newmp10

ReviewFoodpowders:SurfaceandformcharacterizationrevisitedI.
Murrieta-Pazosa,b,C.
Gaiania,,L.
Galetb,R.
Calvetb,B.
Cuqc,J.
ScheraaUniversitédeLorraine,LIBio,2AvenuedelaforêtdeHaye,B.
P.
172,54505Vanduvre-lès-Nancy,FrancebUniversitédeToulouse,MinesAlbi,CentreRAPSODEE,CNRS,UMR5302,CampusJarlard,81013AlbiCedex09,FrancecMontpellierSupAgroINRA,UMR1208UnitforEmergingTechnologyandPolymerEngineering,2,PlaceViala,34060MontpellierCedex1,FrancearticleinfoArticlehistory:Received15November2011Receivedinrevisedform24February2012Accepted1March2012Availableonline20March2012Keywords:FoodpowdersSurfacecharacterizationXPSAFMICGFunctionalpropertiesabstractTheamountofinterestingmethodsthatallowsurfacecharacterisationoffoodpowders,boththoserecentlyusedandindevelopment,aregrowing.
Untilnow,amajorproblemfacingresearchersandman-ufacturerswasthelackofacentralsourceofinformationtoprovidepracticalknowledgefocusedonlyonfoodpowdersurfacesandform.
Therstgoalofthisreviewistopresentrecentandinnovatingmethod-ologiesusedtocharacterizethesurfaceandformofvariousfoodpowders.
Inaddition,relationshipsbetweenfoodpowderssurfaces(surfaceenergy,composition,structure,etc.
)aswellasformandfunc-tionalproperties(wettability,caking,owability,etc.
)arehighlighted.
2012ElsevierLtd.
Allrightsreserved.
Contents1.
Introduction22.
X-rayphotoelectronspectroscopy(XPS)22.
1.
UseofXPSinthedairypowderfield22.
1.
1.
Reconstitutionproperties.
52.
1.
2.
Cakingphenomena72.
1.
3.
Lipidsoxidation72.
1.
4.
Flowability72.
2.
UseofXPSfornon-dairyfoodpowders.
72.
3.
Interestingcomplementarytechnique83.
Microscopytechniquesmakingsurfacecharacterizationpossible103.
1.
Electronmicroscopytechniques.
103.
1.
1.
ClassicalSEMcharacterization.
103.
1.
2.
Interestingcomplementarymethods103.
2.
Atomicforcemicroscopy(AFM)113.
3.
Transmissionelectronmicroscopy(TEM)123.
4.
Confocallaserscanningmicroscopy(CLSM)124.
Laserdiffractionanddynamicimageanalysis135.
Dynamicvaporsorption(DVS)136.
Surfacechemicalextractiontechniques147.
Inversegaschromatography(IGC)157.
1.
IGCandmoistureadsorptionisothermstoinvestigateinteractionsbetweenhumidityandfoodcomponents157.
2.
IGCatechniqueusedtostudysurfaceamorphouscontent160260-8774/$-seefrontmatter2012ElsevierLtd.
Allrightsreserved.
http://dx.
doi.
org/10.
1016/j.
jfoodeng.
2012.
03.
002Correspondingauthor.
Tel.
:+33(0)383595877;fax:+33(0)383595804.
E-mailaddress:claire.
gaiani@ensaia.
inpl-nancy.
fr(C.
Gaiani).
JournalofFoodEngineering112(2012)1–21ContentslistsavailableatSciVerseScienceDirectJournalofFoodEngineeringjournalhomepage:www.
elsevier.
com/locate/jfoodeng7.
3.
IGCtoinvestigateinteractionsbetweenflavorcompoundsandfoodcomponents177.
4.
IGCtoassessthemodificationsofsurfacesaftercoatingbyemulsifiers.
188.
Conclusionandperspectives18Acknowledgments19References191.
IntroductionTheselast10years,alotoffoodproductshavebeendevel-opedandcommercializedinapowderedform.
Asaconsequence,anewbranchofscienceandengineeringmaybeidentied.
Suchdisciplinedealswiththeintegrationoffundamentalscienticelds(processengineering,particleengineering,surfacephysicsandchemistry,physico-chemistry)withinsomeappliedscien-ticelds(foodbiochemistry,foodtechnology,functionalproperties,andfoodquality)(Cuqetal.
,2011;Ortega-Rivas,2009).
Forthefoodindustry,theinterestwithpowderformsismainlylinkedtotheirstability(chemicalandmicrobiological),tothereducedtransportcostsandgeneralconvenience.
Inindus-trypowderscanbeconsideredasendproducts(sugar,salt,coffee,spices,driedmilk.
.
.
)andalsoasintermediateproductsbetweenseveralindustries;forexample,thoseproducingpow-dersandalternativelythoseusingpowdersasingredientsforfoodproducts(fruits,starch,eggs,milk,cereals,etc.
).
Forconsum-ers,quickandcompletereconstitutionoftheseproductsisoneofthemainqualityindicators(Fornyetal.
,2011).
Foodpowdersrepresentalargevarietyofpowdermaterialsthatdifferintheirchemicalcompositionandphysicalcharacteristics.
Sourcesoffoodpowdersareasdiverseasfoodingeneral(Fig.
1),thereforedifferencesinforms,structures,compositionandbehaviorsoffoodpowderscanbebetterunderstoodbyknowingpowders'ori-gins(Cuqetal.
,2011).
Itisimportanttoremarkthatpowderscanalsobeamixofingredientsmakingitscompositionandstudymorecomplex.
However,scienticandtechnicaldescriptionsofthefoodpowderpropertiesremainincomplete.
Itisknownthatthecharacteristicsandthepropertiesoftheparticles(andmoreparticularlythesurfaceproperties)playacentralroleinthemechanismsinvolvedduringpowdersproduction(milling,spraydrying,orcrystallization),anduse(storage,ow,agglom-eration,dispersion,solubilisation.
.
.
).
Untilnow,thepropertiesoffoodpowdersareclassicallydescribedusingbulkparame-ters.
Nevertheless,itisbeingrecognizedthatthefunctionalpropertiesoffoodpowdersarelargelydependentofthesurfacecompositionandsurfacecharacteristicsoftheparticles(Gaianietal.
,2006;Kimetal.
,2002;Millqvist-Furebyetal.
,2001).
Thisisoneofthereasonswhyseveralpowderpropertiesmaybeexplainedbyabetterknowledgeandcharacterizationofparti-clesurfacesandphysicaland/orchemicalinteractionsamongthemandtheirenvironment(Gaiani,2006;Kim,2008).
Thecharacteristicsoftheparticlesurfacemaydependondifferentfactors:bulkcomposition,operatingconditionsandstorageconditions(Fig.
2).
Powdersurfaceinvestigationrequiresverypreciseandelabo-ratetechniques.
Untilnowfewinvestigationshavebeenappliedtofoodpowdersurfaces.
Consequentlyresearchisstilllimitedandthisisthereasonwhythedevelopmentofnewsurfacecharac-terizationtechniquesmaybeanextensiveeldtoexploitwithconsiderableinteresttothefoodindustry.
Thisreviewisgoingtohighlighttheexperimentaltechniquesthatenablethecharacterizationoffoodpowderssurfacesand,whenitisreported,toconnectthisinformationwiththeirfunc-tionalproperties.
2.
X-rayphotoelectronspectroscopy(XPS)XPS1(alsocalledESCAorelectronspectroscopyforchemicalanalysis)isananalyticaltechniquewidelyusedinsurfaceanalysis(Briggs,1994;RouxhetandGenet,2011).
Itprovideselementalandchemicalstatedatafromtherstnanometersofthesurfaceofsolidsamples.
ThesampleisplacedinanultrahighvacuumandirradiatedwithphotonsfromasoftX-raysourcewithawelldenedenergy.
Themethodisbasedonsurfaceirradiationwhichcausesacompletetransferofphotonenergytoatomicelectrons(Bosquillonetal.
,2004).
Whentheelectronbindingenergy(Eb)islowerthanthepho-tonenergy(ht),theelectronisemittedfromtheatomwithakineticenergy(Ek)equaltothedifferencebetweenthephotonenergyandthebindingenergy,minusthespectrometerworkfunctionU:EkhtEbU1BecauseXPSisanultrahighvacuumtechnique(108kPa),itmaypresentslimitationsforfoodwithwaterpresent,butnotforpow-deredfood(JamesandSmith,2009).
2.
1.
UseofXPSinthedairypowdereldTherstdevelopmentsusingthisequipmentintheeldofdairypowdersweredonebyFldt(1995).
Then,theuseofXPSwasreg-ularlyreportedforthedeterminationofthesurfacecompositionofdairypowders(Kimetal.
,2002,2009a–c;Gaianietal.
,2006,2007;Gaianietal.
,2010,2011a;Millqvist-Furebyetal.
,2001;Millqvist-FurebyandSmith,2007;Shresthaetal.
,2007)andsugarmixedwithdairyproteinspowders(Jayasunderaetal.
,2010,2011a–c)atanelementallevel.
FromtheC,OandNpercentages,surfacecontentsinprotein,lactoseandlipidswerecalculatedwithama-trixformulawheretheelementalcompositioninthesampleisas-sumedtobealinearcombinationofpurecomponentsmakingupthesample(Kimetal.
,2002;Gaianietal.
,2006;Jayasunderaetal.
,2009).
Milkpowdersaregenerallycomposedoflipids,pro-teinsandlactosebutalsovitaminsandtracesofmineralelements.
Byusingtheprecedentmatrix,onlylactose,lipidsandproteinsweretakenintoaccount;othercomponentswereneglected(Fldt,1995;Gaianietal.
,2006;Kim,2008).
Oneofthemostimportantresultsobtainedwiththistechniqueconcernedtheover-representationofsomecomponentsatthepowdersurfaceincomparisonwiththebulkcomposition(Shres-thaetal.
,2007;Kimetal.
,2002;Gaianietal.
,2006;Vignollesetal.
,2009).
Lipidsandproteins(surfaceactivecomponents)weresystematicallyfoundover-representedatthesurfacewhereaslac-tosewaslessrepresented(Tables1a,1band1c).
Indeed,whenfatispresentintheformulation,eveninverylowquantity,for1Abbreviations:AFM,atomicforcemicroscopy;CLSM,confocallaserscanningmicroscopy;PL,phospholipids;CP,creampowder;DSC,differentialscanningcalorimetry;DVS,dynamicvaporsorption;EDX,energydispersiveX-rayspectros-copy;ESCA,electronspectroscopyforchemicalanalysis;GAB,Guggenheim–Ander-son–Boer;HPLC,highperformanceliquidchromatography;GC,gaschromatography;IGC,inversegaschromatography;MPC,milkproteinsconcentrate;NMC,nativemicellarcasein;NL,neutrallipids;NWI,nativewheyisolate;RH,relativehumidity;SEM,scanningelectronmicroscopy;SMP,skimmilkpowder;SMPG,skimmilkpowdergranulated;SPI,soyproteinisolate;TEM,transmissionelectronmicroscopy;ToF-SIMS,timeofightsecondaryionmassspectrometry;WMP,wholemilkpowder;WMPG,wholemilkpowdergranulated;XPS,X-rayphotoelectronspectroscopy.
2I.
Murrieta-Pazosetal.
/JournalofFoodEngineering112(2012)1–21exampletheskimmilkpowder,thefatisstillpresentatthesur-face.
Alternatively,proteinwillgovernthesurfaceinabsenceoflipidsorsharethesurfacewiththefatpresent.
Nevertheless,thelipidscoverthemajorityofthesurfaceinthepresenceofbothcomponents.
Finally,lactosewasobservedintheinterioroftheparticleafterfreefatextraction(Table1c).
Thistendencytoobserveanoverrepresentationofthelipidsandthentheproteinsatthesurface,isobservedatallproductionscales,independentoftheproductionconditions.
Resultsforlabo-ratory(Table1a),pilot(Table1b)andindustrial(Table1c)dryersareshownconrmingthistendency.
Fig.
2.
Factorsaffectingthepowdersurfacesproperties.
FruitsandvegetablesCerealsandleguminousHerbs,Flowers,DairyMeatEggsMushroomsSaltsVegetalAnimalFungusInorganicPrincipalrawmaterialsoriginsPrincipalproductionPrincipalfoodpowdersFlavors,Fruitpowders,colorants,starches,tea,additives,endulcorants,flours,Dairypowders,eggpowder,meatpowder,Separation,Comminution,Aglomeration/Granulation,Cristallisation/Prescipitation+drying,Mixing,MineralsYeastsFig.
1.
Principaloriginsoffoodpowders.
I.
Murrieta-Pazosetal.
/JournalofFoodEngineering112(2012)1–213Inlaboratoryconditions(Table1a),NijdamandLangrish(2006)studied2dryingtemperaturesand6formulations,mixingwholemilkpowder(WMP)andskimmilkpowder(SMP)inordertochangethelipidconcentration.
Asmallchangeintheaveragefatcontentresultsinalargechangeinthesurfacefatcoverage,how-ever,thesurfacefatcoverageislessaffectedbyincreasesintheaveragefatcontentathigherfatconcentrations.
Highertempera-tureresultedinlargerfatandlactosecover.
Nevertheless,theaug-mentationoflactoseatthesurfacedoesnotcorrespondtotheprotein-lactoseproportioninbulkcomposition.
Authorspostulatethatatlowerdryingtemperatures,proteinhasmoretimetomi-gratetothesurfaceofthedropletbeforesufcientmoistureisevaporatedtoformaskin.
Similarresultsintermsoflactose-pro-teinsurfacecompositionwhereobservedbyShresthaetal.
(2007)whostudiedpowdersconformedbymixturesofSMPandlactose.
LaterKimetal.
(2009c)studied3solidconcentrationsinTable1aBulkcompositionandsurfacecompositionobtainedfromXPSandlinearequationrelatingelementalcomponentstolactose,proteinandfatinmilkpowdersandmilksub-productpowdersobtainedfromlabscalespraydryers.
PowdersystemFeedsolids(%)NumberofhomogenizationpassesTin/Tout(°C)%Ofsurfacelactose(bulk)%Ofsurfaceproteins(bulk)%Ofsurfacefat(bulk)ReferencesWMP-SMP1.
1%fat41.
2–120/8041*(59.
6)51*(39.
3)8*(1.
1)NijdamandLangrish(2006)WMP-SMP1.
8%fat41.
2–120/8035*(59.
2)45*(39.
0)20*(1.
8)WMP-SMP3.
4%fat41.
2–120/8031*(58.
3)38*(38.
4)31*(3.
4)WMP-SMP6.
7%fat41.
2–120/8029*(56.
3)33*(37.
0)38*(6.
7)WMP-SMP14.
0%fat41.
2–120/8023*(52.
1)24*(33.
9)53*(14.
0)WMP-SMP29.
8%fat41.
2–120/8019*(43.
0)21*(27.
3)60*(29.
8)WMP-SMP1.
1%fat41.
2–200/12552*(59.
6)31*(39.
3)17*(1.
1)WMP-SMP1.
8%fat41.
2–200/12542*(59.
2)29*(39.
0)29*(1.
8)WMP-SMP3.
4%fat41.
2–200/12536*(58.
3)28*(38.
4)36*(3.
4)WMP-SMP6.
7%fat41.
2–200/12535*(56.
3)24*(37.
0)41*(6.
7)WMP-SMP14.
0%fat41.
2–200/12527*(52.
1)24*(33.
9)49*(14.
0)WMP-SMP29.
8%fat41.
2–200/12520*(43.
0)16*(27.
3)64*(29.
8)SMP:Lac(3:1)35–180/8029(63)61(26)10(1)Shresthaetal.
(2007SMP:Lac(1:1)35–180/8031(75)58(17)11(0.
8)SMP:Lac(1:3)35–180/8039(88)57(9)5(0.
25)SMP10–145/8510*(51.
0)46*(36.
0)44*(1.
0)Kimetal.
(2009c)SMP20–145/8516*(51.
0)48*(36.
0)35*(1.
0)SMP30–145/8551*(51.
0)24*(36.
0)25*(1.
0)SMP10–205/10518*(51.
0)48*(36.
0)34*(1.
0)SMP20–205/10522*(51.
0)50*(36.
0)28*(1.
0)SMP30–205/10529*(51.
0)51*(36.
0)20*(1.
0)WMP106145/850*(36.
6)3*(27.
9)97*(26.
6)WMP206145/850*(36.
6)3*(27.
9)97*(26.
6)WMP306145/850*(36.
6)3*(27.
9)97*(26.
6)WMP106205/1050*(36.
6)3*(27.
9)97*(26.
6)WMP206205/1050*(36.
6)3*(27.
9)97*(26.
6)WMP306205/1050*(36.
6)3*(27.
9)97*(26.
6)WMP102145/850*(36.
6)2*(27.
9)98*(26.
6)WMP202145/850*(36.
6)2*(27.
9)98*(26.
6)WMP302145/850*(36.
6)2*(27.
9)98*(26.
6)WMP102205/1050*(36.
6)2*(27.
9)98*(26.
6)WMP202205/1050*(36.
6)2*(27.
9)98*(26.
6)WMP302205/1050*(36.
6)2*(27.
9)98*(26.
6)NMC15––/700.
8(0.
2)93.
9(87.
3)5.
3(0.
3)Gaianietal.
(2010)NWI15––/700.
1(0.
5)66.
1(91.
9)33.
8(0.
4)NMC+Lac15––/7014.
3(26.
6)76.
8(63.
1)8.
9(Tra)NWI+Lac15––/709.
5(28.
5)62.
9(64.
4)27.
6(0.
5)NMC+NWI15––/700.
3(0.
3)89.
6(88.
8)10.
1(Tra)NMC15––/800.
6(0.
1)99.
4(86.
4)0.
0(0.
8)NWI15––/800.
0(0.
6)69.
8(92.
2)30.
2(0.
3)NMC+La15––/8016.
0(26.
6)79.
3(62.
0)4.
7(0.
7)NWI+Lac15––/8012.
7(28.
9)66.
3(65.
7)21.
0(T)NMC+NWI15––/800.
0(0.
6)95.
6(86.
1)4.
4(T)NMC15––/1102.
2(0.
1)97.
8(86.
7)0.
0(0.
5)NWI15––/1100.
0(0.
8)88.
6(92.
2)11.
4(T)NMC+Lac15––/11016.
5(26.
7)83.
5(62.
7)0.
0(T)NWI+Lac15––/11018.
8(28.
5)81.
1(66.
1)0.
1(T)NMC+NWI15––/1100.
2(0.
6)94.
3(89.
1)5.
5(T)NMC15––/1301.
5(0.
4)98.
5(87.
6)0.
0(0.
5)NWI15––/1300.
0(1.
3)88.
1(92.
3)11.
9(0.
6)NMC+Lac15––/13019.
7(27.
9)80.
3(63.
2)0.
0(T)NWI+Lac15––/13020.
8(29.
3)79.
2(65.
6)0.
0(0.
5)NMC+NWI15––/1300.
0(0.
5)92.
9(86.
8)7.
1(T)NMC15––/1503.
5(0.
3)96.
5(86.
5)0.
0(0.
3)NWI15––/1504.
0(0.
7)85.
4(91.
6)10.
6(0.
4)NMC+Lac15––/15019.
7(25.
6)80.
3(63.
3)0.
0(T)NWI+Lac15––/15019.
2(26.
6)77.
0(67.
8)3.
8(T)NMC+NWI15––/1500.
8(0.
5)99.
2(88.
7)0.
0(0.
6)Lac,lactose;NMC,nativemicellarcasein;NWI,nativewheyisolate;SMP,skimmilkpowder;Tin/Tout,inlettemperature/outlettemperature;T,Traces;WMP,wholemilkpowder.
Valuesdirectlyextractedfromgraphics.
4I.
Murrieta-Pazosetal.
/JournalofFoodEngineering112(2012)1–21spraydryingfeedsolutions,2dryingtemperaturesforSMPandWMPand2homogenizationpassesforWMP.
Theauthorpostu-latedthathigherfeedsolidscontentwouldgiverisetomorevis-cousdroplets,preventingthemigrationofcomponentsandredistributionatthesurface.
Theauthorsgoesontodescribenowlactoseconcentrationisstrongerathighertemperatures,agreeingwithNijdamandLangrish(2006)proposalthatthefatsurfacecon-centrationisreducebyhightemperaturesinSMPanddoesnotpresentanimportantinuenceinWMP.
InadditionanydifferenceisnotedwiththeincreaseofhomogenizationpassesperformedinWMPfeedingsolutions.
Gaianietal.
(2010)observedanenrich-mentofthesurfaceinlipidsandproteinsregardlessofthespray-dryingtemperature(thepowderwasdriedat5differentoutlettemperatures)ortheformulationobtainedbycombinationsofNa-tivemicellarcasein(NMC),Nativewheyisolate(NWI)andlactose.
Furthermore,lipidsenrichmentisstrongerinpowderscontainingNWIthanNMCandhighertemperaturesincreasetheprotein-lac-tosesurfacecontentandreducethesurfacefatcontent.
Atpilotscale(Table1b),Gaianietal.
(2006)producedandana-lyzedthesurfaceofparticlesofNMC,andmixturesofNMCwithproteinultraltrateorlactose,consequentlysurfaceparticleswasmodied.
Thenatureoftheingredientaddedwasdeterminantinthesurfacemodication.
Laterthesameauthors(Gaianietal.
,2007)studiedtheeffectofstorageinNMCpowderat20and50°C,stokedintwodifferentpackage(standardorwatertightbags),thestoragetimewas15,30and60dayseachsample.
Re-sultsrevealedsignicantsurfacechangesonlyafter60daysofstorage,whenpowderisstockedinwatertightbags.
Whenpow-dersarestoredinstandardbags,changesareregisteredafter30daysofstorage.
Theseresultssuggestthatpowderconservationispossiblebefore30daysofstorageormoretimeiftheyarestockedinwatertightbags.
Temperaturedidnotdemonstrateaneffectinsurfacecompositionmodication.
Atindustrialscale(Table1c),itwasobservedthesurfacecom-positionofWMP,SMP,creampowder(CP)andwheyproteincon-centrate(WPC)(Kimetal.
,2002,2005b).
Later,thesameauthor(Kimetal.
,2009b),determinedtheeffectofstorage(6months)forthesepowders,amigrationoffattothesurfacewassystemat-icallyobservedinallthepowders.
WMP,SMPandinstantmilkpower(IMP),werecollectedindifferentpointsofthespraydryinganduidizedbedprocesses(Kimetal.
,2009a).
Surfacedidnotpresentstrongchangesinthestructureaccordingtothecollectionpoint,resultssuggestthatsurfacecharacteristicsaredevelopedindryingandtheyarenotmodiedinthesubsequentlysteps.
Murri-eta-Pazosetal.
(2012)comparedthesurfacecompositionofWMPandSMPwiththeagglomeratedmilkpowderversions:WMPgran-ulated(WMPG)andSMPgranulated(SMPG).
Asimilarcomposi-tionwasobservedbetweenWMPandWMPG,thesameeffectwasobservedbetweenSMPandSMPG.
Theagglomerationprocessconsistsintheadditionofneparticlesbeforethedryingstep,thenthesuspensionofnesandmilkisdried.
Thestudydemonstratesthatthissupplementarystepdoesnotchangethesurfacecompo-sition.
Fyfeetal.
(2011)studiedtheeffectofstorageinmilkpro-teinsconcentrate(MPC)after14,30,60and90daysat25and40°C.
Thepowderswerestockedinrecipientswithrelativehumi-litiesat44%,66%and84%.
Nosignicantchangestothesurfacecompositionwereobserved.
Finallydifferentsolventsandtreatmentsareappliedtofattydairypowders(WMP,WMPG,CP)inordertoextractthesurfacefreefat(Kimetal.
,2002;Murrieta-Pazosetal.
,2012).
Theef-ciencyofthetechnicscanbeobservedafteranalysisofsurfacecompositionin''surfacefatfree''powders,thenthesepowderswereusedtoevaluatetheevolutionoffunctionalproperties.
Differentmechanismsofpowdersurfaceformationwerepro-posedanddiscussedfromtheseresultssummarizedinTables1a,1band1c,theyallagreeswiththeformationofafatsurface,thenthedryingofthenextlayerformingaskinwithasubsequentlydryingofthecore.
Recently,thistechnique(surfacecompositionbyXPS)hasbeensuccessfullyappliedtoinvestigatelinksbetweenparticlesurfacechemicalcompositionandparticlefunctionalproperties.
2.
1.
1.
ReconstitutionpropertiesBycomparingcaseinpowderscontainingvariablecombinationsofhygroscopicmaterial(lactoseand/orminerals),thepresenceoflactoseatthepowdersurfacecalculatedbythematrixmodelfromXPSresults,wasfoundtoimprovethewettingproperties(Gaianietal.
,2010).
NMCwasdriedat5differenttemperatures.
Afteradditionof30%oflactosetotheformulation,lactosepresentinthesurfaceincrease(Table1a)andwettingtimewasreducedfrom932to639sand623to201srespectively.
ThesamestudywasperformedforNWI.
Afteradditionof30%oflactoseintheformula-tion,thesurfacelactosealsoincreases,showingawettingtimeimprovementfrom1498to1085sand991to499s,respectively.
Surfacefatcoverseemstohaveaveryimportantinuenceinthepowderwettingproperties.
Forthe25powdersstudied(Gaianietal.
,2010),adirectcorrelationbetweenfatsurfacecontentandwettingtimewasobserved.
Forexample,forthesurfaceswithTable1bBulkcompositionandsurfacecompositionobtainedfromXPSandlinearequationrelatingelementalcomponentstolactose,proteinandfatinmilkpowdersandmilksub-productpowdersfrompilotscalespraydryers.
PowdersystemEvaporationcapacity(kgh1)Tin/Tout(°C)%Ofsurfacelactose(bulk)%Ofsurfaceproteins(bulk)%Ofsurfacefat(bulk)ReferencesNMC70–120–0.
0(0.
4)100.
0(86.
7)0.
0(0.
3)Gaianietal.
(2006)NMC+Lactose70–120–8.
9(22.
1)89.
4(66.
3)1.
7(0.
4)NMC+Ultraltrate70–120–3.
4(21.
3)91.
3(62.
2)5.
3(0.
4)NMC–215/700(1.
5)94(80.
6)6(0.
4)Gaianietal.
(2007)NMC-A15DS-20°C-WB–215/700(1.
5)94(80.
6)6(0.
4)NMC-A30DS-20°C-WB–215/700(1.
5)94(80.
6)6(0.
4)NMC-A60DS-20°C-WB–215/700(1.
5)89(80.
6)11(0.
4)NMC-A15DS-20°C-SB–215/700(1.
5)94(80.
6)6(0.
4)NMC-A30DS20°C-SB–215/700(1.
5)87(80.
6)13(0.
4)NMC-A60DS20°C-SB–215/700(1.
5)83(80.
6)17(0.
4)NMC-A15DS-50°C-WB–215/700(1.
5)94(80.
6)6(0.
4)NMC-A30DS-50°C-WB–215/700(1.
5)94(80.
6)6(0.
4)NMC-A60DS-50°C-WB–215/700(1.
5)86(80.
6)14(0.
4)NMC-A15DS-50°C-SB–215/700(1.
5)94(80.
6)6(0.
4)NMC-A30DS-50°C-SB–215/700(1.
5)88(80.
6)12(0.
4)NMC-A60DS-50°C-SB–215/700(1.
5)83(80.
6)17(0.
4)AxDS,afterxdaysofstorage(x=15,30or60);NMC,nativemicellarcasein;SB,standardbag;Tin/Tout,inlettemperature/outlettemperature;WB,watertightbag.
I.
Murrieta-Pazosetal.
/JournalofFoodEngineering112(2012)1–215Table1cBulkcompositionandsurfacecompositionobtainedfromXPSandlinearequationrelatingelementalcomponentstolactose,proteinandfatinmilkpowdersandmilksub-productpowdersfromindustrialinstallations.
PowdersystemStorageconditionsSolventnatureExtractiontime(h)%Ofsurfacelactose(bulk)%Ofsurfaceproteins(bulk)%Ofsurfacefat(bulk)ReferencesSMP–––36(51.
0)46(36.
0)18(1.
0)Kimetal.
2002(2005b)WMP–––2(36.
6)0(27.
9)98(26.
6)CP–––1(12.
3)0(11.
5)99(71.
5)WPC–––6(7.
4)41(80.
4)53(5.
6)SMP–––27(50.
0)61(34.
0)12(1.
0)Shresthaetal.
(2007)SMPAfter6months––36(51.
0)44(36.
0)20(1.
0)Kimetal.
(2009b)WMP––1(36.
6)0(27.
9)99(26.
6)CP––0(12.
3)0(11.
5)100(71.
5)SMP-ASFB–––42*(51.
4)40*(35.
0)18*(0.
8)Kimetal.
(2009a)SMP-A2VFB–––40*(51.
4)42*(35.
0)18*(0.
8)SMP-A3VFB–––42*(51.
4)39*(35.
0)19*(0.
8)WMP-ASDC–––97*(37.
5)0*(26.
5)3**(26.
8)WMP-A3VFB–––98*(37.
5)0*(26.
5)2*(26.
8)IWMP-ASDC–––98*(36.
1)0*(28.
0)2*(26.
8)IWMP-A1VFB–––98*(36.
1)0*(28.
0)2*(26.
8)IWMP-A2VFB–––98*(36.
1)0*(28.
0)2*(26.
8)MPC–––1.
8*(4.
8)68*(84.
7)30*(1.
5)Fyfeetal.
(2011)MPC-A14DS20°C,44RH%––1.
6*(4.
8)67*(84.
7)32*(1.
5)MPC-A30DS––1.
2*(4.
8)69*(84.
7)30*(1.
5)MPC-A60DS––1.
6*(4.
8)68*(84.
7)30*(1.
5)MPC-A90DS––3.
6*(4.
8)68*(84.
7)28*(1.
5)MPC-A14DS40°C,44RH%––1.
2**(4.
8)66*(84.
7)32*(1.
5)MPC-A30DS––1.
5*(4.
8)69*(84.
7)29*(1.
5)MPC-A60DS––1.
6*(4.
8)70*(84.
7)28*(1.
5)MPC-A90DS––3.
0*(4.
8)69*(84.
7)28*(1.
5)MPC-A14DS20°C,66RH%––3.
0*(4.
8)67*(84.
7)30*(1.
5)MPC-A30DS––1.
8*(4.
8)67*(84.
7)32*(1.
5)MPC-A60DS––2.
2*(4.
8)67*(84.
7)30*(1.
5)MPC-A90DS––3.
2*(4.
8)67*(84.
7)29*(1.
5)MPC-A14DS40°C,66RH%––1.
5*(4.
8)65*(84.
7)33*(1.
5)MPC-A30DS––2.
2*(4.
8)67*(84.
7)30*(1.
5)MPC-A60DS––1.
0*(4.
8)69*(84.
7)30*(1.
5)MPC-A90DS––3.
5*(4.
8)67*(84.
7)29*(1.
5)MPC-A14DS20°C,84RH%––1.
6*(4.
8)66*(84.
7)33*(1.
5)MPC-A30DS––1.
7*(4.
8)64*(84.
7)33*(1.
5)MPC-A60DS––1.
2*(4.
8)75*(84.
7)24*(1.
5)MPC-A90DS––4.
6*(4.
8)–*(84.
7)–*(1.
5)MPC-A14DS40°C-84RH%––1.
8*(4.
8)67*(84.
7)33**(1.
5)MPC-A30DS––2.
2*(4.
8)64*(84.
7)30*(1.
5)MPC-A60DS––2.
2*(4.
8)66*(84.
7)30*(1.
5)MPC-A90DS––3.
5*(4.
8)67*(84.
7)29*(1.
5)WMP–––0.
5(52.
0)6.
2(37.
1)93.
3(1.
4)Murrieta-Pazosetal.
(2012)AWMP–––1.
3(36.
7)7.
5(26.
2)91.
2(27.
3)SMP–––30.
9(52.
0)45.
1(37.
1)22.
8(1.
4)ASMP–––36.
3(36.
7)39.
3(26.
2)23.
2(27.
3)SMP–Petroleumether0.
1745(58)50(41)5(1)Kimetal.
(2002)–2444(58)55(41)1(1)–4845(58)54(41)1(1)WMP–Petroleumether0.
175(40)9(31)86(29)–249(40)10(31)81(29)–4810(40)22(31)68(29)CP–Petroleumether0.
1723(13)10(12)67(75)–2424(13)12(12)64(75)–4826(13)15(12)59(75)WPC–Petroleumether0.
177(8)92(86)1(6)–249(8)90(86)1(6)–489(8)90(86)1(6)SMP–Hexane0.
1744(58)53(41)3(1)–2459(58)41(41)–(1)–4862(58)38(41)–(1)WMP–Hexane0.
173(40)24(31)54(29)–2463(40)18(31)19(29)–4867(40)19(31)14(29)CP–Hexane0.
174(13)0(12)96(75)–244(13)0(12)96(75)–485(13)0(12)95(75)WPC–Hexane0.
178(8)92(86)0(6)–2410(8)90(86)0(6)–4810(8)90(86)0(6)6I.
Murrieta-Pazosetal.
/JournalofFoodEngineering112(2012)1–21higherfatcontent,valuesobtainedbyNWIdriedat70°C(33.
8%)gaveamaximumregisteredwettingtimeof1498s.
ThefastestwettingtimeswereregisteredforNMCwithadditionintheformu-lationof30%oflactoseandspraydriedat110,130and150°C;thisgave0%surfacefat.
TheseresultsagreedwiththoseobtainedbyKimetal.
(2002)studyingWMPandCP.
HerethewettingtimesforWMPandCPwerehigherthan900s,andafterfreefatextrac-tionthewettingtimeswerereducedto35and100sforWMPandCP,respectively.
Lecithinationofpowdersisapracticerecurrentinthefoodpowderindustrythatimproveswettingandrheologyofpowders.
Millqvist-FurebyandSmith(2007)addedlecithintoSMP,WPCandlactoseinordertoadaptthemethodrelatingelementalanal-ysisofXPStosurfacecompositionofpowderscoveredwithleci-thin.
Thisadaptationwasdevelopedwithalayermodelindicatingthatlecithinwouldcoatthewholeparticlesurface.
Sur-facecompositionforSMP+Lecithin,WPC+Lecithinandlac-tose+lecithinwas54.
3%,54.
8%and0%ofproteins,17.
9%,23.
5%and51.
3%oflactoseand27.
8%,21.
7%and48.
7%oflecithinrespectively.
Authorsattributethelowlecithinvaluestothethicknessofthecoverage.
Thelecithinlayerthicknessisestimatedatapproxi-mately2.
5nm.
Thisisthinnerthantheanalysisdepth(10nm).
Fromthisvalue,estimationofthesurfacelayerthicknessforeachpowderwascalculated:1.
6nmforSMP+Lecithin,0.
8nmforWPC+Lecithinand1.
9forlactose+lecithin.
AnotherstudyrelatedthewettingtimeofNMCpowderwithfatmigrationfromthebulktothesurfaceduringstorage(Gaianietal.
,2007).
Wettingvaluesgrewfrom12sinfreshpowdersto35s(watertightbag)and73s(standardbag)after60daysstorageat20°C.
Resultsweremoredrasticwhenthepowderisstoredat50°Cwith148s(watertightbag)and265s(standardbag).
Thisdelayinthewettingtimewasattributedtoalargerfatcoverage.
ForSMPthesamephenomenonwasobserved.
Thefatsurfacecoverageinfreshpowderwasdeterminedat18%andafter6monthsofstorageatroomtemperature(10–30°C),thefatcover-ageshiftedto20%.
ForWMPandCP,thefatsurfacecoveragewasimportantevenforfreshpowder(98%and99%).
Howevernosig-nicantchangeswereobservedafter6monthsstorage(Kimetal.
,2009c).
Inordertoimprovethereconstitutedpowderproperties,othersstudiedtheeffectofprocessingparametersonthepowdersurface.
Highspray-dryingtemperatures(Gaianietal.
,2010),highsolidcontentandhomogenization(Kimetal.
,2009c),appeartoproducepowderswithlesssurfacefat(Tables1a,1band1c)allowingshort-erwettingtimesasdemonstratedintheworkofGaianietal.
(2010).
Theinuenceoftheproteindenaturation(mainlywheypro-teins)oncomponentsrepartitioninthedryparticlewasalsostud-iedbyMillqvist-Furebyetal.
(2001).
Aslightincreaseinsurfacefatwasobservedwiththedenaturationpercentagewhereasthelac-tosecoveragewasalmostconstantandtheproteincoveragede-creased.
Thewettingtimewasaugmentedfrom21to40.
2sforthecorrespondingdegreeofdenaturationof4%and51%withaconsequentialincreaseinthesurfacefatcontent.
2.
1.
2.
CakingphenomenaCakingisaprevalentsituationthatcancauseproblemsinoper-ation,equipmentsurfacesorproductyield(Adhikarietal.
,2001).
NijdamandLangrish(2006)relatedthedegreeofcakingtothesur-facecompositionofmilkpowderspresentingdifferentfatcontents.
Theresultsindicatedthatthedegreeofcakingwashigh(>90%)forpowderscontainingbetween5%and30%ofsurfacefat.
Ontheotherhand,thecakingwasimportantlyreduced(160lm,NativesemolinaandSemolinaSieved315lm.
Wheatpar-ticledisplayvaluesofelongationbetween2.
04and2.
11,circularityfrom1.
13to1.
17,compactnessbetween0.
690and0.
707andnal-lyconvexityfrom0.
902to0.
873.
Thewettingbehaviorofasolidparticlemaybeinuencedbytheparticlesize.
Thewettabilitytimewassystematicallyshorter(88–115s)forlarge($400lm)particlesinthecaseofcaseinpow-ders(Gaianietal.
,2005).
Indeed,fasterwetting(4.
1sstudying4gofsievedskimmilkpowder)isoftenrecordedwithlargeparticles(>1000lm)doetotheformationoflargepores,highporosityandsmallcontactanglesbetweenthepowdersurfaceandthepene-tratingwater(Freudigetal.
,1999).
Verylittleworkhasbeencar-riedoutforfoodpowdersonparticlemorphology(Gaianietal.
,2011b;Pereaetal.
,2009)whereastheliteraturewasveryfur-nishedformineralspowders(Ulusoy,2008;Chauetal.
,2009).
Nevertheless,Pereaetal.
(2009)foundsomerelationshipsbetweenthemorphologyofmilkpowderagglomeratesandtheirrehydra-tionproperties.
Anincreaseofthesolubilityandthewettabilitywasrelatedwithanincreaseoftheparticlecompactnessandshapefactor.
ThestudyofGaianietal.
(2011b)showed,forthersttime,acorrelationbetweenpowderrehydrationpropertiesandparticlesshape,inadditiontotheparticlesizeandcolor(mainlyrelatedtochemicalcomposition).
Thesphericitywastheshapeparameterdemonstratingastrongerinuenceinrehydrationproperties,sphericityvalueswereregisteredbetween0.
5and0.
9fordairypowders(NMC,NWI,SMP,WMPandSemi-SMP),smallparticlespresentinghighsphericitiesvalues($0.
9)obtainedlowerwettingtimes,SMP=1750s,Semi-SMP=1650s,NMC=2500s.
Further-more,aregressionmodelwasdevelopedtoreplacetime-consum-ingmeasurementsfordispersibilityandsolubility.
5.
Dynamicvaporsorption(DVS)TheDVSapparatusprovidesfullyautomated,rapidandaccu-ratemeasurementsofgravimetricmoistureuptakeinsolidmateri-alsatawidetemperaturerangeusingdynamicenvironmentcontrolandultra-sensitiverecordingmicrobalance.
Sorptioniso-thermswereperformedforcaseinpowderduringstoragebyGaianietal.
(2009).
ByapplyingthemodelofGuggenheim–Anderson–Boer(GAB),after60daysofstorage,adecreaseofthemonolayercapacitywasregisteredfrom0.
0632to0.
0617kg/kgat20°Candfrom0.
0632to0.
0524kg/kgat50°C.
Thisdecreaseinthewaterafnitywasrelatedtothesurfacefatincreasesduringstorage.
ItwashypothesizedthatalayeroffatmayprogressivelycovertheTable5Characterizationoffoodpowdersbyconfocallaserscanningmicroscopy(CLSM).
MethodsPowdersystemsReferencesSpraydryingInstantwholemilkpowderInstantwholemilkpowderMcKennaetal.
(1999)WholemilkpowderKimetal.
(2002)MilkmodelwithlowfreefatMilkmodelwithlowfreefatafterfreefatextractionVignollesetal.
(2009)MilkmodelwithhighfreefatMilkmodelwithhighfreefatafterfreefatextractionMillingProteinsincornourChanvrieretal.
2005I.
Murrieta-Pazosetal.
/JournalofFoodEngineering112(2012)1–2113surfacemakingitmorehydrophobic,theappearanceofthisfatlayerwasconrmedbyXPS(Tables1a,1band1c).
Wheatouriso-thermswerealsoregisteredbySaadetal.
(2009).
IsothermswerettedtoGABmodel,thevaluesshownaslightlyincreaseinthemonolayercapacity,fromvaluesobtainedinnativeour(0.
085kg/kg)tothoseregisteredafterrstpassre-grinding(0.
084kg/kg),secondpassre-grinding(0.
085kg/kg)andthirstpassre-grinding(0.
0864kg/kg),evenwhenXPSpresentsadecreaseinthenumberofhydrophobicbondsincontrasttohydrophilicbonds.
Authorsattributedthehigherwaterafnitytoastarchgranulerupturecausedbythere-grindingprocess.
MathlouthiandRogé(2003)correlatedthewatervaporadsorptionisothermtothecak-ingandowabilityofsievedand/orpulverizedsucrose,studdingfromamorphousand/orcrystalline(RH>86%)forms.
Flowabilitymeasuredasfriabilityanglewasregisteredfrom35–55°atHR=30%to90°atHR=90%forallthesizes.
Thecakingofcrystal-lineformsdoesnotallowtodecakingthepowderbecauseofanagglomerationphenomena.
Murrieta-Pazosetal.
(2011)relateddataobtainedfromthesorptionisothermtothepowdersurfacecomposition(EDX,AFMandXPS).
Thecurvesofdiffusivityweredi-rectlycorrelatedtothechemicalstateoflactosecrystallized(HR>54%)oramorphous(HR25103atm),waterclustersareformedshowingthatwater–waterinteractionsarefavored.
ThisisshownbythevalueoftheclusterfunctionC1G11upperto0(Table7).
WaterisothermsweresuccessfullyttedtotheBET,GABandFreundlichisothermmod-els.
Riganakosetal.
(1994)comparedthegravimetric(thestaticmethodwithsaturatedsaltslurries)withtwoIGCmethods(calledIGCandCIGCrespectivelycorrespondingtoseveralinjectionsorasinglelargesoluteinjection)toobtainwatersorptionbywheatandTable7Zimm–Lundbergclusteranalysisfortwosystems:water–rafnoseandwater–wheatourat30°C.
Systema(mgH2Og1solid)p.
103(atm)aw(p/p0)C1G11ReferencesWater–wheatour100.
370.
010.
35Riganakosetal.
(1989)201.
850.
040.
65304.
630.
110.
854014.
800.
350.
605023.
870.
570.
166027.
200.
650.
057029.
970.
720.
298032.
380.
770.
559034.
600.
830.
8510036.
630.
871.
14Water–rafnose1.
07.
20.
170.
25Demertzisetal.
(1989)2.
017.
00.
41+0.
073.
022.
80.
52+0.
544.
026.
90.
64+1.
284.
527.
70.
66+1.
545.
028.
70.
69+1.
86a,wateruptake;aw,wateractivity;C1G11,clusterfunction;p,pressureofwater.
I.
Murrieta-Pazosetal.
/JournalofFoodEngineering112(2012)1–2115soyour.
ThepublicationofCoelhoetal.
(1979a)givesthedetailsabouttheplotofthemoisturesorptionisothermwiththesetwomethods.
Therewasanexcellentagreementbetweenmonolayervaluesusingthethreemethods(Table8).
Thesameauthorsalsoobtainedmoisturesorptionisothermsonpolysaccharidessuchasappleandcitruspectin(Demertzisetal.
,1991)andoncrystallinerafnose(Demertzisetal.
,1989).
ThemonolayervaluesforcrystallinerafnosecalculatedwiththeBETmodelatdifferenttemperaturesaremuchlower(1.
30mgH2Og1solidat35°C)thanthosereportedforothersugarssuchaslactose(32mgH2Og1solidat34°C)andsucrose(99mgH2Og1solidat35°C).
Thiscouldbeattributedtothehighdegreeofcrystallinityofrafnose,thehigheristhedegreeofcrystallinity,thehigherthehydrophobiccharacterofthesugarandtheten-dencytoformclusters.
Thisleadstoalowerwatermonolayerva-lue.
Thewater–waterinteractionsarefavoredwithregardtothehydrophobicsurface–waterinteraction.
ResultsoftheZimm–Lundbergclusteranalysisshowthatclusterformationisfavoredonrafnoseevenatrelativelylowwaterpressures(Table7).
TheclusterfunctionC1G11isgreaterthan0fromapressureequalto17103atm.
Ifwecomparethetwopowders,wheatourandrafnose,atanygivenpressure,thewateruptakeismuchlowerforrafnosethanforwheatour.
TheeffectofcrystallinitywasalsoreportedbySmithetal.
(1981)onwatersorptionisothermsofsucrose(crystallinesaccharose)andamorphousglucose.
Theabilitytosorbagivenamountofwaterisgreaterfortheamor-phoussugarthanforthecrystallineone.
Howevertheauthorsoverlookedsomekeyaspectsduringtheinvestigations.
Thenitro-genspecicsurfaceareaofthetwosugarsthatcaninuencewatersorptionwasnottakenintoaccount.
Also,theBETequationwasusedtocalculatethemonolayercoveragewithwater,howeverthedatadidnotconformtothelinearizedBETequation.
Theauthorstheninterpretedthisnon-conformityasaresultofacom-plexsorptionmechanismoccurringintheverylowwateractivityrangesstudied.
HelenandGilbert(1985)comparedwatersorptionisothermsoftwobakeryproducts:crackers(highinfatandlowinsugar)andsweetbiscuits.
Thecrackerabsorbssignicantlymoremoisturethanthesweetbiscuit,indicatingahigherhygroscopicityofthecrackers.
Theclusteringanalysisindicatedthatwater–foodinteractionswerefavoredinthecrackerscomparedwithwater–waterinteractionsinsweetbiscuits.
Anexperimentconsistingofaddingincreasingamountsofcrystallinesucrosetocrackersleadstoadecreaseoftheirhygroscopicity.
Thisfavourstheformationofwaterclusteringandshowstheisothermofcrackerstendtothatofthesweetbiscuit.
Thisstudyalsoconrmsthathigheristhecrys-tallinecharacterofapowder,smalleristhecapacitytoabsorbwaterandtheformationofwaterclusteringisfavored.
Pastaprod-uctswereanalyzedbyLagoudakietal.
(1993),whocomparedmoisturesorptionisothermsofconventionalanddietspaghetti.
Thecapacitytosorbwaterishigherforconventionalspaghettithanfordietspaghetti,duetoitshighercarbohydratecontent.
Thesameauthors(LagoudakiandDemertzis,1994)alsocomparedtheeffectsofmoistureandtemperatureonthewatersorptionofdehydratedfoodconstituentssuchaspotatostarch,eggalbuminandwheatgluten.
Table9gatherstheBETandGAPisothermcon-stantsforwatersorptionat30°Conpotatostarch,eggalbumin,wheatglutenandspaghetti.
7.
2.
IGCatechniqueusedtostudysurfaceamorphouscontentPerformanceofasolidindifferentprocessescanberelatedtoitsamorphouscontentespeciallylocatedatthesurface.
SotechniqueslikeIGCwhichareabletoquantifyamorphouscontentonasolidsurfaceareofgreatinterest.
DifferentworkswerecarriedoutonlactoseusingIGC.
Ticehurstetal.
(1996)examinedfourbatchesoflactose(BatchesA,B,CandD),whichexhibitedvariableprocess-ingperformancebutwererevealedidenticalbyusualphysicalandchemicaltechniques.
OnlyIGCledtodifferentsurfaceproperties.
Table10gathersvaluesofthedispersivecomponentofthesurfaceenergy,cDSandspecicfreeenergyofadsorption,DGspofdifferentpolarprobesforthefourbatches.
IfthecDSarecomparable,theDGspforpolarprobesexhibitsignicantdifferences,indicatingvaria-tionsinthepolarsurfacepropertiesbetweenthebatches.
Thelactosewasalsostudiedtoshowsomerelationshipsbe-tweenIGCparametersandamorphouscontentonthesolidsurface(Newelletal.
,2001a;NewellandBuckton,2004).
ThreesamplesoflactosewerecomparedbyIGC:acrystallinelactose,aspraydried100%amorphouslactoseandamilledlactosewithlessthan1%amorphouscontentbymass.
Themilledlactosewasnotedtohaveasimilardispersivesurfaceenergy(41.
6mJ/m2)tothe100%amor-phouslactose(37.
1mJ/m2),indicatingthattheamorphouswaspreferentiallylocatedonthesurface.
Thisresultrevealedthatmill-ingdisruptsthesurfacemorethanthebulk.
Forcomparison,thedispersivesurfaceenergyvalueforthecrystallinelactosewasTable8BETandGABisothermconstantsforwatersorptioninwheatandsoyoursusingthestaticgravimetric,IGCandCIGCsorptionmethodsat30°C(Riganakosetal.
,1994).
MethodPowderBETmodelGABmodelVm(g/g)CWm(g/g)CKGravimetricWheatour0.
06836.
900.
06526.
480.
94IGC0.
06334.
280.
06320.
280.
91CIGC0.
06130.
480.
06220.
840.
91GravimetricSoyour0.
05015.
280.
04820.
480.
90IGC0.
05520.
780.
05025.
300.
96CIGC0.
05114.
040.
05317.
200.
94Table9BETandGABisothermconstantsforwatersorptioninspaghetti,potatostarch,eggalbuminandwheatglutenat30°C.
SampleBETmodelGABmodelReferencesVm(g/g)CWm(g/g)KCConventionalspaghetti0.
0604±0.
00187.
77±4.
20.
0770±0.
01120.
84±0.
087.
48±1.
22Lagoudakietal.
(1993)Dietspaghetti0.
0548±0.
00607.
13±2.
50.
0589±0.
01550.
84±0.
306.
54±1.
37Potatostarch0.
0675±0.
005514.
04±1.
660.
0906±0.
00830.
73±0.
0810.
48±1.
72LagoudakiandDemertzis,1994Eggalbumin0.
0537±0.
00587.
91±1.
730.
0576±0.
00730.
77±0.
087.
17±1.
33Wheatgluten0.
0440±0.
00487.
49±1.
150.
0530±0.
00550.
85±0.
017.
32±1.
57Table10Surfacepropertiesofa-lactosemonohydrateat30°Cafterconditioningat40°C(Ticehurstetal.
,1996).
SamplescDS(mJ/m2)DGsp(kJ/mol)AcetoneTHFEtherEthylacetateBatchA44±29.
1±0.
37.
3±0.
26.
0±0.
28.
6±0.
2BatchB405.
74.
42.
95.
4BatchC41±38.
2±0.
36.
6±0.
25.
2±0.
27.
8±0.
2BatchD428.
76.
95.
47.
716I.
Murrieta-Pazosetal.
/JournalofFoodEngineering112(2012)1–21equalto31.
2mJ/m2.
Thesameauthors(Newelletal.
,2001b)alsoshowedthatunderhumidconditions(0–20%RH),thedispersivecomponentofthesurfaceenergyofamorphouslactosewasre-ducedtothevalueofthecrystallineone,givingevidenceofcrystallization.
Ambarkhaneetal.
(2005)comparedIGCandgravimetricvaporsorptiontostudythebehaviorofamorphouslactoseduringthewatersorption.
Thedatamadeitpossibletodeterminate:(1)arsttransitionatlowRH(ca.
10%RH)correspondingtotheonsetofsignicantmolecularmobilityintheamorphousmaterial;(2)theglasstransitionfollowedbythecollapseofamorphouslac-toseoccurringbetween30%and40%RH;and(3)theonsetofcrystallizationabove45%RH.
TheauthorsshowedthatateachtemperatureTofanalysis,theamorphouslactosecrystallizeswhenTgmix(usingtheGordon–Taylorequationtakingintoac-countthemassesandTgofwateranddryamorphouslactose)is32°CbelowT.
Recentlytherstpaperwherequanticationofsurfaceamor-phouscontentwasrealisedthankstothemeasurementofthedis-persivesurfacecomponent,waspublished(BrumandBurnett,2011).
Theauthorswrote,forasolidcomposedoftwokindsofsur-faces(e.
g.
aphysicalmixtureofcrystallineandamorphoussolids)theeffectivesurfaceenergyofthemixture,cDSeff(theneteffectoftheheterogeneoussurfaceontheprobe)isrelatedtothelinearcombinationofthesquarerootsofthesurfaceareanormalizeddis-persiveenergytermsofeachsolidcDS1etcDS2:cDSeff1=2/1cDS11=2/2cDS21=22where/xaretherespectivesurfacefractionsofeachsolid.
ThevaluescDS1andcDS2aredeterminedbythepuresolidsrefer-ence.
Thiscalculationneedscrystallineandamorphousreferences.
Theauthorswarnedagainstthereferencematerial;iftheamor-phouscontainsothersurfacedisorders(i.
e.
fractures,defectsites,etc.
)itsenergieswillbeinterpretedagainstamorphousreferences.
Thersttestreviewedonlactose.
Crystallinea-lactosemonohy-drateandspray-driedlactosewererespectivelytakenasthecrys-tallineandthefullyamorphoussurfacereferences.
Fromthesereferencematerials,severalphysicalmixtureswerepreparedinor-dertomeasurethedifferenceincDSandtocomparethemwiththetheoreticalvalues.
Thereisexcellentagreementbetweenexperi-mentaldataandthetheoreticalpredictionbasedonthesurfaceenergiesofthecrystallineandamorphousreferences.
IGCgivesonlythesurfaceamorphouscontent.
Abulktechnique,DSC,wascarriedouttoevaluatethebulkamorphouscontent.
ComparingtheIGCandDSCamorphouscontentshowedhowdisorderwasdis-tributedthroughouttheparticle.
Forthemicronizedsample,thedisorderresidesonlyatthesolidsurface.
Thepartiallyrecrystal-lizedspray-driedsamplepresentsanenergeticsurfaceaswellasbulkcorrespondingtoasignicantamorphouspercentage($70%).
Theballmilledparticlesleadtoveryhighsurfaceamor-phouscontentwhilethebulkgivesaround5%.
Toconclude,IGCappearsasanefcienttooltoevaluatethesurfaceamorphouscontentandtheamorphousphase,whichcanbedesirable(e.
g.
tostabilizeproteins)orundesirable(e.
g.
candecreasethestabilityandinducechangesinproductperformance).
7.
3.
IGCtoinvestigateinteractionsbetweenavorcompoundsandfoodcomponentsIGCisalsoofinterestinthefoodeldregardingthestudyofinteractionsbetweenavorcompoundsandfoodcomponents.
Thesecompoundshaveagreatimpactontheavorofthenalfoodproduct.
IGCisapowerfultooltoinvestigatetheadsorptionofavorcompoundsontosolidsupportsuchasproteins,starchandsugars.
OneoftherststudiesonthissubjectwasrealizedbyMcMullinetal.
(1975),whichdemonstratedthatlactosehasagreatabilitytoadsorbaromas.
Theheatsofadsorptionofalargevarietyoforganiccompounds(esters,aldehydes,ketones,alcoholsandhydrocar-bons)onanhydrouslactosewerecompared(Table11).
Foragivennumberofcarbonatomsalcoholshavethehighestheatsofadsorp-tion,hydrocarbonshavethelowest,andtheotherfunctionsadsorbwithintermediatestrengths.
Thehydrogenbondsformedbetweenthelactoseandthefunctionalgroupsoforganiccompounds,suchashydroxylforalcohols,wassupposedtobethemajorfactorin-volvedinthestrengthofadsorption.
Soyproteinisalsoofmuchinterestinthefoodeld.
Differentauthorsalsostudiedinteractionsbetweensoyproteinandaromacompounds.
Crowtheretal.
(1981)comparedadsorptioncoef-cientsandheatsofadsorptionofanumberofvolatileorganicsontosoyproteinisolate(SPI)aftertreatmentsinvolvingdifferentlevelsoftemperature,moistureandshear.
Theyobservedchangesinadsorptioncoefcientsofthetreatedsamplesattributedtoade-creaseinbindingduetotheproteindenaturation.
AspelundandWilson(1983)alsomeasuredheatsofadsorptiontodeterminestrengthsofadsorptionofavorsontoSPI(Table11).
Theynoticedthatthehydrocarbonsadsorbedtheweakestandthealcoholsthestrongestontodrysoyprotein.
Theformerinteractonlywithnon-specicinteractions(VanderWaals),thelatterinteractnotonlywithnonspecicinteractionsbutalsowithspeciconesandespeciallyhydrogenbonds.
ZhouandCadwallader(2004)alsoar-rivedatthesameconclusionasAspelundandWilson(1983).
Table11Heatsofadsorptionontwosolids:soyproteinisolateandlactoseobtainedbydifferentauthors.
Flavor–DH(kcal/mol)SoyproteinisolateLactoseAspelundandWilson(1983)Crowtheretal.
(1981)ZhouandCadwallader(2006,2004)McMullinetal.
(1975)n-Hexane––6.
8–n-Nonane6.
52––9.
24n-Decane8.
36––10.
55Hexanal8.
8911.
110.
311.
63Methyln-butyrate––10.
65Methyln-pentanoate6.
71––12.
14Methyln-hexanoate8.
19––13.
572-Pentanone2.
9210.
1–10.
812-Hexanone6.
0411.
010.
512.
032-Heptanone8.
1112.
7–13.
091-Pentanol11.
2513.
1–16.
031-Hexanol13.
8916.
716.
317.
571-Heptanol18.
0616.
8–17.
18I.
Murrieta-Pazosetal.
/JournalofFoodEngineering112(2012)1–2117Volatilepolarprobessuchas1-hexanolandhexanalhavehigherbindingafnitiesthananapolarone(hexane)duetohydrogenbindinginteractionswithSPI.
Theretentionofthesepolarprobesareweakerat30%RH,indicatingpossiblecompetitionforbindingsitesontheSPIsurfacebetweenthesevolatileprobesandwatermolecules.
Thesameauthors(ZhouandCadwallader,2006)com-pletedtheirrststudyonSPIbyinvestigatingtheinuenceofa-vorcompoundchemicalstructure,includingfunctionalgroups(hydrocarbons,esters,ketones,aldehydesandalcohols)andste-reochemistry(positionofadoublebond,orthedistancebetweenadoublebondandanhydroxylgroup)onbinding.
Theycomparedthermodynamicandsorptiondataunderdifferentrelativehumidities.
Boutbouletal.
(2000)investigatedtheinteractionsbetweenaromasandnativecornstarch.
Theyobservedthatretentionwashigherunderhumidconditionsthanunderdryconditionsespe-ciallyforalcohols.
Theauthorsproposeddifferenthypotheses;ononehandapredominantadsorptionphenomenoninvolvinghydro-genbondsbetweenaromacompoundssuchasalcohols,andglu-coseresiduesofthestarch.
Ontheotherhand,asolvationofaromacompoundsbywatermoleculesallowsfortheirdiffusionthroughthestarchmatrix.
Boutbouletal.
(2002)alsoobtaineddif-ferentsorptionisothermsonstarchdependingonthearomacom-poundsandtheinteractionsdevelopedbetweenthestarchandthearomacompounds(typeIIforanester,typeIIIford-limoneneandlinearforanaldehydeandanalcohol).
7.
4.
IGCtoassessthemodicationsofsurfacesaftercoatingbyemulsiersIGCisalsoausefultoolfortheassessmentofthemodicationsofsurfacepropertiesofpowdersafterdifferenttreatments.
Theevolutionofsurfacepropertiesofsucrosecoatedbyemulsierscommonlyusedinchocolate,lecithinorpolyglycerolpolyricinol-eate(PGPR),wasmonitoredbyIGC(Roussetetal.
2002)(Table12).
Theadsorptionoftheemulsiersdecreasestheacidiccharacter(Kaparameter)originatingfromthehydroxylgroupandconsequentlyincreasesthelipophilicityofthesucrose.
Thesucrose–sucroseinteractionsareweakerinducinganincreaseintheuidityoffat-basedsuspensionslikechocolate.
8.
ConclusionandperspectivesForabetterunderstandingoftherelationshipsbetweensurfacepropertiesandfunctionalpropertiesitisabsolutelynecessarytocharacterizethepowdersurfaceindetail.
Forthispurpose,specicanalyticalmethods(physico-chemistryandsurfacephysics)abletoevaluatethesurfacepropertiesofthefoodpowdersareneeded.
Sometechniquesarenowwelldevelopedinthefoodpowderelds(XPS,SEM).
Howeverothersmayneedmoreattentionfromthesci-enticcommunity(TOF-SIMS,particlemorphology,EDX).
InFig.
3,anexampleofmultiscalesurfaceinvestigationispresented.
Cou-plingatomic,molecular,microstructuralandphysicalapproachesTable12EffectofadsorbedlecithinandPGPRatthesucrosesurface(Roussetetal.
,2002).
GranulatedsucroseJetmilledsucroseWithoutemulsiersWithlecithinWithPGPRWithoutemulsiersWithlecithinWithPGPRcDS(mJ/m2)30.
330.
631.
136.
530.
930.
0KA102181515191616KB102232833222629Fig.
3.
Techniquesforsurfacecharacterizationatdifferentlevelsregardinginformationcontentandscale.
18I.
Murrieta-Pazosetal.
/JournalofFoodEngineering112(2012)1–21maybeaninterestingoptiontobestunderstandthesurfacereac-tivity.
Concurrently,sometechniques,likeIGC,wererarelyusedonfoodpowdersandmaybeanefcienttooltoevaluatethemodi-cationsofsurfacepropertiesofapowderunderwetconditions,ortheadsorptionofavorcompoundswhichhasagreatimpactontheavorofthenalproduct.
Recently,IGCwasalsocarriedouttoquantifythesurfaceamorphouscontentandtheamorphousphase(desirableorundesirable)forthestabilityofthepowder.
Concurrently,researchisneededtobindbasicapproacheswithtechnologicalapplications,whileintegratingthecontributionofbothparticlesurfaceandprocessparametersoccurringfrompow-dermanufacturingtoend-products.
Theprincipalfunctionalprop-ertiesofafoodpowdermaybelinkedtowater,thermaland/ormechanicalconstraints.
Fig.
4highlightssomelinksbetweensurfacecharacterizationandconstraints(hydric,thermalandmechanical).
Inconclusion,thesurfacepropertiesdeterminationscouldbeofgreatimportanceasthesurfacegovernssomeessentialfunctionalproperties:wetting,dispersibility,stickiness,owability,etc.
Inspiteoftheonlyrecentuseofsometechniques,allthosepresentedhavebeensuccessfullyusedinthestudyoffoodpowders.
AcknowledgmentsANRfundingfromthe''ReactivePowder''programisgratefullythanked.
Inaddition,therstauthoracknowledgestheResearchNationalAssociationinFrance,theMexicanNationalCouncilofScienceandtechnologyandtheComplementaryScholarshipsofSEPinMexicofornancialresources.
CarlSitchisalsothankedforEnglishre-reading.
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