Implications of industrial espionage
Industrial espionage was implicated in the capacitor plague, in connection with the theft of an electrolyte formula. A materials scientist working for Rubycon in Japan left the company, taking the secret water-based electrolyte formula for Rubycon's ZA and ZL series capacitors, and began working for a Chinese company. The scientist then developed a copy of this electrolyte. Then, some staff members who defected from the Chinese company copied an incomplete version of the formula and began to market it to many of the aluminium electrolytic manufacturers in Taiwan, undercutting the prices of the Japanese manufacturers. [1] [25] This incomplete electrolyte lacked important proprietary ingredients which were essential to the long-term stability of the capacitors [5] [23] and was unstable when packaged in a finished aluminium capacitor. This faulty electrolyte allowed the unimpeded formation of hydroxide and produced hydrogen gas. [26] [27]
There are no public court proceedings related to the alleged theft, as Rubycon's complete electrolyte formula remained secure. However, independent laboratory analysis of defective capacitors has shown that many of the premature failures appear to be associated with high water content and missing inhibitors in the electrolyte, as described below. [26]
Unimpeded formation of hydroxide (hydration) and associated hydrogen gas production, occurring during "capacitor plague" or "bad capacitors" incidents involving the failure of large numbers of aluminium electrolytic capacitors, has been demonstrated by two researchers at the Center for Advanced Life Cycle Engineering of the University of Maryland who analyzed the failed capacitors. [26]
The two scientists initially determined, by ion chromatography and mass spectrometry, that there was hydrogen gas present in failed capacitors, leading to bulging of the capacitor's case or bursting of the vent. Thus it was proved that the oxidation takes place in accordance with the first step of aluminium oxide formation.
Because it has been customary in electrolytic capacitors to bind the excess hydrogen by using reducing or depolarizing compounds, such as aromatic nitrogen compounds or amines, to relieve the resulting pressure, the researchers then searched for compounds of this type. Although the analysis methods were very sensitive in detecting such pressure-relieving compounds, no traces of such agents were found within the failed capacitors.
In capacitors in which the internal pressure build-up was so great that the capacitor case was already bulging but the vent had not opened yet, the pH value of the electrolyte could be measured. The electrolyte of the faulty Taiwanese capacitors was alkaline, with a pH of between 7 and 8. Good comparable Japanese capacitors had an electrolyte that was acidic, with a pH of around 4. As it is known that aluminium can be dissolved by alkaline liquids, but not that which is mildly acidic, an energy-dispersive X-ray spectroscopy (EDX or EDS) fingerprint analysis of the electrolyte of the faulty capacitors was made, which detected dissolved aluminium in the electrolyte.
To protect the metallic aluminium against the aggressiveness of the water, some phosphate compounds, known as inhibitors or passivators, can be used to produce long-term stable capacitors with high-aqueous electrolytes. Phosphate compounds are mentioned in patents regarding electrolytic capacitors with aqueous electrolytic systems. [28] Since phosphate ions were missing and the electrolyte was also alkaline in the investigated Taiwanese electrolytes, the capacitor evidently lacked any protection against water damage, and the formation of more-stable alumina oxides was inhibited. Therefore, only aluminium hydroxide was generated.
The results of chemical analysis were confirmed by measuring electrical capacitance and leakage current in a long-term test lasting 56 days. Due to the chemical corrosion, the oxide layer of these capacitors had been weakened, so after a short time the capacitance and the leakage current increased briefly, before dropping abruptly when gas pressure opened the vent. The report of Hillman and Helmold proved that the cause of the failed capacitors was a faulty electrolyte mixture used by the Taiwanese manufacturers, which lacked the necessary chemical ingredients to ensure the correct pH of the electrolyte over time, for long-term stability of the electrolytic capacitors. Their further conclusion, that the electrolyte with its alkaline pH value had the fatal flaw of a continual buildup of hydroxide without its being converted into the stable oxide, was verified on the surface of the anode foil both photographically and with an EDX-fingerprint analysis of the chemical components.