Liquida. Component High Maltose 42DECS 62DECS HFCS42. Cargill. Staley Sweetose. SatinSweet65 1300. Oligos > 3DP 16. 54. 25. 7. Maltotriose 15. 13. 9. 0.
STRUCTURAL STABILITY OF INTERMEDIATE MOISTURE FOODS:
BEYOND WATER ACTIVITY Louise Slade and Harry Levine GENERIC ISO-MOBILITY CONTOUR MAP IDENTIFY LOCATION OF SYSTEM ON t-T-M MAP ISO-FUNCTIONALITY CONTOUR LINES || Tg CURVE
USING THE FOOD POLYMER SCIENCE APPROACH: TO EMPHASIZE KINETIC (NON-EQUILIBRIUM) DESCRIPTION OF FOOD SYSTEMS TO RELATE TIME - TEMPERATURE - MOISTURE (MOBILITY TRANSFORMATIONS) TO ESTABLISH REFERENCE CONDITIONS OF TEMPERATURE AND MOISTURE CONTENT
FOCUS ON NON-EQUILIBRIUM BEHAVIOR OF SMALL CARBOHYDRATE-WATER SYSTEMS Abstract For pragmatical timeframes and conditions (temperature, concentration, pressure), where real-world systems are usually far from equilibrium, familiar treatments based on the equilibrium thermodynamics of very dilute solutions fail. Successful treatments require a new approach to emphasize the kinetic description, relate time-temperature-concentration-pressure through underlying mobility transformations, and establish reference conditions of temperature and concentration (characteristic for each solute). Small carbohydrate-water systems provide a unique framework for the investigation of non-equilibrium behavior: definition of conditions for its empirical demonstration, examination of materials properties that allow its control and description, identification of appropriate experimental approaches, and exploration of theoretical interpretations. [Slade and Levine (1988a,b, 1991a,b)]
NEW APPROACH TO FOOD RESEARCH MOISTURE MANAGEMENT "WATER ACTIVITY" PRODUCT RH THEORY OF CONTROL
PROCESS CONTROL STORAGE STABILITY GLASS TRANSITION EFFECT ON PROCESSING AND SHELF LIFE
FOOD POLYMER SCIENCE WATER DYNAMICS
GLASS DYNAMICS
FAR FROM EQUILIBRIUM PRACTICAL PROBLEMS OF FOOD SCIENCE AND TECHNOLOGY GRAININESS AND ICINESS IN ICE CREAM CRYOPROTECTION AND CRYOSTABILIZATION OF FROZEN OR FREEZER-STORED PRODUCTS BAROPROTECTION SUGAR AND FAT BLOOM CAKING AND STICKINESS OF DRY POWDERS COOKING OF CEREALS AND GRAINS EXPANSION, COLLAPSE, AND STALING OF BAKED GOODS RAW MATERIAL SELECTION AND DESIGN GELATIN MANUFACTURING AND CONSUMER CONVENIENCE
BEYOND WATER ACTIVITY MOISTURE MANAGEMENT WATER DYNAMICS
WHAT IS THE LINK
?
PROCESS CONTROL STORAGE STABILITY GLASS DYNAMICS
FOOD POLYMER SCIENCE
IS Texpt ABOVE OR BELOW Tg ? BELOW Tg => SCRATCHABILITY
ABOVE Tg => CREEP
(NOT JUST THIN & FLEXIBLE)
FOOD POLYMER SCIENCE
Tg and Tm control relaxation timescales ==> link structure to function
Tg + 10° 36 days Tg - 10° 200 years
FOOD POLYMER SCIENCE CENTRAL CONCEPT OF FPS APPROACH STRUCTURAL ASPECT
Tg Ti
FUNCTIONAL ASPECT
DEFINITION OF THE GLASS TRANSITION TEMPORAL ps to min OPERATIONAL mechanical relaxation mobility transformations
Tm
time / temperature / pressure / stuctural composition / dimensions
10 nm domains
DIMENSIONAL BIG polymers
SMALL plasticizers
diffusion distances
FOOD POLYMER SCIENCE STRUCTURAL ASPECT Partially crystalline glassy polymers Non-equilibrium solid state
FUNCTIONAL ASPECT Mobility transformations
ins a m do e Homologous families ur t a r pe les Tg and linear DP predict function m te esca e Nonhomologous families n efi n tim d Tm/Tg predicts function m on tio i T t a nc nd relax u a f to Tg trol e r n tu co c u r > Ti == k st lin
Fringed Micelle Model
based on the glass transition ... we can construct state diagrams and create mobility transformations across 4 dimensions of T, t, composition, and P Snapshot for ~10nm diffusion distances
Tg
Tm
Tg’ Wg’ glass after maximum freeze concentration
e Pr
e ur s s
TEMPORAL DEFINITION OF Tg MOBILITY TRANSFORMATIONS Tg CURVE OF ISO-RELAXATION-TIME AS MATERIAL-SPECIFIC REFERENCE CONTOUR TO RELATE
Arrhenius T > Tm nanosec
TIME - TEMPERATURE - PRESSURE - DIMENSIONS MOISTURE CONTENT - SOLUTE TYPE
Tg and Tm define Tdomains control relaxation timescales => link structure to function
WLF T Tg + 20 C hours Tg + 10° 36 days If process at Tg = century Tg - 10° 200 years
Arrhenius T < Tg centuries
Dramatic evolution of timescales in “parallel” contours above Tg WLF kinetics
OPERATIONAL DEFINITION OF Tg ORIGIN OF FUNCTIONAL DOMAINS OF TEMPERATURE WLF KINETICS PHYSICO-CHEMICAL MECHANISM OF RELAXATION PROCESSES (T- -TTgg) log / g = - -CA1 (* T B T --TTgg) C2++( (T log
/
g
(poise) due to
log/g
5
17 orders
0
of magnitude from Tm to Tg !!
-5
S. aureus 0.5 µ trip across wheat starch granule 30 µ takes a century in the glassy state
-10 -15 -20 2
1.5
1.0
0.5
T / Tg ( K ) SAME COEFFICIENTS IN WLF EQUATION FOR TYPICAL SYNTHETIC POLYMERS, ANHYDROUS GLUCOSE, AND SUCROSE SOLUTIONS BUT NOT FRUCTOSE
DIMENSIONAL DEFINITION OF Tg TINY !
CO2 ~ 0.512 nm
Water ~ 0.4 nm
-D-Glucopyranose -D-Fructofuranose TRANSLATIONAL CONSTRAINT Tm / Tg ~ 1.42 Tg 31oC Tg' - 43oC
ROTATIONAL CONSTRAINT Tm / Tg ~ 1.06 Tg 100oC Tg' - 42oC Nucleation Dielectric loss
Mixture Behavior 1:1 Glucose:Fructose Tg 20oC Mobility more like glucose alone than like fructose alone
6 glucose units = 1 turn amylose helix = 0.8 nm Tg' -14.5oC 18 glucose units ~ 6 DE maltodextrin ~ 2 nm Tg' - 6oC Biopolymer (globular protein) hemoglobin
= 6.4 nm Tg' - 5oC
TRANSLATIONAL CONSTRAINT Tm/Tg ~ 2 Tg - 135oC
TRANSLATIONAL CONSTRAINT Tm/Tg ~ 1.39 Tg 12oC
Growth
Crystallization Microwave heating Observed rvp of sample Microbiological stability Bulk moisture migration Baking functionality
SAMPLE RH IS LINEAR WITH Tg, NOT WITH MOISTURE CONTENT Sorption isotherm at 23C
Tg versus sample RH at 23C
Nylon 66
Tg (measured as peak T of loss modulus) versus sample moisture content
Tg curve
[ Starkweather (1980) ]
SAMPLE RH IS LINEAR WITH Tg, NOT WITH MOISTURE CONTENT
Nylon 66 at 23C
Tg
[ Starkweather (1980) ]
and GLASS TRANSITION TEMPERATURE °C
For synthetic polymers
Amorphous food materials sucrose sucrose/fructose sucrose/waxy corn starch horseradish strawberries
100
50
0
- 50
[ ROOS AND KAREL, 1991a ] - 100
0
20 40 60 80 SAMPLE RELATIVE HUMIDITY %
APPLICATION: edible barrier films based on food proteins
100
EXAMPLES OF CASE 1: EFFICIENT HOMOGENEOUS NUCLEATION OF SOLUTE Tm/Tg
Note: Value of Wg' also plays a role
~ 1.42
EXAMPLES OF CASE 2 AND CASE 3 : HOMOGENEOUS NUCLEATION IS CASE 3: PREVENTED
FRUCTOSE Tm/Tg
CASE 2: SEVERELY RETARDED
~ 1.06
GENERIC MOBILITY MAP WITH ISO-FUNTIONALITY CONTOURS
Cryopreservation
n i k a B
e i c S g
e c n rvp Stability
T MAGNITUDE OF WLF REGION
KINETIC BEHAVIOR OF
between Tm and Tg depends on composition coefficients and T of WLF equation depend on moisture content
TRANSLATIONAL DIFFUSION OF WATER T C
c1 orders of magnitude from Tg to above Tm
Dramatic non-Arrhenius behaviour of undercooled water
c2 T above Tg for ½ of c1
Solute
Onset of non-Arrhenius kinetics below room T
Tg
Angell (1982) in Water (Vol. 7)
( cp )
Temperature
Tm
Tm Water
Tg
Te Equilibrium exists,
Tg'
but not observed near glass curve
Water
Only see Arrhenius kinetics when T above Tg ~ 155C
103 K / T
1977
Translational diffusion of undercooled water Slow diffusion
WLF
Example of Tm/Tg >> 1.5 Anomalous magnitude >> 100° of WLF region Do not begin to observe Arrhenius behavior until
T above Tg ~ 155°
T - Tg ~ 155°
Fast diffusion Arrhenius
6º 3º log Local Viscosity
log Relaxation Time
2º
Water
Glucose Fructose
CONTRAST KINETICS ARRHENIUS WLF
log Relaxation TIME
HYPERBOLIC
Temperature
KINETICS
FORM OF EQUATION
RECTANGULAR HYPERBOLA
INTERPRETATION OF COEFFICIENTS
TRANSLATED AXES FAR ABOVE Tg MICHAELIS-MENTEN
[ Slade and Levine (1993a) ]
BETWEEN Tg AND Tm
WLF
KINETICS INTERPRETATION OF COEFFICIENTS
FORM OF EQUATION
RECTANGULAR HYPERBOLA
TRANSLATED AXES
BELOW Tg AND ABOVE Tm ARRHENIUS KINETICS
WLF KINETICS C1 = maximum orders of magnitude change in relaxation times or rates at a temperature far above initial Tg, passing through WLF and Arrhenius regions
C2 = temperature above intial Tg required to achieve half max change in relaxation scale in WLF region above initial Tg AND to reach X asymptote in Arrhenius region below Tg
log Relaxation RATE
BETWEEN Tg AND Tm
Temperature avove Tg
LOSS TANGENT - VARIATION WITH FREQUENCY Dielectric Microwaves
Visible UV
Electromagnetic radiation spectrum (Lewis, 1987)
Wavelength Radio waves
Infrared
Gamma and X -rays
Frequency (Hz)
~ 120 ps
DIELECTRIC RELAXATION BEHAVIOR OF WATER, OTHER HYDROGEN BONDING SOLVENTS, AND AQUEOUS SOLUTIONS INITIAL DIELECTRIC RESPONSE OF PURE WATER TO VARIATION OF INITIALTEMPERATURE INITIAL DIELECTRIC RESPONSE AT CONSTANT INITIAL TEMPERATURE
~ 120 ps
DSC OF CALFSKIN GELATIN ENERGETICS
Non-equilibrium melting after T > Tg 1
Heat Flow
(mcal/sec)
KINETICS
Trans
Tg
cis isomerization at T » Tg
Tm (275 Bloom, 9.8% moisture content) 0 Temperature K
Ti
2N NaCl : Soy Flour 1:1
20 min
EFFECT OF HHP
CONTROL NO HHP 25C
60C
90C
200 Mpa 400 600 200 Mpa 400 600
Aqueous salt solution is NOT a glass-forming solvent
200 Mpa 400 600
50% Sucrose : Soy Flour 1:1
CONTROL NO HHP
25C
ENERGETICS
200 Mpa 400 600
60C
200 Mpa 400 600
90C
200 Mpa 400 600
20 min
KINETICS Order of addition effect of glass-forming sugar-water plasticizer blend on soy protein Td ( denaturation peak temperature = end of glass transition region )
BAROPROTECTION
ROLES OF SOLUBILITY PARAMETER (ENERGETICS) AND
Tg (KINETICS) IN FLOUR POLYMER PERFORMANCE
Examples: Trouton ratios for flour-water doughs Rye gene flour sticky doughs
1982
Modified by Slade (Nov 1991)
Tg
SRC is the standard method to measure the Solubility Parameter of polymers.
SRC
EFFECT OF SUGAR CONCENTRATION Sugar Snap Cookie AACC 10-52 74 - 80%
SRW Flour
MIXING
Wire-cut Cookie AACC 10-53 ~ 67%
3 0 10 20 30 40 50 Sucrose (w%) 5.5 ml with 5 g Flour
Cr ac ke r
90 80 70
SE O R SUC
Cr ac ke r
BAKING
KINETICS
Ri ch
100
Le an
Starch Gelatinization Peak = Tg end
oC
Time to Peak (min)
18
OF MIXING < 50oC
E OS C E U GL TOS UC FR
OF BAKING > 50oC
60 50 0
10 20 30 Sugar Concentration
40 (w%)
50
Graham cracker 62-66%
KINETIC effect !!!!!!! Do NOT confuse kinetic behavior observed for DSC with limited solvent and elevated temperature with ENERGETIC effect as in EXCESS SOLVENT for SRC (no shear, no heat)
WHAT IS A PLASTICIZER ? A plasticizer depresses initial Tg to below T or increases t / Polystyrene blends with non-crystallizing diluents Ferry (1980)
THE BEST PLASTICIZER is a compatible diluent with the lowest Tg (but not always the lowest molecular weight)
Tg oC
Maximum potential plasticization =
Tg pure polymer - Tgpure diluent Plasticization of food polymers by water is potentially excellent (avoid ice) Tg pure diluent ~ -135oC
Weight Fraction Diluent Concentration
WHAT IS A GLASS ?
SORPTION ISOTHERMS OF CRYSTALLINE AND AMORPHOUS SUCROSE
0.1 ION DESORPT
N TIO RP O S AD
RELATIVE VAPOR PRESSURE
NOTE Hysteresis observed, with desorption isotherm located at higher water content than adsorption isotherm, due to Tg dependence of nonequilibrium sorption behavior, as expected for material that is partially crystalline and partially amorphous
Revised from Niediek (1988) Food Technol.
3 RECRYSTALLIZATION OF AMORPHOUS SURFACE
2 TIO N
0.2
20oC
SO RP
0.3
SUCROSE WITH ~ 10% AMORPHOUS SURFACE AFTER DRY- MILLING OR ABRASION
1
AD
20oC
WATER CONTENT % (AMORPHOUS PORTION ONLY)
WATER CONTENT % (TOTAL SAMPLE BASIS)
COMMERCIAL CRYSTALLINE SUCROSE
TION DESORP
RELATIVE VAPOR PRESSURE
NOTE Apparent rvp reaches ZERO, but sample water content is NOT zero Confirms that system is not at equilibrium Adsorption contour begins below desorption isotherm as expected, but exaggerated water uptake by amorphous region leads to recrystallization when its water content exceeds ~ 2%, even though total sample water content is only ~ 0.2%
w% H2O 25
Tg contour g H2O ________ 100g dm
w% H2O 13
Below or FAR above Tg : almost no temperature dependence, only moisture content dependence NEAR above Tg : dramatic temperature dependence, T-t-%m transformation, and max hysteresis between desorption and resorption In both transforms, desorption/dehumidification/drying contour always lies at higher water content than resorption/rehumidification/wetting contour.
The mechanical relaxation time decreases as the temperature T increases, according to WLF kinetics in the T region from Tg to Tm, versus according to Arrhenius kinetics below Tg and above Tm. At each value of time t, t/ varies with T ("real time" tDSC ~ 200 sec by convention) t/ >> 1
Rotate 90 counterclockwise to compare to other transforms of iso- contours, such as iso-rvp
Operational Tg Transport behaviour far above Tg t/ >> 1
t/ > 1 Transport behaviour below Tg
log MOBILITY Figure 11-1 JD Ferry, Viscoelastic Propeties of Polymers, 1980, Wiley Original Ferry data for poly(n-octyl methacrylate) compliance used to develop the WLF equation t/ Glucose 397F melts into molten fructose
=> Equivalent to order of addition experiment during heating !
303 Kelvin
DEFINITION OF Tg OF A BLEND Tg of a blend = Tg of “reporter molecule” with τ
O-τ = IS
T CON
∝ Mw of blend composition
OUR
CONCENTRATION (WEIGHT FRACTION) Temperature location of Tg predominated by: • Mn and free volume at small extent of dilution (steep curvature) • Mw and local viscosity at large extent of dilution (shallow curvature) Accounts for shape of contour and monotonic depression of Tg, when concentration expressed as weight fraction.
Bulk viscosity = macroscopic network High network modulus viscosity but low local viscosity
Bulk viscosity = microscopic local viscosity
Segmental vs Supramolecular Structure - Function Relationships Oriented polymer system model for uniaxially stretched gluten films: network reinforced by anisotropic fibrils
SEGMENTAL Tg constant above Mc BUT NETWORK Tg continues to increase g T k
*M
lecu lar T g
= Mo
Seg men tal T g
Tg
c
( Research & Development, October 1988 )
or w t Ne Segmental Tg Entanglement Region
* DP ~ 12 to 30
Linear Degree of Polymerization
DESPITE THE COMPLEXITY OF THE HEXAPLOID WHEAT GENOME FOR GLUTEN PROTEINS ---POLYMERIZATION OF GLUTENINS TO MACROPOLYMERS AND ASSOCIATION AS FIBRILS AND NETWORKS COLIN WRIGLEY CFW 48:261 2003 PREDOMINATE OVER GENETICS AS DETERMINANTS OF DOUGH STRENGTH
LEVELS OF MOLECULAR
S
F ENTANGLEMENT
RELATIONSHIPS SUPRA-MOLECULAR
1D
MONOMER POLYMER
FIBER
2D
FILM
FILM
3D
GLASSY MATRIX
GLASSY MATRIX NETWORK GEL
INGREDIENT SELECTION FOR STRUCTURE & FUNCTION WATER & FOOD MONOMER OLIGOMER IN EVERY CATEGORY
SUGAR ALCOHOLS
POLYMER COMPONENT
STARCH AMYLOSE GLUTEN GLUTENIN
POLYDEXTROSE
STARCH AMYLOPECTIN GLUTEN GLIADIN
RESISTANT STARCHES
STARCH AMYLOSE GLUTEN GLUTENIN
FOOD POLYMER SCIENCE APPROACH TO INGREDIENT SELECTION WATER AT EVERY LEVEL !!!
MOISTURE MANAGEMENT I
SOY
*
MOISTURE MANAGEMENT III MOISTURE MANAGEMENT II
SUGAR ALCOHOLS
* POLYDEXTROSE
* * *
*
*
*
SOY
FOR REDUCED CHOs
RESISTANT STARCHES
MOISTURE MANAGEMENT 3 REGIMES
Scott (1953) Related S. aureus growth at 30°C to “Aw” Controlled rvp with sucrose;
CONTROL
Tg = Tg’ = - 32°C
HYDRATION DRYING FREEZING PRODUCT RH MOISTURE MIGRATION BIOLOGICAL STABILITY
~ 64 % sucrose
HOW TO INTERPRET 3 ZONES OF GENERIC SORPTION ISOTHERM
rvp predicts BOTH surface and bulk moisture loss
III T >> Tg
growth when rvp = 0.88 with ~ 62 % sucrose no growth when rvp = 0.86 with ~ 67.5% sucrose
Labuza Food Stability Map
T > Tg
II TTg rvp predicts ONLY surface evaporation NOT bulk moisture loss
I TTg
MOISTURE CONTENT ISOTHERM
Wg’
RVP
Aw
0 --------------------- rvp = NErvp------------------------------------------------------- 0.95 rvp ~ Aw 0.995 rvp = mole fxn water concentration 1.0 NONequilibrium Equilibrium Equilibrium NONideal NONideal Ideal 100% reference sucrose concentration ~ 43% ~ 6% 0%
HOW Tg OF SOLUTE COMPOSITION CONTROLS OBSERVED VALUE OF SAMPLE RELATIVE HUMIDITY 100 milk
80
Tg 60
bi o
po l
GLASSY STATE
20
potato NFDM chip
0
cookie
20 - 100
bread dough
ym er
l ito rb so
40
0
fresh meat
Tg
% Total Moisture
FLUID STATE
sausage jam condensed sweet milk
Tg depends
on solute composition pasta
candy
40
bread flour
60 0
% RH 80
100 100
200
Temperature C
RAISINS ARE CLASSICAL EXAMPLE OF DESORPTION HYSTERESIS ; SOLUTE COMPOSITION DOMINATED BY FRUCTOSE 100 milk
Tg
60
fresh meat
bi o
Tg
40
po l
bread dough
ym er
sausage jam
l ito rb so
% Total Moisture
80
20
raisin
pasta
0
potato NFDM chip
0
cookie
bread flour
candy
20 - 100
condensed sweet milk
40
60 0
% RH
80
100 100
200
Temperature C "NEW RAISIN" dried to < 5%moisture content, then infused with low Tg solute solution to soften
BREAD AND CHEESE ARE CLASSICAL EXAMPLES OF THERMOSETS ; PERMANENT PROTEIN DISULFIDE NETWORKS EASY TO DEHYDRATE SURFACES; DIFFICULT TO REMOVE BULK WATER CONTENT 100 milk
Tg
60
fresh meat
bi o
Tg
40
po l
bread dough
ym er
sausage
20
condensed sweet milk
pasta
0
potato NFDM chip
0
cookie
20 - 100
Tg perm
anent netwo rk
d rea db ke ba se ee ch
jam
l ito rb so
% Total Moisture
80
bread flour
candy
40
60 0
% RH
80
100 100
200
Temperature C
MULTIPLE TEXTURE STABILIZATION REQUIRES CONTROL OF MOISTURE CONTENT, SAMPLE RH, Tg molecular, Tg network Bread and cheese are thermoset permanent protein disulfide networks => easy to dehydrate surface, but difficult to remove bulk water content
100
Solute composition Tg controls observed value of sample RH
Tg
60
40
po l
ym er
0
20
bread dough
Tg depends on solute composition
sausage jam
condensed sweet milk
pasta
netwo
rk
bread flour
candy
40
- 100 Temperature C
controls bulk water migration
Tg permanent d rea db ke ba se ee ch
potato NFDM chip
cookie
Tg permanent network
l ito rb so
0
bi o
GLASSY STATE
20
milk
fresh meat
Tg
% Total Moisture
80
FLUID STATE
60 0
% RH
80
100 100
Tg molecular controls water vapor migration
200
Starting from the same dough …. drying to a given moisture content versus baking to the same moisture content gives a different product, as reflected by the observed different product RH values. 100
80
Tg 60
Tg
bi op ol ym er
network bread dough DESORPTION HYSTERESIS EASIER TO REMOVE BULK WATER
raisin
jam
pasta
0
0
cookie
20 - 100
anent netwo rk
condensed sweet milk
THERMOSETS
EASY TO DEHYDRATE SURFACE; DIFFICULT TO REMOVE BULK WATER
bread flour
candy
40
60 0
% RH
controls bulk water migration
Tg perm
sausage
20 potato NFDM chip
Tg permanent
d rea db ke ba se ee ch
40
fresh meat
l ito rb so
% Total Moisture
milk
80
100 100
200
Temperature C
Tg molecular controls water vapor migration
Insight into why Tg' occurs at a particular location on the Tg contour
BACKBONE STRUCTURE DOES NOT PREDICT MOBILITY
Hevea rubber
IN THE ABSENCE OF WATER *, PREDICT RELATIVE MOBILITY AT Tg OR T > Tg BY KELVIN Tm/Tg
11 &
* Or very low water content, much lower than Wg'
IN THE PRESENCE OF WATER *, PREDICT RELATIVE MOBILITY AT Tg' OR T > Tg' BY Mw (local viscosity) or Mn (free volume) or Mw/Mn (local viscosity for given free volume) ( calculated from Wg'+Cg' composition of freeze-concentrated glass at Tg' )
* Water content near or > Wg'
Moisture Content %
o
+
x x
Relative Humidity % at 25C
Alignment of RH & Moisture Content NaCl series
X X X X
X X
Glycerol series X
MAP OF WATER - RH RELATIONS FOR PREDICTIVE RH MODELS Single Point Saturated Solutions Commercial Syrups X
Moisture Content w%
COMPLETE CONCENTRATION CURVES FPSC Data
Mannitol
Glycerol-water o Fructose-water o Sucrose-water +
Galactose LS NOTE Fructose saturated solution from literature does not coincide with Fructose-water at same 80% from FPSC
Maltose Glucose
Literature value is incorrect due to difficulty of making a true saturated solution of fructose. X
o
X X
Sucrose Liq Sugar Sorbitol PDX X HFCS 42 HFCS 55 Fructose CS 24DE CS 62DE
Literature Data FPSC Data
Relative Humidity % at 25C
X
MAP OF WATER - RH RELATIONS FOR PREDICTIVE RH MODELS Single Point Saturated Solutions Commercial Syrups X
Moisture Content w%
COMPLETE CONCENTRATION CURVES FPSC Data Glycerol-water o Fructose-water o Sucrose-water +
o
Mannitol
o Galactose Maltose Glucose
o X
o o
X X
Sucrose Liq Sugar Sorbitol PDX X HFCS 42 HFCS 55 Fructose CS 24DE CS 62DE
Literature Data FPSC Data
Relative Humidity % at 25C
X
Of the common sugars, only lactose is guaranteed to remain completely crystalline, rather than dissolve to a sticky syrup in humid storage. Even if water uptake occurs, crystalline lactose monohydrate would avoid creation of syrup.
Temperature oF
Melting temperature oF of sucrose crystals IN % dissolved sucrose, means that crystals will be COMPLETELY melted above the solidus curve
% DISSOLVED Sucrose
COMPOSITION OF INGREDIENTS AS % OF SOLIDS
HIGH MOLECULAR WT
HIGH 43DE HFCS MALTOSE CS 42
GLUC MALTO SYRUP 180
100%
MALTODEXTRIN
16%
54% 7%
15%
13%
MALTOSE
65%
14%
FRUCTOSE GLUCOSE
4%
OLIGOSACCHARIDES
MALTOTRIOSE
LOW MOLECULAR WT
MALTODEXTRIN
OLIGOSACCHARIDES
MALTOTRIOSE MALTOSE
19% 51%
100%
GLUCOSE FRUCTOSE
42% HIGH 43DE MALTOSE CS
FIRMNESS (HIGH Tg)
HFCS GLUC 42 SYRUP
MALTO 180
SOFTNESS (LOW Tg)
NOT COHESIVE PARTICULATE TO SYRUP RATIO TOO HIGH
COHESIVE MEDIUM RATIO SYRUP TO PARTICULATES
SYRUP TO PARTICULATE RATIO TOO HIGH NOT COHESIVE
HARDER
DENSER
SOLID
DRY
CRUMBLY
HIGH MOLECULAR WEIGHT CARBOHYDRATES e.g. MALTODEXTRIN 180
CRISPY / SOFT
MOIST
CHEWY
+ MEDIUM + HIGH MOLECULAR WEIGHT CARBOHYDRATES IN OPTIMIZED BLEND e.g. HIGH MALTOSE CARGILL SATIN SWEET 65 43DE CORN SYRUP STALEY 1300 LOW
LOW MOLECULAR WEIGHT SUGARS e.g. HFCS42 GLUCOSE SYRUP SOFTER
LIGHT
FLUID
WET
GOOEY
Ingredient Relative sweetness (by weight, solids) Sucrose 1.0 Glucose 0.7 Fructose 1.3 Galactose 0.7 Maltose 0.3 Lactose 0.2 Raffinose 0.2 Hydrolysed sucrose 1.1 Glucose syrup 11 DE
