#MC

Not Just Products. Partners.

Marine Col loid§' Carrageenan

General Technology
For Pharmaceutical And Other Applications

REPRESENTANTE

wrú,n¡rs t ctA. PRoDucros Qurürcos s.A.

MAGARIÑOS CERVANTES 1944 - 1 1600 MONTEVIDEO- URUGUAV
TEL. 47 05 12 -TELEX 26941 WILIAMS UY
FAx (OO5982) 47 06 10

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Marine Golloids" Carrageenan:
lntroduction
Carrageenan is a naturally-occuning
family of polysaccharides extract-
ed from red seaweed. From this
natural source, FMC develops and
customizes blends of carrageenans
for specific gelling, thickening, and
stabilizing properties desired by
many formulators in pharmaceutical,
nutritional, cosmetic, and industrial
applications.
FMC's Pharmaceutical Division is
the largest and most experienced
producer of carrageenan extracts
worldwide. During the past 50
years FMC has established a
tradition of providing high quality
carrageenans, technical expedise,
and service.
FMC builds quali§ and performance
into its canageenan products at
three levels-seaweed sourcing,
extract manufacturing, and under-
standing the functional properties
of each product.

Three Basic Types of Carrageenan:

Figure 1. Figure 2 Figure I C

Kappa lota Lambda

. Strcng, rigict ge!, some syraresis, foms hetix with . Elaátic gets, lorms helix with Ca++. Limited aggre- . No get, randm distribution ot potymü chains.
K+ iom, Ca++ carees ñerrbes to aggregaté and the gat:,on conttibuts to elastic&, ao syréresrb.
gel to contract and becomé br¡ttle. .Highvisffiu
, Clear gel.
. Slishtly opaque gel. Beñm6 ctear with sugal : Approximately §yo ester sul¡áte and t¡tÚle or no A
I Frezelthaw stable. 6-AA.
. ApprcrtmaÉIy áo/o ester sulfate and 34% g, &AA.
, fupuimately go/o ester sulfate and fi,A 3,6.Ac,

Contents Page
Manufacturing ............................. 1

Chemistry Functions,
And Properties .......... ..........2-6
Water Systems .......................3
GelTexture ............4
Factors Affecting
Water Gels .......... ...............4
pH............. .............5
Thixotropy .............6
How to Disperse l

l
And Solubilize........... ..............7
ul l
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 +MC
Manufacturing

Quality control of carrageenan Figure 4.--¡llanuf acfun:rg Precess

extracts begins with the harvest.
FMC sources its raw materials Cms sefióñ redseárcd
from independent seaweed har-
vesters worldwide as well as FMC
operated cultivation sites in the
Asia-Pacific region (Philippines,
lndonesia/Malaysia) and East
Africa. The main seaweed types
are Eucheuma, Chondrus and Céllula6lc qaffagéo¡iafl ->üHotExtruc'Í¡ñ
mdtar1¡a¡ f,lrs space§
Gigartina, which yield kappa, iota óetr,yért I
eelIs
and lambda carrageenan.

33,.?1§",?"i.:r'X?lsflÍl'3illtfl "n cPnirca"m

baled to maintain its quality.
ñ
Following extensive w.ashing to !
ensure maximum quality, the sea-
weed undergoes a hot extraction
process to separate the car-
rageenan from the extraneous
plant fiber. The dissolved car-
rageenan, which makes up about
2-7% of the wet seaweed plant,
mr--*
is separated from the extraneous
.*
solids by filtration. The car-
rageenan is precipitated into a ElI
w*ffi
fibrous or gel material, dried,
ground, and sampled to quali§
control for testing. The entire
process is closely monitored to W*'*** eonceñtration

. obtain optimum gelling or viscos- t

characteristics. JJJJIJ
tr,* ffi! ,Dtyh?g
JJJ]JJ

t
&= §tbrdhlg

- e=
qw
a-
Blendiñg

§2

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Marine Colloid§" Carrageenan:
Chemistry, Functions, and Properties

Canageenan is a high molecular
weight polysaccharide made up of
repeating galactose and 3,6 anhy-
drogalactose (3,6-AG) units, both
sulfated and nonsulfated. The units
are joined by alternating alpha 1-3
and beta 1-4 glycosidic linkages.
The primary differences which temperature of the carrageenan
influence the properties of kappa, and produce lower strength gels,
iota and lambda carrageenan are or contribute to gel inhibition
the number and position of the (lambda carrageenan).
ester sulfate groups on the repeat-
ing galactose units. Higher levels
of ester sulfate lower the solubility

Fls{nB §,+rirpiilürs ot C,iliag6érre¡, o

Kappa lota lambda

"H>*€L",-"'f,f@< p.€}-.
: an¡ot{ cH¡ ¿HroH' clr §rüox G!l,o3o,-

ye§ ye§ ye§

2O"CWater : Nat s¿lt soluble Na+ sah soluble yes

K+, Ca++ and NHa+ Ca++ salt swells

§alt swells to form thixotropic
dispersion

5% $ált §olution
swell soluble
':-Cóld
:Hg_t
.
no no: soluble

Gelaüond{éat to l?5"FJCr¡d to'(120of

§trorgeetSels with K+ ion with Ca++ ion no gel

Gel Texture brittle elastic. no gel

Bagelalian After §hear no )re§ no'

ye§ no no

Freeze/Tharar. §tability no yes ye§

Syneqism With 0ther ye§ no no

Gums.
Ac¡d §áñ&ility"
Hot §ols no no 'no
Gels slablé above pH 3.8 stable above pH 3.8 Not applicable

-Hyúolysls in ll}u. pH
*ysiem* a6celerated by heat

Functions
. Suspends Particulates-The 3
dimensional network functions
to suspend padiculates. For
example, pharmaceutical
ingredients and dense coloring
pigments can be maintained in
suspension for extended peri-
ods of time without remixing
or shaking. Upon agitation,
or shea6 the suspensions
become flowable.
. Stabilizes EmulsionyAlthough
carrageenan is not a surfactant,
it will stabilize existing emulsions.
Its thickening and thixotropic
properties give integrity to
the system and inhibit the oil
from coalescing and forming a
separate phase.
. Controls Flow Properties-
Controlling flow propefties of
formulations is important from
processing to the final product
consistency. Carrageenan is
thermally reversible, so at high
temperatures it will impart
minimal viscosity to the system
allowing for easier processing
conditions and improved heat
transfer. Upon cooling the cana-
geenan will thicken. With most
gelling carrageenans, solutions
will begin to solidify and form
gels when cooled below 12O'-
130'F.
. Produces Stable Gels at
Room TemperatureMost
kappa and iota carrageenan
sols will set into a gel structure
at ambient temperatures. The
gels require heat to melt into
a fluid state for reprocessing.
Formulating and casting/molding
a product at elevated tempera-
ture followed by cooling,. res-ulls
in a carrageenan-based binder
that holds the shapes of the
casting mold or cavity filling
material.
. Binds Water-Carrageenan has
excellent moisture binding capa-
bilities. This allows high water
content gels and lotions to be
formulated for topical applica-
tions, and for moisture retention
and pliabili§.
Water Systems
Carrageenan should be dispersed
in cold water and then heated
Flguré § iGelail$1 lúeÉlÉrrisrn
- GEÍ
above its solubili§ temperature to
obtain maximum functionali§.
Upon cooling and in the presence
of appropriate cations, (K, Caft),
kappa and iota carrageenan poly-
mers align themselves to form
double helices. These helices
associate with divalent cations,
i.e. calcium, to form a gel matrix.
Figure 6 is a schematic represen-
tation of the gelling mechanism
for carrageenan.
. Kappa carageenan binds water
to form strong, rigid, brittle gels.
Potassium salts are essential in
order to form this firm gel struc-
ture. As the level of potassium
is increased, the gel structure
becomes tightly aggregated and
+MC
may result in syneresis (mois-
ture on the gel suface).
. Iota carrageenan also binds
wate6 but forms dry elastic
gels in the presence of calcium
salts. The divalent calcium ions
form bonds between the car-
rageenan molecules to form
helices. The negative charges
associated with the 2-sulfate
groups on the iota carrageenan
molecule does not allow the
helices to aggregate to the
same extent as Kappa car-
AG¡GEEGATEO
oEt
rageenan. The gels are more
elastic, dry and provide excel-
lent freeze thaw stability.
. Lambda carrageenan is highly
sulfated and therefore less likely
to form a gel structure. The ester
sulfate does not associate with
potassium ions to form helices
so the polymer tends to remain
randomly distributed in water and
forms viscous solutions upon
cooling. Lambda carrageenan is
primari[ used to thicken liquids,
suspend particulates, and mod-
ify the mouthfeel of chewable
dosage forms.
3
 Marine Colloid§' Garrageenan:
Ghemistryn Functions, and Properties
Gel Texture
The gel texture of the basic car-
rageenans can be modified by
blending carrageenans to meet
specified gel texture parameters.
Figure 7 illustrates the penetration
or elasticity of carrageenan gels
before the gels are fractured. The
gels can be made more elastic or
less elastic by combining kappa
and iota carrageenans until the
desired texture is achieved.
Figure 7-Gel Texture
o
I
G O.2
0 0.50
o
=
e
U
G
F
o potassium in an aqueous solution
r.5
PENETRATION IN MM.
Gels prepared with carrageenan
are thermally reversible. The gel
will become fluid when heated
above the gel melting point and
will reset into a gel when cooled
with minimal loss of its original
strength.
*.
Factors Affecting Water Gels The set and melt temperatures
. Cations-As the absolute con- of carrageenan gels are depen-
centration of cations increases dent on cation concentration.
Figure 9 illustrates the effect that
. dispersion improves increasing the level of calcium or
. temperature at which the car-
rageenan goes into solution g-4dditimal Catiú lncreaM
increases
Figure
Tempenture
Gelling
. gelling temperature increases
. remelt temperature increases
o l.Of IOTA wlfH C!++
a
Figure 8.-Cation Effect on Gel Strength ,
É
E
u
4
1dx,
u
= t.o* K¡ppl wtrH
F K+
o
2
)U
o
o.il 0.8 O.E
GELLING CATION IN SOLUTION,IBYWT.
f Kcl
Potassium and calcium ions are
essential for effective carrageenan will have on gelling temperatures.
3.0 gelation. lncreasing the level of This allows formulators to regulate
potassium ions increases the gelling and melting temperatures
strength of the resulting gel. to accommodate their process-
Figure 8 illustrates the relative ing parameters. Most other
increase in gel strength when hydrocolloids do not offer this
the level of potassium (%KCl) flexibility.
is increased.
. TemperatureAs discussed
earlier, carrageenan gels are
thermally reversible. The gels
can be subjected to repeated
heat/cool cycles with very little
effect on the resulting gel struc-
ture (at neutral pH).
 fMC

. Synerg¡sm w¡th other
gum+Kappa carrageenan is
synergistic with locust bean
gum and konjac flour. The inter-
action significantly increases
gel strength, improves moisture
binding capabilities and modi-
fies gel texture to be more
elastic and resilient, as shown
in Figure 10 below.
. pH-Sols and gels formed with Figure l2.-Eff*t of pH on Gel Strength
carrageenan are stable at room
and refrigerated temperatures.
At high temperatures cana- .E
'6
geenan sols at low pH exhibit E
E
some loss in viscosity and
potential gel strength. Figure a
12 illustrates the effects of pH 6
o
on the gel strength of '/r%o K-
CGN gels. ln low pH systems,
it is recommended that the M¡ñutes Holdiñg T¡ms (80'C)

Figure lo.-Ael Strength acidulant be added at the last 0.5% Kappa CdEgeenan + 0.2olo KCI

600 step of processing.

500

400

300

200

100

0
ol1ú tol% ml& §lto §tú sl* ñt1o 7ol§
M10 0F rcA OR XOñI¡C fO C§rcEEN

. Synergism with StarcFlota car-

rageenan increases the viscosity
of starch systems by a factor of
10 compared to the viscosity of
the starch alone. When kappa

q!¡¡
, cdrrdSeenan is added to starch
systems no increase is noted.
Figure 11 compares the effects
of shear on a starch-only system,
with starchlota canageenan and
starch/kappa carrageenan sys-
tems. The starch system exhibits
a loss in its viscosity when sub- 'o5 .o.2

jected to shear. The presence of % Caragffian

kappa or iota canageenan allows

the system to recover to its pre-
shear viscosity.

lL
Marine Golloid§' Carrageenan:
Chemistry, Functions, and Properties

Thixotropy Figure Í3.-Thixotrcpic Prcperties oi Dilute lota Camgeenen Gels

At low concentrations iota gels
have thixotropic rheological prop-
erties. They can be fluidized by YIELD POINT,
agitation or shear and will form
elastic gels when allowed to stand
quiescently. Figure 13 illustrates the
gel structure of the breakdown of
a dilute iota canageenan as shear GEL
is increased to 1,000 RPM; the STRUCTURE
gel structure is recovered when -a BREAKDOWN
shear is removed. This thixotropic
property is especially useful for
8
a
soo
suspending insoluble particulates
in a flowable system such as an
antibiotis suspension.
STRUCTURE
Water gels formed with kappa
carrageenan are not thixotropic;
RECOVERY
once the gel is broken it will not 0
reset unless the gel is heated and 500 1000
cooled again. SHEAR RATE
 +MC
Marine Colloids'' Garrageenan:
How to Disperse and Solubilize

Generally, carrageenan should How To Mix

be dispersed in cold wate[ and
then heated above its solubili§
temperature to obtain optimum
functionality. The solubility tem-
perature will depend on the level
of potassium and calcium ions
associated with the carrageenan
or the amount of salt present in
the water. Both kappa and iota
r :arrageenans typically require
'§neating to 170-175"F for com-
plete solubility.

For easy dispersion and to

avoid lumping, use any of the
following recommendations:
. Premix the carrageenan with a
dispersant, such as sugar. Use DO aa¿ the stabitizer slowly to DON'T Ailow to lump by trying to
rapidly agitated water. dissolve the stabilizer too fast,
a minimum of 3 parts by weight
of the sugar before dispersing
into cold water. The carrageenan
can also be blended with the dry
ingredients in the formulation to . MAINTAIN vigorous agitation
avoid lumping, OR with a high speed mixer.
. Disperse carrageenan in liquid . THEN heat carrageenan to
suga[ salt or glycerine if pre- 180"F to solubilize, unless the
sent in the formulation. These carrageenan is designated to
:¡- ingredients retard the hydration
of carrageenan which make it
be cold soluble or swelling.
Cold soluble carrageenans may
easier to disperse and dissolve.
be dispersed into cold water by
. THEN add the carrageenan adding the carrageenan powder
product slowly at the vortex of slowly with agitation. Premixing
rapidly agitating fluid. with sugar is recommended.

7
#MC
FMC Corporation
Pharmaceutical Division

USA:
1735 Market Street
Philadelphia, PA 19103
Phone Numbers:
Techn ical Assistance : 21 5-299 -6534
Fax: 215-299-6821
CustomerService: 800-362-3773
Fax: 302-453-6518
Europe:
Avenue Louise 480-Bg
'1050 Brussels Belgium
Phone: 32-2-645-9578
Fax, 32-2-640-0564
Patent Position tf
FMC Corporation does not warrant against ¡nfringement of
patents of third parties by reason of any uses made of the product
¡n combinat¡on with any other material or in the operat¡on of any
process; purchasers assume all risks of patent infringement by rea-
son of any such use, comb¡nat¡on, or operation. FMC Corporation
is owner or licensee of several United States patents related to
products of its Pharmaceutical Division. The FMC products
described herein may be covered by one or more United States
patents, by pending patent applications, or by patents or applica-
tions in other countries. For further informat¡on call (800) 362-3773.

Warranty
Because of the numerous factors affecting results, FMC ingre-
dients are sold on the understanding that purchasers will make
their own test to determine their suitability of these products for
their particular purpose. The several uses suggested by FMC
Corporation are presented only to assist our customers ¡n
exploring possible applications. All information and data pre-
sented are believed to be accurate and reliable, but are
presented w¡thout the assumption of any liability by
FMC Corporation.

TechnicalSeruice
The information contained ¡n th¡s bul-
letin is intended to be general in
nature. Techniques and data pertain-
ing to specific uses for FMC ingredi-
ents and new developments will be
published periodically ¡n the form
of supplemental application bul-
let¡ns. Our technical staff is
ready to offer assistance ¡n the
use of Marine Colloids
Carrageenan products.
#tC, Gelcarin, Marine
Colloids, SeaSpen, and
V¡scar¡n FMC trademarks.
@1993 FMC Corporation. All
r¡ghts reserved.

V'
CARR
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