Study of Corrosion Mechanism in Brazed Cu Joints
Authors: Kim Choong-Un , Ni Geng , Chang Je-Young , Lee Jae-Ho 
Published: May 2020

The mechanism behind corrosion of Cu and Cu alloys has been the subject of extensive studies within their applications in various engineering components. These studies explore the electrochemical mechanisms along with the contributing factors impacting the corrosion behaviors such as pH, temperature, and solution chemistry. Thanks to these studies, the corrosion behavior of Cu and Cu alloys is reasonably well understood to a degree to predict their reliability under conditions that have been a concern of related industries. However, it is noted that studies are very limited to the impact of a microscopic structure that forms a galvanic pair with Cu and Cu alloys. One of the most obvious but least studied examples of such a case is the corrosion located in the joint that is created by brazing material. The Cu or Cu alloy components with a brazed joint is commonly found in water handling devices and facilities (such as a heat exchanger). Since the filler material used for the brazing of Cu and Cu alloys contains a substantial number of elements other than Cu the joint changes chemically and microstructurally different. It then becomes a source of a galvanic couple. In this case, the most corrosion prone part is the area near or at the joint as the corrosion is accelerated by the galvanic potential. While such joints are abundantly placed in various engineering components (and therefore the concern for corrosion should be focused more on those parts), studies on the corrosion mechanism with the brazing joint are extremely limited. This is probably due to sufficient material redundancy in the joint and thus causing immunity to failure by corrosion. However, a recent development of an advanced cooling system, where heat from electronic devices such as a microcontroller is removed by the use of recirculating coolant, the redundancy is no longer valid and the corrosion at the brazed joint becomes a matter of critical and practical concern.
Motivated by the growing need to better understand the corrosion mechanism active in advanced cooling system, we have investigated the nature of corrosion in Cu plate with a variation in filler materials (Cu-Ag eutectic alloy, Cu-Ag-P alloys), liquid type (water, water mixed with PG), and temperatures. One of the most challenging part of our investigation is the fact that there are multiple sources of galvanic potential due to the existence of multiple phases in the sample. For example, when a Cu-Ag-P alloy was chosen as a filler material, the joint contained three phases, Cu-rich, Ag-rich and Cu3P intermetallic phases. An example of such a microstructure is shown in Fig.1, where an SEM micrograph of the joint is displayed. In this case, the galvanic potential exists not only between the filler materials as a whole and the surrounding Cu, but also among these three phases. In order to overcome the difficulty of studying corrosion behaviors in such a structure, we adapted two different experimental approaches. The first is to measure the corrosion current under the configuration of ZRA (zero-resistance-analysis). The ZRA uses the Cu and the joint as the counter/working electrode as shown in Fig.2 and measures the galvanic potential and current across the joint. The second is to make a mini-galvanic cell consisting of a pure Cu plate and a Cu plate with the brazed part. Spaced by an O-ring, these two plates are forced to make a galvanic cell with a liquid filled the gap and an external short circuit. We were able to measure the resulting corrosion current, direction and the amount of which can be related to the galvanic corrosion created by the braze.
This study presents some of our highlighting findings suggesting that the galvanic corrosion can be better characterized by the use of techniques employed in our study. An example of such evidence can be found in Fig.3 where the ZRA scan signal (voltage and current) in 1M KCl solution is shown with the filler area as the working and surrounding Cu as the counter electrode. Note the instability in the galvanic potential with time, which is attributable to the lack of sustainable passivation layer on top of Cu3P and is responsible for the complex corrosion response of the brazed part to the solution chemistry. A detailed description of such findings along with theoretical explanation will be provide in this paper.

Figure 1