CARBOMERS THEORY

Detergents Division

P.O. Box 219 Via Torquato Tasso, 58 24100 Bergamo (Italy)

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 WORKING MECHANISM

Carbomers are three-dimensional network

polymers

Carbomers work through a swelling mechanism of

particle dispersed in water (through the break-down
of the inter-particle forces)

The electrostatic repulsion between carboxylic

groups is the main factor influencing the viscosity

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 SWELLING MECHANISM

“ The electrostatic repulsion between adjacent carboxylic groups is

the main factor influencing the polymer swelling degree and then
the thickening capability of carbomer’s dispersions.”

Acidic Medium Alkaline Medium

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 THICKENING MECHANISM

Carbomer polymers as supplied are dry, tightly coiled acidic molecules.

Once dispersed in water, the molecules begin to hydrate and partially
uncoil.
To achieve maximum thickening it’s needed converting the acidic
Carbomer to a salt. This is easily achieved by neutralization with a
common base such as:

Sodium hydroxide

Potassium hydroxide

Triethanolamine

Diisopropanolamine

Inorganic base  aqueous solution -- good clarity

Organic base  alcoholic solution -- good clarity
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 HYDRODINAMIC VALUE (HDV)

Carbomers influence rheological properties of the fluids due to the large

volume occupied.

The solution volume occupied by the swollen polymer is known as
hydrodynamic volume (HDV).

HDV is affected by:

Polymer type (chain, length)

Polymer concentration, Polymer MW

Electrolytes (primary or secondary)

pH

Solvent type

Temperature

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 HYDRODINAMIC VALUE (HDV)

HDV is related to intrinsic viscosity:

HDV=[η
η]*MW

MW= molecular weight

[η]= intrinsic viscosity

Intrinsic viscosity is the volume (HDV) occupied

by an isolated molecule at a known temperature.

It is related with the hardness of the molecule

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 KEY PARAMETERS:
Intrinsic swellability (Qi)

Qi
[η ] ∝
δp
Qi=intrinsic swellability (intrinsic volume-swelling
ratio)
δp=particle density

We can consider polymer molecules like small rigid

spheres (Einstein model). Viscosity (fluid diluted and
uniformly dispersed) is related to the volume fraction
occupied by all the spheres.
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 KEY PARAMETERS:
Overlap concentration Coverlap

Coverlap is defined as overlap concentration, at

which micro-gels are fully swollen and in touch with each
other.

Assuming Einstein model:

overlap
Φ *δ p
C ∝
Qi

φ = volume fraction
Coverlap is derived from intrinsic viscosity; it is
sensitive to the same parameters.

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THICKENING MECHANISM

When C < Coverlap. The fluid has a Newtonian rheology

without yield value.

driving force  intrinsic viscosity.

When C = Coverlap. We are in a transition regime.

driving force  both intrinsic viscosity

and micro-gel rigidity.

When C > Coverlap. The fluid has a visco-elastic

rheology with a defined yield value.

driving force  micro-gel rigidity.

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THICKENING MECHANISM

Viscosity (η
η)
C>Coverlap It depends strongly on the
chain length.

η∝cbMWd
C<Coverlap It depends mildly on the
chain length.
It depends on the friction
between solvent and chain.

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 GENERAL PROPERTIES:
Cross-linking Degree and
Micro-gel rigidity
Micro-gels are deformable under stress
ρ ρ
F F

As general rule, the higher is their cross-linking degree, the

higher is their rigidity.

low micro-gel rigidity (low cross-linking degree) is useful at the
high electrolyte concentrations.

Hydrophobically modified chains along the polymer back-bone

reduce the micro-gel rigidity.

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 GENERAL PROPERTIES:
Electrolytes

A high amount of electrolytes increases ionic strength.

A high ionic strength reduces electrostatic repulsion
between –COO- groups.

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 Electrolytes (cont’d)

An high amount of electrolytes increases Coverlap.

Increasing Coverlap(at a defined concentration of polymer),
polymer could come back to a C< Coverlap sensitive area
( unstable). However, Polymers with a lower
(theoretical) Coverlap will be favourite:

In presence of electrolytes, the higher is intrinsic
viscosity (low cross-linking, low Coverlap), the higher is its
efficacy;

In presence of electrolytes, the lower is intrinsic
viscosity (high cross-linking, high Coverlap), the lower is its
efficacy.
[η
η] Coverlap Efficacy
+ - +
- + - 13
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 ELECTROLYTES EFFECT

1000
% NaCl added

100 0%
10 0,10% Polygel CA 0,5 %
Pa.s

0,30%
1
0,50%
0,1 1,00%

0,01
0 20 40 60 80 100 1000 % NaCl added
rpm 100 0%
10 0,10%
Pa.s

0,30%
1
Polygel CB 0,5 % 0,50%
0,1 1,00%

0,01
0 20 40 60 80 100
rpm
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 YIELD VALUE

It’s an initial resistance to flow under stress.

Properties linked to Yield value:

SUSPENSION particle dispersed in medium will remain
suspended

SURFACE CLING gelled liquid will not drip or run down a
vertical surface
η0.5rpm - η1rpm
BYV (Brookfield Yield Value)= 100

The Yield value can be changed by materials that affect the swelling of
the polymer
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 DISPERSION TECHNIQUES

Polygel CA, CB and CK have an hydrophillic nature and in

contact with water wet fast creating lumps if not properly
added to the solvent.

DIRECT ADDITION

Add Polygel CA, CB or CK directly to water with moderate

agitation ± 800-1200rpm (conventional open blade impeller).

Hot water doesn’t improve dispersion’s rate: the powder

tends to wet too quickly forming lumps.

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