CONVENTIONAL ENGINE COOLANTS

Introduction The modern anti-freeze engine coolant is a product of long research work and field experience . The development of engine coolant is a continuing activity in which contributions are being made by engine / vehicle builders, coolant manufacturers and research institutions . As a result newer product specifications and evaluation techniques emerge from time to time . The interests of industry , government and citizens with respect to product quality , conservation , environmental pollution and toxicity ( safety in handling ) play leading role in the activity. An engine coolant has to perform the following functions :

Effective removal of heat from internal combustion engines Prevention of freezing in winter and boil-over in summer Corrosion protection to the cooling system components Prevention of radiator clogging and leakage

The essential properties required in an all - season engine coolant are :

Low freezing point High boiling point Corrosion inhibition on system metals Absence of scale / deposit formation Compatibility with hoses , gaskets etc. Absence of foaming tendency Long service life

Evolution of Engine Coolant Water was the early choice for engine coolant because of its ready availability and good heat transfer properties. However the use of water posed limitations due to its relatively higher freezing point and lower boiling point , inherent corrosive nature and tendency to form scales . When water freezes, there occurs a volume increase of about 9% and this is sufficient to rupture a radiator or even an engine block . Hence freezing protection is a critical property required in the engine coolant. As a result alcohols such as methanol and ethanol came into use as engine coolants in early part of this century . These had very low freezing points

but their boiling points were below 100 C . At present the use of alcohol-based coolants is very limited. The development of ethylene glycol(EG) based antifreeze engine coolant began in the 1930s . Various difficulties were encountered in the early days with the use of such coolants in automotive systems but the industry recognized the merits in the use of ethylene glycol which became available as a large volume commodity chemical . Mixtures of EG and water offered the advantages of lower freezing points and higher boiling points than water . The development efforts continued and by the early 1960s inhibited EG coolants became the primary factory-fill coolant for US car builders. During the course of 1970s and 1980s the performance requirements of antifreeze engine coolant became more severe with the induction of more efficient IC engines operating at higher temperatures and the use of light metals (mainly aluminium in engines and radiators) and plastics in the cooling system. The radiator manufacturing has also undergone various changes in the metallurgys used . The coolant technology has also grown with the changes in the material and design of engine cooling system and the resultants needs are met by mostly glycol - based multi-component formulations with balanced additive systems. Base Materials for Engine Coolants As mentioned earlier ethylene glycol (EG) is the base fluid of choice for engine coolants . In certain applications and in some countries propylene (PG) based coolants find use to a certain extent . The preference is due much lower toxicity of PG and a superior performance demonstrated in temperature environment in cooling systems ; however, cost remains a deterrent in the wider use of PG in engine coolants. current glycol to the higher major

A comparison of the significant properties of EG vis--vis PG , methanol and water is presented in the following table : Characteristic Boiling Point C Freezing Point C Pure 50% Aq. Soln. Sp. Gravity 20/20 C Sp. Heat cal/g.C Vapor Pr. @ 20 C mm Hg Flash Point (COC) Deg C Viscosity CP @ 20 C @ 40 C @ 100 C EG 197 (-)13 (-)36 1.116 0.574 0.12 116 20.9 9.1 1.8 PG 187 Supercools (-)33 1.038 0.600 0.18 107 60.5 19.3 2.6 Methanol 64.5 (-)97 (-)45 0.792 0.600 96.1 16 0.6 0.46 xx Water 100 0 xx 1.000 0.998 17.5 xx 1.0 0.65 xx

As a whole the choice of EG based is a compromise between freeze protection required and heat exchange capacity . Water is a better heat exchanger fluid than any mixture of EG and water . On the other hand adding water to EG or vice versa leads to a depression in freezing point. A 68 % vol. solution of EG in water has the lowest freezing point of about (-) 69 deg C ; solutions with higher or lower EG have higher freezing points. Inhibitor Systems Engine coolants are now invariably blended by incorporating corrosion inhibitor additives in the base fluid and may also include an antifoam compound and a dye for identification. Several inhibitors are required to be added to impart corrosion protection to the ferrous and nonferrous alloys present in the cooling circuits . The corrosion inhibitors widely used so far in engine coolants include the following classes of chemicals : Benzoate Nitrate Phosphate Adipate Triethanolamine (TEA) Borate Nitrite Molybdate Sebacate Benzotriazole (BTZ) Carbonate Silicate Mercaptobenzothiazol (MBT) Ethylhexanoate Tolyltriazol (TTZ)

Traditionally the inhibitor types adopted in engine coolants in the three automobile producing areas viz. N. America , Europe and Far East (Mainly Japan ) have varied to a good extent . Early coolants in Europe were based on the use of a combination of TEA , Phosphoric acid and sodium MBT . At present most European coolants are based on a borate - benzoate combination containing varying quantities of nitrite , nitrate , silicate and triazoles . In recent times the carboxylate type inhibitors are also finding increasing usage. In the United States most engine coolants have been base on the use of phosphate and / or borate in combination with nitrate , silicate and triazoles . The Japanese adopted the TEA - Phosphate based coolants earlier but changed gradually to other inhibitor systems . Currently the Japanese OEMs generally use of coolants that do not contain amine , borate and silicate. Over the years some adverse properties of the used inhibitors and their combinations have come into light. For example , NaMBT was found to cause precipitation due to temperature effect and formation of calcium salt in hard water . Hence it is now widely replaced by BTZ or TTZ . Borate tends to cause corrosion of aluminium alloys at high temperatures and phosphates get quickly precipitated in hard water . Silicate is still considered to be an effective inhibitor for aluminium but, if not carefully formulated, causes gelling and precipitate formation in coolants.

While the above limitations of traditional inhibitors were being faced , new research led to the development of carboxylate based inhibitor systems for engine coolants . In recent times this type of additive approach is receiving wider recognition to meet coolant standards as well as to satisfy associated environmental and toxicity concerns. Coolant Specifications In the earlier days most specifications for EG - based engine coolants were composition oriented . Examples are the erstwhile British standards BS 3150 / 3151 and Indian Standard IS 5759 . These covered the following types of coolants : TYPE A B C INHIBITOR(S) TEA - Phosphate Sodium MBT Benzoate - Nitrite Borate APPLICATION Aircraft piston engines and other IC engines built from light alloys General IC engines IC engines with predominantly ferrous components

Over the years a certain amount of uniformity in performance testing of engine coolants emerged among automobile builders, coolant industry and research laboratories . This led to a shift from composition based standards to performance based standards and resulted in the publication of several national standards of this category . Some of the well known examples are :

ASTM D3306 SAE J 1034 BS 6580 JIS K2234

Nevertheless the individual OEM specifications continue to exert major influence in their areas of influence . As a matter of fact they enable continuous upgradation of the national standards as well as the coolant technology . In the Indian market a strong demand for new generation coolant arose from the mid -1980s for which the major thrust came from the MARUTI vehicles . As a result the Japanese standard JIS K2234 became the bench-mark reference for engine coolant in India . The Indian standard IS 5759 was eventually revised taking this into consideration . In the recent past several new car ventures have started manufacturing vehicles in India and these have brought among other things newer demands for engine coolants . These requirements have their origin in the OEM standards of Suzuki , Daewoo , Ford , GM - Opel , Peugeot , Fiat , Mitsubishi , Hyundai and so on. Consequently the current Indian market trends for engine coolants are in with the latest Japanese and European counterparts .

Physico-chemical Properties and Performance Evaluation The evaluation of engine coolants generally consists of four stages :

Tests for physico-chemical properties Laboratory bench tests for corrosion protection Simulated service circulating tests ; and , Field tests in vehicles

The physico-chemical properties widely tested include boiling point , freezing point , density/sp. gravity , pH and reserve alkalinity , water content , foaming characteristics , effect on paint films , elastomer compatibility and storage stability . Some of the specifications call for testing ash content , compatibility with hard water , residual impurities such as chloride, compatibility with proven products and so on. Corrosion protection is one of the most important functions of engine coolant and this is evaluated by laboratory glassware tests , bench-scale circulation tests and vehicle tests in this sequence. Metals required to be protected in engine cooling circuits normally are : Steel and Cast Iron , Aluminium alloys, Copper and Brass, and Lead - based Solders . Corrosion problems of concern in modern engine cooling systems are : pitting in radiator tubes , crevice corrosion in cylinder head packing , deposition of corrosion products , cavitation in coolant pumps and cylinder liners, and high temperature corrosion in engine heads. Several industry standard methods , in-house evaluations and electrochemical tests are used for assessing the ability of coolants to overcome these corrosion problems. Tests are run at the coolant concentrations ranging from 20 to 50 Vol. % taking into consideration the required coolant dilution in actual practice in the area. Test Methods for Engine Coolants A good number of standard methods have evolved over the years in USA , Europe and Japan for the testing of engine coolants . There are common as well as divergent methods among these for the identified characteristics . The ASTM test methods are widely referred and used by the coolant makers and users . Some of the important ASTM tests for coolant performance evaluation are : Glassware corrosion test ASTM D1384 Corrosion of cast aluminium alloy under heat rejecting conditions ASTM D4340 Simulated service corrosion test ASTM D2570 Cavitation - erosion of water pumps ASTM D2809 ; and , Vehicle testing of engine coolants ASTM D2570

Current Trends in Coolant Development As already mentioned the industry continues to seek higher quality levels in the coolants to be used in vehicles . Compositional restrictions on inhibitor types are becoming tougher . The number of universally acceptable chemical classes are a few only . In this context the carboxylic acid based additive systems offer most promise for wider use in future . Environmental and toxicity concerns are expected to be more dominant in the times to come . These will lead to more stress on the recycling and extending useful life of engine coolants through top - up , inhibitor doping as well as purification and reblending of products . In this connection propylene glycol based coolants can be expected to grow in market share. SUMMARY

The importance of engine coolant and its evolution has been discussed . Ethylene glycol is the current base material for most of the antifreeze

engine coolant worldwide . Corrosion protection is the most important concern in modern engine cooling systems . Several inhibitors are required in a balanced formulation to protect all the ferrous and non-ferrous alloys present. Additive technology for engine coolants has evolved through stages and is moving towards novel chemistries. Industry uses several standard and special tests to evaluate coolant performance. Annexure OLD INDIAN STANDARD ANTIFREEZE Type A IS 5759 - 1970 FOR ETHYLENE GLYCOL Type C Borax -IC For use in cooling systems of IC engines with predo- minantly ferrous components . 2.4 - 3.0

Type B

TEA - Orthophosphate 0.9 Sod. Benzoate 5.0 - 7.5 - 1.0 NaMBT 0.2 - Sod. Nitrite 0.45 - 0.55 0.3 For use in cooling For use in general systems of aircraft piston engines . engines and other IC engines built from light alloys predominantly.

These were adaptations of BS 3150, BS 3151 and BS 3152 respectively.

STRENGTH & WEAKNESS OF TRADITIONAL INHIBITORS INHIBITOR Amines Borate STRENGTHS Protects ferrous metals WEAKNESSES

Phosphates Silicates Nitrite

Nitrosamine formation , Can attack copper alloys Acts as buffer, synergy Accelerated corrosion of aluminium at with other inhibitors, heat rejecting surface compatible with hard water , solubility Act as buffer , synergy Hard water incompatibility, Accelerated with other inhibitors corrosion of aluminium at heat rejecting surface Excellent for aluminium Polymerize at near neutral pH , fouling protection of radiator tubes, accelerated corrosion when depleted Excellent for ferrous Nitrosamine formation with sec. amines metal protection , depletion on storage , formation of ammonia at high pH , adverse effect on Cu alloys, attack on some plastics

ACCEPTABILITY OF COMMON INHIBITORS Inhibitor Amines (1) Borate (2) Phosphates Silicates (3) Nitrite (4) USA NO YES YES YES YES EUROPE NO YES NO YES YES JAPAN YES NO YES NO NO

(1) (2) (3) (4)

OK in some French and Japanese plants . Not accepted in some European plants . Still OK in some Japanese plants . Likely to be eliminated early in Europe .

UNIVERSALLY ACCEPTABLE INHIBITORS

INHIBITOR Molybdate Benzoate Nitrate MBT Triazoles Carboxylates

FUNCTION Protects Fe and Al alloys Protects Fe alloys and Solder Protects Al alloys Deactivates Cu metal/alloys Deactivates Cu metal/alloys Protects Fe and Al alloys