Journal of Non-Crystalline Solids 348 (2004) 5158 www.elsevier.

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Water and the glass transition temperature of organic (caramel) glasses

A.V. Cardoso *, W.M. de Abreu
REDEMAT/CETEC Chemistry Division Av. Jose Candido da Silveira, 2000, P.O. Box 2306-CEP 31.170-000, Belo Horizonte, MG, Brazil

Abstract The glass transition temperature (Tg) of sugar-related glasses is close to room temperature and here we report the aect of water concentration on the Tg of caramelwater mixtures. Based on viscosity measurements, thermal analysis and X-ray diraction (XRD) experiments we have investigated the occurrence of the Tg during dierential scanning calorimetry (DSC) runs on cooling (down to $170 K) and heating cycles of the caramel glasses and caramelwater mixtures. The caramelwater mixtures are viscous melts with Newtonian rheology. Their melts bear a resemblance to a silicate melt which do not deviate from VogelFulcherTammann (VFT) equation t as the glass approaches Tg. The DSC measurements did detect low temperature transitions in caramelwater mixtures and the Tg of the dried caramel glass sample. If crystallization is avoided on cooling to $170 K then a glass transition and devitrication of the mixture will occur on heating the sample from $170 K up to the ambient room temperature. The detectability of the glass transition depends on the cooling rate and water concentration. 2004 Elsevier B.V. All rights reserved.

1. Introduction In the eld of food science and biological physics, there has been a growth of interest in the subject of organic glasses and in the glass transition temperature (Tg) phenomenon [13]. The glass transition temperature is considered a tool to understand many aspects of food processing, shelf-life and food preservation. Measuring the glass transition of organic glasses could allow the identication of the water content and the temperature domains where a food product could be either a hard and crispy or soft, rubbery or viscous. This information is crucial because the stability and properties of foods and biological systems are directly dependent on the water concentration level and on the role of water as a plasticizer [4,5].

Corresponding author. Tel.: +55 31 4892320; fax: +55 31 4892200. E-mail addresses: antonio.cardoso@cetec.br, wanderson.marinho@ cetec.br (A.V. Cardoso). 0022-3093/$ - see front matter 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.jnoncrysol.2004.08.125

The non-crystalline material object of our investigation is the caramelwater mixture. Dried caramel glass [6] is the product of sugar heating and subsequent cooling and is a mixture of molecular weight polymers Mw > 10 kDa. As a food color the suspension caramel and water is widely used in beverages such as soft drinks and beer. It is sensitive to small temperature variations that may cause a decrease/increase in viscosity, light absorption and humidity. The rheological properties of caramel colour samples under dierent storage temperatures and shear rates were investigated during 4 months. All samples had newtonian viscosity in all temperatures and shear rates. Caramel glasses are molecular glasses and intermolecular forces are much weaker than chemical bonding [7,8]. Thus, the glass transition temperature (Tg) of caramel glasses is far lower compared to those of ionic or covalent glasses. Generally, the glass transition of hydrated polysaccharides is close to room temperature for low water content <10% weight [9]. The addition of water reduces the thermal energy necessary

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A.V. Cardoso, W.M. de Abreu / Journal of Non-Crystalline Solids 348 (2004) 5158

for the cooperative chain motions associated with the glass transition. Therefore Tg decreases as the water content increases. It should be pointed out that the universally used Tg from calorimetric measurements of pure amorphous solid water (ASW) is 136 K [10] while the Tg of lyophilised caramel is $298308 K. To our knowledge the measurements of the shear viscosity of caramelwater mixtures and the viscosity increase at xed water concentration (stored in sealed plastic bottles) with temperature and time (months) have not been reported before. Our aim is the investigation of these transitions observed in the caramelwater mixture. In this paper, we report measurements of the glass transition temperature (Tg) of two caramel types and the correlation of the Tgs with viscosities. Dierential scanning calorimetry (DSC) was utilised to evaluate Tg, crystallisation and melting of lyophilised and caramelwater mixtures. X-ray diraction (XRD) was used to determine amorphous and/or crystalline phases in the samples.

2. Experimental procedure Commercial caramel samples from Corn Products Ltd (Sao Paulo, Brasil) were utilised throughout the work. We have studied the properties of the brands with the commercial names of type III, IVS (simple color intensity) and IVD (double color intensity) [11]. Caramel samples were received in sealed bottles and were stored at 255 K and 281 K (Eletrolux freezer), 306 K and 313 K (Fanem electric oven) during a period of 120 days. The exact chemical composition of caramel varied from batch to batch because the key commercial product property is color hue [12]. Table 1 present data supplied by the producer of the caramel color for the solid content concentration of the caramel, the light absorption at 610 nm and shelf life in months. Caramel powder samples were obtained via sample lyophilisation (Edwards freeze dryer) [13]. Viscosity measurements were performed using one coaxial cylinder viscometer type (LV-DVIII Brookeld) equipment with 080 s1 shear rate range and another coaxial cyl-

inder equipment (Haake RV-3) with 0900 s1 shear rate range. Coaxial viscometers were calibrated using mineral oils (Cannon) and the methods for determining the reproducibility and accuracy of the viscosity measurements have been reported elsewhere [14]. X-ray powder diraction data were obtained by spectrometer (XRD6000 Shimadzu) using CuK radiation. To determine thermal properties of the caramel water mixtures DSC measurements were carried out. The rst series of DSC experiments was carried out using commercial equipment (Shimadzu DSC50) and utilized samples of about 2025 mg sealed in a aluminum pan and cooled to $170 K under helium atmosphere. A second series of DSC experiments was carried out using another DSC equipment (TA Instruments) that allowed controlled cooling and utilized samples of about 10 mg in weight. The conventional Tg determination method was used; the specimen temperature was rst decreased at a rate of 10 K/min to $170 K and then increased at 10 K/min to $400 K, the heat evolution was recorded automatically as a function of the temperature, the background part at the lower temperatures and the rapidly rising part near Tg were extrapolated, and Tg was determined as the intercept of the two extrapolations. Both apparatus software (Shimadzu DSC and TA DSC) supply these numbers automatically. The direction of exothermic peaks is up and endothermic peaks are down. The caramel suspension weight loss measurements were performed in 10 ml open glass container at ambient temperature. Caramel glass containers were weighted using analytical balance (Sartorius) at dened intervals during a period of 8 h.

3. Results The X-ray diraction patterns of the lyophilized vitreous caramel powder samples are presented in Fig. 1. The X-ray pattern of crystalline glucose, the main raw material of caramel is presented in Fig. 1. The X-ray diffraction patterns of caramel samples heat treated at $353373 K during 72 h are presented in Fig. 2.

Table 1 Physical properties of some commercial caramelwater mixtures Physico-chemical specications Solids (%) Min. Caramel Type III Type IVS Type IVD 64.5 63.7 54.8 Max. 65.4 64.5 57.6 Absorbance at 610 nm (0.4%) Min. 0.535 0.364 0.861 Max. 0.624 0.407 0.986 9 12 12 Shelf life (months)

A.V. Cardoso, W.M. de Abreu / Journal of Non-Crystalline Solids 348 (2004) 5158

53

(a) Glucose
Amplitude (a.u.)

(b) Type III

(c) Type IV D

10

20

30 40 2 Theta (deg.)

50

60

Fig. 1. X-ray patterns of vitreous liophylised caramel powder: (a) crystalline glucose; (b) caramel type III; (c) caramel type IVD.

controlled cooling (10 K/min) and controlled heating (10 K/min) of the sample. The aim was to check the previous DSC results using another equipment and to study the eect of controlled cooling on the thermal events. Fig. 3(d) show the DSC run with the cooling cycle from 300 K to $170 K followed by the heating cycle from $170 K and back to 390 K. There is an exothermic peak 240 K on cooling which we attribute to solidication/crystallization. Fig. 3(e) present in detail the thermal events on heating cycle of type IVD caramel sample. The freeze-concentrated solute or mixture has melted at 265 K. Fig. 3(f) show the cooling and heating cycles of a DSC run of a mixture of freezedried type IVD sample with 30% water added. There is no crystallization during cooling at 10 K/min. However there is an exothermic peak (at 228 K, Fig. 3(f) and (g)) on heating before mixture fusion takes place at $253 K. Table 2 gives the results of the glass transition, crystallization and fusion temperatures from DSC runs. The shear stress versus shear rate for the samples of caramel III and IVD are presented in Fig. 4. The viscosity versus temperature experimental data for the samples of caramel III and IVD are presented in Fig. 5 in the interval 273358 K together with the VFT (VogelFulcherTammann) equation [15] curve tting log g A B=T T 0 ; 1

(a) Type IV D

(b) Type III

10

20

30 40 2 Theta (deg.)

50

60

Fig. 2. X-ray patterns of heat treated (353373 K) caramel samples during 72 h. (a) Caramel type IVD; (b) caramel type III.

where g is viscosity(in Pa s), A, B and T0 are constants. Table 3 presents the calculated glass transition temperatures of the caramel suspensions estimated using the VogelFulcherTammann (VFT) equation. We observe that Tg is not a well-dened temperature for any particular glass, but a range of temperature over which the properties of the glass change with time. For inorganic silicate melts which are good glass formers however it is universally accepted that Tg corresponds to viscosity g(Tg) = 1012 Pa s. We utilize this value (g(Tg) = 1012 Pa s) for the caramelwater mixtures studied here for two reasons: rst caramelwater form viscous melts resembling the silicate melts and secondly the mixtures caramelwater are not chemical crosslinked polymers [3,4]. Fig. 6 display the viscosity versus time (days) plot for caramel samples type III and IVD. Fig. 7 shows the results of percentage weight loss versus time (hours).

Fig. 3(a) shows a DSC (Shimadzu equipment) measurement on a sample of dried caramel powder from samples heat treated at (353373) K during 72 h, Fig. 3(b) and (c) display, respectively, the DSC runs on type IVD and type III caramelwater mixtures. Fig. 3(d)(f) presents a second series of DSC (TA equipment) experiments on the type IVD caramel with

Amplitude (a.u.)

4. Discussion X-ray analysis of the caramel powder samples indicates the vitreous and non-crystallinity of the material. X-ray diraction of Type III and IVD heat-treated caramel samples were also amorphous.

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A.V. Cardoso, W.M. de Abreu / Journal of Non-Crystalline Solids 348 (2004) 5158

1 0 -1
Heat flow (W/g)

-0.2 -0.4 -0.6

298 K Tg
Heat flow (W/g)

218 K

-0.8 -1 -1.2 -1.4 -1.6 -1.8

Tg

-2 -3 -4 -5

fusion 266 K 190 210 230 250 270 290

-2
-6 190
(a)

220

250

280

310

340

370

400

-2.2 170
(b)
8

Temperature, (K)

Temperature, (K)

0 -0.4 -0.8 -1.2

Heat flow (W/g)

240 K

183 K

213 K

crystallization

7 6 5
Heat flow (W/g)

4 3 2 1 0 -1

-1.6 -2 -2.4 -2.8 -3.2

Tg

fusion -3.6 -4 170 190 210 230 250 253 K 270 290
-2 -3 170 190

Tg

fusion 230 250 270 290

210

(c)

Temperature, (K)

(d)

Temperature, (K)

Fig. 3. DSC runs of the caramel samples. (a) Heat treated (353373 K) type IVD caramel powder sample; (b) type IVD caramelwater mixture; (c) type III caramelwater mixture; (d) type IVD caramelwater mixture, cooling and heating DSC controlled cycle; (e) type IVD caramelwater mixture, DSC run near Tg; (f) type IVD [liophylised caramel powder + (30 weight%) water] mixture, cooling and heating DSC cycle; (g) type IVD [liophylised caramel powder + (30 weight%) water] mixture, DSC run near Tg.

The DSC curve of the type IVD caramel powder sample (Fig. 3(a) show Tg at $298 K. The DSC curve of type IVD caramelwater mixture ($55% solids45% water) show fusion at $266 K. We assumed the exothermic peak at $228 K (Fig. 3(f) and (g), [lyophilized type IVD caramel powder +30 weight% water] mixture) a devitrication process because it occurred after Tg on heating [16]. On the other hand, We assumed the exothermic peak at $240 K (Fig. 3(d)) a crystallization/ solidication process because it occurred on cooling without any phase transition being detected. It should be observed that the existence of the crystallization peak on cooling erased the devitrication peak on heating.

When there is no observable exothermic peak on cooling there is a resolved Tg on heating followed by devitrication and then melting. The DSC trace of type III caramel mixture on heating (65% solids35% water) show a crystallization peak at $213 K. From the rheological point of view caramelwater mixtures are newtonian. No shear-thinning (pseudoplasticity) or shear-thickening (dilatancy) has been observed. Although viscosities increase with time in sealed bottles the rheology remain independent of the shear stress and shear rate applied. At room temperature, caramel viscosity is larger than water viscosity indicating that near all resistance to ow is due to caramel. In

A.V. Cardoso, W.M. de Abreu / Journal of Non-Crystalline Solids 348 (2004) 5158
0
0.8

55

-0.2 -0.4 -0.6 Tg

Heat flow (W/g)

217 K
0.6 0.4
Heat flow (W/g)

-0.8 -1 -1.2 -1.4

0.2 0 -0.2 -0.4 Tg

crystallization

-1.6 -1.8 -2 170 190 210

-0.6 fusion

fusion 230 250

265 K 270 290

-0.8 170 190 210 230 250 270 290

(e)

Temperature, (K)

(f)

Temperature, (K)

-0.1 Tg 228 K 193 K

-0.2
Heat flow (W/g)

-0.3

-0.4 crystallization fusion -0.6 170 190 210 230 253 K 250 270 290

-0.5

(g)

Temperature, (K)

Fig. 3 (continued)

Table 2 Estimated (from DSC runs) glass transition, crystallisation and fusion temperatures of caramel samples Caramel color transitions and peak temperatures from DSC Heat treated caramel powder Type IVD Type III Tg (K) 298 218 183 Tcrist (K) 240 (cooling) 213 Tfusion (K) 266 253

an open container caramel loses volatiles and water as indicated in Fig. 7. Viscosity increases with time (days) in sealed bottled samples stored at 306 and 313 K (Fig. 6). The viscosity of water is $0.00068 Pa s at 311 K while caramel viscosity is much larger at this tempera-

ture interval (we considered g(Tg) = 1012 Pa s). On the other hand, there is almost no change in viscosity with caramel samples stored in sealed bottles at 281 and 255 K. The viscosity increase with time is usually explained as a continuous caramelization process [17]. This process is substantially reduced as storage temperature is decreased (Fig. 6). Speculating that the structure is composed of droplets (caramel or water) the increase in viscosity is the result of growth in droplet in size. Droplet size would grow due to thermal agitation [18,19]. Stable dispersions of deformable particles are usually possible with the solid content of the caramel [20,21]. If the microstructure is composed of interpenetrating phases such as water in a sponge, the increase

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A.V. Cardoso, W.M. de Abreu / Journal of Non-Crystalline Solids 348 (2004) 5158
1.7 255K 1.6 1.5
Log viscosity (Pa.s)

800

281K R = 0.95
2

306K 313K

600
Shear stress (Pa)

1.4 1.3 1.2 1.1 R = 0.95

2

400

200 (Shear stress) = 11.41 x (Shear rate) R = 1.00 0

(a)
2

1 0.9

30

60 Time (Days)

90

120

20

40 -1 Shear rate (s )

60

80

(a)
0.2

200
0

255K R = 0.99
2

281K 306K

150
Shear stress (Pa)
Log viscosity (Pa.s)

313K -0.2

-0.4

R = 0.97

100

-0.6

50
(Shear stress) = 0.24 x (Shear rate)

-0.8
2

R = 0.99 0 0
(b)

-1

30

200

400 Shear rate (s )

-1

600

800

(b)

60 90 Time (Days)

120

Fig. 4. Shear stress versus shear rate at room temperature of caramel water mixtures. (a) Caramel type III; (b) caramel type IVD.

Fig. 5. Caramelwater viscosity versus time (days) measured at constant shear rate. (a) Caramel type III; (b) caramel type IVD.

in viscosity is due to the coarsening of the sponge phase [22]. Although the viscosity versus temperature dependence have been measured within a narrow interval of data the VFT equation presented a good t for the experimental data of all the caramel suspension samples studied. Rearranging the VFT equation we estimate glass transition temperature of the caramel suspensions T g T 0 B=log gg A 2

Table 3 Estimated glass transition temperatures from VFT equation tting using experimental points Caramel color Glass transition Tg (K) using VFT (VogelFucherTammann) FIT 219 224 246

Type IVD Type IVS Type III

where Tg is the glass transition temperature, gg = g (Tg) = 1012 Pa s refers to the viscosity at Tg, T0, A and

B are constants. The numbers shown in Table 3 are consistent with the Tgs of sugar/water mixtures reported in the literature [23].

A.V. Cardoso, W.M. de Abreu / Journal of Non-Crystalline Solids 348 (2004) 5158

57

0.6
2

0.5

R = 0.99
1

R = 0.99

0.4

Weight loss (%)

Log viscosity (Pa.s)

0.3

Type III
0.2

Type IV D

-1

0.1

R = 0.97
0

4 6 Time (hours)

10 (a)

-2 15.8

16.3
4

16.8 10 /Temperature, (K )
-1

17.3

17.8

Fig. 6. Weight loss of caramelwater mixtures samples versus time (hours) in a open glass container.

0.5

R = 0.99

The alternative to the VFT t for calculating Tg would be the mixture equation or mixtures rules [24]. The estimation of the Tg of homogeneous mixture using such rules have been strongly criticized in the past by Bondi [6] due to the complex interactions between the polymer and the plasticiser. The degree of homogeneity/heterogeneity of the mixture cannot be accessed using these equations. Bondi observed that in a heterogeneous mixture solvent-polymer the persistence of the glass transition of the components might occur. The knowledge of the degree of structure heterogeneity is essential to Tg calculation. More recent and systematic studies of the viscosity below and above Tg in organic glasses support the view that the equation VFT produces a satisfactory t for organic glasses [25]. We believe that phase separation [7,26,27] investigation might be a reasonable direction to continue the study of the rheological properties of the caramelwater mixtures.

Log viscosity, (Pa.s)

-0.5 R = 0.99
2

-1.5

viscosity 4th month viscosity 11th month

-2.5 28
(b)

30
4

32

34
-1

36

38

10 /Temperature, (K )

Fig. 7. Caramelwater viscosity versus temperature. Experimental data points and VFT (VogelFulcherTammann) t. (a) Caramel type III; (b) caramel type IVD.

Acknowledgments We thank Professor Glaura Goulart (ChemistryICEX-UFMG) for the very helpful collaboration on an extensive DSC work with the caramel samples. This work had the nancial support of CAPES/Ministry of Education of Brazil.

5. Conclusions X-ray diraction conrmed the vitreous state of caramel powder samples and the VFT t gave a reasonable approximation to the low temperature glass transition. The DSC measurements did revealed low temperature transitions in caramelwater mixtures and the glass transition of the caramel sample. The detectability of the glass transition depends on the water concentration. From the rheological point of view caramelwater mixtures are newtonian.

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