氢化棉籽油等温结晶动力学的研究

用脉冲核磁共振(PNMR)法测定了两种氢化条件下氢化棉籽油的固体脂肪含量(SFC)。根据不同温度下固体脂肪含量随时间的变化绘制等温结晶曲线。等温结晶曲线有两种:双曲线和反曲线。当过冷却度高时,结晶曲线为双曲线;当过冷却度低时,结晶曲线为反曲线。用Avrami方程进行氢化棉籽油的等温结晶动力学分析,结果表明:过冷却度与晶体的成核和生长方式有显著相关性。当过冷却度高时,结晶常数较小,晶体成核和生长速率快;当过冷却度低时,结晶常数较大,晶体成核和生长速率慢。研究氢化棉籽油的结晶行为对人造奶油、起酥油和可可脂替代品基料油的选择有一定的指导意义。     

Induction Time of Crystallization in Vegetable Oils, Comparative Measurements by Differential Scanning Calorimetry and Diffusive Light Scattering

ABSTRACT: In this work we compared the induction time of crystallization (τ_i. measured by DSC (τ_iDSC) and scanning diffusive light-scattering (SDLS, τ_iSDLS) in a vegetable oil blend. Several crystallization temperatures and cooling rates (1,10, and 30 °C/min) were investigated. Additionally, rheograms obtained during the crystallization of the oil blends were obtained to differentiate the stages of nucleation and crystal growth. The results obtained showed that independent of cooling rate and crystallization temperature, SDLS provided an earlier detection of triacylglycerides'(TAGS) nucleation than DSC. Furthermore, τ_iSDLS was more consistent (that is, lower standard deviation) than τ_iDSC particularly at high crystallization temperatures and cooling rates. The rheograms showed that τ_iDSC involves a measurement of crystal growth, while τ_iSDLS is associated with the early formation of a solid phase in the oil blend (that is, TAGS nucleation). When the Fisher-Turnbull equation was therefore used to calculate the free energy of nucleation (ΔG_c), τ_iSDLS provided a better estimate of ΔG_c than that obtained by τ_iDSC     

Isothermal batch crystallization of alpha-lactose: A kinetic model combining mutarotation,nucleation and growth steps

A kinetic model combining first-order differential equations of the three consecutive steps of lactose crystallization, i.e., mutarotation, nucleation and crystal growth rate, was developed. Numerical solutions successfully fitted the variations of crystal mass growth rate as a function of lactose concentration during unseeded isothermal batch crystallization, at different initial lactose concentrations and temperatures. The model allowed the induction phase and the influence of seeding to be simulated by taking into account the dependency of crystal growth rate on total crystal surface area and, consequently, on nucleation rate. The proposed model highlights the large influence of the mutarotation step, even in unseeded crystallization kinetics. The effects of high lactose supersaturations that prevail at industrial scale during whey powder manufacturing and the effects of alkaline pH (9.5) on lactose crystallization kinetic were successfully predicted.     

L-抗坏血酸棕榈酸酯对椰子油结晶行为的影响

以椰子油作为模型，利用结晶动力学方程、X-射线衍射（XRD）分析、热力学分析以及偏振光显微镜（PLM）观察等方法研究了L-抗坏血酸棕榈酸酯（L-AP）对椰子油结晶行为的影响。结果表明：L-AP提高了椰子油的结晶速率，改变了晶体成核和生长机制；L-AP以“晶种”的方式诱导椰子油的结晶，对其结晶过程产生了促进作用； L-AP没有改变椰子油晶体的晶型以及堆积方式，却增加了晶体纳米片层的厚度；随着L-AP添加量的增加，晶体结构更加致密有序。     

Avrami法研究微量司盘85对棕榈油结晶动力学的影响

采用差示扫描量热仪（differential scanning calorimetry,DSC）分析棕榈油及其与司盘85混合物的等温结晶及熔融行为,通过Hoffman-Weeks法计算出样品的平衡熔点。采用Avrami方程进一步研究样品的等温结晶动力学,从而得到与结晶动力学相关的参数。结果表明：DSC分析显示司盘85可明显降低棕榈油的结晶率和成核速率。通过Hoffman-Weeks法和Avrami方程求得的温度数据具有良好的线性关系,表明Avrami方程适用于棕榈油结晶过程的研究,但在结晶后期出现偏离。拟合得到的Avrami指数（n）在2.37～2.77之间,可知样品二维和三维晶体生长同时存在;结晶速率（k）和半结晶时间（t1/2）随着添加剂的添加均变小。     

糙米重组米的回生特性

采用差示扫描量热仪和质构仪研究了糙米重组米的Avrami方程及硬度,探讨了糙米重组米的回生特性。结果表明：糙米重组米的Avrami参数n值均小于1,以一次成核的方式结晶;糙米重组米淀粉中的直链淀粉含量对Avrami参数n有非常显著的影响,对支链淀粉的最大回生度没有显著的影响;参数n和结晶速率k之间成极显著负相关;最大回生度与结晶速率k成显著负相关;硬度可以有效地反映出糙米重组米的回生程度。     

椰子油在温度梯度场中定向结晶动力学

目的：了解椰子油在温度梯度场中的结晶行为过程,优化结晶参数（如结晶温度、熔点、冷却速率、搅拌速率等）,以获得具有特种性能的分提产品。方法：以椰子油为原料,采用分级熔融结晶的方法,考察不同温度梯度场下椰子油的定向结晶行为。结果：Avrami方程可以基本适用椰子油的结晶过程,但在结晶后期,均会出现部分偏离。同时,椰子油结晶过程中,其晶体生长方式以及晶体形状随着温度的不同均会有所变化。结论：温度梯度法可以有效得到所需的椰子油分提产品。     

The cooling rate effect on the microstructure and rheological properties of blends of cocoa butter with vegetable oils

The elasticity (G′) and yield stress (σ¹) of blends of cocoa butter (CB) in vegetable oils (i.e., 30% CB/canola and 30% CB/soybean oil) crystallized at temperatures (T_Cr) between 9.5 °C and 13.5 °C and two cooling rates (1 °C/min and 5 °C/min) were determined, evaluating their relationship with parameters associated with the formation and structural organization of the crystal network [i.e., solid fat content (SFC), Avrami index, crystallization rate, fractal dimension (D)]. The results showed that T_Cr and cooling rate had a different effect for each blend on the three-dimensional organization of the crystal network, and on the proportion and size of β′ and β crystals. Thus, under low supercooling conditions at both cooling rates, the crystallized CB/canola oil blend was formed by a mixture of small β′ and large β crystals that provided high G′ and σ¹ at low SFC (i.e., 20.5–20.9%) and D (i.e., 1.66–1.72) values. The CB/soybean oil blend achieved similar G′ and σ¹ independent of cooling rate only at high supercooling. In this case, the crystal network was formed mainly by small β′ crystals with SFC (i.e., 25.4–26.3%) and D (i.e., 2.86–2.79) values higher (P < 0.05) than in the CB/canola oil blend at low supercooling.     

Crystallization kinetics of emulsified triglycerides

Nucleation and crystal growth process of triglycerides in water emulsions composed of trimyristin (c l4:0) admixed with 0, 40, and 80 ml litre^?1 trilaurin (c 12:0) (expressed v per total v emulsion) were followed with NMR (nuclear magnetic resonance) and DSC (differential scanning calorimetry). Mathematical analysis of the time dependence of the phase changes and thermal data distinguished two distinct ‘apparent’ kinetic phases. These phases were tentatively referred to as nucleation and crystal growth. With 40 and 80 ml litre^?1 trilaurin (NMR data at 293 K) nucleation and crystal growth phases of trimyristin were simulated with zero order and second order rate expressions, respectively. Relative to these mixtures, pure trimyristin nucleation was delayed in the initial phase, but crystal growth occurred with fast homogeneous nucleation and slower growth in the second phase. Statistical analyses indicated that homogeneous nucleation similarly occurred when 40 or 80 ml litre^?1 trilaurin was admixed with trimyristin. NMR resolution made it possible to follow the crystallization phenomena in different locations of the crystallization vessel effectively in situ and undisturbed. Statistical analyses in this case revealed a significant trilaurin-location interaction confirming that the rate of nucleation processes was affected both by the concentration of trilaurin and the heat transfer properties of the sample and vessel. The time-location interactions were not significant, confirming the hypothesis that in the absence of tilaurin, zero order nucleation did not occur in the first phase.     

Crystallization kinetics of palm oil in blends with palm-based diacylglycerol

Crystallization kinetics of palm oil (PO) in the presence of different concentrations (2, 5, 10, 30 and, 50% w/w) of palm-based diacylglycerol (PB-DAG) were investigated over different ranges of crystallization temperatures. Addition of 30 and 50% (w/w) of PB-DAG (high concentrations) increased significantly (P < 0.05) the melting point and crystallization onset while addition of 2 and 5% PB-DAG did not have significant (P > 0.05) effect. PO and PO blends with 2 and 5% of PB-DAG showed crystal transformation at crystallization temperatures (T_Cr) of 26, 26, 26.5 °C, respectively as reflected in corresponding changes of the Avrami parameters at below and above these T_Cr. This was especially evident for the blends containing 2 and 5% of PB-DAG. Individual comparison of induction time (T_i), Avrami exponent (n), Avrami constant (k) and half-time of crystallization (t_1/2) of blends classified under various supercooling ranges based on the supercooling closeness (± 0.1 °C), showed that addition of 5% of PB-DAG in most of the supercooling ranges significantly (P < 0.05) reduced nucleation rate as well as crystal growth velocity of PO. This was reflected in the significantly (P < 0.05) higher T_i and t_1/2 and lower k. Although the presence of 2% of PB-DAG was found to have inhibitory effect on PO crystallization, this effect was not significant (P > 0.05). Mode of crystal growth attributed to n was changed significantly only in presence of 5% of PB-DAG. Furthermore, presence of 10% PB-DAG showed ??'-stabilizing effect on PO. On the other hand, high concentrations of PB-DAG were found to significantly (P < 0.05) reduce T_i as well as t_1/2 and also increase k suggesting their promoting effects on nucleation and crystallization rate of PO even with the close supercoolings. In addition, they changed crystal growth mode of PO. Amongst the different concentrations of PB-DAG investigated, blend containing 50% of PB-DAG as compared to PO, not only, have healthier benefits but also, may have greater potential applications in plastic fat products due to its unique physical properties.     

司盘85对棕榈油结晶过程动力学的影响分析

采用核磁共振仪测定棕榈油及添加0.01%~0.1%司盘85棕榈油的等温结晶行为。采用Avrami方程进一步探究样品的等温结晶动力学,研究司盘85对棕榈油结晶行为的影响。结果表明:棕榈油及添加0.01%~0.1%司盘85棕榈油的Avrami指数在1.422~1.912之间,可知样品的晶体生长为二维;司盘85对棕榈油的结晶过程具有抑制作用,且随着司盘85添加量的增大,其抑制作用增强,表现为结晶速率常数减小,半结晶时间延长。     

Influence of diglycerides on crystallisation of palm oil

Palm oil diglycerides and pure synthetic diglycerides of 1,2‐(2,3‐) and 1,3‐dipalmitoylglycerol, dioleoylglycerol and palmitoyloleoyl glycerol were added to purified triglycerides of palm oil. The crystallisation kinetics of the samples were studied by spectrophotometry, NMR analysis of the solid fat content and by X‐ray diffraction of the crystals obtained at 20°C. Palm oil diglycerides inhibited the nucleation process and retarded the crystal growth rate of palm triglycerides. The effect was less pronounced at a higher degree of supercooling. The extent of inhibition depended on the nature of the diglycerides and the concentration. © 1999 Society of Chemical Industry     

米糠蜡对稻米油基凝胶油形成的影响及动力学

以三级稻米油为基料油,研究了米糠蜡(rice bran wax,RBW)添加量对凝胶油形成特性的影响及凝胶油结晶形成的动力学参数。结果表明:在25℃时,RBW添加量为4%时便可形成凝胶油。随着RBW添加量的增加,凝胶油的硬度明显增加,贮藏30 d后凝胶油硬度变化不显著。凝胶油的固体脂肪含量也随RBW添加量的增加呈增多趋势,凝胶油主要为β′晶体。4%和7%RBW添加量凝胶油晶体为絮状,添加量为10%时凝胶油晶体转变为长枝晶状且密度增大。该凝胶油仅有一个结晶峰,采用Avrami方程模型拟合出的直线具有良好的线性关系(R~2=0.934 31),说明Avrami方程能较好地适用于稻米油基凝胶油结晶过程的研究,得到Avrami指数n为1.396 83,表明该凝胶油的晶体成核为均相瞬时成核并按照一维与二维混合结晶方式生长。     

Dendritic growth of ice crystals during the freezing of beef

The morphology adopted by ice in frozen tissues is accepted as one of the factors responsible for freezing damage. For this reason ice nucleation and growing mechanisms have been extensively studied. However, under the conditions used in the industry, where important temperature gradients exist, the classical analysis of nucleation and growth, depending on the supercooling, is complicated by the dendritic growth of crystals as well as by the possibility of the location of the ice crystal inside or outside the cells. In the present paper experiments which verify the existence of dendritic ice growth during the freezing of beef are described. The dendritic growth rate of ice in beef is measured as a function of the supercooling and an analysis of the expected mechanism, according to freezing conditions, is also provided.     

A review on effect of DC voltage on crystallization process in food systems

Crystallization of water and food systems may be affected by electric and magnetic fields. In this review paper, the crystallization of water and food systems assisted by DC voltage (DC-V) is compiled based on existing literature. Two ways of applying DC-V during electrocrystallization can be identified, namely charge flow (CF) conditions with electrical charges flowing through the matrix and static electric field (SEF) conditions. Both processes have shown to interact with nucleation mechanism by reducing supercooling and favouring a higher nucleation rate. The theoretical calculations show that the application of SEF can modify the free energy of formation of ice nuclei in the water phase. Moreover, SEF application can also enhance heat and mass transfer during crystallization process. Various molecular simulations and experimental studies have shown that SEF aligns the water molecules in its direction by the phenomenon of dielectric polarization, and thus, reduces the degree of supercooling (∆T). The freezing process under SEF produces smaller ice crystals in the food products, resulting in less freeze damage; it is thus expected to minimize cell disruption, to reduce the drip loss, to lessen the protein denaturation, and finally to preserve the texture of the fresh food after thawing. Furthermore, freezing under SEF may help to use less energy intensive freezing conditions (higher set point temperature, low air velocity). As a conclusion, the use of DC-V in the case of crystallization of food systems (especially freezing) offers a new perspective to the food industry.     

Sugar crystallization in food products

A review of the recent literature on crystallization of the commercial sugars (fructose, glucose, lactose, and sucrose) is presented. Topics include: NUCLEATION--The formation of the crystalline phase from supersaturated solutions can occur by either a spontaneous or a forced nucleation mechanism. Recent work on the mechanisms, kinetics, and impact of both heterogeneous and secondary (contact) nucleation is discussed. GROWTH--Recent studies on the mechanisms and kinetics of crystal growth will be reviewed. This discussion includes work on the growth rate dispersion exhibited by these sugars. EFFECTS OF IMPURITIES AND ADDITIVES--The presence of impurities and additives (including mixed sugar systems) affects both the nucleation and growth steps. A discussion of the recent work in this area is included. Emphasis is placed on the relationship between these crystallization phenomena and the solution structure for comparison purposes.     

Insights into the chemistry of new particle formation and growth events in Pittsburgh based on aerosol mass spectrometry

New particle formation and growth events have been observed in several urban areas and are of concern due to their potential negative effects on human health. The main purpose of this study was to investigate the chemistry of ultrafine particles during the growth phase of the frequently observed nucleation events in Pittsburgh (approximately 100 events per year) and therefore infer the mechanisms of new particle growth in the urban troposphere. An Aerodyne aerosol mass spectrometer (AMS) and two SMPS systems were deployed at the U.S. EPA Pittsburgh Supersite during September 2002. Significant nucleation events were observed in 3 out of the 16 days of this deployment, including one of the 10 strongest nucleation events observed in Pittsburgh over a period of 15 months. These events appear to be representative of the climatology of new particle formation and growth in the Pittsburgh region. Distinctive growth of sulfate, ammonium, organics, and nitrate in the ultrafine mode (33-60 nm in a vacuum aerodynamic diameter or approximately 18-33 nm in physical diameter) was observed during each of these three events, with sulfate always being the first (and the fastest) species to increase. Ultrafine ammonium usually increased 10-40 min later than sulfate, causing the ultrafine mode particles to be more acidic during the initial stages of the nucleation events. Significant increase of ultrafine organics often happened after 11:00 a.m., when photochemistry is more intense. This observation coupled with a parallel increase of ultrafine m/z 44, a mass fragment generally representative of oxygenated organic compounds, indicates that secondary organic species contribute significantly to the growth of particles at a relatively later time of the event. Among all these four species, nitrate was always a minor component of the ultrafine particles and contributed the least to the new particle growth.     

Crystallization kinetics of lactose in sytems co-lyofilized with trehalose. Analysis by differential scanning calorimetry

The objective of the present work was to study by differential scanning calorimetry phase/state transitions in model systems of amorphous lactose and lactose co-lyophilized with trehalose. The obtained parameters, such as glass transition temperatures (T_g) and enthalpies of crystallization were employed to test the applicability of different proposed models to predict the behavior of these systems. Thermograms of low moisture lactose–trehalose mixtures showed only one glass transition temperature indicating that compatibility exists between both sugars. The increase of trehalose concentration in the mixture promoted a delay of lactose crystallization in isothermal runs, and of the crystallization temperature (T_cr) in dynamic experiments. The presence of trehalose delayed lactose crystallization, without affecting the T_g value. Several factors (thermodynamic, geometric, kinetics) may modify the molecular environment in the combined systems, affecting nucleation and/or crystal growth. Three models [Arrhenius, Williams–Landel–Ferry (WLF) and Vogel–Tamman–Fulcher (VTF)] were used to study the temperature dependence of the crystallization time. Although experimental points were fitted fairly well by all these models in the range of temperature from 14 to 59 °C above T_g value, the VTF equation appears to apply better for sugars.     

Control of ice crystal nucleation and growth during the food freezing process

Freezing can maintain a low-temperature environment inside food, reducing water activity and preventing microorganism growth. However, when ice crystals are large, present in high amounts, and/or irregularly distributed, irreversible damage to food can occur. Therefore, ice growth is a vital parameter that needs to be controlled during frozen food processing and storage. In this review, ice growth theory and control are described. Macroscopic heat and mass transfer processes, the relationship between the growth of ice crystals and macroscopic heat transfer factors, and nucleation theory are reviewed based on the reported theoretical and experimental approaches. The issues addressed include how heat transfer occurs inside samples, variations in thermal properties with temperature, boundary conditions, and the functional relationship between ice crystal growth and freezing parameters. Quick freezing (e.g., cryogenic freezing) and unavoidable temperature fluctuations (e.g., multiple freeze–thaw cycles) are both taken into consideration. The approaches for controlling ice crystal growth based on the ice morphology and content are discussed. The characteristics and initial mechanisms of ice growth inhibitors (e.g., antifreeze proteins (AFPs), polysaccharides, and phenols) and ice nucleation agents (INAs) are complex, especially when considering their molecular structures, the ice-binding interface, and the dose. Although the market share for nonthermal processing technology is low, there will be more work on freezing technologies and their theoretical basis. Superchilling technology (partial freezing) is also mentioned here.     

Influence of shear on fat crystallization

Processing conditions greatly impact fat crystallization kinetics and growth mechanisms. Recently, there has been increased interest in elucidating the role of shear on fat crystallization. This review provides an overview of fat crystallization under static conditions followed by a summary of the current body of work pertaining to the effects of shear on fat crystallization, namely its effects on nucleation and growth, crystal network formation, polymorphic transitions, and microstructure modification at different length scales. The effects of shear are usually tied to critical shear rates but shear generally enhances nucleation and growth, accelerates crystallization and polymorphic transitions, and can cause orientation and structuring of fat crystal networks.