Driers and Metallic Soaps 2

STP500-EB/Jun.
1972
CHAPTER 2.2
DRIERS AND METALLIC SOAPS

G. G. Sward
2.2.1 Introduction Liquid driers are evaluated by both 2.2.2.4 Drying Power
Metallic soaps are compounds of alkaline physical tests and by chemical analysis. On A blend of the drier with raw linseed oil
earth metals or heavy metals and monobasic the other hand concentrated driers are (1 volume + 1 9 volume) is flowed onto a
carboxylic acids of 7 to 22 carbon atoms. evaluated mainly by their metal content. clean glass plate. The plate is placed in a
It is usually convenient to include resinates Metallic soaps are evaluated mainly by vertical position, and the wet-to-touch time
(usually from rosin) and naphthenates in a using them in formulations and noting how
is determined. This is the time elapsed when
discussion of metallic soaps. Their water well they fulfill the function for which they
are used. See Table 2.2-1. the oil does not stick to the finger, or the
insolubility differentiates metallic soaps surface is not marred when the finger is
from ordinary soaps. Their solubility or 2.2.2 Physical Tests on Driers lightly drawn across it. It should be noted
solvation in organic solvents accounts for that this test is somewhat more severe than
their use in paints. Commercial metallic Unless otherwise noted, the tests in this
soaps are made and used in solid, paste, section are described in ASTM Method D the usual set-to-touch point (4.4.2).
564, Testing Liquid Driers, or are specified Carrier [ly coined the name "Aridyne"
and liquid forms. The form depends on the for the unit of drying power. As a standard
metal and its amount, the nature of the in ASTM Standard Specification D 600,
Liquid Paint Driers. with which all liquid driers could be com-
organic acid, and the presence or absence pared, he suggested one containing 6.4 oz
of solvents or additives during manufac- 2.2.2.1 Appearance of oil-soluble lead per gallon, equivalent to
ture. Metals of low atomic weight usually
form soaps of high melting points. Long, If visual inspection discloses suspended about 6 percent of lead by weight, and
straight chain, or saturated fatty acids form matter, the amount may be determined by approximately the amount contained in
soaps of higher melting points than do filtering an appropriate amount, say 1 to 5 commercial driers. This standard would be
short or branched chains, or unsaturated g, washing with turpentine or petroleum "100-proof." However, since commercial
acids. Soaps made by precipitation are spirits, and drying to constant weight at driers usually contain other metals in addi-
49 C. tion to the lead, a 100-proof drier is rela-
likely to be light fluffy powders. Soaps tively weak. For practical purposes, a
made by fusion are hard dense solids. 2.2.2.2 Color 200-proof or a 300-proof solution is recom-
Liquid and paste forms are solutions or The color of a solution of the drier in mended. If the standard contains other
suspensions in petroleum or other solvents. linseed oil is of more interest than that of metals, the strength is designated in this
It is customary to divide metallic soaps the drier itself. Comparison is made with style: "100-proof 10:1 lead:manganese,"
into two functional groups: (1) paint driers Gardner standards (1.1.7.1), dichromate- meaning 6.4 oz of lead and 0.64 oz of
and (2) modifiers of consistency, gloss, or sulfuric acid, or other standards. manganese per gallon. For driers that con-
other properties. The first function is tain no lead, a 100-proof product would
possessed by soaps of lead, cobalt, manga- 2.2.2.3 Miscibility
have the drying power of a 100-proof lead
nese, iron, and to some extent, by calcium The drier is mixed with raw linseed oil drier.
and zinc. The metals found in the second (1 volume + 19 volume) and any cloudi-
group include zinc, calcium, magnesium, ness or other separation, immediately after 1 The italic numbers in brackets refer to the list
barium, and aluminum. mixing, and after 1,2,3, and 24 h, is noted. of references appended to this chapter.
TABLE 2.2-1. Properties of Metallic Soaps
Total Ash, Free Fatty Specific Melting

Metal % Acids, % Gravity Point, deg C Color Solubility
Stearates:
Aluminum- -mono 16.0 4.0 1.01 170 white soluble in mineral oil, benzene, hot turpentine
Aluminum- -di 8.9 10.0 1.01 145 white soluble in benzene, turpentine, hot mineral oil
Aluminum- -tri 7.2 26.0 1.01 115 white soluble in benzene, turpentine, hot mineral oil
Barium 28.0 0.5 1.23 decomp. white slightly soluble in mineral oil, benzene, turpentine
Calcium 9.9 0.9 1.03 160 white slightly soluble in petroleum, benzene, turpentine
Magnesium 8.0 0.5 1.03 145 white soluble in benzene, turpentine, hot mineral oil
Zinc 14.5 0.5 1.09 120 white soluble in benzene, turpentine, hot mineral oil
Palmitates:
Aluminum 8.3 12.5 1.01 120 white soluble in hydrocarbons, benzene
'Murates:
Aluminum 12.75 8.5 1.02 165 white soluble in benzene, hot turpentine, hydrocarbons
7Ieates:
Aluminum 10.0 8.5 1.01 135 cream soluble in benzene, turpentine, mineral oil
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72 RAW MATERIALS
2.2.2.5 Flash Point About 5 ml of nitric acid (HNO3) and 40 to ignited at 500 to 600 C for 15 min, and
The Tag Closed Cup is used (2.7.3.10). 50 ml of dilute sulfuric acid (H2SO4) (1 weighed as PbS04.
volume acid + 1 volume water) are added,
2.2.2.6 Nonvolatile Matter and the system is evaporated to dense white PbS04 X 0.683 = lead
A 1.5-g sample is heated for 3 h at 105 fumes, the evaporation being continued to
2.2.3.7 Determination of Manganese
to 110 C in a tared shallow dish, cooled, a volume of about 5 ml. If the solution
darkens, a few drops of HNO3 are added The heavy metals and calcium are ex-
and weighed. This is essentially the same as tracted by a slight modification of Sub-
Method A for varnish (8.1.5.1). from time to time until it remains colorless
section 2.2.3.3. The modification consists of
after being heated to white fumes. After the
working with a 10-g sample in a 200-ml tall
solution is cool, a few milliliters of 30 per-
2.2.2.7 Specific Gravity
cent hydrogen peroxide (H2O2) are added,form beaker, preliminary evaporation of
Use any convenient method, such as the the thinner, and extraction of the organic
the solution is boiled for a minute, and
Weight-Per-Gallon Cup (3.1.3), Specific acids with beeswax instead of petroleum
carefully diluted to about 100 ml, and di-
Gravity Balance (3.1.4), or a Hydrometer spirits. One himdred milliliters of HCl (1
gested on a hot plate to ensure solution of
(3.1.5). volume concentrated acid -|- 4 volume
anhydrous sulfates.
water) and 5 g of beeswax are added to the
2.2.2.8 Viscosity nonvolatile portion of the drier and heated
2.2.3.3 Metal Separation with Hydro-
The Gardner Bubble Method is recom- chloric Acid [2] to near boiling, with occasional stirrring
mended (3.2.9.1). for 1 h. The system is cooled and filtered,
An appropriate amount of drier (2.2.3.1) the cake of wax is washed, and the wash-
2.2.2.9 Stability is transferred to a 400-ml beaker. One ings are added to the filtrate. Thefiltrateis
After 7-days standing, the drier is ex- hundred ml of dilute hydrochloric acid made ammoniacal, and the metals are
amined for gelling, clotting, or other form (HCl) (1 volume acid + 4 volume water) is precipitated with ammonium monosulfide.
of precipitation. added and the contents of the beaker are The sulfides are collected on a filter, and
heated to near boiling, with occasional stir- thefiltrateis reserved for the determination
2.2.3 Chemical Analysis ring, for 1 h. The contents are cooled, of calcium, if desired.
Classical methods for determining the transferred to a separatory funnel, and ex- Hot HNO3 (1 volume acid, concentrated
metallic content of driers are still used, but tracted with 50 ml of petroleum spirits. + 3 volume water) is poured through the
methods based on flame spectroscopy and The aqueous layer is drained into a beaker. filter, and the filter is washed with hot
on chelate titrations using EDTA (ethylene- The extraction is repeated twice with 25-ml water. Five milliliters of H2SO4 are added
diaminetetraacetic acid) are rapidly replac- portions of the dilute acid, and the petro- to the filtrate, and the system is treated as
ing the older procedures. One important leum spirits is washed with 25 ml of water, described in Subsection 2.2.3.2, beginning
advantage is that there is no need to re- which is added to the aqueous extract. with the evaporation to dense white fumes.
move organic matter. If desired, beeswax instead of petroleum If desired the determination of lead is com-
Among methods for removing organic spirits may be used for the extraction. In pleted as described in Subsection 2.2.3.6.
matter, when necessary, are ashing, wet this event, after the decomposition with The filtrate is reserved for the step in the
oxidation, extraction with mineral acids, HCl, about 5 g of beeswax is added, the following paragraph.
and conversion to insoluble oxalates. contents are stirred until the wax melts, An aliquot of the filtrate is boiled to re-
and then allowed to cool. The cake of wax move the alcohol, cooled in ice water to
2.2.3.1 Metal Separation by Ashing is broken up, filtered through paper, and 15 C or lower, and treated with about 2 g
This is one of the oldest methods for washed with cool water. The paper and of sodium bismuthate for at least 10 min to
destroying organic matter to prepare a wax are dried and ashed (2.2.3.1). The ash oxidize the manganese to permanganate.
sample for inorganic analysis. An appro- is dissolved in warm HCl and added to the Fifty milliliters of dilute HNO3 (3 acid -f
priate amount of drier is transferred to a filtrate. 97 water) is added, the solution is filtered
porcelain or high-silica glass crucible, for through asbestos, and washed with dilute
example: 2.2.3.4 Metal Separation as Acetate [3,4]
HNO3. The filtrate is titrated with 0.1 N
0.1000 to 0.2000-g lead, The sample of drier is dissolved in chloro- KMn04 in the usual manner.
0.0600-g manganese, form or ether, glacial acetic acid is added,
and the system is refluxed. 1 ml of 0.1 N^ permanganate solution =
0.0500-g cobalt,
0.1000 to 0.2000-g zinc, and 0.001099-g manganese
0.1000-g iron. 2.2.3.5 Metal Separation as Oxalate [5]
2.2.3.8 Determination of Cobalt
Heat just to ignition and continue to heat An appropriate amount of drier (2.2.3.1) A 5 g sample is fused in a large porcelain
as required to maintain slow burning of the is transferred to a 5(K)-mI conical flash and crucible with 5 to 10 g of potassium pyro-
organic matter. When no moreflameissues dissolved in 75 ml of alcohol:acetone sulfate (K2S2O7). The fused mass is ex-
from the crucible, continue to heat, over a (1 + 1), warmed slightly, if necessary, to tracted with 50 to 100 ml of dilute H2SO4
flame or in a muffle, to red heat for an hour aid solution. Ten ml of a 10 percent solu- (1 acid + 99 water) andfilteredthrough fine
or so. Dissolve the ash in a minimum tion of oxalic acid in alcohol is added, and paper to remove the insoluble sulfates,
amount of nitric acid, and proceed as the system is refluxed for about 1 h. The carbon, etc., and is then diluted to 500 ml
directed in the appropriate section next. precipitate is filtered and washed with in a volumetric flask. To an aliquot con-
alcohol: toluene. taining approximately 50 mg of cobalt is
2.2.3.2 Metal Separation by Wet Oxidation added 10 drops of 30 percent hydrogen
2.2.3.6. Determination of Lead peroxide, 1 or 2 drops of phenolphthalein
This method is especially suitable for
determining lead as sulfate and is appli- If only lead is to be determined, the metal indicator, and enough 0.5 N sodium hy-
cable to mixed driers containing lead, is isolated by wet oxidation and precipi- droxide (NaOH) solution to precipitate the
manganese, and cobalt. tated as lead sulfate (PbSOi). After stand- cobalt completely and to show an alkaline
An appropriate amount of drier is trans- ing for an hour, the precipitate is collected reaction.
ferred to a 400-ml beaker and heated on a on a tared Gooch crucible, washed with 0.5 Twenty milliliters of glacial acetic acid
hot plate until the solvent is removed. percent sulfuric acid and then with alcohol. are now added. Gentle heat is applied, 1 or
DRIERS AND METALLIC SOAPS 73
2 drops of H2O2 are added, and the heating The reaction may be represented by Indicator—Triturate 0.2 g of Eriochrome
is continued until the precipitate, cobalt Black-T and 100 g of NaCl. Store in a
hydroxide (Co(OH)3), dissolves. The sys- tightly stoppered bottle.
tem is filtered, the filtrate is diluted to 200 " ^H HH HU UH It Standardization of EDTA Solution—
ml with water and heated to gentle boiling, Transfer 40.00 ml of the solution to a 400-
and 75 ml of fresh, hot solution of nitroso- ml beaker, containing 2 ml of benzene and
beta-naphthol (2 g of nitroso-beta-naph- 50 ml of ethanol. Add 10 ml of buffer solu-
thol, 50 ml of hot glacial acetic acid, 50 ml tion and 0.2 g of indicator. Titrate with the
of hot water, filtered) is added. The system standard zinc solution to a red color.
is stirred until the precipitate flocculates Molarity of EDTA solution = (Mzn X ml
and is then allowed to stand for 2 h, and OC CO of zinc solution)/40, where Mzn = molar-
filtered. The precipitate is washed with I I ity of zinc solution.
dilute HC1(1 acid + 19 water) and then with OH HO
hot water, and sucked as dry as possible. Procedure for Calcium, Cobalt, and Zinc
It is then ashed for 1 h at 750 to 850 C, Transfer 0.2 g of drier, weighed to the
cooled, and weighed as cobalt oxide II HM U H H U MH II nearest 0.0001 g, to a 250-ml flask. Add 2
(Co,04). NaOC-C" " C - C " "C-CONa ml of benzene and mix gently. Add 50 ml of
\ / \ ethanol and again mix. Add 40.00 ml of
C03O4 X 0.734 = cobalt standard EDTA solution and 10 to 15 ml
of buffer solution to the flask. Ignore any
2.2.3.9 Determination of Zinc cloudiness that may develop. Add about
0.2 g of indicator and mix thoroughly.
Use a solution in HCl of the ash obtained Titrate with standard zinc solution as in
in Subsection 2.2.3.1. or an aliquot of the standardizing the EDTA solution.
extract obtained in Subsection 2.2.3.3. The
sample should contain about 0.1 g of zinc. percent of metal = 100 X MW X
Manganese, cobalt, nickel, and iron inter- By conducting the reaction in a basic (ml of EDTA)MEDTA - (ml of Zn)Mzn
fere and must be removed. solution, the hydrogen ion is removed, and
the reaction becomes quantitative. What mg of sample
Make alkaline with sodium hydroxide
(NaOH) solution (1 NaOH -|- 10 water). makes the method so attractive in drier where:
Cautiously add a "pinch" of sodium analysis is that extractions or combustions
peroxide (Na202), and boil to decompose are eliminated in many cases. MEDIA = molarity of EDTA solution,
the excess. Filter and wash once or twice In addition to the Lucchesi Method Mzn = molarity of zinc solution, and
with hot water, saving the filtrate and (2.2.4.1) and the Graske Method (2.2.4.2), MW = molecular weight of the metal.
washings. Dissolve the precipitate in HCl, there are four ASTM methods:
reprecipitate, filter, and wash as before. D 2373, Determination of Cobalt in Procedures for Lead and Manganese
Make filtrate acid to litmus with HCl, Paint Driers by EDTA Method (2.2.4.3),
then alkaline with NH4OH, adjust acidity D 2374, Determination of Lead in Paint For lead, follow the above procedure ex-
to 3 milliliters of HCl, and titrate with Driers by EDTA Method (2.2.4.4). cept add 0.5 g of tartaric acid before add-
standard ferrocyanide solution. D 2375, Determination of Manganese in ing the buffer.
In the absence of the interfering metals, Paint Driers by EDTA Method (2.2.4.5). For manganese, add about 0.1 g of
omit the precipitation with NaOH solution. D 2613, Determination of Calcium or ascorbic acid before adding the buffer.
Zinc in Paint Driers by EDTA Method
(2.2.4.6). 2.2.4.2 Graske Method
2.2.3.10 Determination of Iron
Use an aliquot of hydrochloric acid ex- 2.2.4.1 Lucchesi Method By introducing the use of masking com-
tract (2.2.3.3), corresponding to about 0.1 pounds, Graske [7] devised a method for
This method [6] is for single metal driers: the determination of cobalt, zinc, manga-
to 0.2 g of iron. Proceed as directed in Sub- calcium, cobalt, lead, zinc, or manganese. nese, and lead in mixed driers.
section 9.2.36.5 beginning with reduction The drier is dissolved in a benzene-
with stannous chloride. An aliquot of a solution of the drier in
ethanol blend. An excess of standard benzene is diluted with methanol. An excess
If lead is present, precipitate with hy- EDTA solution is added, and the excess is of EDTA solution is added, followed by
drogen sulfide (H2S) as directed in Sub- titrated with standard zinc chloride solu- the appropriate masking agent and the
section 9.2.21.6, and determine iron as out- tion.
lined in Subsection 9.2.36.5. buffer solution. The excess EDTA solution
is titrated with standard magnesium sulfate
Solutions solution.
2.2.4 Chelometric Determination of Drier EDTA Solution, 0.01 M—Dissolve 3.7 to
Metals EDTA, 0.01 M—Dissolve 3.7225 g of the
disodium salt of EDTA in water and dilute 3.8 g of EDTA in distilled water and dilute
EDTA (ethylenedinitrilotetracetate, ac- to 1 liter. Store in a polyethylene or glass to 1 liter. Store in polyethylene or borosili-
cording to American Chemical Society bottle. cate glass bottle.
[ACS) nomenclature, but commonly called Zinc Chloride Solution, 0.01 M—Dissolve Buffer Solution—See Subsection 2.2.4.1.
jthylenediaminetetracetate) combines (che- about 0.6538 g of zinc, weighed to the Indicator—See Subsection 2.2.4.1.
lates) strongly with metals used in driers nearest 0.0001 g, in 25 ml of HCl (1 acid + Standardization of EDTA Solution—
ind metallic soaps. However, it is the 3 water), warming if necessary, and dilute Transfer 25 ml of the solution to a 250-ml
lisodium salt rather than the free acid that to 1 liter. flask, add 10 ml of buffer solution, about
s used in chelometric titrations. The com- Buffer Solution—Dissolve 54 g of am- 0.1 g of indicator, and titrate with standard
jound is also known by trade names, such monium chloride (NH4CI) in 350 ml of magnesium solution to a red color. The
IS Komplexon and Versene. NH4OH and dilute to 1 liter. number of milliliters is Titration A.
74 RAW MATERIALS
Procedure (CuS04-5H20) in water and dilute to 1 Also, to guard against error that may be
Transfer 0.900 ± 0.001 g to a 150-ml liter. introduced by suspended matter if the
flask. Dissolve in 5 ml or less of benzene. Buffer Solution (pH 70)—Dissolve 67.5 g sample is not clear, the suspended matter
Dilute to mark with methanol. of NH4CI in water, add 570 ml of NH4OH must be removed by centrifuging.
Total Metals—Transfer a 25-ml aliquot (sp gr 0.90), and dilute to 1 liter. Other cations that can be titrated with
to a 250-mlflask.Add 25 ml of methanol— Eriochrome Black-T Indicator—See Sub-EDTA in alkaline media interfere and, if
more if solution becomes cloudy. Add 25 section 2.2.11.12. present, must be masked as in the Graske
ml of EDTA solution, 0.1 g of tartaric acid PAN Indicator—Dissolve 0.1 g in 100 ml method (2.2.11.13).
(to unmask lead), 0.1 g of ascorbic acid of ethanol or isopropanol.
(to unmask manganese), about 5 drops of a Staruiardization of EDTA Solution—Dis- 2.2.4.6 ASTM D 2613, EDTA Method
15 percent solution of NaOH, 10 ml of sslve 1.5 g, accurately weighed, of zinc for Calcium or Zinc
buff'er solution, and about 0.1 g of indica- oxide (ZnO) in 10 ml of H2SO4 (8 acid -t- 1 This procedure is essentially the same as
tor. NOTE—Contents of flask should be water) in a 100-ml beaker. Transfer to a that for manganese.
blue; if pink, use a smaller aliquot and 500-ml volumetricflaskandfillto the mark
adjust computations accordingly. Titrate with water. calcium, percent =
excess EDTA with standard magnesium Transfer a 50-ml aliquot to a 500-ml (FiMi - ViMiA.QXjW
sulfate solution as in standardizing. The flask, add 100 ml of water and neutralize
number of milliliters is Titration B. with 8 percent NaOH solution, using zinc, percent
Lead and Manganese—Proceed as for methyl red as indicator. Add 5 ml of buflfer (FiM, - K2Af2)6.54/>f
total metals except, before adding the solution, 0.2 g of Eriochrome indicator,
EDTA solution, add 0.5 g of potassium and titrate with EDTA solution to a blue where:
cyanide (KCN)!! to mask zinc and cobalt. end point. Ki = ml of EDTA solution,
The number of milliliters is Titration C. M = (g of ZnO)/0.814 (ml of EDTA)
Zinc, Lead, and Manganese—Proceed as Vi = ml of ZnClj solution.
for total metals except, before adding the Procedure Ml = molarity of EDTA solution.
EDTA solution, add 0.5 g of KCN!! to Into a 500-ml flask, weigh appropriate Mi = molarity of ZnCU solution, and
mask zinc and cobalt, and 3 ml of formal- amounts of drier—1.0 to 1.3 g for 6 percent W — grams of sample.
dehyde solution (15 ml of 38 to 40 percent cobalt; 0.8 to 1.0 g for 8 percent cobalt.
formaldehyde, 20 ml of water, and 5 ml of Add 5 ml of glacial acetic acid and warm
glacial acetic acid) to unmask zinc. The on a hot plate at low heat, swirling the 2.2.5 Tests on Metallic Soaps
number of milliliters is Titration D. flask until the drier is completely dissolved. Much can be learned about the suitability
Zinc, Cobalt, and Manganese—Proceed In a second flask (blank) add the same of metallic soaps by visual examination.
as for total metals except, before adding the amount of glacial acetic acid, but no drier. For example, those that are readily soluble
EDTA solution, add 0.5 g of diethyldithio- To each flask add 200 ml of isopropanol, and those that impart relatively higher vis-
carbonate to mask lead. NOTE—Color 100 ml of water, 6 ml of concentrated cosities to solutions are almost invariably
change in this titration is green to brown to NH4OH, 10 ml of a saturated solution of finely divided. When mixed with colorless
pink. The number of milliliters is Titration sodium acetate, and 50 ml of EDTA solu- paraffin oil, the morefinelydivided stearates
E. tion. Swirl to ensure complete mixing, and produce milky appearing systems with no
Computations warm both flasks at steam bath tempera- visible coarse particles. Other stearates con-
ture for 5 min. tain lumps or agglomerates that settle
One milliliter of magnesium sulfate To each flask add 2 ml of PAN indicator rapidly and do not break up on stirring.
(MgSOO solution = 0.01 X 0.001 X and titrate with standard CUSO4 solution The microscope reveals the fine structure of
atomic weight of metal in grams. to a blue end point. some specimens, and the particles, although
apparently not crystalline, are clearly de-
percent of metal = percent cobalt = fined and fairly uniform in size. Other
titration X factor X 100 ( g - S ) X M X F X 50 specimens are more or less agglomerated
grams of sample X 100 and very nonuniform. Particles of free acid
By.W
can be often recognized under the micro-
where factor is: where: scope by their semitransparency.
0.002072 for lead, B =ml of CUSO4 solution for blank, Since the selection of the soap depends
0.0005495 for manganese, S =ml of CUSO4 solution for sample, upon its proposed use, all tests applied to a
0.0006538 for zinc, and M =molarity of the CUSO4 solution, soap intended to impart nonsettling need
0.0005894 for cobalt. F =millimolecular weight of cobalt not be applied to a soap intended to impart
(0.05894), and flatting. For the former property the soap
2.2.4.3 ASTM D 2373, EDTA Method W = gof sample. should gel readily; for the latter the less
for Cobalt gelling, the better.
The drier is dissolved in glacial acetic 2.2.4.4 ASTM D 2374, EDTA Method The temperature of gelling varies with
acid, diluted with isopropanol and water, for Lead the type of soap. Those intended for im-
and buffered. An excess of standard EDTA This method is identical to the preceding parting bodying or nonsettling should gel
solution is added, and the excess is titrated one for cobalt. The F in the computation at relatively low temperatures. Free acid
with standard copper sulfate solution to the is 0.2072. greatly influences gelling, a low content
blue end point of PAN indicator. favoring stiff' gels.
EDTA Solution, 0.05 M—Dissolve 18.62 2.2.4.5 ASTM D 2375, EDTA Method Aluminum and calcium stearates and
g of EDTA in water and dilute to 1 liter. for Manganese oleates are used in considerable quantities
Store in polyethylene or borosilicate glass This method is the same as the Lucchesi to impart physical properties, such as body
bottle. (2.2.4.2), except that the standard solutions and nonsettling to various types of paint,
Cupric Sulfate Solution, 0.05 Af—Dis- are 0.05 M instead of 0.01 M, and the flatness to interior wall paint, and a rubbed
solve 12.5 g of copper sulfate-pentahydrate sample weights are correspondingly greater. finish to some furniture varnishes.
DRIERS AND METALLIC SOAPS 75
2.2.5.1 Mallinckrodt Gel Test [8] Licata, F. J., "Properties and Uses of Alumi-
num in the Paint and Varnish Industry," ibid.,
The following directions for examining Vol. 5, 1933, p. 160.
the gelling properties of aluminum stearate
may be applied to other metallic soaps.
Heat 10 g of aluminum stearate with 90
ml of crude paraffin oil in a 200-ml beaker
to 150 C. Stir the contents constantly while
heating. When solution is complete, cool to
10 C. The gel may vary from a soft oily to
a hard solid mass.
Test firmness of the gel in an apparatus
such as shown in Fig. 2.2-1. Set the beaker
containing the gel under the beaker. Pour
mercury or shot into the beaker on the pan
until the disk breaks through the surface of
the gel. Record the weight including the
disk. A more sophisticated apparatus is
shown in Fig. 2.2-2.
2.2.5.2 Licata Gel Test
This [8] is probably the ultimate in
simpUcity. Merely heat 5 g of the metallic
soap with 100 g of toluene in a flask or
beaker, stirring with a thermometer. Note
the temperature at which gelling begins.
REFERENCES
[1] Carrier, C. F., "The Aridyne—A Standard
Unit of Drying Power," Scientific Section
Circular, National Paint,. Varnish, and
Lacquer Association, NAPVA, No. 370, 1930,
p. 510, No. 404, 1931, p. 535.
[2] Weatherburn, A. S., Weatherburn, M. W., and
Bayley, C. H., "Determination of Copper and
Zinc in Their Naphthenates," Industrial and
Engineering Chemistry, Analytical Edition,
lENNA, Vol. 16, 1944, p. 703.
[5] Castiglioni, A., "The Analysis of Lead
Resinate," Annalen Chimica Applicala, Vol. 30,
1941, p. 266.
[4] Tanteri, B., "Determination of Soluble Metal
in Several Metallic Resinates, Using Castig-
lioni Method," ibid.. Vol. 31, 1941, p. 208.
[5] Diener, E. W. and Werthan, S., "A Method for
Determination of True Acid Value of Oils,
Varnishes, Driers, and Soaps," Proceedings,
American Society for Testing and Materials, FIG. 2.2-2. Tecam Gelatin Timer, Measures the
ASTEA, Vol. 30, Part II, 1930, p. 924. length of time required for a specimen to develop
[6] Lucchesi, C. A., "Rapid Determination of the enough strength to support a disk, % in. in
Metal Content of Paint Driers," Offiicial diameter and weighing 16.5 g. The disk is im-
Digest, Federation of Paint and Varnish mersed in the liquid specimen, and a simple
Production Clubs, ODFPA, Vol. 30, 1958, harmonic motion is imparted to it by a syn-
p. 1178. chronous motor. As the specimen sets, a point is
7] Graske, A., "Determination of Cobalt, Zinc, reached where the stiffness is sufficient to support
Manganese, and Lead Found in Mixed Driers, the disk. A neon lamp signals the event, and the
EDTA Complexometric Titration in Benzene elapsed time is shown on a counter. Periods of 1
Solution with Methanol," ibid.. Vol. 33, 1961, and 0.1 min are available. (Courtesy of Techne.
p. 855. FIG. 2.2-1. Simple Apparatus for Gel Strength. Inc.)

Driers and Metallic Soaps 2

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Driers and Metallic Soaps 2

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STP500-EB/Jun.

DRIERS AND METALLIC SOAPS

TABLE 2.2-1. Properties of Metallic Soaps

Total Ash, Free Fatty Specific Melting

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