The Pipe Galvanizing Process

Frequently Asked Questions

The Pipe Galvanizing Process About this Booklet

Frequently Asked Questions

This booklet describes the process and addresses a range of Frequently Asked Questions (FAQs) about automated galvanizing of steel pipe and tube. Detailed information on specific topics is contained in a series of Appendices. While the fundamental galvanizing process has changed little since its inception, engineering developments in the galvanizing of pipe and tube have taken place to make it more automatic in operation, and in controlling the thickness and smoothness of galvanized coatings. Although the overall process has remained essentially the same, operators and managers of pipe galvanizing plants change for various reasons. And while new operators and management might undertake training, some may still have questions about the galvanizing process and methods used for galvanizing pipe. This booklet deals specifically with galvanizing of pipe and tube in plants designed for this purpose. It does not cover in-line (continuous) galvanizing or general (batch) galvanizing, specifically. However, some information may be applicable to the latter. The booklet lists some of the most frequently asked questions and provides answers and explanations. Where possible, the questions have been grouped according to processing step.

DISCLAIMER:
Teck Cominco Metals Ltd. makes no representations or claims as to the suitability of this information for your particular purpose, and that to the extent you use or implement this information in your own setting, you do so at your own risk. The information provided in this booklet is solely for your own use and informational purposes. In no event will Teck Cominco Metals Ltd. be liable for any damages whatsoever, whether direct, consequential, incidental or special arising out of the use of or inability to use the information provided in this booklet.

The Pipe Galvanizing Process Table of Contents

Frequently Asked Questions

About this Booklet . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2 The Process

What is pipe galvanizing? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4 What are the basic steps for galvanizing pipe? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5

Surface Preparation - Pickling

Which acid should be used? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6 How can pickling acid be controlled? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6

Surface Preparation - Fluxing

Why is flux used and how are pipes fluxed? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7 How can flux solution be controlled? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7

Galvanizing Kettles
What are the special requirements for galvanizing kettles? . . . . . . . . . . . . . . . . . . . . . . . . . .8 What factors determine kettle shape? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8 How are pipe galvanizing kettles heated? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8 What is the importance of kettle welds? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9

Zinc Grades
What are the grades of zinc and how do they differ? . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10 What grades of zinc are used in pipe galvanizing? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10 Are there recommendations for sampling zinc ingots? . . . . . . . . . . . . . . . . . . . . . . . . . . . .10

Operating the Galvanizing Bath

What is the normal zinc bath operating temperature? . . . . . . . . . . . . . . . . . . . . . . . . . . . . .12 How does heat input affect kettle life? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .12 Are insulation covers necessary? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .13 Does aluminum affect the galvanizing bath? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .13 What are the sources of lead in the galvanizing bath? . . . . . . . . . . . . . . . . . . . . . . . . . . . . .14 How are pipes submerged in the zinc bath? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .15

Sampling the Galvanizing Bath

Why sample zinc in galvanizing baths? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .16 How should it be done? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .16

Dross and Ash

What is dross? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .18 What are sources of dross? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .18 How can dross be minimized? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .19

Galvanized Coating
How is galvanized coating thickness controlled? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .20 Is it necessary to quench galvanized pipes? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .20

Appendices
Appendix A - Monitoring Sulphuric Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .21 Appendix B - Monitoring Flux Solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .27 Appendix C - Sampling Zinc Ingots . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .31 Appendix D - Monitoring Zinc in Galvanizing Baths . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .32

The Pipe Galvanizing Process The Process

Frequently Asked Questions

Mass produced hot dip galvanized steel pipes and tubes are produced in plants set up specifically for galvanizing these products. While pipe galvanizing plants are usually associated with manufacturers of pipes and tubes, some tubular products are galvanized in batches in plants which provide custom galvanizing services. In addition, a few specialty plants form and galvanize small diameter pipe continuously and cut it to commercial lengths after galvanizing. In that case, only the outside surface of pipe and small diameter tube can be galvanized. Regardless of galvanizing method used, processing variables within each plant need to be monitored and controlled to ensure that product quality and operating efficiency are maintained at the highest levels.

What is pipe galvanizing? Hot dip galvanizing is a universally accepted finishing operation used to protect steel products from corrosion. Large scale galvanizing of pipe is a semi-continuous operation which uses special machinery to transport chemically cleaned pipe through a zinc bath, as shown schematically in Figure 1 (page 5). Galvanized products are automatically withdrawn from the zinc bath and immediately treated to remove molten zinc in excess of coating specifications. Excess zinc is removed from the outside surface by wiping with compressed air, and from the inside by blowing with superheated steam.
While pipe galvanizing equipment has evolved and processes have changed over the years, the underlying objective remains the same clean the steel and metallurgically bond a zinc coating of specified thickness to the pipe surfaces (inside and outside).

The Pipe Galvanizing Process The Process

Frequently Asked Questions

What are the basic steps for galvanizing pipe? Pipe galvanizing is made up of three steps: cleaning, fluxing, and galvanizing. Each step must be completed effectively and efficiently to ensure galvanized coatings are of the highest quality.
Steel can be galvanized only when its surface is chemically clean. In practical terms, this implies that the pipe surfaces are clear of contaminants such as oil and grease used during production, and free of steel-making mill scale and rust. Oil and grease are readily removed in caustic solutions which usually form part of the cleaning process. Pickling in acid is the most widely used method of removing millscale and oxides from steel pipe. The choice of cleaning acid is largely determined by its availability.

DEGREASE RINSE PICKLE RINSE FLUX AIR AIR OUTSIDE WIPE STEAM

INSIDE BLOW GALVANIZING

Figure 1

The Pipe Galvanizing Process Surface Preparation - Pickling

Frequently Asked Questions

Which acid should be used? Both hydrochloric acid and sulphuric acid are effective for removing millscale and rust from steel. While the choice of acid will undoubtedly be influenced by economics and local availability, the opportunities to dispose of used acid and access to effective methods of recycling used acid are becoming increasingly important. How can pickling acid be controlled? Pickling rate is a primary requirement of pipe galvanizers as it has to be completed relatively quickly and keep pace with the galvanizing production rate. Pickling rate is a function of acid concentration, temperature, and iron content whether hydrochloric acid or sulphuric acid is used. In practice, acid concentration and temperature should be monitored and controlled to maintain efficient and effective pickling conditions. It is also critical to monitor iron content and either dispose of the acid when iron content reaches an operating maximum or remove the iron salts and regenerate the acid. Tests for monitoring sulphuric acid for pickling are in Appendix A.
Most pipe galvanizers have favoured using sulphuric acid because its pickling rate is fast and can be matched to the galvanizing production rate. Sulphuric acid is also relatively easy to regenerate.

The Pipe Galvanizing Process Surface Preparation - Fluxing

Frequently Asked Questions

Why is flux used and how are pipes fluxed? The galvanizing reaction will only occur effectively when the surfaces of pipes are chemically clean. In practice, this means that the surface is free of mill scale and rust. Pickling effectively cleans steel surfaces but a freshly pickled steel surface reoxidizes if left unprotected. These oxides are readily dissolved by dipping in an aqueous solution of zinc ammonium chloride - the flux widely used by pipe galvanizers. Zinc ammonium chloride serves two purposes: it prevents additional oxide from forming on the surfaces of pickled pipes, and helps molten zinc react with these surfaces.
The concentration of the flux solution should be monitored and controlled to provide optimum results. Experience shows that fluxed pipes should be dry before they enter the zinc bath otherwise some areas may fail to react with the zinc and leave areas ungalvanized. These defects are known as black spots in the industry. The use of a heated flux solution will help reduce the time needed to dry fluxed pipes. Flux concentration should be adjusted according to ambient humidity and the time delay between fluxing and galvanizing. Immersion of pipes in the flux solution should be kept to a practical minimum to limit buildup of iron salts in the flux tank. Carry-over of iron salts with flux on the pipes will increase dross production and waste zinc.

How can flux solution be controlled? It is necessary to control several key properties of the flux solution to maintain fluxing at an effective level and to keep process economics in line. The following properties should be monitored and controlled:
Flux concentration Flux temperature Iron concentration Sulphate concentration Tests for monitoring flux solution and control methods are described in Appendix B.

The Pipe Galvanizing Process Galvanizing Kettles

Frequently Asked Questions

What are the special requirements for galvanizing kettles? The galvanizing kettle and contained zinc represent the single most expensive part of a galvanizing plant. Unexpected kettle failure (leakage) in service will result in production stoppages and additional costs due to loss of zinc and damage to burners and furnace components. As such, the kettle should be designed and fabricated by experts in this field.
Kettles are commonly made of steel. Ceramic kettles, such as those used in some other galvanizing operations, are typically unsuitable for galvanizing pipe. Kettle fabricators can provide advice on sizing and design of the kettle, and can help select the correct grade and quality of steel for its construction. These fabricators also have equipment for forming heavy steel plates used for kettles and are familiar with the correct welding practices and specifications.

What factors determine kettle shape? The galvanizing bath serves two purposes: 1) to heat the steel pipes to galvanizing temperature during immersion in the bath, and 2) to carry out the galvanizing reaction to produce an adherent zinc coating. The kettle dimensions are largely determined by the maximum production rate expected. Specifically, the kettle length is largely determined by production rate and maximum length of pipes processed. The width will be influenced by the type of handling equipment used to transport pipes through the zinc bath. Kettle depth is mainly determined by the heating method and overall thermal requirements. Pipe galvanizing plants are typically high production units, so thermal requirements are often large. How are pipe galvanizing kettles heated? In general, galvanizing baths can be heated by gas, oil, or electricity but energy choice will be influenced by local availability and economics. Energy requirements include heat to melt the zinc and keep it molten, heat to balance thermal losses due to radiation, convection, and conduction, and heat taken out of the kettle by the galvanized product. All heat required for the process has to be added to the galvanizing bath. Supplying heat through the kettle sidewalls is by far the most widely used method but is limited to heating steel kettles.
Oil and gas are the favoured energy sources for pipe galvanizing. Oil

The Pipe Galvanizing Process Galvanizing Kettles

Frequently Asked Questions

heating allows high production rates but usually gives shorter kettle life. Electrically heated galvanizing baths are not normally used for galvanizing pipe. Oil and gas burners are normally located along the kettle sidewalls but can be set at the corners. Regardless of which type of heating system is used, it is critical to prevent forming "hot spots" as they shorten kettle life and reduce thermal efficiency. Good furnace design, coupled with gas or oil-burning flat flame burners placed along the side walls, helps keep local overheating to a minimum. Some kettles are heated by a single burner set in a combustion chamber located well away from the kettle. In this arrangement, combustion gases are circulated around the kettle. Correctly designed, this set-up provides adequate heat input and relatively long kettle life. High velocity burners, a more recently introduced method for heating galvanizing baths, are being used more widely. Placed at kettle corners, high velocity burners are designed so combustion gases pass along the length of the sidewalls. The burners are programmed to "fire" at slightly different times and for relatively short times so the flow of combustion gases is periodically reversed. This practice eliminates the danger of forming "hot spots".

What is the importance of kettle welds? The galvanizing kettle and contained zinc are major capital items in pipe galvanizing plants. Furthermore, the kettle is indispensable since its failure stops production. Design and fabrication of galvanizing kettles should be entrusted only to experts since kettle integrity is of paramount importance.
Steel kettles are made up of at least three plates welded to form a box. Vertical corners are normally radiused but sidewall-to-baseplate joins are typically square. Welds are a potential source of weakness especially if subjected to overheating and erosion by molten zinc. Where practical, kettle designers locate welds away from directly heated areas and try to place vertical welds at the ends. Welds should be of the highest standard and checked for complete penetration and freedom from porosity. Welds should be faced with low reactivity metal to minimize erosion in service.

The Pipe Galvanizing Process Zinc Grades

Frequently Asked Questions

What are the grades of zinc and how do they differ? There are three commercial grades of slab zinc: Special High Grade (SHG), High Grade (HG), and Prime Western (PW) grade. While the three grades of zinc differ mainly by purity, PW grade zinc also has lead specified as a range. Chemical requirements of slab zinc specified by ASTM B6 (Standard Specification for Zinc) are shown in Table 1 below:
TABLE 1
ASTM B6 Slab Zinc Chemical Requirements (in Wt%)

Element
Lead (Pb) Iron (Fe) Cadmium (Cd) Aluminum (Al) Copper (Cu) Tin (Sn) Total non-zinc Zinc (by difference)

SHG Zn
0.003 max. 0.003 max. 0.003 max. 0.002 max. 0.002 max. 0.001 max. 0.010 max. 99.990 min.

HG Zn
max. max. max. max. 0.10 max. 99.90 min. 0.03 0.02 0.02 0.01

PW Zn
0.5 - 1.4 0.05 max. 0.20 max. 0.01 max. 0.20 max. 2.0 max. 98.0 min.

What grades of zinc are used in pipe galvanizing? Commercial pipe galvanizing specifications define the minimum permissible grade of zinc. Traditionally, pipe galvanizers have used PW grade zinc, but more recently the trend is to use SHG or HG. This trend is due to environmental regulations associated with lead in potable water. Are there recommendations for sampling zinc ingots? Sampling of zinc used in pipe galvanizing plants is rarely necessary since zinc producers provide chemical certification for each lot. However, pipe galvanizers may be required to sample and assay the zinc ingots to satisfy quality control and assurance programs. Sampling of zinc ingots might also be required in rare instances of dispute resolution.

10

The Pipe Galvanizing Process Zinc Grades

Frequently Asked Questions

Most pipe galvanizers can only use 25 kg zinc slabs for bath additions because machinery used to transport pipes through the galvanizing bath prevents the use of larger blocks. However, larger one-ton blocks (jumbo ingots) of zinc produced commercially for other processes can be used for bath additions when galvanizing kettles are suitably modified. Materials handling savings are the main benefit of using jumbos. It is feasible to sample zinc slabs and small ingots to check chemical analysis. Detailed methods of sampling slab zinc are described in ASTM B6. Procedures for sampling zinc slabs by drilling and sawing are described in Appendix C. Sampling of zinc jumbos is not recommended since it is difficult to get representative samples. Disputes concerning the composition of jumbos should be resolved by referring to producer reserve samples. These are samples taken by the zinc producer to certify each production lot.

Figure 2

11

The Pipe Galvanizing Process Operating the Galvanizing Bath

Frequently Asked Questions

What is the normal zinc bath operating temperature? The galvanizing reaction takes place relatively quickly within the temperature range of 440C to 470C (825F to 878F). Operating within this temperature range usually provides sufficient thermal backup to maintain design production levels.
A nominal bath temperature of 450C (840F) is typical. The minimum and maximum operating temperatures are set by practical requirements. As zinc solidifies close to 419C (786F), the minimum operating bath temperature must be maintained somewhat higher with a suitable thermal buffer. Steel galvanizing baths are relatively resistant to attack by molten zinc in the temperature range of 440C (825F) to 470C (880F) but are severely attacked at higher temperatures (see Figure 3). Furthermore, galvanizing at the high end of the operating range can cause the zinc coatings to become fully alloyed, making them brittle and subject to spalling. This tendency to form alloyed coatings is particularly troublesome with steels commonly referred to as "reactive".
Relative Loss of Kettle Steel vs Zinc Temperature
45 40 35 30 25 20 15 10 5 0 420
Relative Loss of Steel

Galvanizing Range

430

440

450

460

470

480

490

500

510

520

Zinc Temperature, C

Figure 3 (Source: American Galvanizers Association - Galvanizing Process Seminar)

How does heat input affect kettle life? Steel used for galvanizing kettles reacts relatively slowly with zinc within the typical operating temperature range (see Figure 3) but dissolves much faster at higher temperatures. Therefore, kettle life is shortened by operating at higher galvanizing temperatures.

12

The Pipe Galvanizing Process Operating the Galvanizing Bath

Frequently Asked Questions

The service life of steel kettles heated through their walls is also influenced by the actual heat input. Projected kettle life decreases rapidly as heat input increases (see Figure 4 - which shows data calculated for 40 mm thick walls). In addition, local overheating causes severe erosion of the kettle steel and can result in kettle failure and subsequent loss of zinc.
Kettle Life vs Heat Input 180,000 160,000 140,000 120,000 100,000 80,000 60,000 40,000 20,000 0 12 24 36 48 60 72
Kettle Life, months

16,000 14,000
Heat Input, Btu/ft2-hr

Heat Input, kJ/m2-hr

12,000 10,000 8,000 6,000 4,000 2,000 0

Figure 4

Burner failure and refractory damage can cause local overheating. Furnace design and burner location should aim for even heat distribution and limit heat input. Thermal requirements which are mainly determined by throughput and thermal efficiency (losses of heat from the surface of the bath and conductivity to kettle foundations) also impact kettle design, especially bath depth.

Are insulation covers necessary? Heat loss from unprotected surfaces of pipe galvanizing baths occurs by radiation and convection. Typical practice is to operate with a layer of molten flux on a large part of the zinc bath. Consequently heat loss is considerably lower than when the zinc bath is uncovered.
Pipe galvanizers find that a layer of molten flux also helps reduce coating defects.

Does aluminum affect the galvanizing bath? Pipe galvanizers can add a relatively small amount of aluminum to the zinc bath to control oxidation and cut down ash formation. This practice also reduces the risk of ash contaminating the galvanized coating.

13

The Pipe Galvanizing Process Operating the Galvanizing Bath

Frequently Asked Questions

Some pipe galvanizers claim that a small concentration of aluminum in the zinc bath also helps maintain a bright finish on galvanized pipe. However, galvanizers should be aware that aluminum readily reacts with chloride-based fluxes used in the process and reduces their effectiveness. Excessive aluminum in the bath can prevent some areas of the pipe from being galvanized. Ungalvanized areas are called bare spots or black spots in the trade. Experience shows that about 0.005% aluminum in the zinc bath is sufficient to provide the benefits mentioned without affecting flux performance. The aluminum concentration in the galvanizing bath is controlled by making appropriate additions of zinc-aluminum master alloys, referred to as brightener alloys. They typically contain 5 or 10% aluminum.

What are the sources of lead in the galvanizing bath? There are two possible sources of lead in pipe galvanizing baths:
1) lead in the zinc additions (e.g. PW zinc), and 2) primary lead added to the zinc bath. Historically, pipe galvanizers used Prime Western grade zinc for bath additions. When PW grade zinc is used, lead in excess of its solubility in molten zinc will precipitate and collect at the bottom of the kettle. This condition can be helpful since dross will float on the layer of lead and make it easier to remove. Lead introduced with PW grade zinc can be in the range 0.5 to 1.4% (see Table 1). Lead levels measured in operating baths are typically 1.2 to 1.4% (i.e. at saturation level). The second source of lead is in cases where lead pigs are used when commissioning new galvanizing baths. Lead helps protect the bottom of the bath and, as noted above, raises dross above the kettle floor plate allowing for easier dross removal.

14

The Pipe Galvanizing Process Operating the Galvanizing Bath

Frequently Asked Questions

TABLE 1
ASTM B6 Slab Zinc Chemical Requirements (in Wt%)

Element
Lead (Pb) Iron (Fe) Cadmium (Cd) Aluminum (Al) Copper (Cu) Tin (Sn) Total non-zinc Zinc (by difference)

SHG Zn
0.003 max. 0.003 max. 0.003 max. 0.002 max. 0.002 max. 0.001 max. 0.010 max. 99.990 min.

HG Zn
max. max. max. max. 0.10 max. 99.90 min. 0.03 0.02 0.02 0.01

PW Zn
0.5 - 1.4 0.05 max. 0.20 max. 0.01 max. 0.20 max. 2.0 max. 98.0 min.

How are pipes submerged in the zinc bath? Chemically cleaned and fluxed pipes enter the zinc bath along the side of the kettle. There are two widely used designs of pipe galvanizing machinery. The main difference between them is the way pipes are submerged in the zinc bath. The pipes should be pushed into the zinc bath at a slight angle to allow air and steam to escape freely. Besides being an important safety feature, putting pipes into the kettle at an angle often improves the quality of the galvanized coating on the inside of pipes. Typically, several pipes are allowed to roll from a loading table into the bath at any one time, often with manual assistance. Once in the bath, a mechanism lowers the pipes at a pre-determined rate. This mechanism can be a pusher-rod type or a notched wheel. After residing in the bath for the prescribed time, the pipes are individually retrieved from the molten zinc.
Pipes are immersed in the molten zinc long enough to raise their temperature to above 440C (824F), at which point galvanizing occurs at a reasonable rate. The desired coating weight will also be a factor. Immersion time, typically 2 to 4 minutes, is governed automatically by controlling the speed of the pipe galvanizing machine.

15

The Pipe Galvanizing Process Sampling the Galvanizing Bath

Frequently Asked Questions

Why sample zinc in galvanizing baths? Sampling zinc in pipe galvanizing baths may be required for one of the following reasons:
To satisfy quality assurance programs To meet customer contract requirements To monitor the zinc bath To help resolve galvanizing problems In general, samples are analyzed to determine the levels of specific elements in the bath. For example, aluminum and lead are typically included. In addition, the levels of any other purposeful bath additions, such as nickel or bismuth (which can affect the coating appearance or thickness), should be known in order to control the process. Occasionally, copper and tin may be of interest, as these impurities can affect the corrosion resistance of the coating.

How should it be done?

While in-process sampling of galvanizing baths is feasible and provides reliable results, differences in plant set-up and equipment arrangement will influence which sampling practices can be used. Access for sampling pipe galvanizing baths is made difficult by the presence of machinery used to move pipes through the zinc bath, as well as ducting used to remove fumes from the galvanizing bath area. A blanket of molten flux on the surface of the bath further limits the opportunities for taking bath samples from pipe galvanizing baths. Considering these limitations, sampling where the galvanized pipes are withdrawn from the zinc bath will likely be the most convenient and practical location.

16

The Pipe Galvanizing Process Sampling the Galvanizing Bath

Frequently Asked Questions

Zinc samples should be taken from the galvanizing bath during normal operation. Samples should not be taken immediately following additions of zinc ingots or master alloys, unless special studies justify sampling at such times. Sampling molten zinc in pipe galvanizing baths is done in two parts: 1) Collecting sufficient molten metal to form a representative sample, and 2) Solidifying the molten sample in a shape suitable for analytical testing. Samples are best formed in permanent molds because chill-casting minimizes segregation of impurities and alloys within them. Pin-shaped samples can be analyzed by Atomic Absorption (AA) and Inductively Coupled Plasma (ICP) spectrometric techniques. Chill-cast disks (shown below) can be analyzed directly by Optical Emission Spectrometry (OES), as well as by the other two techniques. Details are provided in Appendix D.

Figure 5 Illustrations of vertical disk and horizontal disk samples showing preferred target areas for OES as per ASTM E634.

17

The Pipe Galvanizing Process Dross and Ash

What is dross?

Frequently Asked Questions

Dross is an unavoidable product of the galvanizing process. It is a zincrich compound (FeZn13) formed when iron in the galvanizing bath exceeds its solubility in liquid zinc. It is this excess iron that reacts with zinc and precipitates as iron-zinc particles. Most dross settles to the bottom of the bath and is removed before it interferes with the pipes passing through the zinc bath. While there is a market for dross, there is a direct cost resulting from the difference in price between zinc and dross and an indirect cost due to the labour required to remove the dross.

What are sources of dross? Dross is a by-product of the galvanizing reaction and also forms as zinc reacts with the steel kettle. Molten zinc also chemically reduces iron salts to iron which forms additional dross.
There are four primary sources of dross: 1) Pickle salts (iron salts formed by the reaction of pickle acid and steel), 2) Flux salts (iron salts formed by the reaction between flux and steel), 3) Iron-zinc interaction during galvanizing of steel (the direct reaction between steel pipes and molten zinc), and 4) Iron-zinc alloy (formed from the reaction of molten zinc with the steel kettle)

18

The Pipe Galvanizing Process Dross and Ash

Frequently Asked Questions

How can dross be minimized? Although the formation of dross can never be prevented, the amount formed can be kept to an acceptable level by monitoring and controlling the galvanizing process. The following practices can help keep dross production to a minimum:
Keep pickling to a practical minimum Use acid inhibitors to help avoid excessive pickling Control iron concentration in pickle acid Avoid drying work between pickling, rinsing and fluxing Rinse the pipe in water after pickling to avoid contamination of the flux Control iron concentration in flux solution Minimize immersion time in flux Galvanize at the lowest practical temperature Minimize immersion time in zinc Avoid wide fluctuations in zinc bath temperature Practices that reduce dross formation will also lower operating costs. Examples include: Less chemicals required when flux composition is controlled Zinc savings achieved when dross production is kept to a minimum Energy savings achieved when the kettle is operated at a lower temperature Kettle life will be extended Labour savings result from less dross build-up (less frequent removal)

19

The Pipe Galvanizing Process Galvanized Coating

Frequently Asked Questions

How is galvanized coating thickness controlled? Excess zinc dragged out of the galvanizing bath on galvanized pipes is removed automatically. This is done by passing each pipe through a perforated ring blowing superheated air onto the outside of each pipe upon removal from the galvanizing bath. Pressurized steam is used to remove excess zinc from the inside of each pipe. Is it necessary to quench galvanized pipes? Galvanized pipes can be passed through a quench tank to prevent the zinc-iron alloy phase in the coating from extending throughout the thickness of the galvanized coating. The zinc-iron alloy continues to develop until the temperature of the galvanized pipe is well below the galvanizing temperature. Fully alloyed coatings can be brittle and, if too thick, are liable to spall.
Quench tanks usually contain warm water, which also helps avoid distortion during cooling, but may also contain passivation chemicals such as chromate. Such passivation treatments minimize formation of storage stain (white rust) on freshly galvanized products.

20

The Pipe Galvanizing Process

Frequently Asked Questions

Appendix A - Monitoring Sulphuric Acid

Sulphuric acid, typically used as a 10% by weight solution, is widely used for pickling pipes and tubes to be hot dip galvanized. The pickling rate depends on several factors: thickness and type of scale acid temperature acid concentration iron concentration in acid use of inhibitors acid agitation

Acid Temperature
The usual operating temperature for sulphuric acid is in the range 65 85C (150 - 185F). Pickling times increase as acid temperature increases. Sulphuric acid can be used for pickling down to approximately 60C (140F) but the pickling rate may not keep up with the galvanizing production rate. Pickling at temperatures up to 90C (194F) is also possible but steam and mist may create hazardous working conditions unless pickling tanks are adequately vented.

21

The Pipe Galvanizing Process

Frequently Asked Questions

Appendix A - Monitoring Sulphuric Acid

Acid Concentration
Sulphuric acid pickles at rates suitable for most pipe galvanizing operations when used within the 8 to 12% acid concentration range. Pickling rates are relatively high within this concentration range. The effect of acid concentration and acid temperature on pickling rate is shown below.
Typical Pickling Time vs Sulphuric Acid Temperature
80

Pickling Time (minutes)

70 60 50 40 30 20 10 0 2 4 6 8 10 12 Acid Concentration, wt%

Acid Temperature, 80C Acid Temperature, 70C Acid Temperature, 60C

Figure 6 (Source: American Galvanizers Association - Galvanizing Process Seminar)

Iron Concentration
The iron concentration of pickle acid increases with use and causes pickling rate to decrease. While pickling rate can be increased by additions of fresh acid, pickling rate decreases progressively until it is unacceptably low at about 7% iron. At this point, the pickle acid should be replaced or treated to recover remaining free acid.

Use of Inhibitors
Inhibitors retard the attack of acid on the surfaces of cleaned steel and limit the possibility of over pickling. Inhibitors can lower the rate of attack of the acid on chemically clean steel by up to 95% and reduce the amount of hydrogen evolved by the same amount. Some inhibitors form a blanket of foam on the surface of pickling baths and cut down the emission of acid mist. Used effectively, inhibitors reduce costs and lower acid consumption. Other benefits include improved working conditions and safety around pickling tanks.

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Appendix A - Monitoring Sulphuric Acid

The addition of an acid-stable wetting agent to pickle acid will likely improve the rinsing of pickle acid from cleaned work surfaces. Note: Chemical suppliers should be consulted for information on suitable wetting agents and inhibitors. Inhibitors should be used sparingly because excess will significantly decrease pickling rate.

Agitation
Pickling rate can be increased by agitating the pickle acid. Pipes and tubes should also be periodically raised and lowered within the pickling tank to move acid inside the pipes. In the absence of agitation, pickle acid becomes stagnant, acid concentration decreases locally and iron concentration increases. The overall effect is a reduction in pickling rate and effectiveness.

Maintaining the Acid Bath

To operate pickling baths efficiently and economically, it is necessary to know when to add fresh acid and when to treat or replace ineffective pickle acid. Monitoring of pickle acid involves measuring iron and freeacid contents and temperature. This data should be determined regularly and at reasonably frequent intervals. It is also recommended to monitor and record the tonnage of work pickled, additions of fresh acid, and inhibitors, if used. Maintaining the free acid content of the pickle solution is done by making regular additions of small amounts of fresh acid. The pickle bath should be discarded when the iron concentration reaches approximately 7% and the free acid content has been worked down to a minimum practical level. Each 2% of free sulphuric acid consumed in pickling will raise the soluble iron in the pickle bath by about 1%. Therefore, when the iron concentration reaches 4 to 5%, additions of sulphuric acid should be discontinued allowing the free acid to work down to the point where pickling rate becomes too slow. As the acidity is being worked down, the pickling rate should be maintained by increasing the acid temperature.

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Appendix A - Monitoring Sulphuric Acid

Measuring Density (S.G.) of Pickle Acid
The specific gravity (S.G.) of pickle acid can be used to estimate iron concentration. It can be measured directly using a hydrometer for liquids denser than water. Alternatively, density can be measured in degrees Baume (B) and converted to S.G. using the following relationships: S.G. = 145 145 - B B = 145 - (145 S.G.)

Equipment: Thermometer Hydrometer of suitable range Graduated Cylinder Method: 1. Collect sample of pickle acid in graduated cylinder - fill to within 25 mm - 30 mm of top. 2. Adjust solution temperature to 15.5 0.3C (60 1.8F). 3. Warm hydrometer to the same temperature as sample solution; dry hydrometer. 4. Immerse the hydrometer in the sample of pickle acid to a point slightly below the equilibrium level and allow it to come to rest floating an equal distance from the sides of the graduated cylinder. 5. Read the hydrometer at the point where the plane of the liquid surface cuts the hydrometer stem. Check the solution temperature and repeat the test if the temperature has not remained within the 15.5 0.3 C (60 1.8F) range. 6. Record either S.G. or Baume (B) to the nearest 0.05B reading. For control purposes, measurements can be made at higher temperatures and temperature-adjusted as follows: Add 1B if temperature is 38 - 60C (100 - 140F) Add 2B if temperature is 61 - 82C (141 - 180F)

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Appendix A - Monitoring Sulphuric Acid

Measuring Free Acid in Pickle Acid
Equipment: Two - 250 mL beakers 250 mL conical flask Pipette (2 mL) Supply of 0.408N sodium carbonate (21.6 g/L) solution Hydrometer to read S.G. in range 1.0 - 1.3 Small glass funnel and filter papers 50 mL burette Method: 1. Collect a sample of pickle acid (in a 250 mL beaker) and filter it into another 250 mL beaker. 2. Pipette 2 mL of the filtered sample to a 250 mL conical flask to which 100 mL distilled water has been added. Mix diluted sample, add 3 or 4 drops of Methyl Orange indicator, and mix again. 3. Titrate the diluted sample with 0.408N sodium carbonate solution from the burette, agitating the flask continuously. Record the mL of 0.408N sodium carbonate solution required to cause the colour of the indicator to change from red to yellow. 4. Read the acid concentration in g/100 mL directly as the number of mL 0.408N sodium carbonate used. Weight % sulphuric acid = g/100 mL sulphuric acid S.G

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Appendix A - Monitoring Sulphuric Acid

Measuring Iron Content in Sulphuric Acid Pickle
While there are analytical tests to measure the iron content in pickle acid, use of the S.G. - Sulphuric acid - Iron nomogram below will provide data sufficiently accurate for control purposes. The nomogram graphically relates g/L iron in the pickle acid to acid S.G. and sulphuric acid strength (g/L). It is necessary to measure only S.G. and acid strength to determine iron content.

Sulphuric Acid Nomogram

Density, S.G. 1.30 1.25 1.20 1.15 1.10 1.05 1.00 Sulphuric Acid Conc. g/L Iron Content, 0 g/L
100 90 80 70 60 50 40 30 20 10 0

A-A

50 100 150 200 250 300

B-B

Examples: Line A-A; S.G. 1.25; Sulphuric Acid Conc. 50; Iron 85 Line B-B; S.G. 1.15; Sulphuric Acid Conc. 90; Iron 35 Iron content can also be calculated using the following equation: Iron g/L = (393.458333 x S.G.) - (0.25025 x g/L H2SO4) - 393.7375

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Appendix B - Monitoring Flux Solution

Measuring Density of Flux Solution
Density is measured in B with a hydrometer that has a range for liquids denser than water. Equipment: Thermometer Graduated Cylinder Hydrometer of suitable range Method: 1. Collect a sample of flux solution and fill the graduate cylinder to within 25mm - 30mm of the top. 2. Adjust solution temperature to 15.5 0.3C (60 1.8F). 3. Warm hydrometer to temperature of sample; dry hydrometer. 4. Immerse the hydrometer in the sample of flux solution to a point slightly below the equilibrium level and allow it to come to rest floating an equal distance from the sides of the graduate cylinder. 5. Read the hydrometer at the point where the plane of the liquid surface cuts the hydrometer stem. Recheck the solution temperature and repeat the test if the temperature has not remained within the 15.5 0.3C (60 1.8F) range. 6. Record B at 15.5C to the nearest 0.05B reading. For control purposes, measurements can be made at higher sample temperatures and adjusted as follows: Add 1B if temperature is 38 - 60C (100 - 140F) Add 2B if temperature is 61 - 82C (141 - 180F) S.G. = 145 145 - B B = 145 - (145 S.G.)

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Appendix B - Monitoring Flux Solution

Monitoring Iron in Flux Solution
Monitoring iron in flux solution involves two tests: 1) Determining if iron is present in the flux solution, and 2) Measuring the iron concentration. 1) Determining if iron is present in the flux solution 1. Collect about 100 mL of flux solution from the flux bath and add 5 mL of 35% hydrogen peroxide (H2O2) diluted 5:1 with distilled water. 2. Mix and adjust to pH 4.5 - 5.0 with ammonium hydroxide. Iron is present if the solution turns a reddish-colour. If present, iron content in the flux solution should be determined. 2) Measuring the Iron Concentration Potassium Permanganate Method: Iron in the flux solution is in the ferrous (Fe2+) state. Titration with KMnO4 is a direct method of determining iron content in flux solution. The highly coloured permanganate defines the titration end point. Oxidation of Fe2+ to Fe3+ by the permanganate ion (MnO4-) is the basis for this test: (Fe2+ + MnO4 3+ + MnO2). Fe Reagents: Potassium permanganate (KMnO4) 0.100N solution; prepared by dissolving 3.1608 g of KMnO4 crystals in distilled water and diluting to 1 L. (Hold the permanganate solution in a dark bottle and store for 24 hours before using.) Zimmerman-Reinhardt solution; prepared by mixing 67 g manganous sulphate (MnSO4.4H2O) in 700 mL distilled water. Add 56 mL of 1.83 S.G. sulphuric acid (H2SO4) reagent and 133 mL of phosphoric acid (85% meta-H3PO4). Dilute to 1 L. Equipment: 50 mL burette 250 mL Erlenmeyer flasks 10 mL pipette 50 mL graduated rubber bulb

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Appendix B - Monitoring Flux Solution

Method: 1. Pipette exactly 10 mL of sample solution into 250 mL Erlenmeyer flask using rubber aspirator bulb and add about 25 mL of distilled water. 2. Add 25 mL of Zimmerman-Reinhardt solution to flask. 3. Titrate with 0.1N KMnO4 solution to the first pink colour that persists for 20 seconds. 4. Record mL of 0.1N KMnO4 required. 5. Measure and record flux solution density and temperature. Calculation: % Iron = mL 0.1N KMnO4 used x 0.005585 x 100 mL sample x sample density(g/mL)

Controlling Iron Concentration in Flux Solution

The iron concentration in the flux solution should be maintained below 0.5% because excess iron will form additional dross. Iron concentration above 0.5% is a sign of inadequate rinsing after pickling or highly acidic flux. Filtering will remove insoluble iron from flux solution but soluble iron must be treated chemically to precipitate it before filtering. Treatment of flux solution with 35% hydrogen peroxide (H2O2) will precipitate iron as ferric hydroxide which can be separated from the flux by filtering. Alternatively, ferric oxide can be allowed to settle then be removed by suction, or the purified flux solution can be pumped into a clean holding tank.

Procedure for controlling iron in flux solution:

1. Cool flux solution. 2. Add a predetermined volume of hydrogen peroxide to the flux tank. 3. Adjust flux solution to pH 4.5 - 5.5 (ammonia can be used). Note: pH control is important since iron may not be completely precipitated at pH <4.5 and zinc may be precipitated at pH >5.5.

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Appendix B - Monitoring Flux Solution

Example: If flux tank volume Flux density Iron content Total weight of flux = 25,000 L = 1.155(kg/L) = 1.3% = tank volume (L) x density(kg/L) = 25,000 x 1.155 = 28,875 kg Weight of iron in flux = flux weight (kg) x % iron = 28,875 x 1.3/100=375 kg Weight of H2O2 = weight of iron (kg) x 1.3 = 375 x 1.3 = 487 kg

Determining Free Acid in Flux Solution

Method: 1. Collect a sample of flux solution in a 250 mL beaker. 2. Transfer 20 mL of sample to a 250 mL conical flask containing 100 mL distilled water. Mix, add 3 or 4 drops of Methyl Orange indicator solution, and mix again. 3. Titrate with 0.408N sodium carbonate (21.6 g/L) to the indicator colour change. Calculation: Acid concentration, g/100 mL= mL 0.408N sodium carbonate solution used 10

Controlling Free Acid in Flux Solution

The concentration of free acid in flux solution should not be allowed to exceed 2 g/L as it will dissolve iron from the material during fluxing. Iron salts carried into the galvanizing bath will form dross and waste zinc. Free acid in flux solution can be neutralized with ammonia or reacted with slab zinc. Clean waste zinc from around the kettle can also be used to neutralize the acid. Note: Dross should not be used to neutralize free acid since it contains about 3% iron.

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The Pipe Galvanizing Process Appendix C - Sampling Zinc Ingots

Frequently Asked Questions

ASTM specification B6 (Standard Specification for Zinc) describes methods of sampling zinc slabs. Methods of sampling slab zinc by drilling and sawing are described below:

Sampling Slabs by Drilling

Hand-held power drills and bench-mounted drills are suitable for taking samples from 25 kg slabs. Drilling is also suited to sampling small ingots and bars. ASTM B6 recommends the drill used be one twisted from flat stock. The diameter of the drill should be 12.7 mm for sampling SHG zinc and 7.9 mm diameter for sampling HG and PW grades of zinc and zinc alloys. Drilling conditions should be adjusted to give drillings approximately 0.25 to 0.50 mm thick. The drillings should be broken or cut with clean shears into pieces less than 13 mm in length and mixed thoroughly. Two holes should be drilled, preferably from the bottom or brand side of each slab at two points located along one diagonal of the slab so that each point is halfway between the centre and one extremity of the diagonal. Each hole should be drilled completely through the slab. Drilling should be carried out without the use of a coolant or lubricant.

Sampling Slabs by Sawing

Power hacksaws are best used for sampling zinc slabs of 25 kg nominal weight. ASTM B6 recommends using a heat treated high-speed steel saw blade. Two cuts should be made completely through the slab being sampled from one long-side to the other. Each cut shall be approximately halfway between the centre and each end. Sawing should be carried out without the use of a coolant or lubricant. Note: Sawing SHG zinc slabs to obtain samples is not recommended because it is difficult to remove final traces of iron accidentally picked up by the sawings during cutting.

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Appendix D - Monitoring Zinc in Galvanizing Baths

Key parameters related to the galvanizing bath should be monitored regularly to provide a reliable record of operating conditions. Recommended measurements include the following: Zinc bath temperature (measure continuously using thermocouples) Zinc bath chemical analysis (on a daily or weekly basis, as required) Grade and weight of zinc used (when materials are added) Weight of dross removed and frequency of removal (after each drossing) The types of bath samples and how each type of sample can be analyzed are described below. It is recommended that samples of molten zinc taken from galvanizing baths be chill-cast to minimize segregation of impurities and alloyed elements within the sample. Samples for determining the zinc composition are readily chill-cast in permanent molds as pin or disk-shaped castings. ASTM E 634 (Standard Practice for Sampling of Zinc and Zinc Alloys for Optical Emission Spectrometric Analysis) provides guidelines for producing these types of samples. The assaying method to be used will determine which type of sample is preferred and govern how the sample has to be prepared for analysis. Pins: Samples chill-cast as pins are best analyzed by AA or ICP . However, pins (or smaller samples taken from them) can be re-melted, homogenized, cast as disks and analyzed by OES. While this procedure is permitted, it is not recommended since it takes extra time and may introduce impurities to the sample. Disks: Samples formed as disks are designed for assaying by Optical Emission Spectrometry (OES). Disks can be assayed directly following relatively straightforward, yet important surface preparation. This involves removing the face material by means of a lathe or milling machine (rather than a grinding belt). Smaller samples can also be taken from sample disks by drilling, turning, or milling and assayed by AA or ICP .

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