J Soc.½osm,t. Gh•m.

22 43-60 (1971) ¸ 1971Society

of Cosmetic
Chemists
of GreatBritain

Guar gum and its applications

R. J. CHUDZIKOWSKI*

Presented
at theSymposiumon "Gumsand Thickeners",
organisedby the Society of CosmeticChemistsof
Great Britain, at Oxford, on 15th October1969.

Synopsis--The SOURCES and industrial PROCESSING of GUAR GUM are reviewed. An

account is given of its CHEMICAL reactionsand the changesin PHYSICAL preparations
which accompanythem. Somepitfalls in the utilization of guar gumsresulting mainly from
their high rate of ABSORPTION of water are discussedtogether with TECHNIQUES for
avoiding such problems.

INTRODUCTION

There seemsto be a semanticambiguity about the very term "gums".

Accordingto the originaldefinitionwhichmeant broadly"plant exudates",
the term encompassed alsovariousresins,rubber latex, etc. The present
definitionof "gums"is somewhatnarrowerandmorespecific.It comprises
all materialsthat can be dissolvedor dispersedin water to form more or
lessviscouscolloidalsolutionsor dispersions.
Whicheverdefinitionwe accept,it appearsthat "gums"havebeenused
in industryand commercesincethe beginningof civilization.Accordingto
the Bible, myrrh and frankincense accompanied gold at the Manger.Gums
were alsousedby the ancientEgyptians for embalmingthe dead and for
glueing together strips of clothing for binding mummies. In different
application again gum arabic was for them a convenient adhesive for
mineralpigmentsin paint formulations.Likewise,gumswereusedas food
andfor medicinalpurposes by manycivilizations,up to the presentday (1).
Until recently,however,the useof gumswasrestrictedto a relativelylow
*Rimreel Manufacturing Company Ltd., Ashford, Kent.
43
44 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

numberof items,randomlyharvested,and of limited quality and property

range.Only the last decade,or so,has broughtabout revolutionarychanges.
Some gum bearing plants have begun to be cultivated on a commercial
scale.Many natural gums are now treated, and, by undergoingvarious
physicaland chemicalmodificationshave their quality improved,have the
rangeof their propertiesimmenselyincreased.Finally, the creationof new,
organicpolymershas yieldedthe whole classof new, syntheticgums.
Guar gum is one of the outstanding representativesof that new
generationof plant gums. Its sourceis an annual pod-bearing,drought-
resistantplant, called Guar, or cluster bean (Cyamopsistetragonolobusor
C. psoraloides), belongingto the family Leguminosae.
It has beengrownfor
severalthousandyears in India and Pakistan as a vegetable,and a forage
crop. It is interestingto learn that someGuar seedshave even been found
in the recently excavatedPharaoh Zoser'stomb in Sakkarah, nr. Cairo.
The guar plant is about 0.6 m high, and resemblessoyabeanplant in
general appearance,and in its characteristicarrangementof pods along
the vertical stem.The podsare 5-12.5 cmlongandcontainonthe average5-6
round, light brown seeds.
The plant was brought to the U.S.A. at the beginningof this century
and grown there in experimental stations in the semi-arid south west
{South Texas and Arizona). It has been found fairly easy to cultivate,
undemandingand well adapted to mechanicalplanting and harvesting.It
was, however, only about 1940 that guar became a commercialreality.
The war causedshortagesin supply of locust bean gum, to which guar
gum is closely related, and the American paper industry began to look
for possiblereplacements.Guar gum was found to be a suitableone and,
as a result, new plantationsof guar bean began to springup and in 1942
General Mills Inc. introduced - experimentally - the first guar gum to
Americanindustry (2).
The successof that introduction and an increasing demand have
naturally attracted followersand - amongothers- in 1953anothermajor
manufacturer(Stein,Hall & Co. Inc.) entered the market (3). Now, guar
gum is big business in the U.S.A. as may be seenfrom Table I comparing
productionof moreimportantwater solublegumsin 1963(4).
The more important brands in the U.S.A. are: Guartec,Arearexand
"SuperCol"(GeneralMills Inc.), "Jaguar" series(Stein,Hall & Co. Inc.),
"Starguar" (Morningstar- Paisley Inc.), Penguar(S. B. Penick & Co.),
T.I.C. Guar Gum {TragacanthImporting Corp.), Guargum(MeerCorpora-
 GUAR GUM AND ITS APPLICATIONS 45

Table I

Production Market value

t $ x 106

Gum Arabic 21.0 5.2

Gum karaya 10.0 5.1
Locust bean gum 8.0 2.7
Psyllium seed 3.0 1.0
Gum tragacanth 1.6 7.2
Guar gum 26.0 7.8

tion) and severalothers.

In Europe- to the writer'sknowledge- there are the followingbrands
available: "Guaranate" series made by Socidtd Fran9aise des Colloides
and American brands, manufactured by their subsidiaries,i.e. "Guartec
and Supercol"of GeneralMills Inc. in the U.K. (Messrs.TragasolProducts
Ltd., Hooton, Wirral, Cheshire)and "Meypro-Guar" of Stein, Hall & Co.
Inc., in Switzerland(MeyhallChemicalAG - Kreuzlingen,Switzerland.)
The general outline of the manufacturing procedure is as follows:
After having been removedfrom their pods the spherical,brownishseeds,
the size of a small pea, are passedrapidly through a flame and thus
loosened;hard seed hulls are then removed in a scouringor "pearling"
operation.The decorticated,vitreouslookingendospermis separatedfrom
its germ in a milling operationand the resulting"splits" are then ground
to the requiredmeshsize.
This is so calledcommercial"guar flour" and it may be usedwithout
further processing,except for heat treatment to inactivate enzymes
containedin occasionalfragmentsof a seedgerm.Variousgradesare avail-
able dependingon colour(whiteto greyish),meshsize,viscositypotential,
and rate of hydration.

THE CHEMISTRY OF GUAR GUM

The chemicalanalysisof guar flour showsthe following typical com-

position:
To
Nitrogen 0.67 corresponding
with 3.5 - 4.0 proteins
Phosphorus 0.06
Ash 1.07
46 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

Water sol. polysaccharide 86.50

Water insoluble fraction 7.75
Alcohol sol. fraction
{from24 h Soxhletextraction) 1.50
The solventextractedfractionconsistsmainlyof a fatty matterwhile
the waterinsoluble
fractioncontainsproteinsandcrudefibres.Thematerial
alsocontainsbetween10-13% moisture.
The watersolublepolysaccharide fractionis composed - apartfrom
somepentosans,andtracesof proteinaceousmatter- entirelyof approxi-
mately36.6%D-galactoseanhydride,and63.1ø/0 mannose anhydride.The
absenceof uronicaciddifferentiates
this polysaccharide
fromthe great
majorityof plant gumsandmucilages.
The composition
thusfound,identifies
it asa polymerof D-galactose
andD-mannose,
i.e. a galactomannan
(5).
Thechemical
structure
ofthisgalactomannan
hasbeenthesubject
of a
great deal of study (6-8). Various methodshave been used. Chemical:
acidhydrolysiswith subsequentidentification
of the components by their
osazones,or by paperchromatography, methylation,periodateoxidation,
and formationof tolyl sulphonyl-derivatives; biological:
by meansof
selective
enzymehydrolysis; physical:
by studyofopticalrotation,infra-red
spectrography,stress-strain
measurement, and X-ray analysisof filmsof
pure galactomannanand its acetate, etc.
Theconclusions drawnfromthosevarious studiesbymanyindependent
investigatorsare in substantialagreement. The guar gum moleculeis a
linear,or highlyanisodimensional carbohydrate polymerwith a molecular
weightonthe orderof 220000 {9).It is composed basicallyof a straight
chainof D-mannose units,linkedtogether by • {1--•4)glycosidelinkages,
andhavingonapproximately everyalternatemannose a singleD-galactose
unit,joinedto it by an a (1-•6) glycoside
linkage{Fig. 1).
This polysaccharide is representativeof a groupof galactomannan
gums,obtainable frommanyof theLeguminosae plants'seeds,wherethey
serveas foodreserve.Examples:alfalfa,clover,fenugreekand, the best
known,locustbean{carob.) Although closelyrelatedchemically,thegums
differ somewhatin their structure.For instance,the chiefdifferencebetween
guar,and locustbeangumsis that the formeris richerin D-galactose
groups(1:2) thanthelatter(1:4). Thisaccounts
amongothersforguargum
beingmorereadilysolublein water,especially
cold.Also,as1-•6glycosidic
linksarefairlyeasilyhydrolysedby acids,guargumbeingricherin galac-
rosehashigheracidstabilitythanrelativelypoorer(1:4) - i.e.moreeasily
 GUAR GUM AND ITS APPLICATIONS 47

•HzOH C.H•OH

H OH[

Figure 1.

"stripped" locust bean gum, which fairly rapidly losesits viscosityin

acidicmedia.There existsa galactomannanwhichis evenricherin galactose
than guargum,andhascorrespondingly differentproperties.It is obtained
from seedsof Fenugreekplant (TrigonellaFoenumGraecum)(10).
Further processingof crudeguarflour consistsof preparinga mucilage,
which after autoclavingto destroypossibleenzymesis freed from the
insolublepart by centrifugation(supercentrifuge,
40 000 rev min-1). From
suchclarifiedmucilage,the galactomannanis then precipitatedin various
fractionsby the gradualadditionof ethyl alcohol.
Those fractions are then filtered, dried, milled and blended to a desired
gradeto meet a wide variety of industrialprocessand productneeds.The
"natural" galactomannangrades,differ mainly in their purity, particle
size,dispersionproperties,rate of hydrationand viscositypotential.They
are whitish powders,with bland taste, edible, but with relatively little
nutritionalvalue. They meet the requirementsof the U.S. Food and Drug
Administration(G.R.A.S.)and on accountof that and their otherbeneficial
propertiesare usedextensivelyin the AmericanFood Industry.
Guar gum may be identifiedamongothersby its perfect solubilityin
cold water resultingin a viscoussol which gives a gel-like complex with
23
Fehling,
andborax
solutions,
andexhibits
specific
rotation
{a)• q-60in
0.6N NaOH.
Further possibleprocessing
of guar gum dependson chemicalmodifica-
tions.Varioustreatmentsareinstrumentalin developingfunctionalcharac-
teristicsthat make this gum versatileand usefulin a variety of industrial
48 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

applications.
The simplest
changeisby varyingthe degreeof polymerization
by controlledhydrolysiswhich is the meansof controllingviscosity.
Furthermore, the abundanceof hydroxyl groupsin the galactomannan
moleculelendsitself - like in cellulose- to a variety of chemicalreactions.
They canbeeasilyesterified, resultingin a varietyofinteresting
compounds.
Guar triacetate - for instance- obtainedby reactingthe galactomannan
with aceticanhydridein pyridine,is insolublein water, and can be cast
into strong,flexiblefilms,with propertiescomparable with thoseof cellulose
acetate.
Alkoxylationwith ethyleneor propyleneoxidesis alsoeasilycarried
out producingthe corresponding ethers. Carboxyalkyland cyanoalkyl
ethersare anotherexampleof functional modifications,e.g. o-carboxy-
methyl derivative- preparedby reacting galactomannanwith chloro-
acetic acid - formsviscousaqueoussolutionsthat are stable to strongly
alkalinereagents(1).
There are a host of chemical processesinvolving galactomannans-
someof thempatented- designed to endowthenaturalgumswith a variety
of desiredproperties- includinganionicand cationic(galactomannans are
neutral and nonionicin character).
½omplexing reactionsareworthmentioningastheyleadto cross linking
of the moleculesresultingin a three dimensionalnetworkwhichmanifests
itselfin gelformation.Thesereactionsarenotpeculiarto galactomannans,
beingcharacteristicof linear moleculeshaving an abundanceof adjacent
hydroxylgroupsin cis positions.The complexing reactionof polyvinyl
alcoholwith borax is an example.
Among others, copper salts form complexeswith galactomannans.
Fehling'ssolution,for instance,doesnot reducethosepolysaccharides even
on prolongedboiling.An insoluble,gel-like complexis formedinstead.
Salts of Ca, A1, and Cr have the same gel forming capacity at certain
pH levels.
Perhapsthe mostcharacteristic, andimportant,is the reactioninvolving
borateions. Like in the caseof PVA borate ion co-ordinateswith 4 hy-
droxyl groupsof two chain molecules,resultingin a di-diol complex.
This reactionhas traditionallybeen represented by Fig. 2 (3). It is now
thought,however,that hydrogenbondingprovidesa better explanation
for the forcesinvolvedin tiffs cross-linkingaction. In accordance with tiffs,
the followingis suggestedas a more likely representationof the guar
cross-linked molecule{Fig. $). This reactionwill proceed evenat extremely
low concentration of both galactomannan and borateions. The addition
 GUAR GUM AND ITS APPLICATIONS 49

Guar Binate
ion Guar Cross-
linked Guar

• • pH>•8-0
, '• '
H•C•OH HO•C•H pH•7.0 • •0 / •0
• Hydrated • •
Guarsol Guargel
(pH•7.0 ) (pH•8-0)

of as little as 0.05% borax (basedon solutionweight) at alkalinepH is

sufficientto fully gel a 0.25% galactomannansolution.
The gelscan alsobe formedby adding boric acid, and then alkalis to
givean alkalinepH - the optimumbeingbetween7.5-10.5.Thesegelsmay

(Hydrogenbondingshownby ..,)

Figure 3. Hydrogen bonded cross-linkedguar

havesomewhatdifferentpropertiesdependingon the gum gradeand con-

centrationused.In general,they are rubbery masseswhich exhibit cold
flow properties,coalesce
readily after beingsubjectedto shear,and show
no syneresis.They remain essentiallystable for long periodsof time at
alkalinepH, butcanbe,however, easilyreconvertedto thesolformby simply
addingenoughacid to adjustthe pH to lessthan pH7. This reactionis
completelyreversible,and the sol-gd-solsequence may be repeatedas
often as desired.
Anotherinterestingphenomenon
occurswhen the gum, in powder
form, is introduced into an alkaline borated solution. Under these condi-
tions,the gumwill disperse easily,but will neitherhydrate,nor develop
viscosity.This inhibitingactioncanbe overcome by simplyloweringthe
50 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

pH to 7, or below.The gum will then hydrate and developviscosityin the

usual manner.
Thisphenomenon may be utilisedasa way of dispersing guarcontaining
products,that tend to lump, especiallywith not very efficientequipment.
The powderis initially slurfled into an alkalineboratedsolution,whichis
then neutralizedto promotehydration (3).
An interestinguseof someof the propertiesof boratedgalactomannans
is madein a patent (11) for hair straighteningcomposition with sulphites.
The rationaleof this applicationis that suchboratedgumshavea very
low initial rate of hydrationin acidicmediathus enablingthe product- in
powderform - to be easilydispersed in water. The resultingsolutionwets
the hair easilyand convenientlyand after a while developshigh viscosity
(of the orderof $ 500 cP) which,aidedby combing,managesto keepin
the desiredshapethe sulphitesoftenedhair.
Guar gum gradesare alsoavailablepossessing gellingpropertiesbased
on a principle entirely different from that of the borax/galactomannan
system.They eitherutilize an oxidisingcatalystto activatethe complexing
mechanismin a two-stepprocedure,or are "one step" and entirely self
complexingtypes. The latter form solson dispersion,and then develop
into firm, water-tight gels(2, 3).

PHYSICAL PROPERTIES OF GUAR SOLS

Galactomannansare insolublein hydrocarbons,fats, alcohols,esters,

ketones- in fact with a very few exceptions(e.g. formamide)in organic
solventsin general. The only important solvent for galactomannans is
water, for which - on accountof the structureof their molecule- they
have tremendousaffinity - for water in its liquid state - that is. Wate• in
the vapour phasemerely changesthe moistureequilibrium. There is no
hygroscopicity.
When dispersedin water, hot or cold,galactomannans hydrate rapidly
to form colloidalsolutionsof unusuallyhigh viscositycharacteristics even
at very low concentrations.
Table II indicating concentrationsof various hydrocolloidsrequired
to producean apparent viscosityof 800 cP at 20øCshowsthat a brand
of guar gum is - in that respect- a runner-upto Carbopol.
What is evenmoreremarkable,guargum attainsnearly its full viscosity
potentialin coldwater, whileothergums(includingthe relatedlocustbean
galactomannan) requiresometimesprolonged"cooking".
 GUAR GUM AND ITS APPLICATIONS 51

Table II.

Gum •o (w/v) for 800 cP

Tragacanth USP 2.75
Sodium alginate (med. visc.) 1.15
Jaguar brand of guar gum 0.2-0.3 (2SøC)
Methyl cellulose (1 $00 cP) 1.7
Methyl cellulose (4 000 cP) 1.35
Sodium carboxymethyl cellulose (reed. visc.) 1.9
Sodium carboxymethyl cellulose (high visc.) 0.7
Carbopol934 0.17

5O

4O
,•'• Hydrofed 25øC
• Hydrofed 85øC
30 Measurernenfs o1' 25øC
sols

20

10

2
.--
.=-
.--

_J

Figure4. Viscositypotentialof some{commonwater solublegums.

Coldprocessing, however,affectsthe rate of hydrationwhichis greatly

acceleratedby increasing the temperature.For example,with a particular
gradea degreeof full viscositydevelopment requiring5 h at R.T. is accom-
plishedin about10min at the optimaltemperatureof 80øC.
Viscosityis often taken as a commondenominatorand performance
indexin comparingdifferentgradesof guargum.Thereare five variables
that determinethe pattern of viscositydevelopmentand the behaviour
of a given guar gum gradein an aqueoussystem.viz: concentration,
dispersion,temperature,pH, and presenceof foreignsubstances (113).
Understanding their implicationsis of greathelpin formulatingwith guar
gum or processing it.
52 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

As can be seenfrom Fig. 5, the incrementalincreasesin the gum

concentration
resultin almostexponentialincreasesin viscosityup to a
concentration
of about1.5%. At concentrationshigherthan about3%
(dependingon a grade),guargumsformjelly4ikepasteswhich,however,
are not true structural gels.

I00,000

1,000

.[
I00

Concen'l'rafion, %

Figure •. Variation of viscositywith concentration.

For comparingviscosities of guar gumsa "standard"concentrationof

1.0% (w/v) is usedas a rule. Quantitativemeasurementsare bestcarried
outwitha torsion viscometer(e.g.
Brook fieldRVF,Syncro-Lectric typewith
a No.3 spindleat 20revmin-•), although forqualitativecomparisonsother
methods like,forinstance,
"Ford"cup,maybeemployed. It is essential
to
statethe methodof measurement whilequotingviscosity.
Guargumsolutionviscosities - in common with mostotherhydro-
colloids
- arestrongly dependent onshearrate,andcanbemoreproperly
describedas"apparent viscosities".In short,guargumsolsarethixotropic
having,however,a relativelylow yieldvalue.
 GUAR GUM AND ITS APPLICATIONS 53

The prerequisitefor the sol formation is an efficientdispersionof the

gum particlesin water. As in most other hydrocolloids,badly dispersed
lumps tend to become"encapsulated"with a hydrated layer preventing
further water penetration.The tremendousaffinity for water possessed by
guar gum is utilized industrially. It is usedas a "water sealer"in oil well
drilling or in protectingexplosivesfrom getting wet. In the latter case,
water leaking through a chancepuncturein a cartridgeis taken up by
the gumto form a thick solwhichcompletelyblocksthe punctureto prevent
further water entry.
To effectsolution,the gum must be thoroughlydispersed by sprinkling
it ontowater, ascoldaspracticable,with vigorousstirring.On an industrial
scalesifting througha screenor grid from the edgeof a shakertray or the
use of an eductor are recommended.
Other expedientsto promotesolutionincludepremixingthe gum with
other powderedsubstances,e.g. sugar, or dispersingit in pre-retardants
(e.g.alcohol,glycerine,glycols,acetone,etc.) beforeits additionto water.
Finally, the gum may be dissolvedmore readily in certain salt solutions
than in water, e.g. in solutionsof sodiumof calciumchloride.
The effect of temperatureon the rate of hydration and the time to
attain the full viscositypotentialhas already been discussed.As all solu-
tions,the guar solschangetheir viscositywith temperature(Fig. 6).

60
On

5O

40

S01sprepared
and ! '•e•ring
3O
fullyhydrated

20
-
25*
Cbefore
temperature
chencje
I
I ß

_ I
I
I

-•o c• Io 2o 3o 40 50 o 7o Bo 9o

Viscositymeasurement
temperature, øc

Figure 6. Measurementof temperature effect on fully hydrated sol.

54 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

Compared,however,with many other gums' solutionsthey exhibit

excellentretention of viscosityat high temperatures.They can also be
maintainedat high temperaturesfor long periodsof time with practically
no effecton their ultimate viscositymeasuredat roomtemperature.
One of the characteristicsof guar gum solutionsis their stability over
virtually the entire usablepH range. This property is attributed to the
nonioniccharacter of galactomannans.With the exceptionof values over
10.5 the viscositypotential is not greatly affectedby pH. Its peak is
betweenpH valuesof 7-9, and the practicalstabilityrangefrompH 4-10.5.
In the presenceof strongalkalisthe viscosityfalls fairly sharply,although
there is a suggestionthat this may be due to destructionof the proteins
which form a complexwith the carbohydratepolymer (1).
It is possibleto preparefairly high viscosityguar gum solsat high pH
valuesby first effectingtheir hydration at a neutral pH for 30-60 min
and then adjustingthe pH with alkalis.

3.0

c• 2.?

u 2.4

o
u

2 $ 4 'õ 6 7 8 9 I0 I1

pH

Figure 7. Viscosity of a guar gum as a function of pH value.

Moreaffectedby the pH is the rate of hydrationwhichagainis highest

betweenthe pH valuesof 6-9 and the lowestat approximately3.5.
This knowledgeis usefulin preparingsolutionsof "difficult" formula-
tionswhichcanbe easilydispersed in coldwater at pH 3.5, and the solution
obtainedspeedily,with the desiredviscosity"released"by adjustingthe
pH to 8, and - if necessary- heatingthe solutionto 80øC.
Anotherconsequence of the nonioniccharacterof guar gumsis the fact
that their solutionsare uncommonlyresistantto electrolytes.They are
completelyunaffectedby hard water, and will toleratelarge quantitiesof
 GUAR GUM AND ITS APPLICATIONS 55

electrolytesthat will "salt out" most of the other gums. It must be borne
in mind, however,that there is no singlerule as there exist severalmanners
of interactionbetweenthe gum and the dissolvedsubstance.Complexing
with boron,aluminium,copper,chromiumand other salts have already
beendiscussed. Althoughnonionicin nature,the gumparticlesmay acquire
an ionic chargeby absorbingother ionsfrom solution.This in turn may
affecttheir propertiese.g. rate of hydration and ultimate viscosity.It has
alreadybeenmentionedthat sodiumand calciumchloridesolutionspeed
up guar gum hydration without affectingviscosity.Sodiumbenzoate,
however,not only accelerates the rate of hydration,but alsoconsiderably
increasesviscosityof the resultingsolution. On the other hand, salts like
sodium sulphateinhibit hydration of the gum, depressviscosity,and in
large quantitiesmay causeits precipitation.
The explanationof the latter phenomenonseemsto lie in the fact that
the gum,andthe dissolved substance,arecompetingfor water.The stronger
the affinityof the saltfor water- asin saltsforminghydrates- the stronger
the inhibiting effect. This also explainsincompatibilityof the gum with
water misciblesolventslike alcohol,acetoneor glycerine,that rapidly
deprivethe gum of water causingthe former'sprecipitation.The under-
standingof thesefacts also suppliesa rationalefor empiricallyevolved
methodsof dispersingthe gum using dry mixing techniqueswith, say,
sugar, or wetting out with alcohol,acetoneor glycerine.Apart from
mechanicallyseparatingthe particles, when in contact with water, the
inhibitors preferentiallytake it up, slowinghydration of the gum and
allowingit to becomethoroughlywetted,and dispersed. This effectis then
negatedby dilutionuponwhichthe gum'shydrationproceedsnormally
(13).
Another important property of guar gum explaininga great deal of
its behaviouris its hydrogenbondingactivity. This is generallyattributed
to the presenceand behaviourof numeroushydroxyl groups.The basic
straight chain structureof the galactomannanmolecule,along with the
regularityof the singlememberedgalactosebranches,resultin a product
that exhibitsan unusualeffecton otherhydratedcolloidalsystemsthrough
hydrogenbonding.Because guargumwill hydrogenbondto both- hydra-
ted mineral and organic surfaces,there are few systemswhich will be
unaffectedby its action.The addition of even extremelysmall quantities
of guargumcanmarkedlyalter the electrokinetic propertiesof the system
treated. •
As a broadrule, it can be saidthat guar gum in appreciablequantities
56 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

will act as dispersantfor organicsystems,especiallythosewith functional

hydroxyl groups,and as a coagulantfor inorganicones,in particular for
thosewith "clay" characteristics. This property- togetherwith its relative-
ly low yield value - meansthat cautionmust be exercisedwhen usingguar
gum solutionfor pigmentsuspension. Thereare, however,availableanionic
gradesof guar, well suitedfor that purpose{15).
In extremelysmallquantitiesguar gum tends to act as a flocculantfor
both inorganic and organic systems,and this property has beenutilized
in someindustries(e.g.mining)whereguargumis employedasa flocculant,
settlingagent, and filtration aid.
The hydrogenbondingphenomenaexplain,amongothers,the excellent
compatibilityof guar gum solutionswith other hydrocolloids,like agar,
alginates,gumarabic,British gum,locustbeangum, carrageenan, cellulose
derivatives,gums karaya and tragacanth,pectin, starches,gelatin, and
other water solubleproteins.
It is not only a questionof compatibility- there is evidencethat in
many instancesthere is a distinctly synergisticaction. Co-solutionsof
severalof thosehydrocolloids(e.g.starches)with guar, exhibitmuchhigher
viscosities,and stabilities than either ingredient alone. Combination of
guar with agar or carrageenpromotesformationof a structuralgel.
Hydrogen bonding also explainswhy guar gum is such an excellent
beateradditivein the processing of paperpulp.A smallamountof guargum
solutionaddedbreaksup agglomerated cellulosepulp fibres and disperses
them uniformly in the pulp slurry.
Solutionsof most guar gum gradescan be dried to form flexible films
which resistmost organicsolvents,but which readily redissolvein water
or aqueoussolutions.Textile sizings,for instance,use such temporary
films for protectionof fibresduring the weavingprocess.Somederivatives
producewater resistantfilms, guar triacetate being the most prominent
example.
Guar solutionshave slightly acidicreaction(pH 5.5-6.1), and if sterile
are perfectly stablein storage.They are, however,as are the other natural
hydrocolloids,subjectto microbiologicaldeterioration,which resultsin a
lossof viscosityas the first tangiblemanifestationand in a loweringof the
pH value.
If unpreserved,guar gum solutionshouldbe usedwithin 24 h. Should
its usebe delayedpreservativesmust be employed.
In the foodindustry sodiumbenzoateand sorbicand benzoicacidsare
most commonlyusedfor that purpose.Other industriesmay successfully
 GUAR GUM AND ITS APPLICATIONS 57

use formaldehyde, substituted phenols, lauryl sarcosinate,and phenyl

ruercurie acetate.

USES OF GUAR GUM

Table I shows that guar gum is used in massive proportions in

industry.Indeed,due to its uniquecombinationof propertiesit hasproved
to be a valuableaid in a multitude of industrial applications,asdiverseas
alreadymentioned,mining and food, paper and textile.
In the paperindustryit is further used- apart from as a dispersantand
suspendingagent - also for sizingand coating.In the textile industryit
alsoservesas a pigmentdispersingaid, and aboveall as a thickeningagent
for colourprinting pastesfor whichuseit is unsurpassed.
The ceramicindustry also usessizeablequantities of guar gum as a
binder, thickenerand fixing agentfor enamels,porcelain,etc.
In the food industry it is widely usedin salad dressings,ice creams,
lollipopsand sherbets,in bakery productsand confections,meats and
sausages, cheesespreads,and many other applications.
In the pharmaceuticalindustry,dry guar gum is usedas a disintegrant
andin solutionas a binder in compressed tablets manufacture(14). It is
alsousedin liquid dieteticpreparationsasa low caloriethickenerto improve
their mouth feel, body and pour characteristics.On accountof its hydro-
philic propertyand the ability to form bulky, jelly-like masses,it is used
in appetitedepressants as a bulking agentin laxatives, and in gastriculcer
treatment.
It has also suchmiscellaneous usesas a thickener for battery electro-
lytes,printinginks, and as an ingredientin paints,adhesivesand polishes.

GUAR GUM IN THE COSMETIC INDUSTRY

It would appear that a raw material endowedwith sucha variety of

usefulproperties,a formidableviscositybuilderwith an unusual,excellent
cold solubility, a solventresistantfilm former, protectivecolloid,with a
widerangeof compatibilities, untroubledby pH changesand the presence
of salts, stable,nontoxic,safeand cheap,wouldbe immediatelyaccepted
by the cosmeticindustry. This is, however,not the case.The industry
tendsto be shy of materialsnot createdspecificallyfor its use, and slowto
translate to its benefit the experienceof other industries.
58 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

This may alsobe true because,althoughmost guar gum manufacturers

recommendits use in cosmeticsin general, concreteinformation is scarce
as are patentsand availableformulations.
Guar gum is usedon a sizeablescalein the manufactureof tooth paste
to whichit impartsslip, so that the pastecan be extrudedfrom the tube
without applyingexcessivepressure.Similarly it is usedin someshaving
creams,whereit stabilizesthe system,impartsslip in extrusionand on the
skin,while shaving,and improvesfacial skin after feel (16).
It lendsitself perfectlyto be usedin emulsifiedsystems:creamsand
lotions- as a protectivecolloid,increasingemulsionstability, preventing
syneresis, water loss,and phaseseparation.
It alsopreventsdegradationof emulsiondue to freeze-thawconditions
whichcausethe water phaseto condenseout of the system.For instance,
used in an ordinary TriethanolamineStearate type lotion it gives it a
stableviscosity,improvedspreadabilityand impartsto it an agreeableafter
feel associated with bestquinceseedformulatedlotions.
In aerosolsdispensing aqueousliquid preparationsas a sprayor mist
it is said to reducemigrationof "fog" (16).
Guar gum solutionsare compatibleand mix well with mostdetergent
systems(shampoos, cleansers,
etc.) givingthem "body" and abolishingor
minimizingtheir harsh after feel. Excellent hair colourantswere also
preparedusingguargumsolutionas thickener.
Although not an emulsifier- owing to its ready compatibility-guar
gum solutionscan be usedin conjunctionwith other gumsendowedwith
emulsifyingproperties.An excellent,stable emulsionwas, for instance,
preparedin the cold adding30-40% mineraloil into a 10% solutionof
polyvinylalcohol(80% hydrolysislow molecularweight) under vigorous
stirringand then adding3% guargum solutionand mixingto uniformity.
When mineral oil was replacedby ShellsolT the resultingemulsionwas
film forming.
Self-emulsifying
gradesof guar gum are also available.Dry facemask
mixeswereeasilyand convenientlypreparedusingguargum plus additives
which in suchsystemmay even be heat- and moisture-sensitive. In use,
the mixesneedonly to be stirredinto a sufficiencyof cold or tepid water
(half a cupful)to producea rich creamypaste.
It is hoped that these few exampleswill stimulate the interest of
cosmeticformulators,and the content of this paper will help them in
solving,successfully,the ensuingproblems.
(Received:
18thAugust1969)
 GUAR GUM AND ITS APPLICATIONS 59

REFERENCES

(1) Smith, F. and Montgomery, R. Chemistryof plant gumsand mucilages(1959). (Reinhold

Publishing Corp., New York).
(2) "Guartec" (1963). (GeneralMills Inc.).
(3) "Jaguar", (1962). (Stein, Hall & Co. Inc.).
(4) Kirk and Othmer. "Gums, Natural" by M. Gliksman. Encyclopaediaof Chemical
Technology,10 (1966).
(5) I-Ieyne, Eileen and Whistler, Roy L. J. Am. Chem. Soc.70 2249 {1948).
(6) Ahmed, Z. F. and Whistler, R. L. J. Am. Chem.Soc.?9.2524 {1950).
(7) Swanson,J. W. J. Am. Chem. Soc. 71 1510 {1945).
(8) Rafique, C. M. and Smith, F. J. J. Am. Chem.Soc. ?9.,4684 (1950).
{9) Moer, G. Jr. and Meer, W. A. Am. Perturner 77 49 {4, 1962).
(10) Natural Plant Hydrocolloids.Roy L. Whistler. "Guar Gum, Locust Bean Gum and
Others" {Advances in ChemistrySeriet11. Am. Chem.Soc.){1954)
(11) Brit. Pat 1 076 420.
(12) Gerding, P. W. and Sperandio, G. J. J. Am. Pharm. Assoc.Pract. Ed. t5 856 {1954)
(13) Carlson, W. A., Ziegenfuss,E. M. and Overton, J. D. Compatability and manipulation
of guar gum. Food Technol.16 50 (10, 1962).
(14) Eherton, L. E. Platz, P. E. and Cosgrove,F. P. Drug Standards.9.8 No. 2, 42-47
(19SS).
(15) $chimmel Brief No. 401. (September, 1968).
(16) Bulletin 1 GF-5 Supercol Guar Gum - Cosmeticand Pharmaceutical Uses. (General
Mills Inc.).

DISCUSSION

MR. C. A. WATSON:In reply to the statement that guar is used in several leading
dentifrices in the U.S.A. I wish to state that we have not succeededin making satis-
factory toothpastesbecauseof its incompatibility with glycerine, neither have we
found the Jaguar products fully satisfactory. I am not aware of any major U.S.A.
toothpaste brand which relies on guar gum thickener.
THE LECTURER:I do not know which companies are concerned as I have that
information from the guar gum manufacturers' handout. They just state categorically
that a few leading American companies use guar gum as a hydrocolloid in their
toothpastes, and that has struck me as being feasible.
You probably know better but, judging from its properties, guar gum would
seem very useful becauseof its relatively high yield value, quick shear recovery and
generally good compatibility. I have not tried it in toothpaste systems. However, I
have tried guar gum in various emulsifiedsystems- creams and the like - and in my
experienceit has proved quite compatible with all polyols used in cosmeticsup to a
level of approx. 5%.
MR. D. N. MXDDOX:Natural gums such as tragacanth are often highly contamina-
ted with bacteria and as a result products containing them are difficult to preserve.
Is guar gum normally contaminated and, if so, can you give someidea of the bacterial
count?

THE LECTURER:It should not be contaminated in this way, because one of the
processeswhich the natural guar gum undergoesis autoclaving. This expedient is
directed not so much against the bacteria, as against the enzymes which could have
60 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

crept into the flour from the seeds- or rather their germs.The germscontain enzymes
which tend to depolymerise the galactomannan; to get rid of them, the standard
procedureis to autoclave the bulk, and that - at the same time - probably takes care
of the bacteria as well.

I wish to emphasisethat guar gum is widely used in the food industry where the
microbiologicalconsiderationsare certainly important. It is easy to preserve, being
compatible with sodium benzoate, which incidentally has an interesting property of
increasing its viscosity, and with benzoic and sorbic acids, the preservatives most
frequently used in the food industry.
MR. G. A. GREINER:Could you clarify that the "viscosity potential" figures in
pages 50 and 51 are for pure guar gum or are there additives, such as borax in the
product cited?
T•F. LECTURER:This concernsnatural guar gum. The order of viscosities averages
5 000 cP, for a 1% solution.
DR. N. A. R. LERoux: Would you like to comment further about the synergistic
effect of guar gum with other hydrocolloids?
T}m LEcx'•mE•: I have no experienceof that.
MR. ID. M. •BUSF•ELD: It seemsto be widely assumedthat a lot of guar formulations
contain borax. I would like to discount this belief because,in fact, very few guar
formulations need to contain borax to achieve the viscosity potential.
In the literature it has been reported that perhaps the structure of guar gum is
not as simple as you put it in the paper, and one of the common beliefs is that the
structure consistsof short chains of D-galactose units randomly positionedalong the
D-mannose chain, rather than single D-galactose units positioned at regular intervals
on every other D-mannose molecule. This possibly may account for some of the
rheological effects in that if the chains are longer than one molecule units there will
be some entanglement of the branches in the solution. Coupled with the hydrogen
bonding effect this would give two reasonsfor viscosity,and may possibly account for
the pseudothixotropic effect. Would you care to comment?
T• LF_c,ut•.R: You are perfectly right. Both Smith et al (1), and Heyneetal (5)
comment on that. It must be realised that the formula quoted is an idealised one,
and has been arrived at by the way of quantitative analysis which gives about •6%
of galacloseand 63% of mannose;consequentlyit has been assumedthat they are in
the formula in the proportion of roughly 1:2. This has led to an idealised picture but
all investigators agree that this is not as simple as that. First of all, the proportions
notwithstanding, the distribution of side chains may vary according to the natural
process(•s
occurringin the forming of the galactomannan,and further changeswhich
may occur in processing.
Quite a few authors also postulate the ramification of the chains. The existenceof
short branched chains of galaclose rather than units on the mannose chain is said to
explain quite a few anomalies (1, 5).