Rheological Characterization of Blackberry Pulp

Caracterizao Reolgica da Polpa de Amora-Preta

AUTORES
AUTHORS
Charles Windson Isidoro HAMINIUK
Programa de Ps-graduao em Tecnologia de Alimento UFPR CP 19011, Curitiba-PR, Brasil Laboratrio de Biopolmeros UFPR, CP 19081, Curitiba-PR, Brasil e-mail: chaminiuk@yahoo.com

SUMMARY
The effect of temperature on the rheological behaviour of whole blackberry pulp (Rubus spp) was determined, with temperatures ranging from 10C to 60C. The whole pulp was adequately described by the Herschel-Bulkley model and exhibited shear thinning behaviour, whereas decreases in the apparent viscosity and consistency coefficient occurred as the temperature increased, as expected for a fruit pulp. No defined tendency was observed with respect to the yield stress and flow behaviour index. The Arrhenius model gave a good description of the effect of temperature on the apparent viscosity of the pulp and the Ea (activation energy) determined at a shear rate of 50s1 was 18.27 kJmol1.

Maria-Rita SIERAKOWSKI
Laboratrio de Biopolmeros UFPR

Dayane Rosalyn IZIDORO Maria Lucia MASSON

Programa de Ps-graduao em Tecnologia de Alimento UFPR

RESUMO
Foi determinado o efeito na temperatura no comportamento reolgico da polpa integral de amora-preta (Rubus spp) na faixa de temperatura de 10C a 60C. A polpa integral foi adequadamente descrita pelo modelo de Herschel-Bulkley e exibiu comportamento pseudoplstico, sendo que com o aumento da temperatura ocorreu uma diminuio na viscosidade aparente e coeficiente de consistncia, conforme esperado para polpa de fruta. No foi observado uma tendncia definida para a tenso inicial e ndice de comportamento. A equao de Arrhenius descreveu bem o efeito da temperatura na viscosidade aparente da polpa, onde a Ea(energia de ativao) determinada a uma taxa de deformao de 50s1 foi de 18.27 kJmol1.

PALAVRAS-CHAVE KEY WORDS

Pulp; Blackberry; Rheology; Arrhenius. Polpa; Amora-Preta; Reologia; Arrhenius

Braz. J. Food Technol., v. 9, n. 4, p. 291-296, out./dez. 2006

291

Recebido/Received: 30/09/2005. Aprovado/Approved: 20/11/2006.

haminiuk, C. W. I. et al.

Rheological Characterization of Blackberry Pulp

1. INTRODUCTION
Originally from Asia, blackberry fruits were probably introduced into Europe around the XVII century. In Brazil, blackberries were introduced into the State of Rio Grande do Sul via EMBRAPA (Agricultural Research Centre) in the city of Pelotas in 1972 when the first plants arrived, coming from Arkansas University, United States. The blackberry has also been cultivated in other States, such as Santa Catarina, So Paulo, Paran and Minas Gerais, with prominence in the State of Rio Grande do Sul, which is the largest national producer with approximately 700 ton/year (SANTOS et al., 1996). The fruit is dark-red in colour, almost black in the mature stage, with the pulp presenting the same colour as the fruit. Regarding cultivation, it grows well in all Brazilian states, presenting fast growth and good adaptation to different kinds of soil, with a harvest from September to November. The blackberry tree, like the raspberry tree, belongs to the Rubus genus, of the Rosacea family, which includes other important gendera (Malus, Prunus, Pyrus, Prunus, Pyrus, amongst others) for fruit production in Brazil (BIBVIRT, 2005). Due to the low cost of plantation, orchard maintenance and principally the reduced use of agricultural pesticides, this crop has a fast economic return and is considered as an option for family agriculture (ANTUNES, 2002). Besides the raw fruits, manufactured products, such as juices, nectars, ice creams and jellies, contain the pulp as a basic raw material, which is used in the unit operations, such as pumping, mixing and separation processes. For such industrial processes to be technically and economically feasible, it is important to have knowledge of the physical chemical properties. Of these properties, the rheological behaviour is one of the most important (IBARZ et al., 1996). The rheological properties of fluid foods should be taken carefully into account for designing and modelling purposes. Furthermore, rheology is critically important for products like fruit pulps, in which the rheological property is considered as an indicator of product quality. In processes involving fluid flow, such as pumping, extraction or filtration, the calculations require knowledge of the rheological data and the rheology of the product, in order to analyse the flow conditions of various food processes (MARCOTTE et al., 2001). According to BRANCO (1995), knowledge of the rheological parameters is important in industrial applications not only to determine the energy consumption required to pump a highly viscous fruit pulp, but also to solve problems with air incorporation, which causes difficulties in the pumping operation and with undesirable reactions such as oxidation and contamination. Fruit pulps are generally non-Newtonian fluids in which the apparent viscosity decreases with increasing shear rate, and therefore they exhibit a shear-thinning behaviour. Several models have been used to characterize the flow behaviour of fruit pulps, amongst which the most used are the Power Law, Casson, Bingham, Herschel-Bulkley and Mizrahi-Berk models.

Therefore, the objective of this work was to study the rheological behaviour of whole blackberry pulp in a temperature range from 10C to 60C. Three rheological models were used as a tool for the calculation of the relation between shear rate and shear stress in order to obtain the rheological parameters of the pulp. The Arrhenius equation was used to evaluate the influence of temperature on the viscosity.

2. MATERIAL AND METHODS

2.1 Sample preparation The blackberry fruits (Rubus spp) used in this work were obtained from a single batch from Vacaria, Rio Grande do Sul State. The fruits were chosen based on their skin colour, appearance and ripeness (determined from the ratio of oBrix/ titratable acidity), according to HAMINIUK et al., (2006b). The average ratio obtained for the ripe fruits was 6.32. The fruits (5kg) were processed in a depulper (Recifer) with a 0.5mm screen. This mesh was chosen in order to achieve maximum yield in the pulp extraction, according to industrial practice, producing an homogeneous pulp. The pulp was packed in polyethylene bags (100g) to reduce contact with the air, and then quickly plate-frozen and stored at 20C, to avoid the formation of large ice crystals on the surface and damage to the cell structures, and also to inhibit enzyme action (HAMINIUK et al, 2006b). The packed and frozen material was preserved for a period of 2 months. Before analysis, the samples were thawed at room temperature (25C). 2.2 Chemical and physical analyses Soluble solids (oBrix), pH, moisture (%) and titratable acidity (g/100ml) were determined according to the standard A.O.A.C. method (2000). 2.3 Rheological measurements The rheological measurements were carried out using a concentric cylinder Brookfield (DV-III) with a small sample adapter (13R/RP , 19.05mm in diameter and a depth of 64.77mm) and the SC4-34 spindle (9.39mm in diameter and 24.23mm in length) connected to a microcomputer for control purposes and data acquisition. A Thermo Haake B3 (Haake, Model FK-2) was used to adjust the temperature of the sample to the 1060C range. The measurements were made in this temperature range considering that 10C is the usual thawed pulp temperature and 60C corresponds to the industrial pasteurisation temperature. The choice of this system was due to the possibility of obtaining a better control of the temperature during the assays and the use of a small sample size (10mL). Each experimental run lasted 4 min in the upward curve, with a shear rate range from 2.8 to 70 s1, and 4 min in the downward curve, with a shear rate range from 70 to 2.8s1 (this shear rate range was chosen since

Braz. J. Food Technol., v. 9, n. 4, p. 291-296, out./dez. 2006

292

haminiuk, C. W. I. et al.

Rheological Characterization of Blackberry Pulp

it represented a typical process condition used in flow pipes). With both decreasing and increasing shear rate, 25 points of shear stress were obtained, resulting in a total of 50 points, the average value for shear stress being measured for each shear rate. Three experimental runs were carried out for each material and the resulting shear stress was the average of the three experimental values. 2.4 Rheological models Numerous factors influence the selection of a rheological model to describe the flow behaviour of a particular fluid. Many models have been used to represent the flow behaviour of nonNewtonian fluids (STEFFE, 1996). Some of the most widely used rheological models are the Power Law, with two parameters (consistency coefficient and flow behaviour index), Casson, with two parameters (Cassons viscosity and yield stress), and the Herschel-Bulkley (H-B) and MizrahiBerk (MB) models, with three parameters (consistency coefficient, flow behaviour index and yield stress). In this work, the experimental data were statistically evaluated and fitted according to the rheological models of Mizrahi-Berk (equation 1), Herschel-Bulkley (equation 2) and Power Law (equation 3). The rheological model of Ostwald-De-Waele, or power law, is used to characterize the behaviour of juices and fruit pulps because it fits the experimental data well, being a simple model and having wide technological application. The Mizrahi-Berk and Herschel-Bulkley models were also chosen due to their reliability in fitting data and because they include the yield stress term. Mizrahi-Berk model: = K oM + K M nM where: = Shear stress (Pa) KoM = Square-root of the yield stress (Pa) = Shear rate (s1) KM = Consistency coefficient (Pa.sn) nM = Flow behaviour index (dimensionless) Herschel-Bulkley model = oH + K H nH where: = Shear stress (Pa) 0H = Yield stress (Pa) = Shear Rate (s1) KH = Consistency coefficient (Pa.sn) nH = Flow behaviour index (dimensionless) Power Law model = K n (3)
#

where: = Shear stress (Pa) = Shear Rate (s1) K = Consistency coefficient (Pa.sn) n = Flow behaviour index (dimensionless) In order to obtain the rheological (o, n and K) and statistical parameters (R2 and 2) the Software Origin 7.0 (OriginLab Corporation, MA, USA) was used. The choice of the most appropriate model was based on the statistical parameters of the determination coefficient (R2), chi-square (2) and the sum of the squared residuals (SSR). The model that best fits the data is that with the highest values for the determination coefficient (R2) and lowest values for chi-square (2) and the sum of the squared residuals (SSR). 2.4.1 Influence of temperature on apparent viscosity The influence of temperature on the apparent viscosity of non-Newtonian fluids may be expressed in terms of an Arrhenius-type equation (equation 4), involving the absolute temperature (T), the universal gas constant R, the preexponential factor (o) and the energy of activation for viscosity (Ea) (STEFFE, 1996). A shear rate of 50s1 was chosen since this is the speed used in the pumping (start pump) and agitation processes, according to BRANCO (1995). ap = 0e RT
Ea

(4)

(1)

3. RESULTS AND DISCUSSION

3.1 Chemical and physical characteristics The chemical and physical characteristics of the blackberry pulp are shown in Table 1. The pulp showed a soluble solid content of 5.37 oBrix. This result is in agreement with that of ANTUNES et al., 2003 during their study on the post-harvest conservation of blackberry fruits. The value for titratable acidity was lower than those found by GRANADA et al. (2001), which may be explained by the physiological condition of the plant (season and place of cultivation). Regarding moisture and pH, the values found in the analyses were typical of tropical fruits. TABLE 1. Physical-chemical composition of the blackberry pulp.
Parameters pH Soluble solids Moisture (%)
Expressed in citric acid.

(2)

Experimental values 3.20 5.37 0.85 89.00

(oBrix)

Titratable acidity (g/100g)

Braz. J. Food Technol., v. 9, n. 4, p. 291-296, out./dez. 2006

293

haminiuk, C. W. I. et al.

Rheological Characterization of Blackberry Pulp

3.2 Rheological behavior of the pulp Tables 2, 3 and 4 present the rheological parameters of the whole blackberry pulp. From the industrial point of view, the three models were considered suitable to represent the rheological data of the blackberry pulp due to the high values of the determination coefficient. However the Herschel-Bulkley model was chosen to fit the experimental data in this work due to its characteristics of being a full model that could describe all the rheological parameters (yield stress, consistency coefficient and flow behaviour index) well, when compared to the Power Law model (two parameters model) that does not present the yield stress term. Yield stress is an important quality control parameter in industrial processes, particularly for comparing the overall characteristics of products made on different production lines (HAMINIUK et al., 2006a). The experimental data were in better agreement with the Herschel-Bulkley model than with the Mizrahi-Berk and Power Law models, since the H-B model showed values of R2 closer to one and values of 2 and SSR closer to zero. All the estimates and fits were significant at 95% of probability. As shown in Table 3, blackberry pulp showed shear thinning behaviour, the values for the flow behaviour index (nH) being less than 1 (nH<1) at all temperatures. The same TABLE 2. Mizrahi-Berk model parameters for whole blackberry pulp.
Temperature (C) 10 20 30 40 50 60 Yield stress (oM) (Pa) 0.34 0.45 0.87 0.62 0.51 0.66 Consistency coefficient KM (Pa sn) 1.61 1.36 0.21 0.38 0.43 0.12

behaviour was found in previous studies carried out with mango pulp (VIDAL, 2000; SUGAI, 2002), guava pulp (FERREIRA et al., 2002) and Ara pulp (HAMINIUK et al., 2006b). However, a defined tendency for the yield stress and flow behaviour index with increase in temperature was not verified. According to KROKIDA et al., (2001) the heat treatment has a major effect on the consistency coefficient (K) of non-Newtonian fluid foods, analogous to the effect on Newtonian viscosity (). The flow behaviour index (n) was slightly affected by temperature (with a small increase at high temperatures). For the Herschel-Bulkley model, the determination coefficient (R2) values were higher than 0.99 and the chi-square (2) values lower than 0.01 at all temperatures (Table 3). These results show a good fit for the Herschel-Bulkley model. Figure 1 represents the relation between shear stress and shear rate at all the temperatures studied with whole blackberry pulp. The marked points represent the average values for the experimental data of the rheograms and the continuous lines are the fitted results calculated using the Herschel-Bulkley model. It can be observed that for a constant shear rate value, the shear stress value decreased with increase in temperature.

Flow behaviour index nM (dimensionless) 0.18 0.19 0.47 0.34 0.30 0.52

2 0.02 0.00 0.03 0.01 0.00 0.02

SSR 0.07 0.20 0.11 0.37 0.13 0.14

R2 0.99 0.97 0.99 0.98 0.97 0.98

TABLE 3. Herschel-Bulkley model parameters for whole blackberry pulp.

Temperature (C) 10 20 30 40 50 60 Yield stress (oH) (Pa) 0.35 0.29 1.00 0.57 0.45 0.54 Consistency coefficient KH (Pa sn) 1.95 1.12 0.24 0.44 0.45 0.09 Flow behaviour index nH (dimensionless) 0.38 0.44 0.70 0.55 0.50 0.77 2 0.00 0.00 0.00 0.01 0.00 0.00 SSR 0.07 0.21 0.11 0.38 0.13 0.14 R2 0.99 0.99 0.99 0.99 0.99 0.99

TABLE 4. Power Law model parameters for whole blackberry pulp.

Temperature (C) 10 20 30 40 50 60 Consistency coefficient K (Pa sn) 1.72 0.95 0.69 0.75 0.72 0.31 Flow behaviour index n (dimensionless) 0.41 0.48 0.50 0.44 0.42 0.53 2 0.00 0.00 0.01 0.01 0.00 0.01 SSR 0.08 0.22 0.38 0.42 0.15 0.24 R2 0.99 0.99 0.99 0.97 0.99 0.98

Braz. J. Food Technol., v. 9, n. 4, p. 291-296, out./dez. 2006

294

haminiuk, C. W. I. et al.

Rheological Characterization of Blackberry Pulp

FIGURE 1. Relation between shear stress and shear rate for the blackberry pulp fitted according to the Herschel-Bulkley model. The apparent viscosity of the blackberry pulp decreased with increases in temperature and shear rate until the Newtonian platform was reached. When shear force, associated with temperature, was applied, the particles could rearrange themselves in a direction parallel to the shear force, and big particles could break into small particles. The particles flowed easily as a result of the resistance arising from particleparticle interactions, which resulted in a decrease in viscosity (CHARM, 1962). After a sharp reduction, the apparent viscosity changed slightly and became steady at higher shear rates. This could be related to the reduction in size of the colloidal aggregates as the shear rate increased (IBANOGLU, 2002). Several researchers have reported that the decrease in viscosity of fruit pulps is a result of the heat treatment (HAMINIUK et al., 2006b, STEFFE, 1996, SILVA et al., 2005, KAYA et al., 2005). From an industrial point of view, the decrease in viscosity facilitates pulp flow and heat exchange during processing. It is known that fluids with lower viscosity have lower head loss during flow, resulting in a decreased energy demand for the process. The effect of temperature on the apparent viscosity of fluid foods at a constant shear rate can be described by the Arrhenius equation (RAO & TATTIYAKUL, 1999), in which the apparent viscosity decreases in an exponential function with temperature. The Arrhenius model gave a good description of the temperature effect on apparent viscosity in the whole blackberry pulp at a constant shear rate of 50s1, as can be seen in Figure 2. The activation energy calculated for the whole blackberry pulp was 18.27 kJmol1, with a determination coefficient (R2) of 0.97 and a standard error of 0.06. It is not always easy to compare the values for the activation energy of different fluid food, mostly because they are obtained at different concentrations and shear rates. In addition, the activation energy value indicates the sensitivity of the apparent viscosity to temperature changes. Higher activation energy means that the apparent viscosity is relatively more sensitive to temperature change (KAYA et al., 2005). FIGURE 2. Effect of temperature on the apparent viscosity of whole blackberry pulp.

4. CONCLUSIONS
In the light of the results, it can be stated that the rheological behaviour of whole blackberry pulp in a temperature range from 10C to 60C was adequately described by the Herschel-Bulkley model, showing a non-Newtonian shear thinning behaviour (nH<1). The yield stress (o) flow behaviour index (nH) and consistency coefficient (KH) were significantly affected by temperature. The apparent viscosity decreased with increase in shear rate and temperature. The Arrhenius equation represented the effect of temperature on the apparent viscosity of the pulp well, and the activation energy value obtained at a constant shear rate of 50s1 was 18.27 kJmol1.

REFERENCES
A. O. A. C. Official methods of analysis. Arlington: Association of official analytical chemists, 2000. AHMED, J. Rheological behavior and color changes of ginger paste during storage. International Journal of Food Science and Technology, 39(3), 325-330, 2004. ANTUNES, L. E. C. Amora-preta: Nova opo de cultivo no Brasil. Cincia Rural, v.32, n.1, p.151-158, 2002. ANTUNES, L. E. C.; et al. Conservao ps-colheita de frutos de amoreira-preta. Pesquisa Agropecuria Brasileira, V.38, n.3, pp.413-419, 2003. BIBVIRT, Biblioteca Virtual do Estudante de lngua portuguesa. USP (Universidade de So Paulo). Acessed: 16/09/2005, Available on-line: www.bibvirt.futuro.usp.br/especiais/frutasnobrasil/amora.html BRANCO, I. G. Suco de laranja concentrado comportamento reolgico a baixas temperaturas (Dissertao de Mestrado) Faculdade de Engenharia de Alimentos, UNICAMP , 1995, 91p.

Braz. J. Food Technol., v. 9, n. 4, p. 291-296, out./dez. 2006

295

haminiuk, C. W. I. et al.

Rheological Characterization of Blackberry Pulp

CHARM, S. E. The nature of role of fluid consistency in food engineering applications advance, Food Research, v.11, p.356361, 1962. FERREIRA, G. M.; et al. Efeito da temperatura no comportamento reolgico das polpas de caju e goiaba. Revista de Cincias Exatas e Naturais, v.4, n.2, p.175-184, 2002. GRANADA, G.L.; et al. Caracterizao qumica e sensorial de sucos clarificados de amora-preta (Rubus spp. L), Revista Brasileira de Agrocincia, v.7, p.143-147, 2001. HAMINIUK, C. W. I.; et al. Rheological properties of Butia pulp. International Journal of Food Engineering, V. 2, n.2, pp. 1-12, 2006. HAMINIUK, C.W. I.; et al. Influence of temperature on the rheological behavior of whole Ara pulp ( Psidium cattleianum sabine ), Lebensmittel-Wissenchaft und Technologie Food Science and Technology, V. 39, pp. 426-430, 2006. IBANOGLU, E. Rheological behavior of whey protein stabilized emulsions in the presence of gum arabic, Journal of Food Engineering, v.52, p.273277, 2002. IBARZ, A.; et al. Rheology of clarified passion fruit juices, Fruit processing, v. 6, n.8, p.330-333, 1996. KAYA, A.; SZER, N. Rheological behavior of sour pomegranate juice concentrates (Punica granatum L), International Journal of Food Science and Technology, v.40, p.223-227, 2005.

KROKIDA, M. K.; et al. Rheological properties of fluid fruit and vegetable puree products: compilation of literature data, International Journal of Food Properties, V. 4. n.2, pp. 179-200, 2001. MARCOTTE, A. R. T.; et al. Rheological properties of selected hydrocolloids as a function of concentration and temperature, Food Research International, v.34, pp. 695703, 2001. RAO, M. A.; TATTIYAKUL, J. Granule size and rheological behavior of heated tapioca starch dispersions, Carbohydrate Polymers, v.38, p. 123132, 1999. SANTOS, A. M.; et al. Coleo Plantar - A Cultura da Amora-Preta, Braslia: EMBRAPAS-PI, v. 1, n.33, p 28-9, 1996. SILVA, F. C.; et al. Reologia do suco de acerola: Efeitos da Concentrao e Temperatura, Cincia e Tecnologia de Alimentos, v. 25, n.1, p. 121-126, 2005. STEFFE, J. F . Rheological methods in food process engineering, (2nd ed), MI: Freeman Press, 1996, 418p. SUGAI, A. Y. Processamento descontnuo de pur de manga (Magifera indica Linn), variedade Haden: estudo da viabilidade do produto para pronto consumo, (Dissertao de Mestrado) Escola Politcnica, Faculdade de Engenharia Qumica, USP , 2002, 82p. VIDAL, J. R. M. B. Comportamento reolgico da polpa de manga (Mangfera indica L-Keitt), (Tese de Doutorado) Faculdade de Engenharia de Alimentos, UNICAMP , 2000, 159p.

Braz. J. Food Technol., v. 9, n. 4, p. 291-296, out./dez. 2006

296