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REVIEW
Abstract: This short review describes various types of anti-corrosion additives of water-soluble metal
working fluids for aluminum alloy materials. It is concerned with synthetic additives classified according
to their functional groups; silicone compounds, carboxylic acids and dibasic acids, esters, Diels-Alder
adducts, various polymers, nitrogen compounds, phosphoric esters, phosphonic acids, and others. Testing
methods for water-soluble metal working fluids for aluminum alloy materials are described for a practical
application in a laboratory.
Key words: water-soluble metal working fluids, additives, aluminum alloy materials, anti-corrosion property, testing
methods
1 INTRODUCTION
A variety of metal working fluids are used for the
machining operations of cutting, grinding, turning, milling,
drilling, and tapping mainly for iron and aluminum metals.
Many technical books 1, 2) and reviews 3, 4) on lubrication in
metal working and cutting for irons are known. However,
the review of those for aluminum alloy materials is quite
few. Aluminum materials are apt to be blackish by mechanical processing, owing to corrosion of aluminum. Various
attempts to prepare high performance additives for aluminum materials have recently been made. Many patents
on corrosion inhibitors in metal working and cutting of aluminum materials are known. Usually water-soluble cutting
fluids consist of many components. However, the detailed
compositions of the commercial products have not been
known. The most important additive is a surface active
agent having anti-corrosion and other useful properties.
The surface active agent is called a metal working fluid
additive. This short review article describes preparations
and properties of new types of metal working fluids additives which have been developed in our laboratory and
reported in literatures.
Correspondence to: Shoji Watanabe, Akitsu 1-3-5-502, Narashino, Chiba 275-0025, JAPAN
E-mail: s-wata@mui.biglobe.ne.jp
Accepted September 26, 2007 (received for review August 13, 2007)
S. Watanabe
Structure
Test of discoloring
Sebacic acid
HOOC(CH2)8COOH
Dodecanedioic acid
HOOC(CH2)10COOH
Tetradecanedioic acid
HOOC(CH2)12COOH
Hexadecanedioic acid
HOOC(CH2)14COOH
Octadecanedioic acid
HOOC(CH2)16COOH
Eicosanedioic acid
HOOC(CH2)18COOH
pH
Anti-corrosion tests
For aluminum after
24 hr
8.7
8.74
8.61
8.87
8.53
8.72
8.2
8.69
8.72
8.75
8.43
Dodecanedioic acid
8.02
Sebacic acid
7.89
Adipic acid
7.7
Triethanol amine
10.4
Water
S. Watanabe
Table 3 Reaction Products of Various Alcohols with Maleic Anhydride and Their Anti-corrosion Tests for
Aluminum and Hard Water Tolerance 15).
Entry
No.
Alcohols
Acid
anhydride
Molar
ratio
Anti-corrosion test of
aluminum After 24 h
PTMG 650
MA
11
PTMG 650
MA
12
PTMG 1000
MA
11
PTMG 1000
MA
12
PBO 650
MA
12
PBO 1000
MA
12
Ricinoleic acid
NPG
Undecylenic acid
Dodecanoic acid
Numbers of 650 and 1000 are average molecular weights of PTMG and PBO.
Hard water tolerance tests were performed according to the references method 35).
MA is maleic anhydride.
Table 4
Anti-corrosion Test of Thermal Reaction Products for Aluminum Alloy Materials 16).
Dienophiles
Maleic anhydride
Acrylic acid
Methyl acrylate
Methacrylic acid
Linoleic acid
Maleic anhydride
Linoleic acid
Acrylic acid
Linoleic acid
Methylacrylate
Linoleic acid
Methacrylic acid
---
Linoleic acid
---
Dodecanedioic acid
---
(XIV) show excellent anti-rust and anti-corrosion properties for aluminum, magnesium and an alloy of Al and Mg 23).
An additive containing compounds (XV) can inhibit corrosions of tanks composed of aluminum and aluminum
alloys 24). Tetrazole compounds such as compound (XVI) can
be used as an anti-corrosion inhibitor for an article of cast
aluminum 25). 2-Mercaptobenzothiazoles (compound XVII)
are suitable for water-soluble metal working fluids for aluminum and other metals 26). It is reported that water-soluble fluids containing a Schiff's base (XVIII) are good for
high speed grinding of aluminum, copper, tungsten and
S. Watanabe
acid and POCl3 as shown in Fig. 7. Corrosion inhibitor performance against an aluminum material was examined for
aqueous solutions containing the salts of these phosphoric
esters and alkanolamines. The results are summarized in
Table 5. The amine salts of compound (XIX) and phosphoric esters of ricinoleic acid dimer, tetradecylalcohol and
hexadecylalcohol showed good anti-corrosion property for
aluminum alloy materials 29,30) . Recently, a convenient
preparative method of phosphate esters using P2O5 has
been reported 31).
2.8 Phosphonic acid
Ammonium salts of alkylphosphonic acids have been
used as surface active agents 5). Recently, alkylphosphonic
acids have been employed for a water-soluble metal working fluid additive 32). In this section the author describes
the evaluations of some alkylphosphonic acids as an aluminum corrosion inhibitor. Octylphosphonic acid was prepared according to the method described in literature 33).
Then, diethyl octylphosphonate (XX) was prepared by the
thermal reaction of octylbromide with triethylphosphite as
shown in Fig. 8. The hydrolysis of (XX) with hydrochloric
acid gave octylphosphonic acid (XXI). Hexyl- and
decylphosphonic acids were prepared in a similar fashion.
Triethanolamine salts of octylphosphonic acid (XXI) and
decylphosphonic acid showed good anti-corrosion property
for aluminum as shown in Table 6 34). These results indicate
that alkylphosphonic acids have anti-corrosion property
for aluminum alloy materials.
Alkyldiphosphonic acids were prepared by the reaction
Phosphoric esters
Alkanol amines
n-Tetradecyl alcohol
Triethanolamine
Soluble
n-Hexadecyl alcohol
Triethanolamine
Soluble
Ricinoleic acid
Triethanolamine
Diethanolamine
Monoethanolamine
Soluble
Soluble
Soluble
Triethanolamine
Diethanolamine
Monoethanolamine
Slightly
Soluble
Slightly
Triethanolamine
Diethanolamine
Monoethanolamine
Slightly
Soluble
Slightly
9,10-Dihydroxy-stearic acid
Triethanolamine
Diethanolamine
Monoethanolamine
Soluble
Soluble
Soluble
tolerance.
Some monoesters of octylphosphonic acid (XXI) were
prepared by the reactions of some lower alcohols with
octylphosphonic acid dichloride (XXII) as shown in Fig. 9.
Aqueous solutions of diethanolamine salts of monoester
(XXIII) with diethyleneglycol monomethyl ether showed
both the good anti-corrosion property for aluminum and a
Table 6 Anti-corrosion Tests and Hard Water Tolerance of Alkylphosphonic Acids and Their Esters
for Aluminum Alloy Materials 34,35).
Hard water
tolerance
pH 9.0
Concentration %
Hexylphosphonic acid
0.50
0.15
0.05
0.50
0.15
0.05
0.50
0.15
0.05
Decylphosphonic acid
Octane-1,8-diphosphonic acid
0.50
0.15
0.05
0.50
0.15
0.05
Decane-1,10-diphosphonic acid
0.50
0.15
0.05
0.50
0.15
0.05
0.50
0.15
0.05
0.50
0.15
0.05
0.50
0.15
0.05
0.50
0.15
0.05
Sample
S. Watanabe
3 TESTING METHOD
The properties of water-soluble cutting fluids to be analyzed are: surface tension, emulsion stability, pH, chlorine,
total sulfur, foamability, corrosion resistance, friction coefficient, welding load, microbial resistance, hard water tolerance and others. Perfect measurements of these performances are hard. Corrosion tests for aluminum alloy materials are the most important. Practical tests should be performed on good samples. As the measurement of weight
loss before and after the test requires ten days (240 h),
spray (Fog) corrosion test 37,38) is not common for a conve-
4 SUMMARY
The relationship between anti-corrosion and lubricating
properties and chemical structure of organic compounds
has not been well known. For aluminum alloy materials,
further elaboration is definitely desirable to elucidate the
dependence of anti-corrosion performance on the chemical
structures of the molecule.
ACKNOWLEDGMENT
The author is indebted to Dr. Yoneshima of NEOS Co. Ltd.
for his helpful support.
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