Plasticizers

 Plasticizers are another common ingredient added to coating formulations.

 Paint and coating formulations often incorporate high boiling fluids as

plasticizers where rigid or brittle resins fail to meet toughness and flexibility
requirements.

 The primary function of the plasticizer is to impart flexibility to the resin,

thus minimizing film cracking.

 They are typically used to reduce the glass transition temperature, Tg, and
increase coating flexibility.

 They are also added to promote better polymer particle coalescence.

 Commonly used Plasticizers in paints

Class Examples
• Propylene glycol
Polyhydric alcohols • Glycerol
• Polethylene glycols
• Glyceryl triacetate (Triacetin)
Acetate esters • Triethyl citrate
• Acetyl triethyl citrate
Phthalate esters • Diethyl phthalate
Glycerides • Actetylated monoglycerides
• Castor oil
Oils
• Mineral oil
 Selection of suitable Plasticizers in paints

 When it comes to selecting a suitable plasticizer for a coating

formulation, 3 key issues to consider are:

1. Efficiency, which defines how much plasticizer must be added to

produce the desired effect;

2. Compatibility, which indicates how effectively the plasticizer

interacts with the polymer, and the level up to which that
interaction occurs; and

3. Permanence, which relates to both plasticizer-polymer

compatibility and plasticizer volatility
Plasticizers function by reducing the glass transition temperature of the resin to
a point below its application temperature. The chemical mechanism of
plasticization involves a strong polar association of polymer-plasticizer
molecules, but not a chemical reaction between them. Plasticizers fundamentally
reduce van der Waals forces between polymer-polymer molecules in the
amorphous regions and do not penetrate crystallites. The plasticized
morphological phase is then of a different nature than that of the neat polymer
and has unique mechanical properties. The absence of a chemical bond between
the plasticizer and the polymer impairs permanence; plasticizer molecules are
free to leave the polymeric coating by means of extraction and volatility.
 Common general effects of plasticizers used in film-coating formulations:

Property Effect of increased plasticizer concentration

Tensile strength Reduced
Elastic modulus Reduced
Variable, but increased under optimal-use
Film adhesion
conditions

Usually increased, with effect being greater as

Viscosity of coating liquid
plasticizer molecular weight is increased

Variable, depending on physicochemical

Film permeability
properties of plasticizer

Reduced, with magnitude of effect being

Glass transition temperature (Tg)
influenced by compatibility with polymer
 Classification

Plasticizers are mainly classified into five groups:

1. phosphorated plasticizers,
2. chloroparaffins,
3. phthalates,
4. adipates and
5. Sebacates.

 The most common type is the phthalates.

 After phthalates, adipates are commonly used.
The most widely used plasticizers are ‘phthalic acid esters’. They are usually
produced by reaction of phthalic anhydride with an excess of alcohol using p-
toluenesulfonic acid as catalyst. The excess alcohol is recycled.
Commercial phthalate esters are colorless and mostly odorless liquids. Dioctyl
phthalate (DOP) or di-2-ethylhexyl phthalate (DEHP) has been the international
standard PVC plasticizer counting for more than 50% of world plasticizer
consumption. Other broadly used phthalate plasticizers are diisononyl
phthalate (DINP) and diisodecyl phthalate (DIDP).

The bulk of ‘aliphatic ester’ plasticizers are derived from adipic, sebacic, and azelaic
acids esterified with linear or branched monofunctional alcohols of short to medium
chain length, for example, dioctyl adipate (DOA); di(2-ethylhexyl)adipate),
diisononyl adipate (DINA). These materials are distinguished by their low viscosity,
thus making them particularly attractive to the plastisol sector, and giving excellent
low-temperature flexibility properties.
 Plasticizer Analysis

 Determination of plasticizers that are in products and their concentration can

be performed by using Gas Chromatography coupled with Mass
Spectrometry (GC-MS). Plasticizer analysis is important for confirming the
composition of raw materials and finished products.

 Very rarely, laser-induced molecular fluorescence has been used

 Recent trends mark the use of acoustic wave devices. Acoustic wave sensors
acquire their name from the mechanical or acoustic wave which is used as
the sensing mechanism. As this wave propagates through or on the surface
of substrate, any perturbation from the environment of the propagation path
will affect the velocity and/or amplitude of the wave. Changes in amplitude
can be monitored by measuring the loss spectrum of the sensor, where
changes in velocity can be monitored by measuring frequency and phase
properties.
 Resins in Paints

Resin, any natural or synthetic organic compound consisting of a

noncrystalline or viscous liquid substance. Natural resins are typically
fusible and flammable organic substances that are transparent or translucent
and are yellowish to brown in colour. They are formed in plant secretions
and are soluble in various organic liquids but not in water.

In paints:
Resin – the binder to hold the pigment particles together and provide
adhesion to the surface painted. Waterborne paints most often use acrylic
emulsion polymers as binders. Common acrylic polymer types are based on
monomers such as methyl methacrylate and butyl methacrylate. Solvent
based resins come in a very wide range of types. The most common solvent
based resins are termed ‘alkyd resins’ that are normally used in enamel
paints. Urethane alkyds often used in clear varnishes. Protective coating
resins include types such as Epoxy, Urethane, Polysiloxane.
 Types of Resins

1. Thermoplastic Resins
A substance that softens when heated and when cooled, it hardens again.
Thermoplastic product. TPA resin, as it is commonly called, comes in liquid
form as well as in the form of requires. These are used in plastic coatings as
well as in aerosols.
Eg: Alkyd Resins , Polycarbonate Resins, Polypropylene Resins

2. Thermosetting Resins
Thermoplastics and thermoplastic resins are raw, unformed polymers that
strengthens when heated but cannot be remolded. TSA, as generally
acknowledged as, is used in combination with a melamine resin as baking
enamels. In industrial coatings, automotive and two-wheelers, e-rickshaw
coatings, brass coatings, etc. are common applications.
Eg: Phenolic Resins, Polyester Resins, Epoxy Resins
Chemical Parameters Physical Parameters
 Acid Value  Appearance – Solid/Liquid

 Hydroxyl value  Clarity – Whether clear / turbid / hazy /

free of foreign particles % Solids
 Amine value
 Viscosity at specific temperature
 Epoxy Value
 Dilution viscosity
 Isocyanate content  Solvent Tolerance
 Formaldehyde content  Specific Gravity

 Methylol Content  Softening / melting point

 Compatibility with co-resin/other resin

 Gel Time
 Identification of alkyd resins in paints

Phenolphthalein Test
Heat 1 g of paint with 2 to 3 g of phenolphthalein and 10 drops of concentrated
sulphuric acid in a test tube until an orange or brownish-orange melt forms. After
the melt has cooled, extract with water, dilute to 1000 ml and make alkaline with
sodium hydroxide solution. Formation of pink colour confirms phthalate and alkyd
resin.

Resorcinol Test
Heat about 0.5 g of resin with 2 to 3 times the quantity of resorcinol for several
minutes. Cool and extract with boiling water. Dilute to 50 to 100 ml with water.
Make alkaline with dilute sodium hydroxide solution. A green fluorescence
indicates alkyd resin.
 Identification of resins in paints by Py-GC-MS

Pyrolysis Gas Chromatography and Mass Spectrometry

Pyrolysis gas chromatography (PyGC), particularly when combined with mass
spectrometry (MS), is a powerful, fast, and elegant analytical method for the
characterization of substances. In addition to qualitative and quantitative
detection and identification, it also provides additional information about
additives and impurities.

 The sample to be tested, is first injected to the gas chromatograph chamber and
the Pyrolysis is carried out at particular temperature for a definite time period.
 For the MS technique, the electron ionization is achieved using a high energy
electron beam (50 – 70 eV). The MS is usually kept under vacuum
 From the combined analysis of chromatogram and the MS, the identification of
particular resins is possible.
Nuclear magnetic resonance spectroscopy
1H and 13C nuclear magnetic resonance (NMR) are effective for the

characterization of resins in the binders of paints.

Binders for NMR analysis must be isolated from the sample and dissolved
in deuterated chloroform (a very good solvent for many resins as it produces
only small proton impurity peaks and is less expensive than other deuterated
solvents). The NMR spectra of binders provide information about the
functional groups present.
Using flow charts for paints the type of resin employed can be identified, and
in some cases, for example, alkyl and phenolic resins, quantitative
determination of resins can be made from the relative areas of the spectrum
peaks.

13C NMR provides better results than 1H NMR for the resolution of peaks
obtained from high molecular mass and very viscous polymers, but the
instrumentation required is more expensive and a larger amount of sample
and longer analysis times are involved.
 Inorganic Pigments in Paints

Inorganic pigments are generally metal oxides and/or synthetic

chemicals, some of which are very simple in composition but find
wide use in paints and coatings. Previously, the inorganic pigments
were all naturally occurring colored chemicals. Examples of
inorganic pigments include lead oxide, cobalt blue, cadmium
yellow, and titanium yellow. As new environmental laws are very
strict about toxicity, a few of these heavy metal pigments are no
longer in use. However, the surviving inorganic pigments fill a play
double-duty role fillers that provide a greater benefit than simple
coloration of a formulation; they also impact physical properties of
the paint film or the coating film during application and throughout
the product lifecycle.
 Purple Pigments:
Han purple; BaCuSi2O6
Manganese violet; manganese ammonium pyrophosphate, NH 4MnP2O7
Cobalt violet; cobaltous orthophosphate, Co3(PO4)2

Blue Pigments:
Cobalt blue and cerulean blue; cobalt(II) stannate, CoOn·SnO2 (n = 1 or 2)
Egyptian blue; a synthetic pigment of calcium copper silicate (CaCuSi 4O10)
Han blue; a barium copper silicate, BaCuSi 4O10
Prussian blue; a synthetic pigment of ferric hexacyanoferrate (Fe 7(CN)18)

Green Pigments:
Cadmium green; a light green pigment consisting of a mixture of cadmium yellow (CdS)
and viridian (Cr2O3)
Chrome green; chromic oxide (Cr2O3)
Malachite; cupric carbonate hydroxide (Cu 2CO3(OH)2)
Cobalt green; also known as Rinmann's green or zinc green (CoZnO 2)
 Identification

X-ray diffraction spectroscopy (XRD) techniques have been used for the analysis
of inorganic pigments and extenders by analyzing the crystalline structure of the
material rather than its elemental content: e.g., it is typically able to differentiate the
crystalline forms of titanium dioxide, rutile, and anatase. The method is less suitable
for the identification of organic pigments as they do not generally scatter X-rays well
and they are often present in paints only in comparatively small concentrations.
Additional difficulties occur in the interpretation of the results because the diffraction
pattern sometimes exhibits only the most subtle differences within a class of organic
pigments.
Laser-based analytical techniques – such as laser induced fluorescence (LIF),
laser induced breakdown spectroscopy (LIBS), and Raman spectroscopy – are
also used for the identification of pigments, binding media and varnishes. In all
techniques a low-intensity laser is used to excite an extremely small area of a
paint sample. The signals generated provide information that can be directly
related to reference samples of the molecular structure of pigments, inorganic
and organic binding media.

Using LIF both inorganic and organic fluorescent species can be identified by
interpretation of the broadband fluorescence spectra they produce. The
spectrum obtained is characteristic of the species under examination. However,
one limitation of LIF is the analysis of pigments that have low fluorescence
quantum yields, they are almost impossible to detect especially in the presence
of fluorescent impurities.
Raman microscopy has become a powerful tool in the investigation of pigments
and organic media in paintings. The high spatial resolution of the microscope
makes it possible to examine individual grains of pigment in a sample.
Fluorescence from binders can be minimized using an aperture at the secondary
focus of the scattered radiation. If the pigment itself fluoresces the excitation
wavelength of the laser can be altered to a lower frequency to significantly reduce
the fluorescence. On excitation of the sample the inelastic, Raman, scattering gives
rise to many bands, which are known collectively as a Raman spectrum. The
spectra are highly specific in wavenumber, intensity, and bandwidth to the sample,
and thus provide a unique fingerprint of the sample. In a typical setup a microscope
is coupled to a spectrometer with a sensitive diode array or CCD detector.
Infrared spectroscopy
IR spectroscopy provides the most valuable information on the qualitative
composition of paints. Binders, pigments, solvents, and some additives can be
characterized by their corresponding IR spectra. However, the identification of
components can be facilitated if the IR spectra are obtained after separation.

For the characterization of the binder, several drops of the vehicle, previously
separated from the pigment, can be dried on the surface of an appropriate crystal
and the corresponding spectrum recorded. From the presence or absence of typical
bands of the different functional groups in this spectrum, the type of resin
employed can be identified. From the IR spectra it is also possible to analyze
quantitatively mixtures of resins, such as those of the polyester and epoxy type.
Atomic spectrometry
The use of modern analytical techniques based on atomic absorption and emission
spectrometry provides accurate and precise quantitative determination of inorganic
species in paints.

Atomic absorption spectrometry (both using flame and electrothermal atomization)

and plasma emission spectrometry, especially inductively coupled plasma-atomic
emission spectrometry (ICP-AES) provide selective methods for quantification of
inorganic species at different concentrations. These techniques are important for the
analysis of inorganic pigments, charges (especially inorganic extenders), and
additives such as catalysts, driers, and antifouling compounds.

Atomic spectrometry generally requires prior dissolution of the sample, which can be
carried out with either acids or organics solvents, but in some cases necessitates
destroying the matrix by means of a wet acid treatment or a dry digestion. This can
be a serious drawback, but the new strategies for sample preparation, based on the
use of microwave-assisted digestion procedures for sample dissolution and direct
introduction of solid samples as slurries or emulsions, can reduce problems involved
in sample preparation.
UV–visible spectrophotometry

UV–visible spectrophotometry can be employed for identification of

pigments, especially for the characterization of organic compounds or the
determination of light filters. The technique is based on the possibilities
offered by an appropriate combination of solvent extraction or the selective
solubility of each pigment and its characteristic absorbance spectra. The use
of mathematical procedures for the deconvolution of spectra and the use of
derivatives can improve the selectivity of these determinations.