The non-isothermal crystallization kinetics of polyamide 6/diamine-modified multi-walled carbon nanotube （PA6/D-MWNT） nanocomposite was investigated by differential scanning calorimetry （DSC）. The modified Avrami ...The non-isothermal crystallization kinetics of polyamide 6/diamine-modified multi-walled carbon nanotube （PA6/D-MWNT） nanocomposite was investigated by differential scanning calorimetry （DSC）. The modified Avrami equation, the Ozawa equation and the combined Avrami/Ozawa equation were employed to analyze the non-isothermal crystallization data. The crystallization activation energies were also evaluated by the Kissinger method. It was found that the combined Avrami/Ozawa equation could successfully describe the non-isothermal crystallization process. The results showed that D-MWNTs not only acted as effective heterogeneous nucleating agents for PA6 and noticeably increased the crystallization temperature of PA6, but also influenced the mechanism of nucleation and crystal growth of PA6 and then reduced the overall crystallization rate of the neat PA6 matrix. The crystallization activation energy for the nanocomposite sample was greater than that of the neat PA6, which indicated that the addition of D-MWNTs hindered the mobility of PA6 chain segments.展开更多
The non-isothermal crystallization kinetics of reactive microgel/nylon 6 blends was investigated by differential scanning calorimetry(DSC). The Mo equation was employed to analyze the non-isothermal crystallization da...The non-isothermal crystallization kinetics of reactive microgel/nylon 6 blends was investigated by differential scanning calorimetry(DSC). The Mo equation was employed to analyze the non-isothermal crystallization data. The crystallization activation energies were also evaluated by the Kissinger method. The results show that the crystallization onset temperature(T onset) and crystallization peak temperature(T p) decrease with the increase of the content of reactive microgel, while ΔT(T onset–T p), the crystallization half-time(t1/2) and the crystallization enthalpy(ΔH c) increase. The required cooling rates of blends are higher than that of neat nylon6 in order to achieve the same relative crystallinity in a unit of time. The crystallization activation energies of the reactive microgel/nylon 6 blends are greater than those of the neat nylon 6. When the content of reactive microgel is 30%, the relative crystallinity(X t) reaches the maximum.展开更多
Nylon 10 T and Nylon 10T/1010 samples were synthesized by direct melt polymerization. The non-isothermal crystallization kinetics of Nylon 10 T and Nylon 10T/1010 was investigated by means of differential scanning cal...Nylon 10 T and Nylon 10T/1010 samples were synthesized by direct melt polymerization. The non-isothermal crystallization kinetics of Nylon 10 T and Nylon 10T/1010 was investigated by means of differential scanning calorimetry(DSC). Jeziorny equation and Mo equation were applied to describe the non-isothermal crystallization kinetics of the Nylon 10 T and the Nylon 10T/1010. The activation energies for non-isothermal crystallization were obtained by Vyazovkin's method and Friedman's method, respectively. These results showed that Jeziorny equation and Mo equation well described the non-isothermal crystallization kinetics of the Nylon 10 T and the Nylon 10T/1010. It was found that the values of the activation energy for non-isothermal crystallization of the Nylon 10T/1010 were lower than those of the Nylon 10 T at a given temperature or relative crystallinity degree,which revealed that crystallization ability of the Nylon 10T/1010 was higher. The crystal morphology was observed by means of a polarized optical microscope(POM) and X-ray diffraction(XRD). It was found that the addition of sebacic acid comonomer not only did not change the crystal form of the Nylon 10 T, but also significantly increased the number and decreased the size of spherulites. Comparing with the Nylon 10 T, the crystallization rate was increased with the addition of the sebacic acid comonomer.展开更多
This paper aims to investigate the thermal behavior and crystallization kinetics of TiZrHfNiCu high entropy bulk metallic glass (HE-BMG) alloy using the standard procedure of Differential Scanning Calorimetric (DSC) a...This paper aims to investigate the thermal behavior and crystallization kinetics of TiZrHfNiCu high entropy bulk metallic glass (HE-BMG) alloy using the standard procedure of Differential Scanning Calorimetric (DSC) annealing technique.</span><b><span style="font-family:Verdana;"> </span></b><span style="font-family:Verdana;">The alloy was produced using an arc melting machine with a critical diameter of 1.5 mm. The crystallization kinetics and phase transformation mechanism of TiZrHfNiCu HE-BMG was investigated under the isochronal condition at a single heating run based on the Johnson-Mehl-</span></span><span style="font-family:Verdana;"> </span><span style="font-family:Verdana;">Avrami (JMA) theory. In isochronal heating, the apparent activation energy for glass transition and crystallization events w</span><span style="font-family:Verdana;">as</span><span style="font-family:Verdana;"> analyzed by Kissinger and Ozawa methods. The average activation energy value for crystallization of TiZrHfNiCu amorphous alloys in isochronal modes was 226.41 kJ/mol for the first crystallization and 297.72 kJ/mol for second crystallization stages. The crystallization mechanism of the first step was dominated by two</span><span style="font-family:Verdana;">-</span><span style="font-family:Verdana;"> and three-dimensional growth with increasing nucleation rate, while the crystallization mechanism in the second stage was dominated by two-dimensional crystallization growth with a constant nucleation rate. The diffusion mechanism result proved the theory of sluggish atomic diffusion of HEA at elevated temperature.展开更多
Fiber-class modified kaolin and PET have been blended in the twin-screw and granulated to chips containing 4 wt% of kaolin.Non-isothermal crystallization process of kaolin modified polyester was investigated using a d...Fiber-class modified kaolin and PET have been blended in the twin-screw and granulated to chips containing 4 wt% of kaolin.Non-isothermal crystallization process of kaolin modified polyester was investigated using a differential scanning calorimetry （DSC）,and the addition of kaolin enhances either the melting temperature （Tm） or the crystallization temperature （Tc）.The morphology of kaolin modified polyester,the melt of which is cooled at different cooling rate,was observed by scanning electron microscope （SEM）.The relationship between Tc and cooling rate F was studied.Semi-crystalline phase t1/2 makes an exponential decline with increasing F,and the higher the cooling rate,the shorter the time of crystallization completion.Non-isothermal crystallization kinetics parameters and the activation energy were calculated,indicating that the higher rate of cooling needs the higher relative crystallinity in the unit crystallization time,the crystallization rate increased while speeding up the temperature reduction,and the activation energy ΔE was calculated to be-204.1566 kJ/mol for the non-isothermal crystallization processes by the Kissinger＇s methods.展开更多
An equation of non-isothermal crystallization kinetics was derived according to a new model and the crystallizations of both the PET samples under solid state polycon-densation and the pre-orientation yarn of high spe...An equation of non-isothermal crystallization kinetics was derived according to a new model and the crystallizations of both the PET samples under solid state polycon-densation and the pre-orientation yarn of high speeding spinning PET were studied with this equation. The results show that there is a good linear relationship between In {-In[1-X(T)]} and lnΦ. The index m in the equation approximately equals to 3 for PET chips and 1. 3 for pre-orientated yarn. At the same temperature, Q(T) decreases with the increase of PET M. W. and the kinetics parameters obtained by Jeziorny' s method indicate that G also decreases with the increase of PET M. W.. Q(T) and Gc show the same varying tendency in the non-isothermal crystallization process.展开更多
The non-isothermal crystallization kinetics of modified poly(ethylene terephthalate) (PET) with the function of ultraviolet (UV) protection was studied by means of differential scanning calorimetry. The kinetics of th...The non-isothermal crystallization kinetics of modified poly(ethylene terephthalate) (PET) with the function of ultraviolet (UV) protection was studied by means of differential scanning calorimetry. The kinetics of the modified polymer under non-isothermal crystallization was analyzed by Ozawa equation. The crystallization behavior of the modified polymer obeyed Ozawa theory. The additives in the polymer whose function was UV-resistant acted as crystal nucleus in the processing of crystallization, which resulted in the increase of Avrami index and the crystallization rate of the cooling system.展开更多
Polypropylene(PP)with different contents of the second generation hyperbranched polyester(HBP)is prepared by melt blending method.The non-isothermal crystallization kinetics of PP and PP/HBP blends is investigated und...Polypropylene(PP)with different contents of the second generation hyperbranched polyester(HBP)is prepared by melt blending method.The non-isothermal crystallization kinetics of PP and PP/HBP blends is investigated under differential scanning calorimetry(DSC).The Mo equation is used to analyze the DSC data.The results show that the Mo theory is suitable for crystallization kinetics of the blends.Fast cooling rate is not good for crystallizing and nucleating.The values of half crystallization time(t1/2),crystallization enthalpy(ΔHc)and temperature range(ΔT)of PP/HBP blends decrease when HBP is added.The required cooling rate of PP is higher than that of PP/HBP blends in order to reach the same relative crystallinity.Crystallization rate increases with the addition of HBP.The crystallization rate reaches a maximum when the content of HBP is 5%.In addition,the activation energies of PP and PP/HBP blends are calculated by Kissinger equation,revealing that the content of HBP has a little effect on the crystallization activation energy.展开更多
This work deals with isothermal and non-isothermal crystallization kinetics of electrically conductive polyvinylidene fluoride/poly(ethylene terephthalate) (PVDF/PET) based composites. It completes our previous work i...This work deals with isothermal and non-isothermal crystallization kinetics of electrically conductive polyvinylidene fluoride/poly(ethylene terephthalate) (PVDF/PET) based composites. It completes our previous work in which we related the crystallinity of these conductive PVDF/PET based composites to their through-plane resistivity [1]. Isothermal crystallization was described using the logarithmic form of the Avrami equation and it was observed that the crystallization rate of the PVDF phase inside the composite became slower compared to that of neat PVDF. In non-isothermal crystallization, the Avrami exponent of PVDF phase did not show any noticeable variation;however, that of PET phase, which contains the major part of the conductive carbon black (CB) and graphite (GR) additives, showed an evident decrease compared with neat PET. It was also observed that, at the same cooling rate, the crystallization rate of PVDF and PET phases inside the composite was slower than that of neat PVDF and PET.展开更多
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 cool...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.展开更多
In order to improve the recovery rate of rare earth,the effect of P_(2)O_(5) and cooling rate on the selective precipitation of CaO-SiO_(2)-TiO_(2)-P_(2)O_(5)-Nb_(2)O_(5)-CeO_(2)-CaF_(2) slag system was explored using...In order to improve the recovery rate of rare earth,the effect of P_(2)O_(5) and cooling rate on the selective precipitation of CaO-SiO_(2)-TiO_(2)-P_(2)O_(5)-Nb_(2)O_(5)-CeO_(2)-CaF_(2) slag system was explored using X-ray powder diffraction,a scanning electron microscope,an electron probe micro-analyzer and a confocal laser scanning microscope.The apatite(Ca_(2.02)Ce_(7.98)Si_(6.00)O_(26.00))is tiny and difficult to be separated from the slag without P_(2)O_(5).When the addition of P_(2)O_(5) is 6 wt%-10 wt%,the cerium and phosphorus are found to be enriched in britholite(Ca_(5-x)Ce_(x)[(SiO_(4))_(x)(PO_(4))_(3-x)]F)phase while x is negatively correlated with P_(2)O_(5) content in the slag.The influence of P_(2)O_(5) and cooling rate on the non-isothermal crystallization kinetics was also investigated.For the cooling rate between 5 and 40℃/min,continuous cooling transformation diagram of britholite was constructed when the P205 content is between 6 wt%-10 wt%.The modified Avrami model was applied to determine the crystallization mode of slag with 10 wt%P_(2)O_(5).It is shown that the crystallization mode is diffusion-controlled with constant nucleation rate and one-dimensional growth.In consideration of quantity and volume of crystals,the reasonable cooling rate is between 10and 30℃/min.展开更多
The non-isothermal crystallization dynamic behavior and mechanism of plasma sprayed Fe_(48)Cr_(15)Mo_(14)C_(15)B_(6)Y_(2)coating were thoroughly studied.The phase transition and crystallization kinetics of the coating...The non-isothermal crystallization dynamic behavior and mechanism of plasma sprayed Fe_(48)Cr_(15)Mo_(14)C_(15)B_(6)Y_(2)coating were thoroughly studied.The phase transition and crystallization kinetics of the coating were elaborately investigated by differential scanning calorimetry(DSC),X-ray diffraction(XRD),scanning electron microscopy(SEM),and transmission electron microscopy(TEM).The findings reveal that the characteristic temperatures of the coating shift to an elevated temperature at a higher heating rate and the crystallization processes are thermally activated.The 3-rd step of crystallization processes is more susceptible to the continuously increased heating rate while the onset crystallization reaction is less sensitive to the continuously enhanced heating rate.Fe_(23)(C,B)_6 phase is inclined to precipitate than other crystal phases due to the substantial pre-generation ofα-Fe.The onset nucleation and growth ofα-Fe crystals is tough due to a higher onset apparent activation energy.Meanwhile,the transformation from Fe_(23)(C,B)_(6)to FeB is harder in comparison with the precipitation of other crystals.The most parts of the three crystallization processes are dominated by three-dimensional diffusion model due to the fact that most values of local Avrami exponent are higher than 2.5.展开更多
In the cooling crystallization process of thiourea,a significant issue is the excessively wide crystal size distribution(CSD)and the abundance of fine crystals.This investigation delves into the growth kinetics and me...In the cooling crystallization process of thiourea,a significant issue is the excessively wide crystal size distribution(CSD)and the abundance of fine crystals.This investigation delves into the growth kinetics and mechanisms governing thiourea crystals during the cooling crystallization process.The fitting results indicate that the crystal growth rate coefficient,falls within the range of 10^(-7)to 10^(-8)m·s^(-1).Moreover,with decreasing crystallization temperature,the growth process undergoes a transition from diffusion-controlled to surface reaction-controlled,with temperature primarily influencing the surface reaction process and having a limited impact on the diffusion process.Comparing the crystal growth rate,and the diffusion-limited growth rate,at different temperatures,it is observed that the crystal growth process can be broadly divided into two stages.At temperatures above 25℃,1/qd(qd is diffusion control index)approaches 1,indicating the predominance of diffusion control.Conversely,at temperatures below 25℃,1/qd increases rapidly,signifying the dominance of surface reaction control.To address these findings,process optimization was conducted.During the high-temperature phase(35-25℃),agitation was increased to reduce the limitations posed by bulk-phase diffusion in the crystallization process.In the low-temperature phase(25-15℃),agitation was reduced to minimize crystal breakage.The optimized process resulted in a thiourea crystal product with a particle size distribution predominantly ranging from 0.7 to 0.9 mm,accounting for 84%of the total.This study provides valuable insights into resolving the issue of excessive fine crystals in the thiourea crystallization process.展开更多
NaY zeolites are synthesized using submolten salt depolymerized natural perlite mineral as the main silica and alumina sources in a 0.94 L stirred crystallizer.Effects of alkalinity ranging from 0.38 to 0.55(n(Na_(2)O...NaY zeolites are synthesized using submolten salt depolymerized natural perlite mineral as the main silica and alumina sources in a 0.94 L stirred crystallizer.Effects of alkalinity ranging from 0.38 to 0.55(n(Na_(2)O)/n(SiO_(2)))on the relative crystallinity,textural properties and crystallization kinetics were investigated.The results show that alkalinity exerts a nonmonotonic influence on the relative crystallinity and textural properties,which exhibit a maximum at the alkalinity of 0.43.The nucleation kinetics are studied by fitting the experimental data of relative crystallinity with the Gualtieri model.It is shown that the nucleation rate constant increases with increasing alkalinity,while the duration period of nucleation decreases with increasing alkalinity.For n(Na_(2)O)/n(SiO_(2))ratios ranging from 0.38 to 0.55,the as-synthesized NaY zeolites exhibit narrower crystal size distributions with the increase in alkalinity.The growth rates determined from the variations of average crystal size with time are 51.09,157.50,46.17 and 24.75 nm·h^(-1),respectively.It is found that the larger average crystal sizes at the alkalinity of 0.38 and 0.43 are attributed to the dominant role of crystal growth over nucleation.Furthermore,the combined action of prominent crystal growth and the longer duration periods of nucleation at the alkalinity of 0.38 and 0.43 results in broader crystal size distributions.The findings demonstrate that control of the properties of NaY zeolite and the crystallization kinetics can be achieved by conducting the crystallization process in an appropriate range of alkalinity of the reaction mixture.展开更多
The non-isothermal crystallization kinetics of polypropylene （PP）, PP/anhydrite composites were investigated by differential scanning calorimetry （DSC） with various cooling rates. The Avrami analysis modified by J...The non-isothermal crystallization kinetics of polypropylene （PP）, PP/anhydrite composites were investigated by differential scanning calorimetry （DSC） with various cooling rates. The Avrami analysis modified by Jeziorny and a method developed by Mo were employed to describe the non-isothermal crystallization process of these samples. The difference in the exponent n between PP and PP/anhydrite composites indicated that non-isothermal kinetic crystallization corresponded to tri-dimensional growth with heterogeneous nucleation. The values of half-time, Zc and F（T） showed that the crystallization rate increased with the increasing of cooling rates for PP and PP/anhydrite composites, but the crystallization rate of PP/anhydrite composites was faster than that of PP at a given cooling rate. The method developed by Ozawa did not describe the non-isothermal crystallization process of PP very well. Moreover, the method proposed by Kissinger was used to evaluate the activation energy of the mentioned samples. The result showed that the activation energy of PP/anhydrite was greatly larger than that of PP.展开更多
Three types of organic compounds--two carboxylic acids and an anhydride, were used as additives for polyketone （PK）. The effect of the additive structure and their feed ratios on the melting temperature, crystalliza...Three types of organic compounds--two carboxylic acids and an anhydride, were used as additives for polyketone （PK）. The effect of the additive structure and their feed ratios on the melting temperature, crystallization temperature, and crystallization rate of PK were studied. We found that the crystallization temperature could be reduced significantly by introducing a small quantity of organic additive, in particular, an anhydride. On addition of 1 phr of anhydride, the crystallization temperature was reduced by 10.7 ℃. Therefore, the non-isothermal crystallization kinetics of aliphatic PKJanhydride blends with various feed ratios was investigated using DSC. The results were analyzed by various theoretical models, such as Avrami, Ozawa and combined Avrami-Ozawa models.展开更多
Owing to adjustable thermal expansion performance, BaO–CaO–Al_2O_3–B_2O_3–SiO_2(BCABS) glass has a promising commercialization prospect for intermediate temperature-solid oxide fuel cells(IT-SOFCs) sealing. Herein...Owing to adjustable thermal expansion performance, BaO–CaO–Al_2O_3–B_2O_3–SiO_2(BCABS) glass has a promising commercialization prospect for intermediate temperature-solid oxide fuel cells(IT-SOFCs) sealing. Herein, Al_2O_3 with two different contents was added into the same glass formulation, referred to as A and B glass, respectively. In terms of the non-isothermal crystallization kinetic behavior, the effect of Al_2O_3 as the unique intermediate was innovatively studied on the long-term performance of BCABS sealing glass. After the heat treatment at 1023 K for 100 h, the change of the network structure and the expansion coefficient of the glass were characterized. The results showed that the addition of Al_2O_3 as a network forming body could enhance the structure of glass, and increase the activation energy for glass transition, which could effectively inhibit the crystallization ability of sealing glass. Therefore, the B glass with the higher Al_2O_3 content showed the better long-term sealing ability, which was greatly beneficial for IT-SOFCs sealing.展开更多
A kinetic equation of non-isothermal crystamzation was derived by extending Avrami's equation to the non-isothermal situation. More crystallization information can be obtained from this kinetic equation. The curve...A kinetic equation of non-isothermal crystamzation was derived by extending Avrami's equation to the non-isothermal situation. More crystallization information can be obtained from this kinetic equation. The curves of non-isothermal and isothermal crystallizations were analysed and compared for poly (ethylene terephthalate) (PET), and the results were discussed.展开更多
In order to develop limonite and decrease CO_(2) emissions,siderite is proposed as a clean reductant for suspension magnetization roasting(SMR) of limonite.An iron concentrate(iron grade:65.92wt%,iron recovery:98.54wt...In order to develop limonite and decrease CO_(2) emissions,siderite is proposed as a clean reductant for suspension magnetization roasting(SMR) of limonite.An iron concentrate(iron grade:65.92wt%,iron recovery:98.54wt%) was obtained by magnetic separation under the optimum SMR conditions:siderite dosage 40wt%,roasting temperature 700℃,roasting time 10 min.According to the magnetic analysis,SMR achieved the conversion of weak magnetic minerals to strong magnetic minerals,thus enabling the recovery of iron via magnetic separation.Based on the phase transformation analysis,during the SMR process,limonite was first dehydrated and converted to hematite,and then siderite decomposed to generate magnetite and CO,where CO reduced the freshly formed hematite to magnetite.The microstructure evolution analysis indicated that the magnetite particles were loose and porous with a destroyed structure,making them easier to be ground.The non-isothermal kinetic results show that the main reaction between limonite and siderite conformed to the two-dimension diffusion mechanism,suggesting that the diffusion of CO controlled the reaction.These results encourage the application of siderite as a reductant in SMR.展开更多
The kineties of non-isothermal crystallization of Nylon-1010 has been investigated by using differential scanning calorimetry(DSC), DSC curves were obtained under cooling rate(R): 2. 5, 5, 10, 20, 40K/min. Applying Ma...The kineties of non-isothermal crystallization of Nylon-1010 has been investigated by using differential scanning calorimetry(DSC), DSC curves were obtained under cooling rate(R): 2. 5, 5, 10, 20, 40K/min. Applying Mandelkern and Ziabicki theories, the values of the Z kinetic parameter and G the kinetic crystalllzab- ility have been determined. Expenents of Avrami obtained in this work decrease with increase of cooling rate and then level off. The experimental results show disagreements with the Ozawa equation.展开更多
基金Guoxin Sui would like to acknowledge the financial supports of the Hundreds’ Talents Program of Chinese Academy of Sciences.
文摘The non-isothermal crystallization kinetics of polyamide 6/diamine-modified multi-walled carbon nanotube （PA6/D-MWNT） nanocomposite was investigated by differential scanning calorimetry （DSC）. The modified Avrami equation, the Ozawa equation and the combined Avrami/Ozawa equation were employed to analyze the non-isothermal crystallization data. The crystallization activation energies were also evaluated by the Kissinger method. It was found that the combined Avrami/Ozawa equation could successfully describe the non-isothermal crystallization process. The results showed that D-MWNTs not only acted as effective heterogeneous nucleating agents for PA6 and noticeably increased the crystallization temperature of PA6, but also influenced the mechanism of nucleation and crystal growth of PA6 and then reduced the overall crystallization rate of the neat PA6 matrix. The crystallization activation energy for the nanocomposite sample was greater than that of the neat PA6, which indicated that the addition of D-MWNTs hindered the mobility of PA6 chain segments.
基金Supported by the Graduate Innovative Fund of Wuhan Institute of Technology(CX2013019)
文摘The non-isothermal crystallization kinetics of reactive microgel/nylon 6 blends was investigated by differential scanning calorimetry(DSC). The Mo equation was employed to analyze the non-isothermal crystallization data. The crystallization activation energies were also evaluated by the Kissinger method. The results show that the crystallization onset temperature(T onset) and crystallization peak temperature(T p) decrease with the increase of the content of reactive microgel, while ΔT(T onset–T p), the crystallization half-time(t1/2) and the crystallization enthalpy(ΔH c) increase. The required cooling rates of blends are higher than that of neat nylon6 in order to achieve the same relative crystallinity in a unit of time. The crystallization activation energies of the reactive microgel/nylon 6 blends are greater than those of the neat nylon 6. When the content of reactive microgel is 30%, the relative crystallinity(X t) reaches the maximum.
基金Supported by the National Science and Technology Support Program of China(No.2013BAE02B01)the Special Project on the Integration of Industry,Education and Research of Guangdong Province(No.2013B090500003)the Commissioner Workstation Project of Guangdong Province(No.2014A090906002)
文摘Nylon 10 T and Nylon 10T/1010 samples were synthesized by direct melt polymerization. The non-isothermal crystallization kinetics of Nylon 10 T and Nylon 10T/1010 was investigated by means of differential scanning calorimetry(DSC). Jeziorny equation and Mo equation were applied to describe the non-isothermal crystallization kinetics of the Nylon 10 T and the Nylon 10T/1010. The activation energies for non-isothermal crystallization were obtained by Vyazovkin's method and Friedman's method, respectively. These results showed that Jeziorny equation and Mo equation well described the non-isothermal crystallization kinetics of the Nylon 10 T and the Nylon 10T/1010. It was found that the values of the activation energy for non-isothermal crystallization of the Nylon 10T/1010 were lower than those of the Nylon 10 T at a given temperature or relative crystallinity degree,which revealed that crystallization ability of the Nylon 10T/1010 was higher. The crystal morphology was observed by means of a polarized optical microscope(POM) and X-ray diffraction(XRD). It was found that the addition of sebacic acid comonomer not only did not change the crystal form of the Nylon 10 T, but also significantly increased the number and decreased the size of spherulites. Comparing with the Nylon 10 T, the crystallization rate was increased with the addition of the sebacic acid comonomer.
文摘This paper aims to investigate the thermal behavior and crystallization kinetics of TiZrHfNiCu high entropy bulk metallic glass (HE-BMG) alloy using the standard procedure of Differential Scanning Calorimetric (DSC) annealing technique.</span><b><span style="font-family:Verdana;"> </span></b><span style="font-family:Verdana;">The alloy was produced using an arc melting machine with a critical diameter of 1.5 mm. The crystallization kinetics and phase transformation mechanism of TiZrHfNiCu HE-BMG was investigated under the isochronal condition at a single heating run based on the Johnson-Mehl-</span></span><span style="font-family:Verdana;"> </span><span style="font-family:Verdana;">Avrami (JMA) theory. In isochronal heating, the apparent activation energy for glass transition and crystallization events w</span><span style="font-family:Verdana;">as</span><span style="font-family:Verdana;"> analyzed by Kissinger and Ozawa methods. The average activation energy value for crystallization of TiZrHfNiCu amorphous alloys in isochronal modes was 226.41 kJ/mol for the first crystallization and 297.72 kJ/mol for second crystallization stages. The crystallization mechanism of the first step was dominated by two</span><span style="font-family:Verdana;">-</span><span style="font-family:Verdana;"> and three-dimensional growth with increasing nucleation rate, while the crystallization mechanism in the second stage was dominated by two-dimensional crystallization growth with a constant nucleation rate. The diffusion mechanism result proved the theory of sluggish atomic diffusion of HEA at elevated temperature.
文摘Fiber-class modified kaolin and PET have been blended in the twin-screw and granulated to chips containing 4 wt% of kaolin.Non-isothermal crystallization process of kaolin modified polyester was investigated using a differential scanning calorimetry （DSC）,and the addition of kaolin enhances either the melting temperature （Tm） or the crystallization temperature （Tc）.The morphology of kaolin modified polyester,the melt of which is cooled at different cooling rate,was observed by scanning electron microscope （SEM）.The relationship between Tc and cooling rate F was studied.Semi-crystalline phase t1/2 makes an exponential decline with increasing F,and the higher the cooling rate,the shorter the time of crystallization completion.Non-isothermal crystallization kinetics parameters and the activation energy were calculated,indicating that the higher rate of cooling needs the higher relative crystallinity in the unit crystallization time,the crystallization rate increased while speeding up the temperature reduction,and the activation energy ΔE was calculated to be-204.1566 kJ/mol for the non-isothermal crystallization processes by the Kissinger＇s methods.
文摘An equation of non-isothermal crystallization kinetics was derived according to a new model and the crystallizations of both the PET samples under solid state polycon-densation and the pre-orientation yarn of high speeding spinning PET were studied with this equation. The results show that there is a good linear relationship between In {-In[1-X(T)]} and lnΦ. The index m in the equation approximately equals to 3 for PET chips and 1. 3 for pre-orientated yarn. At the same temperature, Q(T) decreases with the increase of PET M. W. and the kinetics parameters obtained by Jeziorny' s method indicate that G also decreases with the increase of PET M. W.. Q(T) and Gc show the same varying tendency in the non-isothermal crystallization process.
文摘The non-isothermal crystallization kinetics of modified poly(ethylene terephthalate) (PET) with the function of ultraviolet (UV) protection was studied by means of differential scanning calorimetry. The kinetics of the modified polymer under non-isothermal crystallization was analyzed by Ozawa equation. The crystallization behavior of the modified polymer obeyed Ozawa theory. The additives in the polymer whose function was UV-resistant acted as crystal nucleus in the processing of crystallization, which resulted in the increase of Avrami index and the crystallization rate of the cooling system.
基金Supported by the Youths Foundation of Wuhan Institute of Technology(Q200902)the Graduate Innovative Fund of Wuhan Institute of Technology(CX201101)
文摘Polypropylene(PP)with different contents of the second generation hyperbranched polyester(HBP)is prepared by melt blending method.The non-isothermal crystallization kinetics of PP and PP/HBP blends is investigated under differential scanning calorimetry(DSC).The Mo equation is used to analyze the DSC data.The results show that the Mo theory is suitable for crystallization kinetics of the blends.Fast cooling rate is not good for crystallizing and nucleating.The values of half crystallization time(t1/2),crystallization enthalpy(ΔHc)and temperature range(ΔT)of PP/HBP blends decrease when HBP is added.The required cooling rate of PP is higher than that of PP/HBP blends in order to reach the same relative crystallinity.Crystallization rate increases with the addition of HBP.The crystallization rate reaches a maximum when the content of HBP is 5%.In addition,the activation energies of PP and PP/HBP blends are calculated by Kissinger equation,revealing that the content of HBP has a little effect on the crystallization activation energy.
文摘This work deals with isothermal and non-isothermal crystallization kinetics of electrically conductive polyvinylidene fluoride/poly(ethylene terephthalate) (PVDF/PET) based composites. It completes our previous work in which we related the crystallinity of these conductive PVDF/PET based composites to their through-plane resistivity [1]. Isothermal crystallization was described using the logarithmic form of the Avrami equation and it was observed that the crystallization rate of the PVDF phase inside the composite became slower compared to that of neat PVDF. In non-isothermal crystallization, the Avrami exponent of PVDF phase did not show any noticeable variation;however, that of PET phase, which contains the major part of the conductive carbon black (CB) and graphite (GR) additives, showed an evident decrease compared with neat PET. It was also observed that, at the same cooling rate, the crystallization rate of PVDF and PET phases inside the composite was slower than that of neat PVDF and PET.
基金financially supported by a grant provided by Mitsubishi Heavy Industries。
文摘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.
基金Project supported by the Major Projects of Inner Mongolia Natural Science Foundation (2018ZD07)Inner Mongolia Natural Science Foundation (2020BS05016)+2 种基金Open Project for Key Basic Research of the Inner Mongolia Autonomous Region (20140201)Open Project for Major Basic Research of Inner Mongolia (0406091701)Scientific Research Project of Inner Mongolia (ZDZX2018032)。
文摘In order to improve the recovery rate of rare earth,the effect of P_(2)O_(5) and cooling rate on the selective precipitation of CaO-SiO_(2)-TiO_(2)-P_(2)O_(5)-Nb_(2)O_(5)-CeO_(2)-CaF_(2) slag system was explored using X-ray powder diffraction,a scanning electron microscope,an electron probe micro-analyzer and a confocal laser scanning microscope.The apatite(Ca_(2.02)Ce_(7.98)Si_(6.00)O_(26.00))is tiny and difficult to be separated from the slag without P_(2)O_(5).When the addition of P_(2)O_(5) is 6 wt%-10 wt%,the cerium and phosphorus are found to be enriched in britholite(Ca_(5-x)Ce_(x)[(SiO_(4))_(x)(PO_(4))_(3-x)]F)phase while x is negatively correlated with P_(2)O_(5) content in the slag.The influence of P_(2)O_(5) and cooling rate on the non-isothermal crystallization kinetics was also investigated.For the cooling rate between 5 and 40℃/min,continuous cooling transformation diagram of britholite was constructed when the P205 content is between 6 wt%-10 wt%.The modified Avrami model was applied to determine the crystallization mode of slag with 10 wt%P_(2)O_(5).It is shown that the crystallization mode is diffusion-controlled with constant nucleation rate and one-dimensional growth.In consideration of quantity and volume of crystals,the reasonable cooling rate is between 10and 30℃/min.
基金Funded by the China Scholarship Council(No.201906710142)。
文摘The non-isothermal crystallization dynamic behavior and mechanism of plasma sprayed Fe_(48)Cr_(15)Mo_(14)C_(15)B_(6)Y_(2)coating were thoroughly studied.The phase transition and crystallization kinetics of the coating were elaborately investigated by differential scanning calorimetry(DSC),X-ray diffraction(XRD),scanning electron microscopy(SEM),and transmission electron microscopy(TEM).The findings reveal that the characteristic temperatures of the coating shift to an elevated temperature at a higher heating rate and the crystallization processes are thermally activated.The 3-rd step of crystallization processes is more susceptible to the continuously increased heating rate while the onset crystallization reaction is less sensitive to the continuously enhanced heating rate.Fe_(23)(C,B)_6 phase is inclined to precipitate than other crystal phases due to the substantial pre-generation ofα-Fe.The onset nucleation and growth ofα-Fe crystals is tough due to a higher onset apparent activation energy.Meanwhile,the transformation from Fe_(23)(C,B)_(6)to FeB is harder in comparison with the precipitation of other crystals.The most parts of the three crystallization processes are dominated by three-dimensional diffusion model due to the fact that most values of local Avrami exponent are higher than 2.5.
基金supported by Priority Academic Program Development of Jiangsu Higher Educatior(PPZY2015A044).
文摘In the cooling crystallization process of thiourea,a significant issue is the excessively wide crystal size distribution(CSD)and the abundance of fine crystals.This investigation delves into the growth kinetics and mechanisms governing thiourea crystals during the cooling crystallization process.The fitting results indicate that the crystal growth rate coefficient,falls within the range of 10^(-7)to 10^(-8)m·s^(-1).Moreover,with decreasing crystallization temperature,the growth process undergoes a transition from diffusion-controlled to surface reaction-controlled,with temperature primarily influencing the surface reaction process and having a limited impact on the diffusion process.Comparing the crystal growth rate,and the diffusion-limited growth rate,at different temperatures,it is observed that the crystal growth process can be broadly divided into two stages.At temperatures above 25℃,1/qd(qd is diffusion control index)approaches 1,indicating the predominance of diffusion control.Conversely,at temperatures below 25℃,1/qd increases rapidly,signifying the dominance of surface reaction control.To address these findings,process optimization was conducted.During the high-temperature phase(35-25℃),agitation was increased to reduce the limitations posed by bulk-phase diffusion in the crystallization process.In the low-temperature phase(25-15℃),agitation was reduced to minimize crystal breakage.The optimized process resulted in a thiourea crystal product with a particle size distribution predominantly ranging from 0.7 to 0.9 mm,accounting for 84%of the total.This study provides valuable insights into resolving the issue of excessive fine crystals in the thiourea crystallization process.
基金supports from National Natural Science Foundation of China(21938009,22308358,22208346,22078332)National Key Research and Development Program(2022YFC3902701)+2 种基金Ningxia Natural Science Foundation(2021AAC01002)the External Cooperation Program of BIC,Chinese Academy of Sciences(122111KYSB20190032)CAS Project for Young Scientists in Basic Research(YSBR-038)are gratefully acknowledged.
文摘NaY zeolites are synthesized using submolten salt depolymerized natural perlite mineral as the main silica and alumina sources in a 0.94 L stirred crystallizer.Effects of alkalinity ranging from 0.38 to 0.55(n(Na_(2)O)/n(SiO_(2)))on the relative crystallinity,textural properties and crystallization kinetics were investigated.The results show that alkalinity exerts a nonmonotonic influence on the relative crystallinity and textural properties,which exhibit a maximum at the alkalinity of 0.43.The nucleation kinetics are studied by fitting the experimental data of relative crystallinity with the Gualtieri model.It is shown that the nucleation rate constant increases with increasing alkalinity,while the duration period of nucleation decreases with increasing alkalinity.For n(Na_(2)O)/n(SiO_(2))ratios ranging from 0.38 to 0.55,the as-synthesized NaY zeolites exhibit narrower crystal size distributions with the increase in alkalinity.The growth rates determined from the variations of average crystal size with time are 51.09,157.50,46.17 and 24.75 nm·h^(-1),respectively.It is found that the larger average crystal sizes at the alkalinity of 0.38 and 0.43 are attributed to the dominant role of crystal growth over nucleation.Furthermore,the combined action of prominent crystal growth and the longer duration periods of nucleation at the alkalinity of 0.38 and 0.43 results in broader crystal size distributions.The findings demonstrate that control of the properties of NaY zeolite and the crystallization kinetics can be achieved by conducting the crystallization process in an appropriate range of alkalinity of the reaction mixture.
文摘The non-isothermal crystallization kinetics of polypropylene （PP）, PP/anhydrite composites were investigated by differential scanning calorimetry （DSC） with various cooling rates. The Avrami analysis modified by Jeziorny and a method developed by Mo were employed to describe the non-isothermal crystallization process of these samples. The difference in the exponent n between PP and PP/anhydrite composites indicated that non-isothermal kinetic crystallization corresponded to tri-dimensional growth with heterogeneous nucleation. The values of half-time, Zc and F（T） showed that the crystallization rate increased with the increasing of cooling rates for PP and PP/anhydrite composites, but the crystallization rate of PP/anhydrite composites was faster than that of PP at a given cooling rate. The method developed by Ozawa did not describe the non-isothermal crystallization process of PP very well. Moreover, the method proposed by Kissinger was used to evaluate the activation energy of the mentioned samples. The result showed that the activation energy of PP/anhydrite was greatly larger than that of PP.
文摘Three types of organic compounds--two carboxylic acids and an anhydride, were used as additives for polyketone （PK）. The effect of the additive structure and their feed ratios on the melting temperature, crystallization temperature, and crystallization rate of PK were studied. We found that the crystallization temperature could be reduced significantly by introducing a small quantity of organic additive, in particular, an anhydride. On addition of 1 phr of anhydride, the crystallization temperature was reduced by 10.7 ℃. Therefore, the non-isothermal crystallization kinetics of aliphatic PKJanhydride blends with various feed ratios was investigated using DSC. The results were analyzed by various theoretical models, such as Avrami, Ozawa and combined Avrami-Ozawa models.
基金financially supported by the research project of National Natural Science Foundation of China (Grant Nos.51662015 and 51462011)
文摘Owing to adjustable thermal expansion performance, BaO–CaO–Al_2O_3–B_2O_3–SiO_2(BCABS) glass has a promising commercialization prospect for intermediate temperature-solid oxide fuel cells(IT-SOFCs) sealing. Herein, Al_2O_3 with two different contents was added into the same glass formulation, referred to as A and B glass, respectively. In terms of the non-isothermal crystallization kinetic behavior, the effect of Al_2O_3 as the unique intermediate was innovatively studied on the long-term performance of BCABS sealing glass. After the heat treatment at 1023 K for 100 h, the change of the network structure and the expansion coefficient of the glass were characterized. The results showed that the addition of Al_2O_3 as a network forming body could enhance the structure of glass, and increase the activation energy for glass transition, which could effectively inhibit the crystallization ability of sealing glass. Therefore, the B glass with the higher Al_2O_3 content showed the better long-term sealing ability, which was greatly beneficial for IT-SOFCs sealing.
文摘A kinetic equation of non-isothermal crystamzation was derived by extending Avrami's equation to the non-isothermal situation. More crystallization information can be obtained from this kinetic equation. The curves of non-isothermal and isothermal crystallizations were analysed and compared for poly (ethylene terephthalate) (PET), and the results were discussed.
基金financially supported by the National Natural Science Foundation of China(Nos.51874071 and 52022019)。
文摘In order to develop limonite and decrease CO_(2) emissions,siderite is proposed as a clean reductant for suspension magnetization roasting(SMR) of limonite.An iron concentrate(iron grade:65.92wt%,iron recovery:98.54wt%) was obtained by magnetic separation under the optimum SMR conditions:siderite dosage 40wt%,roasting temperature 700℃,roasting time 10 min.According to the magnetic analysis,SMR achieved the conversion of weak magnetic minerals to strong magnetic minerals,thus enabling the recovery of iron via magnetic separation.Based on the phase transformation analysis,during the SMR process,limonite was first dehydrated and converted to hematite,and then siderite decomposed to generate magnetite and CO,where CO reduced the freshly formed hematite to magnetite.The microstructure evolution analysis indicated that the magnetite particles were loose and porous with a destroyed structure,making them easier to be ground.The non-isothermal kinetic results show that the main reaction between limonite and siderite conformed to the two-dimension diffusion mechanism,suggesting that the diffusion of CO controlled the reaction.These results encourage the application of siderite as a reductant in SMR.
文摘The kineties of non-isothermal crystallization of Nylon-1010 has been investigated by using differential scanning calorimetry(DSC), DSC curves were obtained under cooling rate(R): 2. 5, 5, 10, 20, 40K/min. Applying Mandelkern and Ziabicki theories, the values of the Z kinetic parameter and G the kinetic crystalllzab- ility have been determined. Expenents of Avrami obtained in this work decrease with increase of cooling rate and then level off. The experimental results show disagreements with the Ozawa equation.
