Astm stp 1335 1999

STP 1335 Engine Coolant Testing: Fourth Volume Roy E Beal, editor ASTM Stock #: STP1335 ASTM 100 Barr Harbor Drive West Conshoshocken, PA 19428-2959 Printed in the U.S.A Copyright by ASTM Int'l (all rights reserved); Sat Dec 26 13:32:57 EST 2015 Downloaded/printed by University of Washington (University of Washington) pursuant to License Agreement No further reproductions ISBN: 0-8031-2610-7 ISSN: 1050-7523 Copyright 1999 AMERICAN SOCIETY FOR TESTING AND MATERIALS, West Conshohocken, PA All rights reserved This material may not be reproduced or copied, in whole or in part, in any printed, mechanical, electronic, film, or other distribution and storage media, without the written consent of the publisher Photocopy Rights Authorization to photocopy items for internal, personal, or educational classroom use, or the internal, personal, or educational classroom use of specific clients, is granted by the American Society for Testing and Materials (ASTM) provided that the appropriate fee is paid to the Copyright Clearance Center, 222 Rosewood Drive, Danvers, MA 01923; Tel: 508-750-8400; online: http:// www.copyright.com/ Peer Review Policy Each paper published in this volume was evaluated by two peer reviewers and the editor The authors addressed all of the reviewers' comments to the satisfaction of both the technical editor(s) and the ASTM Committee on Publications The quality of the papers in this publication reflects not only the obvious efforts of the authors and the technical editor(s), but also the work of the peer reviewers In keeping with long standing publication practices, ASTM maintains the anonymity of the peer reviewers The ASTM Committee on Publications acknowledges with appreciation their dedication and their contribution of time and effort on behalf of ASTM Printed in Philadelphia,PA May 1999 Copyright by ASTM Int'l (all rights reserved); Sat Dec 26 13:32:57 EST 2015 Downloaded/printed by University of Washington (University of Washington) pursuant to License Agreement No further reproductions authorized Foreword The Symposium on Engine Coolant Testing was held 5-7 November 1997 in Scottsdale, Arizona Committee D15 on Engine Coolants sponsored the symposium Roy E Beal, Amalgamated Technologies, Inc., presided as symposium chairman and is editor of this publication Copyright by ASTM Int'l (all rights reserved); Sat Dec 26 13:32:57 EST 2015 Downloaded/printed by University of Washington (University of Washington) pursuant to License Agreement No further reproductions authorized Contents Overview ORGANIC ACID INHIBITOR TECHNOLOGY Testing of Organic Acids in Engine Coolants T w WEIR Incipient Passivating Layers on Heat-Rejecting Aluminum in Carboxylate- and Silicate-Inhibited Coolants: Correlation with A S T M Composition of D 4340 W e i g h t L o s s e s - - F T WAGNER, T E MOYLAN, S J SIMKO, AND M C MILITELLO 23 Fleet Test Evaluation of Fully Formulated Heavy-Duty Coolant Technology Maintained with a Delayed-Release Filter Compared with Coolant Inhibited with a Nitrited Organic Acid Technology: An Interim Report s s AROYAN 43 AND E R EATON Engine Coolant Technology, Performance, and Life f o r Light-Duty Applications-D E TURCOTTE, F E LOCKWOOD, K K PFITZNER, L L MESZAROS, AND 52 J K LISTEBARGER Copper-Triazole Interaction and Coolant Inhibitor Depletion L s BARTLEY, P O FRITZ, R J PELLET, S A TAYLOR, AND P VAN DE VEN 76 TEST METHODS Corrosion and Testing of Engine C o o l a n t s - - R E BEAL Predictive T o o l s f o r Coolant Development: An Accelerated Aging Procedure f o r Modeling Fleet Test R e s u l t s - - A v GERSHUN AND W C MERCER 89 113 Rapid Electrochemical Screening of Engine Coolants Correlation o f Electrochemical Potentiometric Measurements with ASTM D 1384 Glassware C o r r o s i o n T e s t - - o P DOUCET, J M JACKSON, O A KRIEGEL, D K PASSWATER, AND N E PRIETO 133 Long-Term Serviceability of Elastomers in Modern Engine Coolants H BUSSEM, A C FARINELLA, AND D L HERTZ, JR 142 Copyright by ASTM Int'l (all rights reserved); Sat Dec 26 13:32:57 EST 2015 Downloaded/printed by University of Washington (University of Washington) pursuant to License Agreement No further reproductions a vi CONTENTS E n g i n e Coolant Compatibility with the N o n m e t a l s F o u n d in Automotive Cooling S y s t e m s - - J P GREANEY AND R A SMITH 168 Influence of E n g i n e Coolant Composition o n the Electrochemical D e g r a d a t i o n B e h a v i o r of E P D M R a d i a t o r Hoses G L M VROOMEN, S S LIEVENS, 183 AND J P MAES H E A V Y - D U T Y COOLANT TECHNOLOGY Assessment of the Validity of Conductivity as a n E s t i m a t e of Total Dissolved Solids in Heavy-Duty C o o l a n t s - - R P CARR 199 Scale a n d Deposits in H i g h - H e a t Rejection Engines Y.-S CHEN, E I KERSHISNIK, R, D HUDGENS, C L CORBEELS, AND R L ZEHR 210 ENGINE COOLANT RECYCLING TECHNOLOGY Overview of Used Antifreeze and Industrial Glycol Recycling by Vacuum Distillation-D K FRYE, K CHAN, AND C POURHASSANIAN 231 Recycling Used E n g i n e C o o l a n t Using H i g h - V o l u m e Stationary, M u l t i p l e Technology E q u i p m e n t - - M E HADDOCK AND E R EATON 251 D e v e l o p m e n t of Mobile, On-Site E n g i n e Coolant Recycling Utilizing ReverseOsmosis T e c h n o l o g y - - w KUGHN AND E R EATON 261 Heavy-Duty Fleet Test E v a l u a t i o n of Recycled E n g i n e C o o l a n t - - P M WOYCIESJES 270 AND R A FROST Evaluation of Engine Coolant Recycling Processes: Part - - w H BRADLEY 292 ENGINE COOLANT CHARACTERISTICS AND QUALITY M e t h o d s a n d E q u i p m e n t for E n g i n e C o o l a n t T e s t i n g - - s A McCRACKEN AND 319 R E BEAL Silicate Stabilization Studies in P r o p y l e n e G l y c o l - - s A SCHWARTZ 327 Antifreeze: F r o m Glycol to a Bottle o n t h e S h e l f - - M a n u f a c t u r i n g a n d Quality C o n t r o l C o n s i d e r a t i o n s - - j STARKEY AND M COUCH 352 ENGINE COOLANT SERVICE AND DISPOSAL E x t e n d e d Service of " F u l l y F o r m u l a t e d " Heavy-Duty Antifreeze in A m e r i c a n C a r s - - E R EATON AND H S EATON 361 Fleet Test E v a l u a t i o n s of a n A u t o m o t i v e a n d M e d i u m - D u t y T r u c k C o o l a n t Filter/ C o n d i t i o n e r - - A B WRIGHT 370 Copyright by ASTM Int'l (all rights reserved); Sat Dec 26 13:32:57 EST 2015 Downloaded/printed by University of Washington (University of Washington) pursuant to License Agreement No further reproductions au CONTENTS Overview of Engine Coolant Testing in Europe with Particular Regard to Its Development in Germany M B BROSEL Development of an Extended-Service Coolant Filter w A MITCHELLAND R HUDGENS vii 392 D 409 Author Index 427 Subject Index 429 Copyright by ASTM Int'l (all rights reserved); Sat Dec 26 13:32:57 EST 2015 Downloaded/printed by University of Washington (University of Washington) pursuant to License Agreement No further reproductions autho STP1335-EB/May 1999 Overview The Fourth Symposium on Engine Coolants demonstrated many advances and changes in the technology of coolants and their testing procedures A gradual globalization of coolant formulation is occurring in parallel with the world production of specific vehicles that meet the demands of several disparate markets There are still important differences in the direction of technology in the United States, Europe, Japan, and the rest of the world There is now a more widespread acceptance that usefully constructed coolants should be used in any location New engine designs demand coolant fluid discipline Organic acid basic inhibitor technology is the growth area with continued interest in propylene glycol as a substitute for the more commonly used ethylene glycol The new work is in extended life coolants Major vehicle manufacturers are now recommending 10 years or in some instances life of vehicle coolants These factors will slow the total volume of coolant required somewhat, but the total world vehicle population is increasing at the same time There is continued interest in the development, management, and quality control of the modern engine for both OEM and after-market, which is the main purpose of ASTM D15 Committee as the standards body responsible for guiding a consensus towards agreed levels of technical competence to serve an increasingly sophisticated vehicle market The first symposium was held in Atlanta, Georgia, in 1979, and papers presented were published in STP 705, which is still a practical, as well as historical volume Rapid changes in material usage with more aluminum radiators and cylinder heads required inhibitor package modifications and new tests, covered in the second ASTM Engine Coolant Testing conference in 1984 A hot surface protection standard had been developed and propylene glycol was introduced Electrochemistry was highlighted and heavy duty vehicles received attention Presented papers were published in STP 887 A third ASTM Engine Coolant Symposium followed in 1991 which was truly international in character with presentations from Europe, Japan, and the United States Organic acid based inhibitors were introduced, work on sebacic acids, and typical alkaline phosphate silicate formulas prevalent at the time in the United States were covered Cavitation of diesel engine liners and protection, pump seal evaluations, and recycling of coolant were other major areas presented Papers can be found in STP 1192, the third volume in the Engine Coolant Testing Series A look at all three volumes as a compendium reveals an excellent collection of technology in the field and together with this fourth book, makes the most comprehensive review of the engine coolant world past and present with a brief look at its possible future The symposium opened with papers on organic acid inhibitor technology lead by Tom Weir who covered testing of organic acids by examination of the effectiveness of thirty organic acids using electrochemistry, glassware, and galvanic methods In general, aliphatic monoacids provide good aluminum alloy protection, but are antagonistic to solders Aromatic monoacids can be good on steels and cast iron Longer chain acids tend to provide better protection Several organic acids with good overall performance were identified The composition of incipient passivating layers on heat rejecting aluminum in carboxylate and silicate inhibited coolants was the title of the Wagner et al paper, where correlation with ASTM D 4340 weight losses was reported X-ray photoelectron spectroscopy identified the compositional differences between the coolants on 319 aluminum alloy surfaces under heat Copyright by ASTM Int'l (all rights reserved); Sat Dec 26 13:32:57 EST 2015 Downloaded/printed byASTM International Copyright9 1999 by www.astm.org University of Washington (University of Washington) pursuant to License Agreement No further reproductions authorized ENGINECOOLANTTESTING: FOURTH VOLUME rejecting conditions Silica was the primary layer in silicated coolants with hydrated alumina formed in the organic acid coolant family The role of the carboxylate inhibitors is suggested as a promoter of highly protective forms of hydrated alumina on converted metal surfaces, where the silica layer is purely exogenous Mixtures of the two coolants produced increased corrosion and less protection, especially at lower 25% glycol levels, where low levels of cross contamination produced significant loss of protection Clearly, contamination is to be avoided until a protective layer is created on the surface of the components involved with either the silicated or carboxylic inhibited packages Fleet test evaluations of fully formulated coolants for heavy duty application were compared with a standard supplemental coolant additives (SCA) filter charge program Ethylene glycol based coolant with phosphate-silicate, nitrited carboxylic acid technology and a phosphate-free low silicate formula in propylene glycol were investigated by Aroyan and Eaton Results demonstrated that a nitrited carboxylic acid inhibited coolant was similar in performance to the more conventional coolant inhibitor approach in both ethylene and propylene glycol bases All technologies were providing acceptable protection in a 66 fleet test program The overall performance of conventional coolant inhibitor technology compared to the newer organic acid technology has not been previously reported and was investigated by D E Turcotte et al The depleting nature of silicates during service has led to a conservative coolant change recommendation of 30 000 to 50 000 miles (48 279 to 80 465 km) in automobiles Laboratory bench, engine dynamometer, and vehicle service studies were made with the two inhibitor families A new electrochemical test was introduced to examine passivation kinetics on aluminum alloy surfaces Results show that silicate coolants act more quickly and passivate aluminum surface faster than the organic acid coolant Dynamic erosion/corrosion tests tend to favor silicate technology Both silicate and organic acid coolants provide equally long service life when adequately formulated The main advantage of organic acid technology appears to be meeting chemical limitations imposed by some global coolant specifications Bartley et al studied the depletion of tolyltriazole in testing and in service, in extended life coolant using organic acid coolant technology Electrochemical polarization experiments indicate that the tolyltriazole forms a surface layer on copper alloys that is very protective Laboratory tests and radiators retrieved from field tests demonstrate the effectiveness of the tolyltriazole inhibitor in conjunction with organic acid inhibitor packages Simulated rapid coolant aging was achieved by adding finely divided powders of aluminum, iron and copper to the coolants exposed in glassware at about 105~ in air under atmospheric pressure Results from analyses of periodically withdrawn samples correlated well with service experience Good copper protection is achieved with tolyltriazole depletion matching laboratory and field observations The wide range of metals used in vehicle engine and cooling circuits requires careful consideration of the chemical complex that forms an inhibitor package Beal reviewed corrosion aspects of the metals involved, preferred protection processes, and likely contaminants in water that reduce coolant effectiveness Information was gathered from the general corrosion literature as it pertains to coolant, and some of the current standards for testing were discussed The desire for longer life engine coolants emphasizes the need for newer test methods to simulate these requirements and provide needed protection Predictive tools for coolant development enhance experimental studies Gershun and Mercer have defined an accelerated aging procedure for modeling fleet test results The program objective was to predict coolant composition effects after 100 000 miles (160 930 km) or more Cooling system metals used, their respective surface areas and coolant conditions were utilized Degradation products, inhibitor depletion, reduction in pH and the presence of corrosion products in solution were monitored Test coolants were evaluated by ASTM D 1384 glassware and ASTM D 4340 hot surface tests The test procedure developed produces coolant that Copyright by ASTM Int'l (all rights reserved); Sat Dec 26 13:32:57 EST 2015 Downloaded/printed by University of Washington (University of Washington) pursuant to License Agreement No further reproductions authoriz OVERVIEW compares favorably in composition, physical properties and performance with fleet test fluid A rapid evaluation of the effectiveness of a coolant inhibitor package after 100 000 miles (160 930 km) can be performed using the procedure and is useful in the selection of competing formulas Rapid electrochemical screening and correlation with ASTM D 1384 glassware tests was reported by Doucet et al The objective was to identify promising coolants more quickly, to accelerate testing and reduce coolant evaluation time and cost Some success was claimed with a triad galvanic corrosion rate test providing the best correlation Other tests were promising, but further work is needed Elastomers are very important, since most cooling systems involve several hoses under the hood However, there are presently no standard ASTM elastomer evaluation procedures for coolant compatibilities A session devoted to this subject was well received Long-term service of elastomers was studied by Bussem et al Aging effects occur that influence physical and chemical properties over a long time period The authors identified FEPM materials as the elastomer of choice at present for engine coolant application Greaney and Smith used high temperature, short time immersion testing to determine the usefulness of a variety of elastomers and plastics in coolant, covering hoses, radiator tanks, and water pump seals All of the materials tested showed some degradation after exposure to diluted or concentrated coolants with both ethylene and propylene glycol bases Currently used inhibitor packages covered conventional, hybrid and organic acid technologies, which all similarly influenced the chosen elastomers Evaluations included immersion tests, overflow bottle effects, post fluid analyses, tensile properties, and physical values Degradation of EPDM hoses by electrochemical attack was studied by Vroomen et al covering the influences of engine coolant composition or behavior in service conditions EPDM has been used for over 25 years, and a service problem was identified with cracking failure in hoses Investigation had primarily explored factors involved except for the coolant Using a laboratory test with a stainless steel holder and specimens under mechanical strain, an electrical current is forced through the essentially insulating material by having the specimen serve as the anode, and the holder is the cathode Sulfur cured hoses are more susceptible than peroxide cured hoses to the cracking phenomenon Collectively, these papers provide a direction to understanding the needs of a test protocol for nonmetallic materials and their response in coolants Heavy-duty coolants for diesel and larger trucks have particular operating requirements Cart assessed the validity of conductivity measurement to estimate total dissolved solids and determined that it gives satisfactory data with controlled dilution Chen and Kershisnik looked at scale deposits in high heat rejection conditions Key parameters were evaluated and a quantitative relationship of scale formation, water hardness, and heat flux was observed Water soluble polymers prevent scale deposits Glassware hard-water compatibility tests not predict scale or deposit formation results demonstrated by the new test procedure An extended service coolant filter development was covered by Mitchell and Hudgens, depending upon time release concepts that worked actively up to 140 000 miles (225 302 km) Engine coolant recycling has not become as pervasive as earlier thought possible, but the industry is still growing Large-scale recovery by distillation was reviewed by Frye et al., claiming that 15 million gal (57 million L) per year are recovered this way Industry practices are presented with confirmation that ASTM specification engine coolants can be reliably produced by recycling Reverse osmosis has proved itself as a suitable technology applied to engine coolant recycling Haddock and Eaton explain the process and their experience The technique is used in both stationary large plants and for mobile application as described by Kughn and Eaton using similar process equipment A multistage chemical recycling process is described by Woyciesjes and Frost with extensive fleet testing to prove the method Excellent protection Copyright by ASTM Int'l (all rights reserved); Sat Dec 26 13:32:57 EST 2015 Downloaded/printed by University of Washington (University of Washington) pursuant to License Agreement No further reproductions a MITCHELL AND HUDGENS ON SERVICE COOLANT FILTER 417 Initial Evaluation with Beaker Tests and Simulated Service Tests Beaker Evaluations Initial coatings were evaluated using simple beaker tests Ten coated tablets (about 10 to 11 g total weight) were added to 700 mL of 50/50 coolant concentrate/water The solution was heated to 230~ (110~ and tablets were observed thereafter Coolant samples were also taken in order to track release rates Figure shows nitrite release data for SCA coated with three different polymers and for the noncoated SCA Nitrite release is rapid for the noncoated SCA and for polymer-coated WRC No 6, with essentially all of the nitrite in solution for the first sample taken The fact that WRC No and WRC No show delayed release of nitrite confirms that it is possible to slow down the release of active chemistries into the engine coolant by a polymer barrier With the proper polymer barrier, release has been extended, in this case to at least two weeks Simulated Service Rig Evaluations To get a better picture of release for a polymer harrier coating, the barrier coating must be evaluated in a dynamic environment The simulated service rig (per ASTM Test Method for Simulated Service Corrosion Testing of Engine Coolants (D 2570-96)) provides an opportunity for this Two rigs were used for these evaluations One rig is essentially unmodified The other had previously been modified to use a Mack Truck radiator; this increases rig volume to about 10 gal (38 L) Both rigs were then modified to run a Va-in (0.635 cm) line of tubing to a filter 2500 lip 2000 p W W lal p p p p NP mm | m mm m* |* -f -/ 1500 y f I m m* m ommp~)~ ) i I ) ,/ 1000 5O0 [ - - - i,~c#1 |.c l I I I L vwc#7 i i t i i 14 Day FIG Beaker evaluations: nitrite release versus time Copyright by ASTM Int'l (all rights reserved); Sat Dec 26 13:32:57 EST 2015 Downloaded/printed by University of Washington (University of Washington) pursuant to License Agreement No further reproductions authorized 418 ENGINE COOLANT TESTING: FOURTH VOLUME TABLE Method for simulated service rig evaluation of slow-release SCA Modify rig to accommodate a filter adapter Place a premeasured amount of slow-release SCA tablets into an empty filter canister and install on rig, or alternately use a production filter with slow-release SCA Fill rig with the appropriate volumes of antifreeze concentrate and deionized water to achieve 30, 50, or 70% glycol concentrations Turn on rig Allow to circulate 10 and pull initial coolant sample Set temperature control (190, 150, or 204~ (88, 65, or 95~ Adjust flow through the filter to a rate of about gpm (3.7 L/min) Set automatic timers to shut rig off for two, h intervals per week Pull to oz (113 to 226 g) coolant samples at appropriate intervals (usually weekly) adapter and then to the top of the radiator Flow was adjusted to a rate of about 1.5 gpm (5.6 L/min) through the filter adapter (and filter) The method for running this test is described in Table Table and Fig show simulated service results for WRC No (tablets coated with a polyvinyl chloride polymer) Results show gradual release of SCA for the 20-day duration of the test This translates to about 24 000 miles (38 623 km) of service (50 mph (80 km/h) X 20 days • 24 h or about 24 000 miles (38 623 km) of service) Analysis of coolant samples showed chloride levels increased during the 20-day simulated service test It is speculated that the high-temperature conditions of the coolant caused the vinylidene chloride polymer to unzip, releasing small amounts of hydrogen chloride This increase in chloride levels and acidity made the polymer used for WRC No unacceptable Because of the failure of vinylidene chloride polymers to remain stable, WRC No 6, a terpolymer based on vinylacetate, was evaluated Even though WRC No showed no delayed release in beaker tests, simulated service rig results showed a different story Table and Fig show the gradual release of SCA over the 43-day duration of the run (equivalent to about 52 000 miles (83 684 km)) This appeared to be a significant step toward a new slow release product Regarding the performance of the WRC No polymer, tablet shells were examined during the stimulated service run The tablets soften, forming a honeycomb-like mass of material (Fig 10) The SCA must pass through as many as 30 to 40 layers of coating in order to enter the coolant Applications Profile In order to more fully understand performance of the WRC No polymer coating, simulated service tests were run to evaluate the effects of glycol concentration, temperature and propylene glycol versus ethylene glycol on delayed release performance In order to compare product TABLE 2~Simulated service rig: slow-release profile for WRC No polymer-coated SCA Day Boron as B* Nitrite as NO2 Nitrate as NO3 Molybdenum as Mo Chloride as C1 13 20 1.8 4.3 24 33 760 810 1100 1100 430 450 680 690 232 243 334 363 10 15 50 60 *All amounts in parts per million Copyright by ASTM Int'l (all rights reserved); Sat Dec 26 13:32:57 EST 2015 Downloaded/printed by University of Washington (University of Washington) pursuant to License Agreement No further reproductions authorized 419 MITCHELL AND HUDGENS ON SERVICE COOLANT FILTER 1200 - - Boronas B Nitrate as NO3 1000 J ~ Nitrite as NO2 " Molybdenum~ Mo " J 800 P P M mmmmm 600 I I m~m m~mm mmmm ~mmm I mmml 400 • m U I Ill J i1w m m m m m m m I~ IIm m 200 ~ "~i 13 20 DAY FIG Simulated service rig: WRC No inhibitor release versus time release, an average release rate was calculated for each simulated service run, using data for nitrite, nitrate, molybdate and boron Average release rates are compared Ethylene Glycol Concentration Figure 11 examines release of the W R C No polymer versus ethylene glycol concentration, varying glycol from 30 to 70% Results for the three-week tests indicate the slowest release occurs for 50% ethylene glycol In the short-term tests, the release rate in 30% glycol is nearly double the rate in 50% glycol TABLE Simulated service rig: slow-release profile for WRC No polymer-coated SCA Day Boron as B* Nitrite as NO2 Nitrate as NO3 Molybdenum as Mo Chloride as C1 14 20 22 29 43 1.8 7.6 N/A 16 18 19 24 32 730 740 800 870 920 940 1000 1100 1260 440 470 490 500 530 590 650 690 818 245 245 266 N/A 323 282 279 333 262