Exploring the effect of cooling rate on non-isothermal crystallization of copolymer polypropylene by fast scanning calorimetry

Polypropylene is commonly used as a binder for ceramic injection molding,and rapid cooling is often encountered during processing.However,the crystallization behavior of polypropylene shows a strong dependence on cooling rate due to its semi-crystalline characteristics.Therefore,the influence of cooling rate on the quality of final product cannot be ignored.In this study,the fast differential scanning calorimetry(FSC)test was performed to study the influence of cooling rate on the non-isothermal crystallization behavior and non-isothermal crystallization kinetics of a copolymer polypropylene(PP BC03B).The results show that the crystallization temperatures and crystallinity decrease as the cooling rate increases.In addition,two exothermic peaks occur when cooling rate ranges from 30 to 300 K·s^(-1),indicating the formation of another crystal phase.Avrami,Ozawa and Mo equations were used to explore the non-isothermal crystallization kinetics,and it can be concluded that the Mo method is suitable for this study.

Determination of metastable zone and induction time of analgin for cooling crystallization

The solubility, metastable zone width, and induction time of analgin for unseeded batch cooling crystallization in ethanol–aqueous system were experimentally determined. The solubility data could be well described by the van't Hoff equation model. The metastable zone width at various cooling rates was measured, and some parameters of nucleation kinetic were calculated using the Ny'vlt theory. Furthermore, the induction period of various temperatures and supersaturation ratios was also measured. According to classical nucleation theory, some nucleation parameters and interfacial energy was calculated through the induction time(t_(ind)) data. Homogeneous nucleation tended to occur when the supersaturation is high, whereas heterogeneous nucleation was more likely to occur when the supersaturation is low.

Determination of the metastable zone and induction time of thiourea for cooling crystallization

The solubility,metastable zone width(MSZW),and induction time of thiourea for cooling crystallization were experimentally determined in the temperature range of 283-323 K.The solubility data could be well described by the Apelblat equation model as lnx=-99.55+1071.66/T+16.27 lnT.The determinations of the effects of various stirring and cooling rates indicated that the MSZW increased with increasing and decreasing cooling and stirring rates,respectively.Furthermore,the induction times at various temperatures and supersaturation ratios were also measured.The results indicated that homogeneous nucleation could occur at high supersaturation,whereas heterogeneous nucleation was more likely to occur at low supersaturation.Based on the classical nucleation theory and induction period data,the calculated solid-liquid interfacial tensions of thiourea in deionized water at 302.46 and 312.58 K were 2.86 and 2.94 mJ·m^(-2),respectively.

Effect of cooling rate on the crystallization behavior of perovskite in high titanium-bearing blast furnace slag

The effect of cooling rate on the crystallization of perovskite in high Ti-bearing blast furnace（BF） slag was studied using confocal scanning laser microscopy（CSLM）. Results showed that perovskite was the primary phase formed during the cooling of slag. On the slag surface, the growth of perovskite proceeded via the successive production of quasi-particles along straight lines, which further extended in certain directions. The morphology and structure of perovskite was found to vary as a function of cooling rate. At cooling rates of 10 and 30 K/min, the dendritic arms of perovskite crossed obliquely, while they were orthogonal at a cooling rate of 20 K/min and hexagonal at cooling rates of 40 and 50 K/min. These three crystal morphologies thus obtained at different cooling rates respectively corresponded to the orthorhombic, cubic and hexagonal crystal structures of perovskite. The observed change in the structure of perovskite could probably be attributed to the deficiency of O^2-, when Ti2O3 was involved in the formation of perovskite.

Characterization of recrystallized itraconazole prepared by cooling and anti-solvent crystallization

The objective of the present study was to alter the crystal habit of itraconazole(ITZ)by cooling and anti-solvent crystallization and characterize its properties.ITZ was recrystallized in different solvents and the effects of each solvent on morphology of crystals,dissolution behavior and solid state of recrystallized drug particles were investigated.The results revealed that ITZ crystals recrystallized by cooling and anti-solvent crystallization showed the different crystal habits from the untreated ITZ.Using cooling crystallization tended to provide needle-shaped crystals while the crystals obtained from anti-solvent crystallization showed more flaky,plate shape.This indicated the importance of preparation method on nucleation and crystal growth.No change in drug polymorphism was observed,according to determination of thermal property and crystalline state by differential scanning calorimetry and powder X-ray diffractometry,respectively.The recrystallized ITZ showed higher drug dissolution than untreated ITZ and the highest drug dissolution was observed from the samples recrystallized in the presence of PEG 200,which provided the small plate-shaped crystals with tremendously increased in surface area.However,the increasing of drug dissolution is relatively small,therefore,further development may be required.

Evolution mechanism of recrystallization in a nickel-based single crystal superalloy under various cooling rates during heat treatment

The recrystallization behaviors of a nickel-based single crystal superalloy during heat treatment at 1,200℃ for 4 h with various cooling rates were studied.Results show that the thickness of recrystallization layer decreases with the increase of cooling rate.In addition,the microstructures ofγ′phase in the recrystallization region are different in various cooling rates.In the high cooling rates(70,100℃·min^(-1)),small size and high volume fraction ofγ′phases are formed in the recrystallization region.It is also found that irregular fine secondaryγ′phases are precipitated between matrix channels with an average size of 150 nm in the original matric(100℃·min^(-1)).The sizes of the secondaryγ′phase decrease with the increase of cooling rate.In contrast,large size and small volume fraction ofγ′phases are formed in the recrystallization region,and a grain boundary layer is formed under a low cooling rate(10℃·min^(-1)).The evolution mechanism of recrystallization at various cooling rates during heat treatment is analyzed.

Purification of carbazole by solvent crystallization under two forced cooling modes

To identify the effect of solvents and anthracene on the purification of carbazole,the solvent crystallization of carbazole was investigated with xylene,chlorobenzene and tetrachloroethylene(TCE)as solvents under two forced circulation cooling(FCC)modes.The co-crystalline experimental data were obtained from runs carried out at different anthracene levels between 1%(mass)and 10%(mass).The results showed that a uniform flake carbazole crystal obtained when using xylene and chlorobenzene under the FCC-1 mode with gradual cooling rate.Nevertheless,fine flake crystals grown under shock cooling of FCC-2 mode.It is beneficial to improving the purity of carbazole with chlorobenzene as solvent under cooling mode of FCC-1.Anthracene could promote the growth of carbazole in solution,and it has a significant influence on the purification of carbazole.

Kinetic parameter estimation for cooling crystallization process based on cell average technique and automatic differentiation

In this paper,a cell average technique(CAT)based parameter estimation method is proposed for cooling crystallization involved with particle growth,aggregation and breakage,by establishing a more efficient and accurate solution in terms of the automatic differentiation(AD)algorithm.To overcome the deficiency of CAT that demands high computation cost for implementation,a set of ordinary differential equations(ODEs)entailed from CAT based discretized population balance equation(PBE)are solved by using the AD based high-order Taylor expansion.Moreover,an AD based trust-region reflective(TRR)algorithm and another interior-point(IP)algorithm are established for estimating the kinetic parameters associated with particle growth,aggregation and breakage.As a result,the estimation accuracy can be further improved while the computation cost can be significantly reduced,compared to the existing algorithms.Benchmark examples from the literature are used to illustrate the accuracy and efficiency of the AD-based CAT,TRR and IP algorithms in comparison with the existing algorithms.Moreover,seeded batch cooling crystallization experiments ofβform L-glutamic acid are performed to validate the proposed method.

Process Modeling for Batch Cooling Crystallization

The general mathematical model for batch cooling crystallization was established based on the population balance equation considering the change of slurry volume, and simulated with crystallization thermodynamics,kinetics and mass balance employing bed voidage. In the system of vitamin C-water-ethanol, reliability of this model was verified by comparison between simulation results and experimental data. The effects of operation parameters on product quality can be systematically investigated by modeling simulation.

Production of Sucrose Crystals of Uni-Modal Size Distribution by Seeded Batch Cooling Crystallization

From sucrose aqueous solution of high viscosity, sucrose was crystallized by seeded cooling in a batch crystallizer. At low seed loadings, the product crystal size distribution (CSD) was wide-spread because of enormous secondary and primary nucleation. However, at high seed loadings, it became uni-modal, where the crystallization was dominated by seed growth with practically no secondary nucleation. Enough seeding was thus effective in suppressing nucleation even during batch crystallization with high viscosity solution. The volume mean size of the product crystals obtained at high seed loadings agreed with that calculated by a simple mass balance assuming growth-dominated crystallization with no change in the number of crystals.

Optimization of Parameters for Melt Crystallization of p-Cresol

Laboratory-scale experiments were carried out to evaluate the influences of operational parameters on the melt crystallization efficiency for p-cresol purification.The optimal crystallization conditions were determined:dynamic pulsed aeration at 90 L·h-1 and the cooling rate of 0.6-0.8 ℃·min-1,followed by sweating at 0.2-0.3 ℃·min-1 for 40 min.Results also demonstrate that the melt crystallization efficiency is sensitive to feed concentration,which highlights this technology for separation and purification of high purity products.

SOLIDIFICATION AND MICROSEGREGATION BEHAVIORS OF NICKEL-BASE SINGLE CRYSTAL SUPERALLOY SOLIDIFIED AT MEDIUM COOLING RATE

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Effect of Process Parameter Variation on Purity during Rotary Fractional Crystallization of Aluminum

High pure and ultrapure Aluminum is increasingly used in highly corrosion resistant applications or to replace copper in conductive parts such as high voltage cable and transformers due to their higher electrical conductivity properties. Ultrapure Aluminum is also used in semiconductors industry. Hence, the market demands innovative refining technologies, which consume less energy, take less time and lead to higher resource efficiencies. The most common methodology to produce ultrapure Aluminum is zone refining, based on the principle of fractional crystallization. Zone refining is however a very time-consuming process. In order to achieve a purity of 6N, several passes along the crucible with each full day treatment must be carried out. Also this method cannot be conducted continuously. This paper presents first time a new and eco-efficient method, which offers high potential to meet the mentioned multi-dimensional demands. Firstly, distribution coefficients of main impurities in Aluminum—a deciding factor to forecast and assess the removal behavior of impurities-were studied theoretically as a function of temperature using thermo-chemical calculation in FactSageTM. Secondly, the innovative method using a rotating and gas cooled crystallizer (“cooled finger”) was developed to validate the principle. The influencing process parameters such as temperature gradient, cooling gas flow rate, etc. were experimentally investigated and the theoretical results could be verified.

Estimating Influence of Crystallizing Latent Heat on Cooling-Crystallizing Process of a Granitic Melt and Its Geological Implications

Based on the theory of thermal conductivity, in this paper we derived a formula to estimate the prolongation period （AtL） of cooling-crystallization process of a granitic melt caused by latent heat of crystallization as follows：△tL=QL×△tcol/（TM-TC）×CP where TM is initial temperature of the granite melt, Tc crystallization temperature of the granite melt, Cp specific heat, △tcol cooling period of a granite melt from its initial temperature （TM） to its crystallization temperature （Tc）, QL latent heat of the granite melt. The cooling period of the melt for the Fanshan granodiorite from its initial temperature （900℃） to crystallization temperature （600℃） could be estimated -210,000 years if latent heat was not considered. Calculation for the Fanshan melt using the above formula yields a AtL value of -190,000 years, which implies that the actual cooling period within the temperature range of 900°-600℃ should be 400,000 years. This demonstrates that the latent heat produced from crystallization of the granitic melt is a key factor influencing the cooling-crystallization process of a granitic melt, prolongating the period of crystallization and resulting in the large emplacement-crystallization time difference （ECTD） in granite batholith.

Crystallization thermodynamics of 2,4(5)-dinitroimidazole in binary solvents

2,4(5)-Dinitroimidazole(2,4(5)-DNI)is an important organic intermediate,and itself can also be used for energetic material.In this work,the solubility of 2,4(5)-DNI in(methanol+water,acetonitrile+water,acetone+water)binary solvents were measured by using a dynamic test method from 278.15 K to 323.15 K under 101.1 k Pa.The Jouyban–Acree model,van't Hoff–Jouyban–Acree model,Apelblat–Jouyb an–Acree model,Ma model,and Sun model were used to correlate the experimental data.The values of relative average deviation(RAD)and root-mean-square deviation(RMSD)were very small,indicating that the error between the experimental value and the correlated value was very small.The thermodynamic parameters such as dissolution enthalpy,dissolution entropy and Gibbs energy were calculated based on solubility data.High-purity of 2,4(5)-DNI was efficiently obtained by using cooling and dilution crystallization method.

Sympathetic Cooling of ^(40)Ca^(+_27)Al^+ Ion Pair Crystal in a Linear Paul Trap

The 27Al＋ ion optical clock is one of the most attractive optical clocks due to its own advantages such as low black-body radiation shift at room temperature and insensitivity to the magnetic drift. However, it cannot be laser-cooled directly in the absence of 167nm laser to date. This problem can be solved by sympathetic cooling. In this work, a linear Paul trap is used to trap both 40Ca＋ and 27A1＋ ions simultaneously, and a single Dopplercooled 40Ca＋ ion is employed to sympathetically cool a single 27A1＋ ion. Thus a ＇bright-dark＇ two-ion crystal has been successfully synthesized. The temperature of the crystal has been estimated to be about 7mK by measuring the ratio of carrier and sideband spectral intensities. Finally, the dark ion is proved to be an 27Al＋ ion by precise measuring of the ion crystal＇s secular motion frequency, which means that it is a great step for our 2Z Al＋ quantum logic clock.

Crystallization thermodynamics of 2,4(5)-dinitroimidazole in eleven pure solvents

2,4(5)-Dinitroimidazole(2,4(5)-DNI) is an important energetic material, and it is also an important precursor for the preparation of drugs and energetic materials. In this study, the solubility of 2,4(5)-DNI in eleven pure solvents(chlorobenzene, benzene, 1,2-dichloroethane, toluene, water, isopropyl alcohol,ethyl acetate, acetonitrile, methanol, 1,4-dioxane and acetone) were measured by using a dynamic test method from 278.15 K to 323.15 K under 101.1 kPa. Four solubility models were used to fit the experimental data, which were ideal model, modified Apelblat equation, polynomial empirical equation, and λh equation. Meanwhile, the relative average deviation and root-mean-square deviation between the experimental data and the fitted data were also calculated. Furthermore, the three thermodynamic parameters,i.e., dissolution enthalpy, dissolution entropy and Gibbs energy were obtained based on solubility data.Finally, the crude product of 2,4(5)-DNI was crystallized with acetone as solvent, and the purity of the crystalline product was greater than 99.5%.

Cooling of double crystal monochromator with sagittal focus at SSRF

In SSRF, the design of 1st crystal cooling geometry of double crystal monochromator with sagittal focus is mainly reported by China. Our simulation indicates that the broadening of the full width at half maximum of the rocking curve of the double crystal monochromator induced by the heat load is about 3.7 μrad, and is in agreement with the experimental value of 5 μrad. Our scheme showed that the photon flux is reliably linear with electron current of the storage ring, which is extracted from the monochromator.

Imaging protein crystal growth behaviour in batch cooling crystallisation

The temporal and spatial growth behaviour of protein crystals, subject to different cooling strategies in protein crystallisation was investigated. Although the impact of temperature and cooling rate on crystal growth of small molecules was well documented, much less has been reported on their impact on the crystallisation of proteins. In this paper, an experimental set-up is configured to carry out such a study which involves an automatic temperature controlled hot-stage crystalliser fitted with a real-time imaging system. Linbro parallel crystallisation experiments(24-well plate) were also conducted to find the suitable initial conditions to be used in the hot-stage crystallisation experiments, including the initial concentration of HEW lysozyme solutions, precipitate concentration and pH value. It was observed that fast cooling rates at the early stage led to precipitates while slow cooling rates produced crystal nuclei, and very slow cooling rates, much smaller than for small molecules are critical to the growth of the nuclei and the crystals to a desired shape. The interesting results provide valuable insight as well as experimental proof of the feasibility and effectiveness of cooling as a means for achieving controlled protein crystallisation, compared with the evaporation approach which was widely used to grow single large crystals for X-ray diffraction study. Since cooling rate control can be easily achieved and has good repeatability, it suggests that large-scale production of protein crystals can be effectively achieved by manipulating cooling rates.

Momentum-space crystal in narrow-line cooling of ^(87)Sr

The discovery of the momentum space crystal based on the alkaline-earth atom ^(88)Sr in narrow-line cooling has paved the way to explore this novel physical phenomenon in other cold atom systems. In this paper, a momentum space crystal based on the fermions ^(87)Sr in narrow-line cooling of transition^1S_0–~3P_1 is demonstrated. We theoretically analyze and compare the formation principle of the narrow-line with that of broad-line cooling, and achieve the momentum space crystal in experiment. Beyond that we present a series of numerical calculations of those important parameters which influence the distribution and size of the momentum space crystal. Correspondingly, we vary the values of these parameters in experiment to observe the momentum space crystal evolution and distribution. The experimental results are in conformity with the results of the theoretically numerical calculations. These results and analyses provide a detailed supplementary study on the formation and evolution of momentum space crystal. In addition, this work could also give a guideline on atomic manipulation by narrow-line cooling.