Paint & Coating Industry September 2011

September 2011 VOLUME 27, NUMBER 9

INSIDE Driers for Alkyd Coatings Industrial No-VOC Colorants

Paint

Coatings Industry

The Latest Advances in Vinyl Technology

Globally Serving Liquid and Powder Formulators and Manufacturers

Corrosion Resistance

Scan the mobile tag to access news about nanomaterial mixing technology.

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Cinilex Cinile Ci ile lex x Yellow Ye Yel ell llow ow SY1H SY S Y1H H (PY110) (PY11 PY11 PY 10))

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Cinilex Cini Ci nille ex DPP DPP Orange DP Orran a ge SJ1C SJ1C SJ 1C (PO73) (PO O7 73 3)

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Cinilex C nile Ci lex x DPP DPP DP PP Red Re Red ed SR1C SR1C (PR254) SR (PR25 PR R2 25 54 4))

Cinilex Ciniile lex DPP DPP DP P Rubine Rubi Ru bine SR5H SR R5H 5H (PR264) (PR PR26 26 264) 64))

Cinilex Ciniile Cini Ci l x Red R d SR4C Re SR R4C C (PR177) ( R177 (P 77 7)

Cinilex Cinilex x DPP DPP DP P Red Re R ed SR2P SR2P (PR254) (PR PR25 PR 2 4))

Cinilex Cini Ci nile lex x Red Re ed SR3C SR3C SR C (PR177) (PR17 177) 7)

Cinilex Cini Cini nile le ex DPP D P Red DP Re R ed ST ST S T (PR254) (PR R25 54))

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CINIC CHEMICALS(SHANGHAI) CO., LTD. 1730 Huilian Road, Qingpu Industrial Park Shanghai 201707, P.R. China Tel:+86 21 5240 0178 Fax:+86 21 5240 0136 E-mail: [email protected]

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CONTENTS PA I N T & C O AT I N G S I N D U S T RY , V O L U M E 2 7 , N U M B E R 9

September 2011

FEATURES 24 Novel Non-Chrome Thin Organic Hybrid Coating for

Coil Steels, Henkel Corporation 32 Understanding the Latest Advances in Vinyl

Technology for Coatings, Arkema Coating Resins 38 Next-Generation Industrial Waterborne No-VOC

Colorants, Colortrend USA LLC 44 Driers for Alkyd Coatings – an Overview,

Dr. inż. Maciej Umiński 49 Details on Arkema’s Acquisition of TOTAL,

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ONLINE FEATURES w w w. pcimag.com Chromate-Free Primer First to be Qualified by Boeing, PPG Industries New Aluminum Oxide Coating Creates Corrosion Barrier, Sanford Process Corporation A New Technique to Powder Coat Flat Substrates, EMB-Technology Diversity and Importance of Industrial Mixers, JBW Systems, Inc. Rotational Rheometer Helps Develop Industrial Corrosion Protection Systems, Malvern Instruments

DEPARTMENTS 6 8 12 14 22 51 52 54

Viewpoint Industry News Calendar of Events Company News Names in the News Products Classifieds Advertiser Index

Insider Interview ON THE COVER: Photo courtesy of Photos.com.

BUSINESS TOOLS

Mobile tag courtesy of Charles Ross & Son. Co.

50 Supplier Showcase

PCI - PAINT & COATINGS INDUSTRY (ISSN 0884-3848) is published 12 times annually, monthly, by BNP Media, 2401 W. Big Beaver Rd., Suite 700, Troy, MI 48084-3333. Telephone: (248) 362-3700, Fax: (248) 362-0317. No charge for subscriptions to qualified individuals. Annual rate for subscriptions to nonqualified individuals in the U.S.A.: $115.00 USD. Annual rate for subscriptions to nonqualified individuals in Canada: $149.00 USD (includes GST & postage); all other countries: $165.00 (int’l mail) payable in U.S. funds. Printed in the U.S.A. Copyright 2011, by BNP Media. All rights reserved. The contents of this publication may not be reproduced in whole or in part without the consent of the publisher. The publisher is not responsible for product claims and representations. Periodicals Postage Paid at Troy, MI and at additional mailing offices. POSTMASTER: Send address changes to: PCI - PAINT & COATINGS INDUSTRY, P.O. Box 2145, Skokie, IL 60076. Canada Post: Publications Mail Agreement #40612608. GST account: 131263923. Send returns (Canada) to Pitney Bowes, P.O. Box 25542, London, ON, N6C 6B2. Change of address: Send old address label along with new address to PCI - PAINT & COATINGS INDUSTRY, P.O. Box 2145, Skokie, IL 60076. For single copies or back issues: contact Ann Kalb at (248) 244-6499 or [email protected].

Audited by BPA Worldwide

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I am constantly amazed at the variety of ways people can obtain information in this technology-driven age. Lately, mobile tags are everywhere, and gaining in popularity, from cartons of eggs to T-shirts to trade show booths. This month’s cover of PCI features a mobile tag from Charles Ross & Son Co. When the Microsoft Tag Reader application is installed on a mobile device (smart phone), the Tag Reader can be used to scan the tag using the device’s camera. This particular tag will link you directly to information on nanomaterial mixing technology from Charles Ross. You can download the Tag Reader at http://gettag.mobi. A few of our advertisers have started using mobile tags in their ads. Check out Sartomer’s ad on page 16 as an example. You will notice that PCI will be using this new tool throughout our magazine in the future, in both ads and editorial features. Be sure to scan these tags with your smart phones to see what information pops up. Most smart phone browsers allow you to add bookmarks, so you can save the urls from mobile tags for future reference. Another great tool that I wanted to mention is PCI’s LinkedIn group. This site has become a valuable networking resource. Almost daily, people post coatings formulation and application questions for their peers, which opens up a great dialog among those in the group. As an example, someone recently posted the question, “Does the substitution of micron-sized zinc particles with nano-sized ones yield significant improvements in anti-corrosive paints, and is a broad industry adoption of such nano-sized zinc expected?” The responses are very interesting. Another member has questions on storing and using NH3ag at his facility. Several people responded with helpful suggestions. Other people are looking for information about coatings for a specific purpose, products to replace ones they are currently using in their formulations, or software to better run their process. New business has been acquired as a result of these discussions. Jobs are also posted, from powder coating field sales reps to senior coatings chemists. I have also obtained a few technical papers for PCI as a result of information posted on our group site. Be sure to visit www.linkedin.com and join the group for Paint & Coatings Industry, so that you don’t miss out. Also sign up to follow PCI on Twitter and Facebook. Breaking industry news is posted on these sites, as well as information on upcoming trade shows and conferences. Whether you are at work, at home, on the road or in the sky, you have access to all the information you need to keep abreast of the latest developments in the coatings industry. It may take some of us a while to catch on to the latest and greatest resources available to us, but be sure to do it. You will be amazed!

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SEPTEMBER 2011 | W W W . P C I M A G . C O M

By Kristin Johansson, Editor | PCI

Markets:

Architectural Coatings

Industrial Coatings

Container Automotive

Civil Aerospace Engineering

Coatings Technologies:

SolventBorne Coatings

WaterBorne Coatings

Powder Coatings

Surface/Substrate:

Wood

Brick

Concrete

Marine & Maintenance

UV Coatings

Metal

Stucco

High Solids Coatings

Vinyl

Plastic

Brenntag understands change is normal for the Coatings Industry. As the Coatings Industry has evolved through the years, Brenntag’s Paint and Coatings Team continues to provide our customers with the products and services to stay competitive in the marketplace. Whether you face different markets, technologies, or substrate applications, Brenntag’s Paint and Coatings Team can help you to adapt and make change work to your advantage.

Brenntag offers a complete specialty and industrial product portfolio, technical assistance with product development, formulations and applications know-how, superior logistics with versatile blending and re-packaging capabilities, and last, but not least, commitment to quality and safety. Change demands innovation and creativity. Brenntag Understands. Brenntag North America, Inc. (610) 926-6100 Ext: 3858 [email protected] brenntagnorthamerica.com

The Glocal® Chemical Distributor.

I NDUSTRY NEWS

EPA Strengthens Key Scientific Database/ Reviews New Uses of Glymes WASHINGTON, DC – The U.S. Environmental Protection Agency (EPA) announced plans to improve its Integrated Risk Information System (IRIS) licly program. IRIS is a publicly ase available online database that provides science-based human health assessments used to inform the agency’s decisions on protecting public health and the environment. With the improveessments, all new IRIS assessment documents will be shorter, clearer and moree visual visual, concise, and transparent. IRIS users can

expect to see a reduced volume of text and increased clarity and transparency of data, methods and decision criteria. To make the scientific rationale behind tthe assessments and toxicity v values as transparent as poss possible, the EPA will evaluate a describe the strengths and a weaknesses of critical and studies in a more uniform w way. The EPA will also i indicate which criteria w were most influential in eva evaluating the weight of the scient scientific evidence supporting its choice of toxicity values. The EPA will also create a new peer

consultation step early in the development of major IRIS assessments to enhance the input of the scientific community as assessments are designed. For more information about IRIS, visit www.epa.gov/iris. Also in the news, EPA is proposing a regulatory procedure requiring companies to report new uses of chemicals known as glymes in consumer products. EPA’s proposed action is based in part on concerns that additional uses of these 14 chemicals in consumer products could lead to harmful reproductive and developmental health effects. The proposed regulatory procedure is known as a significant new use rule (SNUR) under the Toxic Substances Con-

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SEPTEMBER 2011 | W W W . P C I M A G . C O M

I N DUSTRY N EWS

trol Act. The SNUR would ensure that, prior to the manufacture, import or processing of these chemicals for a significant new use, EPA will have 90 days to evaluate potential risks and prohibit or limit the activity if warranted.

icones, advancing at an above-average pace through 2015. Silicone gains will be bolstered by demand in high-growth new applications. The most rapid increases, however, will be in the construction market. Similar factors will also fuel healthy growth in transportation markets, as

motor vehicle production in the developed world rebounds from recent declines. Elastomers and fluids were the two leading silicone product types in 2010, accounting for over 80 percent of total demand. Of the two, stronger growth is expected for elastomers, which will ben-

Color and Pigments Week 2011 BERLIN – IntertechPira’s Color & Pigments Week 2011, The Future of Pigments, will take place Oct. 24-28, 2011, at the Maritim Hotel Berlin, in Germany. Attendees will learn valuable market intelligence and gain business contacts through the multiple networking events. Visit www.pigmentmarkets.com for additional information.

Demand for Silicones to Reach $16 Billion CLEVELAND – According to a new study released by The Freedonia Group, a Cleveland-based industrial research company, world demand for silicones will rise 6.2 percent per year to $16.7 billion in 2015. Advances will represent a notable acceleration from the 2005-2010 period in which most developed world markets in North America and Western Europe experienced sluggish increases, or even declines, in silicone demand. The Asia-Pacific region will remain the largest and fastest-growing outlet for silicones through 2015. Gains will continue to be driven by the large silicone market in China. Although slowing from the nearly 20 percent growth seen during the 2000-2010 period, the country will post strong double-digit gains going forward. Silicone demand in the region will also benefit from healthy gains in countries such as South Korea, Taiwan and India, although subpar increases in the Japanese market will temper this to some extent. Above-average growth is also forecast for Central and South America, Eastern Europe and the AfricaMideast region, areas in which silicone demand per capita is currently among the lowest in the world. North America and Western Europe, the historical centers of the world silicone industry, saw demand severely hampered by the recent economic recession. Through 2015, however, silicone demand is expected to make a solid recovery, fueled in large part by a strong rebound in construction spending and motor vehicle production. Electrical and electronic products will continue to be the leading outlet for sil-

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I NDUSTRY NEWS efit from the rebounding construction and transportation markets. The fastest increases, however, will be for silicone gels

OBITUARY Industry Loses Tom Grady CHICAGO – Tom Grady, Marketing Director for Metal Building Products of The Sherwin-Williams Co., passed away at the age of 45. Grady came to Sherwin-Williams during the company’s Pratt and Lambert acquisition in the mid-‘90s. At that time, he was a Powder Representative. Through the years, Grady moved into liquid and ultimately into the MBP group. He was instrumental in getting the company’s Kynar coatings into the field through testing and the approval process. Grady is survived by his wife, Jane (Kalinoski) Grady, and daughters Elizabeth and Kaitlyn.

and other smaller-volume products, fueled by emerging opportunities in electronic components and motor vehicles. This new industry study, World Silicones, presents historical demand data and forecasts for 2015 and 2020. Visit www.freedoniagroup.com for additional information.

Partners USB and SW Recognized With Green Chemistry Award WASHINGTON, DC – A unique, four-year partnership between America’s soybean farmers and the Sherwin-Williams Co. has received the Presidential Green Chemistry Award from the Environmental Protection Agency (EPA). The honor recognizes the development of an innovative new paint formulation that utilizes soybean oil and recycled plastic bottles (PET), and reduces VOCs by 60 percent. The EPA presented Sherwin-Williams Co., Cleveland, OH, with one of five 2011 Presidential Green Chemistry Challenge Awards during a ceremony in Washing-

ton, DC. EPA also recognized the United Soybean Board (USB) for its role in the development of the product. Sherwin-Williams, with soybean checkoff funding and technical support from USB, developed water-based acrylic alkyd paints with low VOCs that can be made from soybean oil. These new paints combine the performance benefits of alkyds and low-VOC content of acrylics. The soybean oil helps to promote film formation, gloss, flexibility and cure. In 2010, Sherwin-Williams manufactured enough of these new paints to eliminate over 800,000 pounds of VOCs. The company has used 320,000 pounds of soybean oil, 250,000 pounds of PET and eliminated 1,000 barrels of oil.

ASTM Proposes Several New Testing Standards W. CONSHOHOCKEN, PA – ASTM International has announced several new proposed standards being developed by subcommittees of ASTM Committee D01

I N DUSTRY N EWS

on Paint and Related Coatings, Materials and Applications. ASTM WK 30920, Guide for Corrosion Test Panel Preparation and Rating of Coil-Coated Building Products, is being developed by Subcommittee D01.53 on Coil Coated Metal. According to Ted Best, a scientist with Valspar Corp. and D01.53 member, the standardization of test panel configurations and ratings would allow benchmark comparisons across a broad range of products that includes substrates, pretreatments and coatings. ASTM WK 33642, Test Method for Measurement of Viscosity of Paints, Inks or Related Liquid Materials as a Function of Temperature, is being developed by Subcommittee D01.24 on Physical Properties of Liquid Paints and Paint Materials. “It is useful to know the extent of variation, but we do not know of any ASTM standard that establishes the viscositytemperature variation for these materials,” said Clifford Schoff, Ph.D., Schoff Associates, and Chairman of D01.24.

“The relationship has important implications for viscosity measurement in general and specifically for processes such as hot spray and for sagging and leveling on baking.” The proposed standard will give instruction on how to prepare a viscosity-temperature table or curve. This will be useful when ambient conditions do not allow the measurement at the exact temperature stated in a specification or regulation. Schoff says D01.24 welcomes interested parties to join in the ongoing revision of the ASTM WK 33642 draft and also to participate in interlaboratory testing to establish the precision of the proposed standard. In addition to ASTM WK 33642, the subcommittee is also beginning work on a standard for measuring the yield stress of paints, ink and related liquids. Participants are sought for this activity as well. Another new proposed ASTM International standard is ASTM WK 32143, Test Method for Visual Assessment of Water

Beading on Horizontal Coatings, being developed by Subcommittee D01.42 on Architectural Coatings. It will provide formulators with a practical means for evaluating the water beading capability of a coating. Repeating the test described in ASTM WK 32143 after coated specimens have been put through intervals of aging or weathering will demonstrate the persistence of the coating’s ability to bead water.

Attendance at Latin American Coatings Show Up 31 Percent MEXICO CITY – The Latin American Coatings Show 2011, which took place in July at the World Trade Center, Mexico City, attracted 3,667 attendees, an alltime record performance for the event. The show reported a 31 percent increase in attendance from the event in 2009. Highlights included an exhibition and exhibitor business presentations. Exhibitors interested in booking for the 2013 event should contact Jeff Montgomery at [email protected]. 䡲

Arkema Emulsion Systems delivers innovative products and targeted support that allow you to capitalize on amazing new opportunities. For example, our new SNAP™ 720 Structured Nano-Acrylic Polymer uses advanced particle morphology design to offer formulators excellent gloss and adhesion plus outstanding block resistance and film hardness in a no or low VOC architectural coating. If you haven’t already tried this 100% acrylic binder, it’s definitely worth looking into.

technology that’s really deep.

Visit www.arkemaemulsionsystems.com/SNAP for more information about SNAP™ Structured Nano-Acrylic Polymers. At Arkema Emulsion Systems, we’re focused on your future.

SNAP™ is a trademark of Arkema Inc. ©2011 Arkema Inc.

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C ALENDAR Meetings, Shows and Educational Programs 27-29 Eurocoat 2011 www.eurocoat-expo.com

Rolla, MO http://coatings.mst.edu/basic1.html

SEPT. 13-14 Coatings Trends & Technologies Oak Brook, IL www.coatingsconference.com

26-28 Polyurethanes 2011 Technical Conference Nashville, TN www.americanchemistry.com/polyurethane

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SEPTEMBER 2011 | W W W . P C I M A G . C O M

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18-19 Industrial Minerals 2011 Toronto, Canada www.blendon.com 18-20 RadTech Europe Basel, Switzerland www.radtech-europe.com 23-26 Western Coatings Symposium Las Vegas www.pnwsct.org/symposium-wcs 24-26 Future of Pigments Berlin, Germany www.pigmentmarkets.com

NOV. 1-3 Chem Show New York City www.chemshow.com 2-3 12th Asia Coatings Markets Jakarta, Indonesia www.cmtevents.com 21-23 ABRAFATI São Paulo, Brazil www.abrafati2011.com.br/index_engl.html

We are thinking about the same thing you are… How to make your products greener and their performance pure gold. Our customers come to us to help them stay ahead of competitive pressures by helping to re-formulate existing products and innovate new ones – meeting “green” goals while preserving and even enhancing performance. We call it Greenability. You’ll call it genius. 2 Another fine result of the Innovation Principle – . Let us help you work through the formula for Greenability.

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C O M PANY NEWS Clariant Demonstrates Corporate Social Responsibility in Asia

AkzoNobel Offers Full-Body Monocoat Powder Coating CANNES, France – AkzoNobel’s Interpon has become the first-ever full-body monocoat powder coating to be used on a passenger vehicle in Europe. Showcased at the Cannes SURCAR 2011 Congress, the Citroën DS4 is the first-ever passenger vehicle in Europe to be exhibited using matt black textured powder coatings on the car body. After initial trials with PSA PEUGEOT CITROËN, the parent company of the Citroën DS4, a model was produced using Interpon A 5000, and the decision was made by PSA Peugeot Citroën to showcase the car and its new coating system in Cannes. Powder coatings as a body coating alternative mark the start of a new

Copyright PSA 2011.

era for automotive manufacturers who are keen to reduce both their carbon footprint and their costs without compromising on technical quality or performance. The powder monocoat system reduces the number of process steps and enables a significant reduction in energy consumption.

MUTTENZ, Switzerland – Clariant is extending its worldwide commitment to corporate social responsibility in the AsiaPacific region through hands-on community initiatives and active support for local educational programs. Clariant in Indonesia recently launched its 2011 Responsible Care® program with a new series of community programs focused on education, safety, health and the environment for people living in the vicinity of its manufacturing plant in Tangerang, Indonesia. Initiatives include annual scholarships in collaboration with the Sampoerna Foundation to 32 underprivileged and gifted children for the 2011/2012 academic year, and malnutrition prevention programs in the Tangerang area. Clariant recently introduced an environmental cleanliness movement, including the planting of 500 trees in public spaces, through close cooperation with other companies in the Cibodas Tangerang region. Within China, Clariant has participated in a series of events organized by East China University of Science and Technology and the Association of International Chemical Manufacturers to celebrate the International Year of Chemistry 2011 (IYC2011) under the topic “Chemistry: our life, our future.”

Celanese Emulsions Announces New Technology Center

Zinc Oxide

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Aluminum Oxide

Bismuth Oxide

NanoArc

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DALLAS – The Emulsion Polymers business of Celanese Corp. is advancing its application technology group in the Americas by moving to a new facility in the greater Cincinnati area. Celanese Emulsions will join technology teams from Ticona, the engineering polymers business of Celanese and Celanese EVA Performance Polymers, at a site in Florence, KY.

Univar and Dow Corning Coatings Expand Distribution Agreement BRUSSELS, Belgium – Univar Inc. has expanded its long-standing European distribution agreement with Dow Corning Coatings to include Austria, Turkey, the Baltic region, Central and Eastern Europe, and South Africa.

Elcometer Opens Southeast Regional Office ROCHESTER HILLS, MI – Elcometer Inc. has opened a new office to serve the southeastern United States. Located in Charles-

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SEPTEMBER 2011 | W W W . P C I M A G . C O M

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C OM PANY NEWS ton, SC, the office will serve as a hub for the southeast region, including North Carolina, South Carolina and Georgia. The office will be headed by Kim Thompson.

Lubrizol Wins Ringier Technology Innovation Award CLEVELAND – Lubrizol Performance Coatings, a business division of The Lubrizol Corp., has earned the Ringier Technology Innovation Award in China for the development of its one-component, self-crosslinking polyurethane dispersion technology for wood coatings. Lubrizol’s Turboset™ Ultra Pro waterborne polyurethane dispersion is based on a unique polyurethane technology that does not require the addition of crosslinkers to deliver the performance of a two-component system.

OPXBIO Raises $36.5 Million BOULDER, CO – OPX Biotechnologies Inc. has raised $36.5 million in the first closing of its C-Round private equity financing. The investment will enable OPXBIO to accelerate development and commercialization of an industrial-scale process for producing its first renewable chemical, BioAcrylic. OPXBIO has established a joint development agreement with The Dow Chemical Co. to collaborate on the large-scale demonstration of the process for BioAcrylic production and anticipates full commercialization within three to five years.

Emerald Kalama Chemical Plans New Technical Center CUYAHOGA FALLS, OH – Emerald Kalama Chemical, a division of Emerald Performance Materials, has completed the first of several planned phases of its technical expansion focused on its K-FLEX® nonphthalate plasticizers and coalescents. The business has also increased its technical staff by 50 percent. In addition, the company has approved the investment in a new technical center at its Kalama, WA, site. The new technical center is scheduled to open in spring 2012.

Lonza to Acquire Arch Chemicals

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SEPTEMBER 2011 | W W W . P C I M A G . C O M

BASEL, Switzerland/NORWALK, CT – Lonza Group Ltd. and Arch Chemicals Inc. have signed an agreement in which Lonza will buy 100 percent of Arch Chemicals’ outstanding shares of common stock. Upon completion of the transaction, Lonza will have a leading microbial-control business with 2010 pro-forma sales in this life science market of approximately $1.6 billion.

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C O M PANY NEWS AkzoNobel Announces Acquisitions AMSTERDAM, the Netherlands – AkzoNobel has announced its intention to acquire coatings manufacturer Schramm Holding AG and the coatings activities operated by Schramm’s largest shareholder, Korean company SSCP. Schramm manufactures

and markets coatings for plastics, metals and electrical insulation. SSCP has a strong position in the Korean mobile phone market and also supplies coatings to the wider consumer electronics industry. Additionally, the company is acquiring from Integrated Botanical Technolo-

gies (IBT) its patented Zeta Fraction™ technology. The process developed by IBT makes it possible to harvest and separate constituent parts of a living cell from any plant or marine source without requiring any solvents. AkzoNobel also plans to acquire Boxing Oleochemicals, a leading supplier of nitrile amines and derivatives in China and throughout Asia.

Dow and Saudi Aramco Announce Joint Venture MIDLAND, MI/DHAHRAN, Saudi Arabia – The Dow Chemical Co. and the Saudi Arabian Oil Co. (Saudi Aramco) are planning a joint venture, Sadara Chemical Co., to build and operate a world-scale, fully integrated chemicals complex in Jubail Industrial City, Kingdom of Saudi Arabia. Comprised of 26 manufacturing units, the complex will produce over three million metric tons of chemical products and performance plastics. Construction will begin immediately, and the first production units will come on line in the second half of 2015, with all units expected to be up and running in 2016. The manufacturing units will produce a wide range of performance products such as polyurethanes (isocyanates and polyether polyols), propylene oxide, propylene glycol, elastomers, linear low-density polyethylene, low-density polyethylene, glycol ethers and amines.

Ashland Inc. Begins Construction on Plant in France WILMINGTON, DE – Ashland Aqualon Functional Ingredients, a commercial unit of Ashland Inc., recently began construction on a new nonionic synthetic thickener manufacturing facility in Alizay, France. The new manufacturing facility is scheduled for completion and startup in late spring of 2012 and will significantly increase global capacity of Aquaflow™ nonionic synthetic associative thickeners.

Dow Corning Joins Regenerative Network

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PCI04094Qlab-panel.indd 1

MIDLAND, MI – Dow Corning has accepted an invitation to join the Regenerative Network, a private consortium of leading green building product and service providers whose mission is to advance the green building industry and corporate sustainability objectives through collaboration with members such as architects, engineers and contractors.

SEPTEMBER 2011 | W W W . P C I M A G . C O M 3/19/09 10:53:46 AM

CREATING TOMORROW’S SOLUTIONS

MAKE THE MOVE TO VINNAPAS ® EF 8300 – THE NEW VAE BINDER FOR HIGH PERFORMANCE PAINTS

VINNAPAS® EF 8300 is a new VAE copolymer dispersion that is produced without the use of APEO and ideal for flat to semi-gloss paints. This allows the formulation of paints with low VOC (< 2 g/l), very low residual VAM (< 200 ppm) and overall high performance, e.g. excellent scrub resistance, good block resistance as well as good wet adhesion and water resistance. Make the move to the technology of the future today. Visit us at www.wacker.com

C O M PANY NEWS Cabot to Expand Fumed Silica Capacity in Europe

increase Cabot’s global fumed metal oxide capacity by 35 to 40 percent.

BOSTON – Cabot Corp. will expand production capacity by 25 percent at its fumed silica facility in Barry, Wales. The expansion is expected to be completed in 2012 and is part of a three-year plan to

Tyco International to Acquire Chemguard Inc. SCHAFFHAUSEN, Switzerland – Tyco International Ltd. is acquiring Chem-

guard Inc., a provider of firefighting foam concentrates and equipment, foam systems, services, and specialty chemicals. Chemguard will be integrated into Tyco’s Fire Protection Products business unit.

Quest Construction Products Buys IPC’s Coatings Business PHOENIX, AZ – Quest Construction Products, a division of Quest Specialty Chemicals, has acquired the coatings business of Integrated Paving Concepts (IPC) of Vancouver, Canada. IPC specializes in decorative stamped asphalt and asphalt coating technology.

DSM Acquires Majority Stake in AGI Corp.

The New MCR Series: Modular Rheometers Ready for Everything Whatever your rheological requirements are and will be in the future – MCR rheometers are always efficiently and comfortably adapted to meet your needs.

HEERLEN, the Netherlands – Royal DSM N.V. has successfully acquired a 51-percent stake in AGI Corp. of Taiwan (AGI). AGI offers a broad range of environmentally friendly, UV-curable resins and other products that are used in coatings and inks for wood, flooring, plastic and graphic-arts applications.

Sherwin-Williams Acquires Leighs Paints CLEVELAND – The Sherwin-Williams Co. has purchased U.K.-based Leighs Paints. Leighs Paints manufactures a comprehensive line of intumescent passive fire protection products for the hydrocarbon market.

Arkema Completes Acquisition of TOTAL’s Coatings Resins and Photocure Resins

Find out more about the MCR rheometer series at www.anton-paar.com.

PARIS – Arkema’s acquisition from TOTAL of coatings resins from both Cray Valley and Cook Composites and Polymers and the photocure resins of Sartomer is now final. The Cray Valley and Cook Composites and Polymers resins will join the Emulsion Systems business unit as part of a new structure named Arkema Coating Resins, while the Sartomer activities (photocure resins) will make up a new business unit. Both business units will be part of the Industrial Chemicals segment, with decision centers based in the United States. See page 49 for an in-depth interview with Arkema Coating Resins’ Global Group President. 䡲

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SEPTEMBER 2011 | W W W . P C I M A G . C O M

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N AMES IN THE NEWS 䡲 J. Rich Alexander, PPG Executive Vice President, has been assigned to lead all of PPG’s architectural coatings businesses. Pierre-Marie De Leener, PPG Executive Vice President, has been assigned to lead PPG’s global automotive refinish, protective and marine coatings, and aerospace

businesses. Viktoras R. Sekmakas, PPG Senior Vice President, Industrial Coatings, and President, PPG Asia/Pacific, has been named Senior Vice President, Industrial Coatings, and President, PPG Europe. Michael Horton, Vice President, Asia/ Pacific Coatings, and General Manager,

Automotive Refinish and Architectural Coatings, Asia/Pacific, has been named President, PPG Asia/Pacific, and Vice President, Automotive Refinish and Architectural Coatings, Asia/Pacific.

䡲 Watson Standard has appointed David G. Grant the Market Development Manager for the Rigid Packaging Division.

䡲 David Henke has joined Archway Sales

Inc. as a Credit Manager. Marc Yurco has joined the company as a Technical Sales Representative for the Midwest Region.

䡲 DYMAX Corp.

has appointed Tony Ieraci Marketing Communications Manager.

䡲 The Board of Directors of Ecology Coatings Inc. has elected Jim Juliano as its Chairman. The company also appointed Nick DeMiro and John (Pete) Salpietra to the board.

䡲 Courtney Longacre

has joined Gulf Coast Chemical Corp. in the position of

Inside Sales and New Product Development.

䡲 Dow Performance

Materials has named Carlos Silva Lopes Strategic Marketing Director for the business, which includes the specialty companies ANGUS Chemical Co. and Acima Specialty Chemicals.

Lopes

䡲 Ribelin Sales Inc. announced the promotion of Jordan Muller to President of the company. Muller replaces Bob Spadoni, who will now focus on his other role as President and CEO of Koda Distribution Group. 䡲 Applied Manufacturing Technologies has appointed Richard Saro Automotive Account Manager.

䡲 Sherwin-Williams announced the election of Brian Skerry, Global Technical Director, Protective and Marine Coatings, to a four-year term on the Board of Governors of The Society of Protective Coatings. 䡲 Pump Solutions Group (PSG) has appointed John

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Whalen Vice President of Strategy Integration. Whalen will report directly to Dean Douglas , PSG President. 䡲

SEPTEMBER 2011 | W W W . P C I M A G . C O M 5/6/09 3:25:03 PM

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Winner of the PCI Award for Technical Excellence at Waterborne 2011

Novel Non-Chrome Thin Organic Hybrid Coating for Coil Steels

C

oatings have been used on metal substrates for many years to enhance corrosion resistance, mechanical properties, physical handling and appearance. Typical coatings include inorganic conversion coatings such as phosphates and chromates, directto-metal paints, and dry-in-place passivates hereafter referred to as thin organic coatings (TOCs). TOCs, as an evolving technology, have a changing definition, but at least one definition combines the following features: a significant organic resin component, an inorganic component for conductivity and/or corrosion protection, and a dry film thickness of < 5 μm.1 An intense research focus is the replacement of chromium, especially hexavalent chromium, given the increasing likelihood of chromium regulation. A growing trend of producing environmentally friendly products and the establishment of European RoHS Directive on the restriction of the use of certain hazardous substances in electrical and electronic equipment (2002/95/EC com-

FIGURE 1 | TEM cross-sectional image of new non-Cr TOC coating. Platinum Cap Gold Coating New Non-Cr Coating

Substrate 200 nm

monly referred to as the Restriction of Hazardous Substances Directive or RoHS, adopted in February 2003 by the European Union) have also contributed to this trend to eliminate hexavalent chromium.2 A major obstacle to chromium replacement in TOCs is corrosion performance, as non-chromium coatings are generally less protective than chromium-containing coatings.3 Two types of TOCs in commercial products are fluoroacid-containing coatings and sol-gel coatings. Fluoroacid coatings use fluorotitanic, fluorozirconic and/or fluorosilicic acids as the inorganic basis for the coating, providing adhesion and barrier properties.4 Those acids’ aggressive pH and fluoride content make them hazardous to employees and equipment, and are only compatible with a narrow range of organic components. Sol-gel coatings create an oxide network by progressive condensation reactions of precursors in a liquid medium.5 The network can be oxides of silicon, zirconium, titanium, aluminum, and/or cerium, and has good barrier corrosion resistance qualities. Drawbacks of sol-gel formulae include the VOCs generated upon hydrolysis of the starting materials, and the toxicity of several traditional sol-gel precursors.6 A novel, non-chrome, thin organic hybrid coating for coil application on a variety of metal substrates has been created. This mildly alkaline coating system has robust formulation ranges, performs better than existing non-chrome products and is comparable to commercial chrome products. The coating is based on a combination of unique structural, metal-binding and redox features that are tied to its performance properties. A “brick-andmortar” structural motif with organic resin acting as the “bricks” was found via transmission electron microscopy (TEM). Electrochemical studies and corrosion testing show the benefits of readily accessible metal-binding groups on the polymer as well as having a redox-active metal as part of the coating. In order to facilitate discussion of the various components of this novel, non-Cr hybrid coating system, the following abbreviations will be used: • Hybrid coating = coating with illustrated novel morphology; • Inorganic coating basis for continuous phase = X (Zirconium);

By Brian D. Bammel, B.S., M.S.F.; John Comoford; Gregory T. Donaldson; John D. McGee, B.S.; Thomas S. Smith II, Ph.D.; John Zimmerman, Ph.D. | Henkel Corporation, Madison Heights, MI 24

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SEPTEMBER 2011 | W W W . P C I M A G . C O M

One key design feature of these new hybrid coatings is a novel morphology consisting of two phases; a continuous inorganic phase with a discreet, regular and well-defined dispersed organic phase. Due to the very thin (~1 μm) application and complex composition of the novel, hybrid coating, it is very difficult to image with either the visible microscope or the scanning electron microscope (SEM). Low-vacuum SEM work does give a nondescript topographical image of the coating similar to other amorphous metal coatings at the surface, but no details of the coating structure as it relates to performance can be deciphered. Attempts to mechanically cross-section the coating by imbedding in Bakelite and cutting/polishing down resulted in samples unsuitable for characterization because the sample preparation obscured the features of the very thin coating. Imaging of a cross-section using TEM obtained by Focused Ion Beam confirmed the 1 μm coating thickness and showed a unique morphology (Figure 1). Organic “bricks,” the dark ovals in the TEM images, function as a dispersed phase surrounded by a continuous inorganic “mortar” phase. There is no change to this morphology at either the air/coating or the coating/substrate interface; it is also remarkably consistent throughout the coating. The organic domains are ~100 nm across, which correlates well with the measured particle size of the resin component used. Novel morphology of the hybrid coating provides a favorable balance of properties relative to historical coating types. Specific properties that are enhanced by this morphology include ease of drying during the application, chemical resistance, corrosion resistance and a significant change to the relationship of forming behavior with coating hardness and coefficient of friction.

FIGURE 2 | TGA data for the novel non-Cr hybrid coating and a commercial Cr-based coating. 20

Novel non-Cr hybrid TOC Commercial Cr product

TABLE 1 | Key to discussed TOC formulae. Description

Polymer (P)

Inorganic (X)

I+P X+P I+X+P

√ √ √

√ √

Active Inhibitor (I) √ √

FIGURE 3 | Neutral salt spray (NSS) data for conventional Cr TOC at varied PMT. 100 % Face Rust

Design Features: Novel Coating Morphology

Figure 2 shows the relative drying rates of the novel, hybrid coating to a conventional, organic passivate as measured by thermal gravimetric analysis (TGA). Faster drying translates to a broader application window for the end user. Figures 3 and 4 show that in addition to faster drying, the corrosion resistance, as a function of drying condition during application (peak metal temperature), is provided over a much broader range. Performance advantage of the novel morphology relative to historical coating types is significantly improved at lower peak metal temperatures. Figure 5 shows good forming behavior of the hybrid coating relative to historical coating types. In contrast to historical types, the novel, hybrid coatings are formable while remaining very

80

110 F PMT 122 F PMT 140 F PMT 175 F PMT 200 F PMT

60 40 20 0 0

200

400 600 Hours NSS Exposure

800

1000

FIGURE 4 | NSS data for new hybrid non-Cr TOC at varied PMT. 100

% Face Rust

• Active corrosion inhibitor = I (Vanadium); • Polymer = P (acrylic latex); • Metal adhesion promoter functional group = A (phosphate ester); • Metal binding and topcoat adhesion functional group = B (proprietary); • Active corrosion inhibitor binding functional group = C (proprietary); • Functional polymers = PA, PAB, PABC.

110 F PMT 122 F PMT 140 F PMT 175 F PMT 200 F PMT

80 60 40 20 0

0

200

400 600 Hours NSS Exposure

800

1000

FIGURE 5 | Roll-formed panels coated with discussed TOCs. Commercial Cr

New Non-Cr

Prior Non-Cr

Deriv. Weight (% /min)

15 10 5 0 -5 0

100

200

300 400 500 Temperature (ºC)

600

700

PA I N T & C O A T I N G S I N D U S T R Y

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Novel Non-Chrome Thin Organic Hybrid Coating for Coil Steels

TABLE 2 | Characterization of polymer variations. Polymer Variation

Particle Size, nm

pH

Theo. Tg (°C)

Non-functional P PA PAB

121 119 123

7.9 7.6 6.9

29 29 29

TABLE 3 | Key to polymer variations in TOC formulae. Description

Polymer Functional Groups A B C

Non-functional Polymer PA PAB PABC

√ √ √

√ √

√

Inorganic (X)

Active Inhibitor (I)

√

√

√ √ √

√ √ √

FIGURE 6 | NSS data on Galvalume highlighting components of new non-Cr TOC. % Face Rust

100 80

I+P

60

X+P

40

X+I+P

20 0

0

200

400

600

800

1000

Hours NSS Exposure

FIGURE 7 | NSS data on HDG highlighting components of new non-Cr TOC. % Face Rust

100 80 I+P

60

X+P

40

Design Features: Continuous Inorganic Phase Properties of the liquid coating formulation and applied coating can be greatly enhanced by custom design of the continuous, inorganic phase. In order to characterize cause/effect relationships with respect to corrosion resistance and constituents within the hybrid coating, a study was conducted wherein three model coating compositions were prepared (Table 1). In addition to a hybrid coating made with polymer P and inorganic basis X, variations were made in which the hybrid coating further comprised an active inhibitor I. An additional system was made without inorganic basis X, which resulted in a continuous, organic coating of polymer P. As shown by Figures 6 and 7, protection afforded to Galvalume® and HDG by the hybrid morphology is significantly greater than provided by polymer alone. Also shown is that corrosion resistance is greatly improved with addition of inhibitor I. The morphology of the hybrid coating prepared from inorganic basis X, polymer P and active inhibitor I was analyzed using the TEM technique. A line scan of energydispersive X-ray analysis (EDX) was performed during the TEM imaging to confirm the elemental compositions of both regions (Figures 8 and 9). The line scan confirms the organic versus inorganic area assignments, as well as showing that the active corrosion inhibitor I is located within the continuous phase (high inorganic content areas).

X+I+P

20 0

hard, without the reliance on forming additives like waxes that can have undesirable effects, such as compromised adhesion of subsequent coating layers. The continuous, inorganic phase also provides superior blocking resistance out to 160 °F (71 ºC), minimizing concerns about recoil temperature. This morphology also produces a very chemical-resistant coating – only nitric acid/hydrofluoric acid mixtures reliably remove all coating components from the substrate.

Design Features: Dispersed Organic Phase 0

100

200

300

400

500

600

Hours NSS Exposure FIGURE 8 | Higher magnification TEM image with EDX line scan path (line scanned from the top (inside the coating) to the bottom (inside the substrate).

The origin of the dispersed phase within the novel coating stems from inclusion of waterborne, polymer emulsions. Performance properties of the applied coating can be greatly

FIGURE 9 | EDX line scan showing disperse and continuous phase compositions. Galvalume: Line 3 P 100 X I Al Zn

80

Wt %

60

40

20

0

26

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SEPTEMBER 2011 | W W W . P C I M A G . C O M

0

20

40

80 100 60 Position (nm)

120

140

FIGURE 10 | NSS data on Galvalume for polymer functional groups A and B.

% Face Rust

80

TOC Type Hybrid coating, polymer A Hybrid coating, polymer AB Conventional non-chrome TOC Hex-chrome-based TOC

PAB

40

Conventional Non-Chrome TOC

0 0

200

400

600

800

1000

1200

Hex-Chrome-Based TOC

Hours NSS Exposure

FIGURE 11 | NSS data on HDG for polymer functional groups A and B. 100

Non-Functional Polymer

80

PA

60 40

PAB

20

Conventional Non-Chrome TOC

0 0

100

200

300

400

500

Hours NSS Exposure

600

Hex-Chrome-Based TOC

FIGURE 12 | NSS data on HDG for polymer functional group C with and without I. 100 % Face Rust

80

PAB with I

60

PABC with I PAB without I

40

PABC without I

20 0

Hex-Chrome-Based TOC

0

200

400

600

Hours NSS Exposure

FIGURE 13 | Cathodic polarization data on HDG for polymer functional group C with and without I. 0.9 -1 V ( vs. SCE)

TABLE 4 | Scribed reverse impact data, polyester solventborne paint on Galvalume.

PA

60

20

Corrosion Characterization by Neutral Salt Spray (NSS) As shown in Table 3 and Figure 10, benefits towards corrosion protection on Galvalume-coated steel are provided when functional groups A and B are imparted to the polymer relative to the control polymer made without functional groups in hybrid coating formulations that contain inorganic X and active inhibitor I. Also shown is that the performance of both polymer A and polymer AB-based formulations significantly exceeds that provided by a conventional commercial non-chrome based TOC. The hybrid coating based on polymer AB provides a level of corrosion protection to Galvalume-coated steel that is equivalent to that provided by hexavalent chrome-based TOC. As shown in Figure 11, benefits in corrosion protection on hot-dip galvanized steel are provided when functional groups A and B are imparted to the polymer relative to the control polymer made without functional groups. Also shown is that the performance of both polymer A and polymer AB-based hybrid coatings formulations signifi-

Non-Functional Polymer

100

% Face Rust

enhanced by custom design of the polymer. Polymer-bound, reactive functional groups provide a variety of performance benefits. These properties include corrosion resistance and topcoat adhesion. In this article, a number of performance advantages attributable to these functional groups within a model polymer formulation are highlighted. Acrylic polymer in the form of latex was chosen for this study due to formulation latitude, ease of manufacture and low cost. Polymer functional group A represents a group imparting ionic stabilization and also serves as an adhesion promoter to various metal surfaces. Polymer functional group B represents a group that can bind ionic species containing inhibitor I via coordination and also provide topcoat adhesion by providing covalent bonds with many thermosetting coatings. Polymer functional group C represents a group that can ionically bind species containing inhibitor I. Formulation PAB is the polymer used in the X + I + P formulation in the data above. pH changes within the coating, both during drying at the time of application and within the service environment, can trigger binding or release of I such that prolonged benefits in corrosion resistance can be realized. In this study, polymers with varying functional monomer content were prepared from a common base formulation, within the same polymerization scheme, at the same theoretical Tg and differing only in functional monomers used (Table 2). Each of the functional polymer variations were incorporated into a common hybrid coating formulation based on inorganic precursor X and inhibitor I. Particle size of each emulsion was determined by laser light scattering technique. Observed results are consistent with the size of dispersed organic phase shown within the TEM images.

-1.1

Bare Polymer AB Polymer AB + I Polymer ABC Polymer ABC + I

-1.2 -1.3 -1.4

% Paint Removed 10% 0% 0% 15%

-1.5 -1.6 1.00E-10 1.00E-09 1.00E-08 1.00E-07 1.00E-06 1.00E-05 1.00E-04 1.00E-03 I (A/cm2) PA I N T & C O A T I N G S I N D U S T R Y

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Novel Non-Chrome Thin Organic Hybrid Coating for Coil Steels

cantly exceeds that provided by a conventional commercial non-chrome-based TOC. The hybrid coating based on polymer AB provides a level of corrosion protection to hot-dip galvanized steel that very closely approaches that provided by hexavalent chrome-based TOC. Additional studies were carried out in which a polymer with functional groups A+B was further modified with functionality C, a group capable of binding inhibitor species I (Figure 12). Polymer AB and polymer ABC were made in

Experimental The substrate to be coated was first spray cleaned with Ridoline® 321 at 140 °F (60 °C) for 1 min, followed by a spray deionized water rinse and drying between rollers. TOCs were applied via a wire-wrapped drawdown bar (from R.D. Specialties), with wire gauge chosen to give total coating weights of between 1.3 – 1.6 g/m2 on Galvalume and 1.6 – 2.2 mg/ ft2 on galvanized substrates. The coatings were dried at a peak metal temperature of 200 °F (93 °C) in a convection oven. The commercial Cr-containing TOC used is a hexavalent chromium-based product. The commercial non-Cr TOC is an acidic, fluoroacid-based product. The liquid topcoat used was Akzo Polydure® CLS9872, and the powder topcoat was Rohm & Haas Corvel® 20-7025HY and both were used with their manufacturer-recommended primers. Both paint and primer were applied via a wire-wrapped drawdown bar, with wire gauge chosen to apply the manufacturer-recommended coating thicknesses. Paints were cured per the manufacturer’s instructions. Neutral salt spray testing was performed as in ASTM B117. Stack testing was performed by spraying deionized water on matching coated substrate, which was then clamped coated faces together and placed in a 100 °F (38 °C), 100% humidity chamber. Cleveland condensing testing was performed as in ASTM D 4585. Butler water immersion testing was performed by fully immersing the coated substrate in a glass dish of distilled water with a half inch of clearance below the substrate and three-quarters inch of clearance above, and the dish placed in a 100 °F (38 °C), 100% humidity chamber. Thermal resistance testing was performed in a convection oven at 200 °C for 20 minutes in each of four consecutive heating runs. QUV testing was done with a UVA340 bulb. Crosshatching used a 1.5 mm separation between cuts. Impact tests were at 80–160 inch-pounds of force, per paint manufacturer’s specifications. Thermogravimetric analysis was performed on a TA Instruments Q500 TGA. TEM and electrochemical studies were conducted by Saikhat Adhikari, Kinga Unocic and Professor Gerald Frankel of The Ohio State University Fontana Corrosion Center. RIDOLINE is a registered trademark of Henkel Corporation POLYDURE is a trademark of Akzo Nobel Coatings, Inc. CORVEL is a trademark of Rohm and Haas Chemical LLC GALVALUME is a trademark of Biec International Inc.

identical fashion using a common base formulation, at fixed theoretical Tg, differing only in functional group C. Each polymer was incorporated into two hybrid formulations, one of which contained inhibitor I and one which did not. The resulting hybrid coating formulations were applied to cleaned, hot-dipped galvanized steel by rollcoating at a dry coating weight of 1.88 g/m2 with a peak metal temperature of 200 °F (93 °C). Panels were placed in a NSS cabinet, and face rust was monitored over time. As shown in Figure 12, hybrid coatings containing both inhibitor species I and polymer functional group C show a reduced rate of corrosion relative to the control formulation prepared without polymer functional group C. No benefit attributable to C was observed in formulations prepared without inhibitor species I. Trends observed are attributed to release of inhibiting species with pH shift at the substrate associated with corrosion reactions. Also demonstrated by the study is the fact that the new hybrid coating based on functional polymer ABC provides a level of corrosion protection to hot-dip galvanized steel that fully matches, if not exceeds, that provided by hexavalent chrome-based TOC.

Corrosion Characterization by Electrochemical Techniques A study of the electrochemical aspects of the novel, nonchrome, hybrid coating’s corrosion performance on HDG was undertaken. Cathodic polarization scans produced informative differences between the formula variations. The resulting plots are shown in Figure 13. By extrapolating the lower polarization curve to the corrosion potential on the Y axis, we can then determine the corrosion current density along the X axis, which serves as an indicator of relative corrosion rates. The current densities for each novel, nonchrome, hybrid formula variation are displayed in Figure 14. These measured densities correlate with the NSS corrosion performance previously discussed, with one minor exception. A strong decrease in current density is observed between bare metal and the novel, non-chrome hybrid coating, and also upon addition of the active corrosion inhibitor I. A further benefit is observed with incorporation of the functional group C, both with and without inhibitor I. In neutral salt spray testing no benefit was observed for C without I. The corrosion protection provided by the design features of the novel non-Cr hybrid coating is reflected in both electrochemical analysis and simulated corrosion testing.

Characterization of Paint Adhesion FIGURE 14 | Current density data on HDG for polymer functional group C with and without I. 5

Bare

icorr (μA/cm2)

4 3

Polymer AB Polymer ABC

2

Manufacturing Considerations 1

Polymer AB + l

Polymer ABC + l

0 28

For any end-user application, including utilization in architectural, electronic and appliance goods, post-painting operations may be involved. One key design feature of the new hybrid inorganic-organic composite coating is the ability to utilize functional groups on the polymer to facilitate adhesion of various paints. Incorporation of functional group B to the polymer within the composite coating matrix has been shown to promote adhesion of solventbased, coil-applied paints as well as powder topcoats in post-painting operations (Figure 15, Tables 4 and 5).

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SEPTEMBER 2011 | W W W . P C I M A G . C O M

In order to achieve high levels of corrosion protection with coatings as thin as 1 μm in dry thickness, most approaches rely on the use of highly reactive and highly

Summary A new non-chrome coating for Galvalume and galvanized substrates has the following design features: • Non-fluoroacid, mildly alkaline basis for handling and coating; • A novel coating morphology that provides favorable mechanical and chemical resistance properties as well

TABLE 5 | Adhesion data, polyester powder paint. Galvalume HDG Reverse Cross Reverse Cross Impact Hatch Impact Hatch Adhesion 160 In. Lbs Adhesion 160 In. Lbs

Coating Type Hybrid coating, polymer A

0%

0%

0%

Hybrid coating, polymer AB

0%

0%

0%

0%

Conventional non-chrome TOC

0%

0%

0%

0%

Hex-chrome-based TOC

10%

0%

0%

0%

0%

TABLE 6 | Additional data for the novel non-Cr hybrid system. Stack, 2016 h BWI, 2016 h Cleveland, %corr %corr 1008 h %corr

Galvalume Novel non-Cr hybrid Commercial Cr TOC

3 10

5 3

QUV, 1008 h 6E

1 1

1.9 1.7

FIGURE 15 | T-bend data, polyester solventborne paint on Galvalume. Rating (1-5)

functional constituents. Frequently, mixtures of such highly reactive functional components are subject to undesirable interactions, which can have adverse consequences during product assembly and packaging. In such cases, low manufacturing yields, difficult clean-up of mixing vessels, and inconsistent product quality may arise when lab-scale formulations are transferred to commercial production scale. In the case of these new hybrid coating formulations, specialized manufacturing equipment and cleaning protocols are not required. In addition, new hybrid coating formulations of this type, made in commercial production scale, show no drop in performance relative to prior lab produced materials. Figures 16 and 17, and Table 6 illustrate the performance of a hybrid coating made at production scale and applied on a production line relative to commercial hexavalent chrome-based and conventional non-chrome-based TOC products over Galvalume and hot-dip galvanized steel respectively.

6 5 4 3 2 1 0

Hybrid Coating, PA Hybrid Coating, PAB Conventional Non-Chrome TOC Hex-Chrome-Based TOC

0T

1T

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3T

Bend

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29

Novel Non-Chrome Thin Organic Hybrid Coating for Coil Steels

as reduced thermal requirements during application relative to conventional products; • Active corrosion inhibition involving an inhibitor and interactions with polymer domain functional groups within the coating matrix;

FIGURE 16 | NSS comparison of production-scale formulae on Galvalume.

Acknowledgements

% Face Rust

100

The authors would like to thank Girdhari Kumar of Henkel for useful discussions. Transmission Electron Microscopy and electrochemical studies were conducted by Saikhat Adhikari, Kinga Unocic and Professor Gerald Frankel of The Ohio State University Fontana Corrosion Center.

80 Commercial Non-Cr

60

Commercial Cr

40

Novel Non-Cr

20 0

0

200

400 600 800 Hours NSS Exposure

This paper was presented at the 38th Annual Waterborne Symposium, 2011, in New Orleans.

1000

© Henkel Coporation, 2010, All rights reserved.

FIGURE 17 | NSS comparison of production-scale formulae on HDG.

References

% Face Rust

100

1

80

2

Commercial Non-Cr

60

Commercial Cr

40

Novel Non-Cr

3

20 0

• A robust range of formulation options; • Functional groups on the polymer within the coating matrix that contributes to corrosion protection and adhesion in post-painting operations; • Corrosion performance equivalent to hexavalent chrome-based products. 䡲

4 5

0

100

200 300 400 Hours NSS Exposure

500

600 6

http://www.arcelormittal.com/automotive/sheets/R_EN.pdf (retrieved August 2, 2010). http://eurlex.europa.eu/LexUriServ/LexUriServ.do?uri=OJ:L:2 003:037:0019:0023:EN:PDF (retrieved August 16, 2010). A. Matsuzaki, K. Okai, T. Matsuda, N. Yoshimi, H. Noro, Galvatech 2004 Conference Proceedings, 131. D. Dollman, T. O’Grady, US patent 4191596. C. J. Brinker, G. W. Scherer, Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing, HBJ (Academic Press), (1990). D. Wang, G. Bierwagen, Prog. Org. Coat., 64 (2009), 327.

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SEPTEMBER 2011 | W W W . P C I M A G . C O M

during the

The Technology Forum for the Coatings Industry. Indianapolis, IN, May 7 – 9, 2012

May 8 – 10, 2012 www.american-coatings-show.com

Call for Papers Inspiring Innovation

Important Deadlines

The American Coatings Association (ACA), in partnership with Vincentz Network (VN) is calling for papers to be presented at the American Coatings Conference 2012. This major technology forum for the coatings industry, which will take place May 7 – 9, 2012 in Indianapolis, IN, is held in conjunction with the American Coatings Show, May 8 – 10. As the American Coatings Association’s most valued event, it will again provide a world-class, high-level technical and scientific forum, rallying leading industry experts from coatings manufacturers, their suppliers, universities, and government partners across the nation and beyond.

f

Submission of title and abstract September 30, 2011

f

Notification of acceptance to speakers November 18, 2011

f

Submission of full technical paper for the conference proceedings February 24, 2012

Innovative companies as well as academic/governmental research institutes are kindly invited to submit abstracts detailing highlevel technical contributions to this event, presenting their latest research results that highlight advancements important to coatings as well as to printing inks, adhesives and sealants.

Where to submit?

Important note: The conference organizers will select proposed presentations for the AC Conference based on the following criteria: scientific significance, novelty and potential value-added to the industry. Please note, that this selection is based solely on the content of the abstract submitted. Prospective authors are strongly encouraged to make clear in their abstract the research’s unique contribution aligned with these criteria. Student papers are welcome. A limited number of the accepted student papers will be offered financial support from industry sponsors.

American Coatings Award The most outstanding coatings paper will be honored with the American Coatings Award selected and sponsored by the American Coatings Association and Vincentz Network. This prestigious award is endowed with $ 2,500 and an attractive sculpture.

The Roon Award The Roon Award is a cash prize funded through an endowment managed by the Coatings Industry Education Foundation (CIEF). Authors wishing to have their eventual paper considered for the ACA Roon Award should mark the appropriate designation on the form. As in the past, Roon Award designated abstracts will be evaluated by both the ACC Program Committee and the ACA’s Roon Award Committee. Authors who have been accepted for Roon Award consideration will be notified separately, and will likely need to complete and submit their final papers to the Roon Award Committee before February 24, 2012 to be considered.

We kindly ask you to submit your title and abstract online at www.american-coatings-show.com/callforpapers

Understanding the Latest Advances in

Vinyl Technology

I

n the past 50 0 ye years, ear arss coatings technology has evolved at a rapid pace. As demand, performance requirements and environmental regulations have changed, so has the industry. Some things, however, have not. Cost versus performance has always been, and will always be, a primary motivator among formulators, contractors and do-it-yourselfers. Successful chemists and material manufacturers understand this key truth and design products accordingly. Vinyl acetate-based polymers have helped formulators develop decorative coatings that meet this balance since the 1960s. Because vinyl technology was introduced to the coatings industry nearly one-half century ago, some formulators may have a perception that it is “old technology,” with little new to offer in the continually changing landscape of costperformance needs and regulatory requirements faced by coatings producers today. In fact, there are many advances in vinyl acetate-based polymers that allow these binders to continue as a preferred choice of coatings formulators. New technologies have opened up new options for formulators, including conventional vinyl acrylic binders, vinyl acrylic binders engineered to form films without coalescent, and vinyl acetate/ethylene (VAE) binders also designed to form films without coalescent. These new technologies and choices allow emulsion producers to offer a range of vinyl acetate-based polymers that exhibit a variety of performance attributes in coatings that still meet applicable government and industry regulatory standards. Understanding how these newer products compare to other technologies on the market will help formulators and end users make more informed decisions based on the needs of specific products. This article discusses a wide range of attributes, including scrub resistance, washability and aesthetic properties, and how coatings made with vinyl acetate-based polymers help formulators develop cost-effective solutions that meet these needs.

materi• A common grind was prepared using all ra raw w ma mate teri ri-als except for the binder, coalescent (if required) and adjustment water. • Equal weights of the common grind were poured into individual cans, and the appropriate amount of binder was added to obtain the desired pigment volume concentration (PVC). • Finally, water and, if necessary, VOC-free coalescent were added to achieve the desired volume and volume solids for the formulation.

Defining Consistent Parameters

In-Can Properties Viscosity

The findings in this article are based on an extensive study comparing the properties of many different vinyl acetatebased binders. To ensure consistency, a standard protocol was used for preparing all paints:

KU

FIGURE 1 | Equilibrated viscosity. 140.0 120.0 100.0 80.0 60.0 40.0 20.0 -

VACon VAE VALow 25

50 PVC

65

The binders were divided into three categories: 1. Conventional vinyl acrylics (VACon) a. Glass transition temperature (Tg) range for polymers: 10 °C to 24 °C b. All of these latexes require coalescent to form a film at 5 ºC. 2. Self-coalescing (low minimum film forming temperature [MFFT]) vinyl acrylics (VALow) a. Tg range for polymers: 2 °C to 6 °C b. None of these latexes require coalescent to form a film at 5 ºC. 3. Vinyl acetate/ethylene (VAE) a. Tg range for polymers: 4 °C to 12 °C b. None of these latexes require coalescent to form a film at 5 ºC.

VA-Based Materials Provide a Wide Range of Benefits to Meet Formulator Needs In comparing these three materials, the study showed clear differences between these three sub categories. The results discussed below focus on how the three categories differ and show the performance range based on specific application needs. If the testing yielded no clear differences, the property is not discussed.

Differences noted in viscosity were due to the need for coalescing solvent to form a proper film. The in-can viscosity for the 65 and 50 PVC paints was either in the 80-90 KU and 1.4-1.8 ICI range if formulated without coalescent, or in the 125-135 KU and 1.8-2.2 ICI range with coalescent. The 65 PVC paint utilized RM825 and HMHEC, and the 50 PVC paint used SCT-275 and HMHEC as their thickener system. For the 25 PVC paint formula, the coalescent-free paints were originally in the 70-80 KU range and very runny, so a decision was made to add coalescent to all of the 25 PVC paints. This brought the viscosity up to a range of 110-130 KU and 1.1-1.6 ICI. The addition of coalescing solvent to increase viscosity aids in the swelling of the polymer.

By Michael Kaufman, Applications Development Leader; Wenjun Wu, Ph.D., Principle Scientist; Eric Kaiser, Global Marketing Director; and Chris Miller, Ph.D., Global Director of Research | Arkema Coating Resins, Cary, NC 32

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for Coatings Figure 1 demonstrates the viscosity difference noted between the categories across the PVC range. With different thickener systems at each PVC point it clearly shows that conventional vinyl acrylics have the best thickening efficiency. It should also be noted that differences in viscosity with and without coalescing solvent should drive the development of new thickener systems for low-VOC coatings systems.

Heat Age Stability Heat age stability tests were run for 8 weeks at 122 ºF/50 ºC. In comparing overall polymer types, there appeared to be no effect on heat age stability. These paint formulas have not been optimized for stability with any one polymer.

• Low-Tg Low Lo w-T Tg vinyl Tg vin inyl acrylics; • VAE.

Contrast Ratio Contrast ratio (hiding) in paints is affected by PVC, level of TiO2 pigmentation, extender type, and rheology and film formation. In evaluating the data, the biggest influence on contrast ratio is the paint formulation. It should be noted that all three paints utilized the same TiO2 levels, thus increasing PVC results in creation of air voids and increased hiding. (Figure 4). In further evaluation of the 25 PVC paint formulation by binder category it is possible to show a small but statistically significant difference in hiding for conventional VA over low-VOC VA and VAEs.

Freeze/Thaw Stability % Technology Passing 5 Cycles

FIGURE 2 | Freeze thaw stability of vinyl technologies. VACon

50 PVC

65

FIGURE 3 | Gloss potential of vinyl technologies. 100.00 VACon VAE VALow

80.00 60.00 40.00 20.00 20

60

85

Angle

FIGURE 4 | Influence of paint formulation on hiding. 100.5% 100.0%

Optical Properties Gloss Development

99.5% 99.0% Hiding

Gloss development of the respective paints was very similar in the 65 and 50 PVC paints, with the 20º/60º/85º gloss averaging 1.4/2.2/1.8 for the 65 PVC paints, and 1.4/2.5/2.0 for the 50 PVC paints. The gloss differential becomes the most apparent in the 25 PVC semigloss, where pigment interaction with the latex polymer influences gloss development (Figure 3). By category, the polymers having the best gloss development in each category are: • Conventional vinyl acrylics;

100% 80% 60% 40% 20% 0% 25

Units

Freeze/thaw stability showed a better correlation across the binder categories. Figure 2 shows that conventional vinyl acrylics have a better chance of achieving freeze thaw stability across the PVC range. In evaluating the individual products within the polymer type across the paint formulas, tests show that all of the low-Tg technologies failed freeze/thaw for all paint systems. The conventional technologies showed a progression of more difficult freeze/thaw as the PVC of the paint system became lower. At very low VOC levels, the chance of having a paint that is freeze/thaw stable is directly related to the PVC of the paint and the Tg of the polymer. To achieve good freeze/thaw at low VOC, a substantial improvement in technology development is required. Another factor that comes into play for freeze/thaw stability is the PVC of the paint system. There is a statistically significant difference between the PVCs tested here, showing that there is a much better chance to achieve freeze/ thaw stability in higher-PVC paints. A plausible explanation for this is that at higher PVC levels, paints have lower levels of latex and higher levels of pigmentation, which aids in protecting the polymer particles from coming in contact with each other during freezing.

98.5% 98.0% 97.5% 97.0% 96.5% 96.0%

25

50 Paint PVC

65

All Pairs Tukey-Kramer 0.05

PA I N T & C O A T I N G S I N D U S T R Y

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Understanding the Latest Advances in Vinyl Technology for Coatings

Tint Strength Tint strength generally correlates with the same variables as contrast ratio but is also affected by surfactant levels, particle size and many other factors. In evaluating all the paint formulations, no significant statistical differences in

Average Y Value

FIGURE 5 | Tint strength across PVC range. 0.5900 0.5800 0.5700 0.5600 0.5500 0.5400 0.5300 0.5200 0.5100

VACon VAE VALow 25

50 PVC

65

Delta Y

FIGURE 6 | Touch-up of paints. 0.80 0.70 0.60 0.50 0.40 0.30 0.20 0.10 0.00

Delta 1 ct Delta 2 ct

VACon

VAE Technology Type

tint strength based on binder category were observed. On average, a 3% spread across Y value was observed for each of the different polymers evaluated (Figure 5).

Application/Film Formation Properties Touch-Up There are two main modes of failure in touch-up: color and gloss differential. In Figure 6, data from the study clearly shows that different vinyl technology types show differences in touch-up for color consistency. Conventional wisdom within the coatings industry has historically been that VAEs have better touch-up properties than vinyl acrylics. When compared to conventional vinyl acrylic technologies, this study would support this notion. However, it is also apparent that low-VOC vinyl acrylics have touch-up properties that are comparable to the performance of VAE binders. This is an important finding and demonstrates how conventional wisdom product positioning can sometimes obscure the true evolution of technology development.

Resistance Properties Scrub Resistance Scrub resistance was measured per ASTM D 2486 (method B), using a side-by-side drawdown against a known control. For the 50 PVC paints, the highest scrub-

VALow

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Mason Color’s high performance pigment technology for coatings provides the ultimate in heat resistance, UV durability, and chemical resistance. Our mixed metal oxide pigments meet the most exacting color and durability requirements of the defense, architectural, stove and heating products, and roofing industries. These pigments add vibrant color to building facades, stove equipment, exhaust parts and outdoor furnishings and equipment. These advanced technology pigments can be incorporated into any coating platform including powder coatings, electrocoat, high solids and waterborne paints.

Mason Color Works, Inc. A History of Pigment Technology Excellence Mason Color Works has been manufacturing high temperature, inorganic pigments since 1842. For more than 40 years Mason Color has been a global supplier of high performance pigments to all sectors of the ceramic industry including pottery, artware, bricks, sanitaryware and roofing materials. In the last 45 years, Mason Color has expanded into the high technology Investment Casting Industry. Our ISO Compliant Cobalt Aluminate products are integral in the manufacturing jet turbine blades and medical devices. In the 1990s heralded the emergence of the fireplace gas log industry and Mason Color's participation as a supplier of high quality, high temperature pigments for this use. Soon thereafter, the Swimming Pool and Spa colorant industry embraced Mason's pigment technology. Our high quality pigment exceed the demands for resistance to punishing UV energy and the aggressive chemicals used in swimming pools. Our fully outfitted Powder Coating Laboratory and skilled technicians will help you choose the perfect color for your most demanding requirements.

Understanding the Latest Advances in Vinyl Technology for Coatings

resistant polymers by category are: VAE, > VALow and then VACon; however, within each category there was variability in how the specific binders performed. The coalescent-free vinyl acrylics all scrubbed more or less

Cycles

FIGURE 7 | Scrub resistance. 3500.00 3000.00 2500.00 2000.00 1500.00 1000.00 500.00 0.00

Cycles

VACon

VAE Technology Type

VALow

Blending with Acrylics

FIGURE 8 | 65 PVC scrub resistance. 500.00 Cycles

400.00 300.00

Cycles

200.00 100.00 0.00

VACon

VAE Technology Type

equivalent, whereas the VAEs showed the broadest range with a standard deviation of +/- 1500 scrub cycles, and conventional vinyl acrylics had a standard deviation of +/-500 cycles (Figure 7). Although not shown, the 25 and 50 PVC paints showed the same general trends by category for scrub resistance. Because the 65 PVC is past critical PVC (CPVC), a change in the relative performance by category for scrub resistance is expected. This was found to be true. In these formulations, the VAE and coalescent-free vinyl acrylics performed similarly and there was less of a performance gap with conventional vinyl acrylics (Figure 8). It is apparent that PVC and formulation become dominant factors in scrub resistance above CPVC, whereas below CPVC inherent binder properties play an important role.

VALow

It is common practice in the coatings industry to blend vinyl-based binders with acrylic binders to achieve a desired balance of cost and performance. Vinyl acrylics are a preferred choice in blended systems versus VAE products because they typically demonstrate better compatibility with acrylic systems and corresponding improved performance. As an example, shown in Figure 9, it was observed that in the 25 PVC paints blending of the VAE with acrylic technology resulted in a greater reduction in scrub resis-

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SEPTEMBER 2011 | W W W . P C I M A G . C O M

1/27/09 1:20:31 PM

tance when compared to a low-VOC vinyl acrylic technology. This is an important consideration in binder selection.

FIGURE 9 | Scrub resistance of blended technologies.

In analyzing the washability for each stain in each of the three paint formulations, there were a few stains that stood out as having significant differences. In the 25 PVC paint, pencil proved to be the most difficult to remove. At 25 PVC, the overall washability for these stains (average) was best for low-VOC vinyl acrylics (Figure 10). In the 50 PVC paint, the technology having the most difficulty with stain removal was again the low-Tg vinyl acrylic. This was specifically focused around the removal of mustard and ketchup stains. In evaluating high-PVC paints (65), the technology that had the most difficulty removing stains was the conventional vinyl acrylic. Approaching the critical PVC, a number of performance properties show a marked change in performance. In this study, that change occurred between the 50 and 65 PVC paints as they passed the CPVC point. Choice of pigmentation above CPVC will influence this performance property and improve washability by two mechanisms: rapid film erosion and increased hydrophobicity based on pigment choice.

Conclusion Vinyl acetate-based binders offer coatings formulators proven performance, and this technology continues to advance to meet the evolving needs of the coatings industry. Across the three categories outlined in this study, formulators of interior paints can find many of the attributes needed to meet both customer and industry standards. Additionally, within each category, many different options are available, each with their own unique balance of performance attributes. Table 1 summarizes performance properties across the three categories. If freeze thaw is an important performance feature, conventional vinyl acrylic technology is the best choice today for achieving this property without substantial negative impact on performance. If scrub

4500 4000 3500 3000 2500 2000 1500 1000 0

VALow VACon VAE

100.00% 80.00%

70.00% 50.00% Vinyl

25.00%

0.00%

FIGURE 10 | Washability of paints. 90.0% % Recovered

Washability is similar to stain resistance in this study in that both have a series of stains applied and allowed to sit for a standard period of time before rinsing off. Washability goes further, in that a sponge and cleansing solution are used to try to rub the stain off the surface. The conventional wisdom is that acrylics will do better for washability, followed by vinyl acrylics, with VAEs being the worst for washability. For the purposes of this study, the following stains were used: • Yellow mustard; • Red ketchup; • Grape juice; • Hot coffee; • Fountain pen ink; • No. 2 pencil; • Blue crayola crayon; • Red grease pencil; • Black shoe heel; • Crayola washable marker – black; • E-190 Royal Red lipstick.

Cycles

Washability

85.0%

VACon VAE VALow

80.0% 75.0% 70.0% 65.0% 25

50 PVC

65

TABLE 1 | Performance properties of the binders in this study. Performance

25

VACon 50 65

25

VAE 50

65

25

VALow 50 65

Rheology Heat stability Freeze/thaw stability Gloss development Contrast ratio Tint strength Touch-up Scrub resistance Washability Blendability Weakness Neutral Strength

resistance in unblended systems is important, the formulator might want to consider a VAE. If blending with other technologies is important, along with excellent touch-up and scrub resistance, the formulator should consider conventional and low-Tg vinyl acrylics. By understanding the benefits each provides, as well as the material’s inherent strengths and weaknesses, formulators can make more informed choices that balance product performance with the most cost-efficient solution. 䡲

References 1 Annual Book of ASTM Standards, American Society for Testing and Materials, Philadelpia, PA, Vol 6.01. 2 Asbeck, W.K.; Van Loo, M. Critical pigment volume relationships. Ind. Eng. Chem. 1949, 41: 1470-1475.

Acknowledgements The authors would like to acknowledge the assistance of Lisa Sullivan, Bill Schmitz and Katherine Weatherington for their help in collecting data. We would also like to thank Ron Grieb for his guidance and support. PA I N T & C O A T I N G S I N D U S T R Y

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Next-Generation Waterborne No-

W

ith the amendment of the Clean Air Act in the early 1970s, it was recognized that VOC emissions from paint may accelerate the process by which sunlight and nitrogen oxides generate ozone, which is the major component of smog. Therefore, efforts to regulate VOC emissions in the United States were initiated. The regulations vary depending on the region or state in the United States; however, the most stringent limits were developed in California for architectural and industrial maintenance coatings (AIM). In the colorants industry, many of the solvents used are considered to be Hazardous Air Pollutants (HAPS), and therefore their use in formulas should be limited. As a result, Colortrend USA LLC commenced the development of Chroma-Chem® 897, the next generation of no-VOC colorants, consisting of 15 volumetrically and gravimetrically dispensable colorants, for both depot and in-plant tinting systems. Chroma-Chem® 897 colorants combine minimal VOC levels with superior performance and coloristic properties. These colorants are designed to have a broad range of compatibility with commercially available high-performance waterborne industrial coatings, i.e. aliphatic acrylic polyurethane, modified acrylic terpolymer, epoxy-acrylic, epoxy-amine adduct, acrylic enamel, acrylic urethane, acrylic-modified alkyd, and PUR alkyd. Chroma-Chem® 897 colorants are free of Alkyl Phenol Ethoxylate (APE) and aromatic compounds, therefore helping paint manufacturers reach the proposed VOC content limits without sacrificing the final coating performance. Except for Burnt Umber,

FIGURE 1 | Colorant and tinted paint evaluated properties. r avio Beh ical g o l o hine Rhe Aut.Mac sability Dispen Sterility Dis VO pensab ility C Man Co .Ma nt chin en e t

Colorant Evaluations Colorants were evaluated considering two areas, as shown in Figure 1: • Quantifiable on colorant – The inherent properties of the colorant such as aging stability, freeze-thaw stability, dispensability, VOC, etc. • Quantifiable on paint – The impact of colorants on different paint properties. The colorants were evaluated at 10% by volume for stability in paint, sag resistance, drying, curing (Persoz Hardness), accelerated weathering (both QUV-A and Xenon Arc), condensation test, salt spray, compatibility, leveling, sag resistance, gloss, salt spray, etc.

Quantifiable on Colorant Aging Chroma-Chem® 897 colorants were placed in the oven at 50 ºC, and the viscosity change was monitored over four weeks. After four weeks aging, the strength difference between the aged colorants and the samples kept at room temperature were evaluated. Results showed no significant difference between the samples.

Freeze/Thaw Stability When waterborne colorants are shipped during cold weather, they may experience cycles of freezing and thawing. Freeze/ thaw cycles may cause more damage than when the colorants are subjected to steady freezing. The effect of freeze/ thaw cycling on the viscosity, grind and color strength of Chroma-Chem® 897 colorants was evaluated at -18 °C for 17 h, followed by 7 h undisturbed at room temperature. This procedure was repeated for five cycles. The strength differences between one, three and five cycles were compared with the colorants kept at room temperature. Results showed no significant differences between the samples. The color differences of both the aged and freeze-thawed samples were evaluated in a pastel acrylic-urethane one-component base using a colorant level of 10% by volume.

F

e ez re

Th

aw

ab St

ilit

y

Quantifiable on Colorant

which uses a naturally occurring pigment that contains Manganese, all of the colorants are HAPs free.

e

im

nT

ure

os e COLORANT Exp Op No-VOC Arc on APE-free n e X Rheol. Modifiers stance Sag Resi Humectants Defoamers Oven Stability Pigments Earli Surfactants QU er Wat e C V

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bili

Sta

ce

CT gQ erin ath We rength Color & St Leveling Corro sion Resis tan e

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ss Glo ness Hard Viscosity Drop Adhesion Bloc Ch king em ica

r Res om Exp istan osu pa ce re tib ilit y

Quantifiable on Paint

VOC Evaluation Chroma-Chem® 897 was developed to have VOC lower than 50 g/L by ISO 11890-2 as shown in Table 1. ISO 11890-2 or ASTM D 6886-03 are the preferred methods when the VOC content is expected to be between 0.15% and 15% by mass. There are multiple GC test methods based upon boiling point markers, columns, temperature and time profiles. One of the main differences between ISO and ASTM is that ISO has a boiling point cutoff at 250 °C using n-tetra decane as a marker, while the ASTM method has no cutoff. Therefore, ISO considers anything below the BP as a VOC,

By Jadel Baptista, Applied Technology Manager Colorants Americas | Colortrend USA LLC, Piscataway, NJ 38

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SEPTEMBER 2011 | W W W . P C I M A G . C O M

Industrial VOC Colorants while ASTM considers all non-exempt compounds as VOC. ASTM D 6886-03 has a reported detection limit of 0.05% (500 ppm) though a revision (D 6886-rev) is going to ballot, which will lower the detection limit to 0.005% (50 ppm). ISO 11890-2 does not have a detection limit.

Quantifiable on Paint The colorants were evaluated in nine commercially available industrial waterborne paint base chemistries; 2K aliphatic acrylic polyurethane, modified acrylic terpolymer, 2K epoxy-acrylic, 2K epoxy-amine adduct, acrylic enamel, 2K acrylic urethane, 1K acrylic-modified alkyd, and PUR alkyd. To see the impact of these colorants on paint properties, examples are shown below with the addition of either Yellow Oxide (an inorganic colorant) or DDP Red (an organic colorant) to a 2K aliphatic acrylic polyurethane.

Stability in the Paint An aliquot of 10% by volume of each colorant was added to the paint base and placed in the oven for three weeks at 40 °C. Changes in viscosity, pH and sag resistance were evaluated against the initial sample. Results in Table 2 show that no significant change occurred in the paint’s physical properties compared to the untinted paint. Therefore, no modification of the paint base is needed when tinted with Chroma-Chem® 897 colorants.

Drying Time The drying time was measured according to ASTM D 5895 using a dry time recorder from BYK Gardner, model number BK.3. An aliquot of 10% by volume of each colorant was used and evaluated for drying time differences between the base itself and the tinted base. Results in Table 3 show no differences in dry time with the addition of either the inorganic or organic colorants, demonstrating that the addition of Chroma-Chem® 897 colorants would not have a negative impact on the drying properties of the paint.

Impact on Gloss During UV Exposure The addition of colorants can influence the UV resistance of some coating systems due to chemical incompatibility between the colorant and the binder of the coating. The evaluation of gloss during the time of exposure to UV radiation can provide us with an indication of whether the paint resistance was affected. In order to evaluate the impact of Chroma-Chem® 897 colorants on retention of the film gloss, 10% by volume of colorant was added to the paint base, cured for 7 days, and exposed to QUV-A and Xenon Arc for 3500 h. Results have showed that ChromaChem® 897 colorants will have minimal impact on the gloss of the paint film when exposed to UV radiation.

Impact on Water Resistance Colorant addition may have a negative influence on the

water resistance of some coating systems due to chemical incompatibility between the colorant and the coating binder. The evaluation of adhesion and film integrity of the paint after being exposed to 100% humidity at 40 °C in a QCT condensation tester can provide us with an indication of whether the paint resistance was affected. In order to evaluate the impact of the next-generation colorants on the film integrity under high humidity conditions, 10% by volume of colorant was added the paint base, cured for 7 days and exposed in the QCT for 1680 h. As shown in Figure 2, the coatings tinted with Chroma-Chem® 897 showed no blisters or loss of adhesion, indicating that the colorants will have minimal impact on the coating’s water resistance.

TABLE 1 | Chroma-Chem® 897 VOC content levels. Colorant

VOC

White Carbon Black Phthalo Green Phthalo Blue Carbazole Violet Yellow Oxide Red Oxide DPP Red Medium Yellow Organic Yellow DPP Orange Bismuth Vanadate Quinacridone Violet Quinacridone Red Burnt Umber

8 g/L 5 g/L 9 g/L 8 g/L 14 g/L 5 g/L 4 g/L 5 g/L 6 g/L 3 g/L 8 g/L 13 g/L 3 g/L 5 g/L 11 g/L

TABLE 2 | Impact of DPP Red and Yellow Oxide colorants on the physical properties in 2K aliphatic acrylic polyurethane after 1 and 3 weeks at 40 °C. Physical Properties Viscosity [KU] Paint Control Viscosity [KU] Yellow Oxide Viscosity [KU] DPP Red pH Paint Control pH Yellow Oxide pH DPP Red Sag resistance [μm] Paint Control Sag resistance [μm] Yellow Oxide Sag resistance [μm] DPP Red

Initial 78 80 78 8.5 8.5 8.5 275 275 250

After 1 Week @ 40 °C

After 3 Weeks @ 40 °C

80 77

80 77

8.4 8.4

8.1 8.3

275 250

275 250

TABLE 3 | Impact of DPP Red and Yellow Oxide on paint dry time. Drying Time Base Paint With 10% Yellow Oxide With 10% DPP Red

Tack Free

Dry Through

2.5 h 2.5 h 2.5 h

14.5 h 15 h 14.5 h

PA I N T & C O A T I N G S I N D U S T R Y

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Next-Generation Industrial Waterborne No-VOC Colorants

FIGURE 2 | Impact of DPP Red and Yel-

FIGURE 3 | Impact of the DPP Red and

low Oxide colorants on the film integrity of 2K aliphatic acrylic polyurethane paint base after 1680 h of condensation test (40 °C/100% RH).

Yellow Oxide colorants on the anti-corrosive property of 2K aliphatic acrylic polyurethane paint after 1680 h of salt spray exposure (35 °C).

Impact on the Anti-Corrosive Property of the Coating The addition of colorants can affect the anti-corrosive property of some coating systems, due to chemical incompatibility between the colorant and the binder of the coating. The evaluation of film degradation after being exposed to 1680 h of salt spray at 35 °C can provide us with an indication of whether the paint resistance was affected. In order to evaluate this property, 10% by volume of colorant was added to the paint base, cured for 7 days and exposed in the QCT for 1680 h. Results have showed that Chroma-Chem® 897 colorants have no impact on the coating’s anti-corrosive property (Figure 3).

Impact on Gloss, Hardness and Blocking Resistance

FIGURE 4 | Impact of DPP Red and Yellow Oxide colorants on 60° gloss. 100 90 80 Gloss at 60°

70 60

Base DPP Red Yellow Oxide

50 40 30 20 10 0 A

B

C

D

E

F

G

H

I

Impact on Adhesion

Paint Chemistry

It is commonly known by paint formulators that some surfactants, humectants and defoamers used to formulate colorants can affect the ability of some coatings to adhere to the surface. Chroma-Chem® 897 colorants were tested for crosshatch adhesion according to ASTM D 3359. The results in Figure 7 show that Chroma-Chem® 897 had excellent adhesion compared to another low-VOC colo-

FIGURE 5 | Impact of DPP Red and Yellow Oxide colorants on hardness.

Hardness (Seconds)

200 180 160 140

TABLE 4 | Paint base chemistries.

120

Base DPP Red Yellow Oxide

100 80 60 40 20 0

A

B

C

D

E

F

G

H

I

Paint Chemistry 40

The impact of Chroma-Chem® 897 colorants on gloss, hardness and face-to-face blocking resistance was determined in the paint base chemistries listed in Table 4. For gloss determination, 10% colorant was added, the coating cured for 7 days on metal substrate, and tested for gloss at 60° angle. As shown in Figure 4, excellent gloss retention was obtained. Hardness evaluation was performed by measuring the damping time of an oscillating pendulum according to the ASTM D 4366 method. The equipment used was a pendulum hardness tester with Persoz pendulum from BYK Gardner. Addition of Chroma-Chem® 897 had no substantial impact on the hardness, as shown in Figure 5. The ability for a coating to not stick to itself upon contact when pressure is applied is an important requirement for industrial applications. In order to evaluate how the nextgeneration colorants would affect the blocking resistance of the paint, the ASTM D 4946-89 method was used. Colorant (10%) was added to the bases and applied to the substrate with a 6 mil bird applicator. The specimen was dried for 7 days and placed face to face in the oven at 50 °C, with a pressure of 1.8 psi over the specimen. After 30 minutes, the specimens were removed from the oven, cooled for 30 minutes at room temperature and peeled apart. Chroma-Chem® 897 colorants did not reduce and in some cases improved the blocking resistance of paint bases, as shown in Figure 6.

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SEPTEMBER 2011 | W W W . P C I M A G . C O M

A B C D E F G H I

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Next-Generation Industrial Waterborne No-VOC Colorants

FIGURE 6 | Impact of DPP Red and Yellow Oxide colorants on blocking resistance.

FIGURE 8 | Impact on sag resistance with addition of ChromaChem® 897 Phthalo Green colorant.

12

Blocking Rating

10 8 Base DPP Red Yellow Oxide

6 4 2 0 A

B

C

D

E

F

G

H

rant on the left and a no-VOC colorant on the right. Also, both phthalo blue and green colorants provided improved adhesion in some paint chemistries.

I

Paint Chemistry

TABLE 5 | Summary comparing Chroma-Chem® 897 to competitive colorants. Compatibility Adhesion Blocking Gloss Acrylic urethane Epoxy polyamine Acrylic Acrylicmodified alkyd Aliphatic acrylic PU Modified acrylic terpolymer Epoxy acrylic 1 Aliphatic acrylic polyurethane Epoxy acrylic-2 Acrylic enamel

Pendulum MEK Sag Hardness

Excellent

+

0

-

0

0

+

Excellent

0

0

+

-

0

+

Excellent

0

0

0

+

0

0

Excellent

+

0

-

0

0

0

Excellent

0

0

+

0

0

Excellent

0

+

+

+

0

Excellent

0

+

0

0

+

Excellent

0

+

0

0

+

Excellent Excellent

0 0

0 +

0 0

0 0

0 0

FIGURE 7 | Impact on adhesion with addition of Chroma-Chem® 897 Phthalo Blue and Green colorants.

Impact on Sag Resistance When a coating is applied on a non-horizontal substrate, it may sag due to gravity. Sag resistance is interrelated to the composition, viscosity and thickness of the coating. It is desirable that the paint base preserve its anti-sag property after the addition of colorants. Sag resistance was evaluated according to ASTM D 4400. Results, as shown in Figure 8 for Phthalo Green Colorant, confirm that the addition of 10% by volume of the colorant improved the sag resistance of the paint when compared with competitor colorant.

Dispensability Dispensability of no-VOC waterborne colorants has been a concern in the market due to the colorant tendency to dry in the nozzles. The correct balance of colorant formulation can provide good dispensability of the colorants without compromising other physical properties. Chroma-Chem® 897 colorants were tested in automatic dispensing, closednozzle manual dispensing and opened-nozzle manual dispensing machines. Results obtained showed that colorants had satisfactory performance with both automatic and closed-nozzle manual dispensing machines, and can endure a minimum of three weeks in the opened-nozzle dispensing machine without cleaning the nozzle.

Conclusion The results presented in this article show that the use of the next-generation Chroma-Chem® 897 waterborne no-VOC colorants can help paint formulators comply with current and developing VOC coating requirements. The colorants are not sensitive to pH variation, will provide a broad range of compatibility, have minimal effect on the performance in different paint base chemistries, and in some cases improve the paint physical properties, as summarized in Table 5. This is a new step for no/low-VOC waterborne colorant technology, with Chroma-Chem® 897 becoming the benchmark for no-VOC waterborne industrial colorant technology. 䡲 The author would like to acknowledge Mier Gu, John Gorman and David Rivera from Colortrend USA LLC, and Mark Westera from Colortrend B.V. for their contributions and data.

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Driers for Alkyd Coatings

V

egetable and animal oils and derived products have been used for centuries as binders in varnishes and paints. Oil painting on wood was known in ancient times, but drying time was so long that this technique was not widespread. In the early medieval period, artists using pigments suspended in oils, preferably linseed oil, discovered that contamination with copper or lead decreased the drying time of paints and varnishes. This process was described by Aetius and Teofil the Monk.1,2 Pure unsaturated oils, even in favourable humidity and temperature conditions (20 °C, RH 50%), take a very long time to dry. The same oil boiled in a copper jar or in a vessel containing pieces of copper or lead metal dries over a relatively short amount of time. Varnishes were prepared in such a way in the Middle Ages. The content of metal derivatives, so called driers, promoted a rapid drying process. Further development of this technology led to oil paints used first by artists and later by the general public. In the beginning, paints were manufactured in small quantities, and the formulas were kept as family secrets. The first paint factories began during the European technical revolution in the eighteenth and nineteenth centuries. During that time some research was done and published in the technical literature. During the same time, the manufacturing method of driers based on the reaction of metal oxide with rosin acids was described. The same method is used today, and there are many descriptions of it.

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RH + O2 + cat. Co2+ A ROOH ROOH + Mn2+ A RO· + ·OH + Mn2+ A RO· + OH- + Mn3+ ROOH + Mn3+ A ROO· + H+ + Mn2+ The reaction sequence presented here is catalyzed by small amounts of organic metal salts called driers or siccatives. Organic radicals formed in the process react with double unsaturated chains, forming more reactive conjugated double bonds responsible for polymerization and further film drying reactions.

Oil and Resin Drying Process

Driers – Composition and Mechanism of Catalysis

Used for centuries as binders in coatings, oils contain reactive carbon-carbon double bonds in the aliphatic chains; chemically they are triglycerides of unsaturated fatty acids. The drying process is a chemical reaction of unsaturated carbon-carbon double bonds with atmospheric oxygen i.e., oxidative polymerization. In this way low-molecularweight unsaturated triglycerides transform into high-molecular-weight polymers suitable for film formation. The reactivity of oil in the polymerization process depends on the amount and location of reactive double bonds and the chain structure. Because of polymerization and drying rate, oils are often classified as drying, semi-drying and non-drying. The last group is of very little interest in coatings. In paints manufactured today, alkyd resins are used as binders instead of oils. Alkyd resins are prepared during the condensation process of saturated and unsaturated dicarboxylic acids with polyalcohols and oils. Different alkyd resins are obtained depending on the type of fatty acid, oil and

Driers are metal (often polyvalent) carboxylates, sometimes called metal soaps or salts. Typically cobalt, lead, iron, manganese, vanadium, calcium, strontium, zirconium, zinc, lithium and barium metals are used. The organic component of the drier is comprised of medium- to long-chain linear or branched acids like linoleic, naphthenic, abietic, decanoic, neodecanoic or octanoic. The organic part of the salt improves solubility in solventborne systems. Driers are commonly sold as a solution in aliphatic or aromatic solvent. More and more often, no-VOC solvents are used to minimize the drier VOC impact in the paint formulation. Metal soaps act in different ways to catalyze the curing process of air drying binders that contain unsaturated carbon–carbon double bonds; they are used in relatively small concentrations to control the drying process. During curing a binder undergoes an oxidative polymerization process, yielding a three-dimensional crosslinked alkyd polymer structure responsible for the mechanical and chemical properties of

By Dr. inż. Maciej Umiński | Warsaw, Poland 44

alcohol. Very often phthalic anhydride is used as the dicarboxylic acid precursor, hence the common use of the name phthalate resins for some alkyd binders. Depending upon how much oil is used in the cooking process, the resin may be a long oil type, a medium oil type or a short oil length. Moreover natural resins like copal, dammar, accroides, sandarac, elemi, rosin and shellac are applied as binders for some specific solventborne coatings.3 In some cases, chemical modification is needed to improve natural binder properties. During the low-thickness coating air drying process, an alkyd resin reacts with oxygen from the air, yielding hydroperoxides. The reaction is facilitated in the presence of cobalt salts. In the next reaction step, hydroperoxides form free radicals, starting the oxidative polymerization process. This second process is sped up in the presence of manganese salts.

SEPTEMBER 2011 | W W W . P C I M A G . C O M

– an Overview coatings. The process is catalyzed by active metal cations; the organic moiety facilitates cation transport close to the alkyd resin particles.4 From the chemical point of view, siccatives are homo phase catalysts of a free radical oxidative polymerization reaction. Driers are used for both room temperature and baking curing processes of solventborne and waterborne alkyds and to some extent for unsaturated polyesters. Because of their metal type and function, siccatives are often classified as: • active (primary) driers – cobalt, manganese, lead, iron or vanadium salts; • secondary (auxiliary) driers (working together with active driers) – zinc, aluminium, lead, strontium, lithium, potassium, cerium, bismuth or zirconium salts; • wetting driers – calcium, strontium or barium salts. Active (primary) and secondary (auxiliary) driers may be called “reactive” driers. A different classification also divides driers into three groups: • primary driers (surface or top driers) – act as oxidation catalysts and contain metals with more than one oxidation state like cobalt, manganese and iron; • through driers like zirconium, strontium, lead or lithium – ensure a uniform drying rate throughout the body of the film; • auxiliary driers modify the effect of previous categories of driers – contain calcium, barium, zinc or potassium. The right choice of drier combination allows almost a quantitative reaction of the resin carbon-carbon double bonds and fast, uniform and stable wet coating drying up to 100 μm of film thickness. Any single metal is not sufficient to catalyze fast and uniform drying throughout the entire film.

For this reason, a mixture of driers is used in alkyd paints. Often in decorative alkyd paints, so-called complex driers – trade raw materials containing a mixture of two, three or four different metal salts – find an application. A complex drier always consists of one or two active siccatives, one or two auxiliary siccatives and often a wetting siccative. There are many theories explaining why alkyd resins dry in the presence of siccatives. An active drier is responsible for the curing process. An auxiliary drier stabilizes pH and facilitates the process of free radical formation. Auxiliary driers allow a minimizing amount of primary cobalt salt, increasing drier system stability and decreasing the yellowing tendency of a coating. Organic (especially carbon black) and some inorganic pigments with large surface areas interact with driers. However, a strong surface adsorption of primary or auxiliary drier on the pigment/ extender-binder interface may cause a drier efficiency reduction and be responsible for increased drying time and coating failure. Wetting driers possess a significant surface affinity to the pigment-binder phase border, and by reacting with the pigment surface they are saving “reactive” siccatives. For this reason a wetting calcium siccative is often added at the grinding stage to promote the milling process and to prevent consumption of active or auxiliary drier on the pigment-binder phase border. The properties of commonly used driers are listed in Table 1.5, 6, 7 The amount of drier used depends on the type and amount of alkyd binder and is described as metal percent calculated on solid binder. Usually 0.02 – 0.1% active drier (metal on solid binder) and 0.01 – 0.3% auxiliary drier are added to the paint or varnish. A wetting drier is usually applied in the amount of 0.02 – 0.5%. Moreover,

TABLE 1 | Driers - properties and action. Drier

Type

Lead

Primary/auxiliary

Action

Very active, responsible for through drying and surface drying. Lead toxicity is the issue. The most active drier responsible for surface drying. The dosage should be monitored strictly to Cobalt Primary avoid curling or wrinkling of the film and weak through drying. Toxicity is under discussion but very limited data is available. Cobalt gives some yellow discoloration. Medium activity, generally gives red discoloration. Some iron complexes are interesting Iron Primary substitutes for cobalt. Very active, an interesting alternative for cobalt, a surface drier, it also favours through drying. Manganese Primary Generally gives brown and yellowish discoloration but some complexes do not have this drawback. Very active drier responsible mainly for surface drying. It gives green discoloration, toxicity could Vanadium Primary be an issue. An auxiliary drier used in conjunction with active driers. Responsible for through drying, it Zirconium Auxiliary improves the film hardness. Keeps the film open, thus favours the through drying process. It is used solely with cobalt, and Zinc Auxiliary prevents wrinkling and skinning. Lithium Auxiliary It improves the through drying process, reducing wrinkling and is effective at low temperatures. A wetting drier, it improves the drying stability during storage. It favours the through drying Calcium Wetting process and coating gloss. A wetting drier, it improves the drying stability during storage. It favours the through drying Barium Wetting/auxiliary process and coating gloss. A wetting drier, it improves the drying stability during storage. It favours the through drying Strontium Wetting/auxiliary process and coating gloss. PA I N T & C O A T I N G S I N D U S T R Y

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Driers for Alkyd Coatings – an Overview

anti-skinning agents (antioxidants) are important additives for paints that dry via an oxidative polymerization process. Anti-skinning agents inhibit paint drying in the can, thus preventing dry film (skin) formation on the liquid paint surface. As a consequence, antioxidants may cause an increase in the drying time.

Driers are not only used in alkyd systems; cobalt octoate for example catalyzes the curing of unsaturated polyesters and epoxy esters initiated by peroxides. Cobalt driers are the most often used active siccatives. In the past, lead derivatives were very common. Because of the toxicity of cobalt (II) cations, the The WCS Symposium and Show is the major coatings event in the west this year and features an extensive technical program covering a wide spectrum of topics along the following lines. • New Formulations & Coatings • Management of Technologies in the Coatings Industry

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SEPTEMBER 2011 | W W W . P C I M A G . C O M

Air Products Cardolite Corporation Brenntag Specialties Nanophase Technologies Corp Breckenridge Technologies/Henkel Bayer Material Science LLC OPC Polymers Formulator & Colortec Software The Tryline Group Pan Technology, Inc. Huntsman Polyurethanes Dorsett & Jackson P.T. Hutchins Company Huntsman Performance Products Lipscomb Chemical Company, Inc. Orion Engineered Carbons Reichhold, Inc. Lubrizol Univar Clariant Corp Nichem Quick Blades Case Labs Nu Sil Hauthaway Heucotech Ltd.

use of cobalt driers has recently been under discussion. Toxicological testing was done with soluble cobalt salts such as cobalt (II) sulphate. There is only a small amount of data concerning cobalt driers that are slightly soluble in water (salts of long-chain carboxylic acids) and practically no toxicological results for cured coatings that contain cobalt driers. Only such testing in real conditions may give an answer to the question “Are cobalt driers that are used in coatings harmful to our environment?” The activity of cobalt cations in the dry paint film is certainly different from the activity of cobalt cations dissolved in water.7 A big effort is underway to find safer but equally effective substitutes for cobalt. Extensive research for possible alternatives such as iron, manganese and vanadium derivatives was done. Unfortunately vanadium salts are toxic, and iron and manganese may provide some discoloration in the case of white and pale colours.7, 8 There are positive results for high-solids paints concerning cobalt substitution by manganese complex derivatives, in some cases mixed with other metal salts and an organic drying accelerator. The drying process is fast and there are very limited problems with coating discoloration.7 Certainly a new type of drier should be tested carefully in the formulation to avoid issues and to find out the best metal/resin proportion. Some promising results have been obtained with iron (II) complexes with ascorbic acid derivatives and imidazole. The influence of the iron complex on coating colour is negligible. Effective drying was reported even at a very low (0.04%) iron concentration. Hardness development was similar to cobalt, and skin formation was minimized.8

Driers in Water-Based Alkyd Systems Water-based alkyd resins are used as binders, often as a mixture with acrylic dispersions in waterborne interior and façade paints and also in enamels for wood and inorganic surfaces. The other possibility is an application of a hybrid alkyd/acrylic dispersion as a sole binder. Water-based alkyd resins are prepared from resins containing acid groups by neutralization with amines, often in the presence of surfactants. Proper resin acidity is obtained by introduction of sulphonic or carboxylic groups into the carbon backbone chain.9 To prepare the alkyd emulsion, the phase inversion

technique is often used, in which water is added to the resin/surfactant mixture. At the first moment that a water-in-oil emulsion is obtained, with more water an inversion occurs to an oil-in-water emulsion.10 Generally in water-based alkyd/acrylic systems the acrylic part of the binder dries by a physical process (water evaporation and particle coalescence leads to film formation), and the alkyd part of the binder dries via the oxidative polymerization process catalyzed by driers. Initially, driers typical for solventborne systems were used in waterborne formulations. Because of side reactions with water, amines and other dispersion paint ingredients, driers that are more stable and still reactive are needed. Carboxylates and naphthenic salts in the presence of water undergo hydrolysis, and as a result the availability of metal cations in the organic phase decreases dramatically during paint storage, yielding an increased coating dry time or lack of drying. To overcome this issue, drier complexes with amines and alcohols were introduced. Standard siccatives for solventborne systems may be applied in water-based systems after premixing with nonionic surfactants. Metals used in the drying process are prone to hydrolysis; their reactivity towards water increases as follows: Ba2+ < Ca2+ < Mn2+ < Zn2+ < Co2+ < Zr4+.4 Because of side reactions (e.g. hydrolysis) the efficiency of driers in water-based systems is lower, and

compared to solvent-based formulations usually a 100% excess of standard siccative is needed. A special class of water-dispersible driers for waterborne alkyds was developed to overcome this drawback. Such additives may be easily incorporated during the let down process. The iron complexes with ascorbic acid derivatives are very effective in solventborne and waterborne systems in concentrations below 0.1%. Drier activity is even higher than manganese and comparable with the activity of cobalt salts.8

Coating Defects Connected with Drier Application Typical defects result from either too low or too high a dosage of drier in the coating. Too low a concentration of siccatives increases the drying time, in the extreme situation it is responsible for lack of drying. On the other hand, too high a drier dosage reduces coating flexibility and makes the film brittle. Surface drying may stop oxygen diffusion into the entire coating layer and be responsible for non-uniform drying and bad weathering properties of the dry coating. The other issue is wrinkling, especially in the case of cobalt or manganese over dosage. Paints containing carbon black, some types of titanium dioxide or some organic pigments may lose their initial drying properties (loss of dry effect) during storage; the addition

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Driers for Alkyd Coatings – an Overview

of wetting (mainly calcium) driers in the milling step is beneficial. The amount of individual driers depends on the paint formula and seriously influences both surface- and through-drying time. In the typical case, three types of driers are used: active drier, auxiliary drier and wetting drier. Too small an amount of active siccative reduces the surface drying, too little auxiliary siccative reduces through dry time and too little wetting siccative causes the loss of dry effect during storage.

Conclusions Driers as paint additives are commonly used to promote curing of alkyd solventborne and waterborne coatings. Three different types of driers (active, auxiliary and wetting) are used in the typical paint composition. A proper drier content in the formulation is crucial for paint and coating properties. The amount of driers strongly influences coating properties and should be established in the paint formulation in the empirical way. In waterborne formulations, standard driers are used in excess. Another possibility is to use driers dedicated to waterborne systems. Much research has been done to develop environmentally safer substitutes for cobalt drier. The most promising results are obtained with iron and manganese complexes. 䡲

References 1

2

3 4 5 6 7 8

9

10

Werner, J. Podstawy technologii malarstwa i grafiki (The bases of paint and graphic art technology), PWN, ŁódĨ – Warszawa – Kraków 1974, p. 61-62. Crombie, A.C. Nauka Ğredniowieczna i początki nauki nowoĪytnej (Medieval and early modern science), Publishing Institute PAX, Warszawa 1960, Vol. 1, p. 270. Hare, C.H. Introduction to coating binders – natural resins, Surface Coatings Int. 1995, p. 258- 262, 78, (6). Verkholantsev, V.V. Additives for latex paints – direct and side effects, European Coatings Journal 2001, p. 62 – 69, No. 6. Technical materials of Faci Metalest S.L. company. Technical materials of Rockwood Pigments company. Steinert, A. Effective drying without cobalt, European Coatings Journal 2005, p. 84-88, No. 3. van Haveren, J.; Oostveen, E.A.; Micciche, F.; and Weijnen, J.G.J. Towards sustainability, European Coatings Journal 2005, p. 16-19, No. 1-2. Spychaj, T.; and Spychaj, S. Farby i kleje wodorozcie czalne (Waterborne paints and adhesives), WNT, Warsaw 1996, p. 111. Technical materials of Croda Coatings and Polymers.

This paper was presented at ACT 10 (Advances in Coatings Technology), November 2010, Katowice, Poland. For more information, contact the author at [email protected].

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SEPTEMBER 2011 | W W W . P C I M A G . C O M

OCTOBER 46, 2011 CINCINNATI, OHIO Presented by:

INSIDER INTERVIEW

Details on Arkema’s Acquisition of TOTAL An interview with Richard Jenkins, Global Group President for Arkema Coating Resins On July 1, Arkema acquired the coating assets of TOTAL, including products from Cook Composite and Polymers, Cray Valley and Sartomer. The company has since combined the product lines from Cook Composites and Polymers, and Cray Valley with its existing emulsion polymer line to form a new business unit, Arkema Coating Resins. Arkema Coating Resins provides a wide range of chemistries for both architectural and industrial coating applications. We recently asked Dr. Richard Jenkins, Global Group President for Arkema Coating Resins, a few questions about the new business.

PCI: Why did Arkema choose to purchase these specific assets from TOTAL?

Jenkins: The coatings businesses and assets purchased from TOTAL are complementary and synergistic with our existing emulsions products. The combination gives our customers access to unique and comprehensive product and technology offerings while giving us a global footprint from which to deliver the offering. It provides us with growth options in Asia and also enhances product innovation and the capability to develop sustainable products. For Arkema, this acquisition increases downstream integration, and provides access to a variety of end-use markets. The new business offers chemistries for almost every coating and related industry application, including architectural paints, industrial finishes, powder coatings, construction products, traffic paints, sealants, adhesives, inks and graphic arts products.

PCI: Can you give us an idea of how your product and service offering to coatings formulators has changed since the acquisition?

Jenkins: The breadth and scope of our product and technology offering have increased to cover the range of needs for coatings formulators globally. The combination includes waterborne resins, solventborne resins, fluorinated polymers, powder coatings, UV/ EB and catalyst curing systems. In addition, Arkema will feature Coatex’s extensive line of thickeners and dispersants. These technologies all work together to offer a coherent product offering that helps customers formulate.

PCI: How has this acquisition changed your business in terms of size, product offering, geographic reach and sales?

Jenkins:

Arkema Coating Resins has global reach and critical mass, with revenues in excess of $1.2 billion. With more than 1,700 employees, including more than 150 in R&D, located in 21 plants and five laboratories in 11 countries across four continents, we can address needs raised by global and regional customers. This puts us within the Top 3 global coating materials suppliers excluding pigments, and supplements our existing strong U.S. position with an equally strong position in Europe and a growth platform in Asia. Arkema has already begun construction of Coatex and Coating Resins latex plants in Changshu, China, and now can draw on facilities in the region (India, Malaysia) and on the strong potential of Sartomer’s newly opened plant near Guangzhou, China.

PCI: How does Arkema Coating Resins serve coating formulators worldwide? Jenkins: We listen to customers and respond. We have the complete set of tools to provide solutions to the coatings formulator, combined with a reinvigorated technology competency. Arkema is investing globally to provide advanced products to the coatings industry that drive innovation and allow customers to develop environmentally responsible and regulatory compliant solutions while maintaining outstanding performance.

PCI: Do you have any additional plans for growth or new offerings that you can talk about now?

Jenkins:

Having a robust platform in the United States and Europe, we are looking to accelerate and expand our participation in emerging regions. We are actively developing projects in several locations to grow either by acquisition or organically (or both) in Brazil, Middle East, China, India, Malaysia and South East Asia. Where we invest, we intend to take a platform approach, which will accelerate the total package of technologies. From a product platform standpoint we have added R&D resources and have numerous initiatives underway including development of additional new products in our SNAP™ Structured Nano-Acrylic Polymer line, which allows formulators to raise the performance bar in lowVOC high-gloss coatings.

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SEPTEMBER 2011 | W W W . P C I M A G . C O M

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SEPTEMBER 2011 | W W W . P C I M A G . C O M

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