emulziok, szolok, xerosolok...
TRANSCRIPT
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Sols (liosols S/L), xerosols (*/S solid medium), gels
Bányai István
http://dragon.unideb.hu/~kolloid/
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Emulsifiers
Emulsifiers: -surface active materials, -naturally occurring materials, -finely
divided solids (Pickering stabilization)
1. Carbohydrate Materials: Acacia gum (gumiarábikum), Tragacanth
(tragantmézga), Agar (agar-agar), Pectine. o/w emulsion.
2. Protein Substances: Gelatin, Egg yolk, Caesin o/w emulsion.
3. High Molecular Weight molecules: Stearyl Alcohol, Cetyl Alcohol, Glyceryl
Mono stearate o/w emulsion, derivatives of cellulose, Na
carboxymethilcellulose, cholesterol w/o emulsion. Polyethylen glycol
4. Wetting Agents: Anionic, Cationic, Nonionic
5. Finely divided solids: Bentonite, Magnesium Hydroxide, Aluminum
Hydroxide o/w
emulsion; carbon black w/o
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Emulsion stabilization
Factors favor emulsion stability (see lecture about colloid stability)
1. Low interfacial tension
2. Steric stabilization. Mechanically strong interfacial film (proteins, surfactants, mixed emulsifiers are common. Temperature is important)
3. Electrical double layer repulsions (at lower volume fractions)
4. Relative small volume of dispersed phase
5. Narrow size distribution
6. High viscosity (simple retards the rates of creaming, coalescence, etc.)
7. Reduce gravitational separation: reduce density difference, reduce droplet size, increase continuous phase viscosity
The term “emulsion stability” can be used with reference to three different phenomena creaming (or
sedimentation) , flocculation and a breaking of the emulsion due to the droplet coalescence. Eventually the
dispersed phase may become a
continuous phase, separated from the dispersion medium by a single interface. the time taken for phase
separation may be anything from seconds to years, depending the emulsion formulation and manufacturing
condition.
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Emulsion Inversion
As the concentration
increases (A)
the droplets get closer, and
the agitation pinches them
off into smaller, opposite
type of emulsion (B).
making milk into butter
• Milk is a fairly dilute, not very stable O/W emulsion, about 4% fat. • Creaming produces a concentrated, not very stable O/W emulsion, about 36% fat. • Gentle agitation, particularly when cool, 13 – 18 C, inverts it to make a W/O emulsion about 85% fat. • Drain, add salt, and mix well. Behold! – butter! • What remains is buttermilk.
Typical amulsions: food emulsion, pesticide, cosmetics, proofing,
drilling oil ...
water
oil
w
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Typical food emulsions (reading)
Food Emulsion type Dispersed phase Continuous phase Stabilization factors, etc
Milk, cream O/W Butterfat triglycerides partially crystalline and
liquid oils.
Droplet size: 1 – 10 μm Volume fraction: Milk:
3-4%
Cream: 10- 30%
Aqueous solution of milk proteins, salts,
minerals,
Lipoprotein membrane, phospolipids, and
adsorbed casein.
Ice cream
O/W
(aerated to
foam)
Butterfat (cream) or
vegetable,
partially crystallized fat.
Volume fraction of air phase: 50%
Water and ice crystals,
milk proteins,
carboxydrates (sucrose, corn syrup)
Approx. 85% of the water content is frozen
at –20 oC.
The foam structure is
stabilized by
agglomerated fat globules forming
the surface of air cells. Added surfactants act
as “destabilizers”
controlling fat agglomeration.
Semisolid frozen phase
Butter W/O Buttermilk: milk
proteins, phospholipids,
salts. Volume fraction: 16%
Butterfat triglycerides,
partially crystallized
and liquid oils; genuine milk fat globules are
also present.
Water droplets
distributed in semisolid,
plastic continuous fat phase.
Imitation cream (to be aerated)
O/W
Vegetable oils and fats. Droplet size: 1 – 5 μm.
Volume fraction: 10 –
30%
Aqueous solution of proteins
(casein), sucrose, salts,
hydrocolloids.
Before aeration: adsorbed protein
film. After aeration: the
foam structure is stabilized by aggregated
fat globules, forming a network around air
cells; added lipophilic
surfactants promote the
needed fat globule
aggregation.
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Typical food emulsions (reading) Food Emulsion type Dispersed phase Continuous phase Stabilization factors, etc
Coffee
whiteners
O/W Vegetable oils and fats.
Droplet size: 1 – 5 μm.
Volume fraction: 10 – 15 %
Aqueous solution of proteins
(sodium caseinate),
carbohydrates
(maltodextrin, corn syrup,
etc.), salts, and
hydrocolloids.
Blends of nonionic and
anionic surfactants together
with adsorbed proteins.
Margarine and related
Products (low calorie
spread)
W/O Water phase may contain
cultured
milk, salts, flavors.
Droplet size: 1 – 20 μm
Volume fraction: 16 – 50 %
Edible fats and oils, partially
hydrogenated, of animal or
vegetable origin. Colors,
flavor, vitamins.
The dispersed water droplets
are fixed
in a semisolid matrix of fat
crystals;
surfactants added to reduce
surface
tension/promote
emulsification
during processing.
Mayonnaise O/W Vegetable oil.
Droplet size: 1 – 5 μm.
Volume fractions: Minimum
65% (U.S. food standard.)
Aqueous solution of egg
yolk, salt flavors,
seasonings, ingredients,
etc.
pH: 4.0 – 4.5
Egg yolk proteins and
phosphatides. Lecitin (O/W),
cholesterine (W/O)
Salad dressing O/W Vegetable oil.
Droplet size: 1 – 5 μm.
Volume fractions: Minimum
30% (U.S. food standard.)
Aqueous solutions of egg
yolk, sugar, salt, starch,
flavors, seasonings,
hydrocolloids, and
acidifying ingredients.
pH: 3.5 – 4.0
Egg yolk proteins and
phosphatides
combined with hydrocolloids
and surfactants, where
permitted by local food law.
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HLB Scale 1 2
0
http://www.snowdriftfarm.com/what_is_hlb.html
Griffin: HLB = 20 * Mh / M Mh, M the hydrophilic part and the
whole molecule (Mh+Ml)
50 % Span 60 (HLB = 4.7) és 50 % Tween 60 (HLB = 14.9)?
4.7 x 0.5 + 14.9 x 0.5 = 9.8
? which combination of emulsifiers is appropriate from Span 80 (HLB = 4.3) and
Tween 80 (HLB = 15.0) for “required” HLB 12.0?
(4.3*(1-x) + 15*x = 12; 28% & 72%)
Davies' method: HLB=7+ hydrophilic groups – lipophilic groups
Test examples:
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HLB (hydrophilic -lipophilic balance) values
The amphiphilic nature of many emulsifying agents (particularly
non/ionic surfactant) can be expressed in terms of an empirical
scale of so-called HLB
Applications Dispersibility in water
3-6 W/O emulsions Nil
7-9 wetting agents 3-6 poor
8-15 O/W emulsions 6-8 unstable milky dispersions
13-15 detergent 8-10 stable milky dispersions
15-18 solubiliser 10-13 Translucent dispersion/solution 13- clear solution Ratio of solubility in octanol and water,
logKOW
HLB=7+ hydrophilic groups – lipophilic groups
SDS is an exeption with HLB 40
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Variation of type and amount of residual emulsion with HLB number of emulsifier.
Nature of the emulsifying agent determine the type of
emulsion
(antagonistic action)
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Physical properties of emulsions
• Identification of “internal” and “external” phases; W/O or O/W
• Droplet size and size distributions – generally greater than a
micron
• Concentration of dispersed phase – often quite high. The
viscosity, conductivity, etc, of emulsions are much different than the
continuous phase.
• Rheology – complex combinations of viscous (flowing), elastic
(when moved a little) and viscoelastic (when moved a lot) properties.
• Electrical properties – useful to characterize structure.
• Multiple phase emulsions – drops in drops in drops in drops, …
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Multiple emulsions
W/O/W
double emulsion
O/W/O
double emulsion
Each interface needs a different HLB
value.
The curvature of each interface is
different.
Particles as emulsion stabilizers
Almost all particles are only partially
wetted by either phase.
When particles are “adsorbed” at the
surface, they are hard to remove –
the emulsion stability is high.
Crude oil is a W/O emulsion and is
very old!!
(Pickering stabilization)
bentonite clays tend to give O/W whereas carbon black tends to give
W/O emulsions
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Multiple phase emulsions – drops in drops in drops
Drug delivery
an emulsification technique that encapsulates two different inner drops inside an oil drop
using glass capillary devices with a dual bore injection tube
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Breaking emulsions
First, determine type, O/W or W/O. Continuous phase will mix with water or oil.
• Chemical demulsification, i.e. change the HLB Add an emulsifier of opposite type (antagonistic action). Add agent of opposite charge. • Freeze-melt cycles. • Add electrolyte. Change the pH. Ion exchange • Raise temperature. HLB depends on the temperature. (Solubility) • Apply electric field. • Filter through fritted glass or fibers. Centrifugation.
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Phase inversion temperature
1. As temperature is
increased, ethoxylated
surfactants become less
water-soluble, because the
hydrogen bonding between
the oxygen of ethylene
oxide and the hydrogen of
water is inhibited. The
molecules have more
movement and cludiness
results.
2. inversion O/W- W/O and oil
is separated out.
The oil-in-water emulsions measure just 100 –
300 nanometers, are of very low viscosity and
can thus be applied by spraying.
SEM can provide a visual phase inversion: http://www.chemistrymag.org/cji/2001/03c058pe.htm
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Type of colloids on the basis of structure (appearance)
Porodin
colloids
Incoherent (fluid-like) Coherent (solid-like) gel
Colloidal Dispersions sols
Macromol. solutions
Association Colloids
Colloidal solutions
(porous) Reticular Spongoid
corpuscular fibrillar lamellar diszpersion macromolecular association
liofób liofil liofil
(IUPAC proposal)
categorized by inner / outer phases
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Type of sols (incoherent)
• aerosols • lyosols xerosols, xerogels
L/G liquid in air: fog, mists, spray S/G solid aerosol, solid in gas: smoke, colloidal powder Complex, smog
G/L gas phase in liquid (sparkling water, foam, whipped cream) L/L emulsion, liquid in liquid, milk S/L colloid suspension (gold sol, toothpaste, paint, ink)
G/S solid foam: polystyrene foam L/S solid emulsion: opals, pearls S/S solid suspensions: pigmented plastics
Definitions
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• Sol stability: kinetic (DLVO theory, steric stabilization)
• Sol: incoherent or coherent
• Xerosol: solidified sol, no aggregation no skeleton structure
• Gel: coherent, skeleton structure
• Cream: concentrated emulsion (L/L),
• Grease: fat
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Preparation of sols
Importance of monodispersity:
It is a basic duty to make well controlled size ans size distribution.
Top to bottom technique: With dispergation it is almost impossible.
Precipitation (bottom to top)
AgI sol (AgNO3+ KI), Au (gold) sol (HAuCl4 boiling+ Na-citrate rubin colored sol) sulphur sol (Na2S2O3 and HCl ) iron-hydroxid sol , FeCl3 hydrolysis
Rate of nucleation and growing nuclei are important
Processes after preparation (changes in size)
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Ageing of colloids ; Ostwald-ripening Moving slowly to equilibrium
LaMer-diagram (1950): precipitation
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Gels
• Definition – Coherent colloid system, in which one of the
components forms a skeleton (network) and the medium is around it.
– Transition between liquids (vapor pressure, cinductivity) and solids (shape)
• Types – porodin gels: consist of particles and – Reticular gels: fibers, coarse fibers, bunch of fibers
by means of primary or secondary bonds. – spongoid gels: lamellas, films,
Definition by IUPAC
• Gel:Nonfluid colloidal network or polymer network that is expanded throughout its whole volume by a fluid.[3]
• Note 1: A gel has a finite, usually rather small, yield stress.
• Note 2: A gel can contain:
• (i) a covalent polymer network, e.g., a network formed by crosslinking polymer chains or by nonlinear polymerization;
• (ii) a polymer network formed through the physical aggregation of polymer chains, caused by hydrogen bonds, crystallization, helix formation, complexation, etc., that results in regions of local order acting as the network junction points. The resulting swollen network may be termed a “thermoreversible gel” if the regions of local order are thermally reversible;
• (iii) a polymer network formed through glassy junction points, e.g., one based on block copolymers. If the junction points are thermally reversible glassy domains, the resulting swollen network may also be termed a thermoreversible gel;
• (iv) lamellar structures including mesophases, e.g., soap gels, phospholipids, and clays;
• (v) particulate disordered structures, e.g., a flocculent precipitate usually consisting of particles with large geometrical anisotropy, such as in V2O5 gels and globular or fibrillar protein gels. (above) rather than of the structural characteristics that describe a gel.
• Hydrogel: Gel in which the swelling agent is water.
• Note 1: The network component of a hydrogel is usually a polymer network.
• Note 2: A hydrogel in which the network component is a colloidal network may be referred to as an aquagel.
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Typical gels
a/ reversible polymer gel b/ reversible porodin gel c/ irreversible polymer gel d/ irreversible solid-gas xerogel
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a) Ionic b) hydrophobic c) H-bridge d) van der Waals b) Hairy-micelles f-6 coordination bond
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Porodin gel (silica)
• Silica gel (SiO2x nH2O)
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Porodin gel (clay)
• Example: (Na,Ca)0.33(Al,Mg)2Si4O10(OH)2·(H2O)n
(montmorillonit)
silt: 1. viscosity: taking up solids 2. Cooling and lubrication 3. Pressure to keep away
liquids(density) 4. Cover the wholes of the wall 5. Keeps the stability of the wall
composition: clay+ barit (weight)+xantan carboxi-methyl cellulose (viscosity)
4-5 times water to weight
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Drilling
2007.03.20 14.előadás
Drilling 2
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Sol-gel technology
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Aerogel „frozen smoke”
Az aerogels are the lightest solid material. Good insulators. Silica based aerogel was the first, but today: Al, Cr, Zn or carbon are used
http://www.youtube.com/watch?v=mAJWyRIDDVQ
http://www.youtube.com/watch?v=HoCAxS4vqwQ
Structure of aerogel
http://stardust.jpl.nasa.gov/photo/aerogel.html
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Aerogel
http://www.resonancepub.com/aerogel.htm
http://en.wikipedia.org/wiki/Aerogel
State-of-the-Art Manufacturing Technology
Exhcange the liquid to gas!
Si or Al biocompatible
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In addition, there is no surface tension in a supercritical fluid, as there is no liquid/gas phase boundary. By changing the pressure and temperature of the fluid, the properties can be “tuned” to be more liquid- or more gas-like.
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Sythesis of silica AEROGELS
First hydrogel is made.
Two basic processes:
Hydrolisys: Si(OC2H5)4(al) + H2O Si(OC2H5)3(OH)(al) + C2H5OH
⌠A Si(OC2H5)4(al) tetra-aetoxy-silane in alcohol.⌡
Condensation: ≡Si–OH(al) + HO–Si≡(al) ≡Si–O–Si≡(al) + H2O
≡Si–OR(al) + HO–Si≡(al) ≡Si–O–Si≡(al) + ROH
In this phase Si–O–Si bonds form and nanoparticles
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The size is determined by pH. In acid the hydrolisis is faster The condensation is slow: small particles form. In alcalic medium: opposite: bigger particles, loose structure
TEM pictures
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Lyogels (solvent in the skeleton)
Polimer gels (“intelligent” gels), reversible transformations (T, pH, salt content, etc.)
Disposable diapers
drug delivery
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Hydrogels
http://www.gcsescience.com/o69.htm
(poly (sodium propeonate)) poly acrylic acids. monomer:
randomly coiled molecules, in water swelling happens
Examples of hydrogels: foods, fruit jellys,
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By addition of salt water flows out.
Disposable diapers
Solidification of waste liquid
• Easier to handle
• storage
• Destruction is easier
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Intelligent gels
PDMS: poly(dimethyl-siloxane)
elastomers
Magnetic nano particles
Poli-aspartic acid gel: artifical muscle
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In acidic medium no ions incorporated in it.
Temperature (NIPA)
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N-isopropy.acrylamide gel: 34 oC
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Xerogel coating
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• Interference (anti-reflection coatings for the areas of UV, VIS and NIR.
• Applications: From Architectural
Application to UV protection
• 1992 Prinz Optics (Sol-Gel Dip
Coating Process).
xerogel coating: applications, modern opale
http://www.prinzoptics.de/en/home/index.php
http://www.variotrans-glas.de/htdocs_en/home/index.html
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http://www.molecularexpressions.com/primer/lightan
dcolor/interferenceintro.html