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.

Non-isothermal crystallization kinetics of Nylon 10T and Nylon 10T/1010 copolymers:Effect of sebacic acid as a third comonomer

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.

Non-isothermal Crystallization Kinetics of Polyamide 6/Diaminemodified MWNTs Nanocomposite

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.

Non-isothermal Melt Crystallization Kinetics of Anhydrite-Filled Polypropylene Composites

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.

KINETICS OF NON-ISOTHERMAL CRYSTALLIZATION

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.

Non-isothermal crystallization kinetics of reactive microgel/nylon 6 blends

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.

Non-isothermal Crystallization Kinetics of Kaolin Modified Polyester

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.

Non-Isothermal Crystallization Kinetics of PET Under Solid State Poly condensation

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.

Non-isothermal Crystallization Kinetics of Modified Poly(ethylene terephthalate) with Ultraviolet Protection

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.

KINETICS OF NON-ISOTHERMAL CRYSTALLIZATION OF NYLON-1010

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.

KINETICS OF NON-ISOTHERMAL CRYSTALLIZATION OF POLY (ETHYLENE TEREPHTHALATE) MODIFIED BY POLY (ETHYLENE GLYCOL)

The non-isothermal crystallization kinetics of poly(ethylene terephthalate) (PET) modified by poly (ethlene glycol) (PEG) were determined by DSC. The dual linear regression method was used to evaluate the relationship between the reciprocal of t 1/2 ( the half life of crystallization) and the appropriate temperature variable. The parameters such as the activation energy (Ed) for transport, the equilibrium melting temperature (T_m^0),the nucleation parameter (ψ),themaximum crystallization temperature (T_(e, max)), and the kinetic crystallizability (G) for the copolyesters were obtained. The influence of the PEG content in PET chains on the parameters characterizing crystallization kinetics and crystallization thermodynamics was discussed.

Isothermal and Non-Isothermal Crystallization Kinetics of Conductive Polyvinylidene Fluoride/Poly(Ethylene Terephthalate) Based Composites

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.

THE NON—ISOTHERMAL CRYSTALLIZATION KINETICS OF A LIQUID CRYSTALLINE RANDOM COPOLYESTER WITH DIFFERENT COMPOSITIONS

The non-isothermal crystallization kinetics analysis of liquid crystalline random copolyestercomposed of p-oxybenzoate (B) and 2, 6-oxynaphthoate (N) monomers was carried out by meansof differential scanning calorimetry basing on Ziabicki and Jeziorny method. Although the compo-sition of 58/42 B-N copolyester had poorer thermodynamic crystallizability comparing with thoseof 30/70 and 75/25, its kinetic crystallizability Go was slightly larger. This fact was due to thepoorer match of sequences of 58/42 B-N in domains of nematic melt,and therefore better mobilityof chains during crystallization. The Avrami exponents of three composition species were allabout 2. 5, implying two dimensional growth in so-called non-periodic layer crystallites and a mixture of homogeneous and heterogeneous nucleation.

EFFECT OF N,N,N＇N＇-TETRAALKYL TEREPHTHALAMIDE ON NONISOTHERMAL CRYSTALLIZATION KINETICS OF POLYPROPYLENE

The effect of N,N,N＇,N＇-tetraalkyl terephthalamide （TATA） on the non-isothermal crystallization and melting characteristics ofpolypropylene （PP） was studied. The addition of TATA can lead to the formation ofβ-crystal PP. With the increase in TATA concentration the degree of crystallinity for β-crystal PP increased significantly, and that for a-crystal PP decreased, which indicated that TATA effectively induced the formation of β-crystal PP. WAXD also revealed the existence of β-crystal PP after the introduction of TATA into PP. PP containing TATA crystallized at a temperature range of 5-10℃ higher than that of pure PP, and the half-crystallization time （t1/2） and Avrami exponent （n） of PP at the same cooling rate were decreased by the addition of TATA, indicating that TATA influenced the crystallization rate and crystallization growth mode of PP. The rate constant of crystallization of PP containing TATA （Zc） was larger than that of pure PP, which further indicated that the crystallization of PP was accelerated by the addition of TATA.

Magnetic properties and crystallization kinetics of Zn_(0.5) Ni_(0.5) Fe_2O_4

Precursor of nanocrystalline Zno.sNio.sFe2O4 was obtained by grinding mixture of ZnSO4.7H2O, NiSO4.6H2O, FeSO4.7H2O, and Na2CO3.10H2O under the condition of suffactant polyethylene glycol （PEG）-400 being present at room temperature, washing the mixture with water to remove soluble inorganic salts and drying it at 373 K. The spinel Zn0.5Ni0.5Fe2O4 was obtained via calcining precursor above 773 K. The precursor and its calcined products were characterized by differential scanning calorimetry （DSC）, Fourier transform infrared （FF-IR）, X-ray diffraction （XRD）, and vibrating sample magnetometer （VSM）. The result showed that Zn0.sNio.sFe204 obtained at 1073 K had a saturation magnetization of 74 A.mLkg-1. Kinetics of the crystallization process of Zn0.5Ni0.5Fe2O4 was studied using DSC technique, and kinetic parameters were determined by Kissinger equation and Moynihan et al. equation. The value of the activation energy associated with the crystallization process of Zr0.5Ni0.5Fe2O4 is 220.89 kJ-mol-1. The average value of the Avrami exponent, n, is equal to 1.59±0.13, which suggests that crystallization process of Zn0.5Ni0.5Fe2O4 is the random nucleation and growth of nuclei reaction.

Non-Isothermal Degradation and Kinetics Studies of Some Quinaldine Azo Dye Complexes

4-(R-Phenylazo)-2-methyl quinoline derivatives form (1:1) complexes with nickel chloride, nickel acetate and copper acetate which were syntheses. The three complexes are non-electrolyte in dimethylsulfoxide (DMF). The results of electronic and magnetic measurements show that these complexes are of octahedral structures. The oxygen and nitrogen donate their lone-pair electrons to metal ion to form chelates with formula [MLRm.nH2O]. The relative stabilities of the complexes have been calculated from TG curve using Coats-Redfern and Ozawa methods.

An Efficient Organic Additive to Control the Crystallization Rate of Aliphatic Polyketone: A Non-isothermal Crystallization Kinetics Study

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.

Effect of Al_2O_3 addition on the non-isothermal crystallization kinetics and long-term stability of BCABS sealing glass for IT-SOFCs

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.

Preparation and crystallization action of SiO_2 -Al_2O_3 -CaO-ZnO-R_2O porous glass-ceramics

Using powder-sintering method,SiO2-Al2O3-CaO-ZnO-R2O porous glass-ceramics were produced for analysis. Five samples with different SiO2 /CaO ratios were used in the research. The mechanical properties, microstructures and textures of porous glass-ceramics are investigated by using differential thermogravimetric analysis/differential thermal analysis ( TGA/SDTA) ,X-ray diffraction ( XRD) ,and scanning electron microsco- py ( SEM) . The activity energy of crystallization ( E) and crystallization kinetics parameter ( k) were calculated based on the modified JMA equation. The Avrami parameter n was obtained according to Augis-Bennett function. The results show that the k value of No. 1 sample ( SiO2 /CaO = 61∶ 18) is the largest among all samples, which tends to crystallize more easily,and crystallization processes of all samples are observed bulk crystallization. The main crystal phase observed is parawollastonite ( clinorhombic system) with puncheon shape. Poreforming agents decomposed at 100 - 500 ℃ form a large number of closed pores with micron dimension and several semi-open pores distribute uniformly in the glass-ceramics matrix. This work may be expected to be favorable for industrial scale applications of porous glass-ceramics in the field of building thermal insulation.

Study on crystallization behavior of Tibet butter

Tibetan butter(TB),generally called butter,is a solid oil product extracted from yak milk in the QinghaiTibet plateau area.However,due to the limitations of raw material sources and production technology,there is a shortage of TB,so it is important to find substitutes of TB.This paper studied the crystallization behavior of six kinds of commercial TB products in Tibet to provide the theoretical basis for the development of TB substitutes for the production of TB lamps and flowers.This study assessed the crystallization behaviors of the TB samples,including isothermal crystallization process and non-isothermal crystallization process.The microstructure,isothermal crystallization of TB were evaluated by polarized light microscopy and low-pulse NMR spectrometry,respectively.The non-isothermal crystallization process of TB under temperature scanning were investigated using Rheometer,and the crystallization behavior under different cooling rates were determined by diferential scanning calorimetry(DSC)procedures.The results showed that the TB was crystallized at a higher supercooling(-10,0 and 10℃).Dimensional growth is dominant;at 20℃,spiral growth dominates.The TB has complex crystallization nucleation behavior.The crystal types of TB are mainlyβ’-crystal form andβ’-like crystal form.The lower the cooling rate,the shorter the crystallization induction time,and the more the number of crystal nuclei.Therefore,during producing TB substitutes in the factory,the cooling rate can be controlled at10℃/min to reduce energy consumption and production costs.