Know the types of surfactants used for fire fighting, toothpaste etc.

2 emulsifiers fine tune HLB to formulations, and stabilize surfactants

** find out Incremental method for calculation of HLB values

Lecture 01:
Specialty chemicals- *materials used on basis of performance/function*mixtures of molecules aka formulations*high
value, low volume highly economical chemicals*not possible to interchange 2 chemicals by 2 suppliers*produce by
batch plant and in small amounts

Commodity chemicals: *single pure chemicals produced in large amounts ie. Ammonia & ethylene oxide*two
commodities produced by 2 different suppliers can be interchanged*continuous plant*low cost*AKA bulk chemicals

Fine chemicals:*single pure complex chemicals by chemical structure*active ingredients is fine chemicals but
pharmaceutical drug is specialty chemical *ie. Pharmaceuticals, agriculture, photography chemicals and electronic
chemicals*small quantity by batch plant*cost is high

Key ingredients of special chemicals

Vehicles in formulation is medium in which

ingredients of formulation dissolved or
dispersed. Little or no therapeutic
value*maintain physiologically stability,
improve patient acceptability, improve
function of dosage

Ideal properties for vehicles:*inert and

stable*do not impart taste color and odor*non
toxic, non irritant, non sensitizing*effective in
low concentration*free from microbes*not
interfere with bioavailability of active
ingredient

Vehicle types: liquid(oil/water), solid and semi-solid type

Active ingredients- *affects structure or function of product*sunscreen contains oxybenzones which is active
ingredients to protect from sun, and also contain inactive ingredients like stabilizing agents to extend product’s shelf
life, but does not protect skin*ie. Pesticides active ingredients kill pests*paracetamol active ingredient in Panadol

Excipients*substances formulated alongside

active ingredient*purpose is for long term
stabilization, bulking up formulations ie.
Fillers, diluents etc – confers properties such
as drug absorption, reducing viscosity,
enhance solubility etc.
Surfactant; aka surface active agents reduces surface and interfacial tensions

**Formulation Science is knowledge and practice of blending and mixing components (chemical molecules) in a way that they
do not react, but interact to provide a final product with very specific desirable properties or functions. Surfactant and
polymer are the key building blocks for the formulations.

Interface is boundary between two immiscible phases, surface is 1 of phases is a gas.

Types of interface:*liquid in liquid(emulsion)*gas in liquid(foam)*solid in solid(alloy)*solid in gas(smoke)*liquid in
solid(slurry)*solid in liquid(suspension/dispersion)

Surface tension is tension of surface film caused by dipole-dipole interactions or hydrogen bonding in surface or
interface layer
Surfactants in nature: phosphatidylcholine, glycolipids, glycocholate, cholate, phosphatidylserine, diglyceride,
monoglyceride, fatty acid salts

Surface tension(ƴ) is expressed as ƴ = F/ L – units (N/m) (F= force acting on surface, L= length of surface)
Roles of surfactant: *Detergency to provide cleaning/ dirt emulsification*foam boosting to favour foam or stability
of it*emulsification to allow mixing of 2 immiscible liquids*co-emulsification to assist mixing of 2 immiscible
liquids*conditioning to improve aspect of hair or skin*solubilization to dissolve an oil soluble material in
water*counter-irritation to participate in reduction of irritation*dispersion to aid distribution of solid particles within
liquid*wetting to encourage spreading
Notes on surfactant and surface tension:*amphiphilic molecules*act on surface or interface*surface tension is
tension of surface film caused by hydrogen bonding and dipole-dipole interactions*interfacial/surface free energy
per unit area is also known as surface tension

4 classes of surfactant based on polar head charge group

*negative(anion)-alkyl sulfate (no.1)*
Different polar head groups: alkyl ether carboxylate, alkyl sulfate, alkyl benzyl sulfonate, alkyl phosphate
Applications: foaming agent, detergent, soap, foam stabilizer, toothpaste, plasticizer. Defoamer, agrochemical
dispersant, lubricant, paint drier, fungicide, wetting agent, cosmetic(cleaning agent, makeup)

Counterions types*Na+, K+ (water soluble)*Mg2+/Ca2+(water insoluble)*amine alcohol(soluble in water and oil)

*Soap is Na or K salt of fatty acid derived from animals fats or vegetable oils*sensitive to hard waterneed to
develop synthetic surfactants*forms ca-stearate which is insoluble and to rectify this issue is to replace 25% of C18
tail with C12-14 fatty acids to increase tolerance to hard water
*Synthetic anionic surfactant is made by modification of lipophile tail or hydrophile head or both
Important facts*largest class of surfactant*limited compatibility with cationic surfactants*sensitive to hard water
and sensitivity decreases in order of carboxylate>phosphate>sulfate/sulfonate*short polyoxyethylene chain
between anionic and lipophile tails improves hard water tolerance*ethylene oxide group in tail reduce skin
irritation*short polyoxypropylene chain between anionic group and hydrophobic tail improves solubility in organic
solvents (but reduce biodegradation)*alkyl sulfates hydrolyzed rapidly at low pH in autocatalytic process but other
types are hydrolytically stable

*positive(cation)-fatty amide(no.3)
Nitrogen based compounds in the form of amine(primary, secondary,tertiary with 1,2,3 alkyl groups respectively) or
quaternary ammonium(4 bonds with C)
Common cationic surfactants:*alkyl quat, ester quat, dialkyl quat*fatty amine , fatty diamine salt
Properties related to alkyl chain length(quats)
*Conditioning- larger alkyl chain greater conditioning effect( C22>C12, Saturated>branched>unsaturated)
Conditioning dependent on total alkyl chain distance from polar head and not on total carbon content(shorter
distancebetter conditioningmonoalkyl quats condition better than di-alkyls
*Irritation-smaller alkyl chaingreater irritation (C12>C22)
*Antimicrobial- smaller alkyl groupgreater antimicrobial activity
Quats functions*condition & protect -impart lubricity from hydrophobic groups -improves surface properties
-reduce combing friction/prevents cuticle damage*detangling -reduction in wet combing force -hair fibres slip past
each other w/ less friction*UV protection -benzyl moiety converts UV rays to infra-red -protects hair protein/lipid
oxidation *softening -reduces hair stiffness or storage modulus*anti-static -prevents static repulsion btw hair fibres
-more resistance to humidity changes *substantivity (i)electrostatic attraction where quats carry positive charge
 and hair surface has negative sites damaged hair with high negative sites allows greater quat substantivity to hair
surface (ii)hydrophobic attraction between fatty alkyl groups of cation to hair surface lipidsincreased surface
hydrophobicitygreater contact angle
Cationic surfactant essentially serves purpose as bactericide to clean and aseptize surgery tools
Applications of cationic surfactants: Flotation collector, bactericide, conditioner, anticorrosion agent,
fabric softener, anticaking agent, road surfacing, dispersant, antistatic agent
Applications of cationic surfactants to adsorption of surface*steel(anticorrosion)*mineral ores(flotation
collector)*stones(road surfacing with bitumen emulsion)*inorganic pigments(dispersant)*plastics(antistatic
agent)*fibers(antistatic agent, fabric softener)*hair(conditioner)*fertilizers(anticaking agent)*bacterial cell
walls(bactericide)
Important facts about Cationic surfactant*3rd largest of surfactants and more expensive than anionics*used in
applications cannot be substituted with others such as those requiring a (+) charge and bactericide action*cannot
mixed with anionic*amine type surfactant cannot be used at high pH, while quat is not pH sensitive*many are
bactericides*(+) charge allow operating as floatation collectors, corrosion inhibitors and solid particle
dispersant*adsorb strongly to most surface

*both positive & negative charges(zwitterionic/amphoteric)-betaine(no.4)

Anionic dominates at alkaline pH , cationic dominates at acidic pH
Common zwitterionic surfactants: Betaine, imidazoline, amine oxide,
amidobetaine
Applications*cosmetics*bactericide*wetting agent*hair rinse formulas*fabric softener*corrosion inhibitor
Important facts about zwitterionic*smallest class of surfactant due to high price*normally compatible with all other
types of surfactant*not sensitive to hard water*generally stable in acids and bases*low eye and skin irritation, hence
suited for shampoos and other PC

*no charge(nonionic)-fatty acid ethoxylate; polyether type(no.2)- polyhydroxyl – polyether and polyhydroxyl
Applications*detergent*foaming agent*emulsifier*baby shampoo*fabric
softener*toothpaste*cosmetic*pharmaceuticals*food*wetting agent*dispersant
Important facts about nonionic surfactant*2nd largest of surfactant*do not produce ion, compatible with other
surfactants*not sensitive to hard water*not affected by electrolytes*4-5 ethylene oxide groups ensure good
solubility in water with lipophilic C13 alkyl*ethoxylate based less water soluble(more hydrophobic) at higher temp,
polyol-based more water soluble at high temp

*Special surfactant
(i) silicon surfactant*belongs to polymeric organosilicon and is 1 of several types of silicone oil(polymerized siloxane)
Properties:*optically clear, inert , non-toxic and non-flammable*efficient in lowering surface tension (to
20mN/m)*excellent wetter*powerful defoamer*expensive*hair shiner and slipper*lubricant
(ii) fluorinated surfactant*synthetic organofluorine that have multiple fluorine atoms
Properties:*extremely efficient in lowering surface tension to 15mN/m, half of what attainable by hydrocarbon
surfactant(26-28mN/m)*used for wetting and spreading of aqueous solutions*thermally stable and used as
firefighting agents*tolerance to high salinity and divalent cations*expensive
 Lecture 02:
*C20 is concentration of surfactant needed to achieve surface tension reduction of 20 mN/m. It expresses efficiency
of the surfactant
*Surface tension at CMC cannot be reduced any further*CMC is concentration of surfactant above which micelles
form and it expresses effectiveness of surfactant*value of CMC depends on surfactant type, medium, temperature,
pressure, presence of other substances*CMC is expressed as molarity or mole fraction unit ie. Sodium dodecyl
sulfate in pure water @ 25Cand 1 atm pressure is 8 X 10^-3M (mole/L)*
*Methods for measuring surface tension-capillary rise method-wilhemy plate or ring method
Factors affecting CMC
*chemical structure(traube’s rule: CMC decreases by factor of 2 for ionic and 3 for nonionics on addition of 1
methylene group to alkyl chain*counterions*salt concentration(increasing salt, lowers CMC dramatically for ionic;
effect is moderate for short chain but much larger for long chain)*polymer

CMC can be determined by many physical properties of surfactant solution

Important notes on CMC*surfactant are in unimeric state below the CMC,

above this, the surfactant unimer concentration remained below CMC*CMC
decreases with increasing alkyl chain length*CMCs of nonionic surfactants are
much lower than for ionic surfactants*Cationic surfactants have slightly higher
CMCs than anionic* nonionic surfactant of the oxyethylene variety has
moderate increase of CMC as polar head becomes larger*The valence of the
counterion is significant. While simple monovalent inorganic counterions give
approximately the same CMC, increasing the valence to two gives a reduction
of the CMC by roughly a factor of four*alkyl chain branching, double bonds,
aromatic groups, polar character in hydrophobic part produce sizeable changes
in CMC, but perfluorination in alkyl chain dramatically lowers CMC*small
variations for nonionics surfactants with addition of salts

Effect of polymer on surfactant CMC

Surfactant solubility*depends on temperature- krafft

temperature(Tk) which is temperature above which
solubilityof surfactant increases, it is also the
minimum temperature at which surfactant can form
micelles ie. Surfactant solubility equals to CMC-
increase in alkyl chain length decreases Tk- depends
on head group and counterion of surfactant-divalent
counterions(Ca+2) , Tk is higher
How to develop surfactant with low T k: *introduce
methyl group or branching chain in alkyl chain*introduce doublebond in alkyl chain*introduce polar oxyethylene
group between alkyl chain and ionic head

Surfactant self-assembly: * Surfactant structure (head group, alkyl chain), concentration, ionic strength and
temperature lead to the formation of different micellar structure

Driving forces of self-assembly*insolubility of surfactant hydrophobic part in water*hydrophobic

interactions*balance between hydrophobic interactions(long alkyl chain) and hydrophilic interactions(repulsion
between polar head groups , will have to arrange themselves to minimize unfavourable repulsion to support
formation of micelle)- these interactions of hydrophilic affected by electrolyte and counterions to lower
CMC*counterions of head group

Critical packing parameter(CPP)*Plays important role on structure of surfactant assembly*Reflects balance of

interaction between hydrophobic tail and hydrophilic head and is expressed as:
𝑪𝑷𝑷 = 𝑽/( 𝑨× I )
where V = hydrocarbon tail volume A = Optimum head group area l = Critical hydrocarbon length

CPP >1 when tail is bulky and head is smallDifficult to pack, ultimately form reverse micelle CPP depends on
temperature and salinity (salt type and concentration)

*Micelle is aggregate of surfactant molecules dispersed in liquid colloid* colloid is mixture in which a substance of
dispersed insoluble particles is suspended throughout another substance
*Spherical micelle size and aggregation number*An aggregation number (Za) is number of surfactant molecules
present in micelle*Ionic surfactants Za=10-170, nonionic surfactants Za=30-10,000

*Volume of hydrophobic compound affects size and stability of micelle-------------------

*Mixed micelle composes of more than one surfactant capable themselves of

forming micelle ie. Anionic(sodium dodecyl sulfate) & nonionic-nonylphenol
polyethoxylated*enhances performance of micelle*stabilize micellar
formulation*reduce CMC, and requiring less surfactant to form micelle*increase size
of micelle to increase solubilization power*reduce krafft point/temperature

Where X1 and X2 are the molar fraction of individual surfactants 1 and 2 respectively, in the solution CMC, CMC1 ,
and CMC2 are CMC value of the mixture, and individual surfactants 1 and 2, respectively

Micelles formed In other mediums:*strongly polar organic solvents ie. Formamide and ethylene glycol,
micelles formed with same features as in water- CMC is much higher*nonpolar solvents- association of
amphiphilic compounds is low and only small aggregates, dimers, trimers-introduction of small amounts
water can induce self-assembly to form reverse micelles(nanometer sized of 1-10nm water droplets
dispersed, hydrophilic head is to inner side.
Wo(water content) dictates the size and stability of reverse micelles

Importance of surfactant adsorption at solid-liquid interface*disperse solid particles in aqueous

solution*remove dirt(detergency)from surface*protect solid surface from corrosion
Important Notes on self-assembly of surfactant*In water, aggregation results from insolubility of nonpolar parts in
water (hydrophobic interactions), packing of the hydrocarbon chains results from drive to minimize contact with
water*Aggregation is opposed by hydrophilic repulsion btw polar head groups on micelle surface, head groups will
arrange themselves to minimize unfavorable repulsions*Hydroxyl, aldehyde, ketone, and amine are weak
hydrophilic groups. Hence, for a long-chain alcohol, macroscopic phase separation results rather than micelle
formation*For ionic surfactants, counterion dissociation plays a major role as phase separation becomes entropically
unfavorable due to counterions, consequently there is strong tendency to form small micelles*Cosolutes stabilize
the micelles by reducing hydrophilic interactions. For ionic surfactants, neutralize charges by adding an oppositely
charged surfactant, we can “screen” the repulsions between head groups by adding electrolyte (e.g. NaCl), or dilute
the charges by introducing a nonionic amphiphile, like a long-chain alcohol.

Lecture 03:
Functional additives*small amounts modify final product*impart properties into products to improve
quality*enhance products’ life by increasing physical strength, inhibiting germination of mold/yeast/bacteria,
increasing tolerance of oxygen and protect color.
Components of functional additives include: emulsifier, moisturizer , retarder, wetting agents, dispersant, emollient,
plasticizer, uv blocker, texturizer, antiaging agent, thickener, foaming agent, corrosion inhibitor, antioxidant, color
protector, drier, defoamer, antistatic, preservative.
Sources can be grouped into:*Natural(beetroot juice extracts as colorant)*synthetic(manmade version of natural
substances which are identical copies in benzoic acid as preservative)*artificial(produced synthetically and not
naturally , nisin used as preservative in dairy products)

Coating materials*used in paint in liquid/paste/powder*forms film on substrate*has protective, decorative and

other specific properties.
Components
(i)pigment
(ii)binders
(iii)solvents
(iv) additives*small amounts added to improve/modify properties of finished coating during manufacture, storage,
transport, application.*additives influence adsorption of pigment, association of binders, solubilisation of solvent

Classifications of coating additives*thickener*surface modifiers*surface active agents*levelling agents and

coalescing agents*catalytically active additives*special effect additives
Thickeners*increase volume*increase paint film thickness*impart toughness or abrasion resistance*impart
rheological properties/ viscosity to prevent sedimentation of heavy pigments*levelling, sag resist,
brushability, film thickness, opacity controlled by adjusting viscosity
Types of thickeners
(1) inorganic such as organoclays, which are organically modified laminar silicates widely used in paint and coatings
eg. Hectorite & bentonite. Capable of forming gel-like structures to thicken paint when exposed to sufficient shear
forces within pH range, dispersed in paint, increase viscosity - also silica thickeners ie. Synthetic amorphous
silicates
(2)organic such as hydroxyethyl cellulose to control viscosity at low & high shear forces and to sag resistance.
Used in solvent and water borne paint
-solvent based*viscosity largely determined by binder itself and thickeners(increase viscosity)to counteract
sedimentation of pigments-castor oil(widely used; requires certain degree of dispersion and temperature to be
activated and induce proper properties and operate on basis of gelling), metal soaps(aluminum stearate; easier to
handle as require some shear and added during dispersion. Causes solvent to gel to produce viscosity),
polymeric(polyamide ; thickening ascribed to chelating effect, formation of micelles as a result of their hydrophilic
and hydrophobic ends and the combined association with the pigment particles. Formation of hydrogen bonds also
appear to play a role, particularly in low polarity systems. Polyamides swell & partly looped molecular chains
arranged randomly in resting state, resulting in highly viscous system.), anionic(overbased sulphonates form van
deer waals forces where microstructures formation cause increased viscosity- from calcium sulphonates and gelled
in organic solvent*Advantage: easy incorporation through careful mixing into coating, gel structure is stable, good
sag resistance, does not affect gloss much*Disadvantage:high alkalinity means it cannot be used with acid catalysts.

-water borne thickener(thickens only the water phase w/o interacting with binders and pigments, sometimes starch
derivatives and acrylic are used *
Types: *cellulose ethers - thickens water phase in 2 stages via(i) hydrogen bonds causing slight increase in viscosity
then(ii)raising concentration of cellulose resulting in overlapping of polymer chains and large increase viscosity
produce final viscosity of paint
- drawbacks is the elastic component is high and flow of paints to be applied with brush is insufficient, high MW
cellulose reduce gloss in paints and increased sensitivity to waterleads to development of associative thickeners
such as polyoxyethylenes, acrylic, cellulose ethers (hydrophobic modified to thicken paint with hydrophobic binder)
*starch*acrylic

Surface active agents(sur factants)* amphiphilic molecules having hydrophobic tail and hydrophilic head group*Act
on interface/surface and form micelle of different shape*reduce interfacial energy by breaking hydrogen bond,
reducing interface/surface tension*added into paint to- Wet pigments and substrate surface- Disperse/emulsify
binders, pigments and other components-Reduce or inhibit foaming- Promotes adhesion

Classification of surfactants
(i) dispersing agents*the homogeneous distribution of solids in a liquid medium*Surfactants polyacrylates are widely
used as dispersing agents*Dispersing agents disperse solid pigments and extenders particles in liquid medium such
as binders and water/organic solvent*Dispersion to minimize poor color development, formation of coarse particles,
sedimentation, phase separation, poor application characteristics
(ii) wetting agents(silicon surfactants)*reduce surface tension*pigment wetting is replacement of air inside
cavities between pigment with liquid in which pigment particles are dispersed*wetting defined by contact angle,
which is the angle between surface of liquid and contact surface
(iii) anti-foaming agents*undesired effect of surfactant is that it may stabilize air, which entraps during manufacture
or application of paint in foam bubbles *when bubbles burst, leads to surface defects ie. Craters or pinholes*to
minimize foam bubbles, anti-foaming ie. Silicone or silicon oil(makes hole in foam lamellae and increases drainage to
prevent foam formation)are used.
(iv) adhesion promoters*improve adhesive strength between binder and substrate*defined as resistance of coating
against mechanical separation from substrate*mode of adhesion based on chemical bonds with substrate and
binder w/ increase wetting or with formation of interlayer between them*examples of adhesion promoters: silanes,
silicones, titanium, amides, imines, zirconates, phosphates, specially modified polymers. Also binders, plasticizers,
additives(wetting agents) that have secondary effect of imparting good adhesive. solvents as additives improve
adhesive by improved mechanical anchoring.
Additives modification of coating surfaces:
Resin binder controls surface characteristics including mechanical hardness, scratch/scrub resistance of coating
surface and surface slip. Silicon (modified polysiloxanes) and wax(polyethelene) as additives makes it possible to
control surface characteristics independent from binder.

Matting agents*gives elegant appearance and hide imperfections caused by dust or other irregularities*to matt
surface, requires increasing pigment or filler ratio(not economical) therefore synthetic or natural silicas are
used*waxes used are polyolefins but is insignificant to silica which has better matting performances(combination of
these used to minimize flow behaviour
Flow-levelling agents*Designation for movement of coating material during & after application and before film
formed*affects appearance*polyacrylates impt polymeric levelling additives, cellulose acetobutyrate and specialty
polymers ie. Silicones or fluorinated surfactants also used
Coalescing agents*film formation is result of coalescence of polymeric particles when water evaporates from
emulsion bulk which allows contact and fusion of adjacent polymeric emulsion particlesallows inter-diffusion to
take place*types include: (i)pure hydrocarbons-isoparaffins, cycloaliphatic compounds(ii)more or less polar
compounds with alcohol,ester,ether,keto or combi.
Catalytically active additives*accelerate chemical reaction during film-forming*types include:
(i) driers are also catalyst but diff group*metal soaps of diff carboxylic acids of napthenic, isononanoic, versatic
acids*added to air-drying coating systems accelerating transformation(oxidative cross linking of resin binder by
metallic cation of soap) of liquidsolid*classes of driers-active(ie. Cobalt,iron,lead,vanadium,manganese)-auxiliary
(catalytically not active but enhances active driers)ie. Barium,calcium,potassium
(ii) catalyst*enhances binder and cross linker reactionhigh level coating with good chemical and weather
resistance*acids such as sulfonic acids, salicylic acids, alkali such as KOH & hydroxyl / phenolic group bearing tertiary
amines employed
Special effect additives*for during production,storage,use*anti-skinning prevents formation of film on surface of
liquid paint*light-protection agents*corrosion inhibitors of metal*biocides against microbial degradation*flame-
retardants

Cosmetics
Additives works synergistically with active agents, enable products w/ diff structures like creams, gels, pastes etc
Types: water, preservatives, antioxidant, emulsifiers, thickeners, moisturizers, fragrances, spreader, uv filter,
(I)Water*frequently used in combination with surfactant in O/W , W/O*polar solvent for hydrophilic agents and
additives*increase skin moisture on temporary and long term base
(ii) preservatives*prevent microbial growth or chemical changes*parabens(para-hydroxybenzoates, esters of para-
hydroxybenzoic acid) widely used ; naturally occurring in fruits & vegetables**caprylyl glycol, glycerin, glycols and
sugar sub like sorbitol also gives same function
(iii) antioxidant*vitamins C & E protect sensitive ingredients of cosmetics while providing skin with reliefs*natural
extracts in birch bark, black raspberry, argan oil used *synthetic phenolic antioxidants in butylated hydroxyl toluene
(iv)emulsifiers(affects viscosity)*prepare homogeneous uniform formulation*efficacy depends on MW, CMC,
HLB,PIT and self assemble structure*poly hydroxyl nonionic surfactants such as fatty acid ester of natural polyols
(glycerol sorbitol)*mixed poly hydroxyl and ethylene oxide nonionic surfactants used also as oxide unit helps in
tuning HLB in broader range*natural membrane ie. Ceramide and phospholipids(phosphatidylcholine ;
biodegradable) form layered lamellar structures similar to skin and integrate in*non-biodegradable not metabolized
after penetration into skin; will not integrate in and gradually leads to loss of natural lipid of skin and hence are
avoided
(iv) Thickeners*xanthan, carrageenan, alginate, chemically modified cellulose control viscosity*form gel like
structures which solidify aqueous solutions & emulsions*synthetic polymers in polyacrylates; sodium carbomer to
provide thixotropic or quick break features to allow liquefying upon spreading or contact with skin
(v)Moisturizers*control consistency based on sugar-like structures eg. Xanthan influence hydration of skin due to
water-retaining features*invisible film decreases water loss of skin*mucins(glycoprotein) of aloe vera increase skin
vitality and natural glow
(vi) Fragrances
(vii) Spreader*synthetic esters ie. Isopropyl myristate, diisopropyl adipate*spread for less rub-in time and enhance
glossiness*increase spreading area of aqueous product for better coverage*easily spreading can also be
counterproductive in sensitive areas such as eyes
(viii) UV filter*UVA(320~400nm) & UVB(280-320nm)*prevents UV light from reaching skin by absorbing it or by
scattering*can also protect products and their ingredients*large number of chemicals such as aminobenzoic acid,
cinoxate, octocrylene, zinc oxide, and titanium oxide(coloring agent) used as UV filter in cosmetics

Lecture 04:
Dispersion is defined as solid primary particles or aggregates distributed or dispersed uniformly throughout a
dispersion medium eg. paint in which solid pigment is dispersed in water
Emulsion is dispersion where dispersed and dispersion medium are liquid. Eg. Milk where liquid fat is dispersed in
water*To improve the stability of 2 insoluble phases, 3 rd or more components such as emulsifiers or dispersants are
used*emulsifiers accumulate at interface and form protective layer not broken when droplets collide.
Sizes of dispersed phase*micro 0.2~50um(thermodynamically unstable: coarse macroemulsions, fine
macroemulsions ), nano (thermodynamically stable: microemulsions, micellar solutions, molecular solution)
Types of macroemulsions: *W/O*O/W*Biemulsion O1+O2/W*Multiple or double emulsions O1/W/O2, W1/O/W2
Surfactant is an emulsifier or a dispersant*Surfactant are emulsifiers assist in creating emulsion, determined by HLB
to form stable emulsion

HLB value effects on emulsions*Lower HLB value is lipophilic and higher is hydrophilic 0 – 3(defoamers), 3-8(w/o
emulsions), 7-9 (wetting agents), 8-18 (o/w emulsions), 11-15 (detergents), 15-18 (solubilizers)
Water -soluble emulsifiers gives O/W emulsions, oil-soluble emulsifiers W/O emulsions

HLBM= HLB1*m1+ HLB2*m2+ ------ HLBi*mi

HLBM= HLB of the surfactant mixture
mi= mass fraction of surfactant component i
HLBi= HLB of surfactant component i
Note: m1+ m2+ -------- mi = 1
A formulation is required to formulate an o/w emulsion of the basic formula: Liquid paraffin 50 g Emulsifiers (Tween
80 and Span 80) 5 g Water to 100 g The required HLB of the emulsifiers blend is 10.5. Calculate the fraction of Tween
80 (HLB 15) and Span 80 (HLB 4.3) used to produce a stable paraffin emulsion.
HLBM = HLBt * mt + HLBs * ms ms = 1-mt
10.5 = 15 * mt + 4.3 *(1-mt ) mt + ms = 1
10.5 = 15mt + 4.3 - 4.3mt
10.5 = 10.7mt + 4.3 Where mt = mass fraction of Tween80
6.2 = 10.7 mt ms = mass fraction of Span 80
mt = 0.5794(mass fraction of tween80)
Amount of Tween 80 = 5*0.5794 = 2.89 g Amount of Span 80 = 5-2.89 = 2.11 g

Calculating HLB for O/W lotion: Incremental calculation for HLB:

Factors affecting emulsion instability*van der waals force of attraction between droplets*gravity*random
movement of droplets*temperature*creaming/sedimentation (driven by density difference, reversible)-reduce
density difference by using brominated vegetable oil-increase viscosity by adding thickener*coalescence-2 or more
droplets, bubbles or particles merge during contact to form single droplet, bubble or particle. – to minimize
coalescence, needs to reduce droplet size to reduce collision, increase repulsion among droplets, adding surfactant

Coagulation and flocculation used in combi. Coagulation destabilizes colloidal solution, so polluting matter can form
together and form floccules which may or may not come out of suspension with addition of flocculent.
Phase inversion temperature(PIT) is at which emulsion inverts from O/W to W/O
:Unique for any emulsifier or blend of emulsifier*Occurs in ethylene oxide (EO) based nonionic emulsifier system as
the properties of polyoxyethylene chain are highly temperature dependent.*Link to solubility of emulsifier in the
respective phase*Increasing length of polyoxyethylene chain in nonionic surfactants gives higher HLB numbers, leads
to increase in PIT*more nonpolar the oil, higher the PIT*PIT decreases with addition of electrolyte (e.g. NaCl).
Replacing distilled water by 5% sodium chloride solution gives PIT reduction of the order of 10°C.*The relative
volume of oil to water ratio affects PIT

Temperature affect emulsion properties*Reduces the viscosity of the oil.*Increases the mobility of the water
droplets.*Increases droplet collisions and favors coalescence.*Weakens or ruptures the film and enhances film
drainage.*Increases the difference in densities of the fluids

Measuring emulsion stability*centrifugation to see phase separation*droplet size distribution*voltage potential

change*rheological change*infrared related to coalescence, sedimentation, creaming and flocculation

How to improve emulsion stability*charge stabilization(negative charges repulsion occurs, requires electrolytes
to negate these) and Helmholtz double layer(alternating charge layers) effect to minimize van deer waals
forces*adding non-ionic surfactant(tight packing at interface) to strengthen interfacial film*Adding co- emulsifier
/polar waxes (e.g. cetyl-alcohol) to form additional protective layer and reduce coalescence*Adding co-emulsifier
to build a preventive layer (body) around the droplets*Minimizing density difference using brominated vegetable
oil(density higher than water)*Reducing droplet size to reduce collision*Increasing viscosity by adding thickener
(arabic/xanthan gum)

Wetting agent is the ability of a liquid to spread on surface. Wetting agent assists liquid to spread.
*When θ < 90 the surface is hydrophilic and the liquid spread easily on the surface*θ = 90-150 the surface is
hydrophobic and the liquid slowly spread on the surface*θ > 150 the surface is super hydrophobic and the liquid
cannot spread the surface

Wetting ability of a liquid is governed by liquid surface tension and attractive (adhesive) forces between liquid and
solid surface.

The lower the surface tension, the easier to spread (wet) the surface, aids in surface hydrophilization.eg. Sodium bis
(2-ethyl-hexyl) sulfosuccinate, Acetylene glycol, A silicon based surfactant (Super spreader)
The facts about surfactant as wetting agent:*Surfactants have a strong driving force to go the solid–liquid
interface*They effectively reduce the surface tension*Limited to those surfactant that have a reasonable
concentration of free that is non-micelle bound*They move rapidly to the newly created surface.*Wetting agents
are often branched surfactants because these do not form micelles as readily as their straight-chain
counterparts.*Both nonionic and anionic surfactants are used in commercial formulations
Surfactant that prevents wetting and spreading causes surface hydrophobization and increase in contact angle. Eg.
Silicon, cationic surfactant

Foaming agents
Foam is dispersion of gas in liquid. Gas to liquid ratio (foam number) dictates size and stability of foam. Smaller foam
number, thicker liquid lamellae.
Foaming only occurs when*one component is surface active(surfactant)*foam film(lamellae) exhibits surface
elasticity

Surfactant stabilizes the foam by*Clumping together and forming a cohesive layer on air-liquid interface*Increasing
the lamellae elasticity and viscosity*Forming double layer, which causes electrostatic repulsion, preventing further
thinning the lamellae*Instigating the lamellae liquid mass transfer under stretching

Antifoaming agents(defoamer)
Antifoaming agents are surface active compounds (surfactant) that break foams by spreading on the foam lamellae.

Types of defoamer:
(i) Oil based defoamers(heavy duty defoamer)*defoamer oil liquid (not silicone oil) insoluble in foaming medium,
wax, hydrodrophobic silica to boost performance and surfactants to improve emulsification and spreading in
foaming medium
(ii) Water based defoamers are of oils and waxes dispersed in a water base. These are normally best as deaerators,
which means they release entrained air.
(iii) Silicone-based defoamers(heavy duty defoamer)are polymers with silicon backbones such as
polydimethylsiloxane (Silicon oil). It contains hydrophobic silica dispersed in a silicone oil and surfactant
(iv) Powder defoamers are in principle oil based defoamers on a particulate carrier like silica. These are added to
powdered products like cement, plaster and detergents
(v) Alkyl polyacrylates are suitable for use as defoamers in non-aqueous systems where air release is more important
than the breakdown of surface foam. These defoamers are often delivered in a solvent carrier like petroleum
distillates

Defoamer liquid carries surfactant such as metal stearate and hydrophobic silica as hydrophobic particles and break
the foam. A defoamer liquid consists of Mineral oil 80% Hydrophobic particle 15% Emulsifier 5%

Effect of surfactant packing parameter on foaming and antifoaming

Surfactant as firefighting agent

Surfactant solution or Firefighting foam is a foam used for fire suppression. Surfactant coat the fuel, preventing its
contact with oxygen, resulting in suppression of the combustion Surfactant provides better flow and spreading over
the surface of hydrocarbon-based liquids for faster knockdown of flames. Sodium alkyl sulfate and fluorosurfactants
such as flurotelomers, perfluorooctanoic acid or perfluorooctanesulfonic acid are commonly used as firefighting
agent

Novel surfactants: Gemini surfactant(not yet of commercial importance)Two hydrophobic tails and two head
groups linked together via a short spacer.These surfactant are generally known under the name of gemini (Latin for
twin) surfactants. They are very efficient in lowering surface tension and show very low CMC value.
Types:*Cationic, anionic, heterogemini surfactants
Gemini surfactant as corrosion inhibitor
Novel surfactants: Green surfactant *Biodegradable and versatile*Safe to the end user (LC 50 > 10 mg/l)*Natural
feedstock with no food value or negative impact on ecosystem

-biosurfactant; Surface active molecules (e.g. phospholipids, glycolipids,lipopeptide) produced on living surfaces,
mostly microbial cell surfaces, or excreted extracellularly*(challenges)low concentration in fermentation broth,
expensive due to fermentation and purification cost*(opportunities)cheaper growth media for onsite production of
biosurfactant, engineering microorganism for overproducing biosurfactant, developing cost effective purification
method

-biobased surfactant (phospholipideg. Antimicrobials, peptides, glycerol,saccharides,serine amino acid or fatty

acideg. Sucrose stearate); Surface active molecules that are obtained by modification of natural compounds
including biosurfactant

Lecture 05:
Personal care products: placed contact with external parts of human (epidermis, hair system, nails, lips and external
genital organs), teeth mucous membranes of oral cavity to clean, perfume, changing appearance, correct body
odours, protect, maintain condition.

Cosmetic products formulation components:

(i) Carrier phase (formulation body) serves main body. Impact price, manufacturing
- water, water-alcohol, oil, powder
(ii) Excipients (formulation skeleton) serves feel, stability, aspect
-high concentrations
(iii) Active ingredients (formulation brain)
-low concentration

Categories of Personal care products:

(i)Monophasic: Aqueous & alcoholics eg. Liquid (sprays & aerosol), perfumes, Thickened (Hair gels)
1 phase – based on water, alcohol or a blend of 2
Wide range of viscosity, and solubilization of lipophiles is an important parameter.

Basic formula:
Carrier phase- H2O , H2O- alcohol
Excipients- UV-filter, chelating agent, anti-oxidants, perfumes, preservatives, dye, thickener, solubilizer
Actives- proteins, quats, slimming, antiwrinkle, anti-aging

Common formulation challenges:

(i) Different lipophile solubilization types *alcohol aids in solubilization
(ii) Thickening/gelling *natural thickeners (guar,xanthan, celluloses) *synthetic thickeners (carbomer)
*thickeners ‘cloud’ on drying preventing solvent evaporation
(iii) Skin/hair drying (due to alcohol evaporation)*humectants and moisturizers *water-soluble emollients
(iv)Generally low active delivery- use nanosomes, microencapsulated actives for targeting
(v) Microbial stability- use water-based preservatives
(vi) Aesthetic *incorporation of beads or glitters requires suspending agents (carbomers, xanthan gum)

(ii)Monophasic: Anhydrous Do not contain water eg. cosmetics, skincare, bath & shower, suncare
Characteristics:
-Blends of oils, waxes or combinations
-Wide range of aspect: liquid, semi-solid or solid *Compromise between oil and wax content
-High load of pigments in color cosmetics
-Melting point & pigment dispersion are key
-Expensive formulations
-Difficult to formulate
-Sensitive area to be mild and edible
-Incorporation of aqueous actives is tricky

Basic formula:
Carrier phase: oil, wax, oil & wax blends, powders, other water-insolubles
Excipients(oil-based): UV-filter, Antioxidants, perfumes, preservatives,
dyes, pigment wetters and dispersants
Actives: Vitamins, sunscreen, antiwrinkle, proteins, anti-aging, oil-soluble extracts etc

Common formulation challenges:

(i)structure*balance between oil and wax content *melting point & crystalline or amorphous structure of waxes
(ii)aesthetic*multi-phase systems for liquid oils -based on polarity diff or microemulsion system.
(iii)pigment loading*good pigment wetters(good dispersion, binding and even application
(iv)Feel*low spreading preferred*self-heating by using exothermic chemicals
(v)safety*safe to use at sensitive areas , must be mild/good grade
(vi) Price*expensive formulation and price must justify cost.
(vii) Actives*incorporation of water based is difficult*mixing unlike oils together, use non-ionic emulsifiers HLB 1-3
(viii)Manufacturing*use specialized equipment eg. Roll mills.

(iii) Surfactant systems & soaps

Primary function: Cleansing (skin and hair), detergence (dirt emulsification)
Secondary function: foaming
Ternary function: improving the aspect (conditioning)

Types:
-skincare*facial wash, soap , liquid soap
-haircare*shampoo
-bath & shower*shower gel, foam bath
-men’s products*shaving gels, shaving foams

(iv) Emulsions (O/W, W/O, micro, multiple)

Composition: Water, thickeners, humectant, emollient oils, surfactant emulsifiers

(i) Water *widely used in manufacturing of cosmetics*solvent for ingredients*contain inorganic ions like ca,mg,
na,k*microorganisms
(ii)Humectant eg. Inorganic CaCl, natural organic urea & Amino acids, organic polyhydric alcohols propylene glycol,
glycerol, sorbitol *hygroscopic substance absorb moisture to form film over skin, preventing drying *retarding loss of
H2O, helps spreading of product*act as solvents
Mechanism: Moisturization (plumping of corneocytes), lubrication (decrease of rough feel)

(iii) Thickeners(cosmetics & personal care products

*Sensory perception*flow behavior*suspension of actives*application properties*impart stability*rheology
modifiers

Types of thickeners: *Natural -plant(guar, carrageenan)-microbial(xanthan gum more commonly used as other
natural types have higher production costs, unreliable availability and presence of microbial or contaminants)-
animal(gelatin, keratin)*modified natural-plant(cellulose derivatives, guar)*inorganic-clay, amorphous silicon
dioxde(bentonite, hydrated silica)*synthetic-petroleum based(acrylic acid polymers(carbomer)*mineral salts
***Natural; Xanthan gum*anionic polysaccharide, fermentation*good electrolyte & pH tolerance*wide pH
applicability(3-12)*maintains viscosity at high temperatures*compatible w/ anionics and nonionics; mono and
divalent salts*used in surfactant and emulsions*give tacky/sticky afterfeel*long swelling time

***Modified natural; cellulose & guar*excellent salt tolerance, surfactant compatibility or film-forming*high use
level to build viscosity*thicken alcohol*used in wash off surfactant eg. body wash, liquid soap & shampoos*not
popular in leave on products as sensory not appealing

***Inorganic; naturally occurring, water swellable clays*hydrophilic eg. Bentonite, hectorite, magnesium aluminium
silicate*organoclays eg. Quaternium-18 hectorite*not widely used in cosmetics and persona care as need high shear
and heat to activate, affect color of emulsions and skin feel profile not desired

***Synthetic*polymers structure skin products*unneutralised carbomer partially coiled, upon neutralized carboxyl
groups turns (-) and repulsion of COO- cause chains to extend and thicken power to rise*acrylate/C10-30 Alkyl
acrylate crosspolymer-Acrylic acid based used in cosmetics and PC sold as powders and is efficient thickening and
suspension and able to create clear gels-electrolyte and pH sensitive-long dispersion time-form lumps if not properly
dispersed-hard to correct product viscosity-cannot add to finished emulsions to adjust viscosity

***Liquid dispersion polymers*flowable W/O emulsions*polymers dispersed in internal water phase*paraffinic oils
typical continuous phase(carrier fluid)*small amount non-ionic inverter to invert to O/W to release polymers-easy to
use with minimal or no lumping-use in cold or hot process-can be added any time during process-less efficient than
powders-negatively impact skin feel-dispersion sediment during storage

***Suspending agent*depends on electrolyte content, cost, pH.*commonly used are xanthan gum, carbomer,
veegum, cellulose gum
***Others*salts-efficient & low cost-works well w/ systems SLES-not effective with sulphosuccinates*fatty esters of
long chain polyglycols(PEG 150 distearate)-high melting point waxes(beewax, microcrystalline wax)-fatty alcohol (
cetyl alcohol, stearate alcohol)-fumed silica thicken oil phase

Viscosity builder*salt electrolytes used*NaCl or NH4Cl*inexpensive and effective*increase ionic density of

surfactant to increase micelle size which increase viscosity*excess of electrolyte cause thinning

Viscosity modifier*add salt to solution to SLES drive equilibrium of micelles from spherical to cylindrical
structure*cylinder do not flow around each other easily as spheres and so gives higher viscosity.

(iv)Emollients impart softness by diminishing micro reliefmechanisms -moisturisation ; plump corneocytes -

lubrication(decrease of rough feel)

Types of emollients:
-oils (synthetic eg. Petrochemical derivatives, silicones hydrocarbons, esters; Natural eg. Triglycerides, plant oils,
lanolin)
-butters (solid or semi-solid at ambient temperature)
-waxes (esters of higher fatty acids and alcohols, solid organic compound with high melting and crystals & chemistry)
-hydrocarbons (petroleum, paraffin)
-higher alcohols
-esters
-silicone oils
-higher fatty acids

***Ester = acid+alcohol with H2O as byproduct

Effects on properties of esters
Increase acid chain length higher melting point, more hydrophobic & oilier
Increase alcohol chain lengthhigher melting point, more drag
Ester properties (branching)
-Mono esters*intermediate to high melting point*solid at room temperature*bodying agents*structure builders*dry
skin feel
-branched chain mono esters*liquid at room temperature*good spreading*light emollience*breathable film
-aromatic mono esters*multifunctional*dry skin feel(decrease greasiness/stickness)*provide solvency for pigments
&sunscreens*binding/wetting properties
-Unsaturation Vs saturation*unsaturated lowers melting and increases fluidity*vegetable oils contains more
unsaturated chains to animals fats*prone oxidation which causes rancidity

Properties influencing texture of ester emollient

(i) Skin play defines how easily and duration to be massaged over skin*High -move freely during applying and remain
on surface for spreading and coverage*low-not move freely during applying light ester quickly adsorbed, tenacious
ester rheological do not favour spreading
(ii) Tack*low tack in most applications is beneficial but a certain degree is desirable and advantageous*medium-high
tack possessed by higher viscosity esters
(iii) Emollience
*Classifications of heavy, medium, light

Common sensory evaluation.

-Application*spreading, greasiness/silkiness, tackiness/stickiness, stringiness, absorption, whitening
-After-feel*tackiness/stickiness, greasiness /silkiness, gloss, smoothening
-Sensation*tingling, cooling/warming, smell
-Residue
***Mineral oils
*steam distillation of petroleum*mixtures of paraffinic, naphtenic (unsaturation) & aromatic structres*paraffin,
petrolatum(Vaseline or white soft paraffin)*cheap and inert but inert non polar can cause emulsion problems if high
levels are used in O/W
***Petrolatum
*Intermediate product during refining of microcrystalline wax*consists of colloidal mixture of microcrystalline wax,
paraffin wax and paraffin oils. Mixture gives amorphous semi-solid (melt 30-45 C)
***silicones
*synthetic molecule of repeating silicone and oxygen w/hydrocarbon attached to silica*high water repellency*very
light feel*misc. forms(i)volatile(ii)polymer(iii)waxes
***Natural oils
*plants & animals sources*esters of glycerine & fatty acids in triglycerides*physical forms of oils /fats determined by
fatty acids types and arrangement as simple or mixed*long carbon chains-more solid/higher melting point
triglycerides*unsaturated fatty acids more liquid or lower melting point than saturated*apricot kernel oil- for dry,
sensitive or mature skin.-aromatherapy base oil*avocado oil-past penetrating & high moisturizing-used in skin prep,
bath lotions, soaps*primrose oil-high in essential fatty acid, skin nutrient, moisturizing-used in skin problems eg.
Eczema, dry skin*vegetable oils-from seed or nut-mixture of diff molecules-triglycerides up to 95% to be turned to
soap-free fatty acids and alcohol-remaining steroids, lipophilic vitamins, steroids cannot be saponified
***Natural waxes
*Different sources(leaves coating, seeds)*beewax(ester composing C24-36 alcohols and fatty acids w/ hydrocarbon),
carnauba(used in lipsticks to regulate melting point and impart gloss), jojoba(liquid wax; -composed of mono
unsaturated fatty alcohols C20 & 22-Unsaturated nature of 2 components account for liquid state),candelilla
wax*Crystalline structure that gelify oils*consist of monoesters(1 saturated fatty acid+1 saturated fatty
alcohol)*Contain diesters, free fatty acids and alcohols
***Fatty acids
*Free or from triglycerides(high pressure split)*vegetable, animal, mineral source, synthetic*Long carbon fatty chain
with carboxylic acid*1 or more unsaturation*higher unsaturation, more liquid but less stable due to
oxidation*longer chain, less irritant and more solid(high melting point)*main source of non-ionic surfactants*stearic
acid and oleic acid(causes rancidity) are commonly used as emulsifier for cream, lotion and shaving cream

Performance of emollient
Analytical characterization: *density*refractive index*melting/cloud point*surface & interfacial tension*dynamic &
kinematic*viscosity*tack testing*lubricity
In vivo skin evaluation: *skin spreading*moisturization*barrier repair*smoothening*elasticity*oiliness
Experimental evaluation: *skin penetration*HLB*Dispersability & solubility*foam depreciation
(v)Powders & other solids*solid raw materials blended in a fine mixture*ingredients utilized in powder formulations
ie. Talc, starch, TiO2, silicates, powders are stable and involves specialized mixing in manufacturing , it is critical to
not have water contamination Applications: anti-fungal powders, baby powders

Lecture 06:
Coating is applied on substrate to serve purpose in decorative, functional or both
Types of coating:
(i)decorative/architectural
(ii)protective/industrial
(iii)automotive(OEM/Refinish)*for protection & decoration ie. Water-based acrylic polyurethane enamel widely used
(iv)marine
(v) coil*continuous & highly automated industrial process for coating of metals(prepainted metal); cleaned , treated
to provide tightly bonded finishesmore corrosion resistant than other painted metal
(vi) wood(furniture/fixture)
(vi) powder(coating of metals, household appliances, automobile, bicycle)*applied as free-flowing dry
powder(thermoplastic or thermoset); is typically electrostatically applied and cured with heathard finish is tougher
than conventional paints
***conventional liquid is delivered via evaporating solvent
(vii) can(packaging)*organic layer protects integrity from effects of food; preventing chemical reactions*epoxy based
widely used*food companies replaced bisphenol A -based epoxy with acrylic & polyester, (and recently polyolefin,
non-BPA epoxy) developed due to toxic issues

Paints functions:*help to impart color, prolong, usefulness, providing protection from scratches, rust and
corrosion(induced with active ingredients/factors ie. active metal, water, oxygen, acid, salt, high temperature)
In general: (i)aesthetic appeal*gloss/sheen/matt finishes*color*texture(ii)protection*external environment &
elements-water/rain, UV-micro-organism in algae, fungi-salts such as acid rain*physical impact-
abrasion(iii)functionality/specific attributes*fire-protection*non-stick in cookware*heat management in solar
reflective paints*military-radar absorbance*marine-anti-corrosion*special effects- luminescent

Classification of paints*curing mechanism- baking, air-dry, uv, oxidative, 2 component*solvent for paint-
water/solvent based, solvent free*resin- epoxy, acrylic, polyurethane*market-protective, marine, coil
coating,architectural
Properties of paints*appearance-gloss/matt/semi-gloss*application-brush, roller, sprayer*drying time-
fast/slow*adhesion-substrate/existing coating/intercoating*mechanical properties-hardness/flexibility*resistance-
UV/Chemical/abrasion/fungus/algae*outdoor durability-gloss retention/color/UV*storage stability-settling
tendency/viscosity stability

*Resin binder*- holds paint and functional materials cohesively and provides adhesion to substrate- polymers that
are solvent based- may dissolve as solution or carried as dispersion of small particles in liquid
*emulsion/dispersion/latex*- stable dispersion of polymeric substance in aqueous medium- water based binders

*pigment volume concentration(PVC & CPVC)*- ratio of volume pigment to volume of total non-volatile
materials(pigment & binder)- CPVC(critical PVC): concentration of pigment at which pigment becomes continuous
and enough binder to fill spaces

***non binder additives are ignored

*Paint rheology*- viscosity as function of shear rate- thixotropic flow is pseudoplastic flow common in coatings –
increase in shear rate causes viscosity drop, as shear rate drops to 0, viscosity builds slowly- time to regain full
structure is vital to coating rheology (relates to sag resistance, film build, flow and levelling)
*Tg*- temperature region where polymer transitions from hard glassy state to rubeery, soft material

*minimum film formation temperature*-lowest temperature at which aqueous polymer dispersion/ emulsion, self
coalesces in semi dry state to form continuous polymer film- organic solvent dissolves in particles when added to
latex, it will act as plasticizer that lowers Tg and decrease modulus

*surface tension(beading/wetting)*-elastic tendency of fluid surface which makes it acquire least surface area-units
in dynes / cm

Latex paint coatings*latex colloidal dispersion(suspension)of polymer particles in water*latex particles consist of
polymer molecules of any molar mass (6000~1 x 106)*colloidal stability is either coulombic(charge stabilization) or
steric(adsorption of large molecules on nanoparticle surface to prevent aggregation)*latex dispersions maintain low
viscosity for high solids even at high M polymers

Composition of paint*solvents(liquids)-water added to adjust mill base to proper viscosity for optimum dispersing
such that it is viscous enough for sufficient shearing action, thin enough for sufficient agitation , act as ‘heat sink’ to
prevent overheating- organic solvents with wide range polarity and solvency, diff solvent control drying speed &
viscosity, flammable and has strong odour and contribute to VOC*pigments ie. Monoazo(yellow), azurite(blue)-
natural/ synthetic inorganic or organic dispersed particles(powders)color, opacity, hardness, durability, corrosion
resistance
 *additives*resin (binder) ie. Phenolic / acrylic
resins*filler/extenders common as well- achromatic(no
color) pigments of low refractive index-do not contribute to hiding power of paint (below CPVC) Examples of
extenders: clay(low cost), silicas(flatting, burnish control, abrasion resistance), talc(ease of chalking and cleanliness,
calcium carbonate(improve tint retention, chalk resistance), barytes(frost resist, stain resist) *Co-solvents -antifreeze
and wet-edge aid -delays paint drying and improves lapping/open-time-excessive amounts can cause sagging at high
humidity or early water sensitivity of exterior paints – propylene glycol has good balance of non toxic properties and
contributes to VOC*dispersants-anionic additives increase stability of pigments suspension -protects against
flocculation, aids tint retention and hiding(Hiding power is the ability to hide the surface of an object. When applied
too thin, a coating lacks sufficient hiding power. The hiding power of paint measures its ability to obscure a
background of contrasting color. Aka opacity and contrast ratio), enhances gloss, helps color acceptance & improves
paint stability*Coalescent-are solvent additives have high boiling point-are added to coatings to help film formation
through temporary plasticization-are absorbed on latex to soften it, so less driving force to coalesce
particles*thickener-3rd or 4th expensive ingredient-increase viscosity ort modify rheology-affect application
properties ie. Sag resistance, roller sliding flow, levelling, film build etc – water based ie. Acrylic acid, cellulose ether,
hydrous clay- solvent based ie. Organo clay, waxes fumed silicas*driers-accelerate drying of organic solvent paint by
catalysing oxidation ie. Metal driers are common ie. Cobalt, manganese, Cerium, zirconium, calcium*Preservatives-
(in can/ wet state) increases shelf life, selection and compatibility is critical-(film/ dry state) mildewcides, fungicides,
algicides

Steps in paint formulation: 1. Ingredient selection and measurement 2. Mill-base (pigments dispersion) preparation
for pigment dispersion 3. Let-down (resin, solvent and additives) preparation 4. Addition of Mill-base into let-down
and mix for finished product 5. Canning

Latex paint formulation (Propylene glycol is used in water-based acrylic architectural paints to extend dry time
which it accomplishes by preventing the surface from drying due to its slower evaporation rate compared to water)

(pigment dispersion -mill base , grind)

Water, propylene glycol, dispersant(35%), defoamer, surfactant,biocide(1.5%)- mix liquids at low shear

Titanium dioxide, clay, calcium carbonate- add powders slowly then mill at high shear

(letdown)

Latex (50~55%)

coalescing solvent, defoamer, water- may premix to avoid shocking dispersion

aqueous ammonia(28%), thickener(30%)- adjust final viscosity and pH

film biocide

Surfactant role:*More than one surfactants are used in paint and they play important role such as- Disperse or
emulsify pigment, binder and additive- Reduce surface tension to wet both substrate and pigment particles -
Stabilize the colloidal stability of paints in liquid state- Improve levelling and flow of the paint- Pick up dirt and
remove oil stain- defoam- Enhance drying by acting as catalyst (mainly for oil based paint)

Lecture 07: Lubricant

Lubricant is a substance, usually organic, helps to:
reduce friction(forms oil form on metals surfaces and converts solid to liquid friction, reduces heating and abrasion
essentially), cooling(lubricant helps to absorb or release heat to prevent destruction or deformation of machineries’
parts). It also helps with Load balancing(for components ie. Gear / bearings with limited contact at regions, lubricant
protects them against increasing load by dispersing load in the film) ,Cleaning(prevent corrosion or aging. Cleans out
foreign substances in soot, sludge with soap-like cleaning properties) Sealing(seal macro gaps btw systems to
prevent leakage of gas as well and inflow of external foreign substances. In hydraulic systems, lubricants create a
film) Rust prevention(lubricating film coated on metals to prevent rust formations)
The property of reducing friction is known as lubricity. It can be a fluid, solid, or plastic substance

In general, usage of it is in the • Antiwear, antioxidants, and antifoaming agents. • Demulsifying and emulsifying
agents. • Rust and corrosion inhibitors. • In machinery as engine oils, compressor oils, gear oils, and piston oils. • As
hydraulic, brake, and gear box fluids. • Used in the soap and paint industries. • Lubricants are also used as cutting
fluids in many industries. Oil, water, and oil emulsion are used as cutting fluids. Emulsions of oil in water are most
widely used as cutting fluids

Major types of additives:

Stabilizers/Deposit Control Additives

• Oxidation Inhibitor and Metal deactivator(decompose peroxides remove oxidation promoting free radicals and
reduce catalytic effect of metals and their ions by complexing w/ em • Dispersants(Suspending deposit-forming
species in oil through polar interaction, thereby preventing them from agglomerating and coming out of oil)•
Detergents(Chemical reaction with sludge and varnish precursors to neutralize acids and physical interaction to keep
the products suspended in oil)

Surface protecting agents

• Friction Modifiers(adsorb on metal surface maintain oil film to control countermovements • Antiwear/ Extreme
Pressure Agents(chemical reaction w/ metal surfaces form low friction, low shear strength film, minimizing metal-
metal interactions)

Performance-enhancing Additives

• Rust & Corrosion Inhibitors(form protective films to neutralize corrosive acids) • Viscosity Modifiers(increased
physical association with oil at high temp minimizes temp-related vis drop)• Pour Point Depressants(enable
lubricant to flow at low temp, prevents formation of crystalline structures)• Antifoam Agents(reduce surface tension
to speed up collapse of foam• Seal swell agents(diffuse into seal to prevent shrinkage and prevent removal of
plasticizer

Specialty polymers: *primarily water-soluble polymers w/ functional groups pendent or on backbone*high

performance polymer* big major groups are natural & semisynthetic polymers(biological sources, biopolymers ie.
Polysaccharides, polynucleotides, proteins)synthetic(polymerization of monomers from petroleum or natural gas
precursors)* Specialty polymers are widely used in various fields of industry such as- Agriculture (e.g. hydrogel,
functionalized polymer) -Medicine- Biotechnology -Electronics -flocculants, coagulants and structurization agents -
Prolongers of drugs -Sensor

Categories of specialty polymers:*nonionic (vinyl esters, acrylates, acrylamides, imines, ethers)

*ionic (polyelectrolytes-either cationic or anionic & polyampholytes-have both anionic & cationic)- depends on base
or acid strength, degree of solvation, dielectric constant of solvent

Anionic ie. primarily carboxylic or sulfonic acid functionality, including: poly(acrylic acid), poly(vinylsulfonic acid),
poly(styrenesulfonic acid), poly(2-acrylamido-2- methylpropanesulfonic acid), poly(methacrylic acid), and their salts

Cationic ie. segregated into three main categories - ammonium, sulfonium, and phosphonium quaternaries

Polyampholytes ie. polymeric zwitterions with positive and negative charges off the same backbone, or they can be
polybetaines having both charges on a pendent group
Basic aspect of emulsion polymerization

Start of emulsion polymerization process

Latex is a stable dispersion (emulsion) of polymer microparticles in an aqueous medium

Roles of surfactant in latex formation*surfactant is basis for forming latex particles through micelles
formation*They determine number, size and MW of polymer*Improve colloidal stability

Monomers classification

Water soluble initiators: Ammonium Peroxodisulfate (APS),

, Sodium Peroxodisulfate (NaPS), Potassium
Peroxodisulfate (KPS), Hydrogen peroxide

Chain transfer agents are sometimes called modifiers or

regulators

Major Intervals/stages of Emulsion polymerization

I : Particle nucleation *Particle number increases*Monomer concentration highest in particlesRate of

polymerization increases*Particle growth: surfactant required to cover surface Surfactant concentration drops:
micelles disappear when concentration  CMC

II : Particle growth, monomer dispersed as droplets in water*No more micelles: Particle number constant*Monomer
concentration in particles remains constant through monomer transport from dropletsRate of polymerization
constant *Particles grow by simultaneous polymerization and monomer absorption

III: Monomer depletion* No more monomer droplets: Monomer concentration in particles decreasesrate of
polymerization decreases
 Summary of emulsion polymerization

*Polymerization process with different applications on the industrial and

academic scale*Involves application of emulsifier to emulsify hydrophobic
polymers through aqueous phase by amphipathic emulsifier, then
generation of free radicals with either a water or oil soluble
initiators*latex particles size ranged from 10 nm to 1000 nm in a diameter
and are generally spherical. A typical of particle consist of 1–10,000
macromolecules, where macromolecule contains about 100–106
monomer units*Surfactants are essential in producing polymer latex particles in emulsion polymerization and are
the basis for forming latex particles through micellar nucleation*Amount of surfactant determines the number (and
therefore the size) of the particles*Number of particles also has an effect on the molecular weight of the polymer
formed inside the latex particles*Colloidal stability is another important factor strongly influenced by the surfactant

Lecture 08: Functional additives for various applications (foods, plastics, concretes,
detergents)

Food additives*prolong shelf-life*enhance taste, appearance, or other qualities*direct additives -xanthan gum to
add texture*indirect additives -become part of food due to packaging, storage or handling

Reason for using man made additives other than natural: *no wide range of options of natural additives
available*manmade more efficient in preserving*natural color agents fade*natural additives more expensive

Preservatives*prevent microbes growth*extend shelf-life*ie. Ham , cured meats treated with nitrate & nitrite during
curing Antioxidants*prevent fat/oil containing food from going rancid due to oxidation*prevent browning of fruits,
vege, juices to improve shelf life and appearance*ie. Vitamin C ascorbic acid widely used Colors*restore color lost
during processing/storage*consistent color appearance*enhance color and to consumers *negative effect artificial
food colors on children include sunset yellow, quinoline yellow, carmoisine, allura red, tartrazine and ponceau used
in drinks, sweets, ice cream Flavour enhancers*does not impart own flavour, ie. Monosodium glutamate added to
processed foods Sweeteners*sugar substitute provides sweet taste while containing less food calories*beneficial for
diabetes, tooth decay and diarrhea*intense sweeteners -much sweeter than sugar and normally used in smaller
amounts eg. Drinks, candies, cookies ie. Saccharin (benzoic sulfimide) ; no food energy and much sweeter than
sucrose*bulk sweeteners -sugar alcohols with lesser food energy but similar sweetness eg. Used in confectionery
and chewing gums Food additives; acid, base and buffer*control acidity and alkalinity for safety and stability of flavor
typically pH 6.0~8.0 Anticaking agents*keep powdered foods ie. Salts, milk powder free-flowing, and prevent
moisture absorption Anti-foaming agents*Antifoaming agents reduce or prevent foaming in foods such as fruit juice
Glazing agents*provide protective coating or sheen on food for enhanced shelf-life and shiny appearance
Emulsifiers*ie Lecithins (phospholipid) stabilize homogeneous mixture of water and oils w/ other ingredients in form
of emulsion eg. Mayo, ice cream, milk Stabilizers*ie. Locust bean gum prevents ingredients separation Gelling
agents*ie. Agar, pectin change consistency in jam food. These 3 gives consistent texture of food Thickeners*increase
food vicosity without affecting properties*easily found in food sauces Firming agents*maintain crispiness and
firmness Dough conditioners*produce stable dough Fat replacer*provide expected texture and creamy ‘mouth feel’
in reduced fat foods Leavening agents*promote rising of baked foods Nutrients*replace vitamins and minerals lost in
processing*added to diet which may be lacking Humectants*prevent foods from drying out Tracer gases*allow
package integrity testing to prevent foods from exposed to atmosphere, guaranteeing shelf life

Plastic(polymer) additives*all plastics mixed with additives*w/o it, plastics would not work*can be made safer,
tougher, cleaner , colorful*benefits of additives to plastic include -easier to process -look good -save money -safe
and sound -clean and healthy -work longer -more biodegradable

Antioxidants*e.g. Butylated hydroxytoluene, tris-2, 4-di-tert-butylphenyl-phosphite help prevent

oxidation*Oxidation can cause loss of impact strength, elongation, surface cracks and discoloration*prevent light-
assisted oxidation when plastics are exposed to UV light Antistatic agents*insulating plastics have static build ups
which could affect process procedures and pose hygiene and aesthetic issues*prevent build up of charge*treatment
of materials or surfaces*based on long-chain aliphatic amines and amides, quaternary ammonium salts (e.g.,
behentrimonium chloride or cocamidopropyl betaine), esters of phosphoric acid, polyethylene glycol esters, or
polyols Blowing agents*used in process to produce foam material*classified as- physical blowing agents (don’t take
part in chemical reaction but are volatile liquids that evaporate and make foam) ie. pentane, isopentane,
cyclopentane and liquid CO2 -Chemical blowing agents (take part in chemical reaction and produces gaseous
products to produce foam) e.g. icocyanate and water produces CO2 and used for polyurethane; azodicarbonamide
and sodium bicarbonate for vinyl and thermoplastic foams respectively & also hydrazine Fillers/extenders*improve
strength and lower the cost of the plastic materials*increase overall volume/bulk of plastic*used in plastic molding
compounds include calcium carbonate, talc, silica, wollastonite, clay, calcium sulfate fibers (also known as Franklin
fiber), mica, glass beads, and alumina trihydrate Flame retardants*prevent ignition or spread of flame in plastic
material*added as copolymer during polymerization or mixed with polymer in moulding or extrusion. Classified as -
Inert minerals ie. aluminum hydroxide and magnesium hydroxide -organohalogen; either inert or reactive ie.
organochlorines, organobromines, decabromodiphenyl ethane, brominated polystyrenes and brominated carbonate
oligomers -Organophosphorus ie. organophosphates, resorcinol bis(diphenylphosphate) (RDP), bisphenol A diphenyl
phosphate (BADP), and tricresyl phosphate (TCP) and phosphonates Heat stabilizers*ie. Metal soaps prevent
decomposition during polymer process at high heat*combined with organic co-stabilizers such as polyols or
epoxidised esters to provide synergistic effect of enhanced heat stabilization Lubricants*decrease frictional forces in
-polymer/polymer -polymer/metal -polymer/filler -filler/filler -filler/metal* 2 types of lubricants -
external(insoluble)ie. Polyethylene waxes, Oxidized Polyethylene waxes, Paraffins, Metal Soaps, Esters (high
esterification), Amides, Fatty Acid*for btw polymer & metal surface of process equipments -
internal(partially)ie. fatty alcohols, esters*improve processability of plastics by increasing the flow ability by
lowering viscosity and heat dissipation Impact modifiers*ie.acrylonitrile–butadiene–styrene, methyl
methacrylatebutadiene-styrene, chlorinated polyethylenes and styreneethylene/butylene-styrene*shock absorbing
and resist impact w/o crack*elastomeric or rubbery w/ low modulus than host polymer and absorbs energy of
impact or dissipates it Light stabilizers*ie.Benzophenones, Benzotriazoles*that inhibit the reactions in plastics which
cause undesirable chemical degradation from exposure to UV light Pigments*e.g. Titanium dioxide (white) ; Iron
oxide for yellow Plasticizers*eg. phthalate esters*soften plastics and increase flexibility*degradability is enhanced
when bioplasticizers are used Reinforcements*improve tensile strength, flexural strength and stiffness@ elevated
temp*short glass fibers with a fiber diameter of between 5-25 µm and a length of between 0.1-0.3 mm
Antimicrobials*e.g. N-butyl-1, 2-benzisothiazolin-3-one, Zinc 2 -pyridinethiol-1 –oxide*prevent deterioration by
microbial attack in forms of staining, discoloration, odor and loss of aesthetics, loss of electrical insulating properties,
hygiene and loss of mechanical properties Anti-counterfeiting agents(Taggants)*micro-level security particles
detectable using analytical procedures*incorporated directly into plastics products through compounding*are
approved for use in contact with foodstuffs

Concrete additives*AKA admixtures(other than cement, water, aggregates); chemical compounds used to modify
properties of concrete

Reason for usage of additives*reduce cost of concrete construction*achieve properties effectively in concrete than
other means*maintain quality during mixing, transport, placing, curing in adverse weather*overcome emergencies
during operations

Accelerator*increases hydration rate of cement, shortens time of set in concrete, increases rate of hardening or
strength development*Calcium chloride the most effective accelerator but use is limited due to acceleration of steel
reinforcement corrosion and decrease resistance of cement paste in sulfate environment. Chloride-free accelerators
are typically based on salts of nitrate, nitrite, format and thiocyanate Air-entraining agents*creation of tiny air
bubbles during mechanical mixing*air voids provide empty spaces that act as reservoirs for the freezing water,
relieving pressure and preventing damage to concrete*are surfactants (e.g. salt of fatty and resinous acids) change
surface tension of water -functions to increase resistance to freeze–thaw action in hardened concrete - Increased
cohesion, reducing bleed tendency and segregation - Compaction of low workability mixes including semi-dry
concrete -Stability of extruded concrete -Cohesion and handling properties in bedding mortars Alkali-silica reactivity
inhibitors Colors*Pigments (e.g. cobalt oxides, iron oxide, carbon black) to color concrete for aesthetic and safety
reasons Corrosion inhibitors*ie.calcium nitrite, sodium nitrite, dimethyl ethanolamine, amines, phosphates, and
ester amines*block corrosion reaction of chloride ions by chemically reinforcing and stabilizing protective film on
steel*ferrous & ferric oxide on steel surface can react with chlorides to form complexes and forms rust Hydration-
controlling agents*typical hydration controlling admixtures: carboxylic acids and phosphorous containing organic
acid salts *two-part chemical system -stabilizer or retarder stops hydration of cementing materials ~72 hrs -activator
reestablishes normal hydration and setting when added to stabilized concrete Plasticizers*ie Lignosulfonates,
Hydroxylated carboxylic acids and Carbohydrates *AKA superplasticizers; high range water reducers*produce high-
slump flow concrete*Flowing concrete is highly fluid & workable concrete which can be placed with little or no
vibration or compaction while still free of excessive bleeding or segregation*larger entrained air voids & greater
void-spacing factors than conventional concrete*effectiveness increased with increasing amount of cement and
fines in concrete Retarders*ie. lignin, borax, sugars, tartaric acid and salts*delay rate of concrete setting*High
temperatures of fresh concrete cause increased rate of hardening that makes placing and finishing difficult*Flash set
might take place with hot mix on a warm, windy day. Floor slabs can set up before finishing is completed Shrinkage
reducers*ie Propylene glycol and polyoxyalkylene alkyl ether which may delay setting but not affect slump and air
loss*cracks, curling of structures to be minimized for durability or aesthetic reasons Water-reducer*reduce quantity
of mixing water required to produce concrete of a certain slump, reduce water-cement ratio, reduce cement
content, or increase slump*increase in strength as water-cement ratio is reduced*2 type of water reducers -mid
rangereduce stickiness and improve finishability, pumpability, placeability of silica fume and supplementary
concrete materials and some able to entrain air; -high rangeimpart properties more efficiently than mid-range
Pumping aids*ie -Organic and synthetic polymers -organic flocculants -organic emulsion of paraffin, coal tar, asphalt,
acrylics -bentonite and pyrogenic silicas -hydrated lime*improve pumpability*cannot cure all unpumpable concrete
problems*increase viscosity or cohesion in concrete to reduce dewatering of the paste while under pressure from
the pump Permeability reducing*reduce water transmittance rate through concrete*best method is increase moist-
curing period & reduce water-cement ratio to less than 0.5*silica fumes as supplementary material through
hydration*other materials block capillaries in concrete reduces concrete corrosion in chemical aggressive
environments eg. Admixtures contain aliphatic fatty acid & aqueous emulsion of polymeric & aromatic globules
Bonding admixtures*water emulsions of organic materials including rubber, polyvinyl chloride, polyvinyl acetate,
acrylics and styrene butadiene copolymersadded to cement mixtures to increase bond strength btw old & new
concrete*surface to be dry, clean, sound, free of dirt, dust, paint, grease & proper temperature to allow efficient
bonding*different from bonding agentsadmixtures in concrete; bonding agents applied to existing concrete
surfaces before new concrete placed to glue old & new concrete together Fungicidal, Germicidal and Insecticidal*ie
polyhalogenated phenols, dieldrin emulsions, and copper compounds*effectiveness temporary; high
dosagesreduce compressive strength Anti-washout*ie. water soluble cellulose ether or acrylic polymers *increase
cohesiveness of concrete; limited exposure to water with little loss of cementplacement of concrete in water and
under water*increase viscosity of water in mixture resulting in increased resistance to segregation Grouting*air-
entraining admixtures, accelerators, retarders, and non-shrink admixtures used for of grouting *stabilize
foundations, set machine bases, fill cracks and joints in concrete work, fill the voids in preplaced aggregate concrete
etc Air-detrainers*ie. Tributyl phosphate, dibutyl phthalate, octyl alcohol, water-insoluble esters of carbonic and
boric acid and silicones*reduce air content*Used when air content cannot be reduced by adjusting mix proportions
or by changing the dosage of the air-entraining agent and other admixtures Damp proofing admixtures*ie. Soaps of
calcium or ammonium stearate or oleate and butyl stearate*retard moisture penetration into dry
concrete*generally do not reduce permeability of concretes that have low cement contents, high water cement
ratios, or a deficiency of fines in the aggregate.

Detergent additives*mixtures of compounds including alkyl benzenesulfonates; similar to soap but less affected by
hard water*main ingredients of detergent are builders, alkylbenzene sulfonate and bleaches

Additives type Desired effect Materials

Enzymes Break down fat and protein molecules in food stains Amylase, Lipase, protease

Wetting agent Enhance water spreading and remove dirt/stain from the fabrics Na-salts of α-sulfo fatty esters

Brighteners Make fabrics appear brighter Fluorescent dye

Fabric Soften fabrics, reduce static electricity and crinkling Amines or quaternary
softeners ammonium
 Anti-coagulants Prevent dirt particles removed from deposition onto cleaned Carboxyl methylcellulose
fabrics
Antimicrobials Kill microorganisms and reduce odour Quaternary ammonium
chlorides
Stabilizers Prevent the formation of excess bubbles in washing machine. Silicone
Fragrance Add fragrance to fabrics and detergent Various fragrances

Lecture 09: Lubricant science (Part I)

Lubricant classification: *Engine oil- gasoline engine oil -diesel engine oilautomotive, stationary, railroad, marine
-stationary gas -aviation -two-stroke-cycle *non engine oil -transmission fluidsautomatic, manual, power -gear
oilautomotive, industrial -hydraulic fluidstractor, industrial -turbine -miscellaneous industrial oils -metalworking
fluids -greases

Important properties of lubricant*dispersancy*friction and wear control*oxidation resistance*corrosion

control*low-temperature fluidity*foam control*viscosity index*viscosity/pressure relationship

Application Dispersancy Friction Oxidation Corrosion Low-temperature Foam Control Viscosity

and Wear Resistance Control Fluidity Index

Control

Engine Oils

Gasoline √ √ √ √ √ √ √

Diesel √ √ √ √ √ √ √

Stationary Gas √ √ √ √ √ √

Aviation √ √ √ √ √ √

Two-stroke Cycle √ √ √ √ √

Formulation basics*Base fluid (oils) and a performance package (Combination of different types of additives AKA
additive package)*Additional viscosity modifier for multi-grade oil*compositions to be adjusted base on application
Base oils*make various lubricants and greases across industries*consists from 75% to 99% of a finished lubricant ie.
automotive engine oil, grease or metal processing fluids.
Base stock manufacturer*defines product identifier, specifications and quality management system of base stock(s)
which are produced at one or more manufacturing sites
Oil marketer* Responsible for integrity of brand name and representation of a branded product*own product
specifications of formulated lubricant and responsible for representation of lubricant’s performance*Contract with a
lubricant blender to blend products meeting their specifications
Major types of lubricant additives*Oxidation inhibitor and metal deactivator*dispersants*detergents*friction
modifiers*antiwear/extreme pressure agents*rust and corrosion inhibitors*viscosity modifiers*pour point
depressants*antifoam agents
Difference btw base stock & base oil
*base stock single product defined by viscosity grade base*key building blocks of lubricants &
greases*ExxonMobil produces & supplies(paraffinic from paraffinic crude oil which has good yield stable with high
viscosity index) oil marketers or formulators mix them to make products*broken into 5 categories with quality &
performance characteristics- first 3 from crude oil; III from bio-based -IV fully synthetic polyalphaolefins (PAO) -V do
not fall into other groups
Group I*comprise 3 primary molecule types (paraffinic, naphthenic and aromatic); a variety of sulfur- and nitrogen-
based compounds; a large amount of unsaturated molecules, aromatics and polar compounds*may contain
appreciable sulfur responsible for accelerating aging and degradation of finished lubricants *Base stocks
manufactured by solvent-extraction refining techniqueseparate oil molecules by size and uses solvents to wash
out harmful constituents (some wax, some aromatic species) found in raw crude petroleum* aromatic compounds
and sulfur materials(unstable and react rapidly w/oxygen forming soluble/insoluble oxidation degradation
byproducts) as natural antioxidants in absence of specific oxidation-inhibiting agents (additives), can interfere with
the function of the primary antioxidants (amines and phenols)*hydro treating where hydrogen added to basestock
at high temperatures and in presence of catalyst to stabilize reactive components, improve color and extend life of
lubricant products.( improve quality but not neutralize aromatics) Uses:*least severely refined, and make up the
bulk of the base oil market*used in broad applications ie. industrial lubricants, gear oils and marine.

Group II*processing path similar to G-I products, but G-II oils are “hydrocracked.” And not using solvents*borrowed
from fuel-refining processes, more severe hydrogen processing wherein hydrogen added to base oil feed at much
higher temperatures and pressures. The hydrogen catalytically reacts with base stock, restructures naphthenic and
aromatic molecules and eliminates sulfur and nitrogen components, done through series of molecular
rearrangements (formation of paraffin isomers, breaking of long chain molecules and ring structures) Uses:*less
sulfur & usually more stable than Group I base oils, wider range of uses in high-performance ie. automotive and
heavy-duty engine oils, industrial lubricant and other applications

Group III*same hydrogen processing path as the G-II oils, but are more severely treated (higher pressure, higher
temperature, longer process times)*performs on par with or even superior to synthetic Group IV (polyalphaolefin)
types*Prices higher than previous 2, 3~10 X higher Uses:*primarily in higher tier, low viscosity engine oils, although
they have found increasing use in premium industrial lubricants.*low viscosity of Group III base stocks limits their
applicability to a broad range of industrial lubricant applications

Group IV*man-made, reserved for single type basestock aka PAO/synthetic hydrocarbon(made from ethylene from
petroleum)*Prices higher than first 2, 3~10 X higher Uses:*span a range of viscosities & in variety of
applications*flagship-type products demanding the highest level of performance

Group V*man-made*made from variety hydrocarbon and nonhydrocarbon raw materials*Prices higher than first 2,
3~10 X higher Uses:*polyalkylene glycols (PAGs) and various esters*white oil, a pure lubricant used in cosmetics and
food processing

Base stocks within a specific group can have significantly differing properties, specifically viscosity index, low
temperature viscosity, volatility, and saturates level. Method of predicting performance in field applications is by
actual bench, rig and engine testing.

Base stock Key properties to consider: *Compatibility – mixability of basestocks w/ other hydrocarbons*Additive
response – characteristics determining how base oil and additives work together*Viscometrics – measures of
viscosity, viscosity index and pout point*Safety – flash point and toxicity*Consistency – repeatability from batch to
batch*Oxidation stability – influenced by raw material properties and response to antioxidants*Volatility – flash
point and NOACK volatility (engine oils in particular)*Appearance – color, cleanliness and clarity

Viscosity Sulfur, Saturates,

Group Description
Index wt% %

Classic solvent refined

I ≥80 < 120 > 0.03 < 90
base oil

Hydro-processed base
II ≥90 < 120 ≤ 0.03 ≥ 90
oil

Severely hydro-
III ≥ 120 ≤ 0.03 ≥ 90
processed base oil

IV NA NA NA Polyalphaolefins

V NA NA NA Everything else
Paraffinic base stocks, and paraffinic base oils- from paraffinic crude oil good yield of stable base stocks w/high
viscosity index. All ExxonMobil base stocks are paraffinic

Naphthenic base stocks, and napthenic base oils from naphthenic crude less stable & have a lower viscosity index
than paraffinic base oils, have outstanding low temperature performance characteristics. Transformer oils are often
formulated with naphthenic base stocks.

*base oilmixture of one or more base stocks, properties can vary depending on API(American petroleum institute)
group
Typical lubricant composition

Viscosity modifier and pour point depressant for instance is processed separately from the additive package.
Similarly for the base oil stock. Additive package is sold to lubricant marketer

Additive Passenger Car Heavy Duty

Components Motor Oil Diesel Oil

Dispersant 6.5% 6.6%

Detergent 2.5% 3.3%

Antiwear 1.1% 1.2%

Inhibitor 1.4% 0.8%

Total Additive 11.5% 11.9%

Content

Viscosity Modifier 10.9% 10.0%

Base stock 77.6% 78.1%

Total 100.0% 100.0%

Additives Gasoline Diesel Stationary Gas Aviation Two-Stroke

Engine Oil Engine Engine Oils Engine Oils Cycle Engine
Oil Oils

Dispersant √ √ √ √ √

Detergent √ √ √ √ √

Antiwear/EP Agent √ √ √ √ √

Oxidation Inhibitor √ √ √ √ √

Corrosion √ √ √ √ √
inhibitor/ Metal
Deactivator

Friction Modifier √

Pour Point √ √ √ √
Depressant

Foam Inhibitor √ √
 Viscosity Modifier √ √

Others √

Lecture 09: Ingredients selection guide for specialty chemical (Part II)
Technique in Ingredients selection*Chemical
composition*Concentration*Impurities*Availability*Costs*Familiarity*Performance*handling*stability*production
easiness*sensory*innovation*communication

Surfactant emulsifier selection: *Requirements of surfactant (2in1)*Target cost price*Formulation constraints E.g.
Cold emulsification process, HLB requirements, Compatibility (Anionic & cationic / Careful with amphoteics pH),
Mildness (anionics : Na+<K+<NH4+ / NonIonics : chain length & unsaturation)

Emulsifier selection is an important factor in the success of a product formulation*Emulsion type*Selection based
upon HLB*Use of paired emulsifier*Ease of emulsification*Structure/viscosity defines cream, lotion, milk,
spray*Sensory properties of product*Water solubility*Compatibility with salts(can destabilize emulsion) &
actives*Stability of emulsion – most important

Compatibility of your emulsifier to:*Electrolyte – can your emulsifier handle electrolytes from actives, botanicals,
anti perspirants or preservatives*pH – can your emulsifier choice handle the pH requirements (low pH for Salicylic
Acid to be active)*Charged – will your emulsifier be OK with a charged active(cationic can interact with anionic and
reduce functionality of the active and surfactant) to decrease act*Surface active ingredients – Can the emulsifier
cope with additional surface active ingredients such as natural preservatives

Emollients Selection*In selection of oils and waxes, there is a need to consider the following -What type of sensory
properties do customers want -Can customer feel the effectiveness of oils giving ideal sensory effect in neat form -Is
the cost a factor*Desired skin feel & texture*Required HLB*Spreadability*Solvency / delivery of
actives*Viscosity*Wetting and dispersion properties*Different skin feel*Occlusivity / Comedogenicity

Thickener Selection*Cost of the product*Natural claim of the product*Use of mixture – two or three types of
thickenersynthetic powder most economical, difficult to use & processing time is longer, liquid polymer easy to
incorporate but price is higher than powder*Aesthetic of the product*Type of active to be use*Nature of the
emulsifier