Caking of powder mixtures of crystalline and amorphous solids E. SCHREYER1, S.

PALZER
1)

Nestl Product Technology Centre, Germany

ABSTRACT
The mechanisms leading to caking of powder are known: To provoke caking crystalline particles have to be exposed for a short time to a relative humidity which is above their critical humidity leading to dissolution. Amorphous particles are sintering together forming a powder cake. However the caking of powder mixes remains difficult to predict. In the current study the caking of mixes of different amorphous solids was investigated. In one series of trials different amorphous substances were mixed in their liquid state, the mix was dried and the obtained cake was crushed into particles and stored at controlled temperature and humidity. In a second trial series two other amorphous substances were mixed in their powdered form by varying concentration of the different components. Following, the different mixes were stored at controlled temperature, humidity and consolidation stress for a pre-defined time. The caking was quantified by performing ring shear tests. The caking of molecular mixes of amorphous substances (mixing in the liquid state) could be assessed using the caking index method. The sinter kinetics of such a mix could be predicted knowing the glass transition temperature of the mix and using it to estimate the viscosity of the solid. In case of a powder mix the caking of the mix is not only depending on the thermoplastic properties of the different particles and on the storage conditions but also on the particle diameter and the particle shape, the amount and the distribution of the different components. In case of an approximately equal particle diameter 15-25% of the adhesive component in a powder mix was found to be sufficient to provoke caking of the entire mix.

1. INTRODUCTION
In food industry, particularly in low-moisture and intermediate moisture food, amorphous components are ubiquitous. Food systems are heterogeneous and complex mixtures of carbohydrates, proteins, lipids and water and all of them may exhibit phase transitions while processed or stored[1]. Food powders contain amorphous ingredients in the glassy state such as maltodextrine or yeast extract but also crystalline ingredients such as sodium chloride. As most products are a mix of different substances, it is important to develop knowledge about the behaviour of mixtures containing amorphous and crystalline particles. The fact that food systems are often a complex mixture of different components makes it difficult to predict their behaviour. Moreover during storage and handling, a bulk of powder is exposed to variations in climate conditions (temperature and relative humidity) and the pressure (consolidation stress) is changing. These variations can impair dramatically the properties of the bulk, especially by provoking caking or liquefaction of amorphous ingredients. In case of a powder mix, the properties of the different components of the mix have to be taken into account: particle size, particle shape and concentration of each single component in the mix. Contrary to crystalline substances, amorphous substances do not possess long range arrangement. They do not exhibit a first order transition but a socalled glass transition. According to Le Meste et al.[2], glass transition is the phenomena observed when a glassy material becomes a rubber or a supercooled melt during heating or the reverse changes while

cooling fast. Glass transition occur over a range of temperature, however a single temperature is used to define this transition: the glass transition temperature Tg, usually in the magnitude of 2/3 of the melting temperature Tm[3]. At the glass transition, a Cp jump occurs. This Cp jump can be measured by DSC and the Tg can be taken as the onset, the midpoint or the enset of the Cp jump, or two of these points to evaluate the width of the transition. Amorphous materials are solid and brittle glassy state below their Tg. Above their Tg they show a viscous state with rubbery properties above this temperature[4]. All glass 12 forming material have a viscosity of about 10 Pa.s[3] at Tg. Moisture uptake increases the molecular mobility and thus decreases the viscosity. Therefore water acts as a plasticizer in amorphous matrix and thus decreases Tg leading to stickiness and caking due to the decreasing viscosity[5]. Particles build viscous bridges by viscous flow provoking sintering. Depending on the viscosity, this phenomenon can happen fast. However during storage particles in a bulk are submitted to consolidation stress during a long contact time. In that case, even if the viscosity of the particles remains high, the contact time is long enough to allow the development of sufficient adhesion forces and then the caking[6]. In this work, the influence on caking of the different components of the mix was explored. The caking of binary mixtures of amorphous solids was investigated as a function of time, temperature and consolidation stress. The amount of adhesive material sufficient to provoke caking of a stored bulk was also investigated.

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In a second serial of trials, the caking of binary mixtures of amorphous and crystalline components was investigated. The influence of the storage time, the consolidation stress, the particles size, the amount and the distribution of each component in the mixwas investigated.

2. THEORITICAL BACKGROUND
2.1. Water Plasticization, adhesion mechanisms viscosity and

related to a significant change in their viscosity; if water in the atmosphere diffuses into the matrix. The more wetted the particle is, the more plastic is the behaviour[6]. Thus after a sufficient wetting time, a viscous solution is created at the surface of the particles, allowing viscous flow and material exchange between the particles to take place. This phenomenon is the so-called the sintering process. Rumpf et al.[7] developed a formula, which includes the force Ft applied on the matrix, for calculating the sintering kinetics:

The plasticization of amorphous components by water can be modelled and predicted by the Gordon and Taylor equation (GT)[8]:

2 Ft t x 4 = + 2 a 5 a 5 a

Equation 4

Tg =

k X Tg H 2O + (1 X ) Tg dry k X + (1 X )

Equation 1

Where X is the weight fraction of water, Tgdry the Tg of the dry considered products, TgH2O the Tg of pure water (-135C) and k is the so-called GT constant. So we can observe that the Tg decreases when X increases. While dealing with mixes of similar substances, the Tg of the whole mix can be calculated with the Fox equation[9]:

Where x is the diameter of the bridge, a the diameter of the particle, the surface tension, Ft the force applied on the particle, and the viscosity. A good evaluation of the viscosity from the WLF equation (equation 3) at a given T-Tg allows a good evaluation of the caking velocity. However, this sintering velocity should be the reason for the caking of amorphous materials. 2.2. Ring shear test (RST) as a tool to measure quantitatively the caking

1 w w = 1 + 2 Tg Tg1 Tg 2

Equation 2

Where wi is the mass fraction and Tgi the glass transition temperature for the ith component. The molecules of the component of the blend must be thoroughly dispersed. Above Tg, the viscosity of amorphous matrixes decreases as a function of T-Tg as predicted by the Williams-Landel-Ferry (WLF) equation[10]:

C (T Tg ) log = 1 C + (T Tg ) 2 g

Equation 3

Where is the viscosity at T and g the viscosity at Tg, i.e. 1012 Pa.s. C1 and C2 are constants, determined as C1=-17.44 and C2=51.6K[10]. This decrease of the viscosity as a function of T-Tg leads to an increase molecular mobility and thus to adhesion phenomenon. Adhesion mechanisms can be divided in three types: - Increase of the contact surface due to the viscoelastic deformation - Liquid bridges due to capillary forces - Viscous bridges due to sintering On the one hand crystalline material submitted to water droplets in the atmosphere are partially dissolved at their surface but their viscosity does not vary to a great extend[6]. Thus capillary forces are dominant and when two particles collide, they will lead to the formation of a liquid bridge. On the other hand; as amorphous material shows a viscoelastic behaviour

Karel and Lund in 2003 defined the caking as an undesirable process where free flowing powders are transformed into lumps and aggregates, and eventually into a sticky viscous mass[12]. A simple caking index can be used to evaluate visually the caking severity. This index describes the flowability of the powder in a qualitative way, from the free flowable stage 1 to the lumping onset step 4 and finally the hard cake stage 9. This caking index is based on visual observations and thus is greatly related to the sensitivity of the operator and his experience. Thus the ring shear tester was used to assess quantitatively the caking of powder mixtures. The bulk sample is presheared to a define consolidation stress 1 with a constant shear stress 1 until it reaches the steady-state flow. Then it is released and sheared with a define stress again until it reaches the incipient flow at the normal stress . Repeating this operation with the same 1 and different, but smaller, , delivers the flow function or a yield locus without time consolidation as shown in fig 1.
Incipient flow Steadystate flow preshear shear time c 1 Yield locus

Preshear point

Fig.1: Shear stresses and yield locus (Schulze)[13] The flowability of the powder can also be assessed thanks to the flow function ffc, corresponding to 1

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divided by . The classification of flowability of powders by ffc was published by Jenike in 1970[14]: - ffc<2: - 2<ffc<4: - 4<ffc<10: - 10<ffc: Very cohesive and non flowing Cohesive Easy flowing Free flowing

Time consolidation is the reduction of flowability due to storage and pressure applied on a bulk during storage. This is particularly important in culinary powders, where the bulk material is usually stored in bulk bags of about 1m high. This phenomenon can be assessed with ring shear test, applying a preshear corresponding to the stress of the storage height and storing the bulk with this stress for a determined time before measuring it again. This allows quantitative measurements of flowability and thus of the caking degree of a bulk.

molecular mix has a great influence on the caking severity: the higher the amount is, the worse is the flowability of the particulated molecular mix. After 24h, the water activity at the surface of the particulated molecular mix was constant, but themixes were not at equilibrium. Thus water diffusion was still happening during the storage leading to a higher severity of caking. 9
8

169 h storage at 30 C/ 70% rH

Caking Index / 6

72 h storage at 30 C/ 70% rH

3. EXPERIMENTAL SET-UP
3.1. Molecular mix Preparation of the blends: Blends of maltodextrine DE6 and dextrose syrup (maltodextrine) DE21 with different weight ratios (from 10% to 90%) were prepared by weighing each powder fractions accordingly and add water to create an homogeneous dissolution before drying in a vacuum oven for 48h at 85C. The dry mix was then milled to particles size of 0.25mm. Storage procedure: 15 g of each blend was stored into flat pans at 30C/70% RH. The caking intensity was measured by a predefined caking index. In addition the Tg, the water content and the water activity of each sample were measured over a period of 168h for each samples. 3.2. Powder mix Preparation of the mixes: the 2 amorphous powders, dextrose syrup (maltodextrine) DE21 and yeast extract, were mixed in 5 ratios 100%/0%, 75%/25%, 50%/50%, 25%/75% and 0%/100% respectively. The ratios were determined according to the specific surface area (determined with a laser particle seizer) of each component. The powders were mixed together (30s at 160U/min) in a laboratory mixer. Storage procedure: the powder mixes were exposed at 35% relative humidity and at a temperature of 25C during 96h with consolidation weights representing a storage height of 0.5m, 1.0m and 2.0m. The flowability and the time consolidation were assessed by ring shear test for each consolidation stresses chosen.

24 h storage at 30 C/ 70% rH

initial powder (0 h storage)

1 0 10 20 30 40 50 60 70 80 90 100 Amount of glucose syrup DE21 (in a wet mix with DE6) / %

Fig. 2: Caking intensity as a function of the amount of glucose syrup DE21 and storage time Calculating the Tg of the molecular mix using the Fox equation (equation 2) and measuring the water content, it was possible to apply the Gordon and Taylor model (equation 1). Then it was possible to find the Tg of the mix and to link it with the caking intensity and the amount of each component in the mix. Compared to the experimental measurements of Tg by DSC, it fits very well with the measured data. As in the case of a molecular mix, there was no influence of the particle size and shape of each component, it is possible to predict the Tg of a mix of similar substances using the Fox and the Gordon and Taylor equation. The caking of a molecular mix was observed for a mass ratio of 15% of the adhesive component. 4.2. Powder mix The ring shear test measurements at each 1 allows the calculation of ffc according to Jenike[14]. On figure 3, the resulting ffc curves after storage are represented. At aw=0.35, the Tg of the dextrose syrup DE21 is 60C and the one from the yeast extract is 5C. This means that the yeast extract will be in the rubbery state whilst the maltodextrine remains in the glassy state. Thus yeast extract alone is responsible of the caking of the powder mix. Figure 3 shows that the higher the amount of the more adhesive material is, the greater is the cohesiveness and the caking. Alone, the yeast extract at aw=0.35 is already non free flowing. From the ffc curves, it can be concluded that 25% of this adhesive material is sufficient to provoke caking after consolidation for 96h at every consolidation stresses. The ffc value of this mix at initial aw is superior to 10, so the powder mix is free

4. RESULTS
4.1. Molecular mix The water activities of the blends were at 0.65 after 24h. The Tg of the maltodextrine DE6 is higher than the one from DE21 due to a higher molecular weight. Figure 2 shows that the amount of glucose syrup DE21 in a

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flowable. But at aw=0.35, as soon as the yeast extract is rubbery, the powder mix exhibits a ffc value between 2 and 4. This means that the powder mix is not anymore flowable and has become cohesive.
6000

[3]

ffc=1

ffc=2
100% dextrose syrup initial

[4]
75% dextrose syrup initial 50% dextrose syrup initial

Unconfined yield strength c /Pall c/Pa

5000

4000

[5]

25% dextrose syrup initial 0% dextrose syrup initial 100% dextrose syrup aw=0.35

3000

ffc=4

2000

75% dextrose syrup aw=0.35 50% dextrose syrup aw=0.35 25% dextrose syrup aw=0.35 0% dextrose syrup aw=0.35

[6]

ffc=10
1000

0 0 2000 4000 6000 8000 10000 12000

Principle consolidation stress 1 / Pall

Fig.3: Ffc values of powder mix at initial aw and at aw=0.35

[7]

5. CONCLUSION
Many parameters have to be considered while talking about caking such as time, consolidation stress, T-Tg, RH and aw. The combination of existing models in the case of a molecular mix of similar substances was proven to be a suitable tool to predict caking. It is possible to calculate the Tg of such a mix using the Fox and the Gordon and Taylor models. In the case of a powder mix, ring shear tester was proven to be an efficient tool to assess the caking intensity. In both types of mixes, molecular or powder mixes, the amount of adhesive component sufficient to provoke the caking of the entire mix was 15% to 25%. Further investigations are currently run to evaluate the caking of a mix of crystalline and amorphous substances as a function of particles size. This will provide an evaluation on the minimum amount of adhesive material sufficient to provoke the caking of the entire mix as a function of the particle size of each component of the mix. This will also show the influence of crystalline particles on the caking velocity. [8]

[9]

[10]

[11]

[12]

[13]

REFERENCES:
[14]
[1] [2] Y. H. Roos, Phase Transitions in Foods, Academic Press, 1995. M. Le Meste, D. Champion, G. Roudaut, G. Blond, and D. Simatos, Glass Transition and Food Technology: A Critical Appraisal, Journal of Food Science 67 (2002).

C. A. Angell, K. L. Ngai, G. B. McKenna, P. F. McMillan, and S. W. Martin, Relaxation in glassforming liquids and amorphous solids, Journal of Applied Physics 88 (2000). Y. H. Roos and M. Karel, Plasticizing Effect of Water on Thermal Behavior and Crystallization of Amorphous Food Models, Journal of Food Science 56 (1991). L. Slade and H. Levine, Beyond water activity: recent advances based on an alternative approach to the assessment of food quality and safety., Critical reviews in food science and nutrition 30 (1991). S. Palzer, The effect of glass transition on the desired and undesired agglomeration of amorphous food powders, Chemical Engineering Science Granulation across the length scales - 2nd International Workshop on Granulation (2005). H. Rumpf, K. Sommer, and K. Steier, Mechanismen der Haftkraftverstrkung bei der Partikelhaftung durch plastisches Verformen, Sintern und viskoelatisches Fliessen, Chemie Ingenieur Technik 48 (1976). M. Gordon and J. S. Taylor, Ideal copolymers and the second-order transitions of synthetic rubbers. I. Non-crystalline copolymers, Journal of Applied Chemistry 2 (1952) T. G. Fox, Influence of diluent and copolymer composition on the glass transition temperature of copolymers, Bull. Am. Phys. Soc. 1 (1965) M. L. Williams, R. F. Landel, and J. D. Ferry, The temperature dependance of relaxation mechanisms in amorphous polymers and other glass-forming liquids, Journal of the American Chemical Society 77 (1955). M. Peleg and C. H. Mannheim, The mechanism of caking of powdered onion, J. Food Proc. & Pres 1 (1977) 3. M. Karel, O. R. Fennema, and D. B. Lund, Principle of Food Science: Part II. Physical Principles of Food Preservation, Marcel Dekker Edition, New York, 2003. D. Schulze, Measuring powder flowability: A comparison of test methods Part I, Powder and Bulk Engineering 4 (1996) 45.

A. W. Jenike, Storage and Flow of solids, Engineering Experiment Station, University of Utah, Salt Lake City Bulletin 123 (1970)

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