J Soc.osm, t. Ghm.

22 43-60 (1971)

1971Society of Cosmetic Chemists of GreatBritain

Guar gum and its applications

R. J. CHUDZIKOWSKI*
Presented at theSymposium on "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 seems to be a semanticambiguity about the very term "gums". According to the originaldefinition whichmeant broadly"plant exudates", the term encompassed alsovariousresins,rubber latex, etc. The present definition of "gums"is somewhat narrower andmorespecific. It comprises all materialsthat can be dissolved or dispersed in water to form more or lessviscous colloidalsolutions or dispersions. Whicheverdefinitionwe accept,it appears that "gums"havebeenused in industryand commerce since the beginning of civilization.According to 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 mineralpigments in paint formulations. Likewise,gumswereusedas food andfor medicinal purposes by manycivilizations, up to the present day (1). Until recently, however, the useof gumswasrestricted to a relativelylow
*Rimreel Manufacturing Company Ltd., Ashford, Kent.
43

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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 undergoing various physicaland chemicalmodifications have their quality improved,have the rangeof their properties immensely increased. Finally, the creationof new, organicpolymers has yieldedthe whole classof new, syntheticgums.
Guar gum is one of the outstanding representativesof that new generationof plant gums. Its sourceis an annual pod-bearing,droughtresistantplant, called Guar, or cluster bean (Cyamopsis tetragonolobus or C. psoraloides), belonging to the family Leguminosae. It has beengrownfor severalthousandyears in India and Pakistan as a vegetable,and a forage crop. It is interestingto learn that someGuar seeds have even been found in the recently excavatedPharaoh Zoser'stomb in Sakkarah, nr. Cairo. The guar plant is about 0.6 m high, and resembles soyabean plant 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 causedshortages in supply of locust bean gum, to which guar gum is closely related, and the American paper industry began to look for possible replacements. 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 followers and - 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 production of moreimportantwater soluble gumsin 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 {Tragacanth Importing Corp.), Guargum(MeerCorpora-

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Table

Production
t

Market

value

$ x 106
5.2 5.1 2.7

Gum

Arabic

Gum karaya Locust bean gum Psyllium seed Gum tragacanth Guar gum

21.0 10.0

8.0 3.0 1.6

26.0

1.0
7.2 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 (MeyhallChemical AG - 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, vitreouslookingendosperm is separated from 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 contained in occasional fragmentsof a seedgerm.Variousgradesare available depending on colour(whiteto greyish),meshsize,viscosity potential, and rate of hydration.
THE CHEMISTRY OF GUAR GUM

The chemicalanalysisof guar flour showsthe following typical composition: To Nitrogen 0.67 corresponding with 3.5 - 4.0 proteins Phosphorus 0.06
Ash 1.07

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JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

Water sol. polysaccharide

Water insoluble fraction
Alcohol sol. fraction

86.50
7.75

{from24 h Soxhletextraction) 1.50 The solvent extracted fraction consists mainlyof a fatty matterwhile the waterinsoluble fractioncontains proteins andcrude fibres. Thematerial alsocontains between10-13% moisture.

The watersoluble polysaccharide fraction is composed - apartfrom some pentosans, andtraces of proteinaceous matter- entirely of approximately 36.6%D-galactose anhydride, and63.1/0 mannose anhydride. The absence of uronic aciddifferentiates this polysaccharide fromthe great
majorityof plant gumsandmucilages.

The composition thusfound, identifies it asa polymer of D-galactose

andD-mannose, i.e. a galactomannan (5).

Thechemical structure ofthisgalactomannan hasbeen thesubject of a

great deal of study (6-8). Various methodshave been used. Chemical:

acidhydrolysis with subsequent identification of the components by their osazones, or by paperchromatography, methylation, periodate oxidation, and formation of tolyl sulphonyl-derivatives; biological: by means of selective enzyme hydrolysis; physical: by study ofoptical rotation, infra-red spectrography, stress-strain measurement, and X-ray analysis of filmsof
pure galactomannanand its acetate, etc.

Theconclusions drawn fromthose various studies bymany independent investigators are in substantial agreement. The guar gum molecule is a linear,or highlyanisodimensional carbohydrate polymerwith a molecular weight onthe order of 220000 {9).It is composed basically of a straight chain of D-mannose units, linked together by {1--4)glycoside linkages, andhaving onapproximately every alternate mannose a single D-galactose unit,joined to it by an a (1-6) glycoside linkage {Fig. 1). This polysaccharide is representative of a groupof galactomannan gums, obtainable frommanyof theLeguminosae plants' seeds, where they serveas foodreserve. Examples: alfalfa,clover,fenugreek and, the best known, locust bean {carob.) Although closely related chemically, thegums
differ somewhat in their structure.For instance, the chiefdifference between

guar,and locust beangumsis that the formeris richerin D-galactose groups (1:2) thanthelatter(1:4). Thisaccounts among others forguar gum being more readily soluble in water,especially cold. Also, as1-6glycosidic linksarefairlyeasily hydrolysed by acids, guargumbeing richer in galacrose hashigher acid stability thanrelatively poorer (1:4) - i.e.more easily

GUAR

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HzOH

C.HOH

OH [

Figure 1.

"stripped" locust bean gum, which fairly rapidly losesits viscosityin acidicmedia.There existsa galactomannan whichis evenricherin galactose than guargum,andhascorrespondingly differentproperties. It is obtained from seeds of Fenugreek plant (Trigonella Foenum Graecum) (10). Further processing of crudeguarflour consists of preparinga mucilage, which after autoclavingto destroypossibleenzymesis freed from the insoluble part by centrifugation (supercentrifuge, 40 000 rev min-1). From suchclarifiedmucilage,the galactomannan is 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 industrialprocess and productneeds.The "natural" galactomannan grades,differ mainly in their purity, particle size,dispersion properties, rate of hydrationand viscosity potential.They are whitish powders,with bland taste, edible, but with relatively little nutritionalvalue. They meet the requirements of the U.S. Food and Drug Administration (G.R.A.S.)and on account of that and their otherbeneficial properties are usedextensively in the AmericanFood Industry. Guar gum may be identifiedamongothersby its perfect solubilityin cold water resultingin a viscous sol which gives a gel-like complex with
23

Fehling, and borax solutions, and exhibits specific rotation {a) q-60in
0.6N NaOH.

Further possible processing of guar gum depends on chemical modifications.Varioustreatmentsareinstrumental in developing functionalcharacteristics that make this gum versatileand usefulin a variety of industrial

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JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

applications. The simplest change isby varyingthe degree of polymerization by controlledhydrolysis which is the meansof controlling viscosity.
Furthermore, the abundanceof hydroxyl groupsin the galactomannan moleculelendsitself - like in cellulose - to a variety of chemicalreactions.

They canbeeasily esterified, resulting in a varietyofinteresting compounds. Guar triacetate - for instance- obtainedby reactingthe galactomannan with aceticanhydride in pyridine,is insoluble in water, and can be cast into strong, flexible films,with properties comparable with those of cellulose
acetate.

Alkoxylationwith ethyleneor propylene oxidesis alsoeasilycarried out producingthe corresponding ethers. Carboxyalkyland cyanoalkyl ethersare anotherexampleof functional modifications, e.g. o-carboxymethyl derivative- preparedby reacting galactomannan with chloroacetic acid - formsviscous aqueous solutions that are stable to strongly alkalinereagents(1). There are a host of chemical processes involving galactomannans some of thempatented - designed to endow thenaturalgums with a variety of desired properties - including anionic and cationic(galactomannans are neutral and nonionicin character). omplexing reactions areworthmentioning astheyleadto cross linking of the molecules resulting in a three dimensional networkwhichmanifests itselfin gelformation.Thesereactions arenotpeculiarto galactomannans, beingcharacteristic of linear molecules having an abundance of adjacent hydroxylgroups in cis positions. The complexing reaction of polyvinyl
alcoholwith borax is an example.

Among others, copper salts form complexes with galactomannans. Fehling's solution, for instance, does not reduce those polysaccharides even on prolonged boiling.An insoluble, gel-like complexis formedinstead. Salts of Ca, A1, and Cr have the same gel forming capacity at certain pH levels. Perhaps the mostcharacteristic, andimportant,is the reaction involving borateions. Like in the caseof PVA borate ion co-ordinates with 4 hydroxyl groupsof two chain molecules, resultingin a di-diol complex. This reactionhas traditionallybeen represented by Fig. 2 (3). It is now thought,however, that hydrogen bondingprovidesa better explanation for the forces involvedin tiffs cross-linking action. In accordance with tiffs, the followingis suggested as a more likely representation of the guar cross-linked molecule {Fig. $). This reaction will proceed evenat extremely low concentration of both galactomannan and borateions. The addition

GUAR

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49

Guar

Binate ion

Guar

Crosslinked
,

Guar

pH >8-0
'

'

HCOH
Hydrated
Guar sol (pH 7.0 )

HOCH

pH 7.0
Guar gel (pH8-0)

0 / 0

of as little as 0.05% borax (based on solution weight) at alkalinepH is

sufficient to fully gel a 0.25% galactomannan solution. The gelscan alsobe formedby adding boric acid, and then alkalis to

givean alkalinepH - the optimum beingbetween 7.5-10.5.These gels may

(Hydrogenbondingshown by ..,) Figure 3. Hydrogen bonded cross-linkedguar

havesomewhat differentproperties depending on the gum gradeand concentrationused.In general,they are rubbery masses which exhibit cold flow properties, coalesce readily after beingsubjected to shear,and show no syneresis. They remain essentially stable for long periodsof time at alkaline pH, butcan be,however, easily reconverted to thesolformby simply addingenough acid to adjustthe pH to lessthan pH7. This reactionis completely reversible, and the sol-gd-sol sequence may be repeatedas
often as desired.

Anotherinteresting phenomenon occurs when the gum, in powder

form, is introduced into an alkaline borated solution. Under these condi-

tions,the gumwill disperse easily,but will neither hydrate,nor develop viscosity. This inhibitingactioncanbe overcome by simplylowering the

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JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

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

usual manner.

Thisphenomenon may be utilisedasa way of dispersing guarcontaining products, that tend to lump, especially with not very efficient equipment. The powderis initially slur fled into an alkalineboratedsolution, whichis then neutralizedto promotehydration (3). An interesting useof someof the properties of boratedgalactomannans is madein a patent (11) for hair straightening composition with sulphites. The rationaleof this application is that suchboratedgumshavea very low initial rate of hydrationin acidicmediathus enabling the product- in powderform - to be easilydispersed in water. The resulting solution wets the hair easilyand conveniently and after a while develops high viscosity (of the orderof $ 500 cP) which,aidedby combing, manages to keepin the desiredshapethe sulphitesoftened hair. Guar gum gradesare alsoavailablepossessing gellingproperties based on a principle entirely different from that of the borax/galactomannan system. They eitherutilize an oxidising catalystto activatethe complexing mechanism in a two-stepprocedure, or are "one step" and entirely self complexing types. The latter form solson dispersion, and then develop into firm, water-tight gels(2, 3).
PHYSICAL PROPERTIES OF GUAR SOLS

Galactomannans are 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 tremendous affinity - for water in its liquid state - that is. Wate in the vapour phasemerely changes the moistureequilibrium. There is no hygroscopicity. When dispersed in water, hot or cold,galactomannans hydrate rapidly to form colloidalsolutions of unusually high viscositycharacteristics even at very low concentrations. Table II indicating concentrations of various hydrocolloids required to producean apparent viscosityof 800 cP at 20Cshowsthat a brand of guar gum is - in that respect - a runner-upto Carbopol. What is evenmoreremarkable, guargum attainsnearly its full viscosity potentialin coldwater, whileothergums(including the relatedlocust bean galactomannan) requiresometimes prolonged "cooking".

GUAR

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Table
Gum

II.

o (w/v) for 800 cP

2.75 1.15

Tragacanth USP Sodium alginate (med. visc.) Jaguar brand of guar gum Methyl cellulose (1 $00 cP) Methyl cellulose (4 000 cP) Sodium carboxymethyl cellulose (reed. visc.) Sodium carboxymethyl cellulose (high visc.) Carbopol934

0.2-0.3 (2SC)
1.7 1.35
1.9 0.7 0.17

5O

4O

,'
sols

Hydrofed 25C Hydrofed 85C

30

Measurernenfs o1' 25C

20

10

2
.-.--

.=-

_J

Figure4. Viscositypotentialof some {common water solublegums.

Coldprocessing, however, affects the rate of hydration whichis greatly accelerated by increasing the temperature. For example, with a particular gradea degree of full viscosity development requiring 5 h at R.T. is accomplished in about10min at the optimaltemperature of 80C. Viscosity is often taken as a common denominator and performance indexin comparing different grades of guargum.Thereare five variables that determine the pattern of viscosity development and the behaviour of a given guar gum gradein an aqueous system.viz: concentration, dispersion, temperature, pH, and presence of foreignsubstances (113). Understanding their implications is of greathelpin formulating with guar gum or processing it.

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JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

As can be seenfrom Fig. 5, the incremental increases in the gum concentration resultin almostexponential increases in viscosity up to a concentration of about1.5%. At concentrations higherthan about3% (depending on a grade), guargums formjelly4ikepastes which,however,
are not true structural gels.
I00,000

1,000

.[
I00

Concen'l'rafion, %

Figure . Variation of viscositywith concentration.

For comparing viscosities of guar gumsa "standard"concentration of 1.0% (w/v) is usedas a rule. Quantitativemeasurements are bestcarried

outwitha torsion viscometer(e.g. Brook field RVF,Syncro-Lectric typewith a No.3 spindle at 20revmin-), although forqualitative comparisons other methods like,forinstance, "Ford"cup,maybeemployed. It is essential to statethe method of measurement whilequoting viscosity. Guargumsolution viscosities - in common with mostotherhydrocolloids - arestrongly dependent onshear rate,andcanbemore properly described as"apparent viscosities". In short, guar gum sols arethixotropic
having,however, a relativelylow yieldvalue.

GUAR

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The prerequisitefor the sol formation is an efficientdispersion of 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 tremendous affinity for water possessed by guar gum is utilized industrially. It is usedas a "water sealer"in oil well drilling or in protectingexplosives from getting wet. In the latter case, water leaking through a chancepuncturein a cartridgeis taken up by the gumto form a thick solwhichcompletely blocks the puncture to prevent further water entry. To effectsolution,the gum must be thoroughlydispersed by sprinkling it ontowater, ascoldaspracticable, with vigorous stirring.On an industrial scalesifting througha screen or grid from the edgeof a shakertray or the
use of an eductor are recommended.

Other expedients to promotesolutionincludepremixingthe gum with other powderedsubstances, e.g. sugar, or dispersing it in pre-retardants (e.g.alcohol,glycerine, glycols,acetone, etc.) beforeits additionto water. Finally, the gum may be dissolved more readily in certain salt solutions than in water, e.g. in solutions of sodiumof calciumchloride. The effect of temperatureon the rate of hydration and the time to attain the full viscositypotentialhas already been discussed. As all solutions,the guar solschange their viscosity with temperature(Fig. 6).

60

On
5O

40

3O

S01s prepared and ! 'ering fullyhydrated

20

temperature chencje 25* C before

I
I

I
I
I

-o

Io

2o

3o 40

50

7o Bo 9o

Viscosity measurement temperature, c

Figure 6. Measurementof temperature effect on fully hydrated sol.

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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 temperatures for long periodsof time with practically no effecton their ultimate viscosity measured at roomtemperature. One of the characteristics of guar gum solutions is 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 between pH valuesof 7-9, and the practicalstabilityrangefrompH 4-10.5. In the presence of strongalkalisthe viscosityfalls fairly sharply,although there is a suggestion that this may be due to destructionof the proteins which form a complexwith the carbohydrate polymer (1). It is possible to 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

2.?

2.4

o u

'

I0

I1

pH

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

Moreaffected by the pH is the rate of hydrationwhichagainis highest betweenthe pH valuesof 6-9 and the lowestat approximately 3.5. This knowledge is usefulin preparingsolutions of "difficult" formulationswhichcanbe easilydispersed in coldwater at pH 3.5, and the solution obtained speedily, with the desired viscosity "released" by adjusting the pH to 8, and - if necessary - heatingthe solution to 80C. Anotherconsequence of the nonionic characterof guar gumsis the fact that their solutions are uncommonly resistantto electrolytes. They are completely unaffected by hard water, and will toleratelarge quantities of

GUAR

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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 dissolved substance. Complexing with boron,aluminium,copper, chromiumand other salts have already beendiscussed. Although nonionic in nature,the gumparticles may acquire an ionic chargeby absorbing other ionsfrom solution. This in turn may affecttheir properties e.g. rate of hydration and ultimate viscosity.It has alreadybeenmentioned that sodiumand calciumchloridesolutionspeed up guar gum hydration without affectingviscosity.Sodiumbenzoate, however,not only accelerates the rate of hydration,but alsoconsiderably
increases viscosityof the resultingsolution. On the other hand, salts like sodium sulphateinhibit hydration of the gum, depress viscosity,and in large quantitiesmay cause its precipitation. The explanationof the latter phenomenon seems to lie in the fact that

the gum,andthe dissolved substance, arecompeting for 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 causing the former'sprecipitation. The understandingof thesefacts also supplies a rationalefor empiricallyevolved methodsof dispersing the gum using dry mixing techniques with, 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 become thoroughly wetted,and dispersed. This effectis then negated by dilutionuponwhichthe gum'shydrationproceeds normally (13). Another important property of guar gum explaininga great deal of its behaviouris its hydrogen bondingactivity. This is generallyattributed to the presence and behaviourof numerous hydroxyl groups.The basic straight chain structureof the galactomannan molecule,along with the regularityof the single membered galactose branches, resultin a product that exhibitsan unusual effecton otherhydratedcolloidal systems through hydrogen bonding. Because guargumwill hydrogen bondto both- hydrated mineral and organic surfaces, there are few systemswhich will be unaffected by its action.The addition of even extremelysmall quantities of guargumcanmarkedlyalter the electrokinetic properties of the system
treated.

As a broadrule, it can be saidthat guar gum in appreciable quantities

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JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

will act as dispersant for organicsystems, especially thosewith functional hydroxyl groups,and as a coagulantfor inorganicones,in particular for thosewith "clay" characteristics. This property- togetherwith its relatively low yield value - meansthat cautionmust be exercised when usingguar gum solution for 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 some industries (e.g.mining)whereguargumis employed asa flocculant, settlingagent, and filtration aid. The hydrogen bondingphenomena explain,amongothers,the excellent compatibilityof guar gum solutions with 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 evidence that in many instancesthere is a distinctly synergisticaction. Co-solutions of several of those hydrocolloids (e.g.starches) with guar, exhibitmuchhigher viscosities,and stabilities than either ingredient alone. Combination of guar with agar or carrageen promotes formationof a structuralgel. Hydrogen bonding also explainswhy guar gum is such an excellent beateradditivein the processing of paperpulp.A smallamountof guargum solutionaddedbreaksup agglomerated cellulose pulp 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 solutions have slightly acidicreaction(pH 5.5-6.1), and if sterile are perfectly stablein storage.They are, however,as are the other natural hydrocolloids, subjectto microbiological deterioration,which resultsin a lossof viscosityas the first tangiblemanifestation and in a loweringof the pH value. If unpreserved, guar gum solutionshouldbe usedwithin 24 h. Should its usebe delayedpreservatives must be employed. In the foodindustry sodiumbenzoateand sorbicand benzoicacidsare most commonlyusedfor that purpose.Other industries may successfully

GUAR

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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 uniquecombination of properties it 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 dispersant and suspending agent - also for sizingand coating.In the textile industryit alsoserves as a pigmentdispersing aid, 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, cheese spreads, and many other applications. In the pharmaceutical industry,dry guar gum is usedas a disintegrant andin solutionas a binder in compressed tablets manufacture(14). It is alsousedin liquid dieteticpreparations asa low caloriethickenerto improve their mouth feel, body and pour characteristics. On accountof its hydrophilic 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 electrolytes,printinginks, and as an ingredient in paints,adhesives and polishes.
GUAR GUM IN THE COSMETIC INDUSTRY

It would appear that a raw material endowed with sucha variety of usefulproperties, a formidable viscosity builderwith an unusual, excellent cold solubility, a solventresistantfilm former, protectivecolloid,with a widerangeof compatibilities, untroubled by pH changes and the presence of salts, stable,nontoxic, safeand cheap, wouldbe immediately accepted by the cosmetic industry. This is, however,not the case.The industry tendsto be shy of materialsnot createdspecifically for its use, and slowto
translate to its benefit the experience of other industries.

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This may alsobe true because, althoughmost guar gum manufacturers recommend its use in cosmetics in general, concreteinformation is scarce as are patentsand availableformulations. Guar gum is usedon a sizeable scalein the manufacture of tooth paste

to whichit impartsslip, so that the pastecan be extrudedfrom the tube without applyingexcessive pressure. Similarly it is usedin someshaving creams, whereit stabilizes the system, impartsslip in extrusion and on the skin,while shaving,and improves facial skin after feel (16). It lendsitself perfectlyto be usedin emulsified systems: creams and lotions- as a protectivecolloid,increasing emulsionstability, preventing syneresis, water loss,and phaseseparation. It alsopreventsdegradation of emulsion due to freeze-thaw conditions whichcausethe water phaseto condense out of the system.For instance, used in an ordinary TriethanolamineStearate type lotion it gives it a stableviscosity, improvedspreadability and impartsto it an agreeable after feel associated with bestquinceseedformulatedlotions. In aerosols dispensing aqueous liquid preparations as a sprayor mist it is said to reducemigrationof "fog" (16). Guar gum solutions are compatible and mix well with mostdetergent systems (shampoos, cleansers, etc.) givingthem "body" and abolishing or minimizingtheir harsh after feel. Excellent hair colourants were also prepared usingguargumsolution as thickener. Although not an emulsifier - owing to its ready compatibility-guar gum solutions can be usedin conjunction with other gumsendowed with emulsifying properties. An excellent,stable emulsion was, for instance, prepared in the cold adding30-40% mineraloil into a 10% solution of polyvinylalcohol(80% hydrolysis low molecular weight) 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 conveniently preparedusingguargum plus additives which in suchsystemmay even be heat- and moisture-sensitive. In use, the mixesneedonly to be stirredinto a sufficiency of cold or tepid water

(half a cupful)to produce a 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 ensuing problems. (Received: 18thAugust1969)

GUAR

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REFERENCES

(1) (2) (3) (4) (5) (6) (7) (8) {9) (10)
(11) (12) (13)

(14)
(15) (16)

Smith, F. and Montgomery, R. Chemistry of plant gumsand mucilages (1959). (Reinhold Publishing Corp., New York). "Guartec" (1963). (GeneralMills Inc.). "Jaguar", (1962). (Stein, Hall & Co. Inc.). Kirk and Othmer. "Gums, Natural" by M. Gliksman. Encyclopaediaof Chemical Technology, 10 (1966). I-Ieyne, Eileen and Whistler, Roy L. J. Am. Chem. Soc.70 2249 {1948). Ahmed, Z. F. and Whistler, R. L. J. Am. Chem.Soc.?9.2524 {1950). Swanson,J. W. J. Am. Chem. Soc. 71 1510 {1945). Rafique, C. M. and Smith, F. J. J. Am. Chem.Soc. ?9.,4684 (1950). Moer, G. Jr. and Meer, W. A. Am. Perturner 77 49 {4, 1962). Natural Plant Hydrocolloids.Roy L. Whistler. "Guar Gum, Locust Bean Gum and Others" {Advances in Chemistry Seriet11. Am. Chem. Soc.){1954) Brit. Pat 1 076 420. Gerding, P. W. and Sperandio, G. J. J. Am. Pharm. Assoc.Pract. Ed. t5 856 {1954) Carlson, W. A., Ziegenfuss,E. M. and Overton, J. D. Compatability and manipulation of guar gum. Food Technol.16 50 (10, 1962). Eherton, L. E. Platz, P. E. and Cosgrove,F. P. Drug Standards.9.8 No. 2, 42-47 (19SS). $chimmel Brief No. 401. (September, 1968). 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 satisfactory 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 because of 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 contaminated 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 processes which the natural guar gum undergoesis autoclaving. This expedient is directed not so much against the bacteria, as against the enzymes which could have

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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?
TF. 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. BUSFELD: 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;consequently it 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 changes which
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).