Influence of Electrolyte Aging on Electrotinning in Phenolsulfonic Acid Bath

전기주석도금 반응에 미치는 PSA계 도금용액 노화의 영향

The influence of phenolsulfunate concentrations on electroplating characteristics and electrochemical behaviors was investigated with a viewpoint of electrolyte aging using the circulation cell and potentiostate And comparison of tinplate coating appearance such as glossiness and Image clarify has been also studied with varying of phenolsulfonic acid (PSA) solutions. As the aging of electrolyte proceeded, the limiting current density was moved to a lower current density region by the limitation of mass transfer, and higher phenolsulfunate concentrations resulted in the narrower optimum current density range and deterioration of coating surface of tinplates. The difference of the limiting current density was not remarkable with increasing electrolyte temperature. Thus the electrolyte aging was attributed to the limitation of thermally-activated process such as mass transfer of reducible ions. It has also been considered that the accumulation of phenolsulfonate suppressed normal electrotinning reaction by reducing the mobility of stannous ions, taking into account of the smaller effect of electrolyte aging. Experiments showed similar polarization behavior between the electrolyte of high phenolsufonate solution and the aged one, which comes to conclude that the accumulation of phenolsulfonate is one of the major causes of electrolyte aging.

전기주석도금용 PSA(Phenolsulfonic Acid Bath)계 전기주석 도금액은 장기간 사용하면 노화되어 도금 전류밀도 범위 축소 및 표면특성 열화현상이 일어나게 된다. 본 연구에서는 도금액 노화 현상의 원인을 축적된 phenolsulfonate농도 증가의 관점에서 조사하였다. 동전위와 정전위 분극실험 결과에서는, phenolsulfonate축적농도 증가에 따른 도금액의 노화 정도가 증가함에 따라 음극분극 초기에 나타나는 한계전류밀도가 점차 낮아지는 현상이 나타났다. Sodium phenolsulfonate를 첨가하여 phenolsulfonate끼 농도만을 조절한 도금액에서도 노화된 도금액과 거의 비슷한 분극 특성이 나타남으로써 도금액 노화의 원인이 축적된 phenolsulfonate임을 간접적으로 확인할 수 있었다. 또한 도금액의 온도가 증가할수록 한계전류밀도가 뚜렷하게 나타나지 않고 도금액 노화에 따른 영향이 적어져서 도금액의 노화는 물질이동과 같은 thermally-activated process의 제약에 의한 것이며, phenolsulfonate가 축적되면서 주석 이온의 mobility를 감소시키고, 따라서 정상적인 도금 반응이 억제되는 것으로 판단된다.