ENA Ld tee a felg le] Yt Tel Sel tol a Daal naeIndispensable Reference Tools Now Available Extrusion Dies for Plastics ‘and Rubber Design and Engineering Computations, 3° Edition By Walter Michael 3462 pages, 275 figures and 15 tables Hardcover: $99.95, The new edition ofthis well received ‘book provides comprehensive acount of the the extrusion of plastics and rubber and incorporates ll new develop- ‘mens and innovations inthe Field of extrusion and di design, The Show space up to 17 0010 sqm, 50° increase » Nearly 400 estimated exhibitors ig 000 visitorsFrom RUBBER WORLD The industry's oldest and most comprehensive buyers guide has served the industry for over 60 years with industry professionals relying on it to locate a wealth of sources and services when making important purchasing decisions. = LJ is a must for industry professionals who need comprehensive up-to-date purchasing information on the many products and services available to the rubber industry. + Rubber Machinery & Equipment ) * Laboratory & Testing Equipment * Accessories and Fittings + Rubber Reclaimers & Recyclers * Rubber Chemicals & b nialiic poaame hee Compounding Materials * Synthetic Rubber D * Fabrics and Textiles * Latex and Related Materials J * Educational Courses in Rubber Chemistry and Technology * Technical and Trade Journals listings for more than 1,200 rubber product manufacturers grouped by location and products. Order the 2007 TODAY Send ordre: Linco & Peta, ne Payment enclosed [| Send bill (U.S.) PO. BoxSAs1 © WATW. MerketSt, ¢ Atzon, OH A45tH Charge creditcard: [-] Visa (| Mastercard ["] American Expross _O*Faxt 0) a6tt88 Card number. Date card expires. Signature United States: $118.00 _$ Name Tie ius $8.00 mM pe ‘Company, Outside US: $147.00 $ ‘die, Ohio residents oy State zi add 6.25% tax _S. A ° Phone ncevasm toe seers TOTAL _S E-mail adcressRe MT Ld 414 Tech Service: A new curative for AEM by Bonnie L. Stuck, Kim Boyd, Patricia Czomba and Becky Freeman, Chem Technologies; Edward McBride, DuPont; and Alice Uminska and Kevin Dominic, Gold Key Processing. An HMDA disper- sion is used to cure ethylene acrylic elastomers. 19 Process Machinery: The economics of capital decisions by Karl Walinskas, O.A. Newton. Following the authors formula results in sound, economically Viable capital decisions. Resistance of FKM to ethanol blends by Ronald D. Stevens, DuPont Performance Elastomers. Fuel and permeation resistance of fluo- toelastomers to ethanol blends is described. HNBR use in oil field applications by John E. Dato, E.C. Campomizzi and D. Achten, Lanxess. New HNBR (hydrogenated nitrile rubber) and HXNBR polymers offer performance and. property improvements in ol ld components 22 28 11 Market Focus 12 Patent News 78 Meetings 84 Suppliers Showcase 87 People in the News 89 Literature AUGUST 2007 36 Glass flake particles enhance permeation resistance by Christophar A. Stevens and David W. Mason, NGF Europe. Relatively low loadings of glass flake particles in ‘elastomer compounds significantly reduce permeation. Digital Edition Content SOM eee R el reeks soi homes ur Reon eres oti) sd aa eee Bieter eet cata) ere ee aarti) Cetra) ieee Visit: rubberworld.comDon R. Smith ‘The adage that "necessity is the mother of inven- tion” is being played out as the realities of unabat- ced growth in China and the finite possibilities of ‘energy supplies appear to have become intertwined 1 stir the best emotion motivator - fear. With the realization that feedstock prices won't decrease, but supplies will, the search for alterna tives has intensified. Feedstock substitution is nothing new. Much research has been done on coal gasification, biomass and unconventional oil j ‘Sources. But most ofthat research has been di- rected toward finding alternative fuel for trans- portation or energy generation. Very litle re- search was being conducted for alternative chemical feedstocks. But that seems to be changing. Chemical biggies Dow and DuPont have directed resources for alternative feedstock programs. Dow is in the middle of a methane challenge proj- fect where they are offering up to three awards of approxi- mately $1-2 million per year to any scientists from around the world to "develop more effective ways of converting ‘methane, and to produce ethylene and other building blocks without using syngas and syngas conversion chemistries.” ‘The company says that feedstocks constitute the single Substitution research largest percentage of Dow's manufacturing costs. ‘The challenge was issued in March, and to date there have been close to 100 proposals, Product substitution in the rubber industry in- volves trying to find different sources for rubber to offset the high natural and synthetic rubber Prices. Demand is fueling the price increases and is not going to abate, That leaves the tightness of supply being a major problem and a strong im- petus to look for alternatives It seems every plant that produces any amount of latex has been studied. Guayule, a rubber source for almost a century, is re- ‘emerging. Other sources being considered are dandelions and sunflowers. The best bet ‘would be to increase hevea planting worldwide ‘Another substitution in the offing involves the Penny Test when checking tire tread depth. The Tire Rack, an indepen- ‘dent tire dealer and tester, claims that measuring to the edge ‘of Washington's head on the quarter, rather than the old stan ‘dard Lincoln's head on the penny, results in a 24% shorter braking distance improvement, according to the company’s tests. There is 1/16" more tread on the Quarter test. Click here for a video: (J1JED and here for test results: (E> ‘The Rubber World plus icon appearing throughout the magazine, signi available on that item by accessing the digital edition of Rubber World more information is ;ww.rubberworld.com ubberWorld LN tases Don R. Smith John T. Byors Dr. Walter C, Wamer ‘Job Lippincott el editor technical editor emeritus managing editor ‘electronic publishing director ep coordinator Creative director Jil Rohrer ‘Michele Gaprez~ Overholt Jane McBee ‘Matthew M. Raymond: P.O. Box 5451 1867 W. Market Street ‘Akron, Ohio 44313-6901 Phone: (330) 864-2122 Facsimile: (330) 864-5298, Internet: http:/www.rubberworld.com (Charlene Gohs Sally Dowling Dennis Kennelly CChip Lippincott + Rubber World + Product News * Blue Book: Materials, ‘compounding ingredients, and machinery for rubber Blue Book on CD ROM Blue Book Online Rubber Red Book Red Book on CD ROM Rubber World for China Rubber World e-mag RUBBER WORLD, (ISSN-0095-9572), ‘August, 2007, Vol. 236, No. 5, Copy: fight: Lippincott & Peto, Inc. 2007; all tights reserved. JH. Lippincot, owner. Published monthly with four quarterly ‘Spocial issues at 1867 West Market St ‘Axton, OH 44313-6901 by Lippincott & Po, ine. 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You can now order the 2007 print and CD-Rom editions before they come off the press this spring. We will again be producing a limited number of the 2007 print and CD-Rom editions, soto guaranice your copy, please return the publication order form today. Now available immediately BLUE BOOK ON-LINE! This new way’ of presenting the Blue Book fers you several ret improvements on devin the information you have come to rely on: ‘Always curren Data is continuously updated throughout the year and is available immediately through the on-line version, “No more wating for next years edition tobe printed. Your on-line subscription gives ‘whole year=no mater when you place your onder. * Quick and convenient searches. For example, the Blue Book curently contains hundreds of listings for accelerators on 67 pages inthe print edition. 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Dark Ga ornare one re ‘res omar eA Se " " For orice quolation en newark purchases of CD ROW or Group Online Bue Book orders apecly number o wae Riember af sere | Payment enclosed [| Send bil (US. & Canada) Charge crest cardi [1 VISA (1 MasterCard 1 American Express [erwatCard Number: ‘ate Card Expires: ‘signature: Name Tie Phone ( » company, Date reet Address Country, Jory & state Postal Code/Zip lE-MaitTech Bytes Zinc oxide reduction becoming a necessity For many of us who have developed rubber compounds over the year, it has been “automatic” to use 5 phr of zine oxide and 2 prof stearic acid a the activator for ac- celerated sulfur cure systems, Among the many variables in com- pounding, this activa tor system was known to work well in. most compounds, Now, we ane being faced with an initiative to redesign those compounds 10 re- duce or eliminate zine content because of en vironmental Elevated concentration of zinc in water are known to be toxic to aquatic organisms, in particular many species of algae, crus- taceans and salmonids. IED Although zine is a common natural element that is abundant in the Earth's crus, the hu rman influence is causing alarmingly increased concentrations in waterways, ponds and lakes, and this is altering the balance ofthe ecosystem, Many of the processing aids used in rubber compounds are zine salts of faty acids. Some zinc-ree alternatives for these have been introduced (ref. 1). Finding a suitable replacement John Byers PUT MET rat The Technical Service Magazine for the Rubber Industry Published monthly. Provides the most up-to-date technical serves intron avallabetotody's rubber chemists and formato. ives research, dovelopment and engineers the most current technical tnow-how and provides plat engineering personnel with th ‘uipment and production techtogy. Call (314) 878-6327 for your subscription. for zine oxide in sulfur cure systems will be more difficult. Re- searchers at the University of Twente in the Netherlands have published a number of papers on their investigation of zine ox- ide altematives and zine reduction. This work is discussed in detail in the thesis of Dr. Geert Heideman that is available on- line Inthe summary atthe end of chapter two of his the sis, Dr. Heideman states: “The chances of finding a completely 7ine-free curing system must be reganded as rather small, and ‘would involve a fundamental change in the practice, as well as the chemistry of sulphur vulcanization.” However, some po tential options for significantly reducing the zt are presented that appear to be feasible as shorter-term devel- ‘opments (ref. 2), Their studies also indicate that the zine oxide level can be reduced by about S0% in many compounds with- ut adverse effects ‘The largest usage of zinc isin ani-comrosion protective coat ings for metals. Galvanized metal sheets have been a popular building and roofing material for industrial buildings and stor- age sheds throughout the world for many years. jalvar nized water pipes, storage tanks and galvanized nails are also exposed to water erosion on a continuing basis. These galva nized metal products are undoubtedly primary contributors to increasing concentrations of zine in the aquatic environmen Other common uses of zinc include batteries, dietary supple- ‘ments, animal fed supplements, brass and other metal alloys. Zinc oxide is used asa pigment in paints and coatings. in oint- ‘ments and lotions for sunburn protection and other cosmetics, asa cement additive, in batteries and photocells and a number of other uses. With this abundance of zine-containing products in common use. it i hard to believe that eliminating zine oxide from rub- ber compounds would have a measurable impact on the ecosys- tem. The typical 5 ph level of zine oxide would be about 210 3% by weight of the compound, and only about 0.5 to 06% by volume. Only a small fraction ofthe zinc near the surface of rubber part would be susceptible to leaching by water. Rubber parts that remain intact throughout their life cycle and disposal ‘would not contribute any significant amount of zinc contamina- tion, However, there is one rubber application tha is a known contributor to increasing zinc levels. The rubber dust from wom tires that becomes airbome or collects along the side of roads and highways is a concem due to the high surface area of the finely divided rubber powder and its ready access in drainage and runoft streams. @{JED Zinc reduction should be a priority for tire tread compounds. For most other rubber compounds — probably not References 1. K, Menting, J. Bertrand, M. Hensel and H. Unland, Rubber World, Vol. 229, No. 2, November, 2003. 2. G. Heideman, J.WM. Noordermeer, RN. Datta and B. van Baarle, Rubber Chem. & Tech., 7, p. 336 (2004)Lanxess projects new investment in rubber ‘The chemicals group Lanxess (www.lanxess.com) seeks 0 ‘expand its global position in the butyl rubber market and is, pursuing plans to build a new facility in Asia. This would be the largest investment ACQUISITIONS, in te niswry of he com EXPANSIONS 2s Lames: piano bong the facility on stream pany. Once a site is select- 2010. Lanxess projects an investment of EUR 400 million. Negotiations at tee posible sites, Singapore, Kinatan in Malaysia and Map'Ta Pht in Thailand Rave begun, Lanxess is pressing ahead with the worldwide expan- sion of its butyl rubber business. At its Canadian Sarnia, Ontario site, the company has completed the first phase of plant expansion that will increase its butyl rubber capac ity there by 42%, Lanxess has already started a second phase of expansion at the Sarnia plant increasing annual capacity by another 10% in 2009. In order to satisfy the ‘growing global demand for butyl rubber, Lanxess is also accelerating its expansion in Europe and Asia, At the Zwijndrecht, Belgium, facility, Lanxess already increased capacity by 10% in 2006, Lanxess' Technical Rubber Products (TRP) business tis going to expand production of XNBR (carboxylated nitrile butadiene rubber) in La Wantzenau, France. Nokian Tyres ple of Finland (www.nokiantyres. com) and Lemcon Oy of Russia, which is part of the Lemminkainen Group, have signed a contract agreement ‘on the expansion of Nokian Tyres’ plant in St. Peterburg, Russia. ‘The plant expansion will be initiated immediately ‘and completed in March 2008. The plant's capacity can then be increased from the current 4 million tires per year ‘up to approximately 10 million tres per year. Toyo Tire & Rubber (www.toyojapan.com), Osaka, Japan, announced the establishment of a new tire sales company, Nitto Tire Canada, in British Columbia, Ca- nada, effective June 15. The company markets Nitto-brand products, South Korea's Kumho Tire Group (www kumhousa, com) kicked off operations of its $4 million, 11,000 met- ric tons per year rubber latex plant in Ben Cat district in southem Binh Duong province on June 28. The Kumho ‘Tires plant is expected to use natural rubber latex that has been sourced from the area that will then be processed and delivered to the company’s tire factory. which is currently ‘under construction in the province. Lion Copolymer LLC (www.lioncopolymer.com), Baton Rouge, LA, has completed its acquisition of the ethylene propylene diene monomer (EPDM) and chemical foaming agent (CFA) assets associated with Chemtura’s AUGUST 2007 plant in Geismar, LA. The acquisition was completed effective June 29. The Geismar facility manufactures Royalene, Royaledge, Royaltherm and Trilene EPDM, as well as Celogen CFA. Lion Copolymer, which manu- factures styrene butadiene rubber (SBR) in Baton Rouge, projects combined annual sales of nearly $500 million after the acquisition, QED Degussa GmbH (www.degussa.com) has doubled its production plant capacity for carbon black in Paulinia, Brazil, 1o 100,000 tons per year. With the expansion of capacity at Pavlinia, Degussa is augmenting its position as the world’s second largest manufacturer of carbon black ‘with approximately 1.4 million tons per year. Hankook Tire (www.hankooktire.com) has started production of its EUR $00 million European production facility in Dunaujvaros, Hungary. Hankook Tire plans to double its market share in Europe to 8% by 2010. Malaysian-owned PT Merdee Siger Way Kanan is building a rubber processing plant at Gunung Sangkaran village in Way Kanan district, Lampung province, at a cost (of Rp110 billion, The rubber processing plant will have a capacity of 30,000 tons per year. [SHIANDA YOUR SOURCE FOR CONSISTENT QUALITY PRODUCTS FOR THE RUBBER & PLASTICS INDUSTRIES. CPE-FKM-CSM- CR-ECO Peroxides - Trilink - Coagents Silica - Blowing Agents ISO 9001: 2000 Registered 1340 CORPORATE DRIVE - SUITE 500 HUDSON, OHIO 44236 TEL - (330) 653-8341 FAX- (330) 653-3189 wwwliandacorp.comBayer MaterialScience (www bayerbms.com), Leverku- sen, Germany, in close cooperation with Bayer Technology Services GmbH, has developed technology for the manu- facture of polymer-filled polyether polyols that is said to deliver significantly better products than the conventional process. The process is to be used on a world scale for the first time in a PMPO production facility with an annual ‘capacity of 60,000 tons. It is due to be commissioned at the ‘end of 2008, and will be constructed either in Dormagen, Germany, or in Antwerp, Belgium. GUID Bayer MaterialScience has inaugurated its first integrat- ‘ed systems house in the Indian subcontinent, BaySy India, at Greater Noida near New Delhi. BaySystems India «will provide ready-to-use solutions for various industry sec tors, including automotive, footwear and sports equipment. ‘The cemter is capable of handling testing of materials and fine tuning of PU systems to OEM requirements. Bayer MaterialScience completed its acquisition of the Taiwan Ure-Tech Group on July 1. The move is said to hhave made the company the world's largest supplier of res- ins and films. Bayer MaterialScience intends to move the global headquarters of its Thermoplastic Polyurethanes Business Unit to Hong Kong by October 1 ExxonMobil Chemical (www.exxonmobilchemical com), Houston, TX, announced it will begin construction of a facility in Pensacola, FL, to manufacture new specialty ‘elastomer compounds that can improve the durability of tires, make them lighter weight by using less raw material, and significantly reduce fuel consumption. Startup of the plant is expected in early 2008. The plant will manufae- ture a dynamically vulcanized alloy (DVA) of proprietary Exxpro specialty elastomers and nylon. Dow Chemical (www.dow.com), Midland, MI, and the Bayer Group announced the closing of Dow's acquisition of Wolff Walsrode. The purchase price of $725 million includes a cash component and the assumption of financial ‘debt and pension commitments. received a contract Lanxess, Chinese rubber institute sign agreement Lanxess’ (oyu Janxess.com) Polybutadiene Rubber busi: ness unit has signed a three-year cooperation agreement ‘with the Being Research & Design Institute of the Rub- ber Industry (BRDD) in the CONTRACTS, People's Republic of China. The cooperation will make use LICENSES ‘of BRDI's respective strength in customizing the application of Lanxess' high performance polybutadiene rubber and solution styrene butadiene rubber grades in China Lanxess has found a partner for its global ABS plastics business and is establishing a joint venture with the British ical group Ineos. Lanxess is incorporating its Lustran Polymers business unit into the joint venture and will ini- tially hold a 49% minority imerestin the new com con Tyres (www falcontyres.com), Kolkata, India, has signed a technical assistance agreement with Sumitomo Rubber Industries of Japan for technical know-how for two-wheeler ties. The agreement covers everything from product upgradation and process improvement to the intro- 100] es 60 zo zo 70 70 § «0 & 10 al ae ‘ : | i o 8 HMC HMDA HMDC HMDC HMDC HMDG HMDA “4 "92 8 18 RUBBER WORLDThe economics of capital decisions | was reading my crumpled purple copy of “Rich Dad, Poor Dad!" by Robert Kiyosaki while eating my soggy Special K with Red Berries (I'm not making this up, that's what they call it) this morning, learning how to become independentiy ‘wealthy and not have to do this stuff anymore. 1 could be a philanthropist and save the world from a white-sand beach in the tropics. Wow! I can't wait to get to page 3 t0 see what happens next. Anyway, Robert makes a point to throw the American public education system under the bus because they don't ever teach people even the basics of finance or money man- agement; whats an asset, a liability, which should you own ‘more of, that sort of thing. I had to agree with him on that: 1 didnt learn much about money in engineering school, and ‘when I graduated with the rote knowledge of theorems and differential equations that I was never to use again, it took me a few years in the work world to understand a few things, starting with gross # net and there exists a darstardly player in the universe called the IRS, As somebody with a technical ‘background, I have been confronted time and again with one ‘universal truth: Business decisions are made about money! Oh, that sounds so simple and condescending, doesn't it? The problem is that I have seen many of my colleagues, prospects and customers forget this cosmic axiom. Stated aloud, it’s obvious: but there is a boatload of engineers, GMs, plant managers and operations people from good. profitable companies who are tasked with evaluating the next big expansion or improvement project and are sketchy at best at the basic principles of making sound, economically viable capital decisions. These good people are operating under the belief that the bean counters will take care of that or they are embarrassed to admit that this information is, not second nature to them. I guess companies assume this knowledge is universal and will be absorbed via asmosis by the folks who have been placed in leadership roles. Sort of like public speaking - no CEO likes to admit to anyone he or she is weak at it, afterall they're the CEO! Terminology First, les start with some basic definitions from Karls, “The Capital Projects Bible” (Random House, 2010). Accountants, Karl Walinskas is vie president ofthe Engineered Material Han- dling Solutions division of O.A. Newton, ‘a Delaware-based firm that specializes in material handling solutions that increase ‘capacities and reduce operational ex- pense. TKC Technologies isa division of ‘O.A. Newton that specializes in material ‘challenges forthe tire and rubber indus- ‘ty. Walinskas ean be reached at kar wa- linskas@oanewton.com. AUGUST 2007 CFOs and financial folks, please curb the unquenchable desire to send me corrective or hate-filled emails on the chance that I offend your mental dictionaries with the fol- lowing: Ancillary expense ‘Ancillary expense is a cost currently not incurred that be- comes reality in order to engage in a capital project. If you are expanding to two additional manufacturing lines, over and above the equipment and engineering of the process, ‘you might incur costs for building infrastructure, utilities and another operator. These often are operational expenses such as labor, maintenance and power consumption to run the new toys. Budget ‘The budget is the maximum amount your company is will ing to pay to solve this particular dilemma, usually inclusive of all ancillary expenses, although sometimes these are forgotten because they come from a different bucket of cor- porate funds. This number can be inviolate and can require going through an act of congress if your project looks like it will exceed the budget. Most companies have allowable coverages, say 10%6, which are permitted before calling your representative. Budgets are generally formed with some basic knowledge of revenue potential and ROI (see below) requirements and a working expectation of capital outlay for plant and equipment, often derived from ringing the dinner bell for vendor budgetary quotations. Cost Cost is the expense of implementing a capital project over time, including all ancillary expenses. Cost is @ word some- times carelessly confused with price. Operational gain This is the sum of all the reasons you are doing the project ides straight capacity increase (thought of as financial improvement), converted into dollars and easy to justify ‘when the inquisition comes, Opportunity cost ‘This is the cost of tying up company capital with your proj- ect that could be doing something else, like funding another project or earning interest ina bank. Overage ‘The overage is the percentage or dollar amount of leeway beyond a budget you have before this project i either reject- ed, you need to reduce its Scope or re-jusiify to the corpora tion so the budget can be expanded.Price ‘The price is the one-time, fixed expense of engaging in a capital project, usually the sum of all partner/vendor quota- tions, for their piece of the overall picture. The rule i, you get into the game, you deal with price: to stay in the game, ‘you worry about cost Return on investment (ROD For purposes of capital projects, this is usually thought of in ‘units of time, the time to pay back the overall capital price (often costs as defined here are not included in this caleu- lation) with the additional revenue or decreased expenses resulting from the change you make. A decent ROI for capi- tal projects had been five years not long ago. This is shrink ing to two or less in many industries, particularly with regard to new products, as the market viability of those products ‘may not be certain beyond just a few years. Stagnation cost ‘This i the reverse of the opportunity cost, meaning it isthe cost of your current problem, the continued lost revenue not ‘earned or higher operational expense you'll continue to pay ‘you do nothing, Don't increase capacity to meet demand, forfeit those sales toa competitor. If you'e a deicision-maker or the person tasked with put ting together a capital project, you likely either know these terms or derivatives of them or know what they mean to ‘your submittal. If you dont, for instance if you're an engi- heer who doesn't know the budget limitations of his own project. your company has decided to spend a lot of time, ‘money and energy in do-overs. You can't hit a target that doesnt exist, and chances are slim if its there and you can- not see it How to make the case You'd think that the MBAs in your company. if you have them, would be all over this process, and you would likely bbe wrong, What if you don't have MBAS? You're a plant ‘manager with the factory for 20 years who rose through the ranks because you worked your butt off, and now you're afraid that your name and Peter Principle might be included in the same sentence in a meeting of the top brass. Here is process to know what to ask for, what the company can tolerate, and increase your chances of making something ‘meaningful 1) Know your stagnation cost. What additional opera- tional expenses are draining your company by sitting on its hands? This can take the form of a high ratio of main- tenance fees to output on old, outdated equipment, Using ‘more human resources than necessary for manual processes and capturing the fully loaded expenses is generally used t0 justify automation upgrades. This is also key in evaluating ‘options on major capital projects. It can be the risk factor of an OSHA or EPA fine for knowlingly avoiding a safety ‘or environmental issue. These get management's attention really fast after they happen, but many companies are not pre-emptive and have to pay the fiddler at least once. Sum these and put them in terms of dollars, percent of through- put. per unit time - whatever has the impact necessary to et attention, The CFO will always have the numbers on increasing capacity and what it means to output, that's easy: but they may not be familiar enough with manufacturing to understand the smaller detriments associated with current state, This information helps you later if you need to go for an overage against the current budget. 2) Know your pre-approved budget. If accounting gives you a number without your input on stagnation cost and {knowlege of available solutions, you're already in trouble. ‘You may be tasked with arriving at the budget and justifying it, Re-tead number 1, and combine it with 3) Know the company’s ROI requirement. As aru, those with a financial interest in the company make the decisions ‘on what can be lived with on time to payback, ROL. This ‘may be inflexible, but even if there is wiggle room, you're not going to fly your solution with a ten year ROI past the board of directors when they're anticipating three. You'd bet ter be within 20-30% of expectation, or prepare to suffocate in the tar pits of "Projects-Not-Approved" land. 4) Know the competition. By this, I mean know the op portunity cost your company gives up to fund your improve: ‘ments. It may look really good to demonstrate a nice four ‘year ROI ancl dot all the Is, but if sinking the investment in nother project or an investment portfolio blows it away, ‘you may lose the battle. I say “may lose.” because there are ‘non-financial mitigating circumstances that influence choic~ es here, such as keeping within the core of the business, positioning for future demand (capacity increases come to ‘mind), and the legacy of the ownership, 5) Think cost, not price. This fs the hardest pill to swal- low, because in most cases, the company CFO and CEO are thinking one-time price to meet the ROI desired. By getting that dictated to you, it makes your life simple, but not easy. ‘You don't have to think about all the costs that they should have thought about, but didnt. You're focused and don't need the headache. The problem is, the most obvious decision of | price versus capacity payback alone may only capture 70% of the picture, and the darned 30% is the part that could have gotten the project approved and producing benefits. Those ‘with operational authority are inthe best position to quantify ‘operational gains and stagnation costs into an annual figure to bump into the ROI formula ‘The formula If you get familiar with and buy into the above, the rest is pretty simple. Here is a back-of-the-envelope formula used {o make economic decisions on capital improvements: Budget or price (P)__= ROI or P=ROI* FI Financial improvement ‘The ROI is known, somebody took a swag at annualized financial improvement through margin on increased sales or reduced scrap or something similar, and wahlah! You're left with your budget or allowable price. There is a better way, Grasshopper. Given what I've been talking about. Financial improvement must consider a price (P) in terms (Continued on page 85) RUBBER WORLDDIGITAL EDITION 1 = FREE 2°! Subscription! ONLINE NOW! | | Asal ER ee) |Fuel and permeation resistance of fluoroelastomers to ethanol blends by Ronald D. Stevens, DuPont Performance Elastomers (www dupontelastomers.com) hanol is an oxygen-containing pollution control additive used in automotive gasoline, typically at a level of 6-10% Ethanol usage has been largely limited to the midwestem part of North America due in part to supply and price con- straints. As new manufacturing technology makes th hol more plentiful, and government subsidizes help to con- two] its price, there is a push to use ethanol in automotive fuel at higher percentages, for example at 85% in E8S flex fuel ‘The effect of ethanol-fuel blends on rubber sealing materials such as fluoroelastomers has been reported for 10% blends, but has not been well documented for higher levels of etha- nol, Background ‘Two of the many market forces inthe automotive fuel systems sector driving developments today are the need to lower hy- VIR-8200, NPC FKM types with the "G” prefix, and a combination of magne- sium oxide with calcium hydroxide was used with the bisphe- nol cured F-60SC and VTR-9209 polymers. The complete recipes for the compounds are shown in table 2. The com: pounds were vulcanized seven minutes @ 177°C, then post- ured 16 hours @ 232°C, with the exception of VTR-9208, nce VTR-9208 is intended for use in multilayer fuel and filler neck hose constructions, which are not normally post- ‘cured, the test specimens of VTR-9209 were not postcured for this study, Results and discussion Properties of test compounds Table 1 shows the physical properties, measured per ASTM D412, of the six FKM test compounds. The compounds range in hardness from 68 to 80, depending on the polymer used. ‘The low temperature FKMs tend to have lower hardness (68- 73) whereas the standard FKM types, either peroxide or bis- phenol cured, have a bit higher hardness. The postcured FKMs show tensile strengths of 14-20 MPa, with elongation results of 215-320%. VTR-9208, with no postcure, shows lower tensile strength of 8 MPa with an elonga- tion of 330%. The VTR-9209 compound would have had a higher tensile strength if postcured, but as previ- ‘ous noted, multilayer fuel hose is not normally post- ‘cured. Complete physical properties, including com: pression set and low temperature glass transition re- sults, are shown in table 2 Fuel immersion results - tensile and elongation changes ‘Afier measuring the physical properties of the FKM ‘compounds, they were prepared for fuel immersion tests. The fuel immersion tests were conducted for 168 hours at 40°C per ASTM D471 with tensile, elonga- tion and hardness change, as well as volume swell being measured. Six different tes fuels where used in the testing. The fuels were as follows: ‘© Fuel C (50% iso-octane/50% toluene) AUGUST 2007 # CE-10, 10% ethanol blended into 90% Fue! C; ‘© CE-25, 25% ethanol blended into 75% Fuel C; ‘© CE-S0, S0% ethanol blended into S0% Fuel C; # CE-85, 85% ethanol blended into 15% Fuel C; and CE-100, 100% ethanol. Figures 1 and 2 show the trends scen in tensile and elonga- tion changes after the fuel immersion for 168 hours at 40°C Figure 1, a plot of tensile strength percentage loss on the y-axis vs. percent ethanol in Fuel C on the x-axis, shows that the lower fluorine polymers such as GLT-600S tend to show a higher degree of tensile change than do the higher fluorine FKMs, The second trend seen is that tensile loss is greater in fuel-ethanol blends than in either 100% Fuel C or 100% etha- nol. The last trend seen is that VTR-9209, which is not post- nds to show a lower degree of tensile loss, 2 depicts the changes in elongation after fuel im- ‘mersion. The trends for changes in elongation are similar to those seen for change in tensile, as shown in figure 1. The three low temperature FKM polymers show the highest de- CU Lee CO cn] Pre rd VviR-s203- GEES GBLTS GATS GFS__Fe0sC_ NACgree of loss in elo ower fluorine GLT-6008 show- ing the largest loss in elonga- tion. With these three FKM polymers, the same trend is seen for changes in elongation that were exhibited by changes in tensile, i.e, where straight 100% Fuel C and 100% ethanol do not have as large an effect as do blends of fuel and ethanol. In the case of the three standard FKM polymers, lower loss in ‘elongation is seen, Two of the polymers, F-60SC and VTR- ‘9209, gain elongation after fuel immersion. While very little ‘change is seen with the GF (6008, the F-605C and the VTR- 9209 actually gain more elon- gation (change more) when the fuel is blend of fuel and etha- nol than they do when immersed in either 100% Fuel C or 100% ‘ethanol. Figure 3 shows the changes in hardness of the six FKM poly ‘mers after immersion in the six different fuels. In this case, the three low temperature FKM polymers show less hardness loss from fuel plasticization than do the standard FKM polymers Of the low temperature types, lower fluorine GLT-600S shows the most hardness loss. In the ‘case ofthe three standard FKMs, more loss in hardness is seen than with the low temperature FKM polymers. GF.600S shows the smallest change in hardness ‘of the three, and VTR-9209 shows the most loss in hardness. Since VTR-9209 was not post- ‘cured, its crosslink network is not as tight as the postcured FKM polymers; thus, it shows a higher loss in hardness after fuel immersion and that is not unex- pected or surprising. The other trend seen in figure 3 is that blends of fuel and ethanol cause more hardness loss than either 100% Fuel C or 100% ethanol ‘The biggest change seems 10 ‘occur with the CE-25 and C fuel blends. 24 Ca UR urir} 40-02 A40-03 40-04 A40-05 40-06 GBLES GFLTS — GF-S_—_-F605C_VTR-9209 100 - - : 100 z pe = : 100 : is 5 5 : 100 Z : : : - 100 3 3 3 : - A z ° 3 3 Ey ” ” 30 » 3 3 3 - : 2 2 2 a és Fs zi 2 6 6 198198 198 139 199 temperature: 7 @ 17°C 7 @ I7PCT @I7TCT @ 177°C 7 @ 177 CH @ 162°C Postoure time @ 2c 16hs. 16hvs. 16 hws. 16 hrs. © 16 hvs. None. M25, MPa 13 14 14 16 22 15 M-100, MPa 34 44 55 58 57 32 Tensile, MPa 78 152 7188 142 at (Tensie,psi) (2,580) (2,205) (2,418) (2,865) (2,050) (1,180) 1% 319 216 213, 263 264 331 Hardness, A ps. 68 2 73 5 80, 72 ‘Compression set, Method B, rings 7Ohrs. @ 107°C - : - : : 43 Obs. @ 200°C 28 23, 19 2 27 = Low temperature properties Te DSC, °C 317-275-280 2 78-118 Test procedure ‘ASTM 395, Method B (25% deflection) ASTM D1414, duromotor A ‘ASTM.ES6 (Thwing Abert cups - modified per DuPont Perfomance Elastomer intemal test method) properties ASTM D412, pulled at 85 mm/s (20" nmin.) 100% modus, ensie strength, elongation Swess/stran propers ator fut immersion Volume change in thidls Tg (glass tration) by DSC ASTM 0471 ‘ASTM D471 ‘DuPont Performance Elastomers intemal method (Akron MDSC-Tg) Note: Test temperature is 23°C except where specie’ othenvise Ingredients fst ‘Name CarOH 2 XL Diak 7 Elastomag 170 Zine oxse IMT Black (N00) Varox DBPHSO Dimety: Viton GLT-600S_Fluoroelastomer Viton GBLT-600S_Fluoroelastomer Viton GFLT-5008 Fluoroelastomer Vion GF-6008Fluoroelastomer Vion F-505C -Fluoroelastomer VIR-8200 Fluoroelastomer isa vademark of Morton Chemical Trader rk of RT. Vander fradoraks of DuPont Poformanee Elastomers LLC. ‘Supplier HallStar DuPont Performance Elastomers: Morton Chemical HallStar Ingrediont type Caleium hydroxide Coagent (TAIC) ‘Magnesium oxide Metal oxide (2n0) Carbon black 45% active dispersion of 25 Varox's a ‘Vion and OUAK are racomarke or rogetarodFuel immersion results - volume swell ‘Volume swell test results, tested per ASTM D471, for the six FKM polymers in the six fuel blends are reported in a bar chart in figure 4. The 64% fluorine GLT-GO0S shows the highest swell of the low temperature FKM polymers, followed by (66% fluorine GBLT-600S and 67% fluorine GFLT-600S. The higher fluorine GF-600S and F-605C (both 70%) show the Iowest volume swell, followed by 69% fluorine, non-post- cured VTR-9208, The other strong trend is that low levels of ethanol in Fuel C scem to create a high volume swell for the FKM polymers. Specifically, the CE-25 fuel, with 25% ethanol, consistently showed the highest volume swell for all the FKM polymers being tested. The high fluorine polymers did show less of difference in volume swell among the various fuels and fuel-~ ‘ethanol blends that were tested. In all cases, the lowest swells ‘were seen with the neat fuels, ether Fuel C or ethanol. Permeation test results Permeation resistance was measured on the same FKM polymers, using the same six fuel-ethanol blends. Permeation testing was done per ASTM E96, using the Thwing Albert cup method, which has been described in detail in a previous SAE paper (ref. 5). ‘Testing was run for 672 hours at 40°C, with the results eu being expressed in permeation rate units of grams- a mmvn?iday. The results are shown in figure 5 fe 21 “The permeation results show much the same tendas 48 ‘was seen with the previously reported volume swell results, The lower fluorine GL.T-600S shows the high- ‘est permeation rate, ranging from ~25 g-mnvmm?/day in Fuel C to a peak of ~100 g-mnvm?/day in CE-25 fuel and ~20 g-mnvm2/day in neat ethanol. A strong trend ‘was observed for permeation rates where low levels of 3 ‘ethanol in Fuel C appear to exhibit higher permeation rates. Specifically, the CE-25 fuel, with 25% ethanol, ‘consistently showed the highest permeation rate, re- gardless of the FKM polymer being tested. GBLT- - high fluorine, peroxide cured GBLT-600S and GFLT- (6008, as well as GF-600S, showed lower hardness changes than bisphenol cured F.605C and VTR-9209; = VTR-9208, which was not po J, showed good re- tention of tensile and elongation loss after fuel immersion. VTR-9209 showed a higher loss of hardness afte fuel immer- * Volume swell changes after fuel-ethanol immersions - - lower fluorine FKM showed a higher volume swell than higher fluorine FKM in all the fuels tested; = blends of Fuel C and ethanol swelled all the FKM poly- ‘mers more than they did in neat, 100% Fuel C or 100% etha- nol = the worst case fuel for volume swell of all the FKM polymers was CE-25, Fuel C with 25% ethanol ~ 70.2% fluorine GF-6008 showed the lowest volume swell in ll fuels tested + in low temperature FKM polymer testing, GBLT showed considerably lower volume swell than GLT-6008 in Figure 4 - volume swell, Fuel C/ethanol blends eras GUTS “GBLIS GATS GFS Feec VIRsano- © Ful © CESO CEH0 © CESS © CE25 Ethanol (6008 showed a marked improvement over GLT-600S ‘when comparing the low temperature FKM polymers, and the 70.2% fluorine GF-600S showed the lowest permeation rate of any of the FKM polymers tested in this study. Conclusions “Test results for six different fluoroelastomer polymers, ‘of various fluorine levels, in standard MT black com- pounds with six different Fuel C-ethanol blends exhib- ited the following trends: + Physical property changes after fuel-ethanol im- lower fluorine FKM showed greater changes in tensile and elongation than higher fluorine FKM; - when immersed in blends of Fuel C and ethanol, ‘most of the FKM polymers tested showed higher ten- sile and elongation changes than they did in either 100% Fuel C or 100% ethan; AUGUST 2007 DC Co L Reoed @ 40°C GLIS GBLIS GATS GFS FOC VIRSEID- © FulDA OL DaAers polymers offer several benefits over other earner eas ee | Poa eet et ed Wee aed aoe aar Gaead eka Sue od Peek ey eee iray ene ead ee yd PRT) ed Protea Ty Catt) For information contact: Cee ey Re ae ee ay ae eee eee 26 all fuels; trends in volume swell scem to follow the trends seen in hardness change with the exception of F-605C, and the hose FKM VTR-9209 which was not postcured + Permeation rates after fuel-cthanol immersions; trends in fuel permeation resistance seem to closely fo low the trends seen in volume swell of FKM polymers Jower fluorine FKM showed higher permeation rates than higher fluorine FKM in all the f blends of Fuel C and ethanol showed ates in all the FKM polymers th 100% ethanol: the fuel which showed the highest evels of permeation for all FKM polymers was CE-25, Fuel C with 25% ethanol: n did neat, 100% Fuel C or fluorine GF-600S showed the lowest permeation rates in all fuels tested Of the specialty, low temperature types of FKM tested, GBLT-600S showed a considerably lower permeation rate han did GLT-600S in ll fuels and has a low temperature glass ransition close to that of GLT-6008. This article is based on a paper presented at a meeting of dl Rubber Division, ACS (www.rubber.org). References 1. T. Cackene, Cal. Air es Board, “On the road to clean air ~ zero and near zero evaporative emissions,” SAE/ DuPont Fuel Systems L 2. T. Cacket evaporative emissions,” DuPont Fuel Systems Lunch April 4, 2006, RD. Stevens, SAE paper 880022, “Flu icheon, March 5, 2002. California Air Resources Board, “Reducing r opments for automotive fuel systems,” 1988. 4. WM, Stahl and R.D. Stevens, SAE paper 920163, "Fuel: Juoroelastomers, fluoroplastics ‘and on ils,” Feb, 1992. 5. RD. Stevens, SAE paper 2001-01-1127, “Permeation and alcohol permeation rates 0 stress relaxatio ance of elastomeric fuel seal materi als,” March 2001 RUBBER WORLDCHEMICAL RESISTANCE GUIDE FOR ELASTOMERS Ill Data for more than 100,000 combinations of corrodents vs. rubber and other elastomeric compounds and representing 400% new data. Dear Rubber Industry Leader Rubber World introduces the all new updated Chemical Resistance Guide for Elastomers Ill- a concise guide to chemical and ‘environmental resistance of rubber and elastomeric compounds, when exposed to various hostile media Now 50 rubber and elastomeric compounds are examined in more than 100,00 combinations with corrodents, including 3,000 liquid or dry chemicals, gases, lubricants, household fluids, foods and other ‘environments. In addition, mechanical and physical properties ofthe materiais are ‘covered, including specifi rates of deteroration, time and temperature for ‘selected compounds. {Al data are compled in an easy to find mat format, with coradents TT) fisted in alphabetical order. 800+ chemical ade names ae covered, with parr ‘synonyms listed for more than 1,000 chemicals, gases, etc., and indexed to apse coresponding page numbers. Reeirersertrtd eid Here are just a few ofthe many features that wil help you on the job. + 3,000+ liquid or dry chemicals, gases, lubricants, household fds, foods and other environments are covered + 500¢ chemical trade names covered. *+1,000¢ synonyms of covered chemicals, gases, ec. indexed to page umbers, + Corrodents are listed in alphabetical order. + Data are presented in symbolic formal (A.B,C, NR) with some data at ‘pectic rates of deterioration, ime and temperature. + Where known chemical resistance varies wih concentration and temperature, data are presented in descending order of concentration ‘and temperature. “ Aquick reference summary of chemical resistance for each elastomer ‘compound is provides + Mechanical, physical and electrical properties data for each elastomer ‘compound are proved + Printed on semigloss 60 pound plastic coated bond paper to last several years of use, + Pertect bound hardcover. +780 pages, 8-1/2 x 1 page size ALL NEW - 51,200 New Combinations - 336 More Pages! Rubber World Magazine Payment information P10, Box 545% " ‘nicl Heal 1 chock enclosed (py to Ruber Word Charge tomy creat card: [] visa [] MasterCard [C] American Expres Please send copyis) ofthe Chemical Resistance Guide for Elastomers Ill,, Account number Date card expires Signature, ( pomestic “ ” - UTS. $203.00 pus $10.00 postage and Name Poona handing charges. fio residents add 6.75% tax. SS Company Name Te (] atorners '$243.00 Includes ar mail postage. Cops tobe | Company adress (or UPS delivery) shipped outside the USA must be prepaid in U.S. ‘currency by US, Bank Dra or International Money | Cfy___State_Country_Zip Order. Mail or Fax order to (330) 864-5298HNBR for use in oilfield applications ‘by John E, Dato, E.C. Campomizzi and D. Achten, Lanxess In fundamental terms, fully hydrogenated NBR can be de- scribed as a copolymer consisting of randomly distributed se- ‘quences of ethylene and aerylonitrile monomers. The intrinsic ‘combination of good heat, extreme oil and chemical resis- tance, coupled with outstanding physical properties and ease ‘of processing for HNBR, can be attributed to its composition and structural arrangement. “The use of HNBR for rubber articles such as stators (drilling :motors and progressive cavity pumps), packers, blow out pre~ ventors and drill bit seals, can extend the lifetime of the arti- ‘les, thereby reducing the maintenance frequency or extending the replacement cycles for those parts. This benefit can poten tially translate into substantial operational cost savings without ‘compromise to safety Furthermore, advances in technology have permitted the ‘development of new grades. New low viscosity polymers based ‘on Therban AT (Advanced Technology) provide polymers that ‘can be processed as easily as regular nitrile polymers (NBR), while retaining the advantageous properties of HNBR. Other ‘developments in carboxylate technology have allowed develop- ‘ment of Therban XT (HXNBR), which offers the advantages of ‘carboxylated NBR, but with the improvements in heat resis- tance and abrasion (due to the reduced stiffness of the polymer backbone) afforded by the hydrogenation ofthe polymer back bone. By utilizing the new HNBR polymers. unprecedented latitude of compounding, as well as novel ways of processing. ‘can be attained. This, in tur, opens the door for new dimen- sions of design. Examples willbe given inthe article, Discussion ‘The development of new elastomers with improved perfor- ‘mance profiles has become inereasingly important, particu- Figure 1 - molecular structure of HNBR larly for rubber parts used in the oil industry. Now, demanding methodologies have emerged, such as horizontal drilling and smart well techniques, in combination with increasingly adverse conditions of deeper wells and higher temperatures. The more extensive use of corrosion in- hibitors to protect production equipment from unpredictable mixtures of hydrocarbons, possibly containing sulfur, HS, CO>, CH. and the extensive use of steam and brine injections to improve yields from even the smallest oil pockets have raised demands on standard elastomers to an extent that they are reaching their performance limits. ‘Consequently, equipment containing seals, stators, packers and other parts must be maintained or replaced more frequent ly, leading to increased cost with respect to both parts and to ‘operational down-time. It is readily apparent that reliability and durability of equipment become limiting factors for the total output and overall return for each drilling operation. ‘A number of limiting performance criteria for several rub- ber parts used in the oil well services industry have been tified, These are + Resistance to high temperature and to aging: + resistance to swelling by aggressive fluids and gases: + resistance to explosive decompression; + mechanical properties and resistance to deformation at elevated temperatures: ‘+ abrasion and wear resistance under extremely adverse conditions; and + processing properties o allow a greater freedom of eom- pounding, and new part design and production techniques. Itis well known that HNBR is an oil resistant polymer that is well suited to deliver the performance criteria needed by the oil well sector. This outstanding property profile is attributable to the saturated polymer backbone in combination with the highly polar and inert acrylonitrile functional group. Starting from NBR, still the workhorse polymer for the oil industry, HINBR has a similar ol resistance as NBR, but with signifi- cantly improved chemical and heat resistance as well as im- proved physical properties over a wide temperature range. ‘Through the hydrogenation process the double bonds of NBR. are eliminated, the typical sites susceptible to chemical and oxidative attack, At the same time, the irregularly placed buta- diene units are transformed into polyethylene sequences, which gives HNBR its ability to reversibly crystallize under strain, resulting in physical properties comparable to natural rubber, Hence, the selective hydrogenation of the double bonds in acrylonitrile-butadiene rubber (NBR) produces a specialty elastomer, hydrogenated acrylonitrile-butadiene rub- ber (HNBR), which may be formulated to produce a material conveying an excellent balance of properties including me- ‘chanical and dynamic, as well as improved resistance to hot air, oils, chemicals and abrasion. ‘Therban is characterized by a combination of properties that _make rubber goods resistant to service conditions found in oil RUBBER WORLDSOO ee Ly renee Hardness, durometer Tensile strength, MPa Elongation al break, % Modulus, MPa Mt Rebound resilience, % Compression set, % Tons /27C, To hrs/150°C Abrasion loss, mm?, DIN 53 516 70D 45 500 2 5 0 50 exploration and production environments Typical vulcanizate properties for HNBR are shown in table 1. Appropriate compounding techniques and selection of the ‘most suitable Therban polymer enable the properties of the ‘vulcanizates to be adapted to specific requirements. HNBR ‘vuleanizates also exhibit good resistance to alkaline solutions and dilute acids. The resistance solution %) at 100°C and to a dilute hydrochloric acid solution ¢ (18%) at 50°C is very good. Generally, the chemical and oxi dative stability improve with ine tion, easing degree of hydrogens: Stability under oilfield conditions Rubber articles for oilfield application must withstand both ‘mechanical wear and chemical attack by drilling mud and other aggressive fluids. Depending on the actual well condi tions, the parts may be exposed to mixtures of oil with acids and amines, as well as hydrogen sulfide, methane and carbon dioxide. In addition, high pressure and temperature conditions ly as the well depth increases, Resistance to hydrogen sulfide and corrosion inhibitors Hydrogen sulfide, which occurs in crude oil and natural gas, wells, is an aggressive media encountered with increasing Ce eee ee ae oy frequency. Other substances found in the service environment that tend to aggressively attack rubber articles include amine corrosion inhibitors, carbon dioxide and acids. For the test results described below, use was made of mix tures consisting of diesel oil, sour gas, water and amine-based corrosion inhibitors NACE A and NACE B. Figure 2 shows that the retention of & HINBR based compound is superior to that of standard F1 NBR and XNBR when aged at 150°C in a mixture con of diesel oil, sour Similarly, good retention of tensile strength for HNBR is observed when the corrosion inhibitors NACE A (figure 3) and NACE B (figure 4) are added to the mixtures. In these ceases, the properties of HNBR remain substantially un- changed, whereas those of FKM, NBR and XNBR suffer si nificant reduction nsile strength. For the compounds based ‘on these polymers, the tensile at break after aging is in the range of 7-8 MPa, representing a loss in tensile in the 50-80% range. On the other hand, the tensile at break for the HNBR based compound is sill in the order of about 18 MPa, repre- senting a loss in tensile of about 30% Cee eae ae cic Re CaN ER no) Tensile strength eee ee ee ee and water (aged 7d @ 150°C) eee CMC E CE Ree | Unaged. ‘= Unaged Tensile strength a ace Tensile strength B %, 20 25) 25 20} 20) 2 15 2 15 = = 10| 10] 5| 0 al Therban— FKM NBR XNBR Therban— FKM NBR _XNBR AUGUST 2007 29Results obtained with the oil soluble NACE B (figure 4) show the same behavior as observed when water-soluble NACE A is used, In the described tests, Therban elastomer was compared with FKM, NBR and XNBR, all of which are known to with- stand heat andéor oil swells, Commercially available elasto- mers were chosen forthe tests. In the case of FKM, a bisphe- nol crosslinked compound was used. ‘To improve properties wherever swelling and aging in ‘crude oil is problem, the use of fully hydrogenated high ACN content HNBR, such as Therban A 4307, is strongly recommended Resistance 1o explosive decompression Rubber articles used in the oil industry are also exposed 0 ‘extremely high pressures. At these extreme pressure cond tions, low molecular weight hydrocarbons, as well as other ‘gases, such as carbon dioxide and hydrogen sulfide, are con- siderably more soluble in the rubber article than is the case at normal pressures. Diffusion of the gases into the article occurs ‘until equilibrium is established, ‘Ata sudden pressure drop, as might result through a sudden ‘change in the operating conditions, the dissolved gases tend to Ce ea ed een ee od CE ee ee es cycle in CO2 on tensile strength oe ate RSR — — — escape rapidly from the rubber, causing intemal destruction of the par. The resistance to this “explosive decompression” is polymer and compound dependent. Figure 5 shows that vulcanizates based on HNBR elastomer are highly resistant to explosive decompression. Dry carbon dioxide at 5.2 MPa (750 psi) was used in the test to evaluate explosive decompression resistance. The carbon dioxide gas ‘was introduced into the pressure vessel containing the test specimens. Exposure time was 24 hours at room temperature, after which the specimens were explosively decompressed by ‘opening an exhaust valve, allowing the pressure to drop from 5.2 MPa to atmospheric pressure in less than 10 seconds. The criteria used to rank the compound performance under these test conditions were resistance to blistering and destruc- tion, as well as retention of physical properties, including tensile strength at break, elongation at break and hardness change, Figure 6 shows the effect of explosive decompression test- ing on tensile strength. The specimens were aged as described (after aging in CO, @ 23°C, 5.2 MPa for 24 hs.) and then ‘were tested one hour after the decompression step. These re- sults showed an even greater differentiation among the poly: ‘mers tested. It is generally recognized that explosive decompression is improved by the following: * The solubility of gases in the polymer is low; (high ACN content is recommended): + the polymer should have high impermeabilty 10 gases, (= high filler loading): + the physical properties are as high as possible (+ high tear resistance, tensile strength). For most elastomers, permeability and solubility can be adjusted by means of compounding techniques. Highly filled ‘compounds lead to better results in explosive decompression tests than lightly filled compounds Advanced technology Therban AT In order to meet performance requirements, compounds for ‘many oilfield applications are formulated to high durometer using high levels of fillers. The need for high filler levels often results in high compound viscosities, which are contrary 10 good processing requirementy/nceds. Typically, these prob- lems are overcome by the introduction of plasticizers and process aids; however, these additives are often detrimental 10 product performance, since plasticizers can be extracted and exchanged by media, and they influence permeation and solu- Pee CRC mun nr Product range - typical properties ACN (%6) ML 144 at 100°C RDB (%) 21 39. 0g 34 39 <09 34 39 49 39 30 <09 43, 39 <09 43 39 55 RUBBER WORLDbility of gases, The most recent breakthrough in HNBR technology has been the development of a new class of low viscosity HNBR products by Lanxess, now available commercially AT. Previously, ultra low viscosity HNBR polymers were impossible to manufacture because of limitations in the avail able viscosity for NBR feedstocks. Compared with com tional HNBR products having a raw polymer Mooney viscos- ity in the nominal range of 65, these new Therban AT products \ypical raw polyn of 39. They are available in a wide range of ACN and residual double bond (RDB) lev- els, as shown in table 2. These products have clearly demon- vantages over regular viscosity HNBR Therban strated the followin, grades: + Low molecular weight (low viscosity) provides improved processability, including faster mixing (shorter black incorpo- ration times); significantly better flow and faster mold fillin (shorter cycle times); improved extrusion rates and extrudates having smoother surfaces and sharper ed + Narrower molecular weight distribution helps to maintain excellent physical strength properties, despite a drop in mo- Tecular weight Dee ue ‘Typical viscosity and shear rate processing windows Viscosity (KPa 8) ‘Standard HNBR > HINBR produced using advanced technology provides the broadest processing flexibility Figure 8 - polymer and compound Rema ‘Mooney viscosity (ML 144 at 100°C) HINBR AT ill /Slandard HNBR o> 120 102 100 80 70 ca 60 4o| _39 20 0 Polymer ‘Compound POR Rena Cone erased Therban AT NBR 40 phr N30. SOphr NSO. 40phr NGO Mooney viscosity 57 © 101 (ML 1-4, 100°C) 1M-100 (MPa) 58 75 Tensie strong (MPa) 26.6. Utimaie elongation (5) 273 Hardness (duro A) 64 © + Elimination or reduction of plasticizer is possible to im- properties and prove heat aging, compression set, ph adhesion, + Processability ean be maintained at higher filler loadings, thereby enabling an extended hardness range and providit cost savings potential through higher compound extension. The advantages in processing properties for Therban AT are illustrated in figure 7. Compared with standard HNBR, Ther- ban AT shows lower viscosity levels through the entire range of shear rates typically encountered in rubber processing. Figure 8 compares a standard HNBR with Therban AT both containing 34% AC (0.9% RDB. Therban AT has a significantly lower raw polymer viscosity compared with stan- dard HNBR. This translates to a significantly lower compound viscosity as well Comparison of vulcanizate properties for Therban AT A study was conducted to compare various compound and vulcanizate properties for standard HNBR and Therban AT Both polymers contain 34% ACN, 0.9% RDB. The results, shown in table 3 and figure 9 demonstrate that, at a consta loading of N-330 carbon black, Therban AT provides a dra- ‘matic reduction in compout Modulus, hard and compression set of Therban AT can be easily adjusted by ‘a minor variation in either filler loading or peroxide level 10 ere Oa Cg Effect of peroxide dosage on compression set, a 70 hrs. @ 150°C 2 6 AUGUST 2007 31reach the same or e performances than standard HINBR without losing the The key bei 1g new Therban AT are rized in figure 10. Therban AT can be oilfield applications. A list of potential applications and bene- fits is summarized in figure 11 lized in n Carboxslated technology Therban XT Hydrogenated carboxylated acrylonitrle-butadiene (HXNBR) provides. vuleanizates possessing outstanding mech properties (tensile, elongation and tear) combined with excel lent property retention at high temperatures. In addition, the vvuleanizates exhibit excellent abrasion resistance and adhesive well as improved hot air aging resi carboxylated nitrile. In severe oilfield environments, HXNBR fed for numerous applications, including dril bit seals, ram packers, pipe wipers and seals requiring enhanced ‘metal adhesion, Lanxess produces a commercial HXNBR polymer identi- fied as Therban XT VP KA 8889. It contains 34% acrylonitrile (ACN), 5% carboxylic acid groups and 3.5% residual double bond (RDB) content. The structure of HXNBR js illustrated in figure 12. Cree OP Uae Ld ‘Summary of benefits of advanced technology HNBR Narrow molecular weight distribution combined with Iow viscosity = Retention of excollent physical properties with improved [processing properties Improved mixing, bette flow, faster mod filing, shorter cycle times. ~ Cost reduction, lower injocton/extrusion pressure Reduction or eiminaton of plastcizor resstance Rd es or Applications Benefits Seals ‘= Rotontion force Gaskets = Harcness Oxings = Surface qualty Hoses + Flame resistance BPs, Loading, ED resistance Cables Volume tow Stators Cycle times Packers Weta adhesion Sinica shapes It viscosity is a problem use Advanced Technology HNBR alone or in combination with standard HNBR 10 ‘selectively customize the properties of your compound. 32 Hydrogenation of carboxylated nitrile (XNBR) to produce HXNBR achieves the following vul + Mechanical properties (tensile strength and elongation) °C to elevated temperatures (170°C); ar resistance from 23°C to 170°C: + Pico abrasion resistance + adhesive str and + hot air oxidation resistance. HXNBR can be formulated alone or in blends with HNBR to target ranges within this set of outstanding properties. izate improvements from h 10 substrates such as nylon at 125°C: Resistance to abrasion Resistance to mechanical wear is another basic requirement for elastomer parts used in the oil industry. HNBR is recognized to be superior to most other elastomers. It is capable of providing long term service at high temperatures up to 165°C and short term service up to 185°C. If severe wear is the main reason for ailure of parts, the use of Therban XT, a new HNBR grade 12 5% carboxyl groups, is recommended, To further boost physical properties, Therban XT can be ‘combined with zine diacrylate (ZDA). Blends containing ZDA (available under the brand Therban ART) can achieve a Ce eC ee ae cen) Oat eae srg Re ey eae aL! Bric o rea 210 Tear: DeB @ 150°C Tear strength DieB @ 25°C Scorch iS @ 125°C ico abvasive index RUBBER WORLD‘unique combination of physical properties, including tensile strengths of 40 MPa, 200% elongation at break, DIN abrasion ‘values < 50 mm? and durometer A hardness of 85-95, Figure 13 compares some basic physical properties that can be achieved using standard HNBR, Therban XT and Therban XT in combination with ZDA. Therban XT provides high hardness and modulus, high tear resistance and high abrasion resistance. This combination of properties is useful in various field applications, including dril bit seals, ram packers, and pipe wipers. Resistance to cilfield fluids thas been shown that Therban XT can provide a unique combination of vuleanizate properties for oilfield compo- nents; however, it is also important to consider the perfor- ‘mance of HXNBR in various aqueous fluids. For example, it is generally recognized that XNBR, due to its carboxyl func- tionality, exhibits higher water swell than NBR. A study was conducted to assess the swelling characteristics of Therban XT compared with other typical oilfield polymers, The other poly: ‘mers included standard NBR, low-water-swell NBR, standard HNBR and FKM. In addition, Therban XTT was evaluated in ‘various blend ratios with standard HNBR and also in a blend ‘with Therban ART. For this study, both carbon black and sili- ca fillers were evaluated. The formulations used for the design study are shown in table 4, Stress-strain properties were assessed for each of the com- pounds. Results are shown in figure 14. All compounds were designed to achieve a similar hardness range. All of the NBR and HNBR formulas show very high tensile strengths (2 20 MPa) compared to the FKM formula (12 MPa). All vuleanizates. were NBR LWS 100 65 35 0 100 100 &5X1/ FRM immered io aliiiied WS 1 OE and cal ool BY waar 10°C frei ait ser Basar ovr HS) At 70 168 and 504 hows Koynae 39460 100 he values for volume rome Ra 100 sellin dled water ae Shown infigue 15, Alf Thean XT ms % the HNBR and HXNBR A ee ee Voleamuates how yey Treman aa o fo volume changes They VP KA 8796 provide water swell values Oyneon FKM a) that are equivalent to, or FC2123, * ‘ ais me beter ha te NBR va eae Canzate Te fone Naogare 4s is 5 15 8 sts as caer shows artery wee ES : Do water sal The FRAT Ne80 = vulcanizate shows very NS a go | heh rum change ater me 508 si sists 8 ‘A casts were — 2 immersed in a solution of, ben 2% calcium chloride and fomeen it, 08 08 05) (asi (a5) 05 5 ised voter simul for 0 0 0 0 © 0 w brine environments et Sieecd 050s comer in lil sp Vantre VAM 125 125 125 125 125 125 125 plications. The vuleani- barr BR '2 2 RRR plains, The. vlc ‘Struktol ZP 1014 6 6 6 6 6 6 6 8 Siuklzr ore torpedo 70 1a a SO tous The ves for spitorsutr 0404 Volume sel ia eli Vulcup 40KE 9 9 3 9 9 9 9 chloride are shown in fig- Vunact 22 tre 16, Al ofthe HNBR ee a tnd HRNBIE leans Chae) Sh tow volume chang, case 6 | cxcinmortlts standard ee _and low-water-swell NBR. ee g | The TRO vkanzte Tolal (Ph) 1709 1709 18575 18575 18575 10575 16575 18575 17575 199 | shows particularly high Specific gravity 1.193 1.193 1.177 1.174 1.171 1.169 121 121 1.135 swell after aging 504 Holpoomrohou 12306 | hous i ace cre AUGUST 2007