Composition, Testing, and Control of Hot Dip Galvanizing Flux by Dr, Thomas H. Cook HC 52 Box success of virtually every metal finishing opera- tion. In hot dip galvanizing the fluxing operation is a particularly critical step that directly affects the quality and uniformity of the adhesion of the zinc to the steel as well ss the amount of zine used. This article summarizes a wide range of demonstrated best practices and innovations in managing flux chemistry and the fluxing provess I: is well known that pretreatment is key to the EFFECTS OF VARVING THE QUADRAFLUX FORMULATION ‘An effective flux solution must be periodically tost- ed and adjusted to attain required galvanizing results. Among the most important measures of results is the percent gross zine usage (%GZU). It is calculated: GRU \ used/steel galvanized) x 100% For steel averaging S16 in. thick to V/4 in. thick (about 5 mm to 6 mm) a %GZU of about 5% can be attained using an effective flux solution, For steel which is on average thicker, an even lower %GZU can be attained because of less surface area. For ‘S%GZU no credits for ash or dross are allowed EFFECTS OF VARYING QUADRAFLUX FORMULATION Over the last 20 years the most effective flux solu- tion for “dry” kettie galvanizing has been found to be quadraflus with the composition shown in Table I. For a 12.6 degree Baumé flux solution 2 Ib/US gal (240 gL.) of quadraflux is required. Since quadraflux is not normally available in the marketplace, zinc chloride, or double salt, or triple salt can be mixed Hot Springs, South Dakota 5747; E-mai galvecon@gwie.net with ammonium chloride, It is very important that: for each pound of zine chloride there are 1.60 1b of ammonium chloride, Because zine chloride picks up moisture, any partially used bags or barrels must be properly resealed A Banimé lower than about 11 eauises “black spots” (bare spots) on the steel. A Baunié lower than about 12 causes the flux to release poorly from the zine surface resulting in excess zine “clean-up.” A Baumé higher than about 14 gives excessive zine spatter, excessive ash, more smoke, and thicker zine coatings on the steel. A Baumé of 21 is twiee the concentra- tion of a 12.5 degree Baumé flax and gives terrible zine spatter at the kettle because there is a double layer of flux on the stecl. The outer layer is thin and dry, whereas the innier thiek layer is wet and mushy. This wet, mushy condition requires very slow entry of the steel into the molten zine. This produces a very thick 2ine coatings on the lower portion of the steal products, AMMONIUM CHLORIDE NUMBER ‘The Ammonium Chloride Number (ACN) was coined by the author in 1980. It is a mathematical relationship that equals the ammonium chloride concentration divided by the concentration of all other components in the flux solution. In this case we caleulate it: ACN = %Ammonium Chloride/%Zine Chloride It should be noted that because ACN is a ratio hav- ing ammonium chloride in the numerator and zine chloride in the denominator, units cancel out making ACN unitless, independent of concentration, and the ‘Tube L The Mow Eirouilve Blox Quadraflux: ACNE Deas Band 5 i 125 0 1S 1.009 glo 1.107 gl is Chea) Ton [82 ‘Sulfate 60,107 2 Teoporadure 7 Bitecive Saetactant eee “"Tioss than 0.5% (Camied in from Pickling Acid) {aig tan 3.0% (Cored in fo Sutvie Peking ABD, a2 eR TPG Ted at 008i (0 0.004% Nonvolatile. tmpurities "Other Components ‘Less than. 1.0% (Dey. Basis, 6 Zoro ‘Metal Finishingsame number regardless of units. Thus it has the same value whether one is working in English or metric measures. The names, formulae, ACNs, and common uses for galvanizing fluxes are shown in ‘Table IL. Fluxes with ACNs lower than about 1 do not dry well and collect moisture from the air. These wet, fluxes cause moisture explosions as the steel enters the molten zine. It is known that the lower the ACN, the more thermally stable the flux. A flux used in a high-temperature preheater or drying oven therefore must have a low ACN. Fluxes with ACNs higher than about 2 are thermally unstable and give loud, chemi- cal explosions when immersed into the molten zine, In case of an ACN lower than 1 or higher than 2, the required slow entry into the molten zine, eauses Jowor produetion and thicker zine coatings on the lower portions of the steel product ‘The ACN of'a flux solution usually does not remain constant. It is common practice to reflux galvanized rejects (with bare spots) rather than strip the zine (vith acid). During the refluxing of galvanized rejects some of the zine dissolves in the flux solution forming zine chloride. This refluxing process lowers the ACN, raises the pH, and raises the Baumé. In some plants zine bars, dry ash, or even dross are added to the flux solution to neutralize excess earried-over acid from pickling, Also racking fixtures may be galvanized from a previous cycle and enter the flux tank. Spin baskets for centriflige work may be “cleaned” (partially stripped of zine) in the flux solution. All of these latter procedures also inerease zine chloride that lowers ACN. In moderation, all of these practices are fine as Tongs ACN and pH are readjusted as needed and the Baumné does not get too high. Por some galvanizers this system works so well that they have not added commercial flax (containing, zine chloride) for several years. They just add ammonium chloride as needed and strip rejects, racks, or baskets in order to get the required zinc chloride. Thus # galvanizer initially using triple salt with an ACN of 1.18 (Table I) who introduces zine into his flux will, in time, have a flux solution with a lower and lower ACN, In 1975, a galvanizer using triple salt had his flux tested and it was found to contain 0.56 Ib/gal ammonium chloride and 0.72 lb/gal of zine chloride. Thus the ACN was 0.76 (0.55/0.72) After adding 1,500 pounds of ammonium chloride to ‘this 5,000-gal flux tank (0.30 lbvigal) an ACN of 1.18, was reestablished ((0.55+0,30V0.72). After adding the ammonium chloride, the rejects (steel going througii the zine kettle twice) dropped from 3,146 to 0.2%. Even more importantly, the average zine thickness on the steel dropped from 5.7 mils (145 microns) to 24 mils (61 microns), Zinc icicles that ‘were like pencils hanging from the bottom end of the product became small, thin, and flat like silver gum wrappers. Zine clean-up labor was reduced by half. ‘The zine coating was also remarkably brighter In 1977 in Pakistan (where zine chloride is expen- sive) ammonium chloride alone was used for a flux solution. As a result of stripping zine from rejected parts, enough zine chloride accumulated in the flux to form a flux solution having a Baumé of about 5 and an ACN of 5. The 8-meter steel clectrivity tow- ers took 4 minutes to become submerged into the zine due to intense chemical decomposition of the ‘thermally unstable flax on the product. Fortuitously, adding 1 ton of zine chloride gave a Baumé of 12 and an ACN of about. 1.6. With this improved flux solu tion, the electricity towers could easily be lowered into the molten zine in 80 seconds. Production increased, zine usage was lowered hy 20%, and the product uality wes greatly improved, Most North American galvanizers achieving a %G2U of around 5% use an ACN between 1.4 and 1.6, Some auto- matic pipe galvanizers use an ACN of about 1.9 because it causes much thinner zine coatings, espe- cially on the inside of the pipes. ‘Table I, Flux Types and Uses ‘Amoniumn Chloride aNA aL ‘Mame Chernead Formal Common Use Mono Sale acl, NACL 030) ‘Sheet Galvaniaing * Doulle Sal Zac) SNH,CI O79 Gen. Gal Burope (Dry Oven) ‘le Sate 7a, SNE Lis Gen Gale USA (No Oven) Quadraflux Galv. USA (No Oven). Pentatix TTT Some Pipe ana Wires Tip Fluxes ee Wet Kettles ‘Raigo ACN in Flux Solutions ‘Top Flux Addi Py MetalREDUCING DROSS BY CONTROLLING DISSOLVED IRON Dissolved iron (ferrous; Fe?) iron is carvied from the piecing solution through the rinse into the flux solu tion. Iron (Fe) in the flux does not cause dross in a “dry” kettle. In sharp contrast, iron (Fe) in the flux solution does cause dross in a “wot” kettle. The essen: tial first step lo removing the unwanted dissolved iron (Re) is to determine accurately its concentra tion. The most accurate and reliable test is a volu- metric titration using @ standard potassium dichro. mate solution, After securately testing the pH of the flux solution, it is adjusted up to pH 5 using 26 degree Baumé ammonium hydroxide solution. Next the cal- ‘culated volume of ammonium hydroxide is added [to supply hydroxide ions (OH) for the insoluble Fe(OH}, that will he formed] and then the calculated and diluted volume of 35% hydrogen peroxide is slow ly added. Mixing is done by air bubbling. The flux solution is kept hot during additions. Tt normally takes about 2 days for the insoluble iron III hydrox- ide to properly settle and a suitable floceulent can be added to speed up the settling process. The orange sludge formed is normally put through a filter press treated with diatomaceous earth to reduce the vol ume of sludge hy about ten-fold. Additional peroxide is required if the ux eantains suspended oil, which will be degraded to free carbon, Air bubbling to oxidize soluble ferrous iron (Fo*®) to insoluble fervic iron (Fe**) is not possible at the normal operating pH of the flux. Such bubbling: wastes heat energy and stirs up unwanted sludge that gets on to the stecl product. There is no reason to test for “total” iron (Fe'? and Fe* or insoluble forrie (Fe'®) because the forrie will settle to the bot- tom of the flux tank as insoluble Fe(OH), Only iron (Fe) is of interest and it is the iron that is reacted with ammonium hydroxide and hydrogen peroxide during purification {to form insoluble Fe(OH),). Tn- plant testing methods for iron (Fe"®) in the flux are required so that a person will know when all the soluble ivon has been removed. REDUCING BLACK SPOTS BY CONTROLLING SULFATES, Sulfate ion ($0, is earried into the flux solution in the case of sulfuric «eid pickling. In general, galva- nizing a sulfate concentration over about 1% can cause black spots. In galvanizing where steel immersion times in the molten zine are short, such as sheet, wire, and pipes, a much lower sulfate con- centration — 0.26% or even less — causes black spots, A volumettic titration using barium chioride gives the best sulfate test result. Because barium chloride is extremely toxic, the crystal dihydrate should be used for purification; and proper protec- live clothing and air filter masks are required. As with iron removal, airlines are used to dissolve the barium chloride and for reaction of barium ion with sulfate ion, Anhydrous barium chloride (without water) must be avoided because the dust can be lethal if inhaled. If excess barium chloride is used, then the flux solution will be extremely toxic. An in- plant test for sulfate is required to know when the sulfate has been removed and so that excess barium chloride ean be avoided in the flux solution, CONTROLLING pH FOR OPTIMIZED FLUXING ‘The correct pH for luxing steel prior to hot dip gal- vanizing is 4.2. My experience is that the tradition- al literature citing a pIT of 6 is wrong. At a pH of 4.2, the flux provides a final cleaning of the pickled steel, giving @ clean and bright surface ready to fuse chemically with the molten zine. Levels of pH below about 5.5 attack the steel excessively causing solu- ble iron (Fe*4) to build internally in the flux solu lion, It is true that the lower the pH of a flux, the stronger it is, Values of pH higher than about 4.7 are ineffective in cleaning the sicel surface, Recalling that the pH seale is logarithmic, a pH of 4 has ten times higher concentration of hydrogen ions than a pH of 6. In my experience, pH meters do not work in Mux solvtion, tonding to give readings substantially luwer than reality. Some, but not all, brands of pH papers can be useful. Certain organic dye indicators that have u distinct color change near pH 4.2 works extremely well in maintaining proper flux pH. Tn testing and controlling pH, 1 prefer to use the fol- lowing procedure: To a specific volume of settled or filtered flux solution is added a suitable organic pH indieating dye. Using a plastic syringe filled with, either 1:10 hydrochloric acid or 1:10 ammonium hydroxide (as titrant), the flux solution is titrated to a pH of 4.2. The calculated volume of either concen- trated hydrochlorie acid or concentrated ammonium hydroxide is then added to the process flux tank. In some plants, pF adjustment of the flux solution is required daily It is important to keep in mind that the goal of testing via a titration is to determine how much hydrochloric acid or ammonium hydroxide to add to maintain a pH of 4.2. Knowing the pH —but not knowing what to add or how much to add — is not useful, Lam convineed that a pH meter should never be used, T also contend that zine slabs, zine ash, or dross added to the flux solution causes the pH to slowly go too high and should also never be used ‘A fabricator and galvanizer having a flux solution 6 ‘Metal Finishing { |