Progr Colloid Polym Sci (1999) 112 : 210±213
Ó Springer-Verlag 1999 EXPERIMENTAL TECHNIQUES
L. PedisÏ ic Application of surfactants in emulsifying
M. Sviglin-Marasovic
metalworking ¯uids
Abstract Emulsifying metalworking mulations of emulsifying metal-
¯uids are subject to continuous working ¯uids based on new types of
evolution in order to increase econ- emulsi®ers and their properties are
omy and satisfy growing ecological presented in this paper. The results
and safety requirements. Therefore, of laboratory and application ex-
the composition of modern formu- aminations show that succinic acid
lations is becoming more and more esters and ether carboxylates can
sophisticated so that a great number replace alkylbenzenesulphonates in
of usual components are changed for metalworking emulsions.
new less harmful components. Al-
kylbenzenesulphonates have been Key words Application ±
widely used as emulsi®ers but they Environmentally more acceptable
are not allowed anymore. Nowa- metalworking ¯uids ±
L. PedisÏ ic (&) á M. Sviglin-Marasovic days, dierent ethoxylates, fatty acid Ether carboxylates ± Metalworking
Ina-Industrija Nafte, dd, Maziva Zagreb
Radnicka cesta 175, HR-10000 Zagreb esters or ether carboxylates can be emulsions ± New generation of
Croatia used in modern formulations. For- emulsi®ers
Introduction Experimental
Emulsifying metalworking ¯uids are ¯uids for cooling We used commercial components for metalworking ¯uid formula-
and lubricating during metalworking operations such as tion made by dierent producers. Mineral oil was paranic type
boring, drilling, milling, sawing, etc. Besides constant SN 150 grade. Water was demineralised the preparation of
concentrated ¯uids. Natural water was used for emulsion mixing.
improvement of metalworking machines, the ecological The compositions of the test ¯uids are shown in Table 1. We used
and safety requirements have lately become the main standard methods for examination of the metalworking ¯uids and
promoters of metalworking ¯uid development [1]. their components [6]: ASTM D 4172, ASTM D 1287, ASTM D
So-called ``negative sheets'' listing the harmful com- 1121, DIN 51360/Part I and Part II. The pH value was measured
potentiometrically according to ASTM D 1287. For reserve
ponents for people and the environment are part of the alkalinity determination we used ASTM D 1121 a test solution
very strong European legislations and recommendations (10 ml) is mixed with 90 ml water and titrated with 0.1 N HCl to a
[2, 3, 4]. The deletion of compounds based on chlorine, pH of 7. The corrosion properties were examined by the methods
nitrite, diethanolamine (DEA), compounds with aro- DIN 51360/Part I and II. Part I, known as the Herbert test, is
corrosion cast-iron to steel. Steel chips wetted with the test ¯uid are
matic nuclei, etc. is a very important part of metalwork- placed on the cast-iron plate. After 24 h the plate surface is
ing ¯uid development [5]. The purpose of this observed. Part II is known as the ®lter-paper test. Cast-iron chips
investigation is to ®nd substituted compounds (phos- wetted with the test ¯uid are placed on a ®lter paper. After 2 h the
phoric acid esters, fatty acid esters, triethanolamine, ®lter paper was observed. The extra pressure (EP) properties were
succinic acid derivatives, ether carboxylates) with the determined by two mechanical machines. The ®rst is known as the
four-ball wear test machine (ASTM D 4172). Four metal balls are
same or better application properties. rotated in the test ¯uid under standard load at 75 °C. After 1 h the
diameters of the test balls were measured and their average taken.
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Table 1 Composition of test metalworking ¯uids
Components, %/function Fluid 1 Fluid 2 Fluid 3 Fluid 4
a
Mineral oil, paranic Oil 74 38 32 22.5
Pentapropenyl succinic acid monoamide E+C 19 40 12 ±
Fatty carboxylic acids mixture (oleic, stearic, lauric) E+C ± ± ± 17.2
Boric acid, MEA/TEA saltb C+B ± ± 30 ±
Boric acid MEA salt C+B ± ± ± 44.6
Polyglycol ether of fatty alcohol C16/C18 + 2 ethylene oxide E+D 4 3 6 ±
Ethoxylated oleyl cetyl alcohol E+D ± ± ± 5.95
Carboxylic acid, tallow E 2 2 5 ±
Ether carboxylate E+D ± 4.45
Hydroxystearic acid methyl ester L ± 15 ± ±
Dithiophosphonic acid P-4 amide alkeneamine salt L ± ± 10 ±
Biocide B 1 2 ± 1
Water ± ± ± 5 5.5
Emulsion type Conventional Semisynthetic Semisynthetic Semisynthetic
Oil droplet size (lm) 1±2 0.5±1 0.1±0.5 0.1±0.5
a
E = emulsi®er, D = dispersant, C = corrosion inhibitor, L = lubricant, B = bacteriostatic
b
MEA = monoethanolamine, TEA = triethanolamine
Table 2 Properties of test metalworking ¯uids
Properties, %, methods Fluid 1 Fluid 2 Fluid 3 Fluid 4
Concentrate appearance, visually Clear, brown Clear, brown Clear, brown Clear, yellow
Stability, 0±50 °C/24 h, internal test 1 Stable Stable Stable Stable
Emulsion appearance, 5%, visually Milky white Semitransparent Transparent Transparent
white opalescent yellowish
Stability, 20 °C/24 h, internal test 1 Stable Stable Stable Stable
Alkalinity reserve, ml 0.1N HCl, ASTM D 1121 2.3 4.9 7.0 11.5
pH value, ASTM D 1287 9.3 9.4 9.25 9.1
Corrosion, DIN 51360/I, 1% R0/S0 R0/S0 R0/S0 R0/S0
DIN 51360/II, 2% 0 0 0 0
Foaming, foam volume (ml), 100 95 75 95
after 5 min (ml), internal test 2 29 15 0 7
Extra pressure properties 0.87 0.77 0.67 0.85
Wear scar diameter (mm), ASTM D 4172
Wear scar area (mm2), Reichert balance machine 32.0 26.0 29.4 30.5
The second machine is known as a Reichert balance. Using this
method we measured a scar area on the test rolls. The basic Results and discussion
construction consists of a rotating metal ring and a static roll
immersed in the test ¯uid. The stability of concentrates and their Metalworking ¯uids are produced as concentrated
emulsions was tested visually at dierent temperatures (internal test solutions (concentrates). In applications they are mixed
1). The foaming properties were examined by internal test 2; this
was carried out at room temperature. The test emulsion (50 ml) with water to make working-form emulsions. Concen-
was placed in a graduated glass cylinder (100 ml) and shaken 20 trates must be properly optimised in order to obtain the
times during a period of 15±20 s. We measured the foam volume required emulsion properties. They consist of mineral
immediately and after 5 min. We also used deep-slide strips for oils, emulsi®ers, corrosion inhibitors, EP additives,
microorganism counting, and a testro-refractometer for measuring
the concentration. The data relating to the ¯uids' properties are
biocides, defoamers and others. Emulsi®ers ± surfactants
shown in Tables 2 and 3. are added to the ¯uid to increase emulsion stability. An
After satisfying the required laboratory properties of metal- emulsi®er molecule orients itself with the lipophilic end
working ¯uid formulation, the properties should be checked under immersed in the oil droplet. This natural orientation of
application conditions. Application properties were examined for the emulsi®er molecules generates a surface tension
four metalworking operations as shown in Table 3. For monitoring
the properties of working emulsions we used the same methods as through the attraction or repulsion of the ends of the
for the laboratory examinations. emulsi®er molecule and the water and oil.
The formulation of a metalworking ¯uid is complex and We have chosen the emulsi®ers partly semiempirically,
requires a number of experienced examinations at the laboratory using the hydrophilic-lipophilic balance (HLB) [7]. For
tests.
oil-in-water emulsions, the HLB values are usually high
212
Table 3 Metalworking machines and working conditions for test ¯uids, applications
Working emulsion Fluid 1 Fluid 2 Fluid 3 Fluid 4
Metalworking machine Drilling machine Universal turning Copying lathe Fischer CNC milling machine
Micromat GA machine TNA 400 Norte
Working metal Steel, iron, brass Steel, iron Steel Steel, iron, brass,
aluminium
Metalworking operation Drilling Turning, boring Turning Milling, boring, drilling
Emulsion quantity (m3) 0.10 0.15 0.30 0.25
Working emulsion concentration (%) 5 4 3.2 4.6
Requirements of working ¯uid Cooling Cooling, lubrication Tool wear prevention Lubrication, cooling,
longer working life
Working life (months) >3 >6 >10 >12
Total number of micro-organisms 106 105 <104 <104
in 1 ml, deep-slide strips
(typically 10±12). However, the HLB value of an sion properties, developed by methods with chips, are
emulsi®er depends greatly on the components. The excellent for a minimum emulsion concentration of 2%.
necessary amount of emulsi®er, by three-phase system Reserve alkalinity shows additive concentration: F3 and
rule mixing, according to Miler [8], can be estimated F4 have higher values and also higher resistance to the
with dicult. We used anion-active (fatty carboxylic in¯uence of the environment. F1 a milky emulsion, has
acids, ether carboxylate) and non-ionogenic surfactants the highest foaming tendency so it cannot be recom-
(ethoxylated fatty alcohols, pentapropenyl succinic acid mended for operation at high speeds. From the values of
monoamide, ether carboxylate) in combination. The the EP properties we can estimate that all ¯uids will have
results with the function of each component are good cooling properties. Additionally, F2 and F3 will
represented in Table 1. have good lubrication properties.
After ®nding the theoretical amount of emulsi®er, During the selection of new components the satisfac-
numerous formulations were mixed until we obtained tory application properties of working emulsions should
satisfactory results. The optimum formulation of each be taken into account. These are cooling of the cutting
metalworking ¯uid type is shown in Table 1. Fluid 1 zone, chip ¯ushing, lubrication, corrosion properties,
(F1) is a so-called conventional emulsifying ¯uid that emulsion stability, resistance to microorganisms, capa-
has to contain a minimum of 60% of mineral oil. We bility of slide-way oils emulsifying, no bad smells, etc. [10].
added a polyglycol ether of a fatty alcohol C16/C18 with For formulation F1 a minimum of application
2 mol ethylene oxide and natural carboxylic acid to properties is required. These are cooling and corrosion
improve emulsion stability. For inhibition of bacteria inhibition over a 3 month period. Formulations F2 and
growth we added biocide. F2 and F3 are semisynthetic F3 are emulsions with improved lubricating properties.
types with a maximum of 40% of mineral oil. The The lubricating properties are the result of adding
general dierence between them is in the content of boric dithiophosphonic acid P-4 amide alkeneamine salt or
acid derivatives that improve corrosion and bacteria hydroxystearic acid methyl ester as EP additives instead
stability [9]. F3 contains a boric acid salt of monoeth- of chlorinated paran. The metalworking machines
anolamine (MEA) and triethanolamine (TEA) mixture. where the ¯uids were examined, working conditions
F4 also contains boric acid derivatives but based on and the requirements for each working emulsion are
MEA. In F4 the emulsi®er consists of a combination of shown in Table 3. On the copying lathe, emulsion F3
fatty carboxylic acids improved with one ethoxylated showed the best lubricating properties in its long service
alcohol and alkyl polyether carboxylic acid (ether life. This EP emulsion has the best tool-wear index in
carboxylate). Ether carboxylates are mild surfactants comparison to the other emulsions. F4 showed excellent
showing both nonionic and anionic properties. They are application properties through the longest emulsion
mild to the skin and are readily biodegradable. The ether working life. On measuring the total number of micro-
carboxylate increases the dispersity of the emulsion and organisms in the F3 and F4 emulsions the values did not
thus its stability and service life. The resulting properties exceed the value of 104 per millilitre. The bacteria growth
of the test ¯uids examined in the laboratory are shown in in conventional emulsion F1 is greater and reached 106
Table 2. The application properties at metalworking per millilitre after 3 months. This is below the critical
machines in dierent workshops are shown in Table 3. value of 107 per millilitre. The physical and chemical
All formulations have good pH values that should be properties of the test emulsions during application were
between 9.0 and 9.5 in order to satisfy corrosion monitored: the pH value, concentration, alkalinity
protection and skin reaction requirements. The corro- reserve, odour, appearance and corrosion properties,
213
once a week; EP properties, conductivity, microorganism with less harmful components. They are ``more friendly''
content, total water hardness, twice a month. to the environment and people and also excellent in
In application all formulations exhibited good cor- application.
rosion protection: tools, work pieces and working zone. New metalworking ¯uids consist of alkyl succinic
The stability of the emulsions was excellent in spite of acid amide, ethoxylated fatty alcohols, fatty acids and
varying concentrations, pH values, entering lubricating ether carboxylate as replacements for widely used
oil from slide ways and water hardness. The emulsions emulsi®ers based on alkylbenzenesulphonates. Besides
did not cause sticking, foaming or skin reaction. emulsifying properties, new types of surfactants in
metalworking ¯uids also have remarkable anticorrosion
properties. As a corrosion inhibitor, instead of DEA, it
Conclusion is shown that it is possible to use MEA and TEA salts in
combination with boric acid. Chlorinated paran as an
In accordance with health and environmental require- EP additive has been successfully replaced with a fatty
ments we prepared new emulsifying metalworking ¯uids acid ester and a phosphoric acid ester.
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