ZINC COATING THICKNESS EFFECTS ON HOT DIP GALVANIZED STEEL CORROSION RATES AT A SEVERE MARINE SITE

D. Fullston, W.D. Ganther and G. Thomson* CSIRO Manufacturing & Infrastructure Technology PO Box 56, Highett, Victoria 3190, Australia Damian.Fullston@csiro.au Wayne.Ganther@csiro.au *Galvanizers Association of Australia 124 Exhibition Street, Melbourne, Victoria 3000, Australia
SUMMARY: The effect of zinc coating thickness on hot dip galvanized steel corrosion rates in field exposures were investigated and compared with that of standard rolled zinc plates. Hot dip galvanized steel test samples with nominal zinc coating thickness of 55, 70 & 85 m were exposed at the CSIROs severe marine testing site at Port Fairy for periods of up to 3 years. Salt deposition at Port Fairy, as measured according to ISO 9225, is in the order of 1500 2000 mg/m2day. The corrosion rates for all the hot dip galvanized steel samples were similar during the exposure periods, irrespective of coating thickness. The corrosion rate for the standard rolled zinc specimens over the same exposure periods was about 4 times higher than that of the hot dip galvanized steel samples. The differences in corrosion rates between the hot dip galvanized steel samples and the standard rolled zinc samples may be due to minor compositional variations in the zincs and the Fe-Zn intermetallic layers. It appears that the corrosion rate of the hot dip galvanized steel samples is determined by the zinc coating composition while the zinc coating thickness determines life expectancy. Keywords: Coating thickness, hot dip galvanized, Fe-Zn intermetallics, severe marine exposure. 1. INTRODUCTION
During the batch hot dip galvanizing process heavy sections attain thicker zinc coatings than thinner sections, mainly due to the steel composition, longer immersion times, cooling rate and surface roughness. These thicker zinc coatings generally have thicker Fe-Zn intermetallic layers (1,2,3). However, there have been limited studies on characterizing the field exposure corrosion rates of galvanized coatings as a function of coating thickness and intermetallic microstructure. Sjoukes (4) conducted a literature review on the corrosion resistance of iron-zinc layers and found that in most circumstances the corrosion resistance of iron-zinc alloy layers is better than other zinc layers and that the structure of the alloy layer has a large influence on the corrosion resistance. Porter (5) reviewed the resistance of zinc-iron alloy coatings to atmospheric corrosion and found the information on the corrosion resistance on Zn-Fe alloy layers, alone or in combination with zinc, to be slightly conflicting but suggests and increased corrosion resistance in acid atmospheres, with a slightly reduced corrosion resistance in alkaline atmospheres, as compared to pure zinc. Marder (2) acknowledges the fact that coating microstructure will control the coating properties, but fails to discuss the possibility of Fe-Zn intermetallic phases contributing to corrosion resistance. Numerous studies (6,7,8,9,10,11,12) have been conducted on different Fe-Zn alloy systems formed and tested in a variety of ways (electrochemical plating, galvannealing, high temperature galvanizing and specialty synthesis) and have found that generally the Fe-Zn coatings perform equal to or better than conventional zinc coatings in corrosion tests. This raises the question with galvanized heavier section thicker coatings about whether or not the Fe-Zn intermetallic layers play a role in determining the atmospheric corrosion rate. This study was set up to investigate some of these variables.

Marder (2) provides an in depth review of the galvanizing process and the metallurgy involved during the formation of the different Fe-Zn intermetallics layers that create the galvanized coating. Generally at 450oC in a 0.00 wt% Al bath, four Fe-Zn phases are formed. Outwards from the steel surface and in terms of decreasing iron content they are: Gamma () Fe3Zn10 with 23.5-28.0 wt% Fe; Gamma1 (1) Fe5Zn21 with 17-19.5 wt% Fe; Delta () FeZn10 with 7.0-11.5 wt% Fe; Zeta () FeZn13 with 56 wt% Fe. A solid solution layer of iron in zinc, eta () phase with an iron solubility of about 0.03 wt%, forms on the outermost galvanized surface. The site chosen for the field exposure was a severe marine site located at Port Fairy, Victoria, Australia, which has an average salt deposition rate of greater than 1,500 mg/mday, as measured by ISO 9225 (13). Owing to the very high salt deposition rate, this site is very corrosive and provides for rapid corrosion testing. This site is unique, as the authors are unaware of any other corrosion exposure site around the world with comparable levels of chloride deposition.

2. EXPERIMENTAL 2.1 Exposure and Site Details

The field trail began on 13-12-1999 with all samples being exposed at the same time at CSIROs severe marine site at Port Fairy, Victoria, Australia (Figure I). This site has an average salt deposition rate of greater than 1,500 mg/mday as measured by ISO 9225 (13). The Port Fairy site is in the Temperate climatic zone and is open to the ocean with large volcanic rocks on the shoreline. The racks are within 20 metres of the high tide mark and face southwest into the Southern Ocean. Typical corrosion rates for this site are >30 m/yr for zinc and > 400 m/yr for steel. One sample from each of the three coating categories were retrieved after approximately 12 months (367 days) and 28 months (842 days) to monitor progress and attain interim corrosion rates, with the remaining two samples being returned after 36 months (1086 days). Samples were cleaned and corrosion rates determined according to ISO standard procedures (14,15) with coating thicknesses calculated from the mass loss data. Coating thickness measurements were performed using an Elcometer 345 digital coating thickness gauge, with results being averaged from ten readings.

Port Fairy Melbourne

Figure I: CSIRO's severe marine exposure site at Port Fairy, Victoria, Australia

2.2 Material Exposed

A total of 12 hot dip galvanized (HDG) samples were exposed in three nominal zinc coating of 55, 70 and 85 m (corresponding to nominal coating weights of 390, 500 and 600 g/m2). The initial calculated coating thicknesses of the samples are given in Table I. The 55 and 70 m coatings were applied to 3 mm thick standard specimens of unalloyed carbon steel; this material is used as a standard by CSIRO for monitoring the corrosivity of sites with respect to mild steel. The 85 m coating

was applied to specially prepared 6 mm thick plates of carbon steel. Care was taken to ensure squareness of the edges of these specimens. All of the HDG samples had dimensions of 100 x 150 mm. Galvanising was carried out externally and coatings were specified at 55 m, 70 m and 600 g/m2 (85 m). Samples were passivated with a 0.1% sodium dichromate quench solution. The standard rolled zinc was 99.87% pure with main impurities of 0.117% copper, 0.005% titanium, 0.002% iron, 0.001% lead and aluminium at <0.0025%.

3. RESULTS
Single samples from each of the three coating categories were recovered after approximately 12 months (367 days) for the first three HDG samples and after approximately 28 months (842 days) of exposure for the second three HDG samples. The remaining two samples in each of the three coating categories were recovered after about 36months (1086 days) of exposure. Figure II shows the recovered samples before cleaning. After removal of corrosion products residual coating thickness was calculated and measured (Table I) and corrosion rates determined (Table II). Also included in Table II are values for zinc and mild steel specimens, which were performed in triplicate. Calculated coating thicknesses assume a uniform coverage of zinc, which is not necessarily the case, as seen by zinc filling some of the identification holes (842 day 70 m sample) and the zinc run marks on the sky and ground faces of the 1086 day 85 m sample (Figure II).

367 Days:

55 m

70 m

85 m

Sky

Ground

Sky

Ground

Sky

Ground

842 Days:

55 m

70 m

85 m

Sky

Ground

Sky

Ground

Sky

Ground

1086 Days:

55 m

70 m

85 m

Sky

Ground

Sky

Ground

Sky

Ground

Figure II: Recovered samples still covered with corrosion products

Table I: Calculated and measured coating thicknesses Calculated Days Exposed 367 Coating Category 55 m 70 m 85 m 55 m 842 70 m 85 m 55 m 1086

Residual Measured Sky facing (m) 42 (33) 62 (55) 66 (60) 33 51 69 25, 22 37, 38 Ground facing (m) 40 (29) 58 (53) 65 (62) 30 48 65 18, 19 39, 37 42, 40

Initial Coating (m) 45 60 62 48 60 88 41, 41 58, 56

Coating Left (m) 34 49 52 11 29 47 7, 8 24, 25

70 m

85 m 57, 61 26, 25 42, 43 Bracket = measurement for dark grey areas. Distinct from shiny metallic areas Duplicate plate results Table II: Corrosion rates for hot-dipped galvanized steel, zinc and mild steel at Port Fairy Material Date Collected (Exposed 13/12/1999) 14/9/2000 14/12/2000 9/4/2002 3/12/2002 276 Days 367 Days 842 Days 1086 Days (m/year) (m/year) (m/year) (m/year) 10.7 16.1 11.6 & 11.3 10.4 13.4 11.3 & 10.6 10.4 17.6 10.7 & 12.3 41.6 37.6 39.6 34.4 465 473 412 370

Average Corrosion Rate (m/year) 12.4 11.4 12.8 38.3 430

HDG 55 m HDG 70 m HDG 85 m Zinc Mild Steel

4. DISCUSSION
The samples recovered after 367 days had two visually different areas once the corrosion products were removed shiny metallic areas and dark grey areas. Using optical microscopic and cross-sectioning, Fullston (1) has shown that the shiny metallic areas correspond to an outer most surface layer while the dark grey areas correspond to an outer most surface layer of one of the four Fe-Zn intermetallic phases. Although in Figure II the corrosion products are still present, the sky facing side of the 367 day samples does however show that within about 2 cm of the edges there is significant corrosion product build up when compared to the rest of the plate. Once all of the shiny metallic layer has been removed it is difficult to assign specific areas for coating thickness measurements to differentiate between thinner edge measurements and general coating thickness variations. However, this doesnt mean the variations are not there. Figure II indicates that there are still thinner residual coatings around the edges of the sky facing sides after 842 and 1086 days exposure, where it can be seen for the 55 m samples that there is a prevalence of rust spots/brown staining around the edges. From Table I it can be seen that generally the measured coating thickness of the ground facing side of the samples is consistently about 2-4 m less than the sky facing side. This difference is possibly due to the preferential corrosion of the sky facing edges of the samples, sample orientation during galvanizing or a microscopically larger surface roughness on the sky facing side as compared to the ground facing side. A difference in surface roughness may be due to the rain washing component of the corrosion mechanism, where the removal of deposited salt at an initiated corrosion sites then increases the frequency of initiation sites when the next salt is deposited. Alternatively, the difference can be viewed as the build up of salt deposits on the ground facing sides (Figure II) sustaining more generalized corrosion (1). The calculated residual coating thickness deviates from the measured values and the difference is significantly greater at the longer exposures of 842 and 1086 days where the layer has been removed. The discrepancies may be due to the loss of iron as the Fe-Zn intermetallic layers corrode or a pitting corrosion mechanism or a combination of both. The calculated coating thickness values are based on the weight of zinc added to the sample and do not include iron, so a lower coating thickness will

be calculated when iron is lost in corrosion products. A corrosion process based on micro-pitting would remove mass from the sample but retain a higher measured coating thickness if the pit diameter is less than the diameter of the measuring probe. Slight rust spots/brown staining was only observed around the edges of the 55 m samples after exposure of 842 days or longer at the severe marine site (Figure II). The appearance of these spots corresponds to a measured residual coating thickness of less than about 30 m or less than about 10 m calculated thickness (Table I). The measured coating thickness in the areas of the slight rust spots/brown staining were about 20 m and 15 m for the sky facing 55 m sample after 842 and 1086 days, respectively. Previous studies by Fullston (1) on approximately 45 m thick 0.00 wt% Al galvanized coatings have shown that at a measured coating thickness of 15-20 m the surface layer is approaching the - intermetallic interface, while at 5-10 m the - 1/ intermetallic interface is approached. Cross-sectioning and optical microscopic examination would confirm the intermetallic layer at the surface of these samples and residual coating thicknesses. Porter (5) references studies where the source of the free iron that oxidises to form the brown stains is found to arise from the phase during the - conversion and iron in the molten zinc bath. The corrosion rates for the galvanized samples are higher for the second collection than either the first or last collection (Table II). This trend is also shown in the zinc results but not in the mild steel results. The higher values may be due to the season of collection as these samples were collected in Autumn and the others were collected in Summer. As the results are based on single or duplicate samples statistics can not be performed. However, the closeness of the corrosion rates for each sample in a collection period indicates that all the types of galvanized samples are corroding at a similar rate, which is about 3 times slower than that of the zinc and much slower than the mild steel (Table II). Figure III shows the calculated and measured coating thicknesses remaining for the galvanized samples verses time. Also included are lines of best fit. From the calculated values, all the HDG samples are losing approximately 0.035 m/day (gradient of fitted lines), or 13 m/year, which is consistent with the corrosion rates calculated in Table II of approximately 12 m/year. From the measured values, the 70 and 85 m HDG samples are losing approximately 0.026 m/day (10 m/year) while the 55 m HDG sample is losing approximately 0.020 m/day (7 m/year), which is 4 - 5 times slower than the rolled zinc. The difference in corrosion rates between the calculated and the measured values may be due to the additional loss of iron as the Fe-Zn intermetallic layers corrode and a pitting corrosion mechanism as mentioned earlier. The slower corrosion rate from measured coating thickness values for the 55 m HDG sample could be due to the slower corrosion rate of the higher iron content Fe-Zn intermetallic layers closer to the steel substrate, for example the phase at 7-12 wt% Fe or the phases at 17-28 wt% Fe (5).
80.0 70.0 60.0 Coating thickness (m) 50.0 40.0 30.0 20.0 10.0 0.0 0 200 400 600 Days e xpos e d 55 m Calculated 55 m Measured Linear (55 m Calculated) Linear (55 m Measured) 70 m Calculated 70 m Measured Linear (70 m Calculated) Linear (70 m Measured) 85 m Calculated 85 m Measured Linear (85 m Calculated) Linear (85 m Measured) 800 1000 1200

Figure III: Coating thickness loss on galvanized samples

Figure IV compares the calculated coating loss values between the HDG samples and the zinc. From this graph it can be seen that the galvanized samples all lost coating at about the same rate, which was much slower than the rolled zinc samples. Therefore, in this test there was no unequivocal difference shown between the coating losses from the different galvanized 5

coating thicknesses. Other work by Ganther et. al. (16) has shown that small compositional differences (<0.2%) can influence zinc corrosion rate by almost an order of magnitude and the Fe-Zn intermetallics in the HDG samples could be contributing to the observed differences between the rolled zinc and the HDG samples found in this study.
0.0

-20.0

-40.0 Thickness loss (m) y = -0.0347x R2 = 0.9774 -60.0 y = -0.0318x R2 = 0.9882 -80.0 y = -0.0356x R2 = 0.9007 -100.0 y = -0.1001x R2 = 0.9865 -120.0 0 200 400 600 Days e xpos e d 800 1000 1200 Zinc sample 85 m Galvanised sample 70 m Galvanised sample 55 m Galvanised sample 55 m Calculated 70 m Calculated 85 m Calculated Zinc Linear (55 m Calculated) Linear (85 m Calculated) Linear (70 m Calculated) Linear (Zinc)

Figure IV: Coating thickness loss of galvanized samples and zinc samples

Although a lot of effort went into trying to control the galvanizing during sample preparation to achieve the different coating thicknesses, there were still a number of variables beyond control that affected the quality of the results, i.e. the large variation (57-88 m) in the initial calculated coating thickness of the nominal 85 m samples and no initial measured coating thicknesses to check specifications. Fullston (1) has applied galvanized coatings of between 30 to 90 m thicknesses to identical 1mm thick steel plates using the recently acquired galvanizing capability of CSIRO Manufacturing & Infrastructure Technology, which could provide the resources to conduct future complementary scientific investigations.

5. CONCLUSIONS
The hot-dip galvanized samples corrode at a significantly slower rate than that of the rolled zinc and at a very much slower rate than mild steel under the severe marine exposure conditions of this study. Therefore, the galvanized layer protects the underlying steel and the greater its thickness the longer the coating will last. While this type of rolled zinc has been used by CSIRO as a reference coupon it will not be of the same composition as the zinc used for the galvanising and small compositional differences (< 0.2%) can influence the zinc corrosion rate by almost an order of magnitude. Different methods to determine residual coating thickness of galvanized coatings can give different results and hence different corrosion rates. Calculating coating thickness from mass loss data may underestimate coating thickness, while coating thickness measurements may over estimate coating thickness. The true coating thickness may lie somewhere in between the values given by these techniques. Fe-Zn intermetallic layers may help to slow the corrosion rate of galvanized samples when compared to more pure zinc samples, at least until the steel substrate has been reached and a bimetallic couple is formed. Slight rust spots/brown staining was only observed after 842 days of extreme marine exposure on the 55 m HDG sample. However, there was still a significant amount of galvanized coating left, so this failure is only an aesthetic failure.

6. ACKNOWLEDGEMENTS
The authors would like to thank George King for initiating and conducting the trial before his retirement, Pon Kao for technical assistance during the test and Angela Bradbury and Ben Leong for cleaning the samples.

7. REFERENCES
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. D. Fullston, Unpublished work (2003) A.R. Marder, Progress in Materials Science, 45, pp191-271 (2000) J.D. Culcasi, P.R. Sere, C.I. Elsner and A.R. Di Sarli, Surface and Coatings Technology, 122, pp21-23 (1999) F. Sjoukes, The Corrosion Resistance of Iron-Zinc Layers. A Literature Review, European General Galvanizers Association, (1976) F.C. Porter, Corrosion Resistance of Zinc and Zinc Alloys, Marcel Dekker (New York), (1994) A. Besseyrias, F. Dalard, J.J. Rameau and H. Baudin, Corrosion Science, 39(10-11), pp1883-1896 (1997) Y. De Abreu, A. Da Silva, A. Ruiz, R. Requiz, N. Angulo and R. Alanis, Surface and Coatings Technology, 120-121, pp682-686 (1999) R. Ramanauskas, P. Quintana, L. Maldonado, R. Pomes and M.A. Pech-Canul, Surface and Coatings Technology, 92, pp16-21 (1997) R. Ramanauskas, L. Muleshkova, L. Maldonado and P. Dobrovolskis, Corrosion Science, 40(2/3), pp401-410 (1998) R. Ramanauskas, L. Gudaviciute, L. Diaz-Ballote, P. Bartolo-Perez and P. Quintana, Surface and Coatings Technology, 140, pp109-115 (2001) G. Reumont, J.B. Vogt, A. Iost and J. Foct, Surface and Coatings Technology, 139, pp265-271 (2001) A.R.B Verma and W.J. van Ooij, Surface and Coatings Technology, 89, pp132-142 (1997) ISO 9225 Corrosion of Metals and Alloys Corrosivity of Atmospheres Measurement of Pollution, International Organization for Standardization (Genve), (1992). ISO 8407 Corrosion of Metals and Alloys Removal of Corrosion Products from Corrosion Test Specimens, International Organization for Standardization (Genve), (1989). ASTM G1-90 Standard Practice for Preparing, Cleaning, and Evaluating Corrosion Test Specimens (Reapproved 1999), American Society for Testing and Materials (Philadelphia), (1999). W.D. Ganther, T.H. Muster, R. Edavan and G.A. King, Proc. Corrosion Control and NDT, Melbourne, (2003)