List of Content

Chapter – I 2-7
 Introduction
Chapter – II
 Research History 8-33
 Types
 Heavy Metals
 Classification of Dyes
 Type of Dyes
 OBSERVATION:
 USES
Chapter – III 34-41
 Research Method
 Testing methods
 Materials
 Preparation
 Aniline Ink
 Method of preparation of Gallo-tannic ink
Chapter – IV 42-57
 Data analysis & Result
 Ink testing for food, pharmaceutical and other packaging:
 How to prepare ink at home
 Composition
 Manufacturers
 Durability and security
 Main Chemicals, Compounds, Components
Chapter – V 58-60
 Conclusion, Reference

1
Chapter – I
Introduction

2
1.1 Introduction

Many say that pen is mightier than sword, but ever thought that what

makes the pen mightier? Yes it is the wonder liquid INK. You might

have used ink many times for writing but have you ever bothered that

from where it comes? How it is prepared? What materials are used in its

preparation? Etc. I’m sure your answer would be NO! But don’t worry

this project includes answer of all your questions.

This project throws a light on types of inks from manufacturing point of

view and includes method for preparing them either in chemistry

laboratory or at home.

Traditional ink is comprised of a dispersed colloidal slurry mixture that

includes pigments, binders, solvents, and additives (Ding et al., 2011;

Robert, 2015). Each component of traditional ink shows insecurity due to

limitations in technology and materials, particularly pigments and

additives. Heavy metals, specifically, in pigments and additives pose a

significant threat to human health. Drying agents added to ink include

aromatic solvents such as benzene, xylene, polycyclic aromatic

3
hydrocarbons, and their derivatives, which pollute the air and threaten the

health of print workers as they evaporate (Ink, 2015). Volatile organic

compounds (VOC), also used as drying agents, cause similar problems

(Volatile, 2015). Edible ink, a relatively new alternative to traditional

ink, is comprised of materials such as coloring agents, solvents, binders

(usually edible, natural polymers,) and surfactants that are safe for human

consumption (Chrysavgi et al., 2011; George Savvidis et al., 2013).

Chitosan oligochitosan (COS) is nontoxic, biodegradable, and

antimicrobial, and has been studied for numerous applications in food,

pharmaceuticals, and cosmetics (Yin et al., 2013; Wang et al., 2008; Yin

et al., 2010); its low viscosity, high solubility, and good film-forming and

metal ion chelating properties make COS an effective ink binder. In this

study, different formulations of blue edible inkjet inks were prepared

using COS. The properties of these different ink formulations were

analyzed by measuring their conductivity, surface tension, viscosity, and

antimicrobial properties. Chromaticity, density, and bacteriostatic

4
experiments were also conducted on the ink samples. The results are

compared and discussed below.

Ink is a liquid or paste that contains pigments or dyes and is used to

colour a surface to produce an image, text, or design. Ink is used for

drawing or writing with a pen, brush, or quill. Thicker inks, in paste

form, are used extensively in letterpress and lithographic printing. Ink

can be a complex medium, composed of solvents, pigments, dyes, resins,

lubricants, solubilizers, surfactants, particulate matter, fluorescents, and

other materials.

The components of inks serve many purposes; the ink’s carrier,

colorants, and other additives affect the flow and thickness of the ink and

its appearance when dry. India is among the fast growing printing &

writing ink markets globally spurred by the rapid expansion of the

domestic print markets.

Backed by a strong demand from key end user segments such as package

printing, newsprint, publishing and other commercial printing, the

printing ink market in India has registered strong growth over the years.

5
The printing ink industry is fragmented with hundreds of manufacturers

and a large number of players in the unorganised sector.

Ink is a liquid or semiliquid material used for writing, printing, and

drawing. It consists of a mixture of coloring matter—usually a pigment

or dye—plus a vehicle, or carrier, that may be simply water or a natural

or synthetic chemical compound. Some ink formulas also contain

additives to impart special properties demanded by the method of

application, the material to which the ink is applied (called the substrate),

or some other factor.

The two principal types of inks are those used for writing and those used

in the printing trade. There are others for special use such as stenciling

and fingerprinting or for mimeographs and stamp pads. Electrostatic or

xerographic inks found in office copying machines are not true inks but

consist rather of electrically charged bits of colorant that are deposited on

a paper surface. Magnetic inks on bank checks and other documents that

require source identification are printed with inks containing an iron

oxide pigment capable of being magnetized.

6
Ink is a liquid or paste that contains pigments or dyes and is used to color

a surface to produce an image, text, or design. Ink is used for drawing or

writing with a pen, brush, or quill. Thicker inks, in paste form, are used

extensively in letterpress and lithographic printing.

Ink can be a complex medium, composed of solvents, pigments,

dyes, resins, lubricants, solubilizers, surfactants, particulate

matter, fluorescents, and other materials. The components of inks serve

many purposes; the ink's carrier, colorants, and other additives affect the

flow and thickness of the ink and its dry appearance.

In 2011 worldwide consumption of printing inks generated revenues of

more than 20 billion US dollars. Demand by traditional print media is

shrinking, on the other hand more and more printing inks are consumed

for packagings. Printing ink sector in India witnessed a growth of around

7.5% per annum during the Past years. Printed packaging accounts for

around 27% of the demand for printing inks in India followed by

newspapers at 20%. Commercial printing/promotional and printed

advertising together account for around 19% of the demand.

7
 Chapter –II
Research History

8
2.1 Research History

Ink drawing of Ganesha under an umbrella (early 19th century). Ink,

called masi, an admixture of several chemical components, has been used

in India since at least the 4th century BC. The practice of writing with ink

and a sharp pointed needle was common in early South India.

[3]
 Several Jain sutras in India were compiled in ink.

Many ancient cultures around the world have independently discovered

and formulated inks for the purposes of writing and drawing. The

knowledge of the inks, their recipes and the techniques for their

production comes from archaeological analysis or from written text itself.

Ink was used in Ancient Egypt for writing and drawing on papyrus from

at least the 26th century BC.

9
The history of Chinese inks can be traced to the 23rd century BC, with

the utilization of natural plant (plant dyes), animal, and mineral inks

based on such materials as graphite that were ground with water and

applied with ink brushes. Evidence for the earliest Chinese inks, similar

to modern inksticks, is around 256 BC in the end of the Warring States

period and produced from soot and animal glue. The best inks for

drawing or painting on paper or silk are produced from the resin of the

pine tree. They must be between 50 and 100 years old. The Chinese

inkstick is produced with a fish glue, whereas Japanese glue is from cow

or stag.

The process of making India ink was known in China as early as the

middle of the 3rd millennium BC, during Neolithic China. India ink was

first invented in China, although the source of materials to make the

carbon pigment in India ink was later often traded from India, thus the

term India ink was coined. The traditional Chinese method of making the

ink was to grind a mixture of hide glue, carbon black, lampblack,

and bone black pigment with a pestle and mortar, then pouring it into a

10
ceramic dish where it could dry. To use the dry mixture, a wet brush

would be applied until it reliquified. The manufacture of India ink was

well-established by the Cao Wei Dynasty (220–265 AD). Indian

documents written in Kharosthi with ink have been unearthed in Chinese

Turkestan. The practice of writing with ink and a sharp pointed needle

was common in early South India. Several Buddhist and Jain sutras in

India were compiled in ink.

In ancient Rome, atramentum was used; in an article for the Christian

Science Monitor, Sharon J. Huntington describes these other historical

inks:

Oak galls and iron(II) sulfate .

11
About 1,600 years ago, a popular ink recipe was created. The recipe was

used for centuries. Iron salts, such as ferrous sulfate (made by treating

iron with sulfuric acid), were mixed with tannin from gallnuts (they grow

on trees) and a thickener. When first put to paper, this ink is bluish-black.

Over time it fades to a dull brown.

Scribes in medieval Europe (about AD 800 to 1500) wrote principally

on parchment or vellum. One 12th century ink recipe called for hawthorn

branches to be cut in the spring and left to dry. Then the bark was

pounded from the branches and soaked in water for eight days. The water

was boiled until it thickened and turned black. Wine was added during

boiling. The ink was poured into special bags and hung in the sun. Once

dried, the mixture was mixed with wine and iron salt over a fire to make

the final ink.

The reservoir pen, which may have been the first fountain pen, dates

back to 953, when Ma'ād al-Mu'izz, the caliph of Egypt, demanded a pen

that would not stain his hands or clothes, and was provided with a pen

that held ink in a reservoir.

12
In the 15th century, a new type of ink had to be developed in Europe for

the printing press by Johannes Gutenberg. According to Martyn Lyons in

his book Books: A Living History, Gutenberg's dye was indelible, oil-

based, and made from the soot of lamps (lamp-black) mixed with varnish

and egg white. Two types of ink were prevalent at the time: the Greek

and Roman writing ink (soot, glue, and water) and the 12th century

variety composed of ferrous sulfate, gall, gum, and water. [18] Neither of

these handwriting inks could adhere to printing surfaces without creating

blurs. Eventually an oily, varnish-like ink made of soot, turpentine, and

walnut oil was created specifically for the printing press.

13
2.2 Types

Magnified line drawn by a fountain pen.

Ink formulas vary, but commonly involve two components:

 Colorants

 Vehicles (binders)

Inks generally fall into four classes:

 Aqueous

 Liquid

 Paste

 Powder

14
2.3 Colorants

Pigments

Pigment inks are used more frequently than dyes because they are more

color-fast, but they are also more expensive, less consistent in color, and

have less of a color range than dyes. Pigments are solid, opaque particles

suspended in ink to provide color. Pigment molecules typically link

together in crystalline structures that are 0.1–2 µm in size and comprise

5–30 percent of the ink volume. Qualities such as hue, saturation,

and lightness vary depending on the source and type of pigment.

Dyes

Dye-based inks are generally much stronger than pigment-based inks and

can produce much more color of a given density per unit of mass.

However, because dyes are dissolved in the liquid phase, they have a

tendency to soak into paper, making the ink less efficient and potentially

allowing the ink to bleed at the edges of an image.

To circumvent this problem, dye-based inks are made with solvents that

dry rapidly or are used with quick-drying methods of printing, such as

15
blowing hot air on the fresh print. Other methods include harder

paper sizing and more specialized paper coatings. The latter is

particularly suited to inks used in non-industrial settings (which must

conform to tighter toxicity and emission controls), such as inkjet

printer inks. Another technique involves coating the paper with a charged

coating. If the dye has the opposite charge, it is attracted to and retained

by this coating, while the solvent soaks into the paper. Cellulose, the

wood-derived material most paper is made of, is naturally charged, and

so a compound that complexes with both the dye and the paper's surface

aids retention at the surface. Such a compound is commonly used in ink-

jet printing inks.

An additional advantage of dye-based ink systems is that the

dye molecules can interact with other ink ingredients, potentially

allowing greater benefit as compared to pigmented inks from optical

brighteners and color-enhancing agents designed to increase the intensity

and appearance of dyes.

16
A more recent development in dye-based inks are dyes that react with

cellulose to permanently color the paper. Such inks are not affected by

water, alcohol, and other solvents. As such, their use is recommended to

prevent frauds that involve removing signatures, such as check washing.

This kind of ink is most commonly found in gel inks and in

certain fountain pen inks.

2.4 Health and environmental aspects

There is a misconception that ink is non-toxic even if swallowed. Once

ingested, ink can be hazardous to one's health. Certain inks, such as those

used in digital printers, and even those found in a common pen can be

harmful. Though ink does not easily cause death, repeated skin contact or

ingestion can cause effects such as severe headaches, skin irritation, or

nervous system damage. These effects can be caused by solvents, or by

pigment ingredients such as p-Anisidine, which helps create some inks'

color and shine.

17
2.5 Three main environmental issues with ink are:

Heavy Metals

"Wikipedia" written with self-made iron gall ink

 Non-renewable oils

 Volatile organic compounds

Some regulatory bodies have set standards for the amount of heavy

metals in ink. There is a trend toward vegetable oils rather

than petroleum oils in recent years in response to a demand for

better environmental sustainability performance.

Ink uses up non-renewable oils and metals, which has a negative impact

on the environment.

18
What is Dye?

Plastic toys for children to that fabrics you wear, from food to wood;

hardly there is any industry where coloring material that color

commodities of our day to day use. Dyes are applied everywhere, from a

natural or synthetic substance used to add a color or to change the color

of something. Dyes are the dyes are not used commercially.

A dye is a colored substance that has an affinity to the substrate to

which it is being applied. It is an Ionising and aromatic organic

compounds. The dye is generally applied in an aqueous solution, and

may require a mordant to improve the fastness of the dye on the fiber.

With the help of dyes we can easily manipulate things according to our

liking. At the very basic level the use of color in identifying individual

components of tissue sections can be accomplished primarily with dyes.

The rule that we apply to other chemicals is similarly applicable to

dyes also. They also get completely or atleast partially soluble in

19
which it is being put to. For example certain kind of dyes can be

toxic, carcinogenic or mutagenic and can be hazardous to health.

What makes the Dyes colored?

Dyes are basically ionising and aromatic compounds, they have

Chromophores present in them. Their structures have Aryl rings that has

delocalised electron systems. These structures are said to be responsible

for the absorption of electromagnetic radiation that has varying

wavelengths, based upon the energy of the electron clouds.

Chomophores make the dyes proficient in their ability to absorb

radiation. Chromophores act by making energy changes in the

delocalised electron cloud of the dye. This alteration invariably results in

the compound absorbing radiation within the visible range of colors and

not outside it. Human eyes detects this absorption, and responds to the

colors. Electrons may result in loss of color, their removal may cause the

rest of the electrons to revert to the local orbits. A very good example is

the Schiff's reagent. As Sulphurous acid reacts with Pararosanilin, what

happens is that a Sulphonic group attaches itself to the compound's

20
central carbon atom. This hampers the conjugated double bond system of

the Quinoid ring, and causes the electrons to become localized. As a

consequence the ring ceases to be Chromospheres. As a result, the dye

becomes colorless.

To conclude chromospheres are the atomic configurations which has

delocalized electrons. Generally they are represented as carbon, nitrogen,

oxygen and sculpture. They can have alternate single and double bonds.

2.6 What gives the Dyes Solubility and Cohesiveness?

Auxochrome, the only substance responsible for providing solubility and

cohesiveness to dyes. An auxochrome is a group of atoms attached to a

chromophore which modifies the ability of that chromophore to absorb

light. Examples include the hydroxyl group (-OH), the amino group (-

NH2), and an aldehyde group (-CHO).

The presence of an auxochrome in the chromogen molecule is essential

to make a dye. However, if an auxochrome is present in the meta position

to the chromophore, it does not affect the color.

21
22
2.7 Classification of Dyes

Dyes can be classified in several ways, each class has a very unique

chemistry, structure and particular way of bonding. Some dyes can react

chemically with the substrates forming strong bonds in the process, and

others can be held by physical forces. Some of the prominent ways of

classification are given below

 Natural / Synthetic

 Organic / Inorganic

 By area and method of application

 Chemical classification - Based on the nature of their respective

chromophores.

 By nature of the Electronic Excitation

 According to the dyeing methods

 Anionic (for Protein fibre)

 Direct (Cellulose)

23
US International Trade Commission has advocated the most popular

classification of dyes. This system classifies dyes into 12 types, which

are given below:

Type of Dyes

The Dyes are classified based on the products to which they can be

applied and the chemical nature of each dye. Dyes are complex

unsaturated aromatic having characteristics like solubility, intense color,

sub-stansiveness and fastness. A dye-formulation is supposed to have

approximately 10-80% pure dyestuff. It is mostly observed that dyestuffs

delivered in powder form have a higher value. While a lower value is

obtained for the liquid formulations.

24
2.8 PROCEDURE:

 Place 3 g of anhydrous ZnCl2 in a china dish and 3 ml of

benzaldehyde and 6ml of dimethylaniline to it.

 Cover it with watch glass andheat for about 90 minute on a water

bath. Stir frequently and if the mixture becomes very viscous to

stir, add 1 ml of hot water.

 While the china dish is still on the water bath, add 5 ml of water,

stir the contents with a glass rod to dissolve the maximum dye

and transfer the solution to 400ml beaker.

 Add 125 ml of ice cold water. Leuco form of the dye is obtained.

With stirring, now add a suspension of 2 g PbO 2 in 20 ml of water

and then 4 g of sodium sulphate in 20 ml of water to it. Warm and

filter.

25
2.8.1 OBSERVATION:

A dark green dye is obtained.

USES

Malachite green is traditionally used as a dye. Millions of kilograms of

MG and related triarylmethane dyes are produced annually for this

purpose. MG is active against the protozoan Saprolegnia, which infects

fish eggs in commercial aquaculture, MG is used to treat parasites and is

used as anantibacterial. It is a very popular treatment against

Ichthyophthirius multifiliis in freshwater aquaria. The principal

metabolite, LMG, is found in fish treated with malachite green, and this

finding is the basis of controversy and government regulation. See also

Antimicrobials in aquaculture.

MG has frequently been used to catch thieves and pilferers. The bait,

usually money, is sprinkled with the anhydrous powder. Anyone

handling the contaminated money will find that on upon washing the

hands, a green stain on the skin that lasts for several days will result.

26
 FLOURESCENT DYE

2.8.2 CHEMICALS REQUIRED:

 2g Resorcinol

 2g Phthalic anhydride

 5% NaOH

 2ml Conc. H2SO4

2.8.3 PROCEDURE:

 Take 2g Resorcinol and 2g Phthalic anhydride and add 2ml conc.

H2SO4 to it.

 Heat the content on burner till the content turns black.

 Cool the contents and add 20 ml of 5% NaOH in a conical flask.

 Vary concentration of NaOH and water to obtain different

intensities of colour.
27
2.9 OBSERVATION:

The dye formed shows fluorescence. It appears green from some angle

and orangish yellow from others. The dye when put in sink with a

large amount of water turned into bright yellow color.

Recently, carbon inks made from carbon nanotubes have been

successfully created. They are similar in composition to traditional inks

in that they use a polymer to suspend the carbon nanotubes. These inks

can be used in inkjet printers and produce electrically conductive

patterns.

28
2.10 Carbon

Chinese inkstick; carbon-based and made from soot and animal glue.

Carbon inks were commonly made from lampblack or soot and a

binding agent such as gum arabic or animal glue. The binding agent

keeps carbon particles in suspension and adhered to paper. Carbon

particles do not fade over time even when bleached or when in sunlight.

One benefit is that carbon ink does not harm paper. Over time, the ink is

chemically stable and therefore does not threaten the paper's strength.

Despite these benefits, carbon ink is not ideal for permanence and ease

of preservation. Carbon ink tends to smudge in humid environments and

can be washed off surfaces. The best method of preserving a document

written in carbon ink is to store it in a dry environment (Barrow 1972).

29
2.11 Iron gall (common ink)

Iron gall inks became prominent in the early 12th century; they were

used for centuries and were widely thought to be the best type of ink.

However, iron gall ink is corrosive and damages paper over time

(Waters 1940). Items containing this ink can become brittle and the

writing fades to brown. The original scores of Johann Sebastian

Bach are threatened by the destructive properties of iron gall ink. The

majority of his works are held by the German State Library, and about

25% of those are in advanced stages of decay (American Libraries

2000). The rate at which the writing fades is based on several factors,

such as proportions of ink ingredients, amount deposited on the paper,

and paper composition (Barrow 1972:16). Corrosion is caused by acid

catalysed hydrolysis and iron(II)-catalysed oxidation of cellulose

(Rouchon-Quillet 2004:389). Treatment is a controversial subject. No

treatment undoes damage already caused by acidic ink. Deterioration

can only be stopped or slowed. Some think it best not to treat the item at

all for fear of the consequences.

30
2.12 Indelible ink

Indelible means "unmemorable". Some types of indelible ink have a

very short shelf life because of the quickly evaporating solvents

used. India, Mexico, Indonesia, Malaysia and other developing countries

have used indelible ink in the form of electoral stain to prevent electoral

fraud. The Indian Scientist Dr. M.L. Goel is the founding father of

indelible ink in India and gave the secret formula to NPL (National

Physical Laboratory) of India.

The Election Commission in India has used indelible ink for many

elections. Indonesia used it in its last election in Aceh. In Mali, the ink is

applied to the fingernail. Indelible ink itself is not infallible as it can be

used to commit electoral fraud by marking opponent party members

before they have chances to cast their votes. There are also reports of

"indelible" ink washing off voters' fingers in Afghanistan.

31
What is Ink?

Ink is a liquid or paste that contains pigments and / or dyes and is used

to color a surface to produce an image, text, or design. Ink is used for

drawing and / or writing with a pen, brush, or quill. Thicker inks, in

paste form, are used extensively in letterpress and lithographic printing.

Ink is an essential item for students, teachers, authors and others. Ink

was first, used by the Egyptians around 4000 years ago.

2.13 Ink formulas vary, but commonly involve four components:

 Colorants

 Vehicles (binders)

 Additives

 Carrier substances

How it was prepared in the ancient times.

The history of Chinese inks can be traced back to the 12th century BC,

with the utilization of natural plant (plant dyes), animal (squid ink), and

mineral offset ink based on such materials as graphite that were ground

32
with water and applied with ink brushes. Evidence for the earliest

Chinese inks, similar to modern ink sticks, is around 256 BC in the end

of the Warring States Period and produced using manual labour from

soot and animal glue.

About 1,600 years ago, a popular ink recipe was created. The recipe was

used for centuries. Iron salts, such as ferrous sulfate (made by treating

iron with sulfuric acid), were mixed with tannin from gallnuts (they

grow on trees) and a thickener. When first put to paper, this ink is

bluish-black. Over time it fades to a dull brown.

33
Types of ink

On the basis of use On the basis of Manufacturing

(a) Blue ink, (I) Aniline ink,

(b) Black ink, (II) Gallo-tannic ink.

(c) Blue-black ink,

(d) Green ink,

(e) Red ink,

(f) Stamp pad ink.

In this project you will learn about preparation of Aniline and Gallo-

tannic ink with respect to particular colors

34
 Chapter - III
Research Method

35
3.1 Testing methods

Materials

Inkjet ink consists of colouring agent, solvent, binder and surfactant. The

colouring agent, naturally, determines the colour of the ink, the solvents

disperses pigments, the binder promotes film formation, and the

surfactant adjusts the surface tension of the ink. Natural gardenia blue

pigment is commonly used as a colorant. It has been included in Chinese

GB2760-2011 national food safety standards, “Standards of Using Food

Additives” (QB/T, 2013,). It features bright colour, high pigmentation,

and light and heat resisting properties, with tones in the pH 4~8 range at

favourable stability without precipitation. In addition, it is very soluble

in water and aqueous ethanol and does not fade after heating in 120 ℃

for 60min. The solvent used in this study to dissolve the natural gardenia

blue pigment was deionized water. COS was used as a binder to assist

imprinted film formation. Surfactant with ethanol, which was used here,

increase ink stability and regulate the surface tension and viscosity of the

ink as well as maintaining clear and dry ink impression.

36
3.2 Preparation

The history of Chinese inks can be traced back to the 12th century BC,

with the utilization of natural plant (plant dyes), animal (squid ink), and

mineral offset ink based on such materials as graphite that were ground

with water and applied with ink brushes. Evidence for the earliest

Chinese inks, similar to modern ink sticks, is around 256 BC in the end

of the Warring States Period and produced using manual labor from soot

and animal glue. About 1,600 years ago, a popular ink recipe was

created. The recipe was used for centuries. Iron salts, such as ferrous

sulfate (made by treating iron with sulfuric acid), were mixed with

tannin from gallnuts (they grow on trees) and a thickener. When first put

to paper, this ink is bluish-black. Over time it fades to a dull brown

37
3.3 Aniline Ink

Following substances are mixed for preparing this type of ink:

(1) Main Materials

 Blue-black color - Naphtha blue-black

 Blue color - Acid blue, Methylene blue

 Red color - Scarlet red, Eosin

 Black color - Aniline black

 Green color - Malachite green

 Some aniline colors are also used in preparing ink which is

dissolved directly in water.

(2) Other materials

(i) Glue: Gum Arabic (or gum acacia) is dissolved in hot water and

these results in a sticky solution. Mixing of this in an ink solution, helps

in many ways:

 The ink turns bright.

 The color of ink does not fade with time.

38
  The flow of ink is maintained smooth.

(ii) Glycerin: Sometimes, glycerin is also used in preparing ink. The

mixing of glycerin checks the early drying of ink. This is mainly used in

preparing the stamp pad inks.

(iii) Alcohol: Spirit or alcohol is mixed in ink because it helps in :

(a) Quick drying of ink, and

(b) The ink does not diffuse on papers after writing.

(iv) Boric or carbolic acids: The principal constituents of ink are

organic in nature. The breakdown of these materials spoils the ink and

this causes deposition of constituents in fountain pen of in the ink pot.

Incorporation of boric or carbolic acid to the ink preparation checks this

problem.

(v) Scented Materials: The organic decay of ink gives it sometimes,

foul smell. To avoid this, scented materials are incorporated at the time

of ink preparation.

39
3.4 Method of preparing Aniline Ink

For preparing a particular colored ink, first of all a 2.5% solution of that

color in distilled water is made.

 To this, is added a suitable amount of glue solution.

 Now the solution is mixed well and heated for 5 minutes.

 During heating, the contents are constantly agitated.

 On cooling, the solution is filtered. The process of filtration is a

very important step and is carefully repeated several times.

 To this is now, mixed a little amount, each of boric acid or carbolic

acid, alcohol or spirit and scented material.

 This preparation is filtered again and bottled.

 If one desires to get a stamp-pad ink then glycerin should be used

in place of alcohol during preparation

40
3.5 Gallo-tannic Ink

The following substances are used in its preparations:

(1) Chief constituents: Following substances are the chief constituents:

(i) Tannic and Gallic acids are used as chief constituents to get blue-

black ink.

(ii) Ferrous sulphate and hydrochloric acid also helps in providing blue-

black color to the ink and check the growth of fungus.

Other materials: The other materials used are carbolic acid or boric

acid, gum Arabic or gum acacia, spirit or alcohol, glycerin and scented

material etc. These substances play the same role in this case as in

aniline ink. Basically, it is a mixture of ferrous sulphate, tannic acid and

Gallic acid; it is, therefore, also called Iron-gall ink.

41
3.6 Method of preparation of Gallo-tannic ink

 Dissolve 250 gm of tannic acid and 80 gm of Gallic acid in about 5

liters of distilled water.

 To this solution 250 ml dilute HCl is added.

 Dissolve in a separate container 300 gm ferrous sulphate, 20 gm

carbolic acid about 4 liters of water.

 In a third container, the desired color is dissolved in a little water.

 All the three solutions are mixed together.

 Also add a little of glue solution, alcohol, scented material, mix

well, filter and keep the filtrate for a few days.

 Filter once again and store in bottles. The ink is ready for use.

42
 Chapter – IV

Data analysis & Result

43
4.1 Ink testing for food, pharmaceutical and other packaging:

 Ink and coating product formulation characterisation and impurity

structural elucidation
 NMR Nuclear Magnetic Resonance Spectroscopy, Mass
Spectrometry (MS), Tandem Mass Spectrometry (MS/MS), Liquid
Chromatography - Tandem Mass Spectrometry (LC-MS/MS),
vibrational spectroscopy, UV-vis, fluorescence, viscosity,
headspace Gas Chromatography
 High Resolution Microscopy
 Particulate pigment systems using Transmission Electron
Microscopy (TEM)
 Compatibility of printing technology, such as printheads with ink
using Scanning Electron Microscopy (SEM)
 Coated surfaces and multilayer systems (SEM, TEM, Scanning
Probe Microscopy (SPM) and interferometry)
 Advanced data handling solutions where data manipulation and
interpretation are required
 Statistical measurements of variance between the properties of ink
batches
 This is particularly useful when understanding printed property
data (optical density, L*a*b* colour space, etc.)

44
 Working with polymeric species and providing analytical support
for a variety of chemistries, including acrylated urethanes, epoxies,
polyesters, and acrylics (Gel Permeation Chromatography,
Pyrolysis Gas Chromatography, etc.)
 Trace heavy metals and residual inorganic impurities in material
Ash/ Inductively Coupled Plasma Spectroscopy with Optical
Emission Spectroscopy or Mass Spectrometry detection (ICP-AES
or ICP-MS) in product formulation
 Physical chemistry property determination (pKa, LogP, LogD,
solubility etc.) for formulation components
 Forensic type investigations into ink contamination during
manufacturing process (e.g. plasticisers absorbed from hoses, etc.)
 UV Cure technologies:
 UV-Cure ink formulation characterisation and impurity structural
elucidation including the properties and interaction of the
monomers, photoinitiators, pigment, additives and oligomers
 DSC Differential scanning calorimetry (DSC) for the study of
complex thermal properties at various degrees of curing as an
indicator for the degree of cross-linking
 FTIR Infra-Red Spectroscopy to quantify and monitor residual
functional groups
 Pyrolysis Gas Chromatography- Mass Spectrometry (GC-MS)
identification of polymer constituents in an aqueous ink dispersion

45
4.2 How to prepare ink at home

One drop at a time, add hot distilled water to the bowl of lampblack (you

can make your own by completely burning paper or wood) - stop adding

water before you think you should and if you, accidentally, get too much

water, add more lampblack. Mix until the water is an inky black

(lampblack floats and is difficult to dissolve). Once the water is inky

black, add a small amount of gum Arabic and mix until the gum has

been dissolved in the warm liquid (this homemade ink should be the

same consistency as commercially prepared ink). Store the ink in a small

glass bottle for future use. A variant of this recipe is: mix together one

egg yolk, one tablespoon gum Arabic and 1/2 cup honey; then stir in 1/2

tablespoon lampblack: this will produce a thick paste which you can

store in a sealed container.

46
4.3 Composition

A blot of Quink ink on damp paper – the blue dye has separated from the

other components, which are peach-coloured

Fountain pen ink is almost exclusively dye-based because fountain pens

operate on the principle of capillary action. Pigment-based inks (which

contain solid pigment particles in a liquid suspension) tend to clog the

narrow passages of the pen. Some pigmented inks do exist for fountain

pens, but these are uncommon. India ink, a carbon pigment-based ink,

also contains a binder, gum arabic, which can quickly clog such

pens. The ideal fountain pen ink is free-flowing, free of sediment, and

non-corrosive. These qualities may be compromised in the interests of

permanence, manufacturability and in order to use some widely

available dyes.

47
A form of ink that predates fountain pens by centuries is iron gall ink.

This blue-black ink is made from iron salts and tannic acid from

vegetable sources. Prior to the ready availability of manufactured ink,

iron gall ink was often homemade. Stark's ink was one iron gall ink

recipe, named after the Scottish chemist who devised it after spending

several decades experimenting with hundreds of formulations.

Iron gall ink was used in fountain pens when they were invented but has

the disadvantage of causing corrosion to metal parts. Modern

formulations of iron gall ink are somewhat less corrosive and are still

occasionally used in applications that require permanence.

A bottle of green ink

Red inks usually contain the dye eosin. Blue inks often

contain triarylmethane dye. Black inks are mixtures. In addition to

water, the non-dye components (collectively referred to as the vehicle)

48
might include polymeric resins, humectants to retard premature drying,

pH modifiers, anti-foaming agents, biocides to prevent fungal and

bacterial growth, and wetting agents (surfactants). Surfactants reduce

the surface tension of the ink; distilled water has a surface tension of

72 dyn/cm (72 × 10−3 N/m), but the desirable value for ink is between 38

and 45 dyn/cm (38 to 45 × 10−3 N/m). If the ink's surface tension were

too high, then it would not flow through the pen; if it were too low, then

the ink would run out of the pen with less control.

Some users mix inks to create their own colours. Some combinations of

inks may cause unexpected colour changes, even if the inks are from the

same manufacturer. This is a result of chemical reactions between the

different components. The colour of many dyes depends on pH, and

some lose their colour entirely outside a certain pH range. Mixing inks

may also alter the solubility of some dye components; for example, an

alcohol-based ink may contain components that are insoluble in water,

and these will precipitate or coagulate if the alcohol-based ink is mixed

with a water-based ink.

49
4.5 Manufacturers

Most fountain pen manufacturers also provide a brand of ink. For

example, Parker sells "Quink", Pilot sells "Iroshizuku", Wancher sells

"Silk Road", and Sheaffer sells "Skrip", while manufacturers

like Waterman, Lamy, Hero company, Pelikan, Thornton's Luxury

Goods and MontBlanc sell ink under the same branding as their fountain

pens. The recent resurgence of fountain pen use has also created a

market for companies that specialize in ink, such as the British company

Diamine and American companies such as Private Reserve Ink and

Noodler's Ink. These companies manufacture ink in dozens of different

colours. Some companies that specialize in ink, like Noodler's and

Private Reserve Ink have, also created ink with special properties, like

glow in the dark, waterproofing, highlighting and indestructible

(document) inks.

50
4.6 Durability and security

Noodler's Black fountain pen ink writing samples. This is a 'bulletproof'

permanent ink featuring cellulose-reactive dye.

In the late 20th century, particular attention has been paid by ink

manufacturers to the durability of their products against the effects of

time, light, moisture, and efforts at forgery or falsification. Some of

these inks use pigments – the solid pigment particles lodge between

the cellulose fibers that make up the paper and are unaffected by

attempts to remove them with solvents. Other inks use dyes that

chemically bond with the paper's cellulose, and which likewise resist

removal by solvents. A disadvantage of the dye inks is that, if spilled,

they will form irremovable stains on clothing made from cotton, which

also contains cellulose. Also, some "secure" inks are vulnerable to

removal using powerful infra-red lasers.

51
4.7 Conditions for Color

Due to these chemical concepts, organic colorants must possess certain

Components and properties to show color. It must:

 absorb light in the visible spectrum (see “Wavelength and Color”),

 have a chromophore, and

 be conjugated .

The importance of conjugated chromophores is seen in the image below

where placing an azo group in between conjugated rings instead of

between methyl groups produces a colored substance .

4.8 Varnishes

While colorants provide the visible color for the ink and are the most

recognizable in the process, varnishes are the “backbone” of the ink

produced because they are accountable for carrying the pigments and

making sure that the ink has the indispensable properties that printers

52
require.

Varnishes have three main uses:

 To be a solvent for the dye to dissolve in

 To help the ink transfer from pen to paper

 To bind the ink to the paper so it does not rub off

Varnish is typically a combination of a drying component, resin and a

solvent. These different factors explain how the three main uses of a

varnish are accomplished.

4.9 Drying Component

An ink in its supply form is a liquid but after application it is required to

change to a solid. This change of state is referred to as ink drying and

the varnish in the ink is responsible for this process. To think about this

in laymen’s terms, the drying process describes how ink is transferred

from pen to paper. An ink can dry in many ways but most commonly in

one of three ways; Absorption drying, oxidation drying and evaporation

drying. In absorption drying, an ink dries when it penetrates by capillary

53
action between the fibers of a substrate and when it is absorbed by the

substrate itself. Capillary action is defined as the ascension of liquids

through a slim tube due to adhesive and cohesive forces interaction

between the liquid and the surface. Adhesive force discusses the forces

of attraction between unlike molecules whereas cohesive forces

describes the intermolecular bonding of a substance where its mutual

attractiveness forces them to maintain a certain shape of a liquid. When

intermolecular bonding of a liquid is inferior to a substances surface,

capillary occurs. The ink remains a liquid but because of the degree of

penetration it is effectively dry. An ink dries by oxidation when the

oxygen in the atmosphere chemically combines with the resin system

converting it from liquid to solid. This process is very slow so often a

fluid component is added that can be separated from the rest of the inks

and is absorbed into the substrate which then leaves a film of ink on the

surface which is dry to the touch but still soft and moveable. As

autooxidation proceeds, the ink film becomes hard and tough. This

process can be affected by the pigments and additives but is important to

54
be controlled because it helps determine the rate of production and the

quality of printing.

55
Some inks are formulated to dry by the physical removal of the unstable

solvents from the ink formulation, leaving the resin behind to bind the

pigment to the paper. The rate of evaporation depends on the affinity of

the resin system for the solvents. Generally, the greater the affinity of

the resin the slower the rate of solvent release. This affects the properties

of ink in respect to the print-ability, the drying speed and the retention of

solvents in the ink film.

Additionally, some inks used UV radiation as heating agent in the

autoxidation process. There are other photochemical reactions which can

be used to dry the ink, the majority dry using the ultraviolet mechanism.

UV assists in the penetration of the varnish and is used to speed up the

autoxidation of conventional inks.

4.10 Solvent

Solvents in ink are temporary ingredients that exist purely as a means of

applying the varnish solids to the substrate by way of the printing unit.

In theory, the solvent is then eliminated by evaporation or absorption

and no longer is a part of the printing process. However, in practice this

56
is often an over-simplification. The choice of solvents in ink is

controlled by the resin system to be chose, the press speed, nature of the

design, the substrate, end-use properties of the print and health and

safety considerations.

The chemical nature of the resin system is the most important factor

when choosing a solvent. The more resins blend with a solvent a lower

viscosity will be given. Selection of solvents can be predicted by

consideration of the solubility parameter and the possible hydrogen

bonding associated with a solution of the resin in the system. Solvent

choice can also factor into the gloss of ink as described earlier because it

affects pigment dispersion and the printing viscosity. If a solvent is not a

true solvent, a poor flowing ink can result which can therefore affect the

gloss.

57
4.11 Main Chemicals, Compounds, Components

3 main chemicals used in ink

The Colorant

 This is one of the most important ingredients in ink because it is

what gives the ink its color. There are two different types of

colorant used in ink, which are pigments and dyes. The primary

difference in these two are their solubility. For instance, pigments

are insoluble in water and most solvents, whereas dyes are not.

Colorants can be organic or synthetic, although in modern days ink

manufacturers mostly use synthetic colorants.

The Vehicle/Varnish

 This is another important ingredient for three main reasons. First, it

is used as a solvent for the dye to dissolve in or, in the case of

pigments, a liquid that the pigment is suspended in evenly. Second,

it helps the ink to transfer from the pen to paper. Finally, it helps

bind the ink to the paper so it doesn’t easily rub off the paper. For

these reasons, many vehicles/varnishes are used in making ink.

58
The Additive

 They are often added to give the ink characteristics that

vehicles/varnishes and pigments wouldn’t give by themselves. For

example, oils can give the ink certain flow and lubrication

properties, waxes give the ink toughness and durability, and driers

help promote rapid drying mechanisms.

4.12 Chemistry's Role

Carbon black pigment is the colorant used in this ink. The

vehicles/varnishes used in this ink are water, egg yolk, and gum arabic.

The water is used as a solvent to suspend the pigment while the gum

arabic helps spread the pigment in the solution evenly. The water also

helps the pigment to transfer to the paper and then once it has

evaporated, the gum arabic binds the pigment to the paper. The egg yolk

assists in all of these stages. The honey acts as an additive which, in this

case, gives the ink a higher viscosity (thickness).

59
 Chapter – IV

Conclusion, Reference

60
5.1 Conclusion

Which liquid will make the best invisible ink? If lemon juice, honey, and

milk are tested to make invisible ink then, the lemon juice will make the

best invisible ink because, it is an acidic liquid. The average darkness of

the liquids were a four, and an eight, and a nine the liquid that scored a

four was the honey, the liquid that scored an eight was the milk, and

liquid that scored a nine was the lemon juice. The lemon juice had the

best results. The hypothesis was correct because the lemon juice is an

acidic liquid. During my experiment my family agreed not to bother me

or disturb me. While I was doing my experiment it was quiet and

peaceful. These results are helpful to know, because if you ever want to

make invisible ink instead of going to the store you can just make free

invisible ink unless you need to buy materials at the store. If I could

have made changes to this experiment I would. Some changes I would

have made is if I had tested more liquids because maybe one liquid was

better than the lemon juice. Another change is if I had tested the liquids

more times.

61
5.2 Reference

 Ainsworth, Mitchell, C., "Inks and Their Composition and

Manufacture," Charles Griffin and Company Ltd, 1904.
 N.a. (March 2000), "Bach Scores Turning to Dust in German
Library", American Libraries: 24–25
 Banerji, Sures Chandra (1989). A Companion to Sanskrit
Literature. Motilal Banarsidass. ISBN 81-208-0063-X.
 Barrow, W.J. (1972), Manuscripts and Documents: Their
Deterioration and Restoration, Charlottesville: University of
Virginia Press, ISBN 978-0813904085
 Martín-Gil J., Ramos-Sánchez MC, Martín-Gil FJ and José-
Yacamán M. "Chemical composition of a fountain pen ink".
Journal of Chemical Education, 2006, 83, 1476–78.
 Reißland, Birgit; de Groot, Suzan (August 15–21, 1999), "Ink
Corrosion: Comparison of the Currently Used Aqueous Treatments
for Paper Objects", Preprint from the 9th International Congress of
IADA, pp. 121–129
 Rouchon-Quillet, V.; Remazeilles, C.; Bernard, J.; Wattiaux, A.;
Fournes, L.; et al. (2004), "The Impact of Gallic Acid on Iron Gall
Ink Corrosion", Applied Physics A, 79 (2): 389–392,
Bibcode:2004ApPhA..79..389R, doi:10.1007/s00339-004-2541-1,
S2CID 95990608
 Sircar, D. C. (1996).Indian epigraphy. Motilal Banarsidass. ISBN
81-208-1166-6.
 Waters, C.E. (1940), Inks, U.S. Department of Commerce,
National Bureau of Standards, United States Government Printing
Office

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