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Published:20 June 2008,
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FENG Ligang, JIA Yuxi, CHEN Xiliang, AN Lijia. FINITE ELEMENT SIMULATION OF THE PHYSICAL GELATION OF RENNET CASEIN. [J]. Acta Polymerica Sinica (6):529-536(2008)
FENG Ligang, JIA Yuxi, CHEN Xiliang, AN Lijia. FINITE ELEMENT SIMULATION OF THE PHYSICAL GELATION OF RENNET CASEIN. [J]. Acta Polymerica Sinica (6):529-536(2008) DOI: 10.3724/SP.J.1105.2008.00529.
以酶凝干酪素的凝胶化过程为对象,利用有限元方法数值分析了在凝胶化过程中温度场的空间分布和时间演变规律.在此基础上,基于一阶的凝胶化动力学方程,数值模拟了凝胶体系的复剪切模量场,进而分析了材料配方、体系尺寸与冷却方案对复剪切模量场的影响规律.模拟结果表明,由于热阻的差异,体系表面的冷却速率大于内部,表面首先发生凝胶化;而由于预凝胶化阶段的平均冷却速率决定了无穷复剪切模量的值,最终体系内部的复剪切模量超过表面的.
A physical gel is a three-dimensional network of polymer chains cross-linked by physical junctions
and it can arise either as the result of a phase transition or through some specific molecular association or as a result of entanglements. Due to the complexity of the inner structure and gelation mechanism
it is difficult to obtain purposefully polymer physical gel materials with specific constitution and properties. Thus
the controllable preparation and application of polymer physical gels are a long-term work.As a numerical simulation method in macro-scale the finite element method has been used to the study of chemical gelation
but rarely to physical gelation presently. The reasons may be: compared with chemical gels the gelation process of physical gels is more complex resulting from the bigger complexity of the system composition and physical interactions. Several kinds of interactions and steps may be involved in one physical gelation process. And under different conditions the gelation mechanisms are frequently different. By now the understanding of the gelation mechanisms of many kinds of physical gels is far from being intensive; the phenomenological gelation kinetics models are usually nonlinear; the theory describing the relation between the microscopic and mesoscopic structure and the macroscopic properties is still immature. For all the factors mentioned above the numerical simulation of physical gelation process in macro-scale comes to be a difficult work. In order to optimize raw material formulation and physical gelation conditions
and then obtain polymer physical gels according to requirements
the spatial distribution and time evolution characteristics of the temperature field during the gelation process were studied via the finite element method. On the basis of the temperature field calculated
the complex shear modulus field of gel system was numerically simulated according to a first-order gelation kinetic equation
and the effects of raw material concentration
sample size and cooling modes on the physical gelation were discussed.Rennet casein gel is a kind of particle gel
whose formation is controlled by physical forces including steric-hydration force and van der Waals force
and whose structure and properties are influenced by many parameters including emulsifying salts
pH
thermal and shear history.The formation process of the gel network can be divided into three steps
molecules-particles-flocs-network. Casein flocs are fractal objects that can be partially filled by the constructing units (particles).The fractal dimension of the flocs and the size of the particles are two important parameters determining the gel microscopic structure and rheological properties. Experimental results show that cooling modes will influence the rheological properties of the gel through influencing the size of the particles. The formation of rennet casein gels is a first-order kinetics process.Three examples were studied. The raw material concentrations of example 1 and example 2 are both 18%
but the sample size of the former is five times as that of the latter; the raw material concentration of example 3 is 25%
and the sample size is same with example 1. The gel zone is divided into 136 unites and 163 nodes; the prototype zone is divided into 28 unites and 40 nodes; four representative nodes were selected in the gel zone
and were emphatically studied. The initial system temperature is set at 80℃
and cooling modes include (1) environmental temperature declines from 80℃ to 5℃
and cooling rates are respectively 0.5 K/min
0.25 K/min
0.1 K/min
0.05 K/min
0.025 K/min; (2) environmental temperature maintains 5℃.The simulated results show that (1) the rate of temperature decrease near the surface is larger than that near the center
the gelation occurs on the surface first; as the infinite complex shear modulus is determined by the cooling rate of the pre-gelation phase
the value of the complex shear modulus of the interior exceeds that of the exterior finally. The asymmetric distribution of temperature field results in the asymmetric distribution of mechanical property field of the gel. And with the increase of environmental cooling rate and sample size the asymmetry becomes more obvious.
物理凝胶酶凝干酪素有限元模拟温度场复剪切模量场
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