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absent. Sometimes, a very thin layer of gamma phase material is still observed in this range adhering to the iron. The mixture of these types of crystal and the zinc melt builds up according to a linear time law. Over 515 deg.c., compact layers of the gamma and delta phases are formed once more, and thickness of these increases according to a parabolic time function. The reason for the unusual behaviour in the temperature range from 495 deg to 515 deg.c. is the very slow formation of the zeta phase, so that no consistent zeta layer is created. It has been observed by various investigators that a n increasing level of silicon in the steel has the effect of extending sharply downwards the temperature range within which these structurally insecure alloy layers are formed to lower temperatures. This feature is illustrated in Fig.1. If the silicon content is raised still further, the temperature range narrows once again until, from about 2.9% onwards, compact alloy layers are obtained at temperatures which, on non-alloyed steels, give rise to structurally uncohesive layers. This area corresponding to the formation of layers of alloys with a weakened structure is surrounded by another area within which compact layers are still obtained, although the speed of the reaction exceeds expectations, as well be described later. As examples of the structure of the alloy layers formed on steels containing silicon, Figures 2 a-c show the results obtained with various levels of silicon. Although this effect of silicon on the course of the reaction has been known for some time, it was R W Sandelin (4,5) who observed that even very low levels of silicon can have an unfavourable influence on the formation of the alloy layers. At ordinary galvanizing temperatures around 450 deg.c, in the range from approximately 0.03 to 0.12% silicon, zinc-permeated and structurally uncohesive alloy layers are formed, which are made up basically of small crystals of the zeta phase. This reaction patters, which has subsequently been confirmed on several occasions (6), is found within the mentioned range of silicon contents down to a temperature of about 430 deg.c. (3). This area is separated from the temperature and concentration range, in which structurally uncohesive alloy layers containing coarse angular zeta crystals are fromed, by a zone within which compact and cohesive layers of alloy are treated(7). Here, too, the structurally uncohesive layers build up according to a linear time function, so that in these circumstances very thick coatings of zinc are produced. Consequently, if the quantity of zinc deposited is plotted as a function of silicon content, then, at temperatures over 430 deg.c., the pattern is similar to that initially determined by R W Sandelin (5) (See figure 3b), whereas with a galvanizing temperature of 430 deg.c. the peak at around 0.05% Si does not occur (See Figure 3a) As in the case of the reaction between zinc and steel containing no silicon, above 530 deg.c. compact and cohesive layers of alloy were found with all the levels of silicon under investigation. These comprised the gamma layer next to the iron and the adjacent delta layer. Investigating the speed of the reaction by measuring the iron losses over a period of time at different temperatures has shown that up to about 0.9-1% Si, the rate of attack increases as a parabolic function of time (3); illustrated by Figure 4. With a further increase in the silicon content, the rate of attach falls once more (see Figure 5). It must be stated that, at a given value of the rate of attach, i.e. at a certain iron loss value, there is a transition from the parabolic relationship to an intensified attach which conforms to a linear time relationship. With very high silicon levels we see, at around 500 deg.c., a further slightly intensified attack according to the parabolic time law, but this is so slight that it no longer leads to an attach as a linear time function. Reaction Between Zinc and steels containing silicon
With steel sheet containing very low levels of silicon, differing behaviour on the two sides has often been observed. While, on one side, a normal zinc coating made up of compact layers of alloy is formed, on the other side the coating can be thick, uneven and made up of structurally weak deposits. In pipes made of this type of steel, the phenomenon takes the form of a perfectly satisfactory coating on the inside while, on the outside, the deposit is thick and irregular owing to the uneven structure of the alloy layer. Phenomena of a similar character have already been described and attention has been drawn to the fact that the formation of these uneven alloy layers can sometimes be prevented by grinding and polishing the samples. Other investigations have indicated that, by annealing steels with a very low silicon content around 0.05%, this abnormal reaction, i.e. formation of structurally uncohesive layers, can be overcome. This result can be achieved more easily and quickly by normalizing treatment than by annealing below 850 deg.c. These two special aspects of the reaction may possibly be explained by the fact that the silicon is locally converted into oxide by internal oxidation, so that it is prevented from influencing the reaction. It has recently been clearly demonstrated that such internal oxidation does indeed have this kind of effect on the reaction pattern. Grinding off the surface layer which has been affected by the oxidation has the effect that the original behaviour pattern, with the formation of structurally unsound deposits, is restored. In the case of steels containing about 0.05% silicon, the formation of unsound deposits can sometimes be avoided by blasting the surface. Blasting with glass shot or a coarse blasting medium has no effect, but blasting with fine corundum leads to the formation of compact deposits. It is not yet known to what extent the reaction pattern is affected by the work-hardening of the surface due to the blasting or whether the change should be put down to the nature of the microstructure at the surface.
therefore obtained. In this range the reaction is similar to that between zinc and steel containing no silicon. The transition to the formation of structurally uncohesive layers made up of fragments of delta and angular zeta crystals begins at about 470 deg.c.. This temperature range then extends up to around 520 deg.c. above which compact layers are formed once more. As the silicon content is increased, the temperature range within which the formation of the zeta phase is inhibited and structurally uncohesive layers therefore occur drops to increasingly low levels. Consequently, with a silicon level of above 0.25%, alloy layers of this kind are already formed in the upper range of galvanizing temperatures around 465 deg.c., while with silicon contents in excess of about 0.45% this occurs at very low temperatures around 430 deg.c. Above about 520 deg.c. compact layers are obtained once again. With very high levels of silicon in excess of 2.9%. the speed of reaction between steels of this kind and molten zinc has dropped off to such an extent that, even at temperatures around 500 deg.c., a compact zeta layer can form which isolates delta layer underneath from the zi c melt. This prevents n any dissociation of the layers of alloy. At all temperatures, the reaction then follows a course which declines parabolically as a function of time. Summary Of all the elements present in steel, it is silicon which has the most marked effect on the reaction pattern. The temperature range characterized by the formation of structurally uncohesive alloy layers made up of delta fragments and angular zeta crystals is first extended sharply down-wards by silicon and then tapers off completely at higher silicon levels above approx. 2.9%. Structurally unsound deposits made up of small zeta crystals are also formed with very low levels of silicon between about 0.03 and 0.12%. The causes of this behaviour probably lie in the nucleation of the zeta phase. REFERENCES 1. FSjoukes, The role of iron in the hot dip galvanizing process, 11th International Galvanizing Conference, Madrid, 1976. 2. E C Truesdale, R L Wilcox and J L Rodda, Tech. Pub. 651-E, oct. 1975, Amer. Inst. Mining Metall. Engrs. 3. D Horstmann, The effect of the silicon content of iron and steel on the hot dip galvanizing process, 11th International Galvanizing Conference, Madrid, 1976. 4. R W Sandelin: Wire Prod. 15(1940), 655-676, 721, 749, 941, 16 (1941), 28-35. 5. R W Sandelin: Amer, Hot Dip Galvanizers Ass. Pittsburgh, 1963. 6. Proceedings, Seminar on Galvanizing of silicon Containing Steels, Liege, May 21-22 1975. ILZRO New York 1976. 7. J J Sebisty : Galvanizing of Silicon-Containing Steels Progress Reports No. 2,4 and 6 CANMET Energy Mines and Resources, Ottawa, Canada 1973 and 1974. 8. H Bablik, F Gotzl and E Nell: Arch. Eisenhuttenwes, 31 (1960), 331. 9. J M Sistiaga and A J Vazquez: Rev. Metalurg. (Madrid), 9 (1973), 3-14 10. A J Vazquez and J M Sistiaga, Heat treatment and Stabilisation of the structure of galvanized coatings, 12th International Galvanizing Conference, Paris, 1979.
11. J J Sebisty and G E Ruddle: Proceedings Seminar on Galvanizing of Silicon Containing Steels, Liege, May 21-22, 1975. pp. 219-241. ILZRO, 1975. 12. N.C. Jain, Influence of Silicon Content of Iron and Steel on the Hot Dip Galvanizing Reaction, Seminar on Galvanizing of Concast Silicon Containing Steels, 4-5 August, 1989, New Delhi, Organized by Indian Hot Dip Galvanizers Association Delhi