SUREAGE 3 COATINGS TchNOLOGY ELSEVIER ‘Surface and Coatings Technology 89 (1997) 191-195 The corrosion behaviour of a plasma spraying Al,O; ceramic coating in dilute HCI solution Yan Dianran *, He Jining, Wu Jianjun, Qiu Wangi, Ma Jing Department of Material Engineering, Hebei University of Technology, Tianjin 300132, China Abstract A1,O3 ceramic coatings plasma sprayed on the surface of metals change greatly the corrosion law of metals in strong acid solutions and enhance effectively their corrosion resistance property. In this paper, the corrosion behaviour of a Q235 steel with plasma sprayed Al,O; coatings in a boiling 5% HCI solution is investigated. The corrosion rate of the Al,O, coating sprayed on the surface of Q235 steel is only 1/30 that of the 18-8 austenitic stainless steel under the same corrosion condition. However, the substrate and the Al,O, ceramic coating itself are also subjected to some corrosion because of pores and nonequilibrium ALO; existing in the ceramic coating. The experimental results demonstrate that at the early corrosion stage the corrosion, mechanism is channel corrosion with a large length to diameter ratio for the channels; and the corrosion rate is controlled by the diffusion of corrosion products in the channels; while at the late corrosion stage electrochemical corrosion occurs between the Ni-base alloy bond and the substrate, It was shown that channel corrosion can be restrained and the substrate can be significantly protected by choosing a suitable alloying base layer, increasing appropriately the thickness of the coating, and adopting a porous sealing treatment. Keywords: AiO, ceramic coating; Plasma spraying; Corrosion resistance; Channel corrosion; Porous sealing 1. Introduction. It is well known that engineering quality AIO; ceramic exhibits excellent properties of chemical stability and corrosion resistance [1]. A Al,Os ceramic layer sprayed onto the surface of a metal by plasma spraying can change the corrosion behaviour of the metal in a corrosive solution and shows an outstanding protection against corrosion. Under conditions in which corrosion and wear co-exist, especially at an elevated temperature, an Al,O, ceramic coating offers both proof against high corrosion and high wearability [2,3]; other coatings, such as metallic and organic, etc, cannot compare. However, due to the presence of porosity introduced by plasma spraying in the coating, the metal substrate does suffer corrosion to a certain extent. This paper presents results of the corrosion behaviour of a plain carbon steel with an Al,O5 ceramic coating in 5% HCI solution. 2, Experimental procedure Samples of 30x 25 x 3 mm were cut from a cold-rolled 2235 steel sheet, All the samples were ground to get a = Corresponding a (0257.8972/97/817.00 © 1997 Elsevier Scie PIT $0257-8972(96)02862-9 A. Allright reserved rough surface. The powder used in this study was industrial Al, No.2 grade. The composition and some related physical properties of the powder are given in Table 1. The SEM analysis showed that the Al,0, powder has a plate-like shape, The plasma spraying was carried out in a plasma spraying system supplied by an LP-5OB electric power source and a 781-type spray gun. Prior to spraying Al,Os, a Ni-base alloy bond layer was sprayed onto the surface of the samples in order to increase the corrosion resistance of the sprayed ceramic coating and the adhesive strength of the ceramic coating to the steel substrate. The applied plasma spraying parameters for the Ni-base alloy layer and the Ai,O, coating are listed in Table 2. For the corrosion test, Al,O, ceramic coatings were separated from the steel substrate by submersion in water to dissolve the NaCl layer which was made before spraying. An upgraded organic synthetic was used in the treatment of porous sealing. The corrosion test was performed in a boiling 5% HCI solution, pH=1. The weight-loss method was uti- lized to measure the degree of corrosion of the Al,O3 sprayed samples which were heated to 150°C before weighing with an analysis balance (0.1 mg accuracy).2 D. Yan e¢ a Table 1 ‘The chemical composition and physicial parameters of the A ceramic powder used for the test Chemical composition (wt) Real density Powder size <<. fem?) (um) ALO SiO, FeO, _Na,0 950s 40-60 Table 2 Spraying parameters forthe different spraying materials Ponder Nicbase alloy ALO Are voltage (V) 55 8s ‘Are current (A) 300 350 ‘Plasma gases (an'/b) Ar 2 N 02 q : ‘Totch-o-substeate distance (mz Powder fed rate (g/min) ‘Torch traversing sp Spraying time Coating thickness um) The microstructures of all the samples were observed using an SEM microscope. 3. Experimental results 3.1. Corrosion of the ceramic coating Fig. 1 shows the corrosion weight loss of the substrat free Al;O; coating which was built up by three cycles of, plasma spraying. Tt is seen from the figure that the weight loss of the coating occurs quickly at the early stage of corrosion and tends to be stable thereafter. A comparison of the corrosion course was made using the sample with the Al,O, coating and 1Cr18Ni9Ti(18-8) stainless steel under the same corrosive condition, as Fig. 1. Weight loss curve of a sprayed ALO, sheet in $8 boiling HCI solution, Surface and Coatings Technology 89 (1997) 191-195 shown in Fig.2. It can be seen from Fig.2 that the ‘weight loss of the sample with the sprayed Al,O; coating, ich is then subjected to porous sealing, is evidently smaller than that of the sample which was not treated by porous sealing. However, the latter sample proved to bbe more resistant to corrosion than the 18-8 stainless steel, We can see that the sample sprayed with Al,O3 and with porous sealing has a weight loss which is lower by neatly 2 orders of magnitude than that of 18-8 stainless steel. It was also found that the chemical reactivity of the 18-8 stainless steel sample is retained Guring the whole corrosion test, even after intensive boiling with the 5% HCI solution, whereas for the Al,Oz-sprayed and non-sealed sample only some cracks and bulges were visible in the ceramic coating after corrosion for 18 h. In the case of the sample which was plasma sprayed and porous sealed, no traces of damage were seen in the ceramic coating after 36h corrosion, On examination of the sample with the bulges, it was observed that the Al,O, coating was intact and that there were only a few small corrosion spots on the surface of the steel substrate; in contrast, the Ni-base alloy bond layers were worn away. Fig. 3 shows the corrosion rate of the Al,O,-sprayed Q235 sample, 18-8 stainless steel and Q235 steel. The experimental results indicate that the corrosion rate of the Q235 steel is as large as 2703 mg/em*h, The corrosion rate of the sample with the plasma-sprayed AI,O; coating and treated by porous sealing is merely 1/130 of that of the sample without an Al,O, ceramic coating, and 1/30 of that of the 18-8 stainless steel; the corrosion rate of the sample which is ceramic sprayed and treated by porous sealing is only 1/10 that of the sample without sealing, Tt is evident that the AlOs ceramic coating prevents the substrate from corrosion and greatly decreases its corrosion rate. However, the pores existing in the ceramic coating also directly affect the protection of the coating to the substrate. a | 18-8 stainless stoel| costing net seked coating sealed 3 g 5 E i 5 z Dee ee ORM we Te FFig,2, Weight lose curves of the sample with an Al,O, coating and. 188 stainless steel in 5% boiling HCI solution.D. Yan etal. | Sure and Coatings Technology 89 (1997) 191-195 193 {(vg/enr2h) serio Fig 3. Comosion rate of 18-8 steel and Q235 with and without an 51,0, coating. (1) Q235; (2) 18.8 stainless stel; (3) Q235 with Al, coating, unsealed; (4) Q235 with Al,0; coating, seed: (5) Al:O; 3.2, Microstructures of samples sprayed with AlO3 before and after corrosion test It was shown by SEM that few micropores and microcracks exist on the surface of the Al,O; coating after the corrosion test (Fig. 4). The diameter of the micropores and the length of the microcracks were both Jess than 10 um. By submerging these samples in a Cu,SO, solution, a Cu deposit was seen to appear in the micropores, indicating that there must be some micropores extending from the surface of the lO; ceramic coating to the substrate. The X-ray analysis (Fig. 5) of the Al,O coating and the ceramic powder confirms that a new phase ‘y-Al,O, forms during plasma spraying. It was detected optically (Fig. 6) by the observation that in the micro- structure of the Al,O,-sprayed coating the Ni-base alloy bond layer possessed good adherence (Fig. 6(2)) to the substrate before corrosion; after the samples were cor~ roded, corrosion cracks emerged either in the interface of the two Al,O3 deposits, which were built during two successive cycles of plasma spraying, or in the interface of the Ni-base alloy layer and the AI,O, coating, as shown in Figs. 6(b) and (c). The above phenomena were not found in the sample that was porous sealed, 4, Analysis and discussion of the results ‘The smaller weight loss and corrosion rate of the ALO,-sprayed sample compared to the 18-8 stainless steel and the Q235 steel (Figs.2 and 3) is mainly attributed to the high corrosion resistance of the ceramic coating. The reason is that the ceramic coating keeps the substrate and the solution apart and protects the substrate from being corroded. Micropores and micro- cracks in the ceramic coating play a role in the corrosion course, which is why the non-porously sealed sample Fig 4. Scanning electron micrographs of sample surface with an AIO; ceramic coating, (a) Pores and microcracks; (b) high ma tion SEM of microcracks, shows a larger weight loss and corrosion rate than the sample which was porous sealed. Under corrosive cit- cumstances, the corrosive medium can reach the sub- strate through micropores and microcracks in the Al,O5 ceramic coating, causing the Ni-base alloy bond layer and the substrate to be corroded. This corrosion process is different both from that of a cathodic deposit with some pores and from that of a porous Al,0; film. One reason for this is that in a plasma-sprayed coating micropores have a greater length to diameter ratio: generally >30-40 (diameter of pores <10 qm, and thickness of coating ~ 300-400 ym). On the other hand, because Al,Os does not electrochemically react with a corrosive solution, the Al,Os-sprayed coating itself shows very high corrosion resistance in the corrosion test, and the length to diameter ratio of the micropores in the coating remains almost unchanged according to the data in Fig. 1 It can be seen from these results that, stage of the corrosion test, the corrosion of t covered by an AIO, ceramic coating is of a pattern, in which the corrosion rate is controlled by the diffusion of the corrosion products that have generated during the corrosion process. Such corrosion is charac-