｎ−オクチルアルコールにより所定濃度になるまで希釈した。希釈により白金を１００ｇ／Ｌ含む白金塗布液が得られた。
この白金塗布液を鏡面加工したステンレススチール板の表面に刷毛塗りにて塗布し、室温で表面が乾燥するまで保持し、５００℃の温度で１０分間熱分解を行った。塗れ性が極めて良かったためか、ほぼ均一な厚みの被覆を得ることが出来た。
[Example 2]
Dinitrodiammine platinum was dissolved in deionized water at 60 ° C. in the same manner as in Example 1 except that 10% of isopropanol amine was used as the surfactant relative to the amount of platinum. This solution was dissolved, cooled to room temperature, and diluted with n-octyl alcohol to a predetermined concentration. A platinum coating solution containing 100 g / L of platinum was obtained by dilution.
This platinum coating solution was applied to the surface of a mirror-finished stainless steel plate by brushing, kept at room temperature until the surface was dried, and pyrolyzed at a temperature of 500 ° C. for 10 minutes. It was possible to obtain a coating with a substantially uniform thickness because the paintability was very good.
［実施例３］
液濃度の調整を脱イオン水のみで行ったこと以外は実施例２と同じようにして白金を溶解し、白金塗布液を作製した。
この白金塗布液をムライト焼結板上に塗布し、６０℃で１０分乾燥後ガスバーナーにて加熱熱分解を行った。これにより焼結板の内側にほとんど液が浸透しないで表面に金属色の白金被覆が形成された。これは白金塗布液の塗れ性が比較的悪かったために焼結板気泡内に入らなかったためと考えられた。
[Example 3]
Platinum was dissolved in the same manner as in Example 2 except that the liquid concentration was adjusted only with deionized water to prepare a platinum coating solution.
This platinum coating solution was coated on a mullite sintered plate, dried at 60 ° C. for 10 minutes, and then thermally pyrolyzed with a gas burner. As a result, a metal-colored platinum coating was formed on the surface with almost no liquid penetrating the inside of the sintered plate. This was thought to be due to the relatively poor wettability of the platinum coating solution which prevented it from entering the sintered plate bubbles.
[実施例４]
基材をチタン板からニッケル板に代えたこと以外は実施例１と同じ条件で白金塗布液を作製しかつこの白金塗布液を使用して前記ニッケル板に金属白金被覆を形成した。
[Example 4]
A platinum coating solution was prepared under the same conditions as in Example 1 except that the substrate was changed from a titanium plate to a nickel plate, and a metal platinum coating was formed on the nickel plate using this platinum coating solution.
[対比例]
白金原材料として市販塩化白金酸を使用しこれをイソプロピルアルコールに溶解して、１００ｇ−Ｐｔ／Ｌとなる液を作成し、これに体積で１０％のラベンダーオイルを加えた塗布液を作製した。基材としてサンドブラスト処理を行って粗面化し、更に２％フッ酸水溶液で酸洗したニッケル板を使用した。
前記塗布液を前記ニッケル板に塗布し、室温で乾燥後、空気中５００℃で１０分間熱分解処理を行った。これを１０回繰り返して約１０ｇ／ｍ2の厚みを有する白金被覆ニッケル板を作成した。
[Comparison]
Commercially available chloroplatinic acid was used as a platinum raw material, and this was dissolved in isopropyl alcohol to prepare a solution of 100 g-Pt / L, and a coating solution in which 10% by volume of lavender oil was added thereto was prepared. A nickel plate that was roughened by sandblasting as a substrate and pickled with a 2% aqueous hydrofluoric acid solution was used.
The coating solution was applied to the nickel plate, dried at room temperature, and then pyrolyzed at 500 ° C. for 10 minutes in air. This was repeated 10 times to produce a platinum-coated nickel plate having a thickness of about 10 g / m 2 .
実施例４及び本対比例で得られた白金被覆ニッケル板について、重量増加から白金の歩留まりの計測を行い、また蛍光エックス線分析により白金相の分析を行った。また、これらのニッケル板を温度６０℃、湿度１００％の恒温槽に入れ、５００時間放置し耐食試験を行った。これらの結果を表１に示した。蛍光エックス線分析では対比例の場合、塩化白金酸に起因するとＣｌ（塩素イオン）の存在が認められ、その量は白金に対して０．５から１％量に相当した。部分緑色斑点は、ニッケル基材の腐食によるもので、塩素イオンの存在によるものと考えられた。
この結果から、従来の塩化白金酸を白金源とする対比例の白金塗布液を使用して製造した白金被覆ニッケル板は、白金自体の歩留まりが極めて悪く、また耐食性にも劣るのに対し、非塩素系白金塩又は白金錯体を白金源とする実施例４の白金塗布液を使用して製造した白金被覆ニッケル板は、白金自体の歩留まりが９９％とほぼ１００％に近く、更に耐食性に良好であることが分かった。
With respect to the platinum-coated nickel plate obtained in Example 4 and this comparison, the yield of platinum was measured from the increase in weight, and the platinum phase was analyzed by fluorescent X-ray analysis. Moreover, these nickel plates were put in a thermostat having a temperature of 60 ° C. and a humidity of 100% and left for 500 hours to conduct a corrosion resistance test. These results are shown in Table 1. In the X-ray fluorescence analysis, in the case of comparison, the presence of Cl (chlorine ion) was observed due to chloroplatinic acid, and the amount thereof corresponded to 0.5 to 1% of platinum. The partial green spots were due to the corrosion of the nickel substrate, and were thought to be due to the presence of chlorine ions.
From this result, the platinum-coated nickel plate produced using a conventional platinum coating solution using chloroplatinic acid as a platinum source has a very poor yield and poor corrosion resistance. The platinum-coated nickel plate produced using the platinum coating solution of Example 4 using a chlorine-based platinum salt or a platinum complex as a platinum source has a yield of nearly 100%, which is 99%, and has good corrosion resistance. I found out.
[実施例５]
ジニトロジアンミン白金を硝酸白金に代えたこと以外は実施例１と同じ条件で白金塗布液を作製しかつこの白金塗布液を使用して前記ニッケル板に金属白金被覆を形成した。白金歩留まりは９９％で、ほぼ１００％に近かった。
[Example 5]
A platinum coating solution was prepared under the same conditions as in Example 1 except that dinitrodiammine platinum was replaced with platinum nitrate, and a metal platinum coating was formed on the nickel plate using this platinum coating solution. The platinum yield was 99%, nearly 100%.
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| CN115181965A (en) * | 2022-07-11 | 2022-10-14 | 西安泰金工业电化学技术有限公司 | Method for preparing platinum-plated metal material by flame thermal decomposition method |
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| CN113278935A (en) * | 2021-05-07 | 2021-08-20 | 昆明贵研新材料科技有限公司 | Platinum oxide electrode and preparation method and application thereof |
| CN115181965A (en) * | 2022-07-11 | 2022-10-14 | 西安泰金工业电化学技术有限公司 | Method for preparing platinum-plated metal material by flame thermal decomposition method |
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