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Chemical Composition of a Fountain Pen Ink

Article  in  Journal of chemical education · October 2006

DOI: 10.1021/ed083p1476

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 Chemistry for Everyone

Chemical Composition of a Fountain Pen Ink

J. Martín-Gil,* M. C. Ramos-Sánchez, and F. J. Martín-Gil
Laboratorio de Química Sostenible, Departamento de Ingeniería Agrícola y Forestal,
Universidad de Valladolid—Escuela Técnica Superior de Ingenierías Agrarias, Palencia-3407, Spain;
*[email protected]

M. José-Yacamán
Laboratorios de Microscopía Electrónica de Barrido y Difractometría de Rayos-X,
Instituto Nacional de Investigaciones Nucleares, México, D. F., México

The manufacture of ink is associated with the graphical The different compositions of inks influence their per-
arts, but it is classified as part of the chemical industry. It is manence on paper. There is agreement that the main cause
paradoxical that a substance so easily definable as a fluid or of variation of written text is the iron(II) sulfate content of
viscous material used to write and to print has reached such a the ink, whose effect is stronger than the destructive action
level of complexity and specialization that almost a million of the acids. The mechanism that traditionally has been cited
new formulas appear every year. Within this context, a study is oxidative decomposition of the cellulose by means of the
of a particular ink makes the characterization, as far as pos- free radicals that are generated after the formation of unstable
sible, of its chemical composition and subsequent classifica- complexes of metallic ions with molecular oxygen (2):
tion necessary. In the case of black ink, this classification is • Formation of the organic hydroperoxide (ROO•) and
typically in one of the three prominent ink types: gallotannate other organic radicals
(also called iron-gall) ink, Chinese ink, and printers’ ink. The
gallotannate ink is made from monohydrated gallic acid, crys- Fe2+ + O2 Fe3+ + O2• − (1)
tals of ferrous sulfate, and gum Arabic (Figure 1). In agree-
ment with the Babylonian Talmud, black ink was discovered
Fe3+ + O2• − + RH R• + HOO• + Fe2+ (2)
by Tanna Rabbi Meir (second century C.E.) as reported by
Nir-El and Broshi (1). Chinese ink is made with carbon black,
R• + O 2 ROO• (3)
fish glue, indigo, and camphor. Its primitive formulation, with
carbon black in emulsion with vegetal pigments or animal oils,
ROO• + R′H ROOH + R′• (4)
dates back 4500–5000 years. Printers’ ink (analogous to
ballpoint pen ink) uses varied pigments and includes desic- • Formation of hydrogen peroxide
cants (compounds of calcium and iron), waxes, fats, rubber,
+
and varnish in its composition. Fe2+ + HOO• + H Fe3+ + H2O2 (5)

• The Fenton reaction

−
Fe2+ + H2O2 Fe3+ + HO• + OH (6)

The iron salt-dependent decomposition of hydrogen perox-

ide generates the highly reactive hydroxyl radical, possibly
via an oxoiron(IV) intermediate.
Other equally important reactions are those of the
iron(II) sulfate reduction to pyrite by the action of certain
microorganisms (Desulfovibrio desulfuricans or Desulfoto-
maculum nigrificans) (3, 4):
gallotannic acid − +
2CH2O + SO42 + 2H
a carbon from
source bacteria (7)
H2S + 2CO2 + 2H2O
gallic acid

+
Figure 1. Galls such as these have been widely used in the pro- Fe2 + H2S FeS + 2H+ (8)
duction of inks. Ink recipes require that the powdered or crushed
galls be boiled for several hours (to release the tannins) and that + −
the resultant solution be fermented by mold. As the mold enzymati- RCHOHCOOH + Fe2 + SO42
cally digests the gallotannic acid, the solution is transformed to gallic from components
acid. Gallic acid will produce a purer black color in reaction with of the ink
iron sulfate, while gallotannic acid will produce a comparatively
(9)
browner pigment. RCOOH + 2CO2 + H2O + FeS

1476 Journal of Chemical Education • Vol. 83 No. 10 October 2006 • www.JCE.DivCHED.org

 Chemistry for Everyone

The conversion to pyrite and its subsequently loosening from that have contents of this chemical species greater than 15%
the paper leads to the partial loss of the indelible character of in weight (on the dry basis). The low ferrous sulfate content
the majority of inks and to the loss of clarity in the writing of in the ink makes it less susceptible to deterioration by con-
the documents (5). The objective of this article is to examine version to pyrite and therefore, little decay is anticipated. The
if Parker Quink ink, widely used in 1950–1980 for fountain composition obtained for the black Parker ink (with an evi-
pens, will provide the permanence necessary for the preserva- dent lack of phosphorus) is also not similar to Chinese ink
tion of documents. Quink ink, a combination of Quisumbing (Table 4), which is rich in phosphates from the fish glue.
and ink, was invented and sold to Parker by Philippine chemist
Francisco Quisumbing and began to be used in the 1930s.
Table 1. Elemental Composition
Material and Methods of the Black Parker Quink Ink

The samples examined are the viscous remainders of Color C O Na S K Fe

spontaneous evaporation of the Parker Quink ink. Observa- Black 61.94 24.55 4.71 8.53 0.12 0.15
tions with a microscope indicate that, although homogenous Green 58.73 26.00 5.22 9.67 0.22 0.17
in texture, the ink is composed of tonalities of different col- NOTE: Data determined by EDAX-SEM. The results are in weight
ors: ones entirely black and others black–green and irides- percentage.
cent (these last ones are suggestive of contamination by
pyrite). For this reason, both components have been analyzed. Table 2. Inorganic Element Composition
of the Black Parker Quink Ink
The microanalyses have been carried out using two X-rays
techniques: one based on energy-dispersive X-rays (EDAX) Color S K Ca Mn Fe Ni Cu Zn Cr
generated by scanning electronic microscopy and the other Black 78.21 8.70 9.46 0.27 2.44 0.29 0.26 0.36 —
based on total reflection (this one of great sensitivity). The Green 84.68 5.12 7.44 0.37 1.38 0.22 0.18 0.16 0.44
techniques provide complementary information. EDAX data NOTE: Data determined by total X-ray reflection. The results are in
have been obtained with a new XL-30 Zaphire apparatus con- weight percentage.
nected to a SEM Philips XL30 microscope and total reflec-
tion data with an AXIAL IBM-PC V3.00. X-rays were Table 3. Composition of the Typical Calligraphic
gathered for optimal angles. Gallotannate Inks
Results Weight
Component
(%)
The analytical results are shown in Tables 1 and 2. The a
Aleppo galls , gall-nuts, tannic acid
b

sum of the average percentage of three elements, C, O, and 40–60

and/or gallic acidc
Na, is ∼90% (Table 1). The remaining 10% can be more ac- Ferrous sulfate (FeSO4 ⭈7H2 O) 15–20
curately obtained by multiplying the percentages of inorganic d
Arabic gum 10–15
elements from Table 2 by 0.1. Thus, the most probable com-
Indigoe (logwood) or soluble blue 2– 4
position for the Parker ink is 60% C; 25% O; 5% Na; 8%
S; 0.7% K; 0.8% Ca; and 0.2% Fe. Potassium dichromate/Potasssium aluminum sulfatef 2
If we consider (from the percentage of sulfur) that the Phenol/Boric acid 2
a
percentage of inorganic oxygen (as sulfate) is 16% and that An excrescence on Quercus lusitanica, Lamarck (Quercus infectoria,
the total oxygen percentage is 25%, the percentage of organic Olivier), caused by the punctures and deposited ova of Cynips Gallae
tinctoriae, Olivier (or Diplolepis gallae tinctoriae, of Geoffroy), an
oxygen would be 9%. As the C:O ratio in organic compounds hymenopter indigenous to the country from the Bosporus to Syria, and
is 1.3:1, the percentage of carbon deduced from the percent- from the Archipelago to the frontier of Persia. b Extracted from fermented
age of organic oxygen would be 12%. Consequently, the free c
plant galls with water-saturated ether. Product of the hydrolysis of tannic
carbon content should be 48%. On the other hand, for bitu- acid, it will produce a purer black color in reaction with iron(II) sulfate,
minous compounds, 9% of C corresponds to 23% of global while gallotannic acid produces a comparative browner pigment. dA
water soluble golden-colored sap collected from Acacia trees (Acacia
matter. Therefore a reasonable proposal on the composition senegal). eObtained from the wood of the campeachy tree. Boiled in
of the Parker Quink ink is the following: tap water, it creates a blood-red solution, although it will shift to blue in
• 48% carbon in the elementary state alkaline solutions and to yellow–orange in highly acidic solutions.
f
Chemicals with presumable stabilizing properties for the ink.
• 23% bituminous or resinous organic compounds with
high carbon content Table 4. Black Chinese Ink Composition
• 16% sodium sulfate Component Weight (%)
• 7% calcium sulfate Carbon black (from soot) 25–33
• 4% potassium sulfate Fish glue 66–75
• 1% iron(II) sulfate Indigo 1
• 1% mineral species (not characterized) containing Ni, Camphor 1
Cr, Cu, and Zn NOTE: The black soot is produced by the imperfect combustion of pitch
The first conclusion that can be obtained from this com- resin, or fatty substances, such as naphthalene, in a vessel within a tent
made of sheepskin or paper. The smoke is deposited on the inside of the
position is that the Parker Quink ink, although rich in sul- tent which is then beaten to cause the soot to fall off. The soot is then
fates, is poor in iron(II) sulfate. This feature differentiates it heated several times to a very high temperature in a metal container
from the composition of typical gallotannate inks (Table 3) having small opening in the top, through which the impurities escape.

www.JCE.DivCHED.org • Vol. 83 No. 10 October 2006 • Journal of Chemical Education 1477

 Chemistry for Everyone

On the other hand, the comparison of the Parker ink Table 5. Chemical Composition of the Powders
composition with the printing ink composition (Table 5), Used in the Traditional Printing Inks
referred in 1875 by Rafael Sáez y Palacios (6) (according to Powders Weight (%)
French chemist Henri Braconnot; ref 7 ), led us to observe Carbon 79.4
important similarities, although admitting the following dif-
Resins and bitumen 5.3 + 1.7
ferences:
(NH4)2SO4 3.3
• Although the raw materials are similar for both the
K2SO4 0.4
Parker fountain pen ink and the printing ink, the de-
CaSO4 0.8
gree of pyrolysis is smaller for the former since the per-
centage of carbon in the elementary state is higher in (Fe,Ca)3(PO4)2 0.3
the latter. SiO2 0.6
• Sodium sulfate can perform the same function in the H2O 8
Parker fountain pen ink as the ammonium sulfate in Others 0.5
the printing ink. Note: Data according to Braconnot (7). Ulmine and
unidentified species are included in the "others".
Other conclusions can be obtained from the composi-
tion for Parker Quink ink. Since the deliberate addition of
potassium sulfate to any of the two varieties of fountain pen confers to the fountain pens. The new printers’ inks, primarily
ink seems improbable and since the quantity of potassium those for house or office printers, tend to differ more from
dichromate in the green-colored variety is low, it seems rea- the writing inks and only in rare cases are they analogous: for
sonable to postulate a vegetal origin for the potassium ion. example, the Parker Quink ink is compatible with the ink used
We believe that such vegetal origin for the potassium ion in the cartridges of the printing HP Portable DeskJet. Such
comes from logwood or indigo. Carbon black and indigo have similarities suggests a forward monitoring of writings printed
the advantage of imparting a preservative effect to the ink. with this type of ink-jet. Finally, the microbiological study of
the inks has shown that the addition of phenols is not suffi-
Discussion cient to prevent colonization by bacteria and mold.
This article achieves the aim of exposing undergraduate
As a result of the low iron(II) sulfate content, we can students to the world of printing and publishing. Science stu-
conclude that the Parker Quink ink will be relatively stable dents will gain an insight into the materials and process of
on documents, in suitable conditions, and thus will provide ink production. On the other hand, students in creative dis-
longevity (8–10). However, documents written with this ink ciplines who are interested in the conservation of documents
are partially erased by water immersion and almost totally will learn about the necessity of securing the longevity of writ-
erased when minimum quantities of nonbiological detergent ings and drawings created with computer printers.
are added to the water. The vendor was asked to give an ex-
planation regarding this observation (11): Literature Cited
Parker inks are not designed to meet the specialist require-
1. Nir-El, Y.; Broshi, M. Dead Sea Discoveries 1996, 3, 157–167.
ments laid down for inks intended for use in Official regis-
2. Halliwell, B.; Gutteridge, J. M. C. Biochem. J. 1984, 219, 1–14.
ters [and that the term] permanent [is to indicate that the
3. García-Guinea, J.; Martínez-Frías, J.; González-Martín, R.;
ink] although water-based, contains dyes that have no great
Zamora, L. Nature 1997, 388, 631.
affinity with paper, cotton, wool or any absorbent material
4. Kim, S. D.; Kilbane, J. J.; Cha, D. K. Eniron. Eng. Sci. 1999,
[and that] when subjected to water immersion the soluble
16, 139–145.
dye is washed away, leaving a legible permanent trace.
5. Buquet, A. Int. Criminal Police Rev. 1982, 362, 237.
Tests of stability with respect to water immersion with simi- 6. Sáez y Palacios, R. Tratado de Química Inorgánica Teórico y
lar inks resulted in similar conclusions, although Pelikan 4001 Práctico; Carlos Bailly-Bailliere: Madrid, 1875.
and Cross inks are more indelible (11). 7. Braconnot, H. http://www.cyberlipid.org/chevreul/braconnot.htm
With respect to the comparison established between the (accessed Jun 2006).
Parker Quink ink and old press ink, it is necessary to point 8. Cantu, A. A. J. Foren. Sci. 1988, 33, 744.
out that their analogies are greater than their differences only 9. Fryd, C. F. M. Med. Sci. Law 1974, 14, 87.
on the dry basis. However in suspension the press inks are 10. Patterson, D. J. Foren. Sci. Soc. UK 1964, 4, 200.
greasier and more gelatinous than those of writing inks, and 11. Friend, A. Wessex LMCs Bulletin 2000, Sept. http://
the sticky character of those (inspired by the ink used in Biro’s www.dgitservices.co.uk/wessexlmcs/bullarch/sep00bull/
ballpoint pen) contrasts with the fluidity that ethylene glycol sep00bull.html (accessed Jun 2006).

The structures of a number of the molecules discussed in this article are available in fully
manipulable Jmol and Chime format as JCE Featured Molecules in JCE Online (see page 1568).

Featured Molecules
http://www.JCE.DivCHED.org/JCEWWW/Features/MonthlyMolecules

1478 Journal of Chemical Education • Vol. 83 No. 10 October 2006 • www.JCE.DivCHED.org

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