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`EFFECT OF SILICON ON HOT DIP GALVANIZING REACTION By Dr. N. C.

Jain Page - 1/2


Introduction Iron plays an important role in hot dip galvanizing process. It reacts with molten zinc and forms three zinc-iron alloy layers of different compositions viz. gamma layer containing 22 - 28% Fe, delta layer containing 6.5 -12% Fe and Zeta layer containing 6.2 - 6.3% Fe, in accordance with the Fe-Zn diagram. During dry galvanizing process, as soon as the flux melts, molten zinc comes in contact with the steel and forms zinc-iron alloy layers. The gamma and delta layers are compact whereas the zeta layer is less compact. Zeta crystals can float away into the zinc. They settle on the bottom of the zinc bath and form dross. The amount of dross depends on several factors. The main factor is the structure of the delta layer. If this layer is well formed, the zeta layer is compact and only a few zeta crystals will float away. If, however, silicon killed steel or other reactive steels are galvanized, the zeta layer grows fast and many crystals will float into the zinc and form dross. Iron-Zinc Reaction When silicon killed steels are galvanized, the gain in coating weight is linear with dipping time for bath temperatures up to about 460 deg.c. and almost parabolic at 470 deg.c.. It means that it is better to galvanize silicon killed steels at the higher temperatures if the dipping time is more than five minutes. Also dross formation is less at higher temperatures with this steel. If however, the temperature is raised about 520 deg.c. the coating weight is reduced, but the dross formation is many times more than at 470 deg.c. The overall behaviour, however, varies with the steel chemistry. The solubility of iron in zinc at 470 deg.c. is about twice as at 440 deg.c. This means that if the temperature of the galvanizing bath is suddenly raised from 440 deg.c. to 470 deg.c. the zinc is not saturated with iron and the attack by molten zinc on steel is more severe. On the other hand if the temperature is lowered from 470 deg.c. to 440 deg.c. a lot of dross is formed if the zinc was saturated with iron at 470 deg.c. It can be calculated that under these circumstances, the dross formation is about 750 kg for a bath containing 100 tones of zinc. Structure of Alloy Layers At temperatures up to about 490 deg.c., the reaction between pure iron and the molten zinc produces compact layers of gamma, delta and zeta phases, which build up according to a parabolic time law. Between 495 deg.c. and 515 deg.c., the alloy layers break up to a large extent and a zincpermeated mixture of fragments of the delta phase and angular zeta crystals is formed. At temperatures about 500 deg.c. the later are generally

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.

`EFFECT OF SILICON ON HOT DIP GALVANIZING REACTION

By Dr. N. C. Jain Page - 2/2


A Tentative Description of the Reactions between Zinc Melts and Steel Containing Silicon All the available empirical data demonstrate unequivocally that the special features which characterize the reaction between molten zinc and steels containing silicon can be attributed to the silicon in solution in the ferrite. Internal oxidation of the silicon in the ferrite to form oxide inclusions has the immediate effect that the reaction follows the same course as with steel containing no silicon. Taking now a closer look at the individual reactions, it is necessary to consider separately five different ranges, i.e. silicon contents below 0.03%, from 0.03 to 0.12%, from 0.12 to about 0.25%, from 0.25 to about 2.5% and the range of silicon contents above 2.9%. Where the silicon content is very low, under 0.03%, its effect is so slight that the reaction takes place as between molten zinc and pure iron. Up to about 490 deg.c., compact and cohesive layers of alloy are formed which build up by the diffusion of the iron and zinc through the layers in accordance with the laws governing diffusion. The inhibited formation of the phase in the temperature range from 495 deg.c. to 530 deg.c. has the result that no cohesive layer is formed. This leads to non-equilibrium conditions which, in turn, result in zinc-permeated, structurally uncohesive layers whose thickness increases as a linear function of time since the very thin compact layer next to the steel is unable to build up over a period of time, so that diffusion through this layer is always constant and is not retarded by increasing thickness. Over 520 deg.c. compact layers are formed once more, and the speed of the reaction is determined by the rate of diffusion through these layers. With silicon contents between 0.03 and 0.12% at temperatures from about 430 deg.c. to 465 deg.c. structurally unsound deposits are formed which are made up of numerous small zeta crystals which do not bond together to make a cohesive layers. In view of this structure of the alloy layer it is to be supposed that, in these conditions, nucleation of new zeta crystals occurs with such rapidity that they hinder each others growth and force one another apart, thus constantly allowing molten zinc to penetrate into the interstices between the crystals. It is possible that this process is aided by silicon enrichment of the zinc melt in the vicinity of the steel surface. Since alloy layers having this type of structure are found only in the temperature range mentioned. One must assume that at these temperatures a critical point for nucleation is passed which triggers off the phenomenon. At lower and higher temperatures, this thermal trigger is not actuated, so that compact, layers of alloy are formed as in the reaction between zinc and unalloyed steel. At temperatures above about 485 deg.c. the nucleation of the zeta phase is inhibited to such an extent that no cohesive zeta layer can be formed and structurally unsound deposits are created. Over about 520 deg.c. the layers made up of the gamma and delta phases are then compact once more. Above about 0.12% Si, the nucleation of the Zeta phase, which is given such extraordinary impetus by lower levels of silicon, is once more reduced to such an extent that the individual crystals no longer interfere with each others growth. At ordinary galvanizing temperatures, compact deposits are

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

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