Paint & Coating Industry March 2011

March 2011 VOLUME 27, NUMBER 3

INSIDE Grinding a Thixotropic Material

Paint

Coatings Industry

Pearlescent Effect Pigments New Additives for UV Coatings

Globally Serving Liquid and Powder Formulators and Manufacturers

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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 3

March 2011

FEATURES 22 European Coatings Show and Exhibitor Information 27 Ultrafine Nepheline Syenite as a Durable and Transparent Additive to Accelerate Radiation Cure, Unimin Corp. 36 Grinding a Thixotropic Material, Willy A. Bachofen AG Maschinenfabrik 44 Novel Acrylic Polymer Adhesion Technology for Coating Weathered TPO Roofing Membranes, Dow Construction Chemicals 52 Glassflake-Based Effect Pigments with Extraordinary Sparkle and Colour, ECKART 56 Novel Matting Agent for Low-Gloss UV Coatings, Evonik 62 Cobalt-Free Catalyst Gives New Life to the Alkyd Coatings Market, OMG Americas, Inc.

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ONLINE FEATURES w w w. pcimag.com Patent Awarded for Innovative See-Cure Technology, DYMAX Corporation Corrosion Protection in Harmony with the Environment, Henkel Massage Therapy for Bulk Bags Helps Discharge Materials, Spiroflow Systems, Inc. Nanometer-Thick Metal Oxide Coatings May Help Preserve Silver Artifacts and Art, University of Maryland

DEPARTMENTS 6 8 14 16 20 77 81 82

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

68 VAE Copolymer Dispersions – A Natural Gas-Derived Alternative to Crude Oil-Derived Binders, Wacker Chemical Corporation

BUSINESS TOOLS 74 uv.eb West Exhibit Showcase 74 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].

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Supporting the Next Generation of Scientists I was so pleased to read about the recent career day hosted by The Sherwin-Williams Company, in conjunction with the TH Hilson Company, and Cabot Corp. On February 7, 59 Chicago State University science students were treated to a rare, behind-the-scenes tour of the technical coatings lab and paint manufacturing plant located at SherwinWilliams’ South Chicago facility. The students also learned about the synergy of business between raw material suppliers, distributors and paint manufacturers. In addition, current employees interacted with the science majors regarding career requirements, responsibilities, and local and global opportunities. The event’s purpose was to identify potential recruits for the coatings industry and be supportive of the next generation of scientists. In an innovative partnership, Sherwin-Williams and its suppliers are teaming with the university to develop a chemistry curriculum that will customize academic training for the next generation of professionals in the coatings industry. In addition, students will be eligible for internships and full-time employment opportunities at the paint company and its suppliers.

Beth A. Surowiec

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By Kristin Johansson, Editor | PCI

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

Lori Hilson Cioromski, President of TH Hilson, has actually been very involved over the past year in organizing events designed to teach both high school and college students more about the opportunities that a career in chemistry can offer. Her hope is to engage other specialty chemical distributors and customers to bring a real-life experience to young people through the education system and to attract bright minds to the chemical industry. And since the career day at Sherwin-Williams, several other coatings manufacturers and suppliers have asked to partner with her on similar projects. I applaud these companies in reaching out to the next generation of scientists. As the baby boomer generation enters its retirement years, it is so important to recruit, teach and inspire the next group of chemists and business leaders for this industry. On a side note, many of us will be heading to Nuremberg later this month for the European Coatings Show. I look forward to seeing you there. Please be sure to stop by PCI’s booth, 9-150, to say hello and share your ideas on how we can better serve you. For information about the show, as well as a preview of what many exhibitors will be showcasing, see pages 22-26 of this issue.

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

Global Acrylic Resins Market to Exceed 16.4 Billion Pounds by 2015 SAN JOSE, CA – Global Industry Analysts Inc. has released a comprehensive global report on the acrylic resins market. The global market for acrylic resins is forecast to exceed 16.4 billion pounds by the year 2015. Demand for acrylic resins was negatively impacted by the global economic recession in 2008 and 2009. Significant declines in various end-use markets, including coatings, paper and paperboard, plastics, adhesives, construction, and textiles and fibers, hampered acrylic resin demand. However, sectors such as the do-it-yourself market segment were minimally impacted, driven by a shift in consumption patterns. Going forward, the resins market is likely to bounce back by 2011 and grow steadily in subsequent years. New product introductions that focus on perfor-

mance are likely to help resin manufacturers. Developing markets such as AsiaPacific and others are expected to infuse increased demand for resins and emerge as the hub for resins production. Europe represents the largest regional market for acrylic resins worldwide. In terms of growth, Asia-Pacific is expected to register the fastest growth for acrylic resins. The region is forecast to have a compound annual growth rate of more than three per-

RadTech Europe and Pira International Collaborate on Market Study LEATHERHEAD, UK – Pira International and RadTech Europe have agreed to work together on a new market study named “The Future of Radiation Curing for Packaging.” The study will provide quantitative market sizes for each key material, end-use, region and country. Using extensive primary research, the study will forecast to 2016. In addition, the study will contain important chapters on technology innovations and forecasts, key drivers, and hot topics such as sustainability. Pira International will do the research for the study. RadTech Europe, the European Association for the Advancement of Radiation Curing by UV, EB and Laser Beams, will assist with the marketing and promotion of the market study. The final publication date for the study is the summer of 2011. For additional information, e-mail [email protected].

ASTM Introduces New Carbon Black Standard WASHINGTON, D.C. – New regulations set forth by the U.S. Environmental Protection Agency to mandate greenhouse gas reporting in the U.S. carbon black industry have led to the development of a new ASTM International standard, ASTM D 7662, Test Method for Carbon Content in Carbon Black Feedstock Oils. Measuring the total carbon content of feedstock oils is an important step in calculating carbon dioxide emissions, estimating the yield of a process or assessing product quality. ASTM D 7662 is applicable to most commercial feedstock oils used to produce carbon black products in a furnace or thermal process. 8

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

cent over the period 2007 through 2015. The United States represents another major market for acrylic resins. The coatings sector constitutes the largest end-use of acrylic resins. Acrylic-based coatings deliver improved color stability, flexibility, weatherability and enhanced finishes. Consumption of acrylic resins by end-use markets is projected to exceed 4.4 billion pounds by 2012. Greener products are emerging as a lucrative opportunity for acrylic resin manufacturers. Addressing the needs of eco-friendly and greener requirements for end-use industries has become a prime focus for resin manufacturers. For additional information about the report, titled “Acrylic Resins: A Global Strategic Business Report,” visit www.strategyr. com/Acrylic_Resins_Market_Report.asp.

U.S. Plants Lag on Capital Improvements Spending CLEVELAND – Although manufacturing plants around the world continue to operate well below capacity, nearly half of them plan to increase spending on capital equipment in the coming year. International plants spent significantly more on capital upgrades than U.S.-based facilities in the past year: 10 percent of plant revenue (median) compared to 3.1 percent (median) at U.S. plants. The spending gap looks to continue through 2011, with 55 percent of international plants planning to increase capital spending compared to 44 percent of U.S. plants. The data comes from the MPI Manufacturing Study and is highlighted in the Manufacturing 2010/2011 Executive Summary. This year’s study includes a comparison of U.S. facilities (334 plants) versus plants from around the world (145 plants), vital in an era of increasingly global competition. The study was conducted with support from Thomas International Publishing Co. Visit www.mpi-group.net for additional information.

Coatings Research Institute Offers On-Site Training YPSILANTI, MI – Eastern Michigan University’s Coatings Research Institute (CRI) is offering on-site training on the following topics: coatings and paint technology, color technology, emulsion polymerization and waterborne coatings, principles and practices of coating formulations, emerging technologies in polymers and coatings, improving durability and performance of coatings, understanding coating raw materials, and basics of polyurethane coatings. For more information, e-mail Barbara Hopkins at [email protected].

I NDUSTRY NEWS Sartomer to Host UV/EB Technical Seminar EXTON, PA – Sartomer USA LLC will present a free technical seminar on UV/EB curing chemistries at its headquarters in Exton, PA. The three-day seminar will be held March 29-31, 2011. For additional information, contact James Goodrich, UV/EB Technical Manager, at [email protected]. The complete seminar agenda is available at www.sartomer.com/events.asp.

EPA and ECHA Announce Partnership WASHINGTON, DC – The U.S. Environmental Protection Agency (EPA) and the European Chemicals Agency (ECHA) have announced a partnership that will promote enhanced technical cooperation on chemical management activities. ECHA is the agency that implements the European Union’s chemical management program known as REACH (Registration, Evaluation, Authorization and Restriction of Chemicals). The partnership was formalized through a statement of intent that puts in place a process for working together on a range of issues of mutual interest including toxicity testing, the hazard and risk assessment of chemicals, risk management tools, scientific collaboration, and information exchange. One of the major anticipated areas of collaboration will be on the exchange of data and information. For example, the statement of intent will promote the exchange of non-confidential information on hazards, uses and substance identification between ECHA and EPA, including data collected under REACH. The two agen-

cies will also share criteria for managing confidential business information with the goal to increase the availability of chemical information to the public.

PCI Co-Producing Three Coatings Events in 2011 TROY, MI – PCI Magazine is co-producing three events in 2011 especially designed for coatings professionals. The Windy City Coatings Course will take place April 27-28, 2011, in Rolling Meadows, IL. It is a two-day educational course that offers introductory and advanced sessions led by industry experts. The Windy City Coatings Committee, a combination of representative members from the Chicago Society for Coatings Technology and the Chicago Paint and Coatings Association, are collaborating with PCI on this event. Visit www.windycitycoatingscourse.com for additional information. The Powder Coating Forum will take place June 7-8, 2011, in Columbus, OH. This two-day workshop and symposium provides the basics of powder coating formulation, emerging technologies and trends, and networking with leading industry providers. PCI is co-producing the event with Powder Coating Research Group. For additional information, visit www.powdercoatingsforum.com. Coatings Trends & Technologies (CTT) will take place Sept. 13-14, 2011, in Oak Brook, IL. This event will feature research trends, technical advances and critical issues related to coatings for plastic, wood and metal substrates. The Chicago Society for Coatings Technology is co-producing CTT with PCI.

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I NDUSTRY NEWS Visit www.coatingsconference.com for additional information.

Report on Smart Coatings Available GLEN ALLEN, VA - Industry analyst firm NanoMarkets has added a new report to its portfolio, titled “Smart Coatings

Markets – 2011.” The report addresses the growing market potential that smart coatings promise to deliver to coatings and materials suppliers, as well as companies within the energy, medical device, automotive, building products and military application markets.

Wet grinding and dispersing technology at its best. The newly combined power of Buhler and Draiswerke provides you with unique know-how in all wet grinding and dispersing applications. Our equipment and process solutions are proven, reliable and tailored to the U.S. market. This is especially evident in the new full-volume Centex™ Pearl Mill™ with exceptional media separation and high flow rates. See for yourself, by visiting us at the 2011 European Coatings Show in Nuremberg, Germany. Buhler Booth: #211, Hall 6. Buhler Inc., 13105 12th Ave N., Plymouth, MN 55441, T 763-847-9900 [email protected], www.buhlergroup.com

Smart coatings provide an appropriate and predictable response to changes in environment, which offers a huge commercial potential for additional longevity, safety and efficiency. And, from the perspective of the coatings supplier, smart coatings offer a new way to add value to products, create protectable IP and attract capital. Although many of the most interesting smart coatings are only just beginning to emerge from industrial laboratories, NanoMarkets believes that these coatings have significant future revenue potential. This report identifies where the growth areas are for commercializing and marketing smart coatings, who the major players are and will be, and how smart coatings products will be enhanced in value by the latest developments in nanomaterials and bioengineering. The report also includes an eight-year quantitative forecast by application and material type. Additional information about the report is available at www.nanomarkets.net.

EPA Requires Testing of 19 Widely Used Chemicals WASHINGTON, D.C. - The U.S. EPA is issuing a final rule under the Toxic Substances Control Act (TSCA) requiring manufacturers of 19 high production volume (HPV) chemicals to test the health and environmental effects of the chemicals and submit the data to the agency. This rule is one of a series of actions that EPA is taking to ensure that the agency has the data it needs to adequately review priority chemicals. HPV chemicals are produced in or imported into the United States in quantities of one million pounds or more per year. For more information on HPV chemicals, visit www.epa.gov/hpv.

Missouri S&T Announces Dates for Short Courses

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

ROLLA, MO – The Missouri University of Science and Technology (Missouri S&T) is offering the “Basic Composition of Coatings” short course March 28-April 1, 2011. “Introduction to Paint Formulation” is being offered May 9-13, 2011. “Introduction to Coatings Composition and Specifications” will be offered July 18-20, 2011. For more information, visit http:// coatings.mst.edu/index.html. To register, contact Catherine Hancock at [email protected]. 䡲

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APRIL

5-7 Print & Ink Technology www.pra-world.com 5-7 AeroDef Manufacturing www.aerodefevent.com 10-12 Radiation Curing Technology www.pra-world.com

31-June 2 Aluminium-21/Coatings www.eng.alusil.ru/2006

JUNE 7 Paint & Coatings Basics www.pra-world.com 7-8 Powder Coating Forum www.powdercoatingsforum.com

12-14 Surface Engineering Ukraine 2011 www.weldexpo.com.ua

7-9 NanoMaterials 2011 www.nanomaterialsconference.com

13-15 PDA 2011 Annual Conference www.pda-online.org

14-16 IMFAIR 2011 www.instituteofmetalfinishing.org

17-19 ASC Spring Convention www.ascouncil.org

20-22 Symposium on Polymer Surface Modification http://mstconf.com/surfmod8.htm

27-28 Windy City Coatings Course www.windycitycoatings course.com

JULY 13-14 Latin American Coatings Show www.coatings-group.com

MAY 9-13 Introduction to Paint Formulation http://coatings.mst.edu/ index.html

18-20 Coatings for People in the General Industry, Sales & Marketing http://coatings.mst.edu/index

11-13 Coat Expo China 2011 www.coatexpo.cn/en

24-30 19th International Conference on Composites www.icce-nano.org

11-13 Northwest Coatings Fest www.pnwsct.org

SEPT. 13-14 Coatings Trends & Technologies www.coatingsconference.com

www.kingindustries.com

16-19 Paint Technology www.pra-world.com

14-15 Asia Pacific Coatings Show www.coatings-group.com

or at the European Coatings Show – Hall 8 Stand 519

18-19 Asia Coatings Congress www.coatings-group.com

OCT. 6-8 Turkcoat Eurasia 2011 http://www.turkcoat.com/?dil=en

22-25 SSCT Annual Meeting www.ssct.org

16-18 ASC Fall Convention www.ascouncil.org

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

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C O M PANY NEWS

TH Hilson Co. Receives Distributor of the Year Award WHEATON, IL – TH Hilson Co. was presented with EPS-Materials’ 2010 Distributor of the Year Award. TH Hilson Co. has represented EPS in the Midwest since April 2003. This is the second time that TH Hilson Co. has received this award; the company was the recipient of the 2008 Distributor of the Year Award as well.

U.S. Zinc Partners With Two New Distributors HOUSTON – Officials with U.S. Zinc announced that two new distributors will represent the company’s zinc oxide division within the coatings market. U.S. Zinc signed agreements with E.W. Kaufmann Co. and Gulf Coast Chemical Corp. to distribute zinc oxide in the Gulf Coast, mid-Atlantic and northeast regions of the United States.

Spiroflow Systems Inc. to Represent Pacepacker Services CHARLOTTE, NC – Pacepacker Services Ltd. of the United Kingdom has named Spiroflow Systems Inc. its exclusive North and South American representative to promote, represent and support the company’s international range of manufactured bagging, pick and place, and robot palletizing systems. The arrangement expands Spiroflow’s capability to engineer, design and supply complete turnkey systems from raw material intake through storage, conveying, processing and screening to final packaging and palletizing.

Plasticolors Selects Distributor for Coatings Market in China ASHTABULA, OH – Shanghai Ji JingTrading and Developing Co. has been selected as an independent sales and distribution representative for Plasticolors Inc., Ashtabula, OH. Plasticolors Inc. is a supplier of advanced colorants and chemical dispersions for the thermoset plastics and coatings industries. Shanghai Ji JingTrading and Developing Co. will distribute Plasticolors’ coatings products in China.

E.W. Kaufmann to Represent EC Pigments BRISTOL, PA – E.W. Kaufmann Co. will represent EC Pigments USA Inc. EC Pigments’ product range consists of classical azo pigments, metal salt azo pigments, naphthol pigments and basic dye complex pigments. E.W. Kaufmann Co. will be promoting the products throughout its territory.

Celanese Invests in Ethanol Production Facilities in China DALLAS – Celanese Corp. announced that its wholly owned subsidiary, Celanese Far East Limited, has signed letters of intent to construct and operate industrial ethanol production facilities in 16

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

The TH Hilson Co. represents key suppliers of specialty raw materials for the coatings, graphic arts, adhesives, metalworking and lubricant, personal care, pharmaceutical, and consumer care industries. An established distributor since 1973, the company has offices in Chicago, Minneapolis, Cleveland, St. Louis and Kansas City.

Nanjing, China, at the Nanjing Chemical Industrial Park and in Zhuhai, China, at the Gaolan Port Economic Zone. Pending project approvals, Celanese could begin industrial ethanol production within the next 30 months, with an initial nameplate capacity of 400,000 tons per year per plant and an initial investment of approximately $300 million per plant. The projects will use Celanese’s new technology to produce industrial ethanol. This new process combines Celanese’s proprietary acetyl platform with highly advanced manufacturing technology to produce ethanol from hydrocarbon-sourced feedstocks.

Dixie Chemical Co. Partners With JNS-SmithChem PASADENA, TX – Dixie Chemical Co. has appointed JNS-SmithChem, Paterson, NJ, as product distributor for its line of specialty chemical intermediates. JNS-SmithChem will cover Maine, New Hampshire, Massachusetts, Vermont, Connecticut, Rhode Island, New York, New Jersey, Pennsylvania, Delaware, Maryland, Virginia and West Virginia.

Schepise Chemical Sales LLC is Formed, Launches Web Site BRISTOL, PA – A new company, Schepise Chemical Sales LLC, has been formed and has launched its Web site, www.SchepiseChemicalSales.com. A manufacturers’ representative firm, the new company promotes an array of specialty chemicals including rosin resins, rosin esters, polyterpene resins, hydrocarbon resins, flame retardants and specialty polymers for the adhesives and sealants, coatings, printing ink, and rubber and plastics industries. Additionally, the company promotes dimer acids for oil and lubricants and alkyd resin manufacturing.

PPG Expands Relationship with Asian Paints PITTSBURGH – PPG Industries announced plans to expand its 14-year relationship with Asian Paints Ltd. (APL), India’s largest coatings company, to accelerate growth of the companies’ nondecorative coatings businesses in India. As part of a new agreement, PPG and APL will restructure their existing non-decorative coatings businesses to expand their current 50-50 joint venture, Mumbai-based Asian PPG Industries (APPG), and to create a second 50-50 joint venture.

Because

Life is

©3M 2011. All Rights Reserved

Messy Keeps stone, concrete and other porous hard surfaces looking like new! 3M™ Stain Resistant Additive SRC-220 is a fast-drying, aqueous solution that provides long-lasting repellency and stain release characteristics to porous surfaces such as stone, concrete and unglazed tile. This versatile product can be used alone, as a penetrating sealer – or added to a variety of coating formulations and construction materials, such as grout and caulk, to repel oil or water-based stains and make cleanup easier. Unlike many competitive stain protectors, SRC-220 additive can be used on a broad range of stone, tile and concrete products. And, thanks to our reliable global supply, it is available in most countries around the world. Learn how you can improve your products’ performance and customer appeal. To arrange for a free formulating sample of 3M Stain Resistant Additive SRC-220, call us today at 800-367-8905. Or visit us at www.3M.com/pci.

sSuitable for indoor & outdoor use sEasy to incorporate into existing water & solvent-based products sConsistent high quality sLong-term reliable global supplier

www.3M.com/pci Now available globally in production-scale quantities!

1

C O M PANY NEWS APPG currently serves Indian transportation-coatings markets, and this agreement will expand that company’s scope to additionally serve India’s industrial liquid, marine and consumer packaging markets. The new second venture will serve the protective, industrial powder, industrial containers and light industrial coatings markets.

Clariant Focusing on Phase Two of REACH Legislation MUTTENZ, Switzerland – Clariant is now focusing on Phase Two of REACH legislation following its successful completion of the registration of 152 substances required under Phase One. Phase Two, which concerns more than 300 chemicals, should be completed by June 1, 2013. Phase One substances covered finished products, intermediates and raw materials. Phase Two is concerned with the registration of substances supplied at * 100 tons/annum. Clariant has another several hundred chemicals that fall under this category.

H.B. Fuller Establishes Local Presence in Turkey ST. PAUL, MN – H.B. Fuller Co. has strengthened its foothold in Turkey by entering into a joint venture with Burak Özberk, its longstanding agent there. A new entity will be created, with H.B. Fuller owning majority control. Through this new local entity, H.B. Fuller will better support customers and further solidify its presence in this emerging market.

AkzoNobel Expands Mexico Operations NASHVILLE, TN – AkzoNobel has announced a strategic investment in a new powder coating manufacturing plant in Apodaca, Mexico, a suburb of Monterrey, Mexico. The new facility will include manufacturing, warehousing, research and development labs, administrative offices, and a quality control laboratory. The site will allow the company to more than double its powder coatings business in Mexico and Central America over the

next several years. The new facility is expected to be fully operational in the third quarter of 2011.

WACKER Boosts Supply of VINNOL® Surface Coating Resins MUNICH – The Munich-based chemicals group WACKER can supply significantly greater volumes of VINNOL surface coating resins as of January 2011. VINNOL H 15, in particular, is available in larger quantities than before. Vinyl chloride copolymer-based binders had become scarce in 2010 as a result of consolidation of the binders market. WACKER is also planning to ramp up delivery capacities for its hydroxyl-containing products by the end of the third quarter.

Perstorp Acquires Ashland’s Penta Business PERSTORP, Sweden – Perstorp has, through its subsidiary Perstorp Polyols Inc., signed an agreement with Hercules Inc., a subsidiary of specialty chemicals

C O M PA N Y N E W S

company Ashland Inc., for the acquisition of its Penta business, related technology and certain assets. The deal does not include the manufacturing plant in Louisiana, MO, any real estate or employees.

ALTANA Buys Kometra WESEL, Germany – ALTANA has signed an agreement to acquire Kometra Kunststoff-Modifikatoren und-Additiv GmbH. The company produces polymer modifiers in Schkopau, Saxony-Anhalt, Germany. These modifiers are specific surface-active copolymers, which are used as impact modifiers and adhesion promoters in many applications. The company will be integrated into ALTANA’s BYK Additives & Instruments division.

Univar Announces Two New Acquisitions BRUSSELS, Belgium – Univar has successfully completed the acquisition of the Quaron business in Belgium and the Netherlands.

The company has also signed an agreement to acquire leading Turkish chemical distributor Eral-Protek. Istanbul-based Eral-Protek is a leading player in the region’s mid-size chemical distribution sector and has more than 25 years of experience in the Turkish market.

Rhodia Purchases Guar Unit in China PARIS – Rhodia has purchased the new guar derivatives production unit belonging to the Suzhou HiPro Polymers Co., based in Zhangjiagang, Jiangsu Province, China. The Chinese unit will complement Rhodia’s existing global guar derivatives manufacturing footprint, with production units located in the United States, France and India.

CPS Color Invests in Increased Colorant Production VANTAA, Finland – CPS Color has increased its capacities for colorant production by nearly 40 percent, investing

€3.5 million both in the supply chain and in research and development facilities at several sites. Total production capacity will increase from 9.700K liters up to 13.500K liters company wide. By increasing capacity at production facilities, CPS Color can now satisfy demand during the peak period between April and August without needing to pre-produce and hold large stocks of colorant inventory.

Elcometer Limited Acquires Dakota Ultrasonics Inc. MANCHESTER, UK – Elcometer Limited announced the acquisition of Dakota Ultrasonics Incorporated of Santa Cruz, CA. Dakota Ultrasonics manufactures industrial ultrasonic testing equipment used in the petrochemical, aerospace, automotive and other related industries. 䡲

pcimag.com

The EnVia™ certification program from Arkema Emulsion Systems simplifies your sustainability efforts by providing a choice of coatings raw materials to meet your specific performance and regulatory benchmarks. Our range of EnVia™ certified products includes a variety of product chemistries – 100% acrylic, styrene acrylic, vinyl acrylic and vinyl acetate ethylene binders, and our new SNAP™ 720 Structured Nano-Acrylic Polymer – so you don’t have to compromise performance or value in your final product. And, with Arkema Emulsion Systems’ commitment to EnVia™ certification of all new products, there’s no time like the present to turn over a new leaf in your sustainability program.

sustain yourself.

Visit www.arkemaemulsionsystems.com/EnVia to learn more about the EnVia™ certification program. At Arkema Emulsion Systems, we’re focused on your future.

EnVia™ and SNAP™ are trademarks of Arkema Inc. ©2011 Arkema Inc.

arkemaemulsionsystems.com

N AMES IN THE NEWS 䡲 Fusion UV Systems Inc. has promoted Bell

䡲 C. Michael Buerkle has been appointed Product Manager, Chemicals, for Deeks & Co. Inc. The company has also named Charles Bridges to the position of Product Manager, Containers, and Laurie Barfield has been named Manager, New Markets.

Li to the position of Senior Sales Engineer. Li will continue to be based in Fusion’s Shenzhen, China, office.

䡲 Sean Maggert has been appointed Direc-

tor, Technical Affairs, for CAS-MI Laboratories. He will be responsible for business devel-

䡲 DKSH’s Performance Materials business unit has appointed Natale Capri as Global Head of its Business Line Specialty Chemicals Industry.

Maggert

䡲 Andrew Dirats has accepted the position of General Manager for Stork MMA Laboratories, Newtown, PA.

Willhite

opment for both CAS-MI Laboratories and the CAS-MI Innovation Center.

䡲 ACCESSA Coatings Solutions has hired Mike Manetta to the position of Target Account Executive. Manetta will be working out of the Indianapolis, IN, corporate facility.

䡲 Plasticolors Inc. has appointed Larry Haines to the position of Strategic Development Manager. Haines is responsible for identifying and successfully entering new markets and applications, with a specific emphasis on gaining greater access to global markets.

䡲 Gulf Coast Chemical Corp., a southeast distributor of specialty chemicals, additives and containers, has hired Mike Ray and Greg McDuffie as technical sales professionals.

䡲 Maroon Inc. has hired Rachel Hardman to be the Customer Ser-

䡲 Dixie Chemical Co. has announced the appointment of Gary Warehime as President, Chief Operating Officer.

vice Manager. Hardman will oversee all customer service initiatives that support both internal and external customers.

䡲 David Jukes has been promoted to President of Univar Europe. He replaces John van Osch, who is leaving the company to pursue new opportunities.

䡲 Nuplex Resins has appointed John A. Willhite to be the Technical Manager, Industrial Markets. Willhite will manage all activities of the Applications and Technical Service Laboratory related to the industrial coatings markets. 䡲

Visit ads.pcimag.com 20

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

H A R CR O S O R G A N I C S FOR

YOUR MANUFACTURING SOLUTION...

H IGH P URITY P HOSPHATED A CRYLIC M ONOMERS

HARCRYL® 1228 2 - HEMA PHOSPHATE

Enhances corrosion resistance Promotes adhesion direct to metal and difficult substrates For Samples and Tech Data Sheets or to learn about Harcros’ developments, please visit us at

Research and Manufacturing Division of Harcros Chemicals

www.harcrosorganics.com/harcrylmonomers

[email protected] ©2010 Harcros Organics. "Harcryl" is a registered trademark of Harcros Organics. 1/2011

Photo and logo courtesy of NürnbergMesse

Venue Exhibition Centre Nuremberg Dates of Exhibition Tuesday, March 29 – Thursday, March 31, 2011 Opening Times March 29-30, 9:00 a.m. - 6:00 p.m. March 31, 9 a.m. - 5:00 p.m. Dates of Congress Monday, March 28 – Wednesday, March 30, 2011 Opening Times March 28, 8.30 a.m. - 7:00 p.m. March 29-30, 8:30 a.m. - 5:30 p.m.

Exhibitors

Congress Topics

Approximately 850 exhibitors from 45 countries

Monday, March 28, 8:30 a.m. - 12:00 p.m.

Products on Display • Coating raw materials • Printing ink raw materials • Adhesive raw materials • Intermediates for construction chemicals • Laboratory and production equipment • Testing and measuring equipment • Environmental protection and safety at work • Services

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

Pre-congress Pre-congress Pre-congress Pre-congress Pre-congress Pre-congress Pre-congress Pre-congress Pre-congress Pre-congress Pre-congress

tutorial tutorial tutorial tutorial tutorial tutorial tutorial tutorial tutorial tutorial tutorial

1: Radiation curing 2: Polyurethanes 3: Film formation in latex paint 4: Understanding easy-to-clean 5: Basics on construction chemicals 6: Fundamentals on adhesive bonding 7: Flame retardants fundamentals 8: Corrosion fundamentals 9: Basics on marine coatings 10: Chemistry of offset printing inks 11: Fundamentals of epoxy coatings

VISIT THESE EXHIBITORS AT THE

• Plenary session, Delegates’ survey 12:15 - 12:45 p.m. • Keynote presentation, 12:45 - 1:30 p.m.

Monday, 2:00 - 5:00 p.m. Parallel Parallel Parallel Parallel Parallel

session session session session session

1: 2: 3: 4: 5:

Science today – coatings tomorrow Pigments Production processes Architectural coatings Wood coatings

E U R O P E A N C OAT I N G S S H O W E X H I B I TO R S

• Poster session and after-work reception 5:30 - 7:00 p.m.

Tuesday, March 29, 9:00 a.m. - 12:30 p.m. session session session session session

6: 7: 8: 9: 10:

Adhesives & sealants I Protective coatings I Automotive coatings Smart coatings Radiation curing

Tuesday, 2:00 - 5:30 p.m. Parallel Parallel Parallel Parallel Parallel

session session session session session

11: 12: 13: 14: 15:

Adhesives & sealants II Sustainability & bio-based coatings Protective coatings II Powder coatings Functional materials

Because c

LLife is

Messy ©3M 2011. All Rights Reserved.

Parallel Parallel Parallel Parallel Parallel

3M™ Stain Resistant Additive SRC-220 +EEPSSTONE CONCRETEAND OTHERPOROUSHARDSURFACES LOOKINGLIKENEW


s3UITABLEFORINDOOROUTDOORUSE s%ASYTOINCORPORATEINTOEXISTING WATERSOLVENT BASEDPRODUCTS

www.3M.com/pci

1

EC Show Hall 7 Stand 647

Wednesday, March 30, 9:00 a.m. - 12:30 p.m. Parallel Parallel Parallel Parallel Parallel

session session session session session

16: 17: 18: 19: 20:

Construction chemicals I Novel materials Measuring & testing I Marine coatings Polyurethanes

You Speak. ANGUS Listens. The leader in multifunctional amine technology to the Paint and Coatings market, ANGUS™ Chemical Company provides a range of specialty additives to help formulators get the most out of their formulation. The ANGUS portfolio includes the industry standard AMP™ multifunctional amine and the new AEPD™ VOX 1000 multifunctional amine for low VOC coatings.

Together we deliver.

Wednesday, 2:00 - 5:30 p.m. Parallel Parallel Parallel Parallel Parallel

session session session session session

21: 22: 23: 24: 25:

Measuring & testing II Nanotechnology Printing inks Waterborne coatings Construction chemicals II

Tel: US: +1-800-447-4369 Eur: +800-3-694-6367 Fax: +1-989-832-1465 E-mail: [email protected] www.ANGUS.com

EC Show Hall 8 Stand 111 ®™ Trademark of The Dow Chemical Company (“Dow”) or an affiliated company of Dow ANGUS CHEMICAL COMPANY A Subsidiary of The Dow Chemical Company

Transfer from Rail Station to Exhibition Take the U1 or U11 underground line from the main rail station to the “Messe” station at the exhibition centre. Journey time approximately 10 minutes.

For more information, visit www.european-coatings-show.com/en. Also, keep an eye out for PCI's live coverage of the ECS via our Show E-Newsletter, which will be sent out each day of the event.

Great Individually. Exceptional Together.

Arch Biocides 800.523.7391 [email protected] *This product is not meant for food applications *This product provides preservative properties to protect the product or coating *Arch Biocides is a business unit of Arch Chemicals, Inc. *Some Arch® biocides may not be registered or registered for only certain uses in your country

archbiocides.com/proxelbzplus EC Show Hall 10 Stand 223

As with wine and cheese, when two excellent products with long track records come together, such as Proxel® preservatives and Omadine® antimicrobials, you get an exceptional result: Proxel® BZ Plus Preservative. This unique combination offers a dual mode of action for inhibiting microbial growth in latex emulsions, water-based paints, adhesives and pigment dispersions - preventing discoloration and providing the extra protection you need against mold, mildew and bacteria. Features include: • Color-stable formulations • Dual-action protection • Zero VOCs • CMIT / MIT and formaldehyde free • Long-term preservation • Broad-spectrum activity

PA I N T & C O AT I N G S I N D U S T RY

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E U R O P E A N C OAT I N G S S H O W E X H I B I TO R S

Pour in the profitability.

Grow your market share through innovative products with the help of Greenability. www.BYK.com

EC Show Hall 7A Stand 205

Come learn about the

Power of Water

Please Visit Celanese at Stand 7A-105

www.Celanese-Emulsions.com

Your future is our focus...worldwide.

Buhler - wet grinding and dispersing technology at its best.

The newly combined power of Buhler and Draiswerke provides you with unique know-how in all wet grinding and dispersing applications. Our equipment and process solutions are proven, reliable and tailored to your individual needs. This is especially evident in the new full-volume Centex® pearl mill with exceptional media separation and high flow rates. Buhler and Draiswerke, providing solutions through synergy. www.buhlergroup.com

meet u

s

ecs -159 at 7 h t o at bo

Global supplier of integrated tinting solutions: • CPSCOLOR™ colorants • COROB™ dispensing and mixing equipment • Software • Color marketing • Worldwide service and customer support

EC Show Hall 6 Stand 211

DeFelsko Corporation The Measure of Quality U.S. manufacturer of coating thickness gages and inspection instruments. The simple, durable and accurate PosiTector 6000 Series is ideal for measuring coating thickness on all metals while the PosiTector 200 series measures coatings on non-metals. The New PosiTector® PC Powder Checker® non-contact, uncured powder thickness gage measures powder coatings before going into the oven. Also featured is the PosiTest® Adhesion Tester, among others.

EC Show Hall 7 Booth 245

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

Address: 802 Proctor Ave., Ogdensburg, NY 13669 USA Phone: +1 315-393-4450. Fax: +1 315-393-8471 E-mail: [email protected] Web: www.defelsko.com EC Show Hall 9 Stand 649

Dow Coating Materials When it comes to coatings raw materials, we’ve got you covered.

Kraton® Polymers for Coatings

Dow Coating Materials understands that the global TiO2 shortage is an opportunity to improve your hiding formulation. Visit us at Stand 8-111 at the European Coatings Show and you will re-think your approach to hiding, because when your experts talk to our experts, good things happen.

Kraton Polymers offer a broad range of benefits that make them ideally suited for the production of high performance coatings. Kraton Polymers - Features and Benefits Toughness and Flexibility Adhesion Promotion Water and Chemical Resistance UV Resistance FDA Approved Products Extended Coating Life

www.dow.com/hiding EC Show Hall 8 Stand 111

E U R O P E A N C OAT I N G S S H O W E X H I B I TO R S

Please visit us at the European Coatings Show 2011 Hall 7 Stand 741 For more information, please visit our website at www.kraton.com or email [email protected].

ECS Booth# 10-417

Who’s keeping an eye on your future?

• New Jetfine® is a natural inert talc that confers superior whiteness and hiding power to architectural and industrial paints • Jetfine® has an ultra-fine grind with a high specific area that improves hiding without diminishing gloss (top cut 5μm, median particle size < 1μm)

Providing advanced technology to solve tomorrow’s problems...today. Emerald responds with coalescents, colorants, defoamers, specialty epoxy resins and other additives designed to solve today’s problems and properly prepare for tomorrow’s challenges.

• Jetfine® reduces the overall environmental impact of paints and coatings formulations

Don’t settle for yesterday’s solutions. Visit www.emeraldmaterials.com.

Tel. +1 303 713 5219 www.luzenac.com [email protected]

Jetfine®, your natural solution.

© 2011 Emerald Performance Materials, LLC

EC Show Hall 7 Stand 244

Micro Powders, Inc.

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

EC Show Hall 7A Stand 305

High-Performance Wax Additives The recognized leader in advanced wax technology - visit us at ECS 2011 booth #7-144 to learn more about our new products:

• • • •

MicroMatte 1011 UVW Effective matting & gloss control AquaTex Range Consistent texture effect for waterborne coatings AquaBead 418E Surface slip & clarity Microspersion EZ Surfactant for wax incorporation

Advanced Technology for Waterborne Systems

Visit the new micropowders.com!

Your Global Partner in Coatings EC Show Hall 10 Stand 123

770.277.8819 www.nubiolausa.com

PA I N T & C O AT I N G S I N D U S T RY

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25

OMG Borchers GmbH, Langenfeld, Germany, the coating additive specialist, will present three new additives during the European Coatings Show 2011:

The Shepherd Color Company

Borchi® OXY – Coat 1101 is a new generation of zero-VOC dry accelerators targeted at both waterborne and solventborne systems. It shows superior performance, even under adverse conditions. It is a real alternative to cobalt driers.

Shepherd Color brings an extraordinary leap forward in the science of coloration. DYNAMIX® Pigments are normally required to be processed with a large amount of energy to provide the appropriate level of color and strength. Not any more! A breakthrough in dry dispersion technology that has outstanding performance. Just stir them in!

Borchi® Gen 1051 is a solventborne wetting and dispersing agent developed for organic pigments, especially for difficult-to-stabilize phthalocyanine blue and green pigments.

E U R O P E A N C OAT I N G S S H O W E X H I B I TO R S

Borchi® Gel THIX 921 is a rheological modifier that introduces a thixotropic effect in waterborne paint formulations. It is aimed at general industrial coatings where high performance in thick build systems and/or high chemical resistance are key parameters.

EC Show Hall 7 Stand 119

Hall 7A Stand 521

www.shepherdcolor.com

SiLibeads

®

rman lity The Gspeirit of qu18a54 since

... better grinding Oberwarmensteinacher Str. 38 D - 95485 Warmensteinach www.sili.eu / ECS Booth No. 6 - 438

The World’s Standard Test Substrate t
Clean t
Consistent t
Convenient

EC Show Hall 9 Stand 251 Look for the “Q” shaped hole. It’s our trademark & your assurance of quality.

440-835-8700 www.q-lab.com

1

ACTIVITY IN COATINGS. Shown in our advertisements around the world. Now you can see them for real at the European Coatings Show. 2

You may have seen one of our employees before: 1. Sven K., Logistic Department 2. Stefan M., Export Manager 3. Pete D., Manager General Maintenance … appeared in Worlée adverts.

3

You may meet some of them at the next show. Visit the Worlée Booth 7-637 at the European Coatings Show 2011. Worlée-Chemie GmbH · Soellerstr. 16 · D-21481 Lauenburg Tel. +49(0)4153/596-0 · www.worlee.de · [email protected]

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

Ultrafine Nepheline Syenite as a Durable and Transparent Additive to Accelerate

Radiation Cure FIGURE 2 | R.I. comparison of binder systems with mineral fillers and extenders. 1.25

1.35

Refractive Index (R.I.) 1.45 1.55

1.65

1.75

Mineral Fillers Aluminum Oxide Calcium Carbonate Barium Sulfate Talc Kaolin Fumed Silica Nepheline Syenite Binders Polyurethane Epoxy Alkyd Nitrocellulose Acrylic Urea

FIGURE 3 | Absorbance of micronized nepheline syenite vs. wavelength in a solventborne UV urethane acrylate. 1.6 1.4 1.2 Absorbance

N

epheline syenite is a silica-deficient functional filler and additive used globally in a variety of coating, adhesive and ink applications. It is composed of three minerals: soda and potash feldspar, and the mineral nepheline. Although it is deficient in crystalline silica, nepheline syenite otherwise provides physical performance properties that duplicate ground silica fillers. Also known in the coatings industry as MINEX® functional fillers and extenders, micronized nepheline syenite is valued for its color purity, ability to control gloss, ease of dispersion and durability. Since nepheline syenite functional fillers are naturally derived, and deficient in free-silica and heavy or transition metals, they are typically less burdened by regulatory requirements such as REACH, RoHS and TSCA. Figure 1 shows the typical particle shapes, while Table 1 lists the typical properties of nepheline syenite. Nepheline syenite is c on s ide r e d a FIGURE 1 | SEM photomicrograph of nephmoderate gloss eline syenite at 5,000x. reducer based on its low oil absorption and combination of angular, rectangular and nodular shapes. Mohs hardness on the 1 to 10 sca le is about 6. The particles themselves are moderately hard or rigid and possess high compressive strength, providing scratch and abrasion resistance in the polymer matrix. The low oil absorption contributes to the ease of dispersion and low viscosity build. Chemically, commercial nepheline syenite is anhydrous and consists of sodium potassium alumino silicates. The surface chemistry of nepheline syenite is ideal for 100% solids and low-VOC systems. Owning a net negative surface charge or a natural “detergency” in aqueous systems, nepheline syenite accelerates dispersion times with

8% Nepheline Syenite (N.S.) 12% Nepheline Syenite (N.S.)

1

16% Nepheline Syenite (N.S.)

0.8

Unfilled (solvent UV urethane-acrylate)

0.6 0.4 0.2 0 310

360

410 460 510 Wavelength (μm)

560

little or no polymeric dispersant requirements, although dispersants aid in suspension and shelf life. Micronized nepheline syenite is utilized in air dry, baked and radiation-curable clear coating applications for its purity of color, light transmission and refractive

By Scott P. Van Remortel, Technical Sales Manager; and Robert E. Ratcliff, Coatings Scientist | Unimin Corp., Spruce Pine, NC PA I N T & C O A T I N G S I N D U S T R Y

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Ultrafine Nepheline Syenite as a Durable and Transparent Additive to Accelerate Radiation Cure

FIGURE 4 | Haze, optical clarity and gloss as a function of nepheline syenite top-size and concentration in an aqueous, UV-cure PUD. b) % Optical Clarity 100 90 80 70 60 50 40 30 20 0 5 10

Haze, %

15 R2 = 0.9962

10

R2 = 0.9959

5 0

0

5

10

15

20

% Optical Clarity

R = 0.9949

20

25

Wt. % N.S. on Clear Solids

FIGURE 5 | Gloss change for 50 cycles #1 grade steel wool as a function of nepheline syenite particle size and concentration (1500 g load). 10 0 6

12

18

24

60° Gloss Change (%)

-10 -20 -30 -40

30 μm N.S. 15 μm N.S. 5 μm N.S.

-50 -60 -70 -80

Wt % N.S. on Clear Solids

FIGURE 6 | Micrographs (200x) of coating surfaces before and after scratch testing. a) No Filler

b) 18% 30 μm nepheline syenite i) before

i) before

R2 = 0.9318

R2 = 0.9954 R2 = 0.9485

15

20

25

100 90 80 70 60 50 40 30 20 10

R2 = 0.9781 R2 = 0.9981 R2 = 0.9513

0

Wt. % N.S. on Clear Solids

index (R.I.) features. The R.I. of nepheline syenite is compared with the R.I. for several resin systems and other more common mineral fillers in Figure 2. The R.I. for nepheline syenite is in the range of 1.50 to 1.53, matching several types of resin systems and monomers used for radiation curing. The nepheline syenite R.I., being a particularly close match with acrylic, urea and urethane

0

c) Gloss (60º)

60 Degree Gloss

a) % Haze (ASTM D 1003-61) 25 2

c) 24% 5 μm nepheline syenite i) before

5

10

15

20

Wt. % N.S. on Clear Solids

monomers and oligomers, provides exceptional clarity when properly wet out and dispersed in the host binder system. Clear and opaque protective and packaging coatings, adhesives and inks are increasingly radiation cured to improve process efficiency, reduce energy costs and satisfy sustainability objectives.1 Conventional wisdom suggests filled or pigmented systems do not cure as efficiently as unfilled systems since the pigment or filler can compete for the UV-curing energy required to activate the UV-cure initiator, especially in thicker, opaque systems. The light transmittance behavior of nepheline syenite is unique, especially in the critical UV-curing range. Figure 3 represents an early look into the light absorbance behavior of nepheline syenite. A micronized nepheline syenite was formulated into a radiation-curable, solventborne urethane-acrylate at loadings of 0, 8, 12 and 16% of the dry film weight. The coatings were applied over a thin, UV-transparent, fused quartz disk and then scanned for absorbance versus wavelength. The preliminary findings suggested a radiationcurable urethane filled with micronized nepheline syenite has high light transmission in the visible range (400-700 nm), and even higher transmittance in the ultraviolet range (280-400 nm) compared to unfilled systems.

Ultrafine Nepheline Syenite for Enhanced Optical and Physical Performance New ultrafine sizes of nepheline syenite have recently been developed that offer superior performance in clear wood and industrial coatings compared to more expensive and lower-clarity alternatives. These engineered particle size distributions of nepheline syenite provide desirable gloss modification, optical, surface hardness, and scratch, abrasion and suspension characteristics in clear UV coating systems.2 Extensive testing was completed with the

TABLE 1 | Typical properties of nepheline syenite. Particle shape ii) after 25 double rubs

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ii) after 50 double rubs

ii) after 50 double rubs

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

25

Specific gravity , g/ml Mohs hardness Brightness (Tappi) Oil absorption, % (ASTM 281) Refractive index Moisture, % (ASTM C -566) pH (20% slurry)

Rectangular , angular, nodular 2.56-2.61 6.0 85-94 22-35 1.51-1.53 .05-.15 9.5-10.5

Experimental During development, laboratory testing and in preliminary customer trials, finer particle size distributions of nepheline syenite appeared to have a favorable impact

FIGURE 7 | Relative image clarity of pigment additives at 6% by wt. in aqueous UVcure PUD.

0% unmodified

30 μm nepheline syenite

15 μm nepheline syenite

5 μm nepheline syenite

10 μm Alumina

Synthetic silica

Nano Alumina

FIGURE 8 | Scotchbrite resistance (Fine A) comparison of abrasionresistant pigments at 6% by wt. in aqueous UV-cure PUD. 100 0%, unmodified 30 μm N.S. 15 μm N.S. 5 μm N.S. 10 μm Al2O3 Silica Nano Al2O3

90 60 Degree Gloss

80 70 60 50 40 30 20 10 0

0

10

Cycles

25

50

FIGURE 9 | Coefficient of friction comparison of pigments at 6% by wt. in aqueous UV-cure PUD. 1.8 1.6 1.4 Static COF, kgf

ultrafine nepheline syenite in conventional clear solvent, waterborne and commercial UV-cure resin systems. Figure 4 demonstrates the importance that nepheline syenite particle top-size and concentration play with respect to film haze, optical clarity and gloss. The new, ultrafine, 5 μm top-size nepheline syenite (MINEX 12) has lower haze, higher clarity, and higher gloss as loadings are increased compared to standard 15 μm (MINEX 10) and 30 μm (MINEX 7) top-sizes when formulated neat into a commercial, aqueous, UV-cure PUD system commonly used in wood floor and cabinetry applications. Most often the purpose of adding a hard mineral additive to a clear coating system is to increase physical performance. Figure 5 demonstrates that loading nepheline syenite into a UV-cure PUD provides improved steel wool scratch resistance. Figure 6 compares detailed micrographs of the test surfaces before and after 50 cycles with steel wool. The systems modified with micronized nepheline syenite have little visible surface change, while the surface of the unfilled coating system has been visibly scuffed and eroded. This feature is especially useful in flexible coatings where the hardness cannot simply be increased by elevated crosslinking, since this would cause a loss of flexibility. Ultrafine nepheline syenite is particularly useful for increasing abrasion resistance while retaining flexibility. Ultrafine nepheline syenite fillers also compare favorably with other pigment fillers such as synthetic silica (fumed, precipitated or colloidal suspension) and micron- and nano-size alumina pigment types. Figure 7 demonstrates that ultrafine nepheline has high image clarity relative to micron-size alumina (10 μm particle top-size), nano-size alumina and colloidal silica pigments. Five micron nepheline syenite has the best image clarity and approaches the image clarity of the unmodified UV-cure PUD systems. Figure 8 compares the gloss of the filled and unmodified systems when subjected to Scotchbrite A testing after 10, 25 and 50 cycles. Comparative Scotchbrite scratch resistance confirms hard pigment additives provide improved Scotchbrite A resistance versus the unmodified system, which drops more significantly in gloss. Ultrafine nepheline syenite provides comparable performance with micron and nano-size alumina, or could be blended with alumina to provide systems with even better clarity, higher pigment loading and abrasion resistance. Ultrafine nepheline syenite is also an effective choice to lower the coefficient of friction (COF). COF is the amount of force required to pull or slide like coatings or films apart, and is a good indicator of the handling properties of finished goods. Figure 9 compares the coefficient of friction for a modified and unmodified UV-cure PUD system. Ultrafine grades of nepheline syenite are the most effective at reducing the COF. Ultrafine nepheline syenite can also reduce the tackiness and improve the handling features prior to cure in UV applications. Improved handling behavior lowers the risk of film damage prior to cure, saving time and money otherwise spent on fixing the defect.

1.2 1 0.8 0.6 0.4 0.2 0

0% 30 μm unmodified N.S.

15 μm N.S.

5 μm N.S.

10 μm Al2O3

Silica

Nano Al2O3

on the cure rate in radiation cure applications. Systems where ultrafine nepheline syenite was tested with suspected improvements in hardness or cure time were: UV aqueous cure PUD, 100% solids acrylic and UV-cure polyurethane powder coatings. The UV light transmission properties for nepheline syenite were known to be good. However, the relationship of UV transmission with nepheline syenite particle size had not been investigated in detail in a controlled test matrix. Furthermore, no standard test method existed to study the interaction with light at varying wavelengths when dispersed in a PA I N T & C O A T I N G S I N D U S T R Y

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29

Ultrafine Nepheline Syenite as a Durable and Transparent Additive to Accelerate Radiation Cure

polymer matrix. Also of particular interest was the behavior of finer nepheline syenite in the UVA and UVB regions. Higher transmission in these regions might provide a positive effect in the acceleration of radiation cure times. This would be surprising since it is commonly believed that most hard, durable filler

pigments hinder the curing process, acting as either radiation absorbers or reflectors instead of transmitters.

Light Transmission To investigate the light transmission properties of nepheline syenite based on particle size distribution, three distinct particle

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

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sizes were chosen. Particle size statistics are found in Table 2. One standard size nepheline grade with a 30 +m particle topsize, an existing ultrafine grade with a 15 +m top-size, and the new ultrafine 5 +m top-size were formulated into an aqueous UV-cure PUD (acrylate functionality) formulation, as provided in Table 3. Test formulations were prepared for the three nepheline syenite sizes at 8% by weight based on clear resin solids. Ultrafine grades were sifted into the mixing vessel precharged with resin, UV initiator and the rheology modifier. The filler pigment additive was sifted in slowly and Cowles dispersed using medium speed with good agitation for 20 minutes. Modified and unmodified formulations were applied at three mils over thin, UV-transparent fused quartz disks (25 mm x 500 μm), air dried 10 minutes, forced oven dried for 10 minutes at 49 ºC, and then UV cured in an Edmund ELC-500 UV oven (peak UV, Mercury lamp 365 nm) for nine minutes. Only test specimens that had a film thickness within 3.0 mil ± 0.10 were used. The light transmission was then measured with a Shimadzu Mini 1240 UV/VIS spectrophotometer. Additional fillers were tested using the same procedure.

Cure Rate and Double Bond Conversion vs. Cure Energy Two methods were used to study the cure rate effect of ultrafine nepheline syenite. The aqueous polyurethane formulation (Table 3) was employed for both methods. The first cure rate method involved measuring the surface hardness development as a function of applied cure energy. The second method considered the amount of double bond conversion as a function of applied cure energy measured by FTIR analysis.3 For pendulum hardness, the coatings were applied to glass at a 6-mil wet thickness and allowed to air dry for 10 minutes. The coatings were placed in a forced air oven at 45 °C for 10 minutes. The test panels were then cured with regulated curing energy by turning down the power on an American Ultraviolet Company mini-conveyer, where one pass equals 100 mW/cm2. After each pass, the pendulum hardness was tested and recorded with a Sheen Instruments Persoz pendulum instrument. FTIR double bond analysis was accomplished by applying the coating to a standard polyester transparency (3M CG3300) at a 0.5-mil wet thickness then allowing it air-dry for 15 minutes. Transparencies are fairly thin and have minimal contribution to the FTIR spectra in the range of 802-817cm-1. Small samples were

FIGURE 10 | Percent transmission as function of nepheline syenite top-size and wavelength in aqueous UV-cure PUD at 8% wt. solids.

FIGURE 11 | Percent transmission of fillers as a function of wavelength in aqueous UV PUD at 8% by wt. 90

90 80

80 70 % Transmitance

% Transmitance

70 60 50 40 unfilled 30 μm N.S. 15 μm N.S. 5 μm N.S.

30 20

50 40 30 20 10

10 0 280

60

blank 15 μm N.S. 15 μm SiO2 5 μm N.S. 10 μm barium sulfate 10 μm CaCO3 20 μm calcined SiO2

300

320

340

360

380

0 280

400

300

Wavelength (nm)

then prepared and cured at increasing time intervals in an Edmund Optics ELC-500 oven. Samples were analyzed on a Nicolet Magna-IR 560. Both ovens used mercury lamps for a peak wavelength of 365 nm.

Results and Discussion In the radiation curable industry there has been

320 340 360 Wavelength (nm)

380

400

much speculation about the impact that mineral fillers have on radiation-cure applications. It is widely believed that filled systems do not cure as well as unfilled systems. In some instances, whole cure lines are modified to accommodate certain pigment additions, or lamps with longer wavelengths added to provide adequate cure.

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

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31

Ultrafine Nepheline Syenite as a Durable and Transparent Additive to Accelerate Radiation Cure

TABLE 2 | Nepheline syenite particle size.

Mineral Filler Transmittance in the UV-Curing Range

Test Filler

Median, μm (D50)

99% < μm (D99)

30 μm N.S. 15 μm N.S. 5 μm N.S.

5.0 3.0 1.5

30 15 5

TABLE 3 | Clear, aqueous, UV-cure PUD formulation. % Wt. of Filler on Clear Solids

0%

8%

Ingredient UV-curable PUD

100

100

UV initiator Urethane rheology modifier

1.5 1.0

1.5 1.0

Test filler

0

2.34

DI water

23.33

25.31

Siloxane wetting additive

0.62

0.62

FIGURE 12 | Pendulum hardness development with increasing energy at 6% nepheline syenite by wt. in a UV PUD. 250

Pendulum Hardness (Cycles)

230 210 190 170 150 Unfilled

130

15 μm N.S.

110

5 μm N.S.

UV-Curing Performance

90 70 50 0

200

400

600

800

1000

1200

1400

1600

Energy Density mJ/cm2

FIGURE 13 | Percent acrylate double bond conversion as a function of cure time at 12% nepheline syenite by wt. in UV PUD (FTIR method). 90

Double Bond Conversion (%)

80 70 60 50 40

unfilled

30

5 μm N.S.

20 10 0 0

32

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0.5

1

1.5 2 2.5 Cure Time (min)

3

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

Figure 10 shows the % transmittance results for the 30, 15 and 5 +m nepheline syenite fillers versus the unmodified aqueous, UV-cure PUD formulation. Both the ultrafine 15 and 5 +m grades have similar or greater transmission and with no interference in the UVB (280-320 nm) range. Thirty micron nepheline syenite, with its large particle top-size, does lower the transmission in the UVB range, but starts to recover in the top end of the UVA (320-400 nm) range. The ultrafine 15 and 5 +m fillers provide very little absorption or reflectance over both the UVA and UVB ranges, suggesting they would cure efficiently using typical UV light configurations and photoinitiator types. The higher UV transmittance of ultrafine nepheline syenite also suggests enhanced cure efficiency in radiation-curable coatings is possible. Figure 11 compares the % transmittance of unmodified and modified aqueous UV-cure PUD systems when filled with ultrafine nepheline syenite and several other common mineral filler types. Conventional fillers such as barium sulfate and calcium carbonate reduce the transmission of UV light through the film in both the UVB and UVA curing range. Ultrafine nepheline syenite sizes offer superior transmission properties when compared to these standard filler types. The results suggest that ultrafine nepheline syenite formulations may offer enhanced cure efficiency when compared to the unfilled formulation and when filled with other minerals. Use of ultrafine nepheline syenite as a performance additive in UV-cure applications could also eliminate the need to alter UV-cure equipment and processes.

3.5

4

To verify that the superior light transmission features of ultrafine nepheline syenite lead to enhanced radiation curing, test coatings were prepared with the UV-curable PUD with 15 and 5 μm sizes at 0 and 6% weight on total resin solids. The coatings were then cured one pass on the mini-conveyer and then measured for pendulum hardness. One pass on the mini-conveyor was equal to 100 mW/cm2. Pendulum hardness measures the number of oscillations. Softer coated surfaces deform more easily and thereby absorb more energy, which results in fewer oscillations. Greater pendulum hardness as a function of applied curing energy provides evidence of an accelerated cure rate. The results are shown in Figure 12 and demonstrate that systems filled with ultrafine nepheline syenite develop film hardness at a faster rate than the unmodified system. The 5 μm size is particularly effective for hardness development with less cure energy, suggesting line speeds or production rates could be increased. Energy consumption could also be reduced by as much as 50 percent in systems filled with ultrafine nepheline syenite while providing equal or superior cure. The same test formulation using 5 μm nepheline syenite was also used to measure the double bond conversions by FTIR after half minute cure intervals in the Edmund Optics ELC-500 oven. FTIR analysis can measure the depletion of carbon-carbon double bonds in the acrylate group. The rate at which double bonds decrease is a measure of the cure rate of the formulation.

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Ultrafine Nepheline Syenite as a Durable and Transparent Additive to Accelerate Radiation Cure

The conversion of the double bonds was determined by the formula:

Conversion =

(Ao – At) Ao

where A0 is the area of the peak at 802817 cm-1 before cure. At is the area of the

peak at some cure time (t). This formula gives a percentage of the coating cure. Coatings with little or no haze are required for this method. Normally, nine minutes are required to ensure a complete cure. Figure 13 compares the results for percent double bond conversion versus cure time. Though there is some scatter in

the data, the general trend indicates that this method is viable and agrees fairly well with the pendulum hardness findings, namely that ultrafine nepheline can accelerate cure as measured by more rapid acrylate carbon double bond conversion.

Conclusion Nepheline syenite is a versatile and unique functional filler, offering properties that are useful in a wide variety of clear and opaque coating applications. Newer ultrafine nepheline syenite sizes have refractive index and physical properties that are particularly well suited for use as a performance additive in radiation-curable coatings, inks and adhesives. It was demonstrated that ultrafine nepheline syenite has exceptionally high light transmittance in organic binder systems commonly used for radiation curing in the critical UVA and UVB wavelengths. Thus, unlike other mineral fillers and pigments, ultrafine nepheline syenite is not expected to “interfere” with the UVcuring process. Experiments with regulated curing energy on both pendulum hardness development and double bond conversion rate suggest that it is possible to improve cure efficiency, allowing faster line speeds and/or reduced energy consumption, when ultrafine nepheline syenite is added to the system. Future work will be aimed at developing more precise methods to study the rate of double bond conversion with ultrafine grades, testing other engineered nepheline syenite versions, and evaluating performance in additional radiation-curable applications such as 100% solids, overprint ink varnish and adhesives, to determine additional performance benefits and cost saving opportunities. 䡲

References 1

2

3

Wright, T. Introduction UV/EB Coatings Market Analysis Moving Forward. Coatings World 2008, April. Van Remortel. S.; Ratcliff, R.E. Ultra-fine Nepheline Syenite as a Hard, Transparent Filler for Increased Performance in Clear Wood, Industrial and UV Coatings. Advancement in Coatings Series, September 2009. Yang, B. Investigation of UV-Curable Coatings and Adhesives by Real Time FTIR, Sartomer Technical Publication, 2005.

MINEX® is a registered trademark. All rights reserved.

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34 PCI04094Qlab-panel.indd 1

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

This paper was presented at the RadTech 2010 Technology Expo and Conference, Baltimore, MD, www.radtech.org. 3/19/09 10:53:46 AM

Visit u Coatin s at Europea n Nur g Show 29th t nberg, Germ2011 o 31st March any , 2011

a Thixotropic Material

O

f all the different products that are ground in stirred media mills, many show a non-ideal flow behavior. These non-Newtonian products include paints, varnishes and pigment pastes. They often contain agglomerates and wrinkled polymer structures. The polymers, including polyelectrolytes, are often used for the wetting of particles in the suspension and as dispersants. The solids content is often much higher than 40 weight percent; this means that the probability of agglomeration is quite high because of the low amount of liquid available for wetting the particles. These factors have an influence on flow behavior and, in addition, add to the increase in viscosity caused during grinding by the increase of solid surface area. With decreasing particle size, the adhesive forces increase, further supporting reagglomeration processes. One main reason for a high-solids content is that it is desirable for processes like drying, and as a result, drying is faster with lower energy costs. A high-shear stress often has to be applied at the beginning to make the material flow, and this is often due to the structures mentioned above. Therefore, such materials require a careful choice of equipment as well as process parameters. In addition to the specific energy input and the bead size, the throughput plays a major role in the achievable fineness, as well as the optimal operation of the mill. Strong shear forces should be maintained after the startup in order to attain reasonable grinding progress and to keep the viscosity under control. This can be achieved by adjusting the tip speed in the mill, or by using a gear pump

FIGURE 1 | Experimental setup illustrating the recirculation mode.

along with high stirrer speeds to shear the product before it enters the mill. Short hoses and pipes should be used to reduce the opportunities for the mentioned structures and the viscosity to rebuild. This article addresses the grinding and milling parameters of a thixotropic pigment paste.

Experimental All experiments were carried out in the recirculation mode, as shown in Figure 1. The throughput was measu ure red d online, onli on line ne,, together toge to geth ther er with wit ith h the the density and the viscosity of sured th the product going into the mill, using a ProFIGURE 2 | ECM Poly production mill. th m mass 83I25, which m measures the Coriolis force. In order to produce shear stress in the product, a gear pump T4-95G-GKGM, by Gebr. Steimel GmbH, was applied. The particle size analysis was done using the Mastersizer 2000, which applies the principle of light scattering. The instrument contains a red laser for particles that are larger than 1 μm, and a blue laser to measure particles in the range below 1 μm. 90% of all particles in the product had a particle size below 1 μm before grinding, which means that the dispersion of the particles plays a larger role than “true grinding”. In order to check the flow behavior of the product offline, viscosities were measured using the rotational viscometer ROTO VISCO 1 by Thermo Haake. The pigment paste was run on a mid-sized production mill, the WAB DYNO®-MILL ECM Poly, shown in Figure 2. The applied parameters were the following: • Flow rate 500 kg/h and 4000 kg/h; • Tip speed: 10.9 m/s; • Bead size: 0.8 mm and afterwards 0.3 mm; • Grinding time: 4 h with both bead sizes; • Batch size: 100 kg.

Results and Discussion Particle Size as a Function of Specific Energy Input The experiments were carried out with bead diameters of 0.8 mm and 0.3 mm. Figure 3 shows the particle size D90 as a function of specific energy input with different bead sizes. By Dr. Frank Lang | Willy A. Bachofen AG Maschinenfabrik, Muttenz, Switzerland 36

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

Grinding a Thixotropic Material

Milling Results Using 0.3 mm Beads After grinding with a bead size of 0.8 mm, the bead diameter was changed to 0.3 mm. With the smaller bead diameter there is a high grinding progress up to a specific energy input of 250 kJ/ kg. In the end a particle size below 500 nm was achieved with the smaller beads. However, beyond 1500 kJ/kg, the measured particle sizes did not decrease further, and they even rose slightly, which is a clear sign of reaglommeration.

Particle Size D90 [nm]

FIGURE 3 | Particle size D90 as a function of the specific energy input. 850 800

Bead Size: 0.8 mm Bead Size: 0.3 mm

750 700 650

Deagglomeration

600 550

Reagglomeration

500 450 400

Viscosity and Flow Behavior 0

500

1000

1500

2000

2500

Specific Energy [kJ/kg]

Milling Results Using 0.8 mm Beads Up to a specific energy input of 500 kJ/kg there is practically no grinding progress with a bead size of 0.8 mm. Between 500 – 700 kJ/kg the particle size increases briefly. This is a sign that mainly deagglomeration and wetting of the particles is taking place. Specific energies between 700 kJ/kg and 1700 kJ/kg result in a decrease in the particle size down to less than 700 nm. In this area, some “true grinding” is probably taking place. Beyond 1700 kJ/kg, the particle size hardly decreases any further. This is most likely a sign of reagglomeration, due to the increase in the particle surface area, which is caused by the “true grinding,” and the surface area requires more liquid for the wetting of the particles.

To get further insight into the grinding and dispersing processes, a closer look was taken at viscosity and flow behavior. Figure 4 shows the flow curve, with the shear stress o, and the viscosity d of the raw material, as a function of the shear rate , at a temperature of 30 °C. The flow curve and the viscosity curve of the material, after grinding for four hours, are shown in Figure 5. The shear rate was first increased, kept constant at a value of 1000 s-1 for 30 s, and then decreased back to zero. Initially, a high shear stress is required to make the product flow, the product behaves more like a solid than a liquid, and the viscosity goes towards infinity. When the shear rate reaches 1000 s-1, the viscosity of the raw material goes down to 0.688 Pas. The viscosity of the ground product decreases to 0.74 Pas. Furthermore, the product clearly shows a thixotropic behavior because the viscosities are lower when the shear rate decreases than when it increases for all values of the shear rate. This behavior is probably due to the breakup of agglomerates, which take

some time to rebuild after the shear stress is decreased. Therefore, this is a further indication that the grinding problem at hand is primarily one of dispersion. At the beginning of the grinding process, the primary particles have to be wetted and dispersed in order to break up the agglomerates. The breakage of primary particles down to a lower size probably only occurs after the dispersion is practically complete. Once a finer particle size is reached, the adhesive forces between the particles also increase, and this can lead to reagglomeration, as shown in Figure 3. Since the finer particles have a larger specific surface area, the viscosity increases for all shear rates, which can be seen in Figure 5. The thixotropic behavior becomes more obvious at higher shear rates, as shown in Figure 6, with a maximal shear rate of 3000 s-1 instead of 1000 s-1. When the shear rate first increases to 3000 s-1, the viscosity is 0.419 Pas, and when the shear rate decreases, after 30 s at 3000 s-1, the viscosity goes down to a value of 0.096 Pas. This means that the longer the material is sheared, the less time remains to rebuild structures like agglomerates, and, therefore, the lower the viscosity. It can be concluded that in practice it is desirable to have short hoses and pipes in order to minimize the residence time in areas with low shear stress, where the viscosity can build again. Figure 7 shows the influence of the throughput on the viscosity. At a throughput of 550 kg/h the residence time in areas with low shear stress is quite long, and the viscosity, which was measured on the flow meter before the mill, is over 1400 mPas. Beyond a certain flow rate, the pigment paste is constantly sheared in the gear pump as well as in

FIGURE 4 | Flow curve and viscosity curve of the raw material. 800

5.0

700

4.5 4.0

600

, [Pa]

3.0 2.5

400 , = f (Á) ƒ = f (Á)

300

ƒ [Pas]

3.5 500

2.0 1.5

200 1.0 100 0

0.5 0

200

400

600

800

1000

Á [1/s]

the mill. The minimal shear stress that is required to surpass the flow limit is practically always given. As a result, the viscosity decreases drastically. The product particles are pumped through the mill more often, the probability of a particle meeting a bead increases, and the product is sheared more often, eventually leading to a decrease in the viscosity. Afterwards, a further increase in the throughput does not have any major effect. The viscosity remains at a value of more than 200 mPas. The effect of the flow rate is similar with a bead size of 0.3 mm, but the lowest viscosity is higher than with larger beads because of the lower achievable throughput. A higher throughput would lead to packing of the smaller beads and to a high wear of machine parts.

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Grinding a Thixotropic Material

800

5.0

700

4.5 4.0

600 3.5 500

3.0

, = f (Á) ƒ = f (Á)

400

2.5

ƒ [Pas]

MINEX ® delivers unique physical and photochemical properties ideally suited for clear coats. Its low refractive index is best utilized in transparent wood and furniture coatings, where MINEX can be loaded up to 20% without excessive haze to improve hardness, light stability and moisture resistance.

FIGURE 5 | Flow curve and viscosity curve after four hours of grinding.

, [Pa]

Superior in Clear Coats

2.0

300

1.5 200 1.0 100

0.5

0 0

200

400

600

800

1000

Á [1/s]

FIGURE 6 | Flow and viscosity curves with higher shear rates after four hours of grinding. 5.0

1400

4.5

, = f (Á) ƒ = f (Á)

1200

4.0

1000

, [Pa]

FUNCTIONAL FILLERS AND EXTENDERS

3.5 3.0

800

2.5 600

ƒ [Pas]

®

2.0 1.5

400

1.0 200 0 0

For more information and our complete product portfolio visit:

www.BrilliantAdditions.com ® MINEX is

a registered trademark. All rights reserved. © 2010 SPECIALTY AND PERFORMANCE MINERALS

0.5 600

1200

1800 Á [1/s]

2400

3000

Studies have shown that the viscosity and the flow behavior of particle suspensions depend mainly on the adhesive forces.1 Therefore, the particle size, the solid concentration and the stabilization of the suspension play a major role. It is sometimes assumed that the flow behavior is Newtonian and the viscosity is constant as soon as a certain shear rate is reached.1 However, it is difficult to tell which viscosity the material actually has in the mill because the shear rate in the mill is much higher than the one that can be achieved with a viscometer. With a thixotropic behavior the residence times in different areas, with different shear rates, have an effect. The high shear rate has to be exerted for a certain time in order to achieve the minimal viscosity. Therefore, it is helpful if the product suspension is already sheared, with the help of a stirrer and a gear pump for example, before it goes into the mill. An increased throughput allows less time for the building of structures, like agglomerates, in certain areas such as pipes, hoses and valves. A minimization of the viscosity is especially desirable for the dispersing process in order to avoid the packing of the beads and the clogging of the sieve.2,3 A higher viscosity also means that more energy goes into the displacement of the liquid, leading to a less sufficient grinding process.3 Another parameter that could be optimized in order to increase the shear stress in the product is the tip speed. However, an increase in the tip speed has the disadvantage that the wear of machine parts in the grinding chamber is faster, and reagglomeration might also occur due to the higher energy input, as shown in Figure 3. Therefore, the tip speed was kept constant in these experiments.

Conclusions Experiments with a water-based thixotropic pigment paste have shown that the throughput is a key parameter in the grinding

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Grinding a Thixotropic Material

FIGURE 7 | Influence of the mass throughput on the viscosity. 1600

Viscosity [mPas]

1400 1200

Bead Size: 0.8 mm Bead Size: 0.3 mm

1000 800 600 400 200 0

0

500

1000

1500

2000

2500

3000

3500

4000

4500

Mass Throughput [kg/h]

of such a material with a non-ideal flow behavior. Through the variation of the throughput, the viscosity could be reduced from over 1400 mPas to less than 300 mPas. This effect is smaller when the bead size is decreased, because the maximum throughput, which can be run without packing the beads, is lower in the case of the smaller beads. Since the raw material was already quite fine, and this means that the adhesive forces between the particles are quite large, the problem is mainly one of dispersion rather than “true grinding”. This can also be seen by looking at the particle size as a function of the specific energy input. A dispersion problem means that the viscosity has a major influence on the particle sizes that can be

achieved because particles that are not wetted and dispersed properly build agglomerates, which lead to an increase in the viscosity. With a higher viscosity, more energy goes into the displacement of the liquid instead of the grinding process. Beyond a certain point, an additional input of specific energy leads to reagglomeration because very little energy goes into the grinding and most of the energy is converted directly into heat. After grinding, the viscosity, compared to the one of the raw material, was larger for all shear rates and the thixotropic behavior was even more obvious. The influence of the throughput shows that besides the shear rates themselves, one must take into account the areas with different shear rates and try to keep the areas with lower shear rates as small as possible. Therefore, it is recommended to use short hoses and pipes to allow fewer opportunities for the rebuilding of structures and an increase in the viscosity. 䡲

References 1

2

3

Stenger, F; Peukert, W. The Role of Particle Interactions on Suspension Rheology – Application to Submicron Grinding in Stirred Ball Mills, Chemical Engineering Technology 2003, 26. Schilde, C.; Arlt, C.; Kwade, A. Einfluss des Dispergierprozesses bei der Herstellung nanopartikelverstärkter Verbundwerkstoffe, Chemie Ingenieur Technik 2009, No. 6, Wiley-VCH Verlag, Weinheim. Breitung-Faes, S; Kwade, A. Produktgestaltung bei der Nanozerkleinerung durch Einsatz kleinster Mahlkörper, Chemie Ingenieur Technik 2009, No. 6, Wiley-VCH Verlag, Weinheim.

This article was also published in Farbe & Lack.

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Novel Acrylic Polymer for Coating Weathered TPO Roofing

E

lastomeric roof coatings (ERCs) have been used for many years as a cost-effective means of maintaining, repairing and extending the useful life of many types of commercial roofing substrates, including sprayed polyurethane foam (SPF), rubber [ethylene propylene diene terpolymer (EPDM)], asphalt, modified bitumen and metal. Until now, a major exception has been thermoplastic polyolefin (TPO) roofs, a popular roofing system first introduced commercially to the U.S. market in 1990.1 As some of the earlier TPO roofing systems have begun to show signs of natural wear and tear, the challenge has been developing a viable waterborne (hydrophilic) elastomeric roof coating formulation with sufficient adhesion to the amorphous, water-resistant (hydrophobic) polyolefin surface of weathered TPO roofing membranes that also meets ASTM performance standards and withstands harsh outdoor environments. This article describes highlights of the ongoing laboratory, outdoor exposure and pilot testing of various acrylic polymer emulsion and additive combinations for use on weathered TPO roofing systems. The weathered TPO adhesion challenge was overcome by using a hydrophilic polyacid dispersant, matching the contact angle of the formulation to that of the weathered TPO surface, and by incorporating three separate adhesion technologies to create an acrylic polymer emulsion binder, which ultimately can be used to manufacture an elastomeric roof coating with exceptional TPO adhesion. After nearly three years of field testing using two formulation prototypes at three different sites, the successful acrylic polymer emulsion was commercialized as RHOPLEX™ EC-3100. The new binder opens the door to manufacturing elastomeric roof basecoats that fully adhere to TPO substrates and cost-effectively extend the useful life of ageing TPO roofing systems by five to 10 years or longer.

The TPO Adhesion Challenge Used in a variety of applications, TPO technology was first introduced as a non-reinforced, plasticizer-free roofing membrane in Europe in the 1980s. During the early 1990s, manufacturers began adding reinforcing fabric to TPO roofing membranes to increase tear strength. These reinforced systems have experienced rapid market penetration in U.S. low-slope commercial applications since about 1995. Today, they are the fastest growing segment of the U.S. commercial roofing industry, fueled in large part by cost advantages, ease of installation, and the demand for “cool roofing” – white or light-colored surfaces that reflect, rather than absorb, solar energy.2 TPO membranes are based on polymers defined by ASTM D 5538-07, Standard Practice for Thermoplastic

Elastomers — Terminology and Abbreviations, as “a thermoplastic elastomer – olefinic.” TPO roofing membranes are typically composed of polypropylene plus either ethylene/propylene rubber (EPR) or EPDM, which act as softening agents to make them more flexible. Rounding out TPO roofing membrane formulations are pigments (such as TiO2 and CaCO3), fire retardants, crosslinkers, antioxidants (phenols, amines, phosphites), lubricant/processing aids, and ultraviolet light absorbers.3 The nature of polyolefin chemistry, as a material with only carbon and hydrogen, makes it a low-surface-energy material that is difficult to adhere to. Though additional ingredients are compounded with polyolefins and EPR or EPDM to make a TPO roof membrane, there are few active surface sites for chemical bonding and adhesion. Although TPO roofing membranes have followed the classic pattern of new products, with ongoing refinements to optimize their formulations and to meet the demands of the marketplace, the primary mechanical and chemical properties are determined by the dominant components – propylene plus EPR or EPDM.4 While solventborne elastomeric coatings that adhere to weathered TPO surfaces have been developed, the composition of those coatings is highly flammable and high in odor and VOC content, which can make them complicated to use and apply. The challenge in coating TPO membranes with waterborne elastomeric roof coatings is due to a combination of several factors: • High initial hydrophilicity of unweathered TPO, as measured by their very low contact angles, with higher contact angle after weathering; • Lack of functional groups that can normally promote adhesion; • An amorphous TPO surface, which results from a sheer dependant TPO morphology.

Early Testing During the early 2000s, an increasing number of roof coating manufacturers inquired about potential waterborne formulations for coating weathered TPO roofs. At the time, there were no viable coating options because existing elastomeric roof coatings did not adhere well to weathered TPO surfaces. In 2002, we acquired several square yards of new TPO Membrane Sample #1 (45 mil), cut it into 3- by 6-inch and 8- by 12-foot sample squares and placed them face up in our Spring House outdoor exposure station near Philadelphia, PA. Although our laboratories include a variety of accelerated weathering tools, we believe there is ultimately no substitute for actual outdoor weathering for the final testing of coatings and the preparation of weathered test substrates. As we waited for the outdoor samples to acquire sufficient weathering, we tested various prototype coating

By Joe Rokowski, Group Leader/Principal Research Scientist | Dow Construction Chemicals, Philadelphia, PA 44

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Adhesion Technology Membranes formulations in the lab using other TPO roofing samples: • TPO Membrane Sample #2 (45 mil), 10-year weathered (Georgia exposure); • TPO Membrane Sample #3 (45 mil), six-month weathered (Philadelphia exposure); • TPO Membrane Sample # 4 (45 mil), three-month and six-month weathered (Philadelphia exposure). We evaluated various technologies to improve adhesion, including different adhesion chemistries, emulsion compositions and dispersants. All of this initial formulation work was tested on new TPO membranes or TPO membranes that were weathered outside for no more than six months. During this period, most of the adhesion improvements were low, but some were significant enough to suggest we would need to combine multiple adhesion chemistries into one binder. Following the path toward multiple adhesion chemistries, we developed a new acrylic polymer prototype that combines three different adhesion chemistries. This prototype had improved adhesion to a variety of surfaces, but only showed a 10 percent improvement on weathered TPO. Somewhat puzzled, the research team took a closer look at some of the fundamental mechanisms that govern the adhesion of a coating to a substrate. 1) Wetting. Can the coating wet the surface (i.e., macrowetting)? This is generally influenced by the relative surface energies of the coating and the substrate. Substrates with low surface energy can generally only be wetted with coatings that also have low surface energy. 2) If the coating is able to wet the substrate, upon drying, is there intimate physical contact between the coating and the substrate? If the polymer chains are able to deform enough to contact the micro-surface and the functional groups of the substrate, a strong physical bond can form between the two materials (i.e., not a chemical bond). 3) Finally, if the polymer is able to contact the substrate on a molecular level (i.e., micro-wetting), specific chemical interactions can develop between the coating and substrate, leading to a chemical type of adhesion. Generally, chemical adhesion leads to the strongest type of adhesion between coatings and substrates. But, as outlined above, it is generally effective only when wetting and physical bonding are present. Needless to say, water resistance and hydrophobicity are very important to any roofing substrate. Determining the contact angle of a surface is a well-defined test of hydrophobicity in which a drop of fluid – typically water – is placed on the substrate, and, after a specified period of time, the angle the droplet makes with the surface is measured. A higher contact angle indicates greater hydro-

phobicity. As shown in Table 1, the initial contact angle of water on TPO is relatively low, indicating a somewhat hydrophilic surface. This is quite surprising considering the presumed hydrophobic nature of new TPO roofing membrane. We assume this is due in part to the processing aids and formulation compounds used to manufacture TPO membranes, which presumably can wash off or erode from the surface with exterior weathering. According to the contact angle data, following exterior or WOM (Weather-Ometer) exposure, the TPO surface becomes more hydrophobic and the contact angle increases. The increase in hydrophobicity of TPO with weathering actually makes it more compatible with the wetting characteristics of the elastomeric coating. This compatibility proved to be very important, as will be discussed further below.

Adhesion Breakthrough Our team was pretty certain that the final two fundamental mechanisms were occurring, but we were not getting good enough wetting contact with the surface. This is when we turned our attention to contact angles and macro-wetting. Matching the contact angle of the coating prototypes and weathered TPO test samples was a matter of adjusting the polymers and formulations slightly, and the result was a dramatic increase in adhesion: Dry and Wet adhesion without formulation change: 0.5 PLI / 0.2PLI Dry and Wet adhesion with formulation change: 2.6 PLI / 1.7 PLI (PLI = Pounds per Linear Inch) To solve the wetting problem, we switched from the original TAMOL™ 165A hydrophobic copolymer dispersant, (generally used for good water resistance) to TAMOL 851, a hydrophilic polyacid dispersant. Polyacid dispersants are not normally used when develop-

TABLE 1 | Contact angle of various TPO roofing membranes and coatings. TPO Sample

Average Contact Angle 

TPO Membrane Sample #1, new

48

TPO Membrane Sample #1, 4-year weathered

71

TPO Membrane Sample #2, new

32

TPO Membrane Sample #2, 1-year weathered

66

TPO Membrane Sample #3, new

 44

TPO Membrane Sample #3, 6 months WOM (Weather-Ometer) exposure

Coatings

68

 

Standard ERC#1 ARM91-1

67

Hydrophobic ERC #2

44

RHOPLEX EC-3100- based ERC #3

65

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

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45

Novel Acrylic Polymer Adhesion Technology for Coating Weathered TPO Roofing Membranes

ing a roof coating for hydrophobic surfaces since they are water-sensitive, generally reduce adhesion and can cause blistering in the coating. However, the dispersant change enabled the coating prototype to match the contact angle of weathered TPO and wet out the weathered TPO surface much better. This allowed the polymer’s adhesion chemistries to better interact with the surface via chemical bonding. Even though commercial roof

FIGURE 1 | Wet adhesion of elastomeric coatings. On 4-Year Weathered TPO Membrane 1.8 1.5

PLI

1.2

coating contact angles matched that of weathered TPO, and formulations wetted the surface, the lack of chemical bonding prevented good adhesion. In this stage, the original TPO samples had been weathered for four years, which was sufficient to activate more surface chemistry and make them suitable for adhesion testing. Prototype coatings formulated with matching contact angles and the hydrophilic polyacid dispersant were applied to the four-year weathered samples. Wet adhesion testing confirmed that these prototype coatings not only had the adhesion required – over 1.5 pounds PLI – but also, the hydrophobicity in some prototypes was actually a little higher than standard roof coatings. Figure 1 indicates the improvement in adhesion to weathered TPO surfaces using RHOPLEX EC-3100 binder versus a standard binder.

Final Prototype Polymers/Formulations

0.9 0.6 0.3 0 Standard Binder

RHOPLEX EC-3100 Binder

FIGURE 2 | Early field test results indicated no blistering by polymer candidate #2 (left), while a control formulation blistered off the surface (right).

With the adhesion challenge solved, the research team proceeded to optimize the final polymer and formulation candidates, working through each class of additive to define the optimal adhesion and durability properties: surfactants, wetting agents, thickening agents, pigments and extenders. One major difference from conventional elastomeric coatings is that we found that zinc oxide – a common ultraviolet light protector – interferes with the novel adhesion chemistry of our prototype. Zinc oxide was replaced in our formulations by adding a small amount of titanium dioxide to maintain a constant pigment-to-volume ratio. Several prototype formulations based on different binders were selected for application on the four-year weathered 3- by 6-inch TPO Membrane Sample #1. These coatings were tested for performance according to ASTM D 6083 – Acrylic Elastomeric Roof Coating, (see Appendix 1). Ultimately, two of these prototype emulsions (Candidates #1 and #2) were chosen for final field trials.

Field Trials

FIGURE 3 | Field trial in Tucson, AZ. The middle square is covered with a roof coating that contains RHOPLEX EC-3100.

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

The first field trials commenced on 8- by 10-foot roof deck mockups at the Spring House exposure station in November 2007, with both of the final polymer candidates coated over new, unweathered TPO Membrane Sample #1 (45 mil) Early results showed no blistering, while a control formulation blistered off the surface (Figure 2). A second field trial was initiated in cooperation with Pro-Tech Products in May 2008 in Tucson, AZ, on an existing commercial roof with TPO Membrane Sample #1. After 12 years of weathering, the white TPO membrane had become tan, and the surface was chalked and micro cracked due to high UV exposure in the Southwest United States. The substrate was power washed with water and dried before coating. Candidates #1 and #2 were coated over select large areas of the roof, but not the entire surface (Figures 3 and 4). A third trial began in cooperation with Structural Elastomeric Products in August 2008 on a two-level commercial roof in New Mexico with a seven- to eight-year weathered TPO Membrane Sample #2. Both levels were coated using polymer candidates #1 and #2 as the basecoat on different sections of the roof. A commercial elastomeric roof coating formulation was used as the topcoat.

Novel Acrylic Polymer Adhesion Technology for Coating Weathered TPO Roofing Membranes

Field Trial Results After more than two years of field testing, there was a significant variation in results among the trials. Both candidates performed well overall, with no peeling, cracking, flaking or loss of adhesion. However, while candidate #1 exhibited higher peel adhesion results in lab tests, it also blistered on the roof, while candidate #2 did not. Candidate #2 also exhibited good adhesion strength during scratch/probe tests in active ponded water areas. Although Candidate #1 had superior adhesion in lab tests, Candidate #2 emerged as the better practical option due to better field adhesion, stability, easier application properties and preferred drying characteristics. In the third roof trial, Candidate #2 also exhibited adhesion strength of about 5.0 PLI before failure in the field peel adhesion test based on ASTM D 903: Standard Test Method for Peel or Stripping Strength of Adhesive Bonds. This result is well above the target of 1.5 PLI. Candidate #2 also provided reflectance and emittance performance roughly equivalent to new TPO membranes, restoring the “cool roof” performance of the original roofs. One thing to note is the adhesion technologies utilized in Candidate #2 – now RHOPLEX EC-3100 – reduce the tensile strength of the coating and therefore compromise its compliance to the ASTM D 6083 norm. This suggests that RHOPLEX EC-3100 is an ideal choice as a basecoat binder, which, when coupled with an established ASTM D 6083-compliant elastomeric roof coating as a top coat, provides exceptional TPO adhesion, as well as exceptional durability, water resistance and reflectivity.

FIGURE 4 | A close-up of the Tucson roof shows the uncoated weathered TPO membrane on the left and the coated TPO membrane containing RHOPLEX EC-3100 on the right.

We continue to monitor the performance of both prototypes in all three field trials. An aerial view of the large white trial roof in Tucson can be seen using the free version of Google Earth (http:// www.google.com/earth/download/ge/agree.html): Select “Fly To” and enter: 6025 East Broadway, Tucson, Arizona. Zoom in on the large white roof. The current view is dated 11-20-09, 1.5 years after the trial began.

Conclusion Based on the outstanding results obtained in the field, Dow commercialized Candidate #2 as RHOPLEX EC-3100, an all-acrylic polymer designed primarily for use in pigmented elastomeric basecoats to provide adhesion to weathered TPO roofing membranes. When a coating formulated with RHOPLEX EC-3100 is applied to a suitably cleaned, weathered TPO membrane, and then coated with a durable acrylic elastomeric topcoat, the resulting ASTM D 6083-compliant coating can extend the life of an existing TPO roof by five to 10 years or longer. Designed for use over TPO roofing membranes that have been weathered at least four years, a properly formulated coatings system that includes RHOPLEX EC-3100 provides: • Excellent adhesion to weathered TPO roof substrates; • Excellent blister resistance under extended wet conditions on weathered TPO; • A barrier to ultraviolent light; • Good reflectivity of solar energy, which can help reduce cooling costs; • Excellent flexibility at temperatures as low as 0 ºC or 32 ºF; and • Application by spray, brush or roller at one gallon/square per coat in two coats. 䡲

™ RHOPLEX, SKANE, UCAR and TAMOL are trademarks of The Dow Chemical Company or an affiliated company of Dow. Weather-Ometer is a trademark of Atlas Material Testing Technology LLC. BYK is a trademark of ALTANA Group. Omyacarb is a trademark of Omya AG. TiPure is a trademark of E.I. du Pont de Nemours & Company or its affiliates. Visit ads.pcimag.com 48

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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.

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Novel Acrylic Polymer Adhesion Technology for Coating Weathered TPO Roofing Membranes

APPENDIX 1 | Summary of ASTM D 6083 requirements.

Adhesion dry/wet, pounds/inch (c)

Liquid Property Requirements

Dirt pickup resistance, 24 hr QUV

Physical Property

ASTM

Requirements

Viscosity

D 562

85-141 KU

D 2196

12,000 - 85,000 cP

D 2697

Greater than 50%

% whiteness retained, initial

92%

Total solar reflectance, initial (d)

88%

Thermal emissivity

87%

(a) (b)

Volume Solids

(c) (d)

Weight Solids

D 1644

Evaluation based on 18-20 dry mil film Evaluation based on 15 dry mil film on aluminum panels Mode of Failure: A=Adhesive, C=Cohesive, D=Delamination, PLI=pounds/Linear Inch ASTM C 1549

Greater than 60%

APPENDIX 3 | Elastomeric roof coating formulation based on RHOPLEX EC-3100 binder: In ARM-3100-1 calcium carbonate extended formulation.

Film Physical Property Requirements for Acrylic Roof Coatings Physical Property

ASTM

Requirement

Initial percent elongation (i.e. ability of film to stretch).

D 2370

100% @ 73 °F (23 °C), minimum

Initial tensile strength (max stress) (i.e. ability of the film to resist breakage, damage and tearing).

D 2370

200 psi (1.38 MPa) @ 73 °F (23 °C) , minimum

Final percent elongation (break) after 1000 Weather-Ometer hrs accelerated weathering. (Elongation here is measured after UV exposure, which typically reduces elongation due to oxidation and crosslinking effects.)

D 2370

100% @ 73 °F (23 °C), minimum

Permeance (ability of the film to breathe. Acrylics usually have greater ability to allow water liquid and vapor to pass through them).

D 1653A

50 perms maximum or 17.2 x 10 -10 Kg/sec x M2 x Pa, maximum

Water swelling (the ability of a coating to minimize the absorbance of liquid water).

D 471

D 4798

No cracking or checking

Peel adhesion

C 794

2.0 pli (350N/M) wet, minimum

Fungi resistance

G 21

Zero rating

Tear resistance

D 624

>60 lbf/in (10.5 kN/m)

Low temperature flexibility, after 1000 hrs accelerated weathering (this reflects the ability of a coating to flex and retain elongation at low temperature).

D 522

Pass ½” mandrel bend at -15 °F (-26 °C), (no cracking)

A

B

C

D

E

50.1 64.3

PVC

40.0

Viscosity initial (Krebs units)

110

Viscosity -30 days 50 °C

100

145.00 5.70

0.65

Aqueous ammonia (28%)

3.00

0.39

BYK 012

2.00

0.40

Omyacarb 12

392.50

17.43

TiPure R-960

62.50

1.94

BYK 012

3.00

0.40

RHOPLEX EC-3100 (55%)

490.10

57.00

Water

13.90

1.67

UCAR™ Filmer IBT

6.00

0.76

SKANE™ M-8

3.00

0.35

Propylene glycol*

10.00

1.16

Dow hydroxyethyl cellulose

4.00

0.45

1141.70

100.00

PVC

40.0

Density, lbs/gal

11.4

Viscosity (KU)

105-115

% volume solids

50.0

% weight solids

64.2

pH

10.0

* Hydroxyethyl cellulose powder and propylene glycol are mixed immediately before addition. Guidelines for manufacturing are presented in Dow Technical Data Sheet 83E71-4.

References

Water resistance Permeance (English units at 20 mil)

7

% Swelling: 1 week

12%

Blister resistance on 4-year weathered TPO membrane 14 days immersion @ 120 °F

10 (no blisters)

Mechanical properties(a) Initial: % Elongation at break Tensile strength maximum (PSI) 500 hours Weather-Ometer:

ARM 3100-1 @ 75 º F

1

2

280 120 @ 75 º F

% Elongation at break

262

Tensile strength maximum (PSI)

181

Low temperature flexibility(b)

-15 º F

½” Mandrel

Pass

䡲䡲䡲

17.00

Water TAMOL™ 851

Physical Properties:

ARM-3100-1

Weight solids (%)

Gallons

Adjust final pH with aqueous ammonia to pH 9.0 minimum

RHOPLEX EC-3100 in ARM-3100-1 formulation ASTM D 6083 Method.

Volume solids (%)

Pounds

LETDOWN:

APPENDIX 2 | Summary of physical and performance properties of

Physical properties

Ingredients: GRIND:

20% (Mass), maximum

Accelerated weathering, 1000 hrs. (Films are tested in a Xenon Arc Weather-Ometer to simulate exposure to natural sunlight and water.)

50

3.0A/1.7D

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

3

4

Paroli, R.M.; Simmons, T.R.; Smith, T.L.; Baskaran, A; Liu, K.K.Y.; and Delgado, A.H. Thermoplastic Polyolefin (TPO) Roofing Membranes; The North American Experience, Proceedings of the XIth Congress of the International Waterproofing Association, October 4-6, 2000, Florence, Italy, pp. 173-200. Ober, Randy; and Oliveira, Paul. ASTM News, August, 2003: TPO Roofing Membranes, ASTM Specification Adds Market Credibility to New Roofing Material, http://www.astm.org/SNEWS/ AUGUST_2003/obeoli_aug03.html. ASTM D 5538 – 07: Standard Practice for Thermoplastic ElastomersTerminology and Abbreviations http://www.astm.org/Standards/ D5538.htm. Taylor, Thomas J.; and Yang, Lu-Ying. Physical Testing of Thermoplastic Polyolefin Membranes and Seams, RCI Interface 2010, December, p 4.

'ƌĞĂƚ/ŶĚŝǀŝĚƵĂůůLJ͘džĐĞƉƟŽŶĂůdŽŐĞƚŚĞƌ͘ Visit us ĂƚƚŚĞϮϬϭϭƵƌŽƉĞĂŶŽĂƟŶŐƐ^ŚŽǁ;,ĂůůϭϬ͘Ϭ͕^ƚĂŶĚϭϬͲϮϮϯͿ As with wine and cheese, when two products with long track records come together, such as WƌŽdžĞůΠƉƌĞƐĞƌǀĂƟǀĞƐ and Omadine® ĂŶƟŵŝĐƌŽďŝĂůƐ,LJŽƵŐĞƚĂŶĞdžĐĞƉƟŽŶĂůƌĞƐƵůƚ͗

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Glassflake-Based Effect Pigments with Extraordinary Sparkle and Colour

L

UXAN effect pigments belong to the group of pearlescent effect pigments that are composed of low refractive transparent substrates coated with high refractive metal oxides, e.g., titanium dioxide or iron oxide. This layered structure enables interference effects, creating the typical pearl luster as frequently found in nature. For decades, natural mica was the state-of-the-art substrate for those pearlescent pigments, but mica shows some basic deficiencies, such as naturally occurring deviations of the chemical composition, irregularly shaped platelets with many edges, and thickness deviations within single mica particles. These deviations lead to undesirable scattering phenomena and inhomogeneous interference colours. In contrast, LUXAN pigments are based on artificial borosilicate platelets with a well-defined chemical composition and a uniform individual particle thickness. This homogeneous thickness of the individual glassflakes and also the total thickness (approximately 1 μm), which minimizes the influence of the carrier on the final interference colour of the metal oxide-coated effect pigment, leads to very uniform and pure interference colours.

FIGURE 1 | SEM micrographs of uncoated substrates (left side) and TiO2-coated substrates (right side). SEM: Layered Mica Structure

SEM: Glassflake Structure

Interference Green Based on Mica

Interference Green Based on Glass

In addition, the glassflakes exhibit excellent surface smoothness and high transparency. The metal oxide coating of those superior substrates results in effect pigments with unique colour purity and extraordinary gloss (Figure 1).

Patented Technology Effect Pigments Comprising a Glassflake Substrate The use of a specially developed glass that exhibits extraordinary adhesion tendency to metal oxides results in a very smooth and homogeneous metal oxide coating of the glassflakes. This effect can also be proven by SEM analysis, which clearly shows the difference between ECKART’s coating technology based on the new glass composition versus state-of-the-art products (Figure 2). The macroscopic result of this phenomenon is less diffuse scattering of light and optimized gloss of ECKART’s glassflake-based pearlescent pigments, proven by gloss readings taken from nitrocellulose drawdowns with a BYK micro-trigloss. Both LUXAN products E001 and E241 achieve significantly higher gloss values compared to corresponding customary grades (Figure 3). The metal oxide coating of ECKART’s special glass composition is based on patented technology (EP 1980594). The new glass composition is different compared to all typical standard glasses (e.g. C-glass, A-glass or E-glass) in terms of metal oxide content and chemical properties.

Effect Pigments Based on Artificial Substrates with a Narrow Particle Size Distribution (EP 2093260) The excellent particle size distribution of the LUXAN pigments provides a high colour purity of metal oxide-coated interference products. The effectiveness of the particle size distribution can be quantified by the span, which is defined as: 6D=(D90 -D10 )/D50. A small span corresponds to a narrow particle size distribution. The LUXAN products exhibit a span of approximately 1.0. Figure 4 (micrographs) compares a customary grade with the LUXAN E241 pigment. The picture on the lefthand side shows the LUXAN pigment with a uniform particle size and shape. In contrast, the customary grade (right-hand side) also contains very coarse and fine particles with different interference colours. In this case the small particles have a violet-reddish colour and the coarse

By Dr. Dirk Schumacher, Head of R&D, Pearl Pigments, Artificial Substrates; and Dr. Guenter Kaupp, Global Head of R&D Pearlescent Pigments | ECKART, Germany 52

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

Glassflake-Based Effect Pigments with Extraordinary Sparkle and Colour

TABLE 1 | LUXAN product portfolio. Particle Size

Colour

LUXAN

MOx

Sparkle Effect

80-450 μm 35-150 μm

silver silver gold red blue green silver combigold silver blue

F001 E001 E221 E241 E261 E271 D001 D393 C001 C261

TiO2 TiO2 TiO2 TiO2 TiO2 TiO2 TiO2 Fe2O3/TiO2 TiO2 TiO2

extreme excellent excellent excellent excellent excellent high high gentle gentle

20-100 μm 15-60 μm

FIGURE 2 | SEM micrograph of TiO2-coated glassflakes. ECKART

Customary Grade

1μm

1μm

particles have an orange colour. This effect macroscopically results in a higher colour purity of the LUXAN product.

New Borosilicate Pigments LUXAN pigments were originally introduced at the ECS in 2009 and are today available within the product portfolio listed in Table 1. LUXAN effect pigments distinguish themselves from traditional natural mica-based pigments by their extraordinary luster, sparkle effects and glamorous look. The smooth metal oxide coating of the calcium sodium borosilicate leads to very high transparency and pure interference colours. The product line is available in four different particle sizes (Table 1). The finer C-fraction exhibits a subtle and gentle, but still impressive, sparkle, whereas the extra coarse F-fraction combines highest transparency with extreme sparks. The E-fraction includes pigments with outstanding pure and intense interference colours and extraordinary luster. The latest innovation, LUXAN D393, combines extreme gloss and sparkle effects with a high chroma and very pure golden interference and absorption colour. The effect combination of high transparency and also high chroma colour intensity enables new possibilities for design and styling. Especially in coating applications

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

Milling Grinding Dispersing FIGURE 3 | Gloss readings of nitrocellulose drawdowns (6% pigmentation). 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0.0

120.0 100.0 80.0 60.0 40.0 20.0 0.0 LUXAN E001 Customary Customary Grade 1 Grade 2

LUXAN E241 Customary Customary Grade 1 Grade 2

FIGURE 4 | Micrographs of LUXAN E241 versus customary grade. LUXAN E241

Customary Grade

100 μm

100 μm

LUXAN products show nearly no impact on the base colour of the coating at flat observation angles due to their high transparency. The sparkle and luster effect suddenly appear when changing to the specular viewing angle. LUXAN effect pigments can be used in all kinds of applications of conventional effect pigments, e.g., automotive and industrial coatings, powder coatings, textile and leather coatings, printing inks, plastics and the like.

SHINEDECOR Effect Pigment Concentrates New effect pigment concentrates under the brandname SHINEDECOR, which combine advanced processing options, high compatibility, low influence on the paint properties and improved product quality, have been recently developed. SHINEDECOR pigment concentrates are entirely free of binders and solvents. Besides water, SHINEDECOR only contains small quantities of appropriate wetting and dispersing additives as well as defoamers and rheology additives of the water pollution classes 0 and 1. All criteria for the development of ecologically friendly materials (equivalent to the environmental sign RAL ZU 102) are fulfilled. The most distinguishing features are: VOC free; APEO free; and plasticizer free. The almost universal compatibility with the majority of water-based coating systems provides flexible handling. In addition, the easy incorporation of the effect pigment concentrate should be mentioned here, even “stir-in” by hand is possible. With SHINEDECOR, brilliant effects can be obtained in ecologically correct wall paints, in aqueous leather colouring agents, in water-based varnishes for woodwork as well as in aqueous industrial coatings, and in all other kinds of decorative glazing. SHINEDECOR concentrates are already available for aluminium, bronze powder and pearlescent pigments. Two corresponding SHINEDECOR LUXAN products were introduced into the market in early 2010 (SHINEDECOR E001 and SHINEDECOR D393), and further grades will follow in 2011. 䡲

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55

Novel Matting Low-Gloss UV

Experimental Discussion Matting Agents Studied

TABLE 2 | UV test coating system. UV Test Coating System

77.70 19.40 2.50 0.40 100.00

FIGURE 1 | Comparison of loading to achieve gloss of 15 @ 60°, 15 μm dft. 25 20 15 10 5 0

MA#1 7.8g

First we will outline the physical/chemical properties of the matting agents included in the study, and then review the formulation used and data pertaining to performance. Values tested include matting efficiency @ 60° and 85°, and viscosity build-up, which is a major consideration in UV coatings especially when trying to achieve low-gloss finishes in the area of 10 @ 60°. Other results presented pertain to transparency, surface smoothness and morphological differences in technology as assessed through SEM analysis of films. Table 1 compares the physical and chemical data of the matting agents studied. Matting agents of this class vary in particle size, pH, morphology and treatment type. The main innovation differentiating Matting Agent #4 from other current technology available is the new reactive

Content (%)

Laromer® LR 8889 (amino-modified polyether acrylate) Laromer HDDA (hexandiol diacrylate) Irgacure 184 (photoinitiator) Irgacure 819 (photoinitiator) Total

Content of Matting Agent [g]

M

atting agents, or additives to increase surface roughness, have evolved over the decades based on a variety of sources, and include ground polymeric types to those based on silicon dioxide. This article focuses on those based on SiO2 from precipitated and gel processes, which are marketed specifically for the UV coatings segment. This coatings segment presents its own unique challenges to achieve low-gloss finishes because there is typically no solvent, little film shrinkage, and varying line speeds and curing conditions. The combination of specific amorphous, synthetic silica combined with a specific polydimethylsiloxane surface treatment was found to improve matting efficacy, and a new product designed for low gloss, high transparency and low viscosity was developed for UV coatings. The new matting technology, noted as Matting Agent #4 (MA #4), will be compared to those currently available on the market.

MA#2 14.5g

MA#3 18.0g

New #4 12.8g

MA#5 22.7g

MA#6 15.0g

MA#7 20.0g

MA#8 23.2g

Matting Agent Type

siloxane treatment with acrylate functionality that adds greater compatibility in UV coatings systems.

Gloss and Loading Level Matting agents were all added at varying levels to achieve a gloss of 15 @ 60°. Once the gloss level was fixed, matting efficiency, viscosity build-up and transparency were assessed. Table 2 shows the formulation used for the study. To achieve the desired gloss range, loadings varied for the eight grades tested from a low level of 7.8 g to a high of 23.2 g. Matting Agent #3 showed a very high viscosity increase when transitioning down from a gloss level of 25 to the target area of 15 @ 60°. The higher formula-

TABLE 1 | Matting agent properties. MA#1 Target Base Type APS* pH Surface treatment

UV SiO2 Fumed 9 7.9 Reactive siloxane #1

MA#2

MA#3

GP UV SiO2 SiO2 Precip Si Gel 4.5 11 6 3.5 Wax

Wax

NEW#4

MA#5 MA#6

MA#7

MA#8

UV SiO2 Precip 5 7 NEW reactive siloxane #2

UV UV SiO2 SiO2 Si Gel Si Gel 5.5 7.5 7 3.5

UV SiO2 Si Gel 4.8 - 5.8 6-8

UV SiO2 Si Gel 4.8 - 5.8 6-8

Organic treated

Organic treated

Wax

Wax

*Average particle size as per manufacturer By Hans-Dieter Christian, Reinhard Behl and Andreas Feller, Evonik, Hanau-Wolfgang, Germany; and Maria Nargiello, Evonik, Piscataway, NJ 56

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

Agent for Coatings FIGURE 2 | Clarity comparison in clearcoat of matting grades tested. NEW#4

Unmatted

12.8g

none

MA#2

14.5g

MA#7

MA#6

20.0g

15.0g

FIGURE 3 | UV-Vis transmission of novel grade #4 to matting technologies on the market. UV-Vis Transmission Comparison Curve Transmission %T 95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0 -5

Unmatted UV Test Coating System NEW #4 MA#2

MA#7 / MA#6

tion viscosity encountered presented several application problems, which is discussed in the SEM analysis later in this article. Figure 1 compares the loading differences to achieve the target gloss range.

Clarity Clarity in the formulation itself is loading-level-dependent, however it is also a function of the treatment type. Figure 2 shows a visual comparison of grades tested. The point to note is the very high clarity of the system matted with the

FIGURE 5 | Matting efficiency comparison of 85° at different film thicknesses.

25 20 15 10 5

MA#1 7.8g

MA#2 14.5g

MA#3 New #4 MA#5 MA#6 18.0g 12.8g 22.7g 15.0g

MA#7 MA#8 20.0g 23.2g

FIGURE 6 | Viscosity comparison at different shear rates.

75 85° Reflectometer Value [%]

20 μm 40 μm 60 μm 80 μm

The matting agents were added and dispersed after photoinitiators were added. They also can be premixed with monomers. Typically, dispersants are not suggested, as they could act to reduce matting efficiency. Typically, fast line speed and highly reactive oligomers lead to higher gloss. Slower line speed, allowing for better orientation, combined with the use of lower reactive oligomers, will contribute to improved matting. In this system we worked with two different initiators from BASF, taking advantage of the different sensitivities to the wavelengths. Irgacure® 184 is used for shorter wavelengths, while Irgacure 819 (normally used for pigmented coatings) is used for longer wavelengths. In matted clear coatings the Irgacure 819 has an advantageous influence on the curing process for thicker films. This leads to higher film

20 μm 40 μm 60 μm 80 μm

70 65 60 55 50 45 40

2000

Viscosity [mPa*s]

FIGURE 4 | Matting efficiency comparison of 60° at different film thicknesses. 60° Reflectometer Value [%]

Matting Efficiency Figures 4 and 5 present the gloss data at 60° and 85° over four different film thicknesses of 20, 40, 60 and 80 microns. Coatings were applied by wire wound rod to BYK contrast cards No. 2854. Matting efficiency in UV systems is dependent on several factors, and certainly the physical/chemical properties of the matting agents themselves are influential. Average particle size and surface treatment play a major role. The choice of initiator, level of oligomer reactivity, and curing line speed are also critical factors to consider when matting UV coatings.

Photoinitiators

250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050 nm

0

new technology designated MA #4. This high clarity is directly due to its novel acrylate functional siloxane treatment and the lower loading level needed to achieve the gloss target. The UV-Vis transmission curve comparison in Figure 3 also demonstrates that even though there are 12.8 g needed to achieve this gloss range, there is little reduction in the transmission curve, and the shape mirrors, almost identically, the UV coating system with no matting agent.

4870 2890 22100 1620 14600 19900 3200 2030 mPa‘s mPa‘s mPa‘s mPa‘s mPa‘s mPa‘s mPa‘s mPa‘s D=1 D = 10 D = 25 D = 100 D = 250 D = 1000

1500

1000

500

35 30

MA#1 MA#2 MA#3 New #4 MA#5 MA#6 MA#7 MA#8 7.8g 14.5g 18.0g 12.8g 22.7g 15.0g 20.0g 23.2g

0

MA#1 MA#2 MA#3 New #4 MA#5 MA#6 MA#7 MA#8 7.8g 14.5g 18.0g 12.8g 22.7g 15.0g 20.0g 23.2g

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

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57

Novel Matting Agent for Low-Gloss UV Coatings

FIGURE 8 | Transparency comparsion of gloss 20 @ 60° – clearcoat on PMMA over white.

FIGURE 9 | Matting and transparency comparsion @ gloss 15 @ 60° – clearcoat on PMMA over black.

1.6

20 μm 40 μm 60 μm 80 μm

1.5 1.4 1.3 1.2 1.1 1.0 MA#1 7.8g

MA#2 New #4 MA#5 14.5g 12.8g 22.7g

MA#6 15.0g

MA#7 20.0g

MA#8 23.2g

2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0

NEW polysiloxanemodified

16

20 μm 40 μm 60 μm 80 μm

MA#1 7.8g

MA#2 14.5g

MA#3 18.0g

FIGURE 10 | Roughness measurement with contact profilometer. diamond needlepoint (2)

60º Reflectometer Value

1.7

Density/Transparency

1.8 Density/Transparency

2.5

18

1.9

14

1.5

10

New #4 12.8g

8

1

6 4

0.5

shrinkage and results in improved matting efficiency (lower gloss). Generally it is recommended to use these initiator combinations for thicker films. An interesting trend for matting UV coatings, which differs from other types of coatings, is that we observed that gloss decreased as film thickness increased. In UV systems the higher the film thickness the higher the related film shrinkage effect. To achieve low gloss, the goal is to have the highest volume shrinkage combined with the highest packing density of matting agent. Film shrinkage, comparatively speaking for UV systems, is somewhat limited compared to other technologies, and we observed that finer matting agents were more effective to reduce 60° gloss in thicker films.

Viscosity Build Another critical factor in matting UV coatings is the influence on viscosity build-up that results with some grades, mainly due to the higher loading needed to reduce gloss down to a very matte finish. Higher viscosity build has detrimental effects on application and overall appearance. Figure 6 reviews behavior of the eight products tested. The new MA #4 grade demonstrated the least influence, and after the very low shear rate of 1 sec-1, viscosity behavior was close to being Newtonian, in the range from 10-1000 sec-1.

Cured Films Transparency Cured coating transparency results are reviewed in Figures 7-9. Comparisons were made at different film thicknesses (20, 40, 60, 80 and 120 microns) and at two dif58

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

60º Density/ 120μm

2 0

0 MA#1 MA#2 MA#4 MA#5 MA#6 MA#7 MA#8 7.8g 14.5g 12.8g 22.7g 15.0g 20.0g 23.2g

FIGURE 11 | Definition of the roughness values Ra and Rz. Arithmetic mean roughness value

Ra

DIN EN ISO 4287 The arithmetic mean of the sum of roughness profile values.

The roughness measurement with contact profile meters is a method for the description of surfaces. During the roughness measurement a needlepoint from a diamond (2) slides over the work piece (5) with constant speed (3). The measuring profile (6) is produced by the vertical position shift of the diamond needlepoint (4), which is usually converted in an electric signal. As a result, standardized roughness parameters are won by this electric signal, which can be used for the description of a surface.

2

12

Density (Transparency)

FIGURE 7 | Transparency comparsion of gloss 15 @ 60° – clearcoat on PMMA over white.

Maximum roughness profile height

Rz

DIN EN ISO 4287 Sum of the roughness profile derived from the height of the highest peak Rp and the lowest valley Rv within a single measuring length.

As the vertical distance from the highest to the lowest profile point, Rz is a measure of the range of roughness values in the profile. Statistically Ra is the arithmetic mean of the deviations of the roughness profile about the centre line. Ra provides only very limited information and is insensitive to extreme profile peaks and valleys.

As Rz is generally determined as the mean of 5 single measuring lengths lr of the roughness profile it corresponds to the mean peak-to-valley height according to DIN 4768. Rp is equivalent to the height of the single highest peak above the mean line previously defined in DIN 4762.

ferent gloss ranges (15 @ 60° and 20 @ 60°). To assess transparency, drawdowns were made over polymethylmethacrylate (PMMA) panels at different film thicknesses. These matted, clear-coated panels (with the eight matting agents tested) were placed over both white and black contrast charts. A densitometer was used to assess transparency. In both cases, transparency was measured over white and black contrast, and higher values indicate higher clarity/transparency. (For those not familiar with this type of test, the human eye can typically detect a difference of 0.1.) As expected, when film thickness increased, transparency decreased. With some grades, this difference was very minimal, however, with others the decrease was significant. An overall very good transparency level was maintained using the new grade MA #4. In this case, MA #8 showed the best performance over thicknesses from 20-80 microns. This was also an unexpected result, given this grade required a high loading of matting agent to achieve the targeted gloss of 15 @ 60°. A significant reduction in transparency was observed at higher film builds with MA #7.

Surface Roughness Surface roughness performance is summarized in Figures 10-12. Figure 10 describes the surface roughness (surface profile) measurement using a contact profilometer. Roughness measurement, using contact profilometers, is used to describe coating surfaces. During the measurement, a needlepoint from a diamond (2) slides over the substrate (work piece) (5) with constant speed (3). The measuring profile (6) is produced by the vertical position shift of the diamond needlepoint (4),

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FIGURE 12 | Performance comparison – efficiency/gloss 60° @ 24/20 μm/roughness values/density.

Q

My coating needs a silicone defoamer, but everything I try results in craters or fisheyes! How can I achieve powerful defoaming without causing surface defects?

30

4.0 25 3.5 3.0

20

2.5 15 1.89 10

A

tell me more www.airproducts.com/ surfactants © Air Products and Chemicals, Inc., 2010 (32145) B41

1.5

1.47

1.0 5 0.52

䡲䡲䡲

0.5

0.21

0

0.0

New#4 (12.8g)

MA#3 (18.0g) 60°

Ra

Density

Rz

FIGURE 13 | SEM comparison of cross section cuts of matting coatings.

20μm

New MA#4

20μm

MA#6

which is usually converted in an electric signal. As a result, standardized roughness parameters are detected by the electric signals, which can be used for the surface description. The resulting roughness values that are reported from this measurement are Ra and Rz. The Ra value is the arithmetic mean roughness value from the absolute value of all profile values of the measuring section. The Rz value indicates the distance from the highest peak to lowest part of the trough. These two values together give a description of the roughness by indicating whether there are few or many peaks (high roughness) and the depth of the peaks (whether they are shallow or deep troughs). The technical definitions of these values are given in Figure 11. Results overall show (Figure 12) that the New MA #4 gives a balanced combination of high matting efficiency, with minimal roughness (lower Ra and Rz) values, indicating high surface smoothness with comparable high transparency.

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2.0

1.86

Content of MA in g

Air Products’ Surfy¯nol® DF-178 defoamer was developed to provide the defoaming strength of a silicone-based defoamer but with the superior system compatibility needed in higher gloss and clear coat applications. As a result, this 100% active liquid defoamer is suitable for use in a large number of different resin systems. For polyurethane dispersion, polyurethane/ acrylic hybrid, and two-component epoxy formulations, Surfy¯nol DF-178 defoamer should be the first choice of the formulator because it enables the production of foam-free, defect-free clear and pigmented coatings. Strong performance in two-component polyurethane, water-based alkyd, acrylic and styrene-acrylic systems, as well as in pigment dispersions, has also been observed. Surfy¯nol DF-178 defoamer also acts as a deaerator to provide strong defoaming and microfoam control in spray applications. Recommended use levels of Surfy¯nol DF-178 defoamer in coatings vary from between 0.1–0.75 wt % on finished systems.

4.5

4.31

Roughness Values / Density

Jim Reader Lead Research Chemist

Novel Matting Agent for Low-Gloss UV Coatings

Reflectometer Value / Content of Matting Agent in g

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

20μm

MA#8 Microscopic Analysis Photomicroscopy (Figure 13) indicates differences in morphology and particle distribution of the various grades included in this study. SEM analysis shows that this current technology targeted to matte UV coatings has highly angular and irregular shapes, with wide particle size distributions. Air bubbles can be easily observed in several cross sections of UV coatings matted with technology MA #6, and this can be attributed to the higher formulated viscosity encountered to achieve the target gloss level

Conclusion In summary, the new reactive siloxanetreated, precipitated silica technology represented by MA #4 gives the UV coatings formulator a new and novel option to achieve low-gloss finishes, while maintaining low application viscosity, high clarity and transparency, and achieving high surface smoothness. 䡲 This paper was presented at the RadTech 2010 Technology Expo and Conference, Baltimore, MD, www.radtech.org.

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Cobalt-Free

Gives New Life to the Alkyd Coatings

A

lkyd resins have been used widely in paints designed for durability and high performance. These paints, applied to high-traffic-area surfaces such as doors, trim and cabinets have been an excellent performance choice; however, conventional alkyd paints have been solvent-based. The regulatory shift toward lower VOC levels has moved consumer preferences away from solvent-based alkyds to other low-VOC options, including water-based and high solids paints such as acrylics, latex and polyurethanes. Recently, there has been renewed interest in alkyd technologies as environmental concerns have shifted and resin manufacturers strove to use bio-renewable resources. Alkyd resin manufacturers have found lowVOC options using higher solids resins (requiring less solvent) and water-based or water-reducible resins. One obstacle faced when using these new technologies was keeping the same drying characteristics of the conventional paint. Conventional solvent systems had excellent drying characteristics; with the new low-VOC options,

FIGURE 1 | Schematic representation of the pentadentate organic ligands bound to the Fe(II) centers to form active drying catalysts. N

N

O

N O

N

N O

O

N N

L2 O

N N

N

N

N

N

L1

N N

L3

FIGURE 2 | Schematic representation of radical processes for stain bleaching induced by the iron catalysts.

initation O

OH R'

R

Novel Catalyst

stain bleaching

R'

R

H O

O

R'

R

II

LFe-OH2

O* R'

R

O2 O*

O

H O

III

R'

R

R'

R

LFe-OH

R

stain bleaching

typical paint driers based on metallic salts such as cobalt, zirconium and calcium did not provide the required cure. It was difficult for alkyds to compete against acrylic and latex options in the market. This article highlights a new cobalt-free catalyst that helps to achieve the necessary cure time as well as improve properties associated with water-based, high solids alkyds and alkyd-modified resins. The catalyst provides the missing piece in new, low-VOC alkyd formulations, and kills two birds with one stone by curing the coating without the use of cobalt. Alkyd resins offer excellent performance in the decorative and light-end industrial paint markets, are cost effective and can be derived from renewable resources. With the introduction of this new catalyst, alkyd resins can now better meet the demands of today’s market.

R'

The mechanism of driers in the curing process has been thoroughly studied and is well understood. It involves radical processes to attain polymerization of the unsaturated resins present in paint/ink formulations via activation of alkyl hydroperoxides by the metallic salts/complexes.1,2 Although it was initially created by the detergent industry as a tomato stain bleaching complex, the new catalyst has been found to activate the alkyd drying process in a similar fashion. Previous work to meet the challenges of curing new alkyd resins was based on the modification of traditional metal carboxylates. The new product, however, is the result of a very different approach. Unilever had done extensive research on metal-based catalysts for stain

By Shelley Parkerson, Market Development Manager | OMG Americas, Inc., Westlake, OH 62

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

Catalyst

Market

Water-based Alkyds The new catalyst from OMG, hereafter called Borchi® OXY - Coat (BOC), has now been tested in many alkyd resins including standard oil-based, high solids and waterbased types. Surprisingly, water-based alkyds required the least amount of BOC for suitable dry times. Addition rates of 0.5-2.0% based on total solids were enough to cure most resin systems, and in most cases no additional secondary driers were needed. Gloss and hardness results are similar to those in traditional systems. New resin development consists of a range of modified resins, including modified polyurethane dispersions. These resins are also oxidatively cured and require a curing agent. As shown in Figure 3, Borchi OXY - Coat is highly effective in these systems when compared to cobalt. In the formulation including BOC, dry time was reduced by over 50% initially, and shows a decrease in dry time after 2 months in storage. Other metals frequently used for curing modified waterborne alkyds are combinations of manganese (Mn) and zirconium (Zr). Figure 4 shows an improvement when using the Borchi OXY - Coat over the Mn, Zr combination in a modified polyurethane dispersion. Water-based resins are typically the most difficult to cure because they experience “loss of dry” when a cobalt carboxylate is used. Loss of dry is a result of the cobalt migrating into the water phase upon storage. When the cobalt migrates into the water phase it becomes less active, and the paint takes longer to cure. In three different waterborne alkyd systems BOC improved loss of dry

6 Dry Time (hrs)

Initial 4 2 months 2

0 Cobalt Drier

Borchi OXY - Coat

FIGURE 4 | Dry time comparison of Borchi OXY - Coat vs. Mn, Zr in a polyurethanemodified alkyd.

Dry Time (hrs)

4 3

Initial

2

2 months

1 0 Mn, Zr Drier

Borchi OXY - Coat

FIGURE 5 | Loss of dry in three waterborne alkyds.

6 Dry Time (hrs)

Experiments and Results Dry Time

FIGURE 3 | Dry time comparison of Borchi OXY - Coat vs. cobalt in a PUD.

Initial 4

2 months

2 0 Co, Zr Dri-Rx

2% BOC

Co, Zr Dri-Rx

1.5% BOC

Co, Zr Dri-Rx

0.5% BOC

FIGURE 6 | Curing times under adverse conditions (10 °C at 80% relative humidity). 12 Dry Time (hrs)

bleaching in laundry products. Iron-based catalysts with pentadentate donor ligands were studied in detail (Figure 1). Research has shown that these iron-based catalysts activate hydroperoxides originating from the unsaturated food oils (such as olive or sunflower oil) typically present in tomato stains. Subsequently, radicals are formed that give rise to oxidation of other unsaturated oils, which then form other peroxides with dioxygen (Figure 2).3 These radical processes are similar to those described for the paint/ink-drying processes,1,2 which led to the hypothesis that the catalysts studied for detergent stain bleaching might also be active for polymerization of unsaturated resins used in paints and inks. Preliminary studies using linseed oil supported this hypothesis and showed that catalysts based on ligands L1 and L2 (Figure 1) are much more active than conventional cobalt carboxylates for drying linseed oil.4 On a molar basis, the activity of the catalysts was found to be 10-100 times more active than what had been observed for the cobalt carboxylate.4 As the compound with ligand L1 is more synthetically viable, subsequent detailed studies were done on this compound.

10 8

Control

6

Borchi OXY - Coat

4 2 0 SB White

HS Black

WB Clear

WB Clear

WB White

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

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Cobalt-Free Catalyst Gives New Life to the Alkyd Coatings Market

FIGURE 7 | Optimization of dry time using secondary driers in a high solids

Dry Time (hrs)

yellow enamel. 15

Control Borchi OXY - Coat

10 5 0

0.05% Co Co, Zr, Ca

2.5% 2.5% 2.5% 1% Catalyst Catalyst Zr Catalyst Zr,Ca Catalyst Addition Rate

FIGURE 8 | Borchi OXY - Coat results in higher L* value over standard drier package in a polyurethane-modified alkyd after 2 months in storage. 84 Lightness (L value)

TABLE 1 | Borchi OXY - Coat results in a lower b* value and higher L* value, indicating less yellowing and improved brightness in a non-pigmented waterborne alkyd.

82 80 78

Dark

76

a*

b*

-5.64 -5.47

11.62 9.84

over traditional cobalt systems after the resins had been aged two months. Resins with the BOC catalyst showed dry times close to the initial dry times (Figure 5). In most cases, the resins with typical cobalt systems showed an increased dry time. Another benefit seen with Borchi OXY - Coat in waterborne alkyds is excellent performance in adverse curing conditions. The performance of cobalt driers under conditions of low temperature and high humidity is often poor, with drying times being extended considerably (by 50% or more). Drying tests for several different resin systems under low-temperature and high-humidity conditions showed the performance of Borchi OXY - Coat is not as sensitive to such adverse conditions (Figure 6). In fact the BOC showed better dry times compared to the standard cobalt, zirconium and calcium drier package.

Light

High Solids Alkyds Unlike standard drier packages, the optimal addition level of Borchi OXY - Coat is resin dependent and requires testing with each

74 72

L* 91.65 92.86

Without Drier

Co, Zr Drier

Borchi OXY - Coat

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ADDITIONAL PATENTS PENDING - Rev. 2/3/11

®

Today’s environment is changing and so is Reichhold. Beckosol AQ® is a new platform of low VOC alkyd latex resins made from renewable resources. From stains to metal primers, Beckosol AQ® is the natural selection.

AQ 101 Exterior Stain

AQ 205 Interior Primer

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AQ 210 Metal Primer

AQ 510 Semi Gloss

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Cobalt-Free Catalyst Gives New Life to the Alkyd Coatings Market

resin type to determine proper levels. In many instances, BOC can act as a standalone compound, requiring no additional driers. In some cases, such as with high solids resins, the addition of a calcium, zirconium, or potassium drier can be used to obtain required hardness or enhance the through cure (Figure 7).

Improvement in Color When discussing an iron catalyst, one question that comes to mind is, will there be a yellow tint in the final coating? Another surprise observed with B OC is that there is improved color as compared to standard drier packages (Table 1, Figure 8). This can be

explained by the composition of the molecule. Actual levels of iron in the supplied catalyst are parts per million. Due to the activity of the BOC, the material is supplied as a 1% solution in propylene glycol. The activity of the catalyst comes from the ligand structure; the iron level in the final coating is at trace levels and therefore does not contribute any color.

Anti-Skinning Agents The use of methyl ethyl ketoxime (MEKO) anti-skinning agents is necessary in typical solvent-based alkyds to increase open time and keep the surface from skinning in the can during storage. In cobalt-based systems the MEKO is able to work as an anti-oxidizing agent as well as complex with the cobalt to reduce its activity. MEKO cannot complex with the iron in the system, therefore, it is not as effective and more may be required. Alternative oxime- and phenol-free anti-oxidants are available, such as the Ascinin® Antiskin line from OMG, and work effectively with the catalyst in high solids systems. The use of anti-skinning agents in water-based alkyds is not usually necessary.

Consistency you can see from batch to batch.

Conclusion Lab tests demonstrate Borchi OXY - Coat can reduce dry times, prevent loss of dry, cure in adverse conditions, and improve color in waterborne alkyds and alkyd modified resins. In high solids resins the use of secondary driers may be necessary to obtain optimal dry time and hardness. Borchi OXY - Coat, along with new resins in the market, has given new life to the alkyd coatings market. It will enable resin suppliers to continue to develop low-VOC and waterborne alkyd resins, including those composed from renewable resources. 䡲

,iޘœ`ÃʈÝiÀÃÊ`œÊ̅ÀiiÊ̅ˆ˜}ÃÊLiÌÌiÀIÊ̅>˜Ê>˜Þʜ̅iÀʓˆÝiÀÃ°Ê 7…ˆV…Ê“i>˜ÃÊޜÕÊV>˜Ê`œÊ̅ÀiiÊ̅ˆ˜}ÃÊLiÌÌiÀÊo UʈÝÊۈÃVœÕÃÊ«Àœ`ÕVÌÃÊv>ÃÌiÀ UÊ>ÛiʏiÃÃÊ«Àœ`ÕVÌÊÜ>ÃÌiÊ UʘVÀi>ÃiÊޜÕÀÊ«ÀœwÌ /…iÊ Õ>Ê-…>vÌʈÝiÀʈÃÊ«œÜiÀvՏ]ÊivwVˆi˜ÌÊ>˜`ÊÛiÀÃ>̈i°ÊÌÊ Vœ“Lˆ˜iÃÊ>ʏœÜ‡Ã«ii`ʅiˆV>ÊL>`iÊ>}ˆÌ>̜ÀÊ܈̅Ê>ʅˆ}…‡Ã«ii`Ê `ˆÃ«iÀÃiÀÊL>`iÊ̜ʫÀœÛˆ`iʜ«Ìˆ“Õ“ÊL>ÌV…ÊÌÕÀ˜œÛiÀ°ÊÌʅi«Ã iˆ“ˆ˜>ÌiʅœÌʜÀÊVœ`ÊëœÌÃʈ˜ÊÌi“«iÀ>ÌÕÀiÊVœ˜ÌÀœi`Ê«ÀœViÃÃiÃÊ >˜`Ê«ÀœÛˆ`iÃÊ}Ài>ÌiÀÊVœ˜ÌÀœÊœvÊۈÃVœÃˆÌÞ]Ê«>À̈ViÊÈâi]ÊVœœÀÊ >˜`ʜ̅iÀʵÕ>ˆÌˆiÃÊ>vviVÌi`ÊLÞÊ̅iʓˆÝˆ˜}Ê«ÀœViÃð

References 1

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2

3

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Reynolds Dual Shaft with patented helical blade design

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Bielemans, J.H. Chimia 2002, 56, 184. van Gorkum, R.; Bouwman, L. Coord. Chem. Rev. 2005, 249, 1709. Hage, R.; Lienke, A. Angew. Chem. 2006, 45, 206. Hage, R.; Wesenhagen, P. Liquid Hardening, patent WO 2008003652.

This article is based on a paper that was presented at the 2010 Coating Trends and Technologies Conference, sponsored by PCI Magazine and the Chicago Society for Coatings Technology.

VAE Copolymer – A Natural Gas-Derived Alternative Newer drilling technologies unlock shale gas resources and help increase the cost-in-use savings of VAE copolymers in architectural coatings.

D

espite being introduced into the commercial market more than 50 years ago, vinyl acetate-ethylene copolymer dispersions (VAEs) remained in a niche mode until early in the last decade. Since then, two main drivers have helped raise the profile and importance of VAE copolymers in the U.S. architectural coatings industry. First was the introduction of nationwide VOC regulations in 1999. Reducing VOCs required using binder technology with a lower solvent demand. VAE copolymers provided an ideal solution because they are inherently low-VOC-capable. The more recent driver affecting VAE copolymer utilization has to do with raw material feedstocks. The “shale gale” created by advanced drilling technologies in the last few years has had a revolutionary effect on domestic natural gas feedstocks and has accordingly helped make VAE copolymers more cost competitive. The U.S. Energy Information Administration (EIA) Annual Energy Outlook 2011 Early Release Overview, issued Dec. 16, 2010, forecast “about double the shale gas production and over 20% higher total lower-48 natural gas production by 2035 … A higher updated estimate of domestic shale resources supports increased natural gas

FIGURE 1 | National and regional limits on VOC regulations. LADCO

OTC

CARB

SCAQMD

Source: Wacker Chemical Corp.

production at prices below those in last year’s Outlook.” Bottom line: there is a growing disparity between the cost of natural gas and that of crude oil. Polymer dispersions where the monomers are produced from crude oil are saddled with a fluctuating raw material supply (primarily imported monomers) and volatile, globally driven market prices. In contrast, natural gas-derived VAE copolymers have emerged as the vanguard in coatings technology, with increased supplies and moderating costs extending an already long list of benefits.

A Brief History of VAE Copolymer Technology The first acrylate systems for coatings were introduced to the market in the mid-1950s. Although innovative, it was a slow start – the cost of key monomers was high because of limited scale. A few years later, the first commercial vinyl acrylics hit the market. These systems made use of vinyl acetate as a way to mitigate the high cost of the acrylate monomers. Technologies for vinyl acetate/maleate copolymers in coatings were being explored around the same time, but these also carried a high cost. Early fundamental work showed that ethylene was an effective “soft” monomer that could be used in emulsion polymerization with vinyl acetate. The caveat was conventional reactor trains could not be used due to the higher pressures required. At this point, various companies began research into VAE copolymer dispersion technologies in an effort to leverage the lower raw material cost position. Most notable during this period were DuPont, Air Reduction Co. (Airco) and WACKER in Europe. The primary driver was to prepare lower-cost resins that were suitable alternatives to vinyl maleates and vinyl acrylates. The first two offerings from Airco were developed for the architectural coatings market. WACKER and DuPont also offered commercial grades, but their primary focus appeared to be in other end-use markets. Ultimately, acrylate costs were reduced by economics of scale. The higher capital costs necessary for VAE copolymer production did not sufficiently offset the raw material cost differences between vinyl acrylics and vinyl acetate-ethylene. As the cost advantage of VAE copolymers eroded, so did their initial popularity, and the pri-

By Kevin Merlo, Director, Coatings and Adhesives Technology | Wacker Chemical Corporation, Adrian, MI 68

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Dispersions to Crude Oil-Derived Binders mary uses for VAE copolymer dispersions shifted to other market areas, primarily adhesives.

VAE Copolymer Technology Ideal for VOC Compliance The market for coatings-grade VAE copolymers remained in a niche mode until the 1990s when environmental drivers began to change what was required of the resin. In 1999, the EPA introduced the Architectural and Industrial Maintenance (AIM) regulations as part of the Clean Air Act Amendments of 1990. AIM governed the amount of VOCs in coatings. The main sources of VOCs in a coating come from the solvents that are used for binder coalescence or freeze/thaw resistance. As these solvents evaporate they react with low-level ozone to create smog. VAE copolymers have an inherently low solvent demand and, therefore, became ideal technology to use as allowable VOC levels were reduced. While the EPA enacted AIM, various regions throughout the country adopted their own regulations (Figure 1). The toughest VOC standards were enacted by California’s South Coast Air Quality Management District (SCAQMD), which encompasses Los Angeles, Orange, Riverside and San Bernardino counties. Other regional groups – California Air Resources Board (CARB), Lake Area District Consortium (LADCO) and Ozone Transport Commission (OTC) – passed regulations that surpassed AIM’s requirements, but weren’t quite as stringent as SCAQMD. Regulations have continued to get even more rigorous over time. The EPA is promoting regulations along the line of those followed by CARB, LADCO and OTC. In turn, these three groups are promoting regulations similar to SCAQMD. As the driver for the highest standards in the country, SCAQMD is striving to reach zero VOCs for several coating categories. What makes VAE copolymers inherently low-VOCcapable is that ethylene is directly incorporated into the polymer backbone, making it the ideal internal plasticizer for vinyl acetate polymer dispersions (Figure 2). When polymerized with vinyl acetate, ethylene is more efficient than other co-monomers at reducing the glass transition temperature (Tg) and minimum film formation temperature (MFFT), thus more readily reducing the solvent demand of the polymer. Ethylene (E) reacts more readily with vinyl acetate (VA) than butyl acrylate (BA) does. As a result, VAE copolymers have a more random distribution of monomer throughout the polymer chain. In a typical coatings-grade vinyl acrylic (VA/BA) system, each monomer seeks to react with “itself,” creating a “blockier” copolymer with long chains of both vinyl acetate and butyl acrylate. This makes vinyl acrylics more susceptible to hydrolysis, or “unzipping,” in the presence of an alkaline solution.

In a structural comparison of VAE copolymers to VA/ BA copolymers, ethylene is incorporated into the polymer backbone and provides main chain flexibility (Figure 3). This is beneficial for VAE copolymers because the polymer chains are more flexible, making it easier for them to entangle and coalesce. Butyl acrylate is attached to the polymer backbone as a pendant group, which makes the chain less flexible, hindering entanglement and coalescence.

Improving the Performance of Copolymer Dispersions VAE copolymers exhibit inherently good coalescing properties. That’s one reason these dispersions are becoming the industry standard in low-odor interior paints – mini-

FIGURE 2 | The copolymer structure of vinyl acetate and ethylene monomers. Basic Monomers Vinyl Acetate (VAM)

Ethylene

• Basic raw material • Polar, hydrophilic • Tg ~ 35 ºC (hard) • Toughness

• Tg ~ 100 ºC (soft) • Hydrohobic • Permanent flexibility • High hydrolysis resistance • Ideal co-polymerization with VAM

Copolymer structure

Source: Wacker Chemical Corp.

FIGURE 3 | Structural comparison of vinyl acetate-ethylene (VAE) and vinyl acrylic/ butyl acrylate copolymers (VA/BA).

O

O

O

O O H3C

O CH3

CH3

Vinyl acetateethylene copolymer Main Chain Flexibility

Pendant Group Flexibility O O O H3C

O O O

Vinyl acetatebutyl acrylate copolymer

O

O O

O CH3

CH3

Source: Wacker Chemical Corp. PA I N T & C O A T I N G S I N D U S T R Y

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VAE Copolymer Dispersions

mizing coalescing solvents provides less odor and lower formulated cost. VAE copolymers also offer improved coalescence at low temperatures. This provides better low-temperature touch-up properties, which are critical for the contractor paint market.

FIGURE 4 | Ratio of oil to natural gas costs. Nov. 2010: Oil = $84; NG = $4 Ratio = 21 !!

20 18 16 14 12 10 8 6 4

Jan-1999 Jul-1999 Jan-2000 Jul-2000 Jan-2001 Jul-2001 Jan-2002 Jul-2002 Jan-2003 Jul-2003 Jan-2004 Jul-2004 Jan-2005 Jul-2005 Jan-2006 Jul-2006 Jan-2007 Jul-2007 Jan-2008 Jul-2008 Jan-2009 Jul-2009 Jan-2010

2

Source: Wacker Chemical Corp.

Another advantage of VAE copolymers is that they can be designed to exhibit superior scrub resistance in systems with or without coalescing solvents. Moreover, they can provide significant improvements in key coating properties such as low-temperature coalescence and mud cracking, while reducing the overall formulated cost of the paint.

The Growth of Natural Gas Feedstocks The entire world economy is affected by the ups and downs of carbon-based feedstocks – particularly, the cost and availability of crude oil, natural gas and coal. One key question is, “How much of these resources do we have left?” While nobody knows for sure, expert estimates of feedstock reserves abound. When an estimate changes significantly, it tends to trend downward – maybe there aren’t as many reserves as we thought, or they’re being depleted more quickly. That’s why the advancement of natural gas extraction technology in the United States has been so revolutionary – forecasts of domestic reserves are being revised upward. So prognosticators who only a couple of years ago predicted the U.S. had about 60 years’ worth of natural gas left are now boosting those numbers by as much as 50%. Natural gas trapped in shale deposits was long presumed to be unrecoverable (at least, cost-effectively).

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VAE Copolymer Dispersions

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JUNE 7-8, 2011 THE WESTIN COLUMBUS COLUMBUS, OH

Join us for this 2-day workshop and symposium, or customize the schedule to meet your educational needs. JUNE 7TH In-Depth Presentations: • Powder Coating Formulating Basics • Performance of Powder Coating Chemistries Live Demonstration of: • Powder Coating Manufacturing • Application Processes and Evaluation of Powder Coating Properties JUNE 8TH Educational Topics Include: • The Latest Developments in Fast Color Change Powder Coating Application • Renewable and Bio-based Resin Systems for Coatings with a Focus on Powder • Corrosion Control for Powder Coatings through the Use of Novel Corrosion Inhibitors • Going Green...then Why UV Powder? • High-Performance Functionalized Polyethylene Powder Coatings • The Pure Chrome Effect – The Dawn of a True Metallic-Look Powder

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

However, in the last few years, the development of sophisticated techniques opened access to these “unconventional” resources. One innovative technology starts conventionally at the surface, then involves drilling horizontally into shale formations, opening the deposits to release the gas. In another new extraction method called “fracking,” hydraulic pressure is used to inject a sand/ water mix into the rock, which creates fractures – essentially, pathways that allow the natural gas to flow. In light of this increased production, the EIA’s AEO2011 Early Release highlighted key changes to natural gas projections it made in 2010. This year the agency is more than doubling the estimate of U.S. shale gas resources, with the technically recoverable unproved shale gas resource at 827 trillion cubic feet, 474 trillion cubic feet larger than in the AEO2010 reference case. Further, the AEO2011 reference case predicts U.S. consumption of natural gas will rise 16%, from 22.7 trillion cubic feet in 2009 to 26.5 trillion cubic feet in 2035. (That’s up 1.6 trillion cubic feet from the estimated 24.9 trillion cubic feet in the 2010 reference case.) U.S. crude oil production also is projected to increase, but only through the end of the decade, with 5.4 million barrels per day in 2009 rising to 6.1 million barrels per day in 2019. From there, production levels are projected to decline slightly through 2035.

The Impact on Natural Gas Prices The EIA also is making adjustments to reflect the changing relationship between oil and natural gas prices. The presumption is that increased availability will support lower prices, making it likely that the price disparity between the two commodities will remain wide. In the AEO2011 Early Release, the price of natural gas is consistently lower than it was in AEO2010. Projections through 2022 show the annual average natural gas wellhead price remaining under $5 per thousand cubic feet. The extended forecast is for natural gas wellhead prices (in 2009 dollars) to reach $6.53 per thousand cubic feet in 2035, compared to the EIA’s estimate of $8.19 in the 2010 Outlook. Historically, the ratio of oil to natural gas costs has averaged approximately 6-7 and was based almost exclusively on their respective fuel values. In the past five years, the ratio has seen a steady uptick. In particular, cost disparities vs. fuel value have jumped in the last two years. In November 2010, a barrel of crude oil was approximately $84, while natural gas was only $4 per thousand cubic feet. That’s a cost ratio of 21, three times the “normal” fuel value ratio (Figure 4). Future projections support ratios greater than 2-3 times the fuel value.

Benefits in Application and Industry Within the U.S. paint industry, architectural coatings make up the largest segment. As a whole, the industry shipped approximately 680 million gallons of architectural coatings, with a value of $8.6 billion in 2008, according to the U.S. Census Bureau. VAE copolymer dispersions are ideal to use for architectural coatings with reduced environmental impact. With a variety of benefits including low solvent demand and the ability to be low formaldehyde, low VOC, and developed without the use of APEO (alkylphenol ethoxylate)-containing raw materials, newer VAE copolymers are well suited to meet even the strictest environmental regulations. Characterized by high rotation freedom, low spatial hindrance, high backbone flexibility and stable structure, VAE copolymers also provide a certain degree of water resistance and a desirable

degree of resistance to acids and alkalis. The molecular chains of these copolymers are capable of maintaining stable properties in dilute acid and alkali conditions by adjusting the polymer structure’s copolymer component – for example, the ratio of vinyl acetate, ethylene or special functional monomers – to develop highperformance copolymer dispersions. Moreover, VAE copolymer dispersions are able to fulfill higher application and performance demands and reduce the amount of additives needed in a formulation. Technological advances are addressing ecological and sustainability issues of vinyl acetate and ethylene monomers. Low-VOC-capable water-based VAE copolymer dispersions are being produced with raw materials that do not contain APEO, yet offer full performance and added cost benefits. Today’s natural gas-based VAE copolymers have been developed for a variety of applications to meet specific end uses. Customized solutions take into consideration the different circumstances and needs of each customer, in the coatings industry. Newer VAE copolymer dispersions, such as the latest additions to Wacker Chemical’s VINNAPAS® product line, are allowing formulators to incorporate new or lower-cost raw materials.

turing of shale deposits have opened up unconventional gas resources and exponentially increased the estimates of longterm domestic reserves. For the architectural coatings industry, this means natural gas-derived VAE copolymer dispersions are virtually cer-

tain to play a bigger role in the future. With global oil demand increasing at a significantly higher rate than natural gas, VAE copolymers should remain at a relatively lower, favorable cost point. VAE copolymer production capacity is stable and likely to expand. 䡲

The Future of Natural Gas-Derived VAE Copolymers After an inauspicious introduction more than a half-century ago, vinyl acetateethylene technology finally appears poised to go mainstream in the coatings market. The benefits of copolymers produced through dispersion polymerization of hard monomer vinyl acetate and soft, hydrophobic monomer ethylene have long been recognized. Until relatively recently, the costs of VAE copolymer dispersions were often too high to be widely utilized in the coatings market. Crude oil-derived acrylic-containing dispersions require the use of increasingly more expensive monomers. In contrast, VAE copolymer dispersions use natural gas-derived feedstocks. As a result, the current price disparity between oil and natural gas has helped VAE copolymers in the marketplace. The real game-changer allowing this advantage to be sustainable in the U.S. is the revolutionary advancement in natural gas recovery technologies that have come into use in just the last few years. Horizontal drilling and hydraulic frac-

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Visit these exhibitors at...

March 8-9, 2011 Biltmore Hotel & Suites, Santa Clara CA

Cycloaliphatic Epoxy Resins Synasia is a manufacturer of cycloaliphatic epoxy resins used with UV cationic or conventional curing techniques. Our products are a direct replacement for certain resins. 䡲 UVR-6110/ERL-4221/Syna-Epoxy 21, production capacity: ~2000 ton scale. 䡲 UVR-6105/ERL-4221D /Syna-Epoxy 06 䡲 UVR-6128/ERL-4299 /Syna-Epoxy 28 䡲 UVR-6107-Syna-Epoxy 07 䡲 Synasia supplies Photoinitiators and resin curatives. Synasia also specializes in custom synthesis and contract and toll manufacturing from our three well-equipped fully integrated manufacturing production sites in China. 631-859-3988 www.synasia.com Visit us at uv.eb WEST booth #33

Extreme Duty IBC Mixer

Come see us

One-of-a-Kind Offering for Tote Tank Users ‡ For High Viscosity and High Solids ‡ THOROUGH Tote Tank Agitation ‡ 32" Blades (opposed to std. 12" to 14") ‡

Visit our Media Room at www.warpro.net for a video showing this product IN ACTION!

UV/EB West March 8 - 9, 2011 Biltmore Hotel Santa Clara, California Booth #9

Warren Products • [email protected] • 704-764-7181

SUPPLIER SHOWCASES

“Welcome to Our World”

100 Eames St. Wilmington, MA 01887 ph: 978-988-0880 fax: 978-658-3366 www.allcoattech.com [email protected]

AllUthane 30522 is a solvent free, water-based aliphatic polyurethane dispersion. It has excellent adhesion to a variety of substrates making it suitable for formulating low-VOC coatings for metal, wood and plastic substrates. The polymer exhibits exceptional toughness and has superb abrasion and chemical resistance making it ideal for challenging interior or exterior applications. For product and application information call: Kurt Bimmler at 978-988-0880, ext-311 or email [email protected]

MICROTRON MILL The Microtron Mill is used for the production of nano dispersions by wet milling and fine grinding. Highly efficient use of the grinding media results in fine particles and a narrow particle distribution. Ideal for the production of high quality paints, inks, colorants & chemicals. Low energy costs, minimum wear and ease of operation. Capable of using grinding media from 0.05 to 0.8 mm diameter. Test equipment available in our Chicago area laboratory. Lab & Production equipment available. Contact Microtron to arrange a test today.

CDC MICROTRON USA, INC. [email protected] 847-548-8224

High Performance Disperser 888 E. Belvidere Rd. Grayslake, IL 60030

MODEL 850

The laboratory Mini Mills are ideal for producing realistic dispersion samples for research, and quality control applications. These self pumping & self contained mills can wet mill samples as little as 25 ml’s, providing results that will answer dispersion questions. The Mini Mill is excellent for Investigating Nano dispersions and can use media sizes less than 0.3 mm diameter and capable of producing sub-micron particles. Ideal for paints, inks, colorants and chemicals. Pilot scale and production mills are also available.

Contact EMI - Eiger Machinery, Inc. for more information or to arrange a demonstration.

Tel: 847-548-0044 74

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

Myers Model 850 shows improvements in product quality and mixing time. The dual shaft, four-blade unit outperforms standard dispersers in many instances: Faster pigment loading, less heat buildup, better dispersion, improved particle size and less air entrapment.

Myers Engineering, Inc. A Leader in Mixing & Dispersing for over 60 Years. 323.560.4723 www.myersmixer.com [email protected]

888 E. Belvidere Rd. Grayslake, IL 60030

April 27-28, 2011 DePaul University | Rolling Meadows, IL Exclusive Media Partner

A Unique Coatings Course Designed for Beginners & Advanced Coating Professionals Wednesday, April 27 7:45am-8:15am

Registration & Refreshments

Track 1: Introductory Session 8:15am-9:45am

Introduction to Coatings Burl Anderson, Staff Chemist, Heavy Equipment Group, The Sherwin-Williams Company John Cox, Scientist, Product Finish Group, The SherwinWilliams Company

9:45am-10:15am

Morning Networking Break

10:15am-11:45am

Resin Technology Paul Baukema, Scientist, EPS

11:45am-1:15pm

Networking Luncheon

1:15pm-2:45pm

Pigments Mark Freshwater, Vice President, Sales and Marketing, Lansco Colors

2:45pm-3:15pm

Afternoon Networking Break

3:15pm-4:45pm

Use of Coalescing Aids & Coupling Solvents Doug Booton, Technical Service Rep., Eastman Chemical

AGENDA Track 2: Advanced Sessions Experimental Design & Advanced Formulation Tools Roger Brown, Technology Innovation Manager, AkzoNobel Aerospace Coatings

Compliant Technologies I (Waterborne & High Solids) Masgood Ahmed, PhD, Manager, WB Research, Nuplex Resins LLC Guatam Haldankar, Manager, Applications Lab and Technical Services, Nuplex

Compliant Technologies II (Radiation Curable) Kevin Murray, Founder & President, Applied Polymer Systems Ryan Schwarb, Formulation & Production Manager, Keyland Polymer

Coating Defects & Troubleshooting Chris Howard, Manager, Applied Technology, Evonik Industries, Coating Additives/TEGO

Thursday, April 28 7:45am-8:15am

Registration & Refreshments

8:15am-9:45am

Additives Ernest Galgoci, R&D Director, Münzing NA LLP

9:45am-10:15am

Morning Networking Break

10:15am-11:45am

Properties/Formulation Steven Hallberg, Senior Chemist, Valspar Corp.

11:45am-1:15pm

Networking Luncheon

1:15pm-2:45pm

Manufacture/Application SIX SIGMA

2:45pm-3:15pm

Afternoon Networking Break

3:15pm-4:45pm

Regulatory Issues Michael Kacner, Technical Manager of Regulatory Affairs, Valspar Corporation

Advances in Color Technology and Dispersion Dan Phillips, Group Manager, Colorants Technical Service, Colortrend USA LLC

Crosslinking and Catalyst Steve Knight, Sales Manager, Coating Additives, King Industries, Inc.

Accelerated Testing and Durability Tony Gichuhi, PhD, R&D/Tech Service Director, HALOX

Nanotechnology for Coating Applications Dr. Roger Clayton, Director of R&D, Nanophase Technologies

For session descriptions visit windycitycoatingscourse.com Register by March 31st and Save $100 | Group Discount: Buy 3, get 50% off all additional attendees

2011 SPRING CONVENTION & EXPO APRIL 17-19 | TAMPA MARRIOTT WATERSIDE HOTEL & MARINA | TAMPA, FLORIDA

Featuring These Dynamic Keynote Speakers:

DR. KEN MAYLAND President, ClearView Economics, LLC As the recovery approaches its second birthday (June 2011), economic growth can at best be described as tepid. What headwinds have slowed the bounce back of business, and will they lighten up in the future, allowing for a more vigorous expansion? Will last year’s new stimulus package be offset and negated by spending cuts? How will all this shake out for production (by industry), pricing and foreign trade? All good questions— but you must attend to hear the answers!

MAURY ZIMRING Manager, Corporate Responsibility and Sustainability, Coca-Cola Refreshments Coca-Cola has been a leader in the environmental sustainability space, focusing on carbon reductions, water stewardship and sustainable packaging. The program will review the environmental sustainability agenda Coca-Cola has been pursuing in North America. It will highlight the work to-date, case studies of new technologies and processes and plans for the future.

DR. DAVID CROWE Chief Economist, National Association of Home Builders Hear what NAHB’s chief economist and forecaster thinks about the outlook for the housing industry, one of the largest market segments ASC members sell into. This session will drill down into this critical sector and complement the macroeconomic overview presented in Monday’s keynote session.

TIMELY EDUCATIONAL SESSIONS WILL ADDRESS THESE KEY INDUSTRY TOPICS: ƌɄ 2Ʉ / -$'.ɄƎɄ -& /Ʉ "( )/. ƌɄ
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THE PRELIMINARY PROGRAM IS AVAILABLE ONLINE NOW! VISIT WWW.ASCOUNCIL.ORG TO VIEW AND REGISTER.

Another signature industry event brought to you by:

Come see us UV/EB West March 8-9, 2011 Biltmore Hotel Santa Clara, California Monomers, Oligomers

European Coatings Show March 29-31, 2011 Nuremberg, Germany Monomers, Oligomers

UV/EB Seminar March 29-31, 2011 Exton, Pennsylvania Monomers, Oligomers Technical Presentations James Goodrich

P RODUCTS 䡲 Rheometer

BROOKFIELD: The DV-III™ Ultra Rheometer now features USB connectivity. It combines the features of a rheometer with the yield stress measurement capability of the YR-1 Yield Test Rheometer. In stand-alone mode, the operator enters test parameters, temperature control requirements and starts the program. The results are displayed on the built-in display. Optional Rheocalc32™ software lets operators control all aspects of rheological testing directly from a computer. Call 800/628.8139.

䡲 Mixing System

CHARLES ROSS & SON CO.: This new mixing and dispersion system combines a Ross High Shear Mixer and a specially designed PowerMix for use in manufacturing fine dispersions. The two mixers are mounted on a common base and connected with piping to allow continuous circulation of materials until the desired dispersion is achieved. A built-in control panel permits fine control of all agitator speeds, amperage and run times. E-mail [email protected].

䡲 Resin

CYTEC: The new RESYDROL™ AY6705 waterborne acrylic modified alkyd resin extends durability with its outstanding penetration for timber substrates. An excellent choice for feeding and protecting exterior wood stains and timber decking, its quick drying time and affinity for timber with varying degrees of tannin content promotes fast and easy recoating. Visit www.cytec.com.

䡲 Software

ELCOMETER: ElcoMaster 2.0 allows users to connect and download data from other Elcometer products simultaneously as well as wirelessly via Bluetooth. The software uploads images, schematics, drawings, forms and various types of illustrations, allowing users to create custom reports, utilize built-in statistical functionalities, and produce analysis from all readings. ElcoMaster 2.0 is available for download. Visit www.Elcometer.com.

Bring on all your bright ideas. Our global UV/EB resources help make them winners. Wherever you need UV/EB support, Sartomer is there for you – in the Americas, Europe, and Asia. We deliver leading-edge UV/EB technology and responsive local manufacturing. We can also help with the complexities of product/country registration issues. Our in-depth expertise and high-performance specialty chemicals will help you bring all your ideas to life and get them to market – fast. Now you can take on any job – plastic and metal coatings, inks, display, automotive, adhesives – or even a totally new application. Rely on us from initial concept to final delivery. Formulators choose Sartomer for UV/EB innovation and consistent quality… batch after batch. Our broad line of more than 500 monomers and oligomers leads the world. If your formulation calls for something unique, we tailor a custom fit. Contact us now for the help you want to beat the competition. Call 800-SARTOMER, 610-363-4100 or visit www.sartomer.com.

Visit us at European Coatings Show

Nuremberg, Germany; March 29-31

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P RODUCTS Gain the most current technical knowledge to help you in your coatings formulations. PRODUCED BY:

SEPTEMBER 13-14, 2011 Oak Brook, IL

Save the Date and Plan Now to Attend! Coatings Trends & Technologies 2010 sold out early. Don’t miss out this year!

Register today and SAVE $100 Who Should Attend? • Formulators/Chemists/Technicians • Technical Managers • Raw Material/Equipment Suppliers • Quality/Analytical Testing Personnel • Distributors • Owners/Officers/General Management • Sales/Marketing Personnel • Purchasing Directors • Consultants Paper abstracts are now being accepted. Submit yours online by April 15th for consideration. C ur re n t S p on sor s

䡲 Tanks

ASSMANN CORP.: Open-top tanks molded from a choice of virgin high-density cross-link or NSF/ANSI 61-certified linear polyethylene are used as day tanks or mixing vessels. These flat-bottom vertical tanks are equipped with shoe-box-style covers and are molded with a stiffing lip on top to give the tank rigidity. Features include uniform thickness, optional stainless-steel and mild-steel epoxycoated agitator support stands, and optional stainless-steel or polyethylene hinge. E-mail [email protected].

䡲 Pigment

SHEPHERD COLOR: Green 30C654 expands the Dynamix product line by adding chrome oxide-type pigment. The 11th pigment to be added to the product line, it is the third green pigment and the first product based on a simple-oxide-type pigment. Fully dispersed by just the use of a high-speed disperser, it eliminates the need for a small media milling production step, reducing cycle times, waste, off-color production and dispersion issues. Visit www.shepherdcolor.com. 䡲

GRINDING MEDIA FOR ALL MILLING APPLICATIONS

Any density - any diameter - any composition Zirconium Oxide, Glass, Steel, Steel Shot, Tungsten Carbide, Alumina, Silicon Carbide, Silicon Nitride, Ottawa Sand, Agate, Titanium Oxide, Flint Pebbles, Rare Earth ZrO/CeO, Nickel, Plastics, etc. Precision Glass Balls for ball bearings, check valves, level gauges and low temperature critical applications are also available Small orders welcome. www.glenmills.com

Sponsorship opportunites are still available! Contact your rep today or visit our website for more information.

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bre ath e e a s y.

Have you looked at vinyl-based resin technology lately?

When we introduced our new EcoVAE emulsions last year, we told you Find the balance you’re looking for. Contact us.

that VAE (vinyl acetate ethylene) technology would be the foundation for a new generation of consumer pleasing, eco-friendly paints. After just over a year in the market, formulators of all types of paints have found that EcoVAE strikes the bal-

www.EcoVAE.com [email protected] Brian Duke 973-443-4014

Come visit us at Stand #7A-105

ance that everyone has been looking for in making high quality, high performing, people-friendly products. They’ve discovered that formulating with EcoVAE is uncomplicated. That the paints they make with it show excellent scrub, stain resistance and touch-up performance. And that EcoVAE technology is suitable for a broad range of interior paints – from premium brands to contractor flats.

If you’ve already found EcoVAE, thanks for your support. If you haven’t…maybe it’s time you discovered the next generation low VOC emulsion that everyone in the North American paint industry is talking about.

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AD INDEX 3M . . . . . . . . . . . . . . . . . . . . . 17, 23

CDC Microtron USA Inc.. . . . . .74

HOCKMEYER . . . . . . . . . . . . . . 64

Reitech Corporation . . . . . . . . 48

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www.cdcmicrotron.com

www.hockmeyer.com

www.reitechcorporation.com

Advanced Polymer Solutions . . . . . . . . . . . . . . . . . . .31

Celanese Emulsion Polymers . . . . . . 24, 79

Hoover Color Corporation . . . .13

Reynolds Industries. . . . . . . . . 66

www.advancedpolymersolutions.com

www.EcoVAE.com

Jiangxi Tikon Titanium . . . . . . .4

Air Products . . . . . . . . . . . . 60, 84

CINIC . . . . . . . . . . . . . . . . . . . . . . .9

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www.airproducts.com/newdawn www.airproducts.com/surfactants

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Jyoti Ceramic Industries . . . . . .35

Coating Trends & Technologies . . . . . . 78

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www.coatingsconference.com

www.kingindustries.com

Conn and Co. . . . . . . . . . . . . . . 30

Kraton . . . . . . . . . . . . . . . . . . . . .25

www.connblade.com

www.kraton.com

CPS Color . . . . . . . . . . . . . . . . 3, 24

KW Container. . . . . . . . . . . . . . .61

www.cpscolor.com

www.kwcontainer.com

DeFelsko Corp. . . . . . . . . . . 20, 24

Luzenac . . . . . . . . . . . . . . . . 25, 59

www.defelsko.com

www.riotintomaterials.com

Dow Coating Materials . . . 25, 41

Mason Color Works, Inc. . . . . 49

www.arkemaemulsionsystems.com

www.dow.com/hiding

www.masoncolorpigments.com

Synasia. . . . . . . . . . . . . . . . . . . . .74

ASC 2011 Spring Convention & Expo . . . . . . . . . .76

Elcometer . . . . . . . . . . . . . . . . . 54

Micro Powders, Inc.. . . . . . 25, 83

www.synasia.com

www.elcometer.com

www.micropowders.com

Taber Industries . . . . . . . . . . . . 70

www.ascouncil.org

Emerald Performance Materials . . . . . . . . . . . . . . . 25, 42

MYERS Engineering, Inc. . . . .74

www.taberindustries.com

www.emeraldmaterials.com

Nubiola . . . . . . . . . . . . . . . . 25, 37

www.coatingsgroup.com

EMI . . . . . . . . . . . . . . . . . . . . . . . .74

www.nubiola.com

BASF Corporation . . . . . . . 24, 53

www.EMImills.com

OM Group . . . . . . . . . . . 26, 38-39

E.W. Kaufmann Company . . . .10

www.omgi.com

www.ewkaufmann.com

Perstorp . . . . . . . . . . . . . . . . . . . .26

AllCoat . . . . . . . . . . . . . . . . . . . . .74 www.allcoattech.com

ANGUS Chemical Company . . . . . . . . . . . . . . . . 2, 23 www.ANGUS.com

Arch Biocides . . . . . . . . . . . 23, 51 www.archbiocides.com/ proxelbzplus

Arkema Emulsion Systems . . . . 18-19, 24

Asia Pacific Coatings Show 2011 . . . . . . . . 80

www.basf.us/coatingsindustry

Brenntag North America . . . . . .7 www.brenntagnorthamerica.com

Buhler Inc. . . . . . . . . . . . . . 12, 24 www.buhlergroup.com

Glen Mills Inc.. . . . . . . . . . . . . . 78 www.glenmills.com

Harcros Organics. . . . . . . . . . . .21

www.hoovercolor.com

King Industries. . . . . . . . . . 14, 25

www.myersmixer.com

www.perstorp.com/voxtar

Powder Coating Forum. . . . . . 72

www.reynoldsmixers.com

Ross, Charles & Son . . . . . . . . . .15 www.mixers.com

Sartomer . . . . . . . . . . . . . . . 74, 77 www.sartomer.com

Shamrock Technologies, Inc. . . . . . . . 26, 71 www.shamrocktechnologies.com

The Shepherd Color Company. . . . . . . . . . 26, 73 www.shepherdcolor.com

Sigmund Lindner GmbH . 26, 55 www.sili.eu

Troy Corporation . . . . . . . . 26, 43 www.troycorp.com

Unimin Corp. . . . . . . . . . . . . . . 40 www.BrilliantAdditions.com

Warren Products . . . . . . . . . . . .74 www.warpro.net

Windy City Coatings Course . .75

www.powdercoatingsforum.com

www.chicagocoatings.org/events

Worlée-Chemie GmbH . . . . . . .26

www.harcrosorganics.com/ harcrylmonomers

Q-Lab . . . . . . . . . . . . . . . . . . 26, 34

ww.burgesspigment.com

www.q-lab.com

www.worlee.de

BYK USA Inc. . . . . . . . . . . . 11, 24

Heubach. . . . . . . . . . . . . . . . 25. 33

Reichhold. . . . . . . . . . . . . . . . . . .65

Yuron Chemical Industry . . . .47

www.byk.com

www.heubachcolor.com

www.Reichhold.com

www.yulongchem.com

Burgess Pigment . . . . . . . . 24, 67

82

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

In or out of water Micro Powders waxes make a critical difference. Ideal for waterborne products … and all your formulations!

Whether your products are waterborne or conventional, whether you are looking for abrasion resistance, slip or other essential qualities… Micro Powders gives your formulas the properties you want – with total reliability, flexibility and creativity. For consistent results, personal service and innovative ideas, nothing outperforms Micro Powders specialty wax additives.

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Welcome to a new day of environmentally friendly surfactants for architectural

Carbowet® 13-40 and EnviroGem® 2010 newly hatched, APE-Free surfactants. Whether you’re anticipating U.S. regulations or complying with global trends and laws, switching to Air Products’ newest solvent- and APE-free surfactants is a smart move. Carbowet 13-40 and EnviroGem 2010 surfactants contribute no VOCs to zeroVOC coatings formulations. Additionally, both products offer excellent wetting with very low foam for architectural and industrial coatings, pigment dispersions, and various other systems. To request a free sample, call 1-800-345-3148 or visit us online at www.airproducts.com/ newdawn and look forward to many new days of simple formulating. Easy on the environment and easy on you.

coatings.

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