CONTENTS

1. Measuring Dry Film Coating Thickness According to SSPC-PA 2 2. Cargo Tank Coatings - A Stressful Environment

3. Formulating Polyureas: History and Advances 4. Developments in Waterborne Thermal Insulation Coatings 5. Nine Coatings Projects Receive High Honors at SSPC 2013

6. Coating Concerns for New Chemical and Petroleum ASTs 7. Fluoropolymers for High- Performance Applications

8. In Situ Pipeline Coating Process Passes Saudi Desert Test 9. Preparing Concrete Floors for Coatings

10.

Innovative Coating Systems for Steel Bridges: A Review of Developments

11. 12.

Formulating Options for Polysiloxanes Developments in Zinc Primers for Corrosion Protection

13.

Is Lead Dead? A Look Back and a Look Forward at 20 Years Of

14. 15. 16.

Bridge Painting Under the OSHA Lead in Final Rule and Other Related Standards Exploring Marine Applications for Heat-Reflective Coatings

Measuring Dry Film Coating Thickness According to SSPC-PA 2

From JPCL, April 2013
William D. Corbett PCS, KTA-Tator, Inc. Bill Corbett is the Vice President and Professional Services Group Manager for KTATator, Inc., where he has been employed for 33 years. He chairs SSPC committees C.3.2 on Dry Film Thickness and C.6 (Education). He is an SSPC-approved instructor for four SSPC courses, and he holds SSPC certifications as a Protective Coatings Specialist, Protective Coatings Inspector (Level 3), and Bridge Coatings Inspector (Level 2). He is also a NACE Level 3-certified Coatings Inspector. He was the co-recipient of the SSPC 1992 Outstanding Publication Award, corecipient of the 2001 JPCL Editors Award, recipient of SSPCs 2006 Coatings Education Award, and recipient of SSPCs 2011 John D. Keane

William D. Corbett PCS, KTATator, Inc.

Award of Merit.

Coating thickness shall be measured in accordance with SSPC: The Society for Protective Coatings Paint Application Standard No. 2 (SSPC-PA 2) is a simple enough statement, yet this common specification requirement is often misinterpreted or regarded as a document that simply states how to measure the dry film thickness (DFT) of coatings, something we already profess to know how to do. Yet the requirements of SSPC-PA 2 regarding gage calibration, verification of gage accuracy and adjustment procedures, the number of measurements to obtain, and the tolerance of the measurements are complex and should be fully understood by the specification writer before invoking PA 2 in a contract.

iStock On more than one occasion, I have heard the question, When did SSPC-PA 2 and dry film thickness measurement become so complicated? In fact, when you take a close look, measuring DFT isnt that complex. We have allowed it to become more technologically complex while making the data easier to analyze. We can gather hundreds of gage readings in a relatively short time; batch the measurements; print the data or upload it to a computer for graphing; report the highest, the lowest, the mean, and standard deviation of the collected data; incorporate digital images of the structure or coated area; and even program the gage to produce an audible signal if a spot measurement is outside of the tolerance range. I am no doubt leaving out other bells and whistles, but my point is that while we are able to do a lot with the readings obtained, measuring DFT involves four or five basic steps.

Step 1: Instrument Calibration Step 2: Verification of Gage Accuracy on Certified Coated Standards or Certified Shims Step 3: Base Metal Reading Acquisition or Gage Adjustment (using certified or measured shims) Step 4: Measurement of Coating Thickness Step 5: Correction for Base Metal Reading (if acquired).

After a brief review of the history of SSPC-PA 2, this article will describe each of the five steps, based on the 2012 edition of SSPC-PA 2. Special attention will be

given in the article to how PA 2 addresses the required number of coating thickness measurements; the acceptability of gage readings, spot measurements, and area measurements; nonconforming thickness; measuring DFT on coated edges; and measuring DFT on pipe exteriors. Some History SSPC-PA 2 was originally published as a temporary standard 40 years ago in 1973 (73T) as Measurement of Dry Coating Thickness with Magnetic Gages. The standard referenced gages like the one shown in Fig. 1, which are now all but obsolete. The standard has been updated on multiple occasions. Until 2012, the most recent technical changes were published in May 2004, with a minor editorial revision in 2009 to one of the appendices (regarding measurements on test panels). The SSPC Committee on Dry Film Thickness Measurement began revising and updating the 2004 version in 2007. The revisions took five years to complete. The latest edition of the standard (Procedure for Determining Conformance to Dry Coating Thickness Requirements) is dated May 2012 and was made available to the industry in July 2012.

Fig. 1: One type of magnetic gage referenced in original SSPC-PA 2 for measuring dft Figures courtesy of the author except where otherwise indicated In nearly the same timeframe, the 2005 version of ASTM D7091, Standard Practice for Nondestructive Measurement of Dry Film Thickness of Nonmagnetic Coatings Applied to Ferrous Metals and Nonmagnetic, Nonconductive Coatings Applied to NonFerrous Metals was being revised and updated. It, too, was published in 2012. The most current version of the ASTM standard focuses on proper gage use, while SSPC-PA 2 focuses primarily on the frequency of measurements and the acceptability of the acquired measurements. References to the frequency of measurements were removed from the ASTM standard. The two documents are designed to be used together. It is important to note that both documents address the measurement of the DFT of coatings on ferrous and non-ferrous metal substrates. Before 2012, SSPC-PA 2 addressed

measurement of coatings only on steel, a ferrous metal. (The sidebar on p. 32 in this article summarizes the key changes made to PA 2 in 2012.) Summary of Changes to SSPC-PA 2: 2004 Version and 2012 Version 2004 Measurement of Dry Coating Thickness with Magnetic Gages Addressed measurement of coatings on steel only No referenced standards section Definitions section included Calibration; Verification; Adjustment; Coating Thickness Standard; Shim (foil); Dry Film Thickness Reference Standard; Accuracy; Structure. No. of Area Measurements based on the size of the structure Isolation of nonconforming areas required measurement of each 100 square foot area painted during the work shift. Recommended specifying minimum & maximum thickness range; if no range was specified, thickness value was considered minimum (with no maximum) 2012 Procedure for Determining Conformance to Dry Coating Thickness Requirements Addresses measurement of coatings on ferrous and non-ferrous metal surfaces ASTM D7091 and SSPC Guide 11 included by reference Definitions section includes Gage Reading, Spot Measurement and Area Measurement only. All definitions related to gage calibration, accuracy and adjustment are incorporated by reference in ASTM D7091. Spot measurement definition was expanded. No. of Area Measurements based on the size of the area of coated surface The magnitude of nonconforming thickness assessed by obtaining spot measurements in eight equally spaced directions radiating outward from the nonconforming area If a single value is specified and the coating manufacturer does not recommend a range, the minimum and maximum thickness range is established at 20% of the stated value

Contained a minimum gage No minimum gage accuracy requirement accuracy requirement to qualify for to qualify for use use Conformance to Specified Thickness: Gage Readings: Unrestricted Conformance to Specified Thickness: Five different Coating Thickness Restriction Levels established. If no

Spot Measurements: 20% of specified range Area Measurements: Per Specification Notes section contained principles of gage operation and various substrate/surface conditions that may affect measurements; overcoating; and correcting for low/high thickness. Contained 6 appendices

Restriction Level is specified, default is based on 2004 conformance requirement.

Notes section includes Overcoating and Correcting for Low/High Thickness only ASTM D7091 describes principles of gage operation and various substrate/surface conditions that may affect measurements. Contains 8 appendices. Six appendices from 2004 version included. Added two: Method for Measuring DFT of Coating on Edges

Method for Measuring DFT of Coated Steel Pipe Exterior

Gage Types SSPC-PA 2 addresses two types of DFT gages, both of which are supplied by a variety of manufacturers. Magnetic pull-off gages are categorized as Type 1 (Fig. 2).

Fig. 2: Example of magnetic DFT gage categorized as Type 1 in SSPC-PA 2 These gages were designed in the 1950s. While their use has declined, they are

still readily available and used by some. For these gages, a permanent magnet is brought into direct contact with the coated surface. The force necessary to pull the magnet from the surface is measured and converted to coating thickness, which is displayed on a scale on the gage. The operating principle is simple. Less force is required to remove the magnet from a thick coating, while more force is required to remove the magnet from a thinner one. The scale is not linear, as will be discussed below. Electronic gages are categorized as Type 2 (Fig. 3). These gages use electronic circuitry to convert a reference signal into coating thickness and are more popular than Type 1 gages. They are typically regarded to be faster, more accurate, and easier to use.

Fig. 3: Example of electronic DFT gage categorized as Type 2 in SSPC-PA 2 Gage Calibration, Accuracy Verification, and Adjustment To help assure the reliability of the coating thickness measurements, ASTM D 7091 describes three operational steps that must be performed before taking the measurements. These steps are (1) gage calibration, (2) verification of gage accuracy and (3) gage adjustment. The steps are incorporated by reference in SSPCPA 2 and are completed before obtaining coating thickness measurements to determine conformance to a specified coating thickness range. The steps to verify the accuracy of the gage are based on the principle that you check the

gage by measuring a known thickness before you use the same gage to measure an unknown thickness.Verification of gage accuracy is typically performed using certified coated thickness standards (for Type 1 or Type 2 gages) or certified shims (Type 2 gages). Adjustment of Type 2 gages to compensate for substrate characteristics (described later) is typically performed using certified shims. Measured shims (individually labeled with a stated thickness value) commonly supplied with Type 2 gages can also be used for gage adjustment. Dry film thickness gages are calibrated by the equipment manufacturer, its authorized agent, or an accredited calibration laboratory (under controlled conditions). A test certificate or other documentation showing traceability to a national metrology institution is required. While there is no standard time interval for re-calibration, an interval can be established based on experience, the work environment, and/or the internal equipment calibration procedures of the company using the gage. A one-year calibration interval is a typical starting point suggested by gage manufacturers. Verifying Gage Accuracy To guard against measuring with an inaccurate gage, SSPC-PA 2 requires that gage accuracy be verified (at a minimum) at the beginning and end of each work shift according to the procedures described in ASTM D 7091. If a large number of measurements are being obtained, the user may opt to verify gage accuracy during measurement acquisition (for example, hourly). If the gage is dropped or suspected of giving erroneous readings during the work shift, its accuracy should be rechecked. Verifying the Accuracy of Type 1 Gages The accuracy of Type 1 (magnetic pull-off) gages is verified by placing the gage probe onto a certified coated thickness standard (Figs. 4 and 5). A one-point or two-point accuracy verification procedure can be performed; typically, the twopoint verification provides greater accuracy. If a one-point verification procedure is adopted, the coated standard should be selected based on the intended range of use. For example, if the intended use is between 4 and 6 mils, then a five-mil coated standard is appropriate. Using the same example, if a twopoint verification procedure is adopted, then a two-mil and an eight-mil set of coated standards (slightly below and above the intended range of use) is appropriate.

Fig. 4: (top) and 5 (bottom) Verifying the accuracy of Type 1 gages using certified coated thickness standards The final step in the process is to obtain a set of base metal readings (BMRs) to compensate for substrate characteristics including (but not limited to) substrate metallurgy, geometry, thickness/thinness, and roughness (Fig. 6). These readings represent the effect of the substrate conditions on the coating thickness measurement device. SSPC-PA 2 states that a minimum of 10 (arbitrarily spaced) locations should be measured (one reading per location) and then averaged. This average BMR is then deducted from subsequent coating thickness measurements to remove any effect of the base metal surface and its conditions.

Fig. 6: Obtaining base metal readings with Type 1 gage Because Type 1 gages cannot be adjusted, some gage operators believed that a correction value could be applied to the coating thickness readings to compensate for the inaccuracy of the gage. For example, if a gage reading was 5.7 mils on a five-mil coated standard, a 0.7-mil correction value could be deducted (by the gage operator) from subsequent coating thickness measurements. However, because Type 1 gages are non-linear, one cannot assume a linear (mil-for-mil) correction value across the full range of the gage. While the gage may be out of tolerance by 0.7 mils at 5 mils, it may be out of tolerance by more or less than 0.7 mils at a different thickness. Accordingly, SSPC-PA 2 states that the practice of using a linear correction value is not appropriate. However, Note 6 in the standard states, A correction curve can be prepared by plotting the actual gage readings against the stated values on the (coated) test blocks (standards). Subsequent coating thickness measurements can be corrected by plotting the measurements along the correction curve. The correction curve may or may not cover the full range of the gage, but should cover the intended range of use. The Base Metal Readings (BMR) described in 6.1 may also need to be plotted on the correction curve. This requirement makes Type 1 gages very difficult to use. While some gage operators may simply subtract a fixed amount (for example, 0.5 mils) from any reading, such a practice is not in compliance with SSPC-PA 2. Verifying the Accuracy of Type 2 Gages The accuracy of Type 2 (electronic) gages can be verified by placing the gage probe onto a certified coated thickness standard (described for Type 1 gages) or certified shims (Figs. 7 and8). The certified shim should be placed onto a smooth, uncoated metal surface to remove any effect of the surface roughness during this process. A one-point or two-point accuracy verification procedure

can be performed (as described earlier for Type 1 gages).

Fig. 7: Verifying accuracy of Type 2 gage on a certified coated standard

Fig. 8: Verifying accuracy of Type 2 gage using a certified shim Adjusting Type 2 Gages The final step in the process is to adjust the gage on the surface to which the coating will be applied. Adjustment is accomplished by placing a certified or measured shim (or shims) onto the prepared, uncoated metal surface and adjusting the gage (when feasible) to compensate for substrate characteristics including (but not limited to) substrate metallurgy, geometry, thickness/thinness, and roughness (Fig. 9). The gage reading is adjusted to

match the thickness of the shim, which effectively removes any influence from the underlying surface.

Fig. 9: Adjusting Type 2 gage using a measured shim on the surface to which the coating will be applied This step sounds reasonably straightforward but poses several hidden challenges. First, once the surface is coated (for example, with a primer), an uncoated surface may no longer be available for subsequent gage adjustments, so the user may want to have a similar uncoated surface prepared and reserved for future gage adjustments on a given project. Naturally, this surface must be representative of the metallurgy, geometry, thickness/thinness, and roughness of the actual surface, which can be a challenging requirement. Second, some Type 2 gages cannot be adjusted. In such cases, the user will need to obtain BMRs from the prepared, uncoated substrate (described earlier for Type 1 gages). While many Type 2 (electronic) gages have a zero-set function, the gages should never be adjusted to zero unless the surface is smooth. Required Number of Coating Thickness Measurements The section of SSPC-PA 2, Required Number of Measurements for Conformance to a Thickness Specification, causes many users confusion, which can result in either under- or over-inspection. Arguably the most critical section in the document, Section 8, describes how many areas to check, the size of the areas, the number of measurements to obtain in each area, and the steps

to take if spot or area measurements do not conform to the specification. SSPC-PA 2 contains three definitions that are critical to understanding this next area of discussion.

Gage Reading: A single instrument reading. Spot Measurement: The average of at least three gage readings made within a 4-cm (1.5-inch) diameter circle. Acquisition of more than three gage readings within a spot is permitted. Any unusually high or low gage readings that are not repeated consistently are discarded. The average of the acceptable gage readings is the spot measurement. Area Measurement: The average of five spot measurements obtained over each 10 m2(100 ft2) of coated surface, or increment (portion) thereof.

An area is defined as approximately 100 square feet. Within each area, five randomly spaced spots are selected. Each spot consists of a 1.5-inch diameter circle. A minimum of three gage readings is obtained in each spot, culminating in a minimum of 15 gage readings within an area. Unusually high or low gage readings that cannot be repeated consistently are discarded. The average of the three acceptable gage readings is the spot measurement; the average of five spot measurements is the area measurement. Figure 10, from Appendix 1 in SSPC-PA 2, depicts an approximate 100-square-foot area containing gage readings and spot measurements.

Fig. 10: Approximate 100-square-foot area containing gage

readings and spot measurements, as depicted in Appendix 1 of SSPC-PA 2. Courtesy of SSPC The number of areas that must be measured for coating thickness varies, depending on the size of the coated area. There are three categories of coated area: less than 300 square feet; 300 to 1,000 square feet; and greater than 1,000 square feet. For areas containing less than 300 square feet of coated surface, every 100-square-foot area must be measured for coating thickness. For areas of coating 300 to 1,000 square feet, three random areas are selected and measured. For areas of coating exceeding 1,000 square feet, three random areas are selected from the first 1,000 square feet, along with one additional area for each additional 1,000 square feet. Because areas of coating often exceed 1,000 square feet, our example will be based on this third tier (>1,000 square feet). Lets assume that the total coated area (perhaps the area coated during a work shift, although SSPC-PA 2 does not equate coated area with work shift) is 12,500 square feet. A total of 15 areas must be measured (three in the first 1,000 square feet and one additional area in each of the 12 remaining 1,000-square-foot areas or portions thereof). This culminates in a total of 75 spot measurements (15 x 5) and a minimum of 225 gage readings (15 x 5 x 3). If spot measurement variances result in area measurements that do not meet the specification, then additional spot measurements are acquired (radiating outward in eight directions from the nonconforming area) to determine the magnitude of the non-conforming thickness. This process is described later in this article. Acceptability of Gage Readings, Spot Measurements, and Area Measurements While individual gage readings that are unusually high or low (and cannot be repeated consistently) can be discarded, there are limitations on the thickness values representing the spot measurements (the average of three gage readings). A minimum thickness and a maximum thickness are normally specified for each layer of coating. However, if a single thickness value is specified and the coating manufacturer does not provide a recommended range of thickness, then the minimum thickness and maximum thickness for each coating layer are established by SSPC-PA 2 at 20% of the stated value. For example, if the specification requires 3 mils DFT and the coating manufacturer does not provide any additional information regarding a recommended thickness range, then, by default, the specified range is established as 2.4 3.6 mils. Because the coating may not perform at the lower thickness, it is important for the specifier to indicate an acceptable range for each coating layer. To assist the specifier, the 2012 edition of SSPC-PA 2 incorporates a Restriction Level Table (Fig. 11). The Table enables the specifier to select from five different restriction levels related to spot and area measurements.

Fig. 11: Coating Thickness Restriction Levels (as shown in Table 1 of SSPC-PA 2, Section 9) Courtesy of SSPC Level 1 is the most restrictive and does not allow for any deviation of spot or area measurements from the specified minimum and maximum thickness, while Level 5 is the least restrictive. Depending on the coating type and the prevailing service environment, the specifier can select the DFT restriction level for a given project. The specifier may also invoke a maximum thickness threshold for Level 5 Spot or Area Measurements for a generic product type and/or service environment that will not tolerate an unlimited thickness. If no Restriction Level is specified, then the default is Level 3, which is based on the 2004 version of SSPC-PA 2 (what many users of the standard have become accustomed to). For the purpose of final acceptance of the total DFT, the cumulative thickness of all coating layers in each area must be no less than the cumulative minimum specified thickness and no greater than the cumulative maximum specified thickness. For example, assume that the specification requires a four- to six-mil application of primer. The actual minimum and maximum spot and area thickness requirements are shown in Fig. 12 for each of the five restriction levels.

Fig. 12: Coating Thickness Restriction Levels Based on a Four-toSix-Mil Requirement Derived using the 2012 edition of SSPC-PA 2, Table 1, Coating Thickness Restriction Levels Determining the Magnitude of Nonconforming Thickness Another change in the 2012 version of the standard is the procedure for identifying nonconforming areas (Fig. 13). In the 2004 edition, if spot or area measurements were out of conformance, each 100-square-foot area coated during the work shift had to be measured, and nonconforming areas had to be demarcated. On a larger structure with multiple applicators, the measurement and documentation process could be extensive, so the approach was changed in the 2012 revision. If a nonconforming area is identified, spot measurements are made at five-foot intervals in eight equally spaced directions radiating outward from the nonconforming area, as shown in Fig. 13.

Fig. 13: Depiction of procedure for identifying nonconforming areas, as described in the 2012 edition of SSPC-PA 2. Courtesy of SSPC If there is no place to measure in a given direction, then no measurement in that direction is necessary. Spot measurements are obtained in each direction (up to the maximum surface area coated during the work shift) until two consecutive conforming spot measurements are acquired in that direction, or until no additional measurements can be made. Acceptable spot measurements are defined by the minimum and maximum values in the contract documents. No allowance is made for variant spot measurements (for example, 20%), which is consistent with the practice followed when determining the area DFT. On complex structures or in other cases where making spot measurements at five-foot intervals is not practical, spot measurements are taken on repeating structural units or elements of structural units. This method is used when the largest dimension of the unit is less than 10 feet. Spot measurements are obtained on repeating structural units or elements of structural units until two consecutive units in each direction are conforming or until there are no more units to test. Non-compliant areas are demarcated using removable chalk (or another specified marking material) and documented. All of the area within five feet of any non-compliant spot measurement is considered non-compliant. For a given measurement direction or unit measurement, any compliant area or unit

preceding a non-compliant area or unit is designated as suspect, and, as such, is subject to re-inspection after corrective measures are taken. Appendices to the Standard There are eight appendices in the 2012 version of SSPC-PA 2. Two of the eight appendices were added in 2012 (the remaining were in the 2004 edition) and are highlighted below. The appendices to SSPC-PA 2 are not mandatory but may be invoked by contract documents. Appendix 6: Method for Measuring the Dry Film Thickness of Coatings on Edges For decades, the industry was cautioned about taking coating thickness measurements within one inch of an edge, let alone on an edge. However, several Type 2 (electronic) gage manufacturers offer a variety of probe configurations, some of which are less affected by proximity to edges and are designed to better measure the thickness of coatings on edges (Fig. 14). Obviously, the gage operator should consult the gage manufacturers instructions before measuring coating thickness on edges.

Fig. 14: One of a variety of Type 2 gage probe configurations designed to better measure DFT of coatings on edges Before measuring coating thickness on edges, the user should verify the gage and probe for accuracy by placing a thin, flexible shim (certified or measured) onto the prepared, uncoated edge. Adjustments to the gage may or may not be required. This procedure also verifies that the probe configuration will accommodate the edge configuration before acquiring coating thickness data. Once verification of accuracy and adjustments are made, a minimum of three gage readings are taken within 1.5 linear inches of coated edge. The average of the gage readings is considered a spot measurement. The number of spot measurements along the edge will vary, depending on the total length of the coated edge.

Appendix 7: Method for Measuring Dry Film Thickness on Coated Steel Pipe Exterior Appendix 7 was added to accommodate pipe coaters that need to determine coating thickness conformance on non-flat (or non-plate) areas, including smaller pipe sections on a cart or rack and longer pipe spools. Pipe sections loaded onto a cart or rack can be considered a complete unit (Fig. 15). The total number of spot and area measurements is based on the total square footage of pipe on the cart or rack. The square footage is calculated as shown on p. 35.

Fig. 15: (top and bottom): Appendix 7 of the 2012 edition of SSPC-PA 2 describes a

method for measuring DFT on non-flat steel, such as pipe sections that can be loaded on racks or carts. Photos courtesy of Turner Industries Group, L.L.C. Some carts may have several small pipe sections, and the total coated surface may exceed 100 square feet. In this case, a Pipe DFT Frequency Factor shown below may be invoked.

Pipe DFT Frequency Factor 2 = (length of each pipe x circumference) x number of pipe sections on cart or rack = (number of spot measurements) x2 Pipe DFT Frequency Factor 3 = (length of each pipe x circumference) x number of pipe sections on cart or rack = (number of spot measurements) x3 Pipe DFT Frequency Factor 4 = (length of each pipe x circumference) x number of pipe sections on cart or rack = (number of spot measurements) x4 Pipe DFT Frequency Factor 5 = (length of each pipe x circumference) x number of pipe sections on cart or rack = (number of spot measurements) x5 Pipe DFT Frequency Factor 6 = (length of each pipe x circumference) x number of pipe sections on cart or rack = (number of spot measurements) x6

Based on the example above, if Pipe DFT Frequency Factor 4 was invoked, 20 spot measurements would be taken (5 spots x Frequency Factor 4) Pipe spools that are not loaded onto a rack or cart are typically measured individually (Fig. 16). The number and locations of spot measurements are based on Appendix 7s Table A7 (Fig. 17). Three sets of four circumferential spot measurements should be obtained on pipe spools less than 10 feet in length.

Fig. 16: DFT of pipe spools not loaded on cart or rack are typically measured individually.

Fig. 17: Number and Locations of Spot MeasurementsPipe Spools (Table A7 from 2012 edition of SSPC-PA 2, Appendix 7) Courtesy of SSPC Conclusion SSPC-PA 2 has undergone significant changes in an attempt to make it more complete; more in concert with ASTM D7091; easier to use in the shop and field; and more flexible in providing the specifier with options for coating thickness restrictions based on the type of structure, the coatings to be applied, and the service environment. SSPC-PA 2 and ASTM D7091 are both undergoing additional technical and editorial changes to bring them into even greater alignment with one another.

Get the Latest Standards on Dry Film Thickness of Coatings The 2012 edition of SSPC-PA 2, Procedure for Determining Conformance to Dry Coating Thickness Requirements, is available from the SSPC: The Society for Protective Coatings through sspc.org, under the Standards tab at the top of the home page. The 2012 edition of ASTM D7091, Standard Practice for Nondestructive Measurement of Dry Film Thickness of Nonmagnetic Coatings Applied to Ferrous Metals and Nonmagnetic, Nonconductive Coatings Applied to NonFerrous Metals, is available from ASTM International through astm.org under the Standards at the top of the navigation bar on the site. Change is never easy. Communicating the new requirements of this standard to the industry is challenging but essential. One conduit is through training and education. For example, SSPC offers a short course, Using SSPC-PA 2 Effectively, that was recently updated to reflect changes made to the standard. Free webinars are available through SSPC/JPCL for those who cannot participate in instructor-led training. Updates to SSPC and other industryprovided inspector training and certification courses (and the associated instructor education) will be critical to fully understanding and effectively communicating the requirements of this highly regarded industry standard.
THE JOURNAL OF PROTECTIVE COATINGS & LININGS 2013 Technology Publishing Company

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Cargo Tank Coatings - A Stressful Environment

From JPCL, March 2013
Trevor Parry Coating Consultant Trevor Parry, CSci, CChem, FRSC, MICorr., is an independent coatings consultant who recently retired from full-time work after over 40 years in the industry. A chemist by training, Parry worked for Scientific and Technical Services Ltd. from 1971-2010, eventually becoming Technical Director and owner of the company. He has been a key figure in both domestic and international standardization work, as well as a leader in investigating and solving marine coating problems and Trevor Parry failures. Parry now works with clients (mainly marine) on a selective basis, evaluating coating failures and providing advice. He is a recipient of JPCLs Top Thinker: The Clive Hare Honors 2012 award, and a JPCL Editors Award winner. Bill Woods Marinspec Associates Ltd. Bill Woods is a co-founder and associate at MarinSpec Associates, Ltd., a consulting group in the U.K. that specializes in the cleaning and coating of cargo tanks. Involved in the development of marine and cargo tank coatings since 1964, Woods served as General Technical Manager at Camrex Chugoku Ltd.; European Business Development Manager for Newbuildings at Courtalds Coatings (now International Paints); Marine Coatings Consultant at Milbros Shipping AS; and an Bill Woods independent consultant, before forming MarinSpec in 2003. Woods is also a former chair of the British Coatings Federation and a founding member of the Marine Coatings Forum.

iStock Marine cargo tank coatings come under a variety of stresses during their service lifetime. If the stresses are not considered at the design and development stages, they can lead to premature failure and costly replacement. This article identifies these stresses and considers how they relate to coating failure. Illustrations of typical coating failures are also included. Cargo Tank Coatings Cargo tank coatings (CTCs) come in a number of generic types, such as alkali zinc silicate, ethyl zinc silicate, epoxy novolac (phenolic), epoxy amine, epoxy amine adduct, and polyurethane. All currently available CTCs can be divided into two broad classifications: organic and inorganic. Alkali zinc silicates (water-borne zinc silicates) and ethyl zinc silicates (solvent-borne zinc silicates) are both completely inorganic after application and curing. All the other CTCs are organic when applied, and remain so when fully cured. This distinction is simple but important because both classes behave differently when subjected to different stresses. To understand more clearly how stresses can affect coatings, coatings specifiers and end users need to understand the fundamental differences in morphology and curing mechanisms of inorganic and organic CTCs. Inorganic Zinc Silicates Waterborne (alkali) zinc silicates cure initially by the evaporation of water from the wet film into the surrounding atmosphere. Solvent-borne (alkyl) zinc silicates cure initially by absorbing water from the surrounding atmosphere into the film. Although the actual curing mechanisms are complex and different, the end result in both cases is the formation of a cross linked, three-dimensional matrix of zincoxygen-silica. General industry consensus is that at the steel surface, the hydrated zinc-silica matrix reacts with ferrous ions, and the reaction creates a chemical bond to the steel. The bond provides the coating with a high level of adhesion and high resistance to undercutting. High concentrations of metallic zinc dust, above the CPVC (Critical Pigment Volume Concentration), are used in the formulations to achieve adequate film formation. Hence, the zinc particles are not fully coated with binder, and the voids between the particles are not fully filled with binder. The resulting film is porous. At this stage in the film formation, in the places where there is no binder, there is contact among the zinc particles themselves as well as between the zinc particles and the steel surface. This contact ensures good corrosion prevention properties, which are initially galvanic. Then, another set of reactions occurs, this time involving moisture and carbon dioxide from the atmosphere. The porosity decreases over time because of these reactions in the matrix. They form zinc corrosion products that plug the pores, making the film denser and less permeable. At this point, the corrosion protection mechanism becomes

increasingly barrier in nature. Organic Cargo Tank Coatings By contrast, organic CTCs are bound together much differently. All the particles of pigment and extenders in these dry films are completely encapsulated by the binding resin(s). To facilitate spray application, which is the most commonlyused method, organic solvents are usually needed to reduce the viscosity. Other additives are included in the formulation to improve properties such as storage stability and sag resistance. No reaction occurs between the binding resin(s) and the pigments. Adhesion to the steel surface, unlike adhesion of zinc silicates, is considered to be predominantly mechanical. The stresses that may occur during the lifetime of a CTC are listed below and discussed in the order in which they are likely to occur. 1. Drying and initial curing stresses 2. Post-curing stresses 3. Operational stresses
o o o o o o

Cargo cycling Cargo absorption and desorption Cargo interaction Tank cleaning Water absorption and desorption Temperature changes

Drying and Initial Curing Stresses When they cure, both waterborne (alkali) and solventborne (alkyl) zinc silicates form rigid networks. Application of overly thick films creates stresses in the film that cause it to crack. The cracking resembles the appearance of a dried up riverbed, hence the commonly used term, mudcracking (Fig. 1). The margin of error between satisfactory and excessive thickness is quite small. Applicators must be careful to avoid excessive film thickness. If mudcracking does occur, the only solution is re-blasting the surface to completely remove the paint and reapply ita time-consuming and expensive remedial measure. (It should be noted that a few centimeters of cracks at fillet welds are fairly common and would not in practice require re-blasting.)

Fig. 1: Mudcracking Figures courtesy of the authors By contrast, organic coatings have much more forgiving application characteristics. For some systems, individual layers can be applied at more than twice the thickness that is specified without showing any immediate visible problems. Indeed, many manufacturers allow for the extra thickness in their coating specifications. Internal stress at this early stage is primarily related to evaporation of solvents and other volatile additives, followed by shrinkage during the curing reaction. Even if areas of unacceptably high thickness are identified in individual coats of the system, the excess coating thickness can be removed by local treatment of the affected area without resorting to total re-blasting. Post-Curing Stresses Most zinc silicate coatings do not need to be post-cured after application and initial curing. All that is required is to ensure that the coating is washed with either fresh or salt water (according to the manufacturers requirements), and the coating is ready for full operational use. However, the same is not the case for organic CTCs. Generally, a post-curing operation is required for coating systems on chemical tankers. And for many organic coatings, such a process is mandatory if the full chemical resistance of the coating is to be realized. Organic CTCs used in the transport of less aggressive cargoes such as clean petroleum products (CPPs) are not and cannot be post-cured, so they are resistant to fewer cargoes. Post-curing involves raising the temperature of the coating to a specified level and maintaining that temperature for a specified time. The temperature can be as high as 90 C or as low as 50 C, and the time can be as long as 14 days or as short as 3 hours, depending on the coating and the manufacturer. The process removes residual solvent, enabling and driving further chemical reactions in the coating. These reactions lead to further cross-linking and shrinkage. The result is a coating that is highly cross-linked, very chemical resistant, but very rigid, and can be highly stressed.

To achieve a satisfactory post-cure, coatings applicators have tried many methods, such as

hot air circulation; circulation/stowage of hot fresh water, or salt water; and circulation/stowage of a suitable hot cargo.

All of the above methods have met with varying degrees of success or failure. The inherent difficulty in all of these methods is ensuring that all coated surfaces reach the specified temperature for the specified time. Steel temperatures can be recorded with thermocouples, connected to data loggers placed in adjacent ballast or cargo tanks. Due to the impracticality of recording the temperature on all areas in a tank, a degree of uncertainty would remain. There are means by which the state of cure of a CTC on a vessel can be measured using samples of the coating taken from panels placed in the tanks at the time of coating application and subsequent post-curing. Even this approach does not guarantee that all areas have reached the same degree of cure. Other considerations should also be taken into account, such as the overly thick areas mentioned earlier. How do these areas behave under such post-curing regimes? Figures 2, 3 and 4 illustrate some typical locations where thick paint films are likely and what may happen to them during or after post curing operations. We should also be concerned about other locations on the vessel. For example, what effect does post-curing of the CTCs have on coatings in adjacent ballast tanks (side tanks, and double bottoms) and on the main deck? All of the coatings in these locations will also be placed under considerable stress during the postcuring operation.

Figs. 24 (left to right): Potential crack locations Operational Stresses Operational stresses are created during the normal operation of the vessel. These stresses are described below. Impact of Cargoes, Cargo Resistance, and Cargo Cycling The resistance of a CTC to a cargo is related to chemical compatibility, which is the interaction or lack of interaction between the CTC and the cargo.

Because of their inorganic nature and inertness to many neutral cargoes, zinc silicate coatings tend to display excellent resistance to organic cargoes. Included among these cargoes are many low molecular weight and aggressive products such as methanol, and chlorinated hydrocarbons such as ethylene dichloride (EDC). However, zinc silicate coatings have the inherent problem of containing zinc, which is a reactive amphoteric metal. Therefore, it is not resistant to acidic or alkaline cargoes outside a pH range of 5.5 to 10 (depending on cargo and coating supplier). With organic coatings, the binder can be chemically attacked by incompatible or unsuitable cargoes, such as palm fatty acid distillate (PFAD) and other vegetable acid oils in a pure epoxy-coated cargo tank. (Cargo compatibility varies among different manufacturers products, and the cargo resistance list should be consulted.) Chemical attack (by PFAD and vegetable acid oils) usually results in detachment of the paint film, and, more often than not, will be accompanied by severe wrinkling of the detached film. Figures 5 and 6 illustrate these typical symptoms.

Figs. 5 (top) and 6: Poor resistance to cargo Absorption and Desorption of Cargoes Inorganic zinc coatings freely absorb and release many volatile cargoes without showing any signs of swelling or contraction. This characteristic is due to their inorganic nature and their initial open porous structure. Unfortunately, they will absorb oil-like cargoes also, which do not desorb easily, resulting in potential

cleaning and contamination issues. Organic coatings are different. Even though an organic coating may be classified as resistant to a particular cargo, the coating may still absorb a certain amount of the cargo, depending on the its nature, its length of stowage, and the stowage temperature. The absorption and desorption process can result in softening and a degree of, but not necessarily full, recovery of the paint film, which is clearly a stressful and potentially damaging condition. This cycle of absorption and desorption can also result in cargo interaction and subsequent cargo contamination if not managed properly. Figure 7 shows the varying absorption/desorption profiles of four coatings of the same generic type during the stowage and after unloading of an absorbing cargo (EDC). This difference in absorption, desorption and retention properties also occurs, often to a greater extent, in other generic types of organic CTCs.

Fig. 7: Absorption, desorption, and retention properties of four phenolic epoxies Table 1 illustrates the increase in dry film thickness of various types of CTCs at maximum absorption of a range of cargoes. Different generic types of coating absorb the same cargoes to different degrees. The degree if absorption is reflected in the swelling of the coating, detectable by an increase in film thickness.
TABLE 1

Increase in Paint Film Thickness at Maximum Absorption Average % increase in Thickness

Cargo name

Coating

Benzene Benzene Benzene Xylene Xylene Xylene Styrene Styrene Styrene Butyl Acetate Butyl Acetate Butyl Acetate Methyl Isobutyl Ketone Methyl Isobutyl Ketone Methyl Isobutyl Ketone Vinyl Acetate Monomer Vinyl Acetate Monomer Vinyl Acetate Monomer

1 2 3 1 2 3 1 2 3 1 2 3 1 2 3 1 2 3

12.5 11.2 5.2 17.2 11.2 3.8 16.6 10.6 2.7 16.75 12.5 1.5 14.75 8.5 1.5 14.9 9.3 12.7

Coating 1 Polyurethane; Coating 2 Epoxy Isocyanate; Coating 3 Epoxy Phenolic Cargo Interaction Many cargoes may be carried without affecting the coating, even though the cargo may have been absorbed to some extent. If one cargo is followed by a different cargo that is acceptable for the existing coating and is also absorbed, the cargoes have the potential to react with each other to produce a harmful environment within or behind the coating. A typical example would be the reaction of an absorbed halogenated cargo or an ester cargo with a subsequent water-based cargo or with water from a tank cleaning operation. The consequence of these reactions is usually blistering of the coating, which will be followed eventually by cracking and detachment of the blisters (Figs. 8 and 9).

Fig. 8: Unbroken blisters

Fig. 9: Cracked/detached blisters Tank Cleaning Tank cleaning in all its forms has the potential to place significant stress on the CTC, particularly when cleaning temperatures are as high as 85 C. For inorganic zinc silicate coatings, the cleaning chemicals must not be too acidic or alkaline, particularly if they are to be used neat or in a concentrated solution for spot cleaning. Zinc silicates are generally unaffected by hot or cold water washing in the short term, although dissolution of zinc does occur over time, with the rate depending on the frequency of the operation and the operation itself. Organic coatings are again different. They are generally satisfactory for shortterm contact with both acidic and alkaline concentrated cleaning chemicals used for spot cleaning at ambient temperatures. But compared to zinc silicates, organic CTCs are more affected by regular hot tank cleaning episodes. Organic CTCs absorb water, some CTCs more than others, and this absorption creates internal stresses in the paint film. It is also accepted that fresh water tends to be

absorbed more quickly than seawater. Figure 10 shows the varying water absorption and desorption characteristics of three coating systems of the same generic type. It is of interest to see that one of the coatings (green) continues to absorb water after two of them (blue and red) have reached equilibrium in longterm exposure. Note, however, how quickly all the coatings absorb water during the early stages of exposure, as would be the case in tank cleaning operations.

Fig. 10: Water absorption/desorption of three generic pure epoxy coatings Temperature Changes Temperature changes impose stress on the coating system and influence the absorption and desorption of water and cargoes. The temperature effects are from a variety of sources, such as cargo temperature, sunlight on deckhead plating and subsequent cooling at night, hot cargoes in adjacent tanks, and hot tank cleaning. (Note that some cargoes are heated to facilitate loading and unloading, some are carried hot, and others are carried at ambient temperature.) Temperature changes affect organic CTCs to a greater extent than zinc silicates. Summary We have attempted to highlight just how hostile the environment inside a cargo tank of a chemical tanker can be to the coating applied to it and some of the failure symptoms that can result. Apart from the stresses applied during the normal structural movement of the vessel, we have to add the cumulative impact of post-curing stress, and operational stresses. Of those operational stresses, repeated episodes of hot tank cleaning interspersed with the cyclic carriage of a wide range of cargoes at varying temperatures cause the coating to swell and contract continually while at the same time absorbing and desorbing water, and/or cargo. The coating system has

to be very resilientmaintaining good adhesion and cohesion, protecting the substrate from corrosion, and remaining as a continuous film for a number of years. Given the very aggressive conditions of the cargo tank, it is not surprising that premature failures do sometimes occur. These difficult conditions set challenges for both the formulators and users of CTCs. The coating manufacturers must recognize all the stresses that occur in practice and accommodate for them in the formulation and testing of CTCs. Owners and operators must also recognize the stresses, and minimize them by careful selection and considerate stowage of cargoes, to reduce the need and impact of tank cleaning, particularly at elevated temperatures. Editors Note: This article is part of the Top Thinker Award series published in JPCLin 2012 and 2013. Trevor Parry is one of 24 recipients of JPCLs 2012 Top Thinkers: The Clive Hare Honors, given for significant contributions to the protective coatings industry over the past decade. The award is named for Clive Hare, a 20-year contributor to JPCL who shared his encyclopedic knowledge of coatings in many forums. Professional profiles of all of the award winners, as well as an article by Clive Hare, were published in a supplement to the August 2012 JPCL.
THE JOURNAL OF PROTECTIVE COATINGS & LININGS 2013 Technology Publishing Company

Formulating Polyureas: History and Advances

From JPCL, March 2013
Kevin A. Buck Huntsman Kevin Buck is the Marketing Manager for Huntsman Polyurethanes Adhesives, Coatings, and Elastomers (ACE) Group in the Americas. With 20 years of experience in the polyurethanes industry, including both technical and commercial positions, he has spent the past decade focused on the coatings, adhesives, sealants, and elastomers markets. He is an active member of the Polyurea Development Association (PDA), the International Concrete Repair Institute (ICRI), and SSPC: The Society for Protective Coatings.

Kevin A. Buck Huntsman

Polyurea coatings are suitable for a number of high-performance applications, including railcar interiors, petrochemical storage tank interiors, and secondary containment. Photos: iStock The concept of polyurea spray elastomer technology was introduced more than 20 years ago. This new application was based on the reaction of an isocyanate component with an amine blend to produce a high-performance elastomer system. Since this original work, a number of advances in both the chemistry and application equipment for polyureas have enabled polyurea elastomer coatings to

compete with (and often displace) their traditional counterparts in highperformance applications. Chemistry Differences Urethane coatings are derived from the reaction of an isocyanate component with a formulated resin blend. Depending on the composition of the resin blend, the coating can be classified into one of three categories:

polyurethane, polyurea, and hybrid polyurethane/polyurea.

Common among these catagories is the isocyanate component. The isocyanate can take on a number of characteristics, such as aromatic, aliphatic, or a blend of the two. It may also contain monomeric isomers, polymeric isomers, an isocyanate quasi-pre-polymer, or a pre-polymer. The pre-polymer or quasi-prepolymer can be made of an amine-terminated polymer resin or a hydroxylterminated polymer resin. Although the difference in the technology is primarily in the resin component, additives such as pigments, fillers, solvents, and adhesion promoters can be introduced to all of the coatings. Polyurethane Coatings A purely polyurethane coating is the result of a reaction between an isocyanate component and a resin blend made with only hydroxyl-containing resins (Fig. 1). The final coating will contain no intentional urea groups. A polyurethane system will probably contain one or more catalysts and may need additives, such as moisture scavengers and anti-foam agents.

Fig. 1: Reaction of isocyanate and resin containing only hydroxyls results in polyurethane. courtesy of Huntsman Polyurea Coatings A polyurea coating is the result of a one-step reaction between an isocyanate component and a resin blend component (Fig. 2). The resin blend must be made up of amine-terminated polymer resins, and/or amine-terminated chain extenders and should not have any intentional hydroxyl moieties. Any hydroxyls are the

result of incomplete conversion to the amine-terminated polymer resin.

Fig. 2: Reaction of isocyanate and resin containing amineterminated polymer resins or chain extenders results in polyurea. courtesy of Huntsman Hybrid Polyurethane/Polyurea Coatings A polyurethane/polyurea hybrid coating has a composition that is a combination of the two above-mentioned coating systems. The isocyanate component can be the same as either the polyurea or the polyurethane system. The resin blend may be a blend of amine-terminated and hydroxyl-terminated polymer resins and/or chain extenders. To bring the reactivity of the hydroxyl-containing resins to the same level of reactivity as the amine-terminated resins, the addition of one or more catalysts may be necessary (Fig. 3).

Fig. 3: Components of polyurea, hybrid, and polyurethane resins courtesy of Huntsman Advantages of Polyurea Polyurea elastomer coatings offer many advantages over traditional alternative chemistries. These advantages may include the following.

Fast cure: Polyurea can be sprayed on sloped surfaces without drip or run formation. Foot traffic can resume on coatings applied to horizontal surfaces within 30 seconds. Relative insensitivity to moisture and temperature during application: Little effect is encountered on adhesion or coating performance due to weather variations (e.g., high humidity, temperature, and residual moisture). 100% solids: Two-component, one-coat systems can be sprayed or poured at 1:1 volume ratio, which eliminates the need for multi-coat applications.

Excellent physical properties: These include tensile strength, tear strength, elongation, and thermal stability. Formulation flexibility: The chemistry can be adjusted to produce soft or hard elastomers. Also, pigments, fibers, and fillers can be added to further differentiate the end product.

Equipment Since the catalyst-free isocyanate/amine reaction is normally rapid and proceeds to completion within a few seconds, working times (gel times) are generally less than 10 seconds. Because of this fast reaction, the coating requires specialized high-pressure and high-temperature application equipment. Specifically, two-component spray machines equipped with impingement mixing have proven an efficient and adequate option for sufficient blending and rapid dispensing of the polyurea raw materials. It is chiefly this equipment that allows polyurea technology to venture outside of the realm of reaction injection molding (RIM). Having the capability of heating the components before mixing is a key requirement of the spray equipment. Heating of the materials before spraying helps to reduce the viscosity, thus improving the mix, flow, and leveling of the applied material. These enhanced properties will lead to significant improvement in the performance and appearance of the coating. For polyurea elastomer coatings, the normal mix ratio of the components is 1:1 by volume (usually 1.1 to 1.2:1 by weight), correlating to an isocyanate index of 1.05:1. Applications By selection of the appropriate isocyanate component and amine blend, a variety of end properties and applications are possible. Slower reacting systems may be used for a variety of sealant and caulking applications. However, because the formulations can be varied, polyurea elastomer systems are well-suited for application to areas such as pipeline, secondary containment, synthetic stucco, concrete, railcars, tank interiors, various structures requiring waterproofing, and floor joints or seams. In addition, polyurea continues to be evaluated for use in numerous niche applications requiring high-performance coatings that allow equipment to be returned to service nearly immediately. Polyurea elastomer coatings exhibit excellent adhesion to clean substrates such as concrete, wood, asphalt, and fresh blasted steel. However, as with other rapid cure coatings, the rapid cure may limit surface wetting and penetration, leading to decreased mechanical bonding. For this reason, end users are cautioned to test the adhesion of any material on target substrates to assess bonding of the coating. In certain cases, surface primers and adhesion promoters may be necessary. In addition, because the polyurea film exhibits strong physical properties and remains intact as it is pulled from the substrates surface, greater adhesion may be necessary for specific applications.

Physical Properties Since a wide range of polyurea elastomer coatings are possible, ranging from soft rubbers to hard elastomers, a variety of physical properties are achievable. It is strongly recommended that both polyurea applicators and customers thoroughly evaluate potential material selection before commercial application to ensure suitability in the intended service. Figures 4 and 5 provide typical physical properties for hardness, tear strength, tensile strength, and elongation. These properties have been obtained from sample films produced in controlled laboratory conditions. Optimal performance is obtained with an isocyanate index in the range of 1.05 to 1.20.

Figs. 4 (left) and 5 (right): Hardness and tear strength according to isocyanate index (left); tensile and elongation strength according to isocyanate index (right). courtesy of Huntsman Actual in-field performance will be heavily dependent on the skill and ability of the applicators. The applicators need to have formal training in the application, operation, and maintenance of the plural-component application equipment, along with formal training in both material handling and proper safety procedures. Recent Developments Although polyurea elastomer coatings have been applied for a number of years, there have not been any concise standards or specifications established. As a result, SSPC: The Society for Protective Coatings initiated work in this area, beginning with performance-based standards, such as SSPC-PS 28.01, TwoCoat Zinc-Rich Polyurethane Primer/Aliphatic Polyurea Topcoat System, as well as SSPC-Paint 43, Direct-to-Metal Aliphatic Polyurea Coating, PerformancedBased. Most recently, SSPC-PA 14 was published. This is specific to the Application of Thick Film Polyurea and Polyurethane Coatings to Concrete and Steel Using Plural-Component Equipment. This standard focuses on the field application of polyurea, polyurethane, and polyurea/polyurethane hybrid coatings with a thickness greater than 20 mils. It brings together, as a reference, standards from

a number of industry groups, including ASTM International, SSPC, NACE International, and the International Concrete Repair Institute, to present a comprehensive reference document. Safety Considerations for Handling and Using Polyurea Before undertaking any spray work, the applicator should be thoroughly familiar with the safe operation of the equipment and should follow all instructions and safety precautions provided by the manufacturer of the equipment. Particular care should be taken so that the spray nozzle is never directed toward anyones face or body during operation. Under normal equipment operating conditions, the isocyanate component and the resin component of the polyurea elastomer coating react almost instantaneously so that there is no excess of either isocyanate or amine exiting the spray nozzle. However, even under ideal operating conditions, very small amounts of un-reacted material may be present as an aerosol or vapor. Before handling or using any component of a polyurea elastomer coating or engaging in polyurea spray work, the applicator should review the Manufacturers Safety Data Sheet (MSDS) for both the isocyanate component and the resin component for recommendations for appropriate respiratory and dermal protection measures when handling, using, or spraying the companys product (Fig. 6).

Fig. 6: Applicators must take appropriate measures to protect themselves while spraying polyurea. courtesy of Huntsman Additional information will be available from the manufacturers about safe handling of the different components and should be consulted as well. To minimize any risk due to exposure to chemicals used or the particulate matter

created in polyurea spray applications, spraying should be done only in wellventilated locations (either outdoors or indoors with mechanical fans), or in a properly ventilated spray booth. Applicators should wear the appropriate personal protective clothing and equipment. Conclusion While polyurea elastomer coatings offer properties not found in other systems and often may be desirable for particular jobs, they are not recommended for all applications. Applied correctly, and with the proper equipment, polyurea elastomer coatings can provide superior features suited to industrial maintenance, including chemical resistance and physical strength. Editors Note: This article is the third in JPCLs 2013 series on generic coating types.
THE JOURNAL OF PROTECTIVE COATINGS & LININGS 2013 Technology Publishing Company

Developments in Waterborne Thermal Insulation Coatings

From JPCL, March 2013
Sudhir Achar The Dow Chemical Company Sudhir Achar is a Technical Service Specialist at Dow Coating Materials with over 20 years of experience in product development and technical service in pigments, architectural and industrial coatings, UV and E-beam coatings, and epoxy curing agents. He earned a Masters Degree in Chemistry from Polytechnic University Brooklyn, New York, and he holds two patents in epoxy curing agents and one each in foam control and radiation curable coatings.

Sudhir Achar

Leo J. Procopio

Leo J. Procopio The Dow Chemical Company Dr. Leo Procopio is a Technical Service Group Leader in the Dow Coating Materials business at The Dow Chemical Company. Procopio earned his Ph.D. in Inorganic Chemistry from the University of Pennsylvania and has spent the last 21 years carrying out exploratory research, new product development, and technical service work in the area of waterborne coatings for the industrial maintenance and industrial metal and wood finishing markets. He is a member of the American Chemical Society, ACA, NACE and SSPC, and currently chairs the SSPC committee C.1.4.c on Waterborne Acrylic Coatings.

The inadvertent transfer of thermal energy in the form of heat leads to a variety of issues in industrial settings. Issues include heat loss from processing equipment and piping, increased energy usage, worker injuries from contact with hot substrates, and associated costs. The traditional insulation methods to combat these issues include use of materials such as fiberglass and polyurethane foam; however, thick layers of insulation can often hide severe maintenance problems such as corrosion under insulation (CUI). An alternative to traditional insulation is the use of thin-film thermal insulation coatings based on waterborne acrylic and epoxy resins. This article describes our efforts to better understand the polymer design and formulation parameters for these thin-film waterborne thermal insulation coatings. Their potential use in thermal insulation Photo courtesy of the Dow Chemical will be described through test results on Company thermal conductivity, safe-touch properties, and corrosion performance in multilayer systems that can be applied by traditional methods. Both onecomponent waterborne acrylic and two-component waterborne epoxy resins and coating formulations have been evaluated and compared to commercial insulation coatings. The use of two types of low thermal conductivity fillers, hollow glass microspheres and silica aerogel, is also described. How Heat Transfers Heat transfers between materials by one or more of three main processes: conduction, convection, and radiation. Heat moves through a solid by conduction, and the rate of the conduction depends on the chemical nature and structure of the solid. Some solids, like extruded polystyrene foam, are designed to inhibit conduction, while others, like copper, are highly conductive and allow heat to pass freely. Convection is the transfer of heat by the movement of a fluid, such as a liquid or gas. Heat can also be emitted by an object through radiation in the form of electromagnetic waves such as infrared light. Radiation of heat leads to the familiar warming sensation experienced when we near a fire or hot wood stove. Thermal conductivity (k) is the rate at which heat flows through a material between points at different temperatures, and is measured in units of watts per meter per degree Kelvin (W/mK). Heat flux (Q), or the rate at which heat energy is

transferred through a given surface (units of W/m2), is most often determined by measuring a temperature difference over a piece of material with known thermal conductivity. For a material to exhibit thermal insulative properties, it must have very low thermal conductivity. Table 1 gives thermal conductivity values at room temperature of some common materials. Types of Thermal Insulation for Industrial Plants Thermal insulation found in most industrial plant operations is used on reaction vessels, pipelines (e.g., steam or chilled water), transfer pipes, heat exchangers, storage tanks, and other equipment. Traditional materials in these settings include calcium silicate,1 expanded perlite,2 cellular glass,3 organic foams (e.g., polyurethane, polyisocyanurate, elastomeric, phenolic, polystyrene),4 and manmade mineral fibers (e.g., fiberglass).4 To maintain its effectiveness and to prevent corrosion issues, insulation typically requires a separate moisture barrier or jacketing to keep out water. Insulated surfaces for carbon steel operating above 149 C (300 F) and below -4 C (25 F) are generally thought to not present major corrosion issues. However, for equipment operating between these temperatures, significant corrosion can occur underneath the insulation. The traditional insulation materials create a significant barrier to inspecting the steel surface. CUI can result in equipment failures, production losses, and increased costs.5 Corrosion occurs when moisture comes into contact with steel surfaces underneath the insulation. CUI can go undetected because the damage is not visible until the insulation is removed. The maintenance costs resulting from CUI have led to enhanced interest in better coating and insulating material systems and the development of functional, liquid-applied thermal insulation coatings. Replacing thick jackets of insulation with a relatively thin, liquid-applied coating with thermal insulation properties has several advantages, including greater ease of application, through traditional methods; application to surfaces with complex geometries; and prevention of CUI through easier inspection for corrosion of metal surfaces. The insulation coating becomes part of the overall coating system, and it can be used with primers and topcoats to provide a system with good durability and corrosion resistance. Thermal insulation coatings also must protect workers against burns from contact with very hot surfaces. Human skin is very sensitive to temperature within a narrow range. Burn injuries depend on three primary factors: 1) surface temperature of the object being touched, 2) thermal conductivity of the surface, and 3) contact time with the surface. Metals such as steel or aluminum have much higher thermal conductivities than other construction materials, such as wood or concrete (Table 1). The higher thermal conductivity translates into more thermal energy being transferred from the substrate to the skin. Thermal insulation coatings with low thermal conductivities can therefore help protect workers by lowering the surface temperature and slowing down the transfer of

thermal energy from the surface to human skin.6-7

TABLE 1

Thermal Conductivity of Common Materials Material Air Aluminum Calcium silicate Carbon steel (max 0.5% C) Concrete (lightweight) Copper Expanded polystyrene foam Glass (borosilicate glass) Hollow glass spheres Polyurethane foam Rock wool Silica aerogel Stainless steel (austenitic, type 304) Water Wood (Eastern white pine, oven dry) Thermal conductivity, k (W/ mK) 0.02 237 0.05 54 0.10.3 385 0.03 1.14 0.030 0.03 0.04 0.0040.03 15 0.6 0.09

The current dominant insulation technology is one-component waterborne acrylics coatings, formulated with low thermal conductivity fillers such as hollow glass or ceramic microspheres, and, more recently, with silica aerogels. 8 The hollow glass microspheres are made from sodium or aluminum borosilicate glass with a small amount of air trapped in the micron-sized void space. The trapped air is still, which contributes to the low thermal conductivity. The silica aerogel particles are extremely porous, hydrophobically treated silica with an open pore structure. The highly hydrophobic nature of the particles keeps water out of the pore space of silica aerogel. Aerogel silica provides low thermal conductivity because of the still air in the very small pores (approximately 20 nm diameter) and very low density. The liquid-applied insulation coatings are therefore composite materials made of

functional fillers bound together with a polymer that provides cohesive strength, adhesion to the substrate, flexibility, and stability to constant high service temperatures. Commercial acrylic-based insulation coatings are recommended for use up to approximately 204 C (400 F). With high pigment volume concentrations (PVC) and low polymer glass transition temperatures (Tg), these coatings can be formulated at low VOC levels and high solids. They can be applied directly to the substrate or over a corrosion-inhibiting primer and then topcoated. The primers provide the corrosion protection in a multi-coat system, and the topcoat provides decorative properties and protection to the insulation coating. Our efforts to understand and further develop formulation knowledge of thin-film, liquid-applied thermal insulation coatings are described in the remainder of this article. Experimental We carried out initial experiments using design of experiments (DOE) methodology to quickly screen and narrow the choice of potential polymer and filler candidates for a low thermal conductivity insulation coating. From these experiments, two waterborne acrylic-styrene latex polymers (EXP-A and EXP-B) and one waterborne epoxy resin dispersion (EXP-C) were chosen for further formulation development because of their ability to be formulated at low VOC and high volume solids, and to provide coatings with low thermal conductivity and good corrosion protection. Both acrylics have a hydrophobic backbone, and offer excellent water resistance properties. EXP-A has a Tg of 19 C and EXP-B has a slightly lower Tg of 13 C. The waterborne epoxy dispersion EXP-C is a dispersion of a Type 1 solid epoxy, with a minimum film formation temperature of 13 C and an epoxy equivalent weight of 1050. It was cured with a waterborne polyamine adduct with 50% weight solids and an amine hydrogen equivalent weight of 300. The three resins were formulated into insulation coatings using the two fillers chosen from the DOE experiments for their ability to give low thermal conductivity values and good coating processing. Commercially available, the fillers included a hollow glass microsphere (GL) and a silica aerogel (AER). Coatings were prepared according to the design in Table 2. The fillers were used as the sole filler as well as in combinations. Formulations based on the epoxy resin EXP-C and containing silica aerogel filler (AER) did not have good processing, with high viscosities or gelling, and were not evaluated further.
TABLE 2

Coating Identification for Insulation Coatings Evaluated Polymer Filler GL @ 75% PVC EXP-A EXP-B EXP-C WB acrylic WB acrylic WB epoxy A-1 B-1 C-1

(hollow glass spheres) GL @ 50% PVC / AER @ 25% PVC GL @ 25% PVC / AER @ 50% PVC AER @ 75% PVC (silica aerogel) A-2 A-3 A-4 B-2 B-3 B-4 not tested not tested not tested

The insulation coatings, prepared using a conventional paint making process, are very high-solids (approximately 70% volume solids), low VOC waterborne coatings. Examples of model formulations are provided in the original paper given at SSPC 2013 (sspc.org). Experimental insulation coatings based on EXP-A, EXP-B and EXP-C were compared with two commercially available insulation coatings, COM-1 and COM2. Both of the commercial coatings are reportedly based on waterborne acrylic technology, although the supplier technical literature does not reference specific filler technology. Coatings were tested for thermal conductivity according to ASTM C518, which describes the method for determining thermal conductivity of a flat specimen at a steady state condition using a flow meter.9 The thermal conductivity of an uncoated polycarbonate sheet of known thickness is measured. The insulation coatings were applied to the 8-inch x 8-inch clear poly-carbonate panels at a dry film thickness (DFT) of approximately 80 mils (2 mm) and cured for seven days at room temperature. The thermal conductivity is determined by measuring the sample thickness, heat flux, and temperature difference across the two plates within the flow meter (Fig. 1). Using the known values of thermal conductivity and thickness for the polycarbonate, the temperatures of the bottom and top plates, the thickness of the coating, and the measured value of heat flux (Q) for the system tested, the thermal conductivity of the coating can be calculated using Fouriers Law of Heat Conduction.

Fig. 1: Schematic diagram of heat flow meter configuration for thermal

conductivity testing Figures courtesy of the authors Free films of the coatings at 40 mils DFT were cast on release paper and tested for tensile and elongation according to ASTM D638. Adhesion was tested according to ASTM D3359 for coatings applied to clean, smooth cold-rolled steel at 25 mils DFT. Humidity resistance was evaluated by casting films on clean, smooth cold-rolled steel at 50 mils DFT, drying for a week at room temperature, and placing the panel in a Cleveland condensation cabinet, according to ASTM D4585. Films were evaluated for blistering and rusting at various exposure times. Corrosion resistance of systems, including the insulation coatings as a topcoat over an anti-corrosive primer, was tested according to ASTM B117. The primer was an experimental two-component waterborne epoxy formulated with inhibitive pigment. The primer was applied at 3 mils DFT on smooth cold-rolled steel and cured for seven days at room temperature, then topcoated with 50 mils DFT of insulation coating and dried for another seven days. Panels were scribed before exposure and rated for blistering and rusting. The ability of the insulation coating to reduce the surface temperature of hot steel was determined by placing a coated piece of steel on a hot plate and measuring the surface temperature of both uncoated and coated steel with a handheld infrared thermometer. A piece of smooth cold-rolled steel was coated with 75 mils DFT of the insulation coating and allowed to dry for seven days before testing. Panels were placed directly on a hot plate set to 180 F and allowed to equilibrate. Surface temperature was measured every 10 minutes until it reached an equilibrium value. A side-by-side comparison with an uncoated piece of steel was done in every instance. Results and Discussion Table 3 shows the results of thermal conductivity measurements for the various combinations of binder and filler. The main contribution for the low thermal conductivity values is from the functional fillers, which, for the experimental formulations, are either the hollow glass microspheres (GL) or the silica aerogel (AER). The exact type of filler used in the commercial coatings is unknown. The experimental formulations display values from 0.08 to 0.13 W/mK, which are similar to those observed for the commercial coatings COM-1 and COM-2 at 0.07 and 0.11 W/mK, respectively.
TABLE 3

Results of Thermal Conductivity Measurements Coating Polymer Polyme Hollow glass Silica Thermal aeroge conductivit Thermal conductivit

r Type

microspher l y, k (W/mK) e (%PVC) (%PVC )

y, k (mW/mK)

Uncoated polycarbonat e

N/A

N/A

N/A

N/A

0.1649

164.9

COM-1 COM-2

unknow n unknow n

acrylic acrylic

0.070 0.106

70 106

A-1 A-2 A-3 A-4

EXP-A EXP-A EXP-A EXP-A

acrylic acrylic acrylic acrylic

75 50 25 0

0 25 50 75

0.080 0.080 0.130 0.120

80 80 130 120

B-1 B-2 B-3 B-4

EXP-B EXP-B EXP-B EXP-B

acrylic acrylic acrylic acrylic

75 50 25 0

0 25 50 75

0.0850 0.0880 0.127 0.104

85 88 127 104

C-1

EXP-C

epoxy

75

0.107

107

Although a low thermal conductivity was achieved with all the experimental formulations, there are differences among formulations containing the same polymer but different filler combinations, even though the PVC is held constant at 75%. For example, in the formulations with acrylic EXP-A, the coating with only hollow glass microspheres (A-1) has the lowest thermal conductivity, while the coating with only silica aerogel (A-4) has the highest. This result is somewhat surprising because the silica aerogel is a lower density material and should lead to a lower density coating, presumably containing a higher level of still air. The lower density in the wet state is confirmed by measurements of wet density that

closely match the calculated values. Although we have not yet confirmed the reason through experiments, we postulate that the difference may be due to the density of the dry film, and we suspect that some polymer intrusion into the open cell pore structure of the silica aerogel may be occurring and displacing air. The ability of the insulation coatings to provide safe-touch properties was evaluated by measuring the decrease in surface temperature of coated steel compared to uncoated steel. At the film thickness tested, all of the coatings gave a significant decrease in surface temperature (Fig. 2). Most of the coatings gave a surface temperature of 140 F (60 C) or below, which is needed to pass the fivesecond contact that would result in a first-degree burn.6-7

Fig. 2: Surface temperature of insulation coatings at 75 mils DFT on steel heated to 180 F Some differences were noted among the experimental insulation coatings based on filler type, and correlate with the thermal conductivities discussed above. Hollow glass microspheres were more efficient at lowering the surface temperature than the silica aerogel at the same PVC. For example, in coatings made with acrylic polymer EXP-A, coatings A-1 (75% PVC hollow glass microspheres) and A-2 (50% PVC glass microspheres/25% PVC silica aerogel) had surface temperatures of 140 F and 138 F, respectively, compared to coatings A-3 (25% PVC glass spheres/50% silica aerogel) and A-4 (75% PVC silica aerogel) with surface temperatures of 146 F and 148 F. The ability to provide safe-touch properties depends not only on the thermal conductivity and heat flux properties of the coating, but also on the service temperature of the metal surface and film thickness of the coating. At higher metal temperatures, thicker films will be needed to bring surface temperatures down to the required levels for safe-touch protection.

The insulating properties of the coatings are largely due to the low thermal conductivity of the functional fillers. The polymer in the insulation coating also contributes to important properties such as adhesion to the substrate, flexibility, and barrier properties (water and corrosion resistance). In some ways, the role of the binder in the highly filled insulation coatings is similar to the role of the binder in highly filled organic zinc-rich primers. The main role is to hold the functional filler particles together in a cohesive film that will adhere to the substrate and withstand the stresses imposed on the coating (e.g., impact, flexing, UV light and water). Table 4 shows results of tensile and elongation measurements, adhesion testing, and barrier properties. Adhesion was measured on a smooth steel substrate, and all of the experimental and commercial coatings performed well, with no failure in crosshatch tape adhesion testing. Elongation measurements on free films demonstrate that all of the experimental acrylicbased coatings performed much better than the commercially available coatings and the epoxy-based coating C-1. COM-1 and C-1were too brittle to prepare a free film to get an accurate measurement, and COM-2 had only 30% elongation. Compared to COM-2, the experimental acrylic coatings had from two to ten times the percent elongation, ranging from 61 to 325% elongation. The type of filler significantly affected percent elongation. In general, higher levels of silica aerogel provided higher percent elongation. The correlation between silica aerogel level and percent elongation is strong for the acrylic-based coatings, and represents a key reason to include this filler in insulation coating formulations. Higher elongation typically translates into improved flexibility, which suggests that coatings containing some silica aerogel will be less prone to cracking when placed under stress. We are currently examining this hypothesis through thermal cycling, impact and flexibility, and exterior exposure testing. Barrier properties for the coatings were examined through humidity (Cleveland condensation cabinet) and salt spray exposure testing (Table 4 and Fig. 3). The coatings were applied directly to smooth cold-rolled steel for humidity testing, and performed very well after 1,000 hours exposure to condensation, with no blistering or rusting. Salt spray testing was performed over smooth cold-rolled steel panels that were first primed with 3 mils DFT of an experimental waterborne epoxy primer and topcoated with 50 mils DFT of the insulation coatings. Pictures of several salt spray panels after 2,016 hours exposure are shown in Fig 3. Both commercial coatings performed poorly as part of the coating system, with heavy rusting bleeding through the insulation coatings COM-1 and COM-2. The formulation parameters for the commercial coatings are unknown, but film porosity and water permeability may be higher than the experimental coatings due to choice of polymer and filler type and levels. In general, the experimental coatings performed well in a system over the waterborne epoxy primer, with no blistering and little rust bleed. Only coating A-2 showed appreciable rust spots bleeding through the insulation coating. Additional testing over waterborne acrylic primers showed similar performance, although the systems primed with the waterborne epoxy did slightly better in blister resistance. Although their main function is to provide insulation properties, insulation coatings can add to the corrosion resistance of a coating system due to their barrier properties. The use

of hydrophobic acrylic polymers and highly cross-linked waterborne epoxy resins with the proper choice of fillers yields a thick-film coating that helps resist corrosion by preventing water and electrolyte from reaching the steel surface.
TABLE 4

Results of Tensile, Elongation, Adhesion, Humidity, and Salt Spray Testing for Insulation Coatings Coating Tensile strength (psi) Elongation at Adhesion break (%) 1,000-hr Humidity exposure 2,016-hr Salt spray exposure blisters

COM-1 COM-2

brittle 169

brittle 30

5B 5B

no blisters or rust no blisters or rust

none none

A-1 A-2 A-3 A-4

185 196 204 173

61 103 156 243

5B 5B 5B 5B

no blisters or rust no blisters or rust no blisters or rust no blisters or rust

none none none none

B-1 B-2 B-3 B-4

113 137 182 182

73 93 325 300

5B 5B 5B 5B

no blisters or rust

none

no blisters or rust no blisters or rust

none none

C-1

brittle

brittle

5B

no blisters or rust

none

Fig. 3: Panels coated with insulation coatings, after 2,016 hours of salt spray exposure. Panels were primed with a waterborne epoxy. Conclusions Entrapped air between the fibers or cell structure of traditional insulation leads to very low thermal conductivity for those materials. A class of functional fillers, including hollow glass microspheres and silica aerogel, are available for use in coatings and building products, and derive their low thermal conductivity from the presence of air trapped in their small voids and pores. When incorporated into waterborne coatings based on acrylic or epoxy polymers, the functional fillers lead to a new class of insulating materials: waterborne thermal insulation coatings. These insulation coatings offer a number of advantages compared to traditional insulation, including easy spray application, less risk of CUI and easier inspection, simple application to complex geometries, improved personal protection (i.e., safe-touch) properties, and energy savings through their insulating properties. Excellent elongation properties have been observed with the acrylic insulation coatings, particularly when silica aerogel is included as part of the functional filler. Higher elongation compared to commercially available coatings should translate to better flexibility in situations where it is needed. Finally, the ability of the insulation coating to perform its functional purpose, i.e., insulation, is important, but we have also shown that it can take part in the protective qualities of the coating system. We have demonstrated that a waterborne system consisting of a waterborne epoxy primer topcoated with a waterborne insulation coating can offer good corrosion resistance properties on steel. For the experimental insulation coatings described in this work, the acrylic and epoxy resins and functional fillers such as silica aerogel are hydrophobic by design, and, with proper formulation, offer a good barrier to water and electrolytes and thus improve the corrosion resistance of the overall system.

Editors Note: This article is based on a paper the authors presented at SSPC 2013, held January 14 to 17 in San Antonio, TX. The original paper is published in the conferenceProceedings (sspc.org).
REFERENCES

1. ASTM C533-11, Standard Specification for Calcium Silicate Block and Pipe Insulation, ASTM International, 2011. 2. ASTM C610-11, Standard Specification for Molded Expanded Perlite Block and Pipe Thermal Insulation, ASTM International, 2011. 3. ASTM C552-12, Standard Specification for Cellular Glass Thermal Insulation, ASTM International, 2012. 4. NACE SP0198-2010, Control of Corrosion under Thermal Insulation and Fireproofing MaterialsA Systems Approach, NACE International, 2010. 5. See for example: a. Delahunt, J.F., Corrosion under Thermal Insulation and Fireproofing: An Overview, Proceedings of Corrosion 2003, NACE International, Paper 03022 b. Hanratty, T., Corrosion under InsulationThe Hidden Problem, Hydrocarbon Asia, pp. 54-56, April-June 2012. c. ODonoghue, M.; Datta, V.; Andrews, A.; Adlem, S.; Giardina, M.; de Varennes, N.; Gray, L.G.S.; Lachat, D.; Johnson, B., When Undercover Agents Cant Stand the HeatCoatings in Action (CIA) and the Netherworld of Corrosion under Insulation, Journal of Protective Coatings & Linings, pp. 2443, February 2012, and references therein. 6. ASTM C1055-03, Standard Guide for Heated System Surface Conditions that Produce Contact Burn Injuries, ASTM International, 2009. 7. ASTM C1057-03, Standard Practice for Determination of Skin Contact Temperature from Heated Surfaces Using a Mathematical Model and Thermesthesiometer, ASTM International, 2010. 8. Pidhurney J, Pescatore P . Aerogel for Highly Thermally Insulative Coatings,CoatingsTech, pp.46-48, June 2012. 9. ASTM C518-10, Standard Test Method for Steady-State Thermal Transmission Properties by Means of the Heat Flow Meter Apparatus, ASTM International, 2010.
THE JOURNAL OF PROTECTIVE COATINGS & LININGS 2013 Technology Publishing Company

Nine Coatings Projects Receive High Honors at SSPC 2013

From JPCL, February 2013
Charles Lange JPCL

On Monday, Jan. 14, at SSPC 2013 in San Antonio, TX, SSPC President Steve Collins and Executive Director Bill Shoup presented the Societys seventh annual Structure Awards, given for noteworthy coatings projects on an array of interesting and complicated structures. This years winners faced a variety of challenges completing these jobs, from performing work at extreme heights, to dealing with sweltering temperatures inside of containment structures, to restoring a beautiful mural high above the ground on an elevated water storage tank. The winners are presented over the next several pages. The photo essay is based on nomination materials submitted to SSPC in 2012 and on information given at the awards ceremony. MILITARY COATINGS PROJECT AWARD OF EXCELLENCE: (EX) USS Iowa, BB-61 Exhibit

The Military Coatings Project Award of Excellence honors exceptional coatings work performed on U.S. military ships, structures, or facilities.

Military Coatings Project Award of Excellence recipients Hector Trujillo and David Ashton, Bay Ship & Yacht Co.; and Julio Mojica, PPG Protective and Marine Coatings, Technical Service Representative. Award ceremony photos courtesy of SSPC

Photos courtesy of Jeremy Bonelle, Pacific Battleship Center The third-ever recipient of the award is the (EX) USS Iowa, an 887-foot-long World War II-era battleship that is now an exhibit at the Pacific Battleship Center. Approximately 133,000 square feet of superstructure were water-blasted and recoated with two-component, marine-style epoxies and a single-component acrylic polysiloxane finish. This project presented several key challenges. Previously, the ship had received little to no maintenance for over 20 years. In addition, contractors needed to work in a compressed schedule to meet a firm deadline for towing the ship to its docking point. Due to environmental concerns, contractors performed all work with the ship in water. The complex superstructure of the historic ship also required use of extensive scaffolding to finish the job.

Location: San Pedro, CA Structure Owner: Pacific Battleship Center Contractor/Applicator: Bay Ship & Yacht Co. (SSPC-QP 1) Coating Material Supplier: PPG Start Date: March 5, 2012 Completion Date: May 19, 2012

GEORGE CAMPBELL AWARD: Trails Arch Bridge This year, three projects received the George Campbell Award, given for outstanding achievement in the completion of difficult or complex industrial or commercial coatings projects. Named in honor of the late George Campbell, founder of Campbell Painting Company in New York, the award recognizes owners and contractors who overcame issues such as extreme environmental conditions, strict time constraints, limited access or high-traffic areas, complex structural components, or coordination with multiple trades and subcontractors.

Photos courtesy of Joel Harry, Brock Services LLC The 97-year-old Trails Arch Bridge, a former U.S. 66 route that now carries a natural gas pipeline over the Colorado River, required extensive rehabilitation and recoating, including a sizable amount of lead abatement. As a result, the

project called for extra attention to environmental and safety concerns, as well as to quality and scheduling considerations. Using a calcium-silicate abrasive additive to encapsulate the lead, the contractors removed over 150,000 square feet of lead-based paint on the bridge, yielding over 1 million pounds of non-hazardous waste that needed to be contained over the river. On some days, temperatures inside of the containment structure shot up to 130 F, necessitating carefully scheduling the workers to help protect them from overexposure to the heat.

Geroge Campbell Award recipients Doug Moore, Carboline Company; Kellin Ebert, El Paso Pipeline (Kinder Morgan); Tomas Franco, The Brock Group; Gonzalo Martinez, The Brock Group; Hunter McKeever, Pacific Gas & Electric Corp.; Don Pomi, Pacific Gas & Electric Corp.; Paul Parslow, Pacific Gas & Electric Corp. Weight limitations on the bridge made constructing and maintaining over 1.3 million pounds of scaffolding access equipment a constant challenge, as well. Access to the bridge posed another issue, with contractors navigating backroads between Arizona and California to get to the sites only access point. With careful planning and execution, though, the contractors successfully completed the project in three phases.

Location: Spans Colorado River, connecting Topock, AZ and Needles, CA Structure Owner: El Paso Pipeline (Kinder Morgan) / Pacific Gas & Electric Corp. Contractor/Applicator: Brock Services, LLC (SSPC-QP 1 and QP 2) Coating Material Supplier: Carboline Company Abrasive Additive Material Supplier: Blastox (TDJ Group) Start Date: November 2011

Completion Date: September 2012

GEORGE CAMPBELL AWARD: BC Place BC Place, one of Canadas most well-known sporting venues, needed some coatings help during a recent facelift. This 30-year-old, 59,841-seat stadium hosted the opening and closing ceremonies of the 2010 Vancouver Winter Olympics. The stadium closed after the Olympics in 2010 for a round of major renovations and reopened in 2011 with a new cable-supported retractable roof, making it the worlds largest stadium of its kind.

Photos courtesy of BC Pavilion Corporation Certified Coating Specialists, Inc. provided NACE-certified inspection and repair services throughout the last renovation of BC Place. CCS oversaw the installation of new shop-coated steel items on the new roof and throughout the stadium. After installation and inspection, CCS workers performed necessary repairs, including hand- and power-tool cleaning spots to Bare Metal (SSPC-SP 11) and recoating the steel with various epoxy systems.

SSPC President Steve Collins presents the George Campbell Award to Cliff Harper, Certified Coating Specialists, Inc.; Brian Griffin, BC Pavilion Corp.; and Dr. Mike ODonoghue, International Paint, LLC. Many of the repairs took place at heights of over 300 feet, so the contractors made use of rope access techniques, swing stages, and specially designed

access platforms during construction. Workers also received extensive fall prevention and rope access training. This attention to detail, especially with regard to safety, helped the contractors meet a tight deadline with no lost-time accidents over the nine-month duration of the project.

Location: Vancouver, BC, Canada Structure Owner: BC Pavilion Corporation Contractor/Applicator: Certified Coating Specialists, Inc. Coating Material Supplier: AkzoNobel Start Date: April 4, 2011 Completion Date: December 20, 2011

GEORGE CAMPBELL AWARD: Miller Park Stadium Constructed in 2001, this 42,200-seat stadium serves as the home of Major League Baseballs Milwaukee Brewers. The project involved cleaning and recoating select steel trusses and metal ceiling panels on the underside of the stadiums retractable roof, roughly 270 feet above the playing field surface. Specifications called for abrasive blast-cleaning, hand and power-tool cleaning, and recoating the steel with moisture-cured urethane systems.

Photos courtesy of BASE Group Several factors made this a complicated and challenging project. The extreme height and difficult access of the roof surfaces being painted required contractors to employ various rope access techniques. The contractors carefully crafted a plan with the owners to avoid the cost and inconvenience of traditional access equipment. The contractors use of low -impact rope access negated the need for swing staging.

SSPC President Steve Collins presents the George Campbell Award to Rich

Purnell, BASE Group; and Sid Oakes, The Sherwin-Williams Company. Additionally, the short period between the end of the baseball season in September or October and the cold, non-paint-friendly Wisconsin winter made for a very tight time frame for completion. Also, when the roof opened or closed, the trusses being painted moved hundreds of feet in midair, forcing the contractors to coordinate work accordingly. Thanks to conscientious planning and hard work, however, the newly painted roof was up and running for the Brewers next season.

Location: Milwaukee, WI Structure Owner: Southeast Wisconsin Professional Baseball District / Milwaukee Brewers Contractor/Applicator: BASE Group Coating Material Supplier: The Sherwin-Williams Company Start Date: October 2011 Completion Date: November 2011

WILLIAM JOHNSON AWARD: Hollywood, FL Water Tank The William Johnson Award represents outstanding achievement in aesthetic merit in industrial or commercial coatings projects. The awards namesake is the late William Johnson, a former consultant with KTA-Tator, Inc., whose work in coatings formulation, failure analysis, and surface preparation paved the way for future advances in the coatings industry. SSPC presented William Johnson Awards for two projects at this years awards ceremony.

Photo courtesy of Tnemec Company, Inc. This 1 MG elevated tank in Hollywood, FL, features a colorful ocean scene mural, complete with loggerhead sea turtles and fish. Tanks like these, with such intricate, artful designs, naturally require more attention to detail than your standard water tank rehab project.

William Johnson Award recipients Sean Carlin, Tnemec Coatings Consultant; and Paul Jette, Utility Service Co. For this tank, the contractors Brush-Off blast-cleaned (SSPC-SP 7) and recoated the exterior surfaces with an epoxy primer, an aliphatic acrylic polyurethane intermediate, and a fluoropolymer finish, before repainting the tank mural with a two-coat fluoropolymer system. The final design used 19 different colors of paint, from tank white to different blues, greens, and browns. The fluoropolymer system is expected to keep the mural looking like new and protected from the harsh Florida coastal environment for years to come.

Location: Hollywood, FL Structure Owner: City of Hollywood, FL Contractor/Applicator: Utility Service Co., Inc. Coating Material Supplier: Tnemec Company, Inc. Tnemec Representative: Florida Protective Coating Consultants Mural/Lettering Painter: Jim Kelly, Industrial Commercial Signs Design Consultant: Team Consulting, LLC Start Date: Spring 2011 Completion Date: Spring 2011

WILLIAM JOHNSON AWARD: The Earthoid Water Tank Another tank project garnering recognition at this years awards ceremony is the repainting of the Earthoid tank on the campus of Montgomery College in

Germantown, MD. Constructed in 1980, this 2 MG, 100-foot-tall spheroid storage tank was painted by famed muralist Peter Freudenberg to resemble an astronauts view of earth from space, even complete with a cloudy ozone layer.

Photos courtesy of Tracy Holmes,

Washington Suburban Sanitary Commission Horizon Bros. Painting Company assisted the tanks owners in performing periodic evaluations of the tanks previous coatings system and in recommending a suitable coatings system. Based on the contractors recommendations, the interior of the tank was cleaned and relined with an epoxy system, while the exterior was fully blasted inside containment and recoated. The newly painted tank remains both an aesthetically pleasing civic landmark and a thriving example of functional art.

William Johnson Award recipients Gregory R. Chip Stein, Tank Industry Consultants, Inc.; Tracy Holmes, Washington Suburban Sanitary Commission; Brian Monczka, Horizon Brothers Painting; and Kevin Morris, The Sherwin-Williams Company.

Location: Montgomery College, Germantown, MD Structure Owner: Washington Suburban Sanitary Commission Contractor/Applicator: Horizon Bros. Painting Co. Coatings Consultant: Tank Industry Consultants, Inc. Coating Material Supplier: The Sherwin-Williams Company Muralist: Eric Henn, Eric Henn Murals Start Date: June 6, 2011 Completion Date: December 5, 2011

E. CRONE KNOY AWARD: Wind Tower Segments Sometimes its not just the structure being recoated, but also the recoating process itself, that makes a project stand out. The E. Crone Knoy Award, named after the late founder and president of Tank Industry Consultants, Inc., recognizes outstanding achievement in industrial or commercial coatings work that demonstrates innovation, durability, or utility. One of this years two recipients, a project out of Give, Denmark, involved shopcoating interior and exterior surfaces of onshore and offshore steel wind tower sections with new fully-automated robotic coating devices. These devices coated the steel with a multi-layered, high-level corrosion protection system.

Photos courtesy of Muehlhan A/S

E. Crone Knoy Award recipients Vandad Pachai, Muehlhan A/S; Mark Mason, Hempel A/S. This new highly-industrialized coating process has several key economic and environmental benefits. It resulted in a reduction of paint consumption of up to 25%, as well as a reduction in harmful VOC emissions of up to 25%. In addition, coating thickness distribution improved, with a reduction in the standard deviation of DFT distributions of up to 50%. While robots certainly wont be replacing all human workers, advances in technology like this can help owners and contractors complete projects more efficiently and with less harm to the environment.

Location: Give, Denmark Structure Owner: Welcon A/S Contractor/Applicator: Muehlhan A/S Coating Material Supplier: Hempel A/S Start Date: August 2011 Completion Date: May 2012

E. CRONE KNOY AWARD: Nestle Plant Expansion When Nestle Nutrition announced plans for an $89.9 million expansion project at its Gerber facility in Fort Smith, AR, Coatings Unlimited, Inc., was brought in to handle the coatings work of the project. The contractors installed new FDAcompliant protective coatings for concrete walls, floors, and ceilings throughout the expanded, state-of-the-art 900,000-square-foot facility. Approximately 30 highly experienced coatings applicators profiled and resurfaced over 170,000 square feet of concrete surfaces, hand-trowelling over 70,000 square feet of process flooring, and using more than 12,500 bags of epoxy concrete repair materials. In total, contractors went through more than 200 tons of abrasive and 11,000 gallons of coating materials.

To meet the strict specifications regarding concrete moisture and relative humidity, contractors made use of hot and cold dehumidification equipment. With outside temperatures ranging from below 30 F in the winter to above 100 F in the summer, and without a working HVAC system in the building, the contractors also made efforts to maintain surface temperatures between 50 F and 80 F throughout the project. These measures paid off, with over 42,000 incident-free worker-hours logged in the end.

Photos courtesy of Billy Myers, Coatings Unlimited, Inc.

E. Crone Knoy Award recipients Larry Getz, The Sherwin-Williams Company; Byron Beamer, Sika Corp.; Mark Jelinek, The SherwinWilliams Company; Eric Hanson, Nestle Nutrition; Billy Myers, Coatings Unlimited, Inc.; Steve Philipp, Jr. Coatings Unlimited, Inc.; Steve Philipp, Sr. Coatings Unlimited, Inc.

Location: Fort Smith, AR Structure Owner: Nestle Contractor/Applicator: Coatings Unlimited, Inc. (SSPC-QP 1 and QP 2)

Coating Material Supplier: The Sherwin-Williams Company Concrete Repair Material Supplier: Sika Start Date: November 15, 2011 Completion Date: November 30, 2011

CHARLES G. MUNGER AWARD: Hallidie Building The winner of this years Charles G. Munger award for longevity is the Hallidie Building project out of San Francisco, CA. This award, named after the late Charles Munger, honors an outstanding industrial or commercial coatings project that demonstrates the long service life of the original coating. The structure may have had spot repairs or overcoating with the original coating still intact. This years winning project, a curtain wall remediation project, took place at the Hallidie Building, the countrys second building to feature a glass curtain wall. Designed by architect William Polk and constructed through 1917 and finished in 1918, the building is listed on the U.S. National Register of Historic Places. While the building only took two years to construct, recent restoration work took over twelve years to complete the intricate detailing that this project entailed, including repainting of the decorative gold building trim and other surfaces. Contractors cleaned select building surfaces to the SSPC standards specified and recoated the surfaces with an organic zinc-rich primer, an aliphatic urethane intermediate, and a fluoropolymer finish. With new coatings, this historic gem of a building will remain a treasure in the middle of a modern, ever-changing city.

Charles G. Munger Award recipients Sean Carlin, Tnemec Coatings Consultant; Greg Jeffress, ABC Painting; and Annie K. Lo, McGinnis Chen Associates, Inc.

Location: San Francisco, CA

Structure Owner: Edward J. Conner and Herbert P. McLaughin, Jr. Owners Representative: The Albert Group, LLC Contractor/Applicator: Abrasive Blasting & Coating, Inc. Coating Material Supplier: Tnemec Company, Inc. Consultant Architect: McGinnis Chen Associates, Inc. Constructor: Cannon Constructors North, Inc. Engineers: Murphy Burr Curry, Inc., Toft, de Nevers & Lee Historic Preservation Architect: Page & Turnbull Start Date: Spring 2012 Completion Date: November 2012
THE JOURNAL OF PROTECTIVE COATINGS & LININGS 2013 Technology Publishing Company

Coating Concerns for New Chemical and Petroleum ASTs

From JPCL, February 2013
Warren Brand Chicago Coatings Group Warren Brand is the founder of Chicago Coatings Group, LLC, a consulting firm he formed in 2012. Before opening his consultancy, Brand was the president of Chicago Tank Linings. He has more than 25 years of experience as a coatings contractor, is an SSPC-certified Protective Coatings Specialist and a NACE-certified Level 3 coatings inspector, and holds an MBA and a BA in Journalism.

There are many different designs of aboveground storage tanks (ASTs), particularly in chemical and petrochemical facilities. In fact, listing all of the different types, sizes, composition, and functionalities would fill a small book. And these tanks typically call for coating work. But are coating concerns considered during the design process? This article will address the question. Warren Brand Chicago Coatings Group Process tanks simply have too many design parameters to address in a single article. Parameters can vary because of the wide range of storage needs, from products stored at ambient temperatures and under no pressure to products stored at pressure, at elevated or reduced temperatures, under agitation, and under many other conditions.

So, for the purposes of this article, we are going to focus specifically on design issues and coating considerations for field-erected ASTs that are not insulated and are used for bulk storage. In particular, we will look at two basic types of welds in ASTs and coatings issues related to the welds. To avoid complicating the article with issues pertaining to the cold wall effect, we will not address insulated tanks. Further, we will also avoid issues pertaining to corrosion under insulation (CUI). Well save those topics for another day. Field-Erected ASTs: The Basics ASTs vary in size and dimensions. They can, for example, be 25 feet in diameter and 15 feet tall with a capacity of approximately 55,000 gallons, or 250 feet in diameter and 48 feet tall with a capacity of more than 17 million gallons.

Typical tank farm All figures courtesy of CB&I By field-erected tanks, we mean those that are too large to fabricate in a shop and ship to a facility, as well as those that are intended for areas where shop fabrication and shipping are not economically feasible. For example, picture for a moment that a section of Los Angeles was shut down for more than two days while moving the space shuttle Endeavor over 12 miles of streets and highways, from Los Angeles International Airport to the shuttles new home at the LA Science Center. The shuttle is approximately 122 feet long and 78 feet wide, and two space shuttles easily fit in some of the larger ASTs. So shipping tanks can become problematic. ASTs can have floating roofs (steel pan, pontoon, etc.), domed roofs, umbrella roofs, and other roof designs (Fig. 1). Regardless of the roof type, they are made predominantly from carbon steel, which is particularly prone to corrosion, compared to more noble types of materials such as stainless steel or other alloys. The use of more noble alloys, as you can imagine, is generally cost prohibitive for ASTs. So to protect carbon steel ASTs from corrosion, coatings are typically used.

Fig. 1 (Right): Column-supported cone roofs under construction Inset (Left): Detail of column-supported cone roof The general anatomy of a field-erected tank is relatively simple. The tank is highly engineered, specifically designed, and pieced together like a behemoth jigsaw puzzle in the field, with welds holding everything together (Fig. 2).

Fig. 2: Hand welding Tank Design and Coatings: The Big Picture Conceptually, we must first understand that from a coating perspective, the coating doesnt know if its being applied to one square inch of steel or 100,000 square feet of steel. In the vast majority of cases, more than 97% of any AST is flat or curved plates of steel. Coating flat or curved steel is not typically the problem. The problem, from the perspective of coating the tank, generally comes into play with the remaining percentage of the steel tankwelds, angles, support columns, and other appurtenances. Welds are particularly troublesome and are hence our focus. For our purposes, we will focus broadly on the two fundamental types of welding processes (and welds) used during construction of a field-erected AST: butt welding and lap welding. Within these two basic types of weld processes and welds are numerous subsets, such as double butt welds, vee groove welds, double-vee groove welds, single butt welds, fillet welds, double and single welds, and girth welds. Organizations such as NACE, API, ANSI, and AWWA publish documents that discuss the types of welds and their characteristics. But there appears to be a fundamental gap between the guidelines and coating considerations. That is, the folks who design and build the tanks follow very specific guidelines for tank volume, structural integrity, ability to withstand various winds, and other structural considerations. However, frequently absent from the design considerations are coating considerations. For the most part, the designers and builders of the tank rely on others for coating information. At some pointusually after the tank has been designed or is under constructionthe engineering firm, a coating consultant, or a coating manufacturer is asked to recommend a coating system (Fig. 3).

Fig. 3: Tank farm before painting. Often, coatings are not considered until the tanks have been designed. An RFQ for coating application is produced, and bids are obtained. A good specification will, of course, have detailed guidelines and relevant NACE (RP0178-95) and SSPC references on how to prepare the welds to be coated. So, the tank is built, and the coating contractor installs the coating system. But herein lies the rub. In countless cases, coating contractors have spent significant amounts of time and money addressing weldsgrinding them, smoothing them, removing weld spatter, and stripe coating them. The good news is that, assuming that appropriate QA/QC protocols were followed during the erection of the tank and subsequent coating, the facility owner ends up with a well-designed asset that is properly protected against corrosion. The bad news may be, however, that for lack of simple communication, the owner may have overpaid. Our research and experience indicate that a bit more communication between the tank builder and the coating specifier may lead to significant savings in cost and time. But well say more about that later. A Closer Look at Building the Tank and the Problems with Welds For now, lets get back to the guidelines for building an AST and the problems with welds. At this point, we are going to concern ourselves only with the broader terms of butt and lap welding. Butt welding is taking two pieces of steel, placing them edge to edge, and welding them together (Fig. 4). Lap welding, which is typically faster and less costly, takes one piece of steel and places it on top of the other piece of steel, with an overlap of, say, 2 inches; then, the two pieces are welded on top of each other. Lap welds must be welded on one side, of course, but, depending on the specification, can be welded on both. While both welds have issues pertaining to coatings, lap welds, as we will discuss later, can pose very serious issues for long-term corrosion protection (Figs. 5 and 6).

Fig. 4: Butt weld seam grinding

Fig. 5: Non-sealed lap weld at roof support showing problems resulting from open (non-sealed) side It is at the juncture of these two technical issues, technical design of the tank, including its welds, and coating surface preparation requirements for the welds, that we first see a possible disconnect between tank design and coating considerations, particularly, for the purpose of this article, coating the tank for corrosion protection. Lets go through the process of how an AST tank is conceived. A company, lets call it, Acme, is fortunate in these hard times to require additional storage capacity. Design and process engineers of the owner typically will meet to determine the required storage capacity. The next steps are to develop an RFQ, submit it to various tank erectors or engineering firms, and look for the lowest bid. At some point in the process, either Acme or the bidding firm comes up with

specifications for building the tank. The specifications, at this point, are concerned only with structural issues. All parties want to ensure that the tank is structurally sound to hold the enormous weight and volume of the stored fluids, and can also withstand environmental stresses, such as wind, rain, and snow. The parties involved will determine factors such as the type of roof, the types of welds, and the location and number of manways and vents. In most cases, these specifications are blind to coating considerations. It is highly unusual during the design and fabrication process for anyone to ask a question such as: Hey, should we reconsider the types of welds were using here because we know the tank is going to be coated once it is erected? And because such questions are typically not asked, coating concerns are left out of the initial design-build phase. The owner, fabricator and engineering firm are, again, concerned and incentivized to deliver in two fundamental ways: quality and price. And, the unspoken mantra within the industry is: If its not in the spec, it doesnt get done. And this mantra brings us back to the troublesome lap weld. If a lap weld meets the required design specifications, and is considerably less costly to use than any other weld, thats what will be used. For a moment, lets take a look at the anatomy of a lap weld. First, there are two general types, a single fillet and double fillet. From a coatings perspective, overcoating a lap weld, particularly when using a thin-film coating system, say, less than 12 mils, is problematic because the weld is somewhat of a cross between a right angle (requiring stripe coating or edgeretention coatings) and a flat piece of steel. This design requires more work from the coating installer (Fig. 6).

Fig. 6: Typical detail for a lap weld, welded on both sides Butt welds, on the other hand, if specified properly, can be made almost perfectly smooth, requiring, in many cases, no additional attention from the coating installer other than perhaps a stripe coat (Figs. 7 and 8). Of course, a butt weld is more costly.

Fig. 7: Typical detail for full fusion (twosided) butt weld, done properly

Fig. 8: Coated vertical hand-welded seal seam of butt weld Full fusion butt welds are primarily used for the body of the tank (straight walls), but the roof and floor of the tanks are typically pieced together with lap welds. Of particular concern from a coating perspective is the roof, which has the open side of the lap weld on the tank interior (Fig. 9). The floor of the tank has the open side on the tank bottom, which may present other issues due to bottomside corrosion (underneath the tank), but bottom-side corrosion is also beyond the scope of this article.

Fig. 9: Inside view of open side of lap weld. Rust is coming from the open side of the weld, which is difficult to protect with coatings. The open side of a lap weld can be highly problematic from a coatings perspective. The open side will, by definition, present a gap, and that gap can vary in size. In many petroleum tanks, it is customary to apply coatings to the bottom and several feet up the walls. This practice is common because many petroleum products are not corrosive and, in fact, protect the steel from corrosion. The bottom areas are frequently coated to protect against water precipitating out of the product and ending up in the bottom of the tank. In some crude oils and other products, sulfur may be present and, over time, could precipitate into dilute sulfuric acid at the tank bottom. Potential exposure to sulfuric acid, of course, would require the correct coating identification and specification to resist acid attack. Coating systems on tank bottoms can be fundamentally different from the coating systems on the straight wall or ceiling, due to the oil-canning effect, the tendency of the tank bottom to flex downward under pressure. When a large tank is filled with tons of fluid, it is not uncommon for the bottom to flex downward because of all of the weight of the material. For example, it is possible that with a 250-footdiameter tank, the tank bottom may deflect in the center dramatically during filling and emptying, thus requiring a coating system designed for significant movement. Alternatively or concurrently, coatings on tank bottoms can differ from those for the walls or ceiling because of a desire to protect against bottomside corrosion. Tank bottoms are routinely coated with epoxy coating systems, with or without fiber-glass reinforcement. In the open areas of lap welds confined to the roof of ASTs, corrosion may be

less of a concern, depending on the product being stored in the tank and its environment. Further, virtually all coating manufacturers have a mastic, putty, or some other material/specification to address the issue of sealing open and exposed seams. There are, however, two fundamental issues pertaining to lap welds exposed in the tank interior. First, if the tank is ever going to change service and require complete internal coating, it may be very costly and difficult to coat the entire interior because the product stored in the tank would have likely penetrated the open space of the lap weld. Second, even if the liquid level never reaches the top of the tank, vapors, humidity, and other contaminants can enter into the space, causing coating difficulties. Removing this residue would be required, and, depending on the product, might be very difficult and costly to accomplish. However, there doesnt appear to be anyone in the manufacturing and design process conducting a cost benefit analysis of comparing the costs of modifying the welding protocols to accommodate a subsequent coating installation. That is, is it less costly during tank erection to provide butt welds to NACE Weld Preparation Standard A, or is it less costly for a tank erector to leave the weld modification to the coating contractor? In simplest terms, is it less costly to have the erector remove weld spatter (or, if possible, prevent it in the first place), or is it less costly for the coating contractor to do it? For example, in a large tank, there can be a lot of welds. The average sheet of plate steel measures 8 feet x 8 feet. Therefore, in a tank measuring 250 feet in diameter, there will be roughly 4,000 linear feet of welding. If the tank is erected and the welds require modification by the coating contractor before coating application, the costs could be considerable. For instance, if the welds require grinding, removal of weld spatter, and filling with mastic, those are all additional costs that, perhaps, could have been mitigated by communication between the coating specifier and fabricator. So if it takes a coating applicator two man-hours for every 10 linear feet of weld requiring modification and the cost per man hour is $65.00 per hour, that is an additional cost of $52,000.00, not including material, scaffolding or costs of delays. Weve just briefly touched upon our concerns about internal corrosion associated with welds and coatings. We have not talked about welds and external corrosion or welds and bottom-side corrosion. While we are leaving these topics for other articles, there are a couple of points about them to keep in mind, as long as we are on the subject of welds. Many designers and professionals are less concerned with external corrosion issues because the outside of the tank is readily accessible. If there are failures or other coating deficiencies, they are typically apparent to the naked eye (unless,

of course, the tank is insulated). Further, the coating concerns for the outside of the tank typically receive less attention than those for the inside because it is understood within the industry that the welds and general appearance of the tank exterior need to have some aesthetic appeal, whereas the inside does not. So, even if were dealing with single fillet lap welds, the weld will be on the tank exterior, leaving the open side of the weld on the interior. But what about that tank bottom and bottom-side corrosion concerns? In many cases, owners will leave the underlying bottom uncoated and opt for laying down a bed of material that is naturally non-corrosive and/or use cathodic protection. Some companies have also taken to installing double-walled tank bottoms (and in some cases, retrofitting older tanks to have double walls). A double-walled tank bottom allows for monitoring the interstice, which will provide an indication of through-corrosion and leakage, but does nothing to effect or engender corrosion protection. Moreover, the double wall requires welding, which in turn creates additional corrosion concerns. Closing Thoughts There are numerous other types of welds, fittings, nozzles, columns, beams, and other appurtenances within the various types of ASTs. There are coating specifications associated with these, and we chose to focus on welding for two reasons. 1. It is endemic to all non-bolted ASTs. 2. It is an area that designers and erectors have some control over. At the end of the day, there needs to be a connection or some communication among the owner, the tank builder and coating specifier. Some questions that need to be answered are the following. 1. Is there a chance that the service of the tank will change? If so, it may be advantageous to consider double fillet lap welds throughout the tank roof. 2. What is the product to be stored? If a tank is storing oil and the service will never change, then single fillet lap wells may be sufficient. Further, perhaps it would be more cost effective for the welder, not the coating contractor, to properly prepare the welds on the bottom and 3 feet up the side walls to reduce the costs of coating application and of putting the tank in service. It appears that the typical manner in which an AST is built is driven, first and foremost, by capacity and cost. But it doesnt appear that coating cost is typically included in the pricing matrix. In fact, it may be more cost effective to identify the appropriate coating after the capacity and type of tank is determined. Then, the coating professional

(manufacturer, installer, consultant, etc.) and tank designer could discuss and determine the best types of welds to use and the most efficient means for finishing the welds for coating application, thus reducing the overall cost to the client. Acknowledgment The author would like to acknowledge the invaluable assistance of Ken Jacobi of CB&I in reviewing the article, offering insights, and providing illustrations for it.
THE JOURNAL OF PROTECTIVE COATINGS & LININGS 2013 Technology Publishing Company

Fluoropolymers for High- Performance Applications

From JPCL, February 2013
Bob Parker AGC Chemicals Americas Bob Parker is a technical service chemist for AGC Chemicals Americas in Exton, PA. He has been involved in formulating paints and coatings for over 30 years. He received his BS in chemistry from Alvernia College. He is currently responsible for technical service for LUMIFLON fluoropolymer resins in the U.S.

This article is the second in JPCLs 2013 series on generic coating types.

Fluoropolymer on the Tsurumi Tsubasa Bridge over Yokohama Bay in Japan.

The Akashi-Kaikyo Bridge has fluoropolymer protection against the aggressive environment of Japans Akashi Strait. Photos courtesy of AGC Chemicals Americas In the increasingly complex world of protective finishes, fluoropolymer-based coatings have gained a respectable position in todays marketplace. Originally restricted to OEM applications, this family of fluorine-rich hydro-carbons has expanded to include coatings that can be applied in the field as single-component coatings and as catalyzed finishes. The common thread of their performance is their resistance to degradation caused by the ultraviolet (UV) rays of the sun. This article describes the two most popular fluoropolymer resin technologies, which are the backbone of fluoropolymer coatings, and explains their role in the protective coatings field. PVdF Resin Technology The first family of fluorinated resins is the polyvinylidene fluoride (or PVdF) products. Introduced to the marketplace in 1960, PVdF resins originally were targeted for applications where the PVdF exceptional resistance to chemical degradation would be put to the test. The basic chemical structure is shown in Fig. 1. The PVdF resin is a long, repetitive chain of the structure in Fig. 1 and is known as a thermoplastic polymer or resin. This type of polymer can best be described as one that becomes flexible as its temperature increases and returns to its rigid state as the temperature cools. This behavior is in contrast to that of thermosetting polymers, which will change their chemical structure when exposed to higher temperatures and maintain a greater level of rigidity that did

not exist before their exposure to heat.

Fig. 1: Structure of Polyvinylidene fluoride These fluorinated systems are still predominantly used as factory-applied finishes for aluminum and steel substrates. The number of exterior markets is quite extensive: door and window frames, curtain walls on commercial buildings, metal roofs and facades, skylights, and decorative railings. Coatings based on PVdF resins can also contain a certain level of acrylic polymers, which increases their adhesion to the metal substrates. The percentage of acrylic resin as part of the total resin system of the coating can be either 30% or 50%. At a 30% level of acrylic resin, PVdF systems will tolerate 10 years of exterior exposure in South Florida and will still pass a long list of performance criteria that is spelled out in AAMA 2605 (a specification written by the American Architectural Manufacturers Association). The 50% level of acrylic resin will reduce the performance, but will still survive 5 years of exterior South Florida exposure and meet the requirements of another AAMA specification, 2604. PVdF resins have also been successfully emulsified in water and incorporated into single-component, ambient-cured formulations for a variety of markets. These PVdF emulsions behave quite similarly to conventional acrylic emulsions, with the resin particles forming a dry film by fusing together as the water evaporates from the coating. Coalescing solvents play a big part in these formulations, helping to soften the resin particles before they pack together and form a film. Some of the markets that have introduced commercial water-based PVdF products are roof coatings, plastic siding finishes, wood composite decking finishes, and particularly consumer house paints. The performance properties that accompany a PVdF-containing coating are excellent weatherability and color

fade resistance, dirt pickup resistance, and mildew resistance. Also, the level of VOC is less than 100 grams/liter. The application methods for these systems are the same as those used for conventional water-based acrylic coatings. However, in markets such as roof coatings, the standard application methods need to be modified. Because the main intent of the PVdF roof coating is to provide a surface that will retain its color and reflectivity, thus extending the cool roof properties of the roof and reducing energy costs, the dry film thickness (DFT) of this coating need not be greater than 3 mils. The work of sealing the roof still relies on thicker acrylic basecoats applied before the PVdF topcoat. FEVE Resin Technology The second family of fluorinated resins is the fluoroethylene-vinyl ether (or FEVE) products. The basic chemical structure of the FEVE resin family is shown Fig. 2.

Fig. 2: Structure of FEVE resin components The long chain of alternating fluoropolymer segments (blue components) and vinyl ether segments (green components) is the backbone of every member of this family of resin products. The R groups that are pictured as side chains of this backbone will vary from resin to resin, depending on the desired properties of each product. It is the side chains that give coating-friendly properties like solvent solubility and compatibility with non-fluorinated resin components to the FEVE fluoropolymer resins.

UV resistance from a fluoropolymer coating on the roof of the Ferrari World Theme Park in Abu Dhabi, UAE. The FEVE resin technology was first introduced to the coatings market in 1982. The first product came as a resin solution in a solvent carrier. Attached to its side chains were hydroxyl functional groups, which gave the FEVE the ability to be crosslinked with both amino resins and isocyanates. This property allowed the resin to be used in factory-applied, oven-cured finishes and in field-applied coatings. It was then possible to use fluoropolymer resin technology in protective coatings for metal and concrete structures that could be coated only after they had been erected on site. The field-applied coatings were two-component products, applied by methods identical to those used for the conventional polyurethanes in the industrial coating market at that time. The simple reaction of an isocyanate and a fluorinated FEVE polyol is shown in Fig. 3.

Fig. 3: Isocyanate-Polyol reaction The isocyanate resin typically has two or three reactive groups (-N=C=O) attached to each resin particle, which allows this resin to connect the hydroxyl groups (-OH) of the polyol resin particles together to form a crosslinked matrix. The increase in molecular size of the cured polymer film gives the polyol the properties such as film toughness and water resistance, which are lacking when there is only a simple polyol resin particle in the liquid coating. Since 1982, there have been numerous additions to the FEVE fluoropolymer line. In the group of FEVE resins sold as resin solutions, there are several different levels of hydroxyl functionality. Higher numbers of hydroxyl groups on the side chains will create higher crosslink densities in the cured film, which can improve properties such as solvent and chemical resistance. There are also solution resins with lower molecular weight that can produce coatings with a lower VOC content than earlier FEVE fluoropolymers. This modification has proven to be quite important because the VOC limits for industrial coatings continue to be reduced in several geographic areas of the USA. All of these resins can be blended with non-fluorinated coatings to improve the weatherability and chemical resistance of these non-fluorinated systems. In addition to the solution resins, several solid flake FEVE resins have been added to the fluoropolymer line. This collection of raw materials can be broken down into two segmentsresins for powder coatings and resins for coatings with low or no VOC content.

The FEVE powder coating resins are manufactured specifically for the architectural building component market. They can be utilized in formulations the same way as conventional (e.g., polyester) powder resins. The FEVE powder coating resins can be used as 100% of the polyol portion of the formulations, or they can be added as modifying resins.

Japans new Tokyo Gate Bridge is protected with a system that includes a fluoropolymer topcoat. The other flake resins are too soft to function in a powder coating formulation. They are simply 100% solids versions of FEVE solution resins. The benefit is the formulators ability to choose the complete solvent system for their formulations, which can lower VOC levels to comply with local government regulations as needed. In 1992, FEVE resin technology was incorporated into water-based emulsion products. This technology opened a new window for these hybrid fluoropolymers, which was the ability to form a protective film without the presence of a crosslinker. The molecular weight of the emulsion particles is high enough that the curing mechanism of an FEVE emulsion coating mimics that of a typical latex paint, which is the coalescing of the emulsion particles during the drying of the paint. The standard coalescing solvents used for latex paints will also be sufficient to soften the FEVE emulsion particles for proper film formation. The markets for these FEVE emulsion coatings are many. The substrates include metal, plastic, masonry, and wood. Although these types of FEVE-based coatings do not have the degree of chemical and solvent resistance and hardness level of the two-component coatings, they still retain excellent weatherability properties. Also, the resins are perfect candidates for use as blending emulsions, with a wide variety of acrylic emulsions already tested for their degree of compatibility with the FEVE emulsions. Figure 4 shows a comparison of two typical water-based, direct-to-metal black formulations, one containing 100% acrylic resin and the other having a 20% modification of the binder with the FEVE emulsion:

Fig. 4: QUV Weatherometer exposure of metal panels coated with Black DTM Coating; Light source is UVA-340 bulbs One of the FEVE emulsions also has hydroxyl functionality included in its structure. The OH groups allow crosslinking with water-dispersible isocyanates, which will improve the hardness of the coating film and its degree of water resistance. The VOC levels of these water-based FEVE formulations will meet current state and federal regulations. Application methods for water-based FEVE coatings are similar to the application methods used with conventional waterbased acrylic finishes. A novel water-based FEVE resin, called an FEVE dispersion, was introduced to the marketplace in 2012. The product is manufactured by a different method than the FEVE emulsions. Instead of a synthesized emulsion, the FEVE dispersion is actually a modified flake resin, which means that the dispersion has no additional chemical constituents in its structure. This change in chemical structure for the dispersion allows for improved properties in the coatings that are manufactured with this resin. The one difference that needs attention is the limitation of the FEVE dispersion resin for use only in two-component formulations. Its molecular size is too small to form an adequate film without crosslinking with either water-based isocyanates or amino resins. The markets for coatings based on the FEVE dispersion are as large as those for the solvent-based FEVE coatings. The benefit of this type of coating is its decreased impact on the environment. FEVE dispersion coatings have a lower level of the hazardous characteristics compared to coatings containing solventsnamely, flammability, odor, and toxicity. Again, the application methods required for these types of coatings are the same methods currently in

use for conventional two-component coatings. Corrosion Resistance As protective coatings, both PVdF and FEVE types play a role in the protection of metal substrates from corrosion. First and foremost, their ability to stay intact and resist degradation makes them superior to non-fluorinated coatings as topcoats in multiple coating systems on metal substrates. The barrier that they form on the surface of the metal structure will outlast other coatings by a factor of 4 to 5. One exposure test in a marine environment showed a surface erosion of only 0.2 mils after 16 years of exposure. One mil of an acrylic polyurethane finish, exposed at the same time, eroded away in 13 years. Secondly, the presence of fluorine atoms is a deterrent to water migration through the film. Less water migration means less corrosion. Conclusion It is evident that the future of protective coatings will include fluoropolymer chemistry and its diversified products. The ability of the resins present in these coatings to be used in combination with so many different raw materials and to fine-tune the properties of the coating to a specific level makes them a versatile addition to every formulators tool box. Newer fluoropolymer technologies are still being pursued at the development level. It will be important to keep an eye on what this technology can do to improve protective coatings down the road. Bibliography Yamabe, M. Fluoropolymer Coatings, Organofluorine Chemistry, 397 (1994). Munekata, S. Fluoropolymers as Coating Materials, Progress in Organic Coatings 16, 113-134 (1994). Takayanagi, T. and M. Yamabe. Progress of Fluoropolymers on Coating Applications Development of Mineral Spirit Soluble Polymer and Aqueous Dispersion, Progress in Organic Coatings 40, 185-190 (2000). Yamauchi, M., T. Hirono, S. Kodama, and M. Matsuo. The Evaluation of New Fluoropolymer Emulsion for Exterior Paint Use, The Journal of the Oil & Color Chemists Association 79, 312318 (1996).
THE JOURNAL OF PROTECTIVE COATINGS & LININGS 2013 Technology Publishing Company

In Situ Pipeline Coating Process Passes Saudi Desert Test

From JPCL, February 2013
Baker S. Hammad BSH Engineering Consultant Office Baker S. Hammad is a retired certified Engineering Consultant & Coating Specialist from Saudi Aramco with 30 years of experience in the oil and gas industry. He worked as Responsible Standardization Agent (RSA), Vice-Chair of Paints & Coatings Standard Committee, and Team Leader of the Coatings Unit of Saudi Aramco. He is a member of SSPC, NACE, and the Saudi Council of Engineers. He has written and presented papers for SSPC, NACE, and other International & Middle East Conferences and organizations. Hammad is the founder and chair of SSPCs Saudi Arabia Chapter (2010) and is an SSPCcertified instructor. He is also a NACE-Certified Coating Inspector, an Aramco-Certified Coating Specialist Engineer, an Aramco instructor for coatings and corrosion courses and a certified NACE co-instructor. He holds a U.S patent entitled Economical Heavy CWC for Submarine Pipelines (2011). Licensed by the Saudi Council of Engineers, he holds a B.S in M.E. and an M.S. in Polymers & Coatings Technology.

Surface, buried, and subsea pipelines have been coated in various geographies ranging from the North Sea, North America, Continental Europe, and Africa to Hong Kong and Indonesia. This article details the in situ coating process and then reports on an assessment of the process in rehabilitating pipelines suffering from internal corrosion at an oil desert field complex in Saudi Arabia. A trial was required to qualify the technology within a Saudi Arabia pipelines network system. History of the In Situ Coating Process The in situ coating process was developed to apply an epoxy barrier coating to

Baker S. Hammad, BSH Engineering Consultant Office

The in situ coating process has proven in many parts of the world to be a viable alternative for rehabilitating corroded pipe interiors with a wide range of diameters and lengths. Compared to replacement with new pipeline, this one-run field process is costeffective. The coating effectively controls internal pipeline corrosion through the application of multiple coats of a high-build liquid epoxy that covers the entire internal surface of the pipeline including girth welds, corrosion pits, channels, corrosion lakes or general corrosion and other internal pipeline imperfections, thus delaying leaks and extending the remaining pipeline service life.

the internal surfaces of pipelines to prevent future corrosion and extend pipeline useful life. The process has been successfully undertaken for more than 30 years in many parts of the world. More than 160 new and existing pipelines have been coated successfully, with diameters ranging from 15 to 75 cm (6 to 30 inches) and in lengths up to 25 km (16 miles). The coating process is designed to provide full internal coverage, including the coating of girth welds, bends, pits, general corrosion and erosion, and other surface discontinuities. While the bulk of the applications have been in the oil and gas industry, coatings have been applied to other pipelines including water, chemical, food, and fuel logistics. Exposure environments for all applications have varied widely. The coated pipelines have a long history of post-coating service, with certain lines coated as far back as 1978 that are still in service. To the a uthors knowledge, no pipelines have been withdrawn from service due to a compromise of the coating applied using this process, except for demolished or mothballed pipe. Outside of extending pipeline life (negating the need for pipeline replacement), other benefits of the process include effectively reducing internal pipe friction (high pipeline volumes and reduced energy costs), reducing future scraping requirements and maintenance costs, producing a cleaner product, reducing the use of inhibitors, and reducing fouling. The process is also, potentially, one of the solutions for mitigating the generation of black powder in pipes if the source of the black powder is the uncoated internal pipeline surfaces. Black powder is a broad term for byproducts, mainly iron oxides, in addition to mill scale, dust, and other irons, that formed during pipeline operations. The size of these substances varies between 1 and 100 microns. How the Process Works The in situ internal coating process is primarily based on the use of scrapers propelled by either compressed air or nitrogen. The coating is required to deliver

consistent coverage, a moisture barrier, resistance to the product transported across the scoped operating temperatures, high levels of adhesion when applied and over its useful life, no adverse reaction to the pipeline, sufficient physical strength to resist erosion, a non-toxic and environmentally benign coating, and attractive costs relative to other viable solutions.

Generally completed within 30 days, depending on the pipe length, diameter, and

internal condition, the in situ internal pipeline cleaning and coating process comprises of the following steps, which were followed in most of projects. 1. Field Inspection & Planning: This phase of the operation involves gathering the necessary technical information, including pipe diameter; suitability of line for the passage of scrapers; elevation profile; mapping of junctions, joints, restrictions, and other features, such as access at the launcher and receiver sites; planning; and logistics. 2. Site Preparation: This phase calls for procedures such as installing specialized launchers and receivers; mobilizing compressors and dryers; installing (dropout) spools and shoes; setting up effluent handling facilities; establishing the fuel and water supply; training for operator induction; and situating mobile workshops, compressors, and storage facilities for consumables. It is important for the compressor string to deliver dry and particulate-free air into the pipeline. 3. De-oiling/Dewatering: Depending on the hand-over condition of the pipeline, this phase has the objective of delivering a hydrocarbon-free pipeline that will allow the surface preparation phase to begin in earnest. All effluent will be disposed of in a manner acceptable to the client or facility owner. 4. Mechanical Cleaning: This phase requires removing all loose material (such as rust, mill scale, and dust) on the internal surfaces of the pipeline and is achieved through multiple-run passes of mechanical and brush scrapers through the pipeline in conjunction with water flushes, if necessary (Figs. 1 and 2).

Fig. 1: Mechanical Scraping All photos and illustrations courtesy of MOGSIL.

Fig. 2: Brush Cleaning 5. Chemical Cleaning (Fig. 3): This phase targets the removal of all iron oxide and mill scale and leaves the internal pipe surface cleanliness comparable to a NearWhite Metal finish (SSPC-SP 10/NACE No.2). This degree of cleanliness is required to guarantee the adhesion of the coating to the internal surface of the pipeline. This is achieved by running a dilute HCl solution containing a corrosion inhibitor between two acid-resistant scrapers. (The solution is inhibited to mitigate the risk of a negative impact on the clean internal surface of the carbon steel pipe.) The solution is titrated before and after its passage through the pipeline to determine the degree of depletion of the concentration of the solution. The effluent is also tested for solids. Batching of HCl solutions will continue until both the depletion and solids tests are within acceptable parameters. HCl is then

purged from the line with a water rinse; the rinse water will also be tested for pH, chlorides, and solids. Water rinses continue until these parameters are again within acceptable limits. Where possible, the line at drop-out spools and other access points, such as pipe ends, should be inspected visually to confirm the cleanliness of the pipeline.

Fig. 3: Chemical & Acid Pigging 6. Passivation: This phase serves to remove any oxidation (rust blooming/flash rusting) that results from the previous water rinses and to stabilize the metal surface to prevent any further oxidation. Passivation is completed by running a pH-balanced phosphoric acid wash through the pipeline. 7. Inhibited Water Rinse: To buffer the low pH of the phosphoric acid in the pipeline and further passivate the pipeline, a dilute inhibited water batch is run through the pipeline. 8. Drying: To ensure that the pipeline is dry before applying the coating two procedures are undertaken: solvent drying and dry air purging:

Solvent drying involves running suitable solvent batches through the line to remove moisture from the pipeline. Dry air purging is done slowly using dehydrated air that is tested until dew point measurements are within acceptable limits.

9. Coating Application: The coating is a specially formulated polyamide or aminecured epoxy to ensure a longer pot life and hanging-properties needed for the coating to bond to the internal pipe wall at the 12 oclock position during and after the coating application (Fig. 4). The coating is applied between two modified urethane coating scrapers and, depending on the pipe length and size, the coating is applied over a number of multiple runs, with appropriate coating drying periods, to deliver the specified dry film thickness (DFT).

Fig. 4: Coating Application 10. Testing and Quality Control (QC): Throughout the process and after coating, numerous tests, including DFT and adhesion tests, and other quality control measures, are undertaken to ensure the quality and long life of the final coating. Field Application A 40-centimeter (16-inch) crude oil trunk line was selected to test the in situ internal coating method described above and offered by one of the oil field

service specialist pipe coating companies in Saudi Arabia. The trunk line used in the trial is 10 kilometers (6 miles) long and links two gas and oil separation plants lateral lines, which connect several oil wells in the Empty Quarter desert. The corrosion identified was a combination of general internal corrosion and pitting, concentrated in the 4 to 8 oclock position in the internal surface of the pipe. The corrosion had resulted in a number of leaks recently after the pipeline was commissioned. The process involved the application of an internal epoxy coating with a DFT of approximately 8 mils (200 microns) on the internal surface of the pipeline, providing a barrier to control further corrosion on the internal surfaces. Because the cleaning and coating processes are based on scraper operations, access to the pipes was essential only at either end of the pipeline being repaired, which are identified as the launcher and the receiver. The work involved the intensive process of preparing the pipe internal surface by de-oiling and de-watering, mechanical cleaning, chemical cleaning, passivation, drying and internal coating, including inspection. For the project to begin, the pipeline had to be taken out of service and drained of oil within a specified timeframe and strict schedule. The pipeline was then given to a coating applicator for site commissioning, final de-oiling and hydrocarbon removal, mechanical cleaning, chemical cleaning, passivation, drying, and coating. The pipeline has a maximum elevation differential of 300 m (985 ft), and the launcher end is at 100 m (328 ft) above the receiver end. Figures 5 and 6 illustrate both the in situ internal cleaning and coating overall process and the core cleaning and coating tools of the pipeline respectively.

Fig. 5: In-situ internal cleaning and coating overall process

Figure 6: Standard set of different pipeline pigs/scrapers After the pipeline section was handed over to the applicator, the next step was to establish the site, which took one week. Figures 7 and 8 show the launcher and receiver sites respectively.

Fig. 7: Launcher site

Fig. 8: Receiver site The pipeline had not been purged of hydrocarbons, so after site establishment, the removal of hydrocarbons began and was completed within 14 days. The corroded pipeline (Fig. 9) was successfully cleaned, coated (Figs. 10 and 11) and handed back to facility owner within 21 days of the first scraper being run through the pipeline.

Fig. 9: Internal surface of corroded pipe

Fig. 10: Internal pitted surface of pipe before coating.

Fig. 11: Internal pipe surface finish coating Conclusions The test run at the Arabian deserts oil field confirms the usefulness of the internal pipeline in situ coating process in providing a cost-effective solution for the rehabilitation of corroded and pitted pipelines, delivering effective life extension to the pipelines services. The process can be completed with limited downtime for the pipeline, requiring access to the pipeline for approximately 30 days depending on the pipeline length and diameter. In the trial described above, the coating was proven to effectively cover pits, channel corrosion and erosion, girth welds, bends and other disconformities on the internal surface of the pipeline in the desert. Consequently, the in situ coating is a viable and reliable alternative for pipeline rehabilitations, and due to the success of the trial, has resulted in further internal coating applications in the area. References

Mining Oil and Gas Services, 32 Impala Road, Chislehurston, Sandton, South Africa. BSH Engineering Consulting Office, P.O. Box 76800, Alkhobar, Saudi Arabia (31952) Editors Note: This article is based on a paper the author presented at SSPC 2013, held January 14 to 17 in San Antonio, TX. The original paper is published in the conference Proceedings (sspc.org)
THE JOURNAL OF PROTECTIVE COATINGS & LININGS 2013 Technology Publishing Company

Preparing Concrete Floors for Coatings

From JPCL, January 2013
Tracey Glew Group Managing Director, The Preparation Group, UK

The successful application and durability of resins, coatings, and screeds on concrete floors depends on a sound surface. The key to success is in the preparation. When selecting the correct equipment and methods, consideration must be made for potential problems such as uneven joints, high spots,

contaminants, worn coatings, sticky residues, old tiles, and friable substrates, which all need to be tackled to achieve a clean, profiled surface suitable for the application of the specified coating or covering. There is a wide range of surface preparation machines and accessories on the market and a vast array of techniques that can be employed, with each unit and technique producing a different result. The model, size, and power requirements of the machine, together with the accessories selected and the type, thickness, and composition of the material to be removed, will determine production rates achievable. Other important factors to consider are area size; location and accessibility; the power supply available; and, critically, the profile required for the coating specified. It is important to note that surface preparation machines are also designed to work with dust collection and filtration units to minimize the dust contamination common in the preparation of concrete surfaces. When concrete is not finished correctly, or if it has been broom finished/tamped (packed down and having a light rippled effect), the surface may have a large degree of laitance. To achieve a sufficient bond for the specified material to be applied, this laitance must be removed. This article describes common techniques and equipment for preparing concrete before applying a coating or other system. Multi-Stripping The multi-stripping method is used to remove material from a surface or to clean it. Often, multi-stripping is selected when there are no other effective options available. There are 110-volt, hand-operated, walk-behind machines for clearing small areas, and large, ride-on, three-phase electrical or propane-powered machines for clearing large areas. Blades or picks are attached to the front of the machine and their type, weight, and position affects the removal of the designated surface. A flat blade should be selected to scrape off tiles, latex, adhesives, and elastomeric systems, while a curved blade cuts material into manageable lengths as it strips, so it is ideal to lift up membranes, carpet, and sheet vinyl. Picks are employed to break up hard materials such as ceramics and terrazzo tiles. The operator positions the machine to cut or lift the material as the machine drives forward. In this way, multi-strippers can remove floor coverings such as waterproofing membranes, epoxies, polyurethanes, sticky residues, thermoplastic materials, asphalt, bituminous materials, adhesives, and the various other coverings such as wood, vinyl, carpets, ceramic tiles, latex, and screeds. Once the floor is stripped, additional techniques for floor preparation are often specified in order to provide a suitable surface for application of the resin or

screed, etc., such as the following. Planing You would select planing to remove materials in excess of 2 mm in thickness, when there are multiple layers of coatings, and when a rippled profile is required. Applications include removing old screeds, asphalt, latex, and adhesives, and reducing tamped surfaces and levels. Machines range from small 110-volt, single-phase, to larger three-phase electrically powered petrol or diesel walk-behind models and ride-on versions for large-scale projects and heavy-duty applications. The planing operation is based on a drum rotating at high speed within the body of the machine. The profile or texture is created by the accessories fitted to the drum known as flails (Fig. 1), or picks in the case of ride-on models (Fig. 2). Once contact is made with the surface being treated, the flail configuration cuts with a downward rotary action.

Fig. 1: Underside of small planing machine showing milling flail drum Photos courtesy of the author

Fig. 2: Profile created by ride-on planing machine fitted with pick drum There are different shapes and sizes of flails and picks available for specific tasks and they can be arranged on the drum for light cleaning applications through to heavy-duty grooving. Generally, milling flails are for the removal of thermoplastic line markings (Fig. 3), bituminous materials, and rubber deposits; tungsten carbide-tipped flails are for cleaning, texturing, and roughening concrete; and star flails and beam flails are for removing soft material compositions.

Fig. 3: Walk-behind planing machine removing thermoplastic line markings

Picks can remove and reduce materials in excess of 2 mm and up to 25 mm. It is important to note that hard surfaces may be a problem for smaller planing machines because there is not enough weight to cut into the surface. This can result in the machine malfunctioning and becoming a hazard to the operator. Grinding Grinding would be selected when a flat, level, and smooth concrete surface is required. It is used for removing surface contaminants, adhesives, paint (Fig. 4), sealers, and coatings, and for cleaning.

Fig. 4: Paint removal by a single-head, threephase grinding machine Grinding models are available in single-phase or three-phase electric and in single-head, double-head, and multi-head versions. There are also diesel- and petrol-powered alternatives and variable speed models that can be fitted with provisions for wet grinding and polishing applications. Grinding is achieved by diamond (Fig. 5), tungsten, or resin-bonded plates or discs that are secured to the single or multiple rotating heads. There is a wide range of grades of diamond, resin-bonded, and PCD (Polycrystalline Diamond) shoes for removing adhesives and coatings, and for grinding, smoothing, and polishing decorative screeds and concrete screeds.

Fig. 5: Underside of grinding machine showing diamond plate As a general rule, hard composition surfaces will require a soft bond diamond segment or disc, and soft compositions will require a hard bond. The correct diamond accessory is important because incorrect selection will either simply glaze over the surface without creating the profile or wear out extremely quickly in the initial stages of the operation. Grinding is not recommended if the surface is uneven or if the concrete has been tamped. Shotblasting In the correct conditions, shotblasting is one of the most cost-effective methods of preparation. It is often selected to clean and profile power-floated concrete, to remove laitance (Fig. 6), coatings, and light surface contaminants. Surfaces to be shotblasted must be sound and hard. Shotblasting is not suitable for removing or treating soft compositions or materials thicker than 2 mm.

Fig. 6: Shotblasting machine removing surface laitance Shotblasting machines are available in walk-behind, 110-volt single-phase and three-phase electric and ride-on versions, and all offer different operating widths. The process involves propelling steel shot or abrasive at high velocity (by a rotating wheel contained in the body of the machine) onto the surface to produce the desired profile. The debris removed is then collected in a dedicated vacuum/filtration unit for disposal upon completion of the process, and the shot is recycled. Many profiles can be achieved; each profile is determined by the size or grade of shot or abrasive selected and the speed at which the machine is propelled. Shotblasting will also highlight surface defects in the substrate being prepared, and cannot be carried out in wet or damp conditions. For optimum results, the process requires a smooth, even surface; otherwise, the shot will escape from the machine. Summary Selecting the correct technique for the nature of the concrete surface to be prepared is essential for obtaining the optimum substrate for coating or further treatment.
THE JOURNAL OF PROTECTIVE COATINGS & LININGS 2013 Technology Publishing Company

Innovative Coating Systems for Steel Bridges: A Review of Developments

From JPCL, January 2013
Mike O Donoghue Ph.D. International Paint LLC, Canada Mike ODonoghue, PhD, is the Director of Engineering and Technical Services for International Paint LLC, Canada. He has more than 30 years of experience in the protective coatings industry. Vijay Datta M.S. International Paint LLC, USA Vijay Datta, MS, is the Director of Industrial Maintenance for International Paint LLC, USA. He has more than 40 years of experience in the marine and protective coatings industry. Stan Walker (now retired) Stan Walker, formerly of International Paint LLC, Canada, has over 50 years of experience in the protective coatings industry. Now retired, he offers his services to companies that market and evaluate protective coatings systems. Terry Wiseman International Paint LLC, Canada Terry Wiseman is the Canadian Manager of Strategic Marketing for International Paint LLC, Canada. He has over 20 years experience in the protective coatings industry Peter Roberts International Paint LLC, Canada Peter Roberts is the Engineering & Technical Services Representative for International Paint LLC Canada in British Columbia, Canada. He has 20 years of experience in the protective coatings industry. Norb Repman International Paint LLC, USA Norb Repman is the Regional Sales Manager for International Paint LLC, USA. He has 25 years of experience in the protective coatings industry.

Mike ODonoghue,

For the bridge community, advances in the world of highperformance coating systems have led to a dramatic technological and economic impact on new construction and bridge rehabilitation projects. The present article was condensed from a much longer and more detailed paper. The present article summarizes several key advances in bridge coating systems made mainly throughout the past 15 years. Conventional three-coat systems for bridges are described briefly, with a longer discussion of relatively recent advances in topcoat technology and two-coat technology for rapid recoating. Special attention is given to polyaspartic-polyurethane topcoats, polysiloxane topcoats, and a high-ratio calcium sulfonate alkyd system (to solve corrosion problems in crevice corroded structure-critical connections, complex geometries, and frozen bearings). Laboratory results for conventional and more recently developed systems are given, practical issues bridge engineers face for coating new bridges and recoating existing bridges are discussed, and three case histories are used to illustrate the performance of systems that incorporate polyaspartic and polysiloxane technologies. The longer report is available from the authors. Ph.D., International Paint LLC, Canada

Photos courtesy of International Paint LLC Background For over a century, protective coatings have been the primary means to afford effective and economical corrosion protection on steel bridges. In fact, from around the turn of the 18th century until the 1960s, shop- and field-coated bridge steel has invariably been coated with lead-based or lead-chromium paint systems (or both) applied directly to intact mill scale.1 Significantly, despite the lack of surface preparation before coating application, bridges thus painted have performed well for decades. Why? The reason is simple: the corrosion inhibitors in early oil or alkyd primers imparted truly outstanding corrosion resistance to the coating system. Because of health concerns associated with lead and chromium

Vijay Datta, M.S., International Paint LLC, USA

pigments in the 1960s and 1970s, the coating industry moved away from systems based on lead- or chromium-bearing primers, and alkyd mid and finish coats, to what was termed high-performance coating systems.2 The latter initially consisted of zinc-rich primers followed by one or more vinyl top-coats. Realities associated with the new coating systems have proved costly at times. First, the steel surface preparation, unlike that for the lead-based paint and conventional alkyd systems, was more expensiveabrasive blast to either an SSPC-SP 6, Commercial standard or, for better long-term coating performance, an SSPC-SP 10, Near-White Metal standard. Second, the vinyl mid and topcoats cost more than the alkyds. Vinyl coatings later disappeared from the landscape of protective coatings because of volatile organic compound (VOC) issues, and epoxy coatings replaced vinyls. Although epoxy coatings provide excellent anticorrosive barrier properties, they do chalk and fade. Therefore, a polyurethane finish was necessary to furnish the desired aesthetic qualities of good gloss and color retention. And so the three-coat zinc, epoxy, and polyurethane system Stan Walker (considered the top-of-the-line by the protective coating industry) (now retired) was born. In the main, the system has been used on bridges to this day with great success and still deservedly enjoys favor with many specification authorities despite new and innovative two-coat and one-coat systems and despite concerns regarding free-isocyanate content in polyurethane finishes.3 Significant strides have been made where coating formulators have developed innovative low VOC coating systems for bridges based on new gloss-retentive resin technologies such as polysiloxanes and polyaspartic polyurethanes.4 See Fig. 1.

Fig. 1: Gloss retention of various aesthetic topcoats (QUV-313B laboratory testing) With almost half the bridge inventory in North America requiring field painting, rapid curing and rapid recoat systems have been developed for new and blast cleaned steel.5 Alternative bridge coating practices such as overcoating and zone painting have also been successfully employed. The overcoating system is

applied to cleaned, aged, and intact lead-based paint systems.6 Spurred on by the bridge community, it has been no trifling feat for coating formulators to (a) satisfy tougher accelerated laboratory test requirements to have coating systems specified, (b) meet stricter VOC and HAPS (hazardous air pollutants) regulations, and (c) reduce coating and application costs to be economically attractive. In a nutshell, the desire of more for less is the basis for this approach. Coating Technology for Bridges Modern day bridge coating systems for new construction and maintenance projects are largely the following. (a) New ConstructionShop-applied (abrasive blasting to SSPCSP 5, White Metal)

Terry Wiseman, International Paint LLC, Canada

Zinc/Epoxy/Polyurethanes (3-coat) Zinc/Polysiloxanes (2-coat) Moisture-Cured Urethanes (3-coat) Water-Based Systems (3-coat)

(b) MaintenanceField-applied (abrasive blasting to SSPC-SP 10, Near White, or SSPC-SP 6, Commercial)

Zinc/Epoxy/Polyurethanes (3-coat) Moisture-Cured Urethanes (3-coat) Zinc/Epoxy/Polysiloxanes (3-coat) Zinc/Polysiloxanes (2-coat) Zinc/Epoxy/Polyaspartics (3-coat) Zinc/Polyaspartics (2-coat) Zinc/Polyurethanes (2-coat)

(c ) MaintenanceField-applied (overcoating)

Epoxy Penetrant Sealers/Epoxy/Polyurethanes (2- or 3-coat) High-Ratio Calcium Sulfonate Alkyds (HRCSA) and CSA coatings (1- or 2coat) Moisture-Cured Urethanes (3-coat)

Two-Coat Bridge Systems Two-coat reinforced inorganic zinc (reinforced with a small amount of organic polymer to enhance the effectiveness of zinc) and high-build polyasparticpolyurethane (or acrylic-polyurethane) finish coats have excellent industrial track records for large projects where rapid recoat of the inorganic zinc-rich primer and rapid curing is required to increase shop throughput. These coatings systems can be shop-applied in one shift and potentially shipped to a job site the next day (Fig. 2).

Fig. 2: Shop production The coating innovation provided for DOTs and MOTs is that the same level of protection of a three-coat system can be obtained in two coats and at a reduced overall cost. Success has been reported where bridge sections received a two-coat rapid return to service moisture cured zinc-rich/polyaspartic topcoat in lieu of a NEPCOAT- (North East Protective Coating Committee) approved (traditional) three-coat zinc-rich/epoxy/polyurethane system. The two-coat system saved the owner 26% in direct costs and 24% in indirect costs.7 Rapid Deployment (KTA-Tator) is a relatively recent term used in bridge maintenance painting.8 It describes a process that has been investigated by many DOTs and MOTs. The need for such a process was brought on by the excessive costs related to traffic control during abrasive blasting and painting of bridges over multilane highways. The cost of permanent type barriers for traffic control has been reported to be about $600.00 per foot, and so a new bridge painting methodology was sought. Peter Roberts, International Paint LLC, Canada The concept of abrasive blasting and coating the underside of structural steel on bridges over multi-lane highways while on the go was attractive and ensured that only one lane of traffic would need to be controlled (and then only during off-

peak times such as between 6 p.m. and 6 a.m. in most jurisdictions). Another need quickly became evident: a mobile setup to abrasive blast the bridge structure, which in turn was followed by yet another mobile setup that would contain the painting process. There was also the requirement for confinement to satisfy environmental concerns and to prevent egress of waste and overspray materials otherwise offensive to traffic in adjacent traffic lanes. The containment proposed was to be part of the mobile setup on both the abrasive blasting and application vehicles. The focus then became: Could an innovative two-coat highperformance system provide the necessary dry-to-recoat and cure times while providing the long-term corrosion protection afforded by the traditional three-coat zinc/epoxy/urethane system? The answer lay in the real-life and successful coating applications in other industrial settings using a reinforced zinc primer or appropriate organic zinc primer at 3 mils DFT followed by a polyaspartic-polyurethane finish at 6 mils DFT. This approach Norb achieved the corrosion protection, gloss retention, and color 9 Repman, stability desired by MOTs and DOTs. International The reinforced inorganic zinc can be top-coated within 60 minutes Paint LLC, at temperatures as low as 40 F (5 C), and the USA polyasparticpolyurethane topcoat can then be applied at 6 mils DFT, also at temperatures as low as 40 F (5 C). Alternatively, the more traditional and slower-curing high-build acrylic polyurethanes may be used in lieu of the faster-curing polyaspartic polyurethanes. In addition, the desirable mechanics of the mobile rigs have proven to be attainable as a result of innovation abilities of the painting contractor community in North America. Accelerated Laboratory Testing CPTP Cooperative Paint Testing Program 2008 The Alberta Transportation and British Columbia Ministry of Transportation invited coating manufacturers to submit candidate systems for accelerated laboratory testing which, if accepted, would be placed on the CPTP Recognized Product List.10 The CPTP committee elected to test coating systems for steel infrastructure. The tests consisted of preparing coated panels and scribing to bare metal with a Tungsten carbide lathe tool. The scribe was 5 cm long and on the lower third of each panel at 45 degrees from the vertical. The high-performance coatings submitted by the authors company were as follows.

Reinforced inorganic zinc/hydrocarbon-modified epoxy/acrylic polyurethane

Reinforced inorganic zinc/modified phenalkamine epoxy/acrylic polyurethane* Reinforced inorganic zinc/modified phenalkamine epoxy/acrylic polyurethane Reinforced inorganic zinc/hydrocarbon-modified epoxy/polyaspartic polyurethane Organic zinc/hydrocarbon-modified epoxy/polyaspartic polyurethane Reinforced inorganic zinc/polyaspartic polyurethane* Organic zinc/polyaspartic polyurethane* Reinforced inorganic zinc/adducted phenalkamine epoxy/polyaspartic polyurethane Organic zinc/epoxy polyamide/acrylic polysiloxane* Organic zinc/epoxy polyamide/acrylic polyurethane*

All the systems listed above passed the CPTP test regimen. They were subsequently placed on the Recognized Product List. For the sake of brevity in this article, the scribe undercut results of only five representative coating systems (asterisked above) are shown in Table 1. The scribe resistance for the coating systems was similar (ranking 8 out of 10 or exhibiting approximately 1 mm of undercutting after 3,015 hrs in cyclic weathering), whether or not the zinc primer was an organic zinc, with approximately 90% zinc by weight in the dry film, or a reinforced inorganic zinc, with 62% zinc in the dry film. This resistance accords well with the position held by Hendry that the performance by zinc coatings is more a function of the total coating formulation than that of the zinc content alone.11 The high-build polyaspartic polyurethanes and polysiloxanes and high-quality, thin-film acrylic polyurethane finish coats all had very similar initial gloss and gloss-retentive properties. The corrosion and UV results obtained with the threecoat organic zinc/epoxy/acrylic polysiloxane were excellent. This system is popular where isocyanate-free topcoats are either preferred, or mandated, by bridge authorities. The overall results for the two-coat rapid recoat systems were very similar to the results for the more traditional three-coat systems. Other things being equal, this lends further support to the notion that for new construction or field maintenance bridge projects, the two-coat systems yield similar results to those using threecoat systems. However, while accelerated test results are good indicators of performance, it is important not to over-interpret the data in terms of real-life performance.

TABLE 1

CPTP Test Results Test Panel R4 R8 R9 C26 C27 Zinc Primer Reinforced Inorganic Zinc Reinforced Inorganic Zinc Organic Zinc Organic Zinc Organic Zinc Epoxy Midcoat Phenalkamine NA NA Epoxy Polyamide Epoxy Polyamide Finish Coat Acrylic Polyurethane 1 Polyaspartic Polyurethane Polyaspartic Polyurethane Acrylic Polyurethane 2 Acrylic Polysiloxane Scribe Undercut 1 mm 1.5 mm 1 mm 1 mm 1 mm

Overcoating Bridge coatings that contain lead pigments have been used for more than 100 years. The choice facing DOTs and MOTs is whether to refurbish bridge structures by abrasive blasting and application of suitable coatings or to highpressure water wash/power tool clean them and apply an overcoat system. The cost of surface preparation is markedly different for either scenario. For instance, in 1994, costs ranged from $4$13/ft2 for abrasive blasting, full removal of the lead-based paint coating, and application of the replacement coating system, to $2$7/ft2 for a pressure wash and an overcoat option).12,13 As with most costs, these figures likely have risen substantially. The crux of the matter for successful over-coating is twofold. First, the best candidate overcoat systems for bridges are those that, even under extreme hygrothermal stress from inclement weather conditions, will indefinitely exert minimal stresses on the underlying and intact lead-based paint systems. Second, coatings (typically, penetrant sealers) must perform year-round in structurecritical connections and pack-rusted areas where crevice corrosion has occurred. Preference must be given to low viscosity and high wetting systems with the ability to remain flexible in crevice-corroded joints. Hare emphasized the importance of low viscosity and high wetting penetrant sealers for successful overcoating.14 Epoxy Penetrant Sealers and HRCSA Sealers Given the importance of a coating to penetrate structure-critical connections and consolidate rusty surfaces, the authors have conducted three studies that compared a variety of sealers, including epoxy penetrant sealers and HRCSA

sealers. Key results from these three studies are combined in Table 2. In one study, the authors compared and contrasted the viscosities of epoxy penetrant sealers and several other sealers, but not HRCSA.15 In the 1998 study, the best all-around penetrant sealer was one of several ultra-low viscosity 100% solids epoxies. As evidenced in scanning electron microscope photographs in the study, the sealer possessed air- and water-displacing properties and the ability to impregnate and bind loose rust surfaces. To maximize the penetration, wetting, and capillary action of two-component, 100% solids epoxy penetrant primers (or any primer) on rusted steel or on aged coatings, viscosities of less than 30s in a#4 Ford Cup are required. One of the epoxy penetrant sealers in the 1998 study (Coating A in Table 2) had a viscosity of 13s, i.e., approaching that of the 7s measured for water. This water-thin epoxy technology in the 1998 study was also tested in a low-temperature-curing version (Coating B). Both are suited to applications to structure-critical connections on a bridge. In another study, the authors compared the overcoating properties of HRSCA (Coating K in Table 2), with generic epoxy penetrants, moisture-cured urethanes, thinned high-build epoxies, and methyl methacrylates, including their viscosities.16 Overall, the study showed that the best overcoating technology is afforded by HRCSA coatings. These single-component coatings cure by air oxidization and have a tremendous record of success, not only as bridge overcoat systems but when the specified surface preparation is abrasive blasting to either SSPC-SP 10, Near-White Metal standard, or SSPC-SP 6, Commercial standard. Flexible and exerting minimal shrinkage stress on aged lead-based paint systems, HRCSA coatings do not delaminate even when the full overcoat systems are subjected to large hygrothermal stresses. Moreover, HRCSA penetrants continuously release corrosion inhibitors into joints and connections. An unpublished study by the authors17 showed that an HRCSA penetrant sealer possessed a similar viscosity value to two of the two-component, modified aliphatic amine 100% solids epoxy penetrant sealers from the 1998 study, Coating A and Coating B in Table 2. The authors determined that the viscosity effect of penetrant sealers did not fully predict the capillary and wetting effect of the penetrant sealers, and further work was undertaken to measure the contact angles and surface energies of the penetrant sealer coatings applied to rusted steel (Fig. 3). Surface tension and contact angle results are summarized in Table 2.

Fig. 3: Overcoat study: Surface tension vs contact angle for penetrant sealer coatings A bridge engineers perspective is invariably that mitigating corrosion in crevice corroded joints is paramount. This is especially true in any overcoat project. Overcoat systems based on HRCSA and the modified aliphatic amine 100% solids penetrant sealers are best applied over steel surfaces prepared to SSPCSP WJ4. Care must be taken to first clean the joints and connections by high-pressure water cleaning with specialized soluble salt removers (soluble salts are kept below 10 g/cm2) and then flush joints with clean water. Importantly, overcoating projects and laboratory research have shown that coating adhesion, while important, is one of the least important factors in successful coating applications.18 Based on Reference 18, the present authors hold that the following factors identify the suggested new paradigm for successful overcoating: Wetting and Penetration > Inhibition and Passivation > Moisture Tolerance > Flexibility > Benign Influence > Barrier Properties > Adhesion.
TABLE 2

Penetrant Sealers: Viscosity, Surface Tension and Contact Angle Measurements Coating Epoxy Penetrant Sealer Epoxy Penetrant Sealer Epoxy Penetrant Sealer Epoxy Penetrant Viscosity(s) Surface Tension Contact Angle (dynes/cm) (degrees) Rusted Steel 13 17 334 36 38 40 <2 <2 8.5

A B C

Sealer D E F G H I J K Epoxy Penetrant Sealer Epoxy Penetrant Sealer Epoxy Penetrant Sealer Moisture-Cured Urethane Sealer Polysiloxane Phenalkamine Epoxy (10% thinned) Phenalkamine Epoxy (30% thinned) High-Ratio Calcium Sulfonate Alkyd 54 49 Not measured 63 38 43 14 22 36 40 41 37 39 45 39 30 <2 <2 20 28.8 30 35.3 32.5 12.3

General Discussion Bridge engineers have many critical decisions to make with respect to their field inventory, safety, and selection of the high-performance coating. For instance, when in need of maintenance, should bridges be abrasive blasted and painted or should their old lead-based paint be overcoated? In the case of the former, the relatively new two-coat high-performance coating systems have the potential to provide decades of excellent corrosion protection. To maximize the potential for success, stripe coating must be undertaken.19 Stripe coating is even more crucial in the case of a two-coat system than a threecoat system. This is especially so if the individual coats have been applied at somewhat higher DFTs than recommended by the coating manufacturer. In fact, overly thick coating films have excessive internal stresses, which can cause tensile adhesion failures and lateral cohesion failures of the overall coating system. Hence, to derive the full benefit of a two-coat system, it is crucial to apply the correct film builds of both the zinc-rich primer and high-performance finish coat. As stated earlier, a two-coat system consisting of a reinforced inorganic zinc and a polyaspartic polyurethane system is one of the answers well suited to rapid return to service projects and wet-on-wet coating applications where the primer is topcoated immediately after application. Thousands of tons of structural steel have been coated with this system to provide corrosion protection in harsh

industrial and seacoast environments; it is well suited to the use on bridges. However, a key decision for the bridge engineer is whether or not to use one of the newer technology high-gloss finish coat technologies such as a polyaspartic polyurethane or polysiloxane. (See Case Histories) Case Histories Case History 1: Complete Removal of Old Coating System In a 2007 bridge coating project in the U.S., the original specification sought a polyurethane finish, but due to the deep, forest green color of the bridge, the parties to the contract decided to switch to the more color-fast acrylic polysiloxane finish (Fig. 4). Full containment was used, and the surface preparation was abrasive blasting to SSPC-SP10, Near-White Metal. A three-coat system was employed: an organic zinc-rich primer, an epoxy polyamide midcoat, and an acrylic polysiloxane. As anticipated, five years later, the high gloss and deep green color of the acrylic polysiloxane are outstanding.

Fig. 4: SSPC-SP 10/organic zinc/epoxy polyamide/acrylic polysiloxane Photos courtesy of International Paint LLC Case History 2: Maintenance The first phase of a bridge re-paint began in Saint John, New Brunswick, Canada in 2006. The steel was abrasive blasted to SSPC-SP 10, Near-White Metal, and coated with an inorganic zinc primer, an epoxy midcoat, and a polyurethane finish. The system performed well throughout the summer and fall but during the winter, on the inside spans (above high tide water levels), the humidity exceeded the manufacturers recommendations for a thin-film polyurethane application. As a result, in the following year, the owner and engineer changed the finish coat specification, replacing the acrylic polyurethane finish with a polyaspartic polyurethane topcoat that would not be adversely affected by the high relative

humidity resulting from proximity to water from the high tide (Fig. 5).

Fig. 5: SSPC-SP 10/inorganic zinc/epoxy/polyure-thane on sides, and inorganic zinc/epoxy/polyas-partic polyurethane underneath Case History 3: Complete Removal of Old Coating System In 2010, a bridge coating project in Canada was specified with the options to use a traditional three-coat system with a polyurethane finish or a recently tested and approved (by the local highways authority) two-coat system using a polyaspartic polyurethane. The successful contractor determined that the two-coat system was the most efficient system for this bridge project. Surface preparation was abrasive blasting to SSPC-SP 6 Commercial Standard and the two-coat system employed was an organic zinc-rich primer and a polyaspartic polyurethane finish coat (Fig. 6). The contractor used an epoxy to stripe edges and welds between coats.

Fig. 6: SSPC-SP 6/organic zinc/polyaspartic urethane Fig. 5: SSPC-SP 10/inorganic zinc/epoxy/polyurethane on sides, and inorganic zinc/epoxy/polyaspartic polyurethane underneath Given that the polyaspartic and polysiloxane technologies do not have as many case histories as the older technology types, an understandable reticence exists on the part of many bridge engineers not to be the guinea pig. The authors propose that a smart approach would be for DOTs and MOTs wishing to cautiously adopt new coatings technology to partner with reputable coating manufacturers. Both parties can share the responsibility that the coatings will perform satisfactorily for at least 15 to 20 years. Therefore, any initial hesitancy to stray from the proven realm of three-coat zinc/epoxy/polyurethane systems to innovative two-coat systems is overcome. One simple way to indicate whether or not an existing bridge is a good candidate for overcoating is to abrasive blast test areas on the steel. If holes are blown through the steel on the bridge in question, then forget an overcoat system. Success or failure with respect to overcoating is thought by some to be unpredictable. Poor coating choices and premature overcoating failures gave rise to this perspective. Failure to understand the chemistry of the overcoating system is at the heart of the issue. As highlighted earlier, the use of penetrant sealers for crevice-corroded joints and connections, pack-rusted sections, and bearings cannot be overemphasized. It is in these structure-critical connections areas that bridges invariably fail.20 The use of de-icing road salts is a huge issue as far as corrosion of steel in joints, connections, and bearings. Many DOTs have a team that every two years pressure wash the bridges and remove the salts. The solution to reducing the costs of the cleaning operation is to use superior coating systems and thereby extend the interval between pressure washings. This will save considerable time and money. While industry creates new grades of steel (developments in weathering steel, etc.), coating manufacturers develop new coatings technology; meanwhile, corrosion is an ever-moving and costly target. Against this backdrop, during the past few years, the Ministry of Transport in Canada has identified certain areas of concern over the corrosion of weathering steel. Thus far, the coating systems applied to weathering steel have been used only above concrete areas to eliminate or reduce concrete staining. The Ministry has found evidence of pitting corrosion and flaking of steel elements on the steel as a result of ongoing corrosion. Consequently, it has now undertaken a study program in conjunction with steel producers and universities to develop yet another new grade of

weathering steel to overcome this critical issue. The recently completed (although not formally reported on at the time of writing) test results will confirm that VOC-compliant materials in either two- or three-coat applications at a total DFT of 9 mils did satisfactorily protect the weathering steel. Based on single-component technology, the old lead-based alkyd paint systems were simple to apply, gave long-term corrosion protection, and provided costeffective corrosion protection to bridges for some 100 years. Ironically perhaps, in the present era of high-performance zinc, epoxy and polyurethane coatings as well as other coating types such as moisture-cured urethanes, polyaspartics, polysiloxanes, and high ratio calcium sulfonates research is underway to find a 100-year bridge coating system, albeit in a single-coat application. Kline has discussed how to obtain the desired 100 years of service life using zinc-rich coatings currently available.21 He was instrumental in the rapid return to service approach for bridges.22 In other work, Lee has shown that a single-coat system of HRCSA technology has performed particularly well in comparison to single-coat systems of thermoset coatings such as polyaspartic polyurethanes and epoxy polysiloxanes. 23 Conclusions As the worldwide bridge inventory continues to age, the manufacturers of high performance protective coatings have developed three- and two-coat systems based on zinc primers and polyaspartic, polyurethane or polysiloxane finish coats. The finish coats have more history in three-coat systems than in two-coat systems but are proving their effectiveness in both types of systems. Accelerated laboratory test procedures currently available allow the industry to provide owners a comparison of bridge systems used in yesteryear with innovative, present-day high-performance systems. Overcoating is a viable bridge painting option to give long-term corrosion protection. The best overcoat systems are those based on HRCSA technology. Editors Note: A version of this paper has been published in the Proceedings of the 8thInternational Conference on Short and Medium Span Bridges, 2010, and the present paper is published with the permission of the Canadian Society for Civil Engineering.
REFERENCES

1. Kogler R . Painting Highway Bridges and Structures, Good Painting Practice, SSPC Painting Manual, Vol. 1, Pittsburgh, PA, USA, SSPC: The Society for Protective Coatings: Pittsburgh, PA, 2002. 2. Kline E.S . Durable Bridge Coatings, Modern Steel Construction 2009.

3. ODonoghue M, Garrett R, Datta V.J . Straining at a Gnat and Swallowing a Camel: Health and Performance Issues with Two-Part Polyurethane Finish Coats. JPCL, December 2006, 2837. 4. ODonoghue M, Datta V.J . The VOC Odyssey: An Epic Tale of the Green World of Coating Formulators, JPCL, May 2009, 2638. 5. Kline E.S, Angeloff C.A . P.E., Rapid Deployment: A Potential Approach to Reducing the Costs of Painting Steel Overpass Bridges over Busy Highways, JPCL, January 2000, 7985. 6. Kline H.H . Inorganic Zinc-Rich. Generic Coating Types, SSPC: The Society for Protective Coatings: Pittsburgh, PA, 1996, 165. 7. Castler B . Rapid Deployment Technology: A New Concept for Connecticut, International Bridge Conference, Engineers Society of Western Pennsylvania, Pittsburgh, PA, June 10, 2003, cited in Gardner, G.W., Three-Coat Performance in a Two-Coat System, JPCL/PCE, October 2006, 3847. 8. Kline E.S, Angeloff C.A . P.E., Rapid Deployment: A Potential Approach to Reducing the Costs of Painting Steel Overpass Bridges over Busy Highways, JPCL, January 2000, 7985. 9. ODonoghue M., Garrett R, Datta V.J, Osborne S, Roberts P . Win dmillsFast Production Schedules with Novel Zinc Primers and Polyaspartic Ester Topcoats, Proceedings of the PACE 2005 Conference, SSPC: The Society for Protective Coatings: Pittsburgh, PA, 2005. 10. CPTP, personal communication with Raine, R., Coordinator CPTP (Trans Canada Coating Consultants Ltd.), 2010. 11. Hendry C.M . Inorganic Zinc Rich Primers - Fact and Fancy Materials Performance, 19, 1978. 12. Appleman B.R . Overcoating vs. Removing Lead Paint: A Comparative Analysis. JPCL Special Report, November 1993, 60. 13. Appleman B.R, Kline E.S, Eckert E.J, Semanderes S . SSPC Training Program: Specifications for Overcoating Lead Based Paint, Pittsburgh, PA, USA, 1994. 14. Hare C.H . Preventing Overcoating Failures, JPCL, November 1997, 5059. 15. ODonoghue M, Garrett R, Graham R, Datta V.J, Peer L . Penetrati ng Sealers: A Comparison of Epoxy, Moisture-Cured Urethane, and Siloxane Technology on Concrete, Rust, and an Inorganic Zinc Coating. JPCLDecember 1998, 3047. 16. ODonoghue M, Roberts P, Datta V.J, McManus T . Overcoating Load-Based Alkyd Paint on Steel Penstocks: Practical Experience, JPCLAugust 2009. 17. ODonoghue M, Datta V.J, Peer L . Unpublished study, August 2003. 18. ODonoghue M, Roberts P, Datta V.J, McManus T . Overcoating Load-Based Alkyd Paint on Steel Penstocks: Practical Experience, JPCLAugust 2009.

19. Tritremmel M . 2010. International Paints LLC., Personal communication. 20. Ballinger C, Senick W . Bridge Coatings Blasting is No Way Out, Roads and Bridges September 2003. 21. Kline E.S . Durable Bridge Coatings, Modern Steel Construction 2009. 22. Kline E.S, Angeloff C.A . P.E., Rapid Deployment: A Potential Approach to Reducing the Costs of Painting Steel Overpass Bridges over Busy Highways, JPCL, January 2000, 7985. 23. Lee S-K, Yao Y, Chong S-L . The Most Recent Test Results of One-Coat Systems Applicable to Steel Bridge Structures, The Proceedings of PACE, 2008, SSPC: The Society for Protective Coatings: Pittsburgh, PA, 2008.
THE JOURNAL OF PROTECTIVE COATINGS & LININGS 2013 Technology Publishing Company

Formulating Options for Polysiloxanes

From JPCL, January 2013
Gerald L. Witucki Dow Corning Corporation Gerald (Jerry) Witucki, Associate Coatings Scientist at Dow Corning Corporation, has provided technical support and product development of silicone additives and resins for the paint and coatings industries. He has been with the company for more than 28 years. He has written numerous articles on the use of silicon-based technologies, presented at many industry events, and holds more than 20 patents in the field. He is a graduate of Central Michigan University with an MBA and bachelors degrees in Business Administration and Chemistry.

The industrial protective coatings market has established siliconeorganic hybrid systems as premium topcoat technology. Product offerings designed for use in these hybrid systems are available from both organic and silicone suppliers. For a coatings formulator seeking to create a high-performance finish, the potential combinations of silicon-based and organic materials present a daunting number of options and technical challenges. Gerald L. Over the last quarter century, the role of silicon-based Witucki, Dow technologies has evolved and expanded in the protective coatings Corning markets. Widely known as additives to reduce the coefficient of Corporation friction and enhance the durability of coatings, silicon-based technologies also include: monomeric silanes with organic and inorganic reactivity to serve as adhesion promoters, pigment treatments, cross-linkers and water repellents, resinous silsesquioxanes for improved thermal and weathering performance and an array of additives comprised of polydimethyl siloxanes (both loved and reviled), silicone polyether copolymers and organo-functional siloxanes, supplied neat, as elastomers, solvent solutions, or aqueous dispersions and emulsions. Each specific technology provides enhanced functionality and performance to coatings formulations across the industry. While most of these materials are utilized at incremental levels, silicone resins are typically included as a significant portion of the coatings resin binder. While silicone resins exhibit excellent thermal and ultraviolet radiation resistance, their physical properties are less than ideal for the protective coatings market. Silicone resins formulated to be hard and abrasion resistant are typically inflexible and brittle; soft and flexible silicone resins are easily abraded. The chemical and corrosion resistance of silicones can be described, at best, as fair. Fortunately, valuable performance benefits can be achieved by the hybridization of the siloxane with organic resins. This article describes the development, properties, and uses of siloxane resins, with a focus on formulation options and recent research into new amine silicon functional resins for polysiloxanes.

Polysiloxane finishes have found a wide array of protective coating applications. Photo: Akiyoko74 / Dreamstime.com Early Silicone Hybrids Through the 1960s, traditional silicone-organic copolymers relied on the condensation reaction of hydroxyl functional silicone (solid flake) resins with hydroxyl functional organics, such as alkyds and polyesters. While traditional silicone alkyds can be considered hybrids, in the sense that two dissimilar materials are copolymerized to achieve improved properties, the oxidation cure chemistry of the alkyd remains essentially unchanged. And all of these systems rely on high levels of solvent to ensure miscibility and stability of the siloxane. This technology was augmented in the 1970s with alkoxy functional siloxanes. These silicone resin intermediates were introduced as solventless liquids that allowed for easier loading, lower solvent requirements, and better miscibility in organic systems. This approach resulted in a dual-cure systemthe oxidation or melamine-crosslinking of the organic, along with the hydrolysis and condensation of residual silylalkoxy functionality (Fig. 1). This technology provides coatings with excellent weathering and chemical resistance, but relies on atmospheric moisture, requires the inclusion of titanate (hydrolysis) and tin

(condensation) catalysts, and suffers from the potential for post-cure drift and embrittlement.

Polysiloxane finishes have found a wide array of protective coating applications. Photo: Akiyoko74 / Dreamstime.com

Fig. 1: Hydrolysis and condensation of alkoxy silane to form silicone resin Formulating for Compliance and Performance To achieve the proper balance of regulatory compliance with long-term performance, it is necessary to create organo-reactive, low-viscosity polymers with low levels of volatility and outstanding durability. Owing to the inherent stability and flexibility of the siloxane (SiO-Si) bond, silicones are well-suited to meet this challenge. In addition, silicon-based chemistry allows for the inclusion of many reactive functional groups. The question is: Which reactive groups have the greatest utility across coatings systems?

Table 1 shows the six major resin classes typically utilized in the protective coatings market. While the black box chemistry sets of many formulators contain many secret combinations of ingredients, generally the systems can be distinguished by the reactive groups employed to achieve the basic chemistries.
TABLE 1

Coatings Resins by Functional/Reactive Chemistries System Polyurethan e Epoxy Polyester Alkyd Acrylic Amine Amin Carbin Epox Carbox Acrylat Isocyanat Aldehyd Pheno e ol y y e e e l

Amine and carbinol chemistries have the broadest utility across coatings markets. Both moieties possess excellent potential as the reactive chemistry on a siloxane polymer. Carbinol chemistries are beyond the scope of this article. The remainder of the discussion focuses on properties obtained from recent research on a liquid, amine functional silicone resin designed to improve the flexibility and durability of organic resins, and to have potential utility in the majority of coatings chemistries and applications. Initial formulating work was conducted using a standard aliphatic epoxy resin (Fig. 2). No titanate or tin catalyst is required, and the reliance on ambient moisture is eliminated.

Fig. 2: Initial reaction of amine-functional silicone resin with aliphatic epoxy resin Extensive evaluation of silicone prototypes was conducted to sort through the wide range of potential siloxane structures. Identifying the performance attributes

and test methods was critical to understanding the relationship of structure and performance. Compatibility with organic resin systems and cure rates, along with improving the coatings resistance to water and weather, were selected as the priority benefits. Absorption of water into a coating can result in degradation of the film appearance and lead to subsequent attack and corrosion of the substrate. Figure 3 shows that by replacing a traditional aliphatic amine crosslinker with the amine functional silicone resin, the water uptake of a BPA epoxy was reduced from 2.5% to less than 0.5% over a 3,000-hour test period. Figure 4 shows comparable results with an aliphatic epoxy resin.

Fig. 3: BPA epoxy water absorption (% wt gain)

Fig. 4: Aliphatic epoxy water absorption (% wt gain) Lab data in Table 2 shows that this water resistance translates into improved resistance to aqueous chemical attack. Three drops of various aqueous chemical solutions were placed on the panels; next, the test panels were covered with a watch glass for 24 hours and then evaluated. The data shows that the silicone amine resin provided chemical resistance superior to that of the epoxy/organic amine coating. The polysiloxane sample that is comprised of an epoxy resin, an amine functional alkoxy silane monomer, and an alkoxy functional silicone resin

exhibits the best chemical resistance. This result suggests the use of tailored formulations to attain specific performance benefits.
TABLE 2

Chemical Resistance of Pigmented Topcoats Chemicals Hydrochloric Acid (50%) Formic Acid (10%) Nitric Acid (50%) Phosphoric Acid (50%) Acetic Acid (10%) Sulfuric Acid (50%) Sodium Hydroxide (20%) Potassium Hydroxide (20%) Ammonium Hydroxide (20%) Avg rating for all chemicals Avg rating for acids only Avg rating for bases only Epoxy/Silicone Amine 4.5 4 2.5 3 4 4.5 5 5 5 4.17 3.75 5 Epoxy/Organic Amine 2 2.5 2 2 5 2 5 4 5 3.28 2.58 4.67 Polysiloxane/Epoxy 3 4 2.5 3 4 4.5 4.5 4.5 5 3.89 3.50 4.67

Rating: 0total film failure, 5No effect As shown in Fig. 2 the reaction of epoxy and amine functional groups results in the formation of secondary hydroxyl groups. This residual functionality serves as a point of chemical attack. The inclusion of alkoxy functionality through a silane monomer or a siloxane provides a means by which to cap off the hydrophilic hydroxyl group, increase crosslink density, and thereby improve chemical resistance (Fig. 5) and corrosion resistance (Table 3 and Fig. 6).

TABLE 3

Salt Spray Resistance % SI Aliphatic Epoxy Topcoat Crosslinked with: Scribe Creep (mm) 55 48 37 57 67

50 Amine functional silicone resin and organic amine 60 Amine functional and alkoxy functional silicone resins A 70 Amine functional and alkoxy functional silicone resins B C 0 0 Organic amine (control 1) Two-component polyurethane (control 2)

Fig. 5: Alkoxy-capping of residual hydroxyls

Fig. 6: After 1,500 hours salt spray The reaction rate of the epoxy-amine chemistry is affected by concentration. As a result, polymeric reagents (either organic or siloxane) with a high amine equivalent weight will result in a slower cure rate compared to curing agents with low amine equivalents weights. This is simply due to the fact that at a more dilute concentration, the amine and epoxy groups are less likely to contact each other and allow reaction. For example, with an amine hydrogen equivalent weight of 262 (grams/NH), the cure rate of a coating containing the novel amine functional silicon resin would be expected to be much slower than a coating based on ethylene diamine (15 grams/NH). Along with concentration, amine structure (primary, secondary, or tertiary) will also affect the cure process. Preliminary data (Fig. 7) shows that the silicone amine resin in combination with the aliphatic epoxy provides the anticipated gloss retention after external exposure. Weather induced yellowing (Fig. 8) is much less for the siloxane containing formulations as compared to the control. The silicone amino resin is comparable to the polysiloxane hybrid formulation. The addition of one percent of a UV absorber further reduces yellowing and improves gloss retention comparable to that of a two-component polyurethane.

Fig. 7: Gloss retention of cycloaliphatic epoxy topcoats

Fig. 8: Yellowing of cycloaliphatic epoxy topcoats Utility for polysiloxane topcoat finishes has been found in a wide array of protective coatings applications such as bridges, oil platforms, water towers, and other industrial and municipal facilities anywhere steel structures are exposed to environmental conditions. This technology facilitates the shift from the threecoat (primer/basecoat/topcoat) system to a two-coat (primer/topcoat) operation with less labor cost and downtime. The polysiloxane coatings are applied via spray, brush, or rollermuch like any conventional two-component coating. The amine-epoxy cure of this resin system eliminates the isocyanate exposure concerns related to polyurethanes. Concerns about methanol exposure from alkoxy silane hydrolysis in traditional polysiloxane coatings are also eliminated. As with any coating system, proper care should be taken to minimize exposure and by using personal protective equipment. Conclusions The known benefits of siloxane technology involving thermal, weather, and chemical resistance can provide coatings with outstanding performance on industrial structures. An amine functional silicon resin allows coatings formulators to create simplified polysiloxane hybrid coatings without relying on titanate and tin catalysts. This technology also eliminates the reliance on ambient moisture resulting in a more robust system. Test results with complementary materials demonstrate the potential to tailor the performance needed for specific applications.
THE JOURNAL OF PROTECTIVE COATINGS & LININGS 2013 Technology Publishing Company

Developments in Zinc Primers for Corrosion Protection

From JPCL, May 2013

Pascal Verbiest dr.sc. Umicore Zinc Chemicals After finishing his masters studies in inorganic chemistry at the University of Ghent (Belgium), Pascal Verbiest obtained a Ph.D. in Inorganic Chemistry, focused at Reactions of Organotin-halides, in 1991. His career started at the Belgian steel company Sidmar (now ArcelorMittal) as a researcher in the field of enamelling steels. In 1994 he joined Umicore as a Research Manager in Overpelt, Belgium (at the Business Unit Industrial Products), and then moved to Umicore Research in Olen, Belgium, in 1997 as Senior Project Manager. Since 2000, he has been part of the BU Zinc Chemicals, focusing on development projects related to zinc oxide and zinc powder in a variety of

applications (paints, rubber, cosmetics). In 2009 he became Head of Product Development at the Business Unit Zinc Chemicals.

Fine zinc powder was recommended for use in paints as long ago as 1840. But it is only in the past 50 years, with the development of zinc-rich paints based on synthetic and inorganic paint resins, that zinc powder has become commonly used, specifically in paints for heavy-duty corrosion protection. The main applications for coatings containing zinc are the long-term corrosion protection of industrial and marine constructions (such as steel infrastructure, pipelines, bridges, windmills, and offshore drilling platforms) and the temporary protection of steel sheets (shop primers) during newbuilding of ships. Zinc coatings are specified in standards such as ISO 12944, Norsok M-501, SSPC-Paint 20, and the new IMO Performance Standard for Protective Coatings (PSPC). Zinc primers are considered to be the most effective anti-corrosion paint systems in use and have proven their excellent performance over many decades. The thickness of the zinc primers can vary between 10 and 120 microns; the higher the thickness and the higher the zinc powder content are in the paint, the longer the corrosion protection of the steel will last. Well-known examples of steel structures protected by zinc dust primers are the Beijing National Aquatics Center (the Olympic water cube) and the resund bridge, which connects Sweden and Denmark (Figs. 1 and 2).

Fig. 1: The Beijing National Aquatics Center. The steel

construction is protected against corrosion by zinc-rich primers. Courtesy of the author.

Fig. 2: The resund bridge, connecting Sweden and Denmark. The coating system (using a zincrich primer) has been designed to protect the bridge against corrosion for a period of at least 100 years.

This article reviews types of zinc powder and how they are made, types and composition of zinc primers, the corrosion protection mechanisms of zinc primers, suitable uses of the primers, and tips on application. Zinc Powder: The Main Constituent of Zinc Primers Zinc powders are the main constituent of zinc-rich paints. There are two groups of processes used to produce metallic zinc powders: the distillation and the atomization processes. The choice of the process and the type of feed (pure zinc or zinc residues) affects the particle size distribution of the zinc powder and its chemical purity. Powders produced by the atomization and the distillation technology processes have different morphologies. While the atomization process produces spheroidical powders, the distillation process always leads to spherical powders. Both morphologies are illustrated in Figs. 3 and 4.

Fig. 3: Spheriodical morphology of an atomized zinc powder

Fig. 4: Spherical morphology of a distilled zinc powder The average particle size of paint-grade zinc powders ranges from 3 to 15 microns. The manufacturer chooses the size based on factors such as the

thickness of the paint, paint composition, and paint properties. According to the ASTM D520 and ISO 3549, zinc powders for coatings are divided into three different types (Table 1), depending on their purity and their zinc metal content.
TABLE 1

Types of Zinc Powders According to ASTM D520 and ISO 3549

Type of Powder Total zinc (wt% ) min Metallic zinc (wt% ) min Lead (wt% ) max Iron (wt% ) max Cadmium (wt% ) max Zinc oxide (wt % ) max Type I Type II 97.5 94 6 98 94 0.01 0.02 0.01 Type III 99 96 0.002 0.002 0.001

Remainder Remainder 0.1% 0.8% 3.0%

Coarse particles on a 150-micron sieve None 0.1% Coarse particles on a 75-micron sieve Coarse particles on a 45-micron sieve 4.0% 0.8% 3.0%

Zinc Primers: Types and Composition Based on the zinc content, zinc paints can be divided into two categories: zincrich primers and zinc primers. Zinc-rich paints are paints in which zinc powder is the only active pigment, and it is present in levels above 80 wt% in the dry paint film. Because of these high levels of zinc powder, the paint has the qualities of a metallic zinc film, which allows the paint to protect the steel by an additional mechanismcathodic protection. Zinc-rich paints provide excellent corrosion protection in heavy-duty and marine environments. Zinc primers with lower zinc content (25%70%) are used to protect steel in less aggressive environments and to provide temporary corrosion protection. Although they have a lower proportion of zinc, they also provide an excellent barrier coating and hinder the spread of rust from an edge or scratch. Well-known zinc primers are the shop primersvery thin zinc primers (with a thickness of on average 1015 microns) are used for temporary protection of steel sheets (six months to one year) stored for the newbuilding of ships. Zinc powder paints also contain additives for different purposes. Coloring, antisettling, curing as well as anti-gassing, and thixotropic agents are added.

A more common division of zinc powder paints is based on the binder and the solvent. The main groups used by the industry today are shown in Fig. 5 and described below.

Fig. 5: Division of zinc paints generally used by the paint industry Solvent-borne ethyl silicates are the most commonly used inorganic primers, while zinc epoxies are the most commonly used organic zinc primers. The solvent-borne epoxies are generally two-component systems. Curing agents consist of polyamides and amine adducts. The water-borne epoxies used to be three-component systems (with zinc dust being one of the components) because a combination of zinc and water will react and create hydrogen gas. New technology has resulted in two-component waterborne epoxies that are stable. The waterborne silicates can be made with zero VOC and are more environmentally friendly compared to even waterborne epoxies that need cosolvents to ensure good film formation. Both inorganic and organic zinc primers have many benefits, but some properties are more optimum for a single type of primer. Table 2 compares the different properties of alkali silicate, ethyl silicate, solvent-borne, and waterborne epoxy zinc primers. Because of the properties shown in Table 2, the areas of use are different for inorganic and organic zinc primers.
TABLE 2

Typical Properties of Common Zinc Primers

Property Alkali Silicate Ethyl Silicate Solvent Epoxy Very Water Epoxy

Corrosion

Excellent

Excellent

Very Good

Protection Topcoating Fair Good

Good Very Good Good Good Very Good Very Good Fair Fair Very Good Good 12 Very Good

Adhesion Cohesion

Very Good Fair

Very Good Fair Good

Good Good Good

Surface Tolerant Fair

Mud Cracking

Good

Not Good

Very Good

Welding Cutting Abrasion

Excellent Excellent Excellent

Excellent Excellent Excellent

Bad Bad Very Good

Flexibility Shelf Life, Months Curing Pot Life, Hours Flash Point Overcoating interval 23C/10C Chemical Resistance

Limited 9

Limited 6

Fair 12

5 Days 5 >100C 2h/8h

12 Hours 8-12 <23C 12h/24h

7 Days 24-48 25-35C 1.5h/2h

7 Days 6 >100C 2h/3h

Excellent within pH 6-10

Excellent Not Used within pH 6-10 400C 470 60 Excellent 120C 420 60 Fair

Not Used

Heat Resistance 400C VOC g/L Vol% Solid Tolerance of High Humidity Water 0 75 Very Good

120C 140 55 Very Good

Very Good

Very Good

Excellent

Very Good

Resistance Sovent Resistance Use Friendly Excellent Excellent Very Good Very Good Very Good

Fair. Need special equipment, and water must be removed for drying.

Good. Needs humidity to cure.

Good. Water must be removed for drying.

Typical applications for inorganic zinc silicates are on barge decks (because of the extremely good abrasion resistance); pipelines; power plants; power transmission lines; bridges; ships; tankers (interior and exterior surfaces, including storage tanks, oil rigs, and offshore drilling platforms); water tanks; and steel to be primed in the shop. Typical applications for organic zinc epoxies are as high-performance coatings with good flexibility applied to steel substrates that are impossible or hard to blast to Sa 2 because of cost or accessibility, such as on poorly pre-treated steel; in maintenance projects; and for touch-up of zinc silicate shop-primed steel. Shop primers already mentioned are a specific type of zinc primer used for the temporary protection of steel sheets. The high performance shop primers used today are based on zinc ethyl silicate. These shop primers are excellent for welding and cutting processes because they do not contain any organic materials when cured. (Any organic material still present in the paint film will contribute to gas formation and to pore formation.) The shop primers are unbeatable on back burning, pore formation, and welding fumes as soon as cured. Uncured ethyl silicate has poor welding and cutting properties because it still contains some organic material. The lower the zinc content is, the quicker the welding of the shop primer is. Zinc epoxy was used in the shop primer market for some years, but the consumption has decreased considerably. The reasons are the high zinc content and the organic vehicle that creates pores in the welding seams. Zinc Primers: Corrosion Protection Mechanisms Zinc primers offer four-fold protection. Barrier mechanism, type 1 (Fig. 6)

Fig. 6: Barrier effect provided by a zinc primer on a steel substrate Zinc primers seal the underlying metal from contact with its corrosive environment by creating a barrier against water and oxygen. The corrosion rate of steel is roughly proportional to the concentration of dissolved oxygen. The barrier restricts the oxygen supply and, as such, is a mode of corrosion prevention. The barrier protection is a mechanism provided by any type of coating and is not specific to a zinc primer. Cathodic protection mechanism (Fig. 7)

Fig. 7: Cathodic protection mechanism of zinc-rich primers Zinc-rich primers provide galvanic (also called cathodic or sacrificial) protection. The zinc will sacrifice itself to protect the steel. Iron is under cathodic protection when its corrosion potential has been lowered beneath the value of -850 millivolts versus SCE (standard calomel electrode). Below this value, iron bears such an excess of negative charges that it is impossible, from a thermodynamic point of view, for ferrous ions to leave the metallic lattice. Iron is said to be in a state of immunity. This very efficient protection can be obtained by a galvanic coupling between iron and zinc. The zinc plays the role of an anode that corrodes sacrificially to protect iron, the cathode, where only reduction reactions can occur.

Zinc-rich primers formulated to protect iron cathodically contain a very high concentration of zinc particles. Indeed, for this mechanism of protection to take place, the zinc particles must be in electrical contact with each other and, in turn, with the iron substrate. To provide cathodic protection, the paint has to be formulated at PVC = CPVC (pigment volume concentration = critical pigment volume concentration) or at PVC > CPVC. In essence, this means that the zinc loading of the zinc primer has to exceed 80% in the dry film: Only a zinc-rich primer is able to provide cathodic protection. Barrier mechanism, type 2 The zinc corrosion products (zinc hydroxides, zinc hydroxycarbonates) formed during the lifetime of a zinc primer block porous regions and thus create a second barrier against corrosion. They also seal damaged regions. Alkalinization It is well known that the corrosion rate of steel is lower in alkaline solutions than in neutral ones. The alkalinization of the electrolyte contained in a zinc-rich primer will occur because the corrosion of the zinc powder gives basic zinc corrosion products (zinc hydroxides, zinc hydroxyl carbonates, etc.) and because of the formation of hydroxyl ions on the steel surface during the cathodic protection. This alkalinity certainly contributes to the protection of the steel once the cathodic protection is exhausted. Application of Zinc Primers To protect the steel adequately, correct surface preparation is required. Zinc ethyl silicate paints do not show either good adhesion or adequate wetting properties because of the nature of the binder. Therefore, the surface of the steel should be prepared by abrasive blasting to an Sa 2 finish, or, for severe environmental conditions and for waterborne silicate primers, an Sa 3 is recommended. In addition, it is generally recommended that the roughness of the abrasive blasted surface be in the range 2545 microns, preferably even at the higher end of this range. Zinc primers can be applied by conventional or by airless spray techniques. Zinc primers must be topcoated when exposed to highly aggressive media in order to control the reaction among zinc and water vapor, oxygen, and carbon dioxide coming from the environment. The most common problem resulting from topcoating is bubble and pinhole formation, a phenomenon attributed almost entirely to zinc silicates. (It rarely occurs with zinc epoxies.) The dry film of most self-curing inorganic silicate paints is very porous. When certain reasonably fast-drying organic topcoats are sprayed over a dry self-curing inorganic zinc coating, the pores in the inorganic

zinc film are sealed off, trapping air. Pinholes and bubbles are the result of entrapped air trying to leave the dried paint film. Care needs to be taken during application of topcoats by using a mist coat technique or by using a tie-coat. Editors Note: This article is the fourth in JPCLs 2013 series on generic coating types.
REFERENCES 1. Clive H. Hare, Protective Coatings Fundamentals of Chemistry and Composition, SSPC 94-17, Pittsburgh, PA: SSPC: The Society for Protective Coatings Clive H. Hare, Matthew Steele, and Steven P. Collins, Zinc Loadings, Cathodic Protection, and Post-Cathodic Protective Mechanisms in Organic Zinc-Rich Metal Primers, JPCL September 2001, pp. 5472. Ray Mudd, Organic Zinc-Rich Coatings, JPCL October 1995, pp. 5163. H. Undrum, Silicate or Epoxy Zinc Primers, The Superior Protection, April 2006, www.jotun.com M. Piens, Survey of the Mechanisms of Protection by Zinc-Rich Primers, XIX Congrs AFTPV Eurocoat 91, pp. 114117.
THE JOURNAL OF PROTECTIVE COATINGS & LININGS 2013 Technology Publishing Company

2.

3. 4. 5.

Is Lead Dead? A Look Back and a Look Forward at 20 Years of Bridge Painting Under the OSHA Lead in

Construction Interim Final Rule and Other Related Standards

From JPCL, May 2013

Alison B. Kaelin CQA, ABKaelin, LLC Alison B. Kaelin has more than 25 years of public health, environmental, transportation, and construction management experience in the coatings industry. She is the owner of ABKaelin, LLC, a Pittsburgh, PA-based DBE/WBE (#14029) provider of outsourced quality assurance, auditing, and consulting services to the protective coatings, construction, fabrication, and nuclear industries. She was previously employed by KTA-Tator, Inc., as its QA Manager and Environmental, Health, and Safety Manager. Kaelin also provides SSPC C3, C5, and OSHA training, program review and development services, and contractor certification support services. Kaelin is a certified quality auditor and NACE-certified coating inspector. She was a 2012 JPCL Top Thinker, a 2012 JPCL Editors Award Winner, and an SSPC Technical Achievement Award winner in 2005.

Photo courtesy of the author

On May 4, 2013, OSHAs standard for protecting construction workers from lead exposure (29 CFR 1926.62) celebrated its 20th anniversary. Initially titled, Lead Standard: Interim Final Rule on Lead Exposure in Construction, and now simply titled Lead, 1926.62 was issued because of what was known at the time about the health risks of overexposure to leadrisks such as neurological disorders and reproductive problems. Despite 20 years of training and education for 1926.62 as well as enforcement of it, Occupational Safety and Health Administration (OSHA) statistical data from October 2011 through September 2012 for citations for the SIC code most commonly used for bridge painters, 1721, Painting/Paper Hanging, indicates that citations under 1926.62 remain the top regulatory finding for painting. Moreover, that finding mirrors the regulatory findings over the past 10 years. This article will report statistics on violations of 1926.62 among painting and other construction trades; summarize findings on blood lead levels and current knowledge about the health risks lead exposure poses; review 1926.62 and related regulations affecting lead exposure; and offer observations,

recommendations, and questions for owners and others involved with lead paint removal on bridges and other structures. OSHA Enforcement of 29 CFR 1926.62 Table 1 presents data from OSHA on lead violations from October 2011 through September 2012 in a variety of trades, including painting, based on their SIC codes. (SIC codes 15, 16, and 17 address building and general construction, heavy construction, and special trades.) The data inTable 1 shows that for every inspection of the trades identified, an average of 2 to 12 citations per inspection are issued under 1926.62, with the main code for painters, 1721, showing an average of 4.4 citations per inspection. The sidebar on past and current enforcement of 1926.62 on bridge painting jobs also demonstrates that in some cases, OSHA is still finding egregious violations of 1926.62.
TABLE 1

Violations of 29 CFR 1926.62, Oct. 20112012, by 4-Digit SIC Industry Group

Number of Citations 31 27 18 Number of Inspections 7 10 8 Penalty Amounts ($) 34,035 32,451 6,688

Industry Classification 1721/Painting and Paper Hanging 1795/Wrecking and Demolition Work 1799/Special Trade Contractors, Not Elsewhere Classified 1791/Structural Steel Erection 1542/General Contractors-Nonresidential Buildings, Other than Industrial Buildings and Warehouses 1794/Excavation Work 1741/Masonry, Stone Setting, and Other Stone Work 1541/General Contractors-Industrial Buildings and Warehouses 1629/Heavy Construction, Not Elsewhere Classified

12 8

1 2

19,175 3,600

6 5

2 2

3,375 3,210

4,788

7,000

Blood Lead Levels Blood lead level (BLL) data is no more encouraging than enforcement data for 1926.62. The lead standard for construction requires provision of medical exams

and more frequent testing when BLLs are greater than or equal to () 40 micrograms per deciliter (g/dL), and it establishes a temporary removal threshold due to elevated blood lead level when testing performed at least two weeks apart results in BLLs 50 g/dL. The state-based Adult Blood Lead Epidemiology and Surveillance (ABLES) program, which has tracked laboratory-reported BLLs in U.S. adults since 1994, reported that in 2010, 31,081 adults had BLLs 10 g/dL; among these, 1,388 had BLLs 40 g/dL. The ABLES database for the construction sectors most associated with bridge painting and construction demonstrates that despite the 50% decrease in the national prevalence rates of BLL 25 g/dL levels over the past 17 years, levels remain relatively high in the construction sectors (Table 2). While Table 2 indicates a consistent decrease in Group 17: Construction Special Trade Contractors from 20022008, it also demonstrates that incidences of BLLs above 25 g/dL are 5 to 10 times those of other construction SIC codes. Table 2 also shows that BLLs for the other SIC codes for construction (Group 15 and Group 16) declined in the early 2000s but appear to have increased in the later 2000s.
TABLE 2

Number of Adults with BLL 25 g/dL by Industry Subsector in the Construction Sector
CONSTRUCTION SUBSECTOR SIC CODE 2002 2003 2004 2005 2006 2007 2008

Building Construction General Contractors and Operative Builders Heavy Construction other than Building Construction Contractors Construction Special Trade Contractors

15

105

61

24

42

25

84

85

16

175

212

98

90

111

57

145

17

967

913

852

760

699

616

574

ABLES has concluded that because BLLs are often not available for many leadexposed workers (either not tested or not reported), ABLES data should be considered a low estimate of the true magnitude of elevated adult lead exposures in the United States. Moreover, recent research on health effects of lead (discussed further in the next section) has led to increased concerns about the toxicity of lead at low doses. Therefore, in 2009, the ABLES program updated its case definition for an elevated

BLL to a blood lead concentration 10 g/dL. In 2010, using the new elevated BLL case definition, the ABLES program reported a rate of 26.4 adults with BLLs 10 g/dL per 100,000 employed. ABLES estimates that 95% of adult BLLs above 25 g/dL are work-related, with the data indicating that lead remains a national occupational health problem and that continued efforts are needed to reduce lead exposures. New Studies and Health Effect Data On June 13, 2012, the National Toxicology Program (NTP, U.S. Department of Health and Human Services) issued, Monograph on Health Effects of Low -Level Lead. It was based on NTP researchers evaluations of over 28,900 publications on health effects and exposure to lead. The publications were peer-reviewed literature related to the adverse health effects occurring at BLL of <5 and 10 g/dL in adults and children. Researchers categorized conclusions drawn from the evaluation as having data that was sufficient, limited, or inadequate. They concluded that the health effects at the BLLs identified in Table 3 have sufficient or limited supporting data.
TABLE 3

Summary of Health Effects Categorized as Limited and Sufficient

Health Area Population or Exposure Window NTP Principal Health Effects Conclusion Blood Lead Level Evidence Yes, <5 g/dL Yes, <10 g/dL

Neurological

Prenatal

Limited

Decrease in measures of cognitive function Decreased IQ, increased incidence of attentionrelated and problem behaviors, decreased hearing Decreased academic achievement, IQ, and specific cognitive measures; increased incidence of attention-related and problem behaviors Decreased hearing

Limited

Children

Sufficient Sufficient

Yes, <5 g/dL Yes, <10 g/dL

Adults

Sufficient Limited Limited

Increased incidence of essential tremor Psychiatric effects, decreased hearing, decreased cognitive function, increased incidence of ALS Increased incidence of essential tremor Increased hypersensitivity/allergy by skin prick test to common allergen and IgE (not a health outcome) Increased blood pressure and increased risk of hypertension Increased cardiovascularrelated mortality and ECG abnormalities Decreased glomerular filtration rate Reduced postnatal growth

Yes, <10 g/dL Yes, <10 g/dL Yes, <5 g/dL

Immune

Children

Limited

Yes, <10 g/dL

Cardiovascular

Adults

Sufficient Limited

Yes, <10 g/dL Yes, <10 g/dL

Renal

Adults

Sufficient

Yes, <5 g/dL Yes, <10 g/dL Yes, <10 g/dL Yes, <5 g/dL Yes, <5 g/dL Yes, <10 g/dL Yes, 1520 g/dL Yes, 10 g/dL

Prenatal

Limited

Children

Sufficient Limited

Delayed puberty, reduced postnatal growth Delayed puberty

Reproductive and Developmental

Adults Women Sufficient Limited

Reduced fetal growth Increase in spontaneous abortion and preterm birth

Men

Sufficient Limited

Adverse changes in sperm parameters and increased time to pregnancy Decreased fertility

Unlike OSHA, the EPA is required to periodically evaluate new scientific evidence and draw conclusions and causal judgments (cause-and-effect relationships)

regarding air pollution-related health and environmental effects of lead. In November 2012, the EPA issued its Third Draft Integrated Science Assessment (ISA) for Lead (Related to NAAQS-Lead). Some highlights of the third ISA include the following:

supports existence of a causal relationship for the health effects of lead for children and adults that were expressed in the NTP report; identifies historical and newly deposited lead in soils (which is re-entrained and distributed nearly continuously) as a significant exposure pathway for lead; identifies a likely causal relationship between lead and cancer; confirms causal health effects on plants, and on vertebrae and invertebrates; and states that evidence strongly suggests that cumulative exposure plays a role in adult renal and cardiovascular effects.

Each of the ISAs have shown that progressively lower BLL and airborne exposures are associated with cognitive deficits and behavioral impairments in children and adults. A December 2012 National Research Council of the National Academies publication, Potential Health Risks to DOD Firing-Range Personnel from Recurrent Lead Exposure, affirms that the current OSHA standard is inadequate for the protection of DOD and other worker populations, and the publication suggests that reductions in BLL and airborne concentrations are necessary. It seems that despite 20 years of OSHA regulation and enforcement, we continue to fall short of regulatory compliance with the Lead Standard. At the same time, multiple scientific studies have proven that there are more health effects (including potential cancer risks) at far lower levels than OSHA or the bridge and painting industry ever considered. In light of both trends, the next section of this article reviews the regulations that were put in place around the time of 1926.62, notes the limitations of those regulations, and evaluates what changes (if any) have been made or are currently being considered. Regulations: Background (Then And Now) Definitions of Lead in Paint Consumer Product Safety Act The 1978 Consumer Product Safety Act (CPSA), applicable to the manufacturing of coatings for consumer use, banned paint and similar surface coatings that contained lead or lead compounds and had lead content (calculated as lead metal) in excess of 0.06 percent of the weight of the dried paint (or 600 parts per million, ppm). CPSA also declared such products as hazardous. This definition

and Act explicitly applied to manufacturing of interior and exterior house paints intended for consumer use where risk of childhood lead poisoning exists. The definition and Act has never applied to coatings designed for industrial use. The Consumer Product Safety Improvement Act of 2008 lowered the allowable concentration of lead in residential paint from 0.06 percent (600 ppm) to 0.009 percent (90 ppm). HUD Guidelines The Lead-Based Paint: Interim Guidelines for Hazard Identification and Abatement in Public and Indian Housing (referred to as the HUD Guidelines) were introduced in 1986 to address when abatement of lead-based paints would be required in residential housing. HUD established a level of 5,000 ppm to trigger the removal of lead-based paints. HUD based the level on the detection capabilities of X-ray fluorescent analyzers (XRF) of 1.0 mg/cm2, equivalent to 0.5% (5,000 ppm). The level of 5,000 ppm was technology-driven and has no direct correlation between the lead-related health effects. The HUD Guidelines were updated in 1987, 1988, 1990, 1995, 1997, and 2012. The HUD definition of lead paint of 0.5% (5,000 ppm) was adopted in the Lead-Based Paint Hazard Reduction Act (Title X) of 1992 and 40 CFR 745, Lead; Identification of Dangerous Lead LevelsFinal Rule of 2001. In HUDs July 2012 update of its Guidelines for the Evaluation and Control of Lead-Based Paint Hazards in Housing, it did not lower the lead level in its definition of lead in paint (0.5%); however, HUD stated that HUD and EPA are collaboratively considering whether to lower the threshold level of lead-based paint; they are also looking into whether to lower the lead dust hazard standards HUD, consistent with EPA, CDC and OSHA, notes that paint with lead that is deteriorated or disturbed, even if its lead content is below the current EPA and HUD standards, may still pose a human health hazard The Childrens Health Protection Advisory Committee (CHPAC) has petitioned EPA and HUD to reduce paint and dust thresholds. The 1993 OSHA lead standard for construction concluded that in the absence of any health-based values, the initial protection portions of the standard would apply if any concentration of lead is present in the coating. This requirement remains in effect today. Thus, in 1926.62, OSHA did not define or establish a threshold level for lead in paint. Worker Protection (OSHA) The Residential Lead-Based Paint Hazard Reduction Act, also known as Title X, was enacted to protect families from exposure to lead from paint, dust, and soil. In one part of Title X, Congress directed OSHA to issue a rule to protect workers from exposure to lead in construction (1926.62). The standard was to be as protective as the 1990 HUD Guidelines in place at the time, which were based on the general industry lead standard (1910.1025) published in 1978; however, OSHA

had previously said that 1910.1025 would not work in the construction industry. Thus, from the day it was published, 1926.62 was insufficient to truly protect the health of the industrial blasters, painters, or workers in other construction trades. To issue a standard as soon as possible, OSHA was allowed to bypass normal rule-making procedures, which require issuing a notice of proposed rule subject to public comment before publishing a final rule. As a result, the current standard was not subject to any public or industry input, and was published as an interim final rule. This rule became partially enforceable June 3, 1993, and fully enforceable in October of 1993. On December 13, 1993, OSHA issued a compliance directive for 1926.62. The compliance directive (OSHA Instruction CPL 2-2.58) established OSHAs interpretation of how the requirements of the standard would be enforced by compliance officers during site surveys. In 1996, OSHA established a Special Emphasis Program: Lead in Construction (OSHA Instruction CPL 2.105). In it, OSHA offices nationwide were directed to rigorously enforce 1926.62 and the previous compliance directive, with specific emphasis on lead paint removal projects, including bridges. In July of 2001, OSHA issued a National Emphasis Program (NEP) for Lead (CPL 02-00-130). OSHA reissued the NEP for lead (CPL 03-00-009) in August of 2008. In 2008, as part of the OSHA NEP for Lead, OSHA started using ABLES data to initiate investigations and promote prevention in industries with BLLs above 25 g/dL. This NEP remains in effect today and specifically targets the construction subsector SIC codes of 15, 16, and 17. There have been no changes to 1926.62 (other than those related to the changes in other standards) since 1993. Examples of Past and Current OSHA Enforcement of 1926.62 on Bridge Projects Then The first major enforcement action under 1926.62 was initiated in December 1993 to E. Smalis Painting Co. (Smalis) and resulted in the issuance of a proposed total penalty of $5,008,500. The penalty was ultimately reduced to $1,092,750. Some of the citations were categorized as serious and willful, in part because Smalis had been cited on the same project under general OSHA standards in 1992 (prior to the Lead Standard). The citations included allegations of lead overexposure (monitoring showed worker exposures inside containment to range from 12,604 g/m3 and 33,458 g/m3, failure to have a lead compliance program, failure to maintain employee injury and illness records, failure to provide OSHA with access to employee medical records, failure to implement proper engineering and work practice

controls, and failure to monitor for overexposure. In addition, OSHA cited Smalis for failing to provide its employees with training, adequate respiratory protection, hygiene facilities/practices, medical surveillance, medical removal protection and benefits, and notification of blood lead levels (BLLs) and removal benefits. Another major enforcement action under 1926.62 was initiated in 1994 against Manganas Painting Co, Inc. The citations resulted in proposed penalty amounts of $2,452,500, ultimately reduced to $239,650. The citations included allegations of lead overexposure and failures to monitor all employee exposures, require employees exposed above the PEL to shower, implement medical surveillance, and provide notification of BLLs and removal benefits. Now In January 2013, OSHA issued substantial citations against a bridge painting contractor that included 38 alleged willful and repeat violations for allegedly endangering employees while performing abrasive blasting and repainting of bridges at three different job sites in 2011 and 2012. Alleged citations related to 1926.62 include the following.

Failure to provide a HEPA vacuum for decontamination from lead (This citation was also issued under the Cadmium Standard.) Employee exposures above the PEL not controlled by engineering and work practices Failure to ensure that employees exposed above the PEL showered Failure to conduct initial airborne exposure monitoring, biological monitoring, training; failure to provide appropriate respiratory protection and personal protective equipment for power tool operators, containment movers, and employees performing blow-down and clean-up Failure to provide notification of biological monitoring and airborne exposure monitoring Failure to make initial and periodic biological monitoring available to affected employees Failure of written compliance program to contain all required information Failure to prevent presence of consumption of food, beverages, and cigarettes when exposures exceed the PEL Failure to clean protective clothing or properly store protective clothing after use Failure to use signs

While these citations may be considered to be indicative of rogue painting companies, they demonstrate that after 20 years of enforcement, we are still likely to see gross violations of 29 CFR 1926.62. California Department of Health/Occupational Lead Poisoning Prevention Program In April 2011, the California Department of Health/Occupational Lead Poisoning Prevention Program (OLPPP) began providing information to support revisions to the 30-year-old Cal/OSHA Lead in Construction Standard, with recommendations based on more recent health-based scientific evidence. OLPPP suggests the following changes are necessary.

Provide medical surveillance, including blood lead level (BLL) testing, to all employees likely to be exposed to lead, including annual blood pressure measurements and questionnaires regarding lead-related medical conditions. Require all employees subject to medical surveillance to have a BLL test at least every month for the first three months or upon change in task to a higher exposure, and then every six months thereafter. Test employees with a BLL at or above 10 g/dL at least every three months, and test those with a BLL at or above 20 g/dL at least every four weeks. Once three consecutive BLLs, taken at least four weeks apart, indicate a BLL below 10 g/dL, the testing reverts to at least every six months. Remove workers from lead exposure if a single blood lead concentration is at or above 30 g/dL or if two successive blood lead concentrations measured over a four-week interval are at or above 20 g/dL. For employees who have been medically removed from work, return them to work when two blood lead tests taken four weeks apart are below 15 g/dL. Reduce the Permissible Exposure Limit (PEL) and Action Level (AL) to achieve lower BLLs to reflect new medical/toxicological information on chronic and low-level health effects. Require regular testing of surfaces in eating areas and change areas and more frequent cleaning if lead is found. Establish a quantitative limit for lead on surfaces and specify sample collection and analysis methods. Conduct employee training quarterly. Maximize the use of participatory and hands-on methods during training. Post warning signs in areas where lead is present. Establish and require minimum engineering and work practice controls

unless the employer can demonstrate that such controls are not feasible. Ban high-risk work practices. While none of the above has become law, OLPPP also has a series of posters for occupational adult workers. The posters inform workers about suggested blood lead levels of less than 10 g/dL, recommend hygiene and housekeeping practices, and outline potential health effects of lead for adults. Hazard Communications Standard The 2012 revisions to the Hazard Communication Standard, or HCS (See JPCL, May 2012) modify the language used on signs and labels related to 1926.62 to include the words Danger or Warning and to include specific references to key health effects. Over the next few years, labels and signs for lead will change, as shown in Table 4.
TABLE 4

Current vs. Revised Labels and Signs, Based on the 2012 HCS
CURRENT LABEL TEXT CAUTION: CLOTHING CONTAMINATED WITH LEAD. DO NOT REMOVE DUST BY BLOWING OR SHAKING. DISPOSE OF LEAD CONTAMINATED WASH WATER IN ACCORDANCE WITH APPLICABLE LOCAL, STATE, OR FEDERAL REGULATIONS REVISED LABEL TEXT DANGER: CLOTHING AND EQUIPMENT CONTAMINATED WITH LEAD. MAY DAMAGE FERTILITY OR THE UNBORN CHILD. CAUSES DAMAGE TO THE CENTRAL NERVOUS SYSTEM. DO NOT EAT, DRINK OR SMOKE WHEN HANDLING. DO NOT REMOVE DUST BY BLOWING OR SHAKING. DISPOSE OF LEAD CONTAMINATED WASH WATER IN ACCORDANCE WITH APPLICABLE LOCAL, STATE, OR FEDERAL REGULATIONS

CURRENT SIGN TEXT REVISED SIGN TEXT WARNING: LEAD WORK AREA POISON DANGER: LEAD MAY DAMAGE FERTILITY OR NO SMOKING OR EATING THE UNBORN CHILD. CAUSES DAMAGE TO THE CENTRAL NERVOUS SYSTEM. DO NOT EAT, DRINK OR SMOKE IN THIS AREA

The HCS also requires chemical manufacturers and importers to evaluate and classify each of their chemicals based on new performance-based criteria, to determine the physical and health hazard classes based on 16 physical hazards, 10 health hazards and one environmental hazard and to identify and consider the full range of available scientific literature and other evidence concerning the potential hazards. The HCS specifically requires classifications of hazards for lead, arsenic, and hexavalent chromium (Fig. 1).

Fig. 1: Hazards That Must Be Addressed for Inorganic Arsenic, Hexavalent Chromium, and Lead (based on HCS) Evaluations and classifications that the HCS requires are already being seen in revisions to safety data sheets for abrasives, coatings, solvents, and other materials used in the bridge painting industry. The identification of the presence of lead and hazardous metals in materials and abrasives may result in 1926.62 and other comprehensive health standards being applicable new construction projects involving abrasive blast cleaning (even when no old coatings are involved). Worker Certification and Training (HUD/EPA) Title X also directed EPA to add lead to the Toxic Substance Control Act (TSCA) and to establish a model training curriculum, accredit training providers, and certify lead professionals and workers. EPA published the final rule for housing and child-occupied facilities (40 CFR 745) in 1996. EPA specifically determined that these regulations were not applicable to industrial operations and removed any industrial requirements before issuing the final rule. The SSPC C-3 Course, Competent Person/ Supervisor Course for Deleading of Industrial Structures, was developed to try to meet the expected EPA training requirements for industrial painting; without the course, coatings professionals would have little or no industry-specific training. In July 2012, HUD updated its Guidelines for the Evaluation and Control of LeadBased Paint Hazards in Housing for the first time since 1997. EPA has proposed new regulations under 40 CFR 745 for Lead; Renovation, Repair, and Painting Program for Public and Commercial Buildings. The proposed regulations are similar to the 2001 regulations for residential housing lead abatement but would apply to public, commercial, and institutional buildings. EPA is currently accepting comments on these regulations. EPA National Ambient Air Quality Standards for Lead Ambient lead emissions were addressed in 40 CFR 50.12, National Primary and

Secondary Ambient Air Quality Standards for Lead (NAAQS for Lead). The criterion for the NAAQS for Lead was established in the 1970s as 1.5 g/m3, expressed as a maximum arithmetic mean averaged over a calendar quarter. NAAQS for Lead was used extensively from 1986 onward as a means of evaluating the effectiveness of containments and to verify that the public was not negatively affected by industrial painting operations.
TABLE 5

A Summary of Lead-Related Limits and Standards in Place from the Late 1980s to Current
1980s - 1990s (Then) 1990s 2000s > 2010s (Now)

Lead in Paint HUD Guidelines (Lead in Paint) 1985 1995/1997 2012 5,000 ppm (0.5 %) 5,000 ppm (0.5 %) Reductions to paint level being considered Same

CPSA Lead in Residential 1978 2008 Paints 600 ppm (0.06 %) 90 ppm (0.09%) OSHA 1993 Any Same

Same

Lead in Dust HUD Guidelines (Lead Dust in Housing) 1986-1990 Window troughs - 800 g/ft2 Window sills 600 g/ft2 Floors - 200 g/ft2 1995/1997 Window troughs 400 g/ft2 Window sills 200 g/ft2 Floors - 40 g/ft2 2012 Guidelines Updated. Reductions to dust levels being considered

Lead in Blood CDC (Children BLLs) 1985 25 g/dL to 30 g/dL N/A 1991 10 g/dL >25 g/dL 2012 5 g/dL >10 g/dL <10 g/dL

ABLES (Reporting Adult BLLs) US DHHS

N/A

N/A

Recommendation (Adult BLLs) OSHA Lead Standard BLLs N/A 50 g/dL (Medical Same Removal) Lead in Air OSHA Lead (Worker Airborne Exposures) 1992 Same Action Level - 30 g/m3 8-hr TWA PEL - 50 g/m3 8hr TWA Same

NAAQS for Lead (Ambient Air)

1976 2008 Same 3 3 1.5 g/m over 90 0.15 g/m over 3 day average month rolling average Lead in Soil

Lead in Soil 40 CFR 745 (Title X) Residential

None

2001 400 ppm play areas 1,200 ppm yard Lead in Waste

Reductions to soil levels being considered

RCRA Lead Hazardous Waste

1976 5 mg/L

1984 (Land Ban) 5 mg/L Stabilization to 0.75 mg/L

Same

In 2008, the NAAQS for Lead was reduced to 0.15 g/m3 expressed as a threemonth rolling average. The value is now fully in effect. Several areas of the country are not in attainment with this value. It is uncertain whether monitoring performed at or near industrial painting projects can meet this level due to a variety of factors, including the duration of monitoring, laboratory detection limits when flame atomic absorption spectroscopy is used, and the effectiveness (or lack thereof) of the containment and ventilation systems employed. Clean Water Act (CWA) The Clean Water Act does not permit lead debris to enter bodies of water or storm sewers, or to be located in areas where wind or rainwater could transport it into bodies of water. Storm water management regulations under the Clean Water Act also prohibit the release or storage of lead and other hazardous materials on the

ground where it can be carried into waterways and storm water management systems. There are several petitions requesting the EPA to reduce the drinking water standards for lead and chromium. Waste Handling and Disposal The Code of Federal Regulations addresses waste handling, storage and disposal issues, particularly in terms of hazardous waste, under sections 40 CFR Parts 260-265 and 268. These sections are often referred to as the Resource Conservation and Recovery Act (RCRA). Waste determined to be hazardous through analysis using the Toxicity Characteristic Leaching Procedure (TCLP) must be handled, stored, transported, and disposed of in compliance with RCRA. The hazardous concentration for lead is 5.0 mg/L. The Hazardous and Solid Waste Amendments (better known as Land Ban), issued in 1984 and phased in over the next 10 years, banned the addition of iron filings to lead-containing debris (as illegal treatment), prohibited land disposal of many hazardous wastes, and required that lead hazardous waste be stabilized to 0.75 mg/L before disposal. The ban on adding iron filings to lead-containing debris and subsequent studies shed light upon the fact that during TCLP testing, small particulates of iron (and steel) in the lead debris will plate the lead and make it non-detectable during analysis, giving the appearance of passing the TCLP. The EPA issued various memoranda and interpretations stating that the addition of iron (steel) to lead debris is not effective for long-term stability and is only a temporary stabilizer and that further stabilization is necessary. The EPA also stated that waste generators who do not stabilize lead-containing waste resulting from blast cleaning with iron/steel abrasives may be held liable under the Comprehensive Environmental Response, Compensation and Liability Act (CERCLA) if the lead is eventually released into the environment. Soils In the early 1990s, no regulations specifically addressed lead in soils relative to industrial situations. However, another EPA interpretation under the Land Ban states that discharges of lead onto soils without a permit (for hazardous waste disposal) can be treated as illegal disposal of hazardous waste or operation of an unlicensed treatment, storage, and disposal facility. For residential and child-occupied facilities, 40 CFR 745, Lead; Identification of Dangerous Lead LevelsFinal Rule (in 2001), established soil clearance levels of 500 ppm lead in play areas and an average of 1,200 ppm in the balance of the

yard. California is currently using a residential soil level of 90 ppm. In the years immediately after OSHA issued 1926.62, members of the coatings industry developed and took courses to learn about the hazards of lead and other metals. FHWA, SSPC, NIOSH, and other groups initiated conferences, studies, and reports on technology and regulations. OSHA initiated other comprehensive health standards for cadmium, arsenic, and hexavalent chromium. SSPC initiated or updated new programs and documents to identify regulatory requirements and provide strategies to protect the workers, the public, and the environment, such SSPC-QP 2, C-3 and C-5 training, Guide 6 (Containment), Guide 7 (Hazardous Waste), Guide 16 (Dust Collection), and TU-7 (Environmental Monitoring). At the same time, the industry developed or improved equipment, technologies, and surface preparation and paint removal methods to address requirements for containment and engineering controls. But what have we as an industry done lately? In the past few years, I have heard more than once that lead is dead, and I have participated in or been made aware of projects in which the owners, consultants, and contractors appeared to not understand, to minimize, or to not enforce critical aspects of the OSHA and EPA standards related to protecting the workers, the public, and the environment from lead exposure and other hazards, and to managing hazardous wastes. Based on the information presented in this article, I offer three thoughts on dealing with lead in 2013 and going forward. Health Effects and Lower Exposure Levels The scientific evidence reviewed or provided by our Federal health experts demonstrates repeatedly that overexposure to lead causes significant health effects in adults and children at BLLs as low as 510 g/dL. In addition to the health effects outlined in 1926.62, there is sufficient evidence linking lead exposure to additional adverse health effects in the form of essential tremors, blood pressure, and hypertension, and identifying a likely causal relationship between lead exposure and cancer. OSHAs 1926.62 was never based on construction risks or health effect data and, as such, is not sufficient to protect workers in bridge and other painting work (or any type of construction work). Most other lead thresholds and regulatory values for lead have been reduced significantly in the past 20 years and may be reduced further. In 1926.62, the established OSHA thresholds for BLL exposures are significantly higher than the levels at which health effects may occur. Each employer with employees with potential exposures to lead should consider whether or not to implement intervention or voluntary medical removal at lower BLLs levels than

required by OSHA. Currently, 1926.62 requires implementing ongoing blood lead testing and engineering, worker, and hygiene control practices only when airborne exposure monitoring exceeds the action level and permissible exposure limits. This requirement is ineffective if monitoring is not performed or when wet methods of removal are used, and it does not account for incidental hand-mouth contact or ingestion, which can occur regardless of airborne levels. Should we re-evaluate what protections are necessary based on not only the paint but also the abrasives? Should we implement work practice, hygiene, and engineering controls when lead or other hazardous metals are present instead of implementing such controls based on airborne exposures? New Sources of Lead and Exposure Pathways Under the HCS revisions (based on amounts and how hazards are classified), amounts or levels of lead previously considered incidental or below reportable thresholds might now be reported on safety data sheets (SDSs). I have already seen lead and other hazardous metals (such as cadmium, beryllium, chromium, and arsenic) identified on SDSs for abrasives and other materials. My review of the lead and other comprehensive health standards for arsenic, hexavalent chromium, and cadmium appears to indicate that use of the abrasives or other materials containing hazardous metals may require implementation of initial protection and exposure determinations when these materials are used. The EPA ISA data now identifies soil as a pathway for continuously re-entraining lead into the air and the rest of the environment. We know that the lead levels in soil near roadways and bridges have generally higher lead levels due to leaded gasoline and to breakdowns of previous coatings systems. Is this historic lead in the soil contributing to our worker and ambient exposures? Should we implement more pre- and post-soil sampling to identify these potential pathways? Challenges with Compliance Despite 20 years of OSHAs 19226.62 (and the annual training required by it), targeted enforcement by OSHA, and many training courses, articles, and guidance documents, the trades associated with bridge painting and construction continue to remain at the top of OSHAs list for violations of 1926.62. Are we complacent in our training, implementation, and innovation? Some transportation agencies have taken a step back from 1926.62, as well as from EPA issues related to lead, and the agencies seem to have reduced their specifications and requirements related to lead over the last several years, rather than tightening them. I wonder if this trend is due in part to a loss of organizational knowledge about lead as DOT staffing is reduced through retirement, layoffs, outsourcing, shrinking painting budgets, and a shift in focus to other issues. If so, have we thus handicapped the next generation in terms of our understanding and

compliance with 1926.62 and other standards? Are the requirements for competitive-bid (low-bid) contracting and intense competition for limited work encouraging contractors to look for ways to reduce costs through reduced compliance? If you work for a transportation agency (or other owner), I ask you five questions. 1. Who is your expert on lead and other hazardous metals? 2. Do your consultants have expertise in health and safety issues, risks, and controls for lead exposures? 3. When was your last lead training? 4. Do you understand why the requirements for worker and environmental monitoring and for containment are important in your specifications? 5. Are you appropriately managing your coating removal waste resulting from blast cleaning with steel abrasive? If you are a general or painting contractor, I ask you three questions. 1. Are you adequately protecting your workers based on the health risks of lead or the regulatory requirements? 2. Can you risk a real or perceived overexposure to lead by a worker, workers child or family member, or the public, especially given the health risks now known to be related BLLs lower than BLLs previously identified? 3. Are you using currently-available technology, work practices, and recommendations to access and control worker and public exposures? All evidence suggests that the health and environmental effects of lead are present through more sources and at lower airborne and BLLs than we previously thought; therefore, current regulatory levels established by OSHA may not be low enough to protect our health. I close with two questions for all of us in the coatings industry. 1. Do the lead projects today reflect the best available technology, engineering controls, and work practices necessary to reduce worker and environmental exposures? 2. Is it time for a reawakening about the hazards of lead exposures? Bibliography ABLES website (http://www.cdc.gov/niosh/topics/ABLES/ables.html). EPA website (http://www.epa.gov). Third Draft Integrated Science Assessment

(ISA) for Lead (Related to NAAQS-Lead), November 2012. FHWA Publication No. FHWA-RD-94-100, Lead-Containing Paint Removal, Containment and Disposal. National Cooperative Highway Research Program Synthesis 251, Lead-Based Paint Removal for Steel Highway Bridges, 1997. National Research Council of the National Academies publication, Potential Health Risks to DOD Firing-Range Personnel from Recurrent Lead Exposure, December 2012. NTP Monograph Health Effects of Low-Level Lead (National Toxicology Program), June 2012. OSHA website (http://www.osha.gov). OSHA Lead in Construction Standard: Interim Final Rule.
THE JOURNAL OF PROTECTIVE COATINGS & LININGS 2013 Technology Publishing Company

Exploring Marine Applications for Heat-Reflective Coatings

From JPCL, May 2013
Rob Portsmouth

Huntsman Pigments Dr. Rob Portsmouth is the Business Development Director at Huntsman Pigments, a division of Huntsman International LLC.

The suns energy, when absorbed by exterior surfaces, can transfer through to the interior of a building, vessel, or vehicle, raising the internal temperature. This increased temperature can make the interior more uncomfortable and place heavy loads on air conditioning or cooling systems. These effects, in turn, can lead to a rise in associated energy consumption, as well as in carbon dioxide and greenhouse gas emissions. Solar reflective coatings are an economical, easytouse, and increasingly popular way of helping to prevent all of these effects. This article describes the background to this technology and then discusses the potential advantages to be gained by using this in the marine coatings sector. Emerging Standards for Solar Reflectance The U.S. began using solar reflective coatings in the 1990s. They were used in cool roofs to carry out research on energy saving. This started the Cool Roof Rating Council program, which saw the solar reflectance (SR) standard set at 25 percent. Legislators and influencers globally have used this platform to formulate a series of policies, standards, and user recommendations, including the following.

The European Cool Roof Council (ECRC) has been formed to make an important contribution to mitigating climate change through increasing the energy efficiency of buildings. The ECRC is promoting the certification of cool roof products and their use across Europe. In France, AFNOR, the French national association for standardization, is reviewing its current standards on solar reflectance to include a total solar reflectance value. Japan has issued the JIS K 5 675 Standards for roof coatings with high

solar reflectance. JIS issues standards for industrial activities in Japan.

In Australia, the City of Melbourne Council has suggested that if the roofs in its commercial building district were painted white, they could theoretically reduce the citys energy consumption by 1.25 million kWhr (4.5 million MJ) per year, equivalent to reducing emissions by 1.5 million kilograms of CO2.1

It is not difficult to envisage how the benefits of cool roofs could be replicated in other industrial sectors. For example, in the marine sector, ocean-going vesselsand freight containers on deckoffer vast surface areas exposed to the heating effects of the sun. Maritime Requirements for Energy Efficiency In 2011, the International Maritime Organization (IMO) introduced a new chapter, making mandatory the Energy Efficiency Design Index (EEDI) for new ships. The regulations are non-prescriptive: Ship designers and builders are free to use the most cost-effective solution(s) for each particular vessel, as long as the required energy efficiency level is attained. The new regulations make mandatory a Ship Energy Efficiency Management Plan (SEEMP) for all ships. The plan must set out how energy efficiency will be achieved on an individual ship. The best measures for each ship will vary depending on ship type, cargo, route, and other factors. These maritime regulations and requirements would appear to offer an opportunity for coating and polymer manufacturers to develop innovative solarreflective coatings for the marine marketin colors to suit customer requirements. Some navies across the world have also specified requirements for the solar reflectance of their gray-colored fleet coatings (a traditionally difficult color or shade to obtain high solar reflectance), because increased solar reflective coatings can reduce the air conditioning loads internally, helping to save precious fuel. Infrared Reflecting Pigments Help Deliver Choice The industry recognizes that to obtain the highest solar reflectance, surfaces exposed to the sun should be white. This recognition is not new. It has long been known that painting houses white in hot and tropical areas can reduce the houses internal temperatures. You only have to go to the Caribbean region to see this. However, we have come a long way since the days when Henry Ford famously prescribed a single color choice for his companys automobiles (any coloras long as its black.) In the modern world, not all people want their roofsor their ships or ocean containersto be white. A novel infrared reflecting pigment helps deliver energy-saving benefits in a wide choice of colors. The pigment is engineered to reflect infrared radiation from the

sun and, when mixed with colored pigments, can yield high solar reflectance in an unprecedented range of colors. For example, in the case of gray marine coatings, the use of the novel pigment can increase the solar reflectance close to the theoretical maximum for the color. Figure 1 demonstrates the effectiveness of this pigment by comparing the total solar reflectance measurements for four paints that have been color matched to within E <2, applied over a black substrate at approximately 75 microns film thickness.

Fig. 1: Comparison of Four Coatings for Total Solar Reflectance In this example, a coating containing the novel pigment and widely available colored pigments outperforms a coating optimized for solar reflectance by 17 points. Such an increase could reduce the surface temperature of the coating by 69 C (1216 F).2 A reduction in temperature depends on the intensity of the suns radiation at a particular latitude. Product testing has been carried out at known exposure sites, but it is interesting to speculate what the benefits might be if such a coating were applied to cargo vessels operating near the equator for a considerable time. Reduced Thermal Cycling Increasing the solar reflectance of a structures surface has significant implications for not only energy efficiency, but also product durability. Reduced thermal cycling stress and coating temperature can lower the probability of delamination or peeling of the coating. This lower likelihood of peeling can result in extended product life and reduced product replacement cycles. High-IR reflective pigments can be produced by crystal size modification of rutile titanium dioxide, and to enhance the photo-catalytic stability of this novel pigment, a specially engineered coating has been applied to the pigment surface for durability. The coating acts like a protective shell around the pigment particles, helping prevent any electron holes that may have formed from reaching

the particle surface and coming into contact with the resin. The increased photocatalytic stability of the pigment was demonstrated using a durable alkyd-melamine formaldehyde paint system that is particularly suitable for testing durability, especially of the photocatalytic property of pigments. The results are shown in Fig. 2.

Fig. 2: Comparison of Coatings with Photocatalytic Pigments The crystal structure can be engineered to give optimal near infrared and visible reflectance ratios, with exceptionally low tint strength (approximately 25 percent of pigmentary titanium dioxide2) to enable dark (L*<40) and vibrant colors to be produced with high solar reflectance. To demonstrate the effect with a black coating, which is often the most difficult color to improve in terms of solar reflectance performance, two different formulations were color-matched close to RAL 9004 black. One formulation contained an infrared reflecting black pigment with titanium dioxide2; the other contained the infrared reflecting black pigment and the new infrared reflecting pigment. These paints were applied over black and white charts at different thicknesses. The results in Fig. 3 show that the use of the new infrared reflecting pigment increased solar reflectance over a standard pigmentary TiO2.

Fig. 3: Comparison of Solar Reflectance of Coatings Based on IR Reflective Pigments Potential Benefits in the Marine Sector

Increasing the solar reflectance levels of ocean-going vessels could open the door to potential savings. Less fuel may be needed to power air conditioning, important for cruise liners, or cooling/refrigeration systems, important for the carriage of many cargoes in the hold. Cooler ships also might help deliver more flexibility in design, shipping routes, and cargo types; and more revenuegenerating free space might be created on board by a reduced fuel requirement. The concept of using heat-reflective coatings on ships decks is not new. In 2002, four sister ultra-large crude carriers (ULCCs) were launched in Japan. The decks and upper hulls were painted white to reflect the suns energy. There were two thoughts behind this: the coatings in the ballast tanks would be subjected to lower temperatures, thus delaying breakdown of the coating because of thermal cycling; and the temperature of the cargo would be lower, thus minimizing evaporative hydrocarbon emissions, a potential loss of profits, and increasing safety. White is not the most suitable color for decks (for aesthetic reasons); moreover, many operators want to have decks painted in their corporate colors. There might be other benefits. For example, could more extensive use of heatreflective coatings have a role to play in the cost-effective protection and preservation of containerized cargo, both onboard and at the dockside? Studies have been carried out to determine the temperature and humidity cycles inside ocean containers. One study found that the most extreme temperature differences were observed on land while the containers were waiting for onward land transportation, and that the highest temperature, 57 C, was recorded in July at the dockside in Memphis, Tennessee.3 Conclusions Coatings and polymers containing the novel IR reflective pigment could have an exciting role to play in delivering advantagesand end user benefitsin a range of marine applications. Potential cost and energy savings, as well as reductions in carbon footprints, are at the top of the benefits list. Greater freedom to venture beyond white as a color of choice is another bonus. The novel pigment offers more design flexibility while delivering improved thermal performance. For instance, it provides the opportunity to incorporate corporate branding colors, or to use color more extensively for ease of product identification. A lower surface temperature also means increased comfort where people are in contact with surfaces. Perhaps this benefit suggests an opportunity for the application of coatings containing the pigment in the super yacht and small pleasure craft market. Extended product life for freight containersand potential benefits for the goods insideis also an opportunity that merits further investigation. Editors Note: A version of this article was published in the Oct.Dec. 2012 Protective Coatings Europe.

REFERENCES 1. www.melbourne.vic.gov.au/AboutCouncil/MediaReleases/Pages/Whiteroofstomak eforcoolerMelbournebuildings.aspx; 24 January 2012. 2. Formulations containing a proprietary novel IR pigment have been compared to formulations containing a proprietary IR reflecting black pigment with titanium dioxide. 3. Summary of Prior Experiments Regarding Temperature in Sea Containers, R. Weiskircher, CSIRO Mathematical and Information Sciences, August 2008.
THE JOURNAL OF PROTECTIVE COATINGS & LININGS 2013 Technology Publishing Company