Influences of halloysite nanotubes on crystallisation behaviour of polylactide

Abstract

The aim of this study was to investigate influences of halloysite nanotubes (HNTs) on the (i) isothermal and (ii) non-isothermal crystallisation kinetics of polylactide (PLA) by differential scanning calorimetry (DSC) analyses, and (iii) crystallinity of injection moulded and then annealed specimens by DSC and X-ray diffraction (XRD) analyses. Nanocomposites were compounded using melt mixing technique via twin screw extrusion. Owing to basically very effective heterogeneous nucleation effect, addition of HNTs resulted in significant increases in the crystallinity of PLA under all three cases. Crystallisation time parameters and Avrami rate constants indicated that crystallisation rate increased under isothermal crystallisation, while it decreased under non-isothermal crystallisation due to the delayed conformational mobility of PLA chains by the physical barrier actions of HNTs. Avrami exponent also revealed that two-dimensional growth mechanism of crystallites transformed into three-dimensional growth during non-isothermal crystallisation, while there was no change during isothermal crystallisation. Crystallinity determinations of the injection moulded and then annealed specimens indicated that, the highest crystallinity degree of PLA, i.e. 47%, could be reached by the addition of only 1 wt-% HNT.     

Poly(ethylene succinate)/single-walled carbon nanotube composites: a study on crystallization

An investigation on the crystallization of composites based on poly(ethylene succinate) and unmodified single-walled carbon nanotube was made in this report. Both isothermal and non-isothermal modes were studied along with subsequent melting behavior using differential scanning calorimetry. Crystal morphology was then explored using X-ray scattering and infrared spectroscopy. It was observed during isothermal crystallization that carbon nanotube (CNT) could contribute to the crystallization rate through heterogeneous nucleation. Furthermore, nanotubes enhanced the crystallinity within low and high undercooling rather than medium undercooling. Similar findings were obtained in non-isothermal crystallization mode. At lower cooling rates, the crystallization rate was more strongly influenced by the nanotubes, while at higher cooling rates the crystallinity was affected to the greater extent. The onset of the cold crystallization of polymer remained unaffected in presence of the nanotube, while its extent was reduced. X-ray diffraction together with infrared spectroscopy found that the polymer crystalline morphology was of α type, and no transition from α to β occurred in presence of the CNT.     

The Numerical Simulation of the Crystallization Morphology Evolution of Semi-Crystalline Polymers in Injection Molding

In polymer processing, crystallization plays a major role in the structure development of polymer, and structure development has important influence on the final properties of the products. Crystallization simulation should be highly concerned with the accurate simulation of polymer processing. In this work, a general formulation system based on the nucleation and growth process of polymer crystallization was adopted to describe the crystallization morphology evolution, and the crystallization process under isothermal and non-isothermal conditions was simulated. The model was introduced in injection molding, and the simulation of morphology evolution of polymer in injection molding was implemented.     

Crystallization of poly(ε-caprolactone)/MWCNT composites: A combined SAXS/WAXS,electrical and thermal conductivity study

In situ crystallization of poly(ε-caprolactone) (PCL) filled with different contents (0.2–5 wt%) of multiwalled carbon nanotubes (MWCNTs) was investigated in X-ray (SAXS/WAXS) synchrotron experiments simultaneously with thermal and electric conductivity measurements. The combined study provides information on nucleation ability of MWCNT, crystallization and melting kinetics, degree of crystallinity as well as the evolution of thermal diffusivity and electrical conductivity of PCL/MWCNT composites during isothermal and non-isothermal crystallization.     

Carbon nanotube surface-induced crystallization of polyethylene terephthalate (PET)

The crystallization of polyethylene terephthalate (PET) and its effect on the electrical behavior of nanocomposites of PET and carbon nanotubes (CNTs) was studied. A series of nanocomposites composed of polyethylene terephthalate/carbon nanotubes (PET/CNTs) containing 0, 1 and 2% wt/wt carbon nanotubes were prepared by melt extrusion. The morphology developed by the nanocomposites during non-isothermal crystallization at different cooling rates was evaluated using various experimental techniques. Thermal analysis showed an increase in the crystallization temperature of the nanocomposites, which was associated with the nucleation ability of the CNTs, and confined growth that resulted in a 3D-to-1D reduction in the crystallite geometry of the nanocomposites. X-ray diffraction indicated that the crystal structure of the nanocomposites was not affected by the presence of carbon nanotubes or the cooling rate. However, the crystallinity of PET and the nanocomposites increased as the cooling rate decreased. The electrical conductivity of the materials as a function of the cooling rate, at a constant CNT content, showed a marked (two orders of magnitude) increase in passing from the amorphous state to the crystalline state. The results of theoretical calculations indicated self-assembly between the surface of the nanotubes and the aromatic ring of PET; it was proposed that the stacking of aromatic rings on the surface of the nanotubes has an effect on the rearrangement of electric charge.     

SEBS-g-MAH对聚乙烯等温及非等温结晶动力学的影响

利用差示扫描量热法结合Avrami方程研究了苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物接枝马来酸酐(SEBS-g-MAH)对线型低密度聚乙烯(LLDPE)等温及非等温结晶动力学的影响。结果表明,热塑性弹性体SEBS及其接枝物的加入阻碍了LLDPE分子链的规则排列,影响了链段在结晶扩散迁移规整排列的速度,使得结晶速率变慢,对LLDPE晶体生长起了抑制作用;LLDPE/SEBS-g-MAH共混体系的半结晶时间t1/2和结晶活化能E明显增大,Avrami指数n对结晶温度有依赖性,kn值随温度的升高而减小。通过Jeziorny法对非等温结晶过程进行处理,试样的Avrami指数n值均在1.1~1.5,表明LLDPE的结晶成核机理和生长方式没有改变。     

Role of multi-wall carbon nanotube network in composites to crystallization of isotactic polypropylene matrix

The composites (iPP/CNTs) made of isotactic polypropylene (iPP) and multi-wall carbon nanotubes (CNTs) were prepared by solution blending. To improve compatibility between CNTs and iPP and to enhance dispersion of CNTs in iPP matrix, CNTs were chemically modified by grafting alkyl chains. The chemically modified CNTs had about 6 wt% grafted alkyl chains. Rheological measurements indicated that CNTs caused gelation in iPP/CNTs due to CNT network formation and the critical gelation CNT concentration was about 7.4 wt%, which was considered to be high due to the low CNT aspect ratio in this study. Crystallization behaviors of iPP/CNTs were studied by using optical microscopy (OM) and differential scanning calorimetry (DSC). Radial growth rates of spherulites during isothermal crystallization of iPP/CNTs with CNT concentrations less than 2.0 wt% measured by using OM showed decreasing trends with increasing CNT concentration. Avrami analysis of the exothermic heat flow curves during isothermal crystallization of iPP/CNTs measured by DSC indicated that crystallization rates were accelerated when CNT concentrations were lower than the critical gelation concentration, because CNTs mainly functioned as nucleating agents for crystallization, while crystallization rates did not change obviously when CNT concentrations were higher than the critical gelation concentration, because CNT network could form and mainly functioned to provide restriction to mobility and diffusion of iPP chains to crystal growth fronts.     

微米铜颗粒对Cu/LDPE/MVQ复合材料非等温结晶性能的影响

采用注射成型法制备了铜/低密度聚乙烯/甲基乙烯基硅橡胶(Cu/LDPE/MVQ)复合材料和低密度聚乙烯/甲基乙烯基硅橡胶(LDPE/MVQ)复合材料,采用差示扫描量热法(DSC)研究了复合材料的非等温结晶行为。结果表明,随着冷却速率的加快,复合材料的结晶度逐渐增大。铜颗粒在复合材料中作为异相成核点,同时阻碍着LDPE分子链的运动。     

聚苯硫醚/碳纳米管复合材料的非等温结晶性能

利用双螺杆挤出机制备了纤维用聚苯硫醚/多壁碳纳米管(PPS/MWCNTs)复合材料。通过差示扫描量热法(DSC)研究了不同降温速率下纯PPS以及PPS/MWCNTs复合材料的非等温结晶过程,并运用Ozawa模型进行了非等温结晶动力学分析。结果表明:降温速率对PPS/MWCNTs复合材料的结晶性能有很大的影响,当降温速率为20℃/min时,PPS/MWCNTs复合材料的结晶能力及相对结晶度最大;MWCNTs在PPS结晶过程中起异相成核剂的作用,使PPS/MWCNTs复合材料的结晶温度较纯PPS升高。     

Non-isothermal crystallization of monomer casting polyamide 6/functionalized MWNTs nanocomposites

Monomer casting polyamide 6(MCPA6)/toluene 2,4-diisocyanate functionalized multi-walled carbon nanotubes (MWNTs-NCO) nanocomposites were prepared via in situ anionic ring opening polymerization, and the non-isothermal crystallization behavior of the nanocomposites were investigated by differential scanning calorimetry with various cooling rates. The commonly used Avrami, Ozawa, Mo, and Urbanovici–Segal models were employed to analyze the non-isothermal crystallization data and the validity of the models on the process of MCPA6 and its nanocomposites was discussed, where Mo and Urbanovici–Segal models could well describe the non-isothermal crystallization process for the samples. The results revealed that MWNTs could accelerate the crystallization process of MCPA6, attributing to the nucleating effect of the nanofillers. Finally, the effective energy barrier for non-isothermal crystallization was evaluated as a function of the relative crystallinity by applying an isoconversional method.     

MCPA6/纳米TiO2原位复合材料的熔融行为

采用差示扫描量热法(DSC)研究了铸型尼龙6(MCPA6)及其纳米TiO2原位复合材料的等温结晶与非等温结晶晶体的熔融行为。结果表明：MCPA6／纳米TiO2原位复合材料等温结晶晶体的熔融行为呈现三重熔融峰,非等温结晶晶体的熔融行为呈现二重熔融峰;其高温熔融峰温随等温结晶温度或降温速率的变化基本不变,而低温熔融峰温则随等温结晶温度的升高或降温速率的减小而提高;纳米TiO2的加入对MCPA6有一定的成核作用,使其熔点提高。     

The electrical properties and crystallization of stereocomplex poly(lactic acid) filled with carbon nanotubes

Multi-walled carbon nanotubes (MWCNTs) filled poly(l-lactic acid) (PLLA) and PLLA/poly(d-lactic acid) (PDLA) composites were prepared through a directly melt mixing process. A special crystalline structure of stereocomplex was formed by PLLA and PDLA, which was easily found when mixing two polymers with identical chemical composition but different steric structures. The electrical conductivities were greatly improved by the formation of stereocomplex compared to that of PLLA/MWCNT composites at same MWCNT content. The percolation threshold of the PLLA/PDLA/MWCNT composite at a PLLA/PDLA weight ratio of 50/50 was 0.35 wt%, while being 1.43 wt% of PLLA/MWCNT composites. The X-ray diffraction, non-isothermal and isothermal crystallization results showed that the formation of stereocomplex greatly increased the crystallinity of the composites, meanwhile MWCNTs acted as heterogeneous nucleating agent, which significantly accelerated the nucleation and spherulite growth. Therefore, the PLLA/PDLA/MWCNT composites have a very low percolation threshold due to the volume exclusion effect.     

PTT的等温与非等温结晶动力学研究

采用DSC方法对聚对苯二甲酸丙二酯进行等温与非等温结晶动力学研究,利用不同动力学模型对其结晶过程进行分析.结果表明,在等温结晶过程中,Avrami指数n和半结晶时间随着结晶温度的升高而增大,结晶速率常数K随着结晶温度的升高而减小;在非等温结晶的过程中,结晶动力学常数Zc和相对过冷度△Tc随着降温速率的提高而上升,Avr...     

低熔点聚酰胺的结晶和熔融行为

采用差示扫描量热法和X射线衍射法对低熔点聚酰胺的结晶和熔融行为进行研究,考察了共聚单体、等温结晶温度和时间对样品结晶和熔融行为的影响。结果表明:经等温结晶后的样品再次升温时,均出现了双熔融峰,且随等温结晶温度的升高或时间的延长,低温熔融峰向高温方向移动,而高温熔融峰则基本不变。等温结晶温度80℃时,两种样品的熔融焓值均较大,并且随结晶时间的延长会变大。X射线衍射结果表明:随着结晶温度的升高或时间的延长,衍射峰变得尖锐,样品的结晶度增大。添加了十二烷基二胺的切片B比添加癸二胺的切片A具有更好的结晶能力,比较适合纺丝加工。     

Anisotropic thermal conductivity of polypropylene composites filled with carbon fibers and multiwall carbon nanotubes

Polypropylene‐based composites filled with carbon fibers and multiwall carbon nanotubes were produced by coagulation precipitation technique. Composite articles were produced by conventional injection molding technique. It was shown that the addition of carbon nanotubes (10% of total amount of carbon fibers) results in significantly increased anisotropic thermal conductivity of the composite due to formation of thermal conductive bridges between carbon fibers, which are oriented during molding. The addition of CNTs has a significant effect with more than a 50–70% increase of both the axial and transverse thermal conductivity of the composite. Produced composites were used for injection molding of polymeric radiators for LED lamps, showing sufficient heat dissipation efficiency allowing using them for industrial application in the field. POLYM. COMPOS., 36:1951–1957, 2015. © 2014 Society of Plastics Engineer     

Throughput calculation with considerations of leakage flow on injection molding plasticizing units

The metering time or melt throughput frequently dictates the cost efficiency of the injection molding process, which means that as accurate as possible an advance calculation must be guaranteed. In the past, leakage flow via the screw flights was neglected in pressure/throughput calculations for plasticizing units on injection molding machines. This paper presents equations for the melt throughput calculation of isothermal/non-isothermal Power Law fluid in multi-zone screws when considering the leakage flow over the screw flights. The concluding comparison of experimental and calculated throughputs shows a good level of agreement.     

Crystallization behavior of biodegradable poly(L‐lactide)/multiwalled carbon nanotubes nanocomposites from the amorphous state

Crystallization behavior of biodegradable poly(L ‐lactide) (PLLA) and its nanocomposites at different carboxyl‐functionalized multiwalled carbon nanotubes (f‐MWNTs) contents from the amorphous state was studied in detail in this work. For the isothermal cold crystallization, the presence of f‐MWNTs enhances the isothermal cold crystallization of PLLA in the nanocomposites compared with that of neat PLLA at the same crystallization temperature; moreover, the overall cold crystallization rate of PLLA increases with increasing the f‐MWNTs content in the PLLA matrix while the crystallization mechanism does not change. For the nonisothermal crystallization, the f‐MWNTs also accelerate the crystallization process of PLLA. In addition, the activation energies of nonisothermal cold crystallization process were calculated using both the Kissinger and Friedman methods. The cold crystallization activation energies of PLLA are higher in the nanocomposites than in neat PLLA, indicating that the addition of f‐MWNTs into the PLLA matrix acts as a physical hindrance to retard crystallization. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Combined effect of shear and nucleating agent on the multilayered structure of injection‐molded bar of isotactic polypropylene

Molten polymers are usually exposed to varying levels of shear flow and temperature gradient in most processing operations. Many studies have revealed that the crystallization and morphology are significantly affected under shear. A so‐called “skin‐core” structure is usually formed in injection‐molded semicrystalline polymers such as isotactic polypropylene (iPP) or polyethylene (PE). In addition, the presence of nucleating agent has great effect on the multilayered structure formed during injection molding. To further understand the morphological development in injection‐molded products with nucleating agent, iPP with and without dibenzylidene sorbitol (DBS) were molded via both dynamic packing injection molding (DPIM) and conventional injection molding. The structure of these injection‐molded bars was investigated layer by layer via SEM, DSC, and 2 days‐WAXD. The results indicated that the addition of DBS had similar effect on the crystal size and its distribution as shear, although the later decreased the crystal size more obviously. The combination of shear and DBS lead to the formation of smaller spherulites with more uniform size distribution in the injection‐molded bars of iPP. A high value of c‐axis orientation degree in the whole range from the skin to the area near the core center was obtained in the samples molded via DPIM with or without DBS, while in samples obtained via conventional injection molding, the orientation degree decreased gradually from the skin to the core and the decreasing trend became more obvious as the concentration of DBS increased. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Isothermal and nonisothermal crystallization kinetics of poly(ε‐caprolactone)/multi‐walled carbon nanotube composites

Differential scanning calorimeter (DSC) and polarized optical microscopy (POM) have been used to investigate the isothermal and nonisothermal crystallization behavior of poly(ε‐caprolactone) (PCL)/multi‐walled carbon nanotube (MWNT) composites. PCL/MWNT composites have been prepared by mixing the PCL polymer with carboxylic groups containing multi‐walled carbon nanotubes (c‐MWNTs) in tetrahydrofuran solution. Raman spectrum of c‐MWNT indicated the possible presence of carboxylic acid groups at both ends and on the sidewalls of the MWNTs. The TEM micrograph showed that the c‐MWNT is well separated and uniformly dispersed in the PCL matrix. DSC isothermal results showed that the introduction of c‐MWNT into the PCL initiates strongly heterogeneous nucleation, which induced a change of the crystal growth process. The activation energy of PCL significantly decreases by adding 0.25 wt% c‐MWNT into PCL/c‐MWNT composites and then increases as c‐MWNT content increases. The result demonstrates that the addition of c‐MWNT into PCL induces the heterogeneous nucleation at lower c‐MWNT content and then inhibits the polymer chain transportation ability during crystallization at higher c‐MWNT content. In this study, we have also studied the nonisothermal crystallization kinetics and melting behavior of PCL/c‐MWNT composites at various cooling rates. The correlation among isothermal and nonisothermal crystallization kinetics and melting behavior of PCL/c‐MWNT composites can be also discussed. POLYM. ENG. SCI., 46:1309–1317, 2006. © 2006 Society of Plastics Engineers     

Improving mechanical performance of injection molded PLA by controlling crystallinity

Currently, use of poly(lactic acid) (PLA) for injection molded articles is limited for commercial applications because PLA has a slow crystallization rate when compared with many other thermoplastics as well as standard injection molding cycle times. The overall crystallization rate and final crystallinity of PLA were controlled by the addition of physical nucleating agents as well as optimization of injection molding processing conditions. Talc and ethylene bis‐stearamide (EBS) nucleating agents both showed dramatic increases in crystallization rate and final crystalline content as indicated by isothermal and nonisothermal crystallization measurements. Isothermal crystallization half‐times were found to decrease nearly 65‐fold by the addition of only 2% talc. Process changes also had a significant effect on the final crystallinity of molded neat PLA, which was shown to increase from 5 to 42%. The combination of nucleating agents and process optimization not only resulted in an increase in final injection molded crystallinity level, but also allowed for a decreased processing time. An increase of over 30°C in the heat distortion temperature and improved strength and modulus by upwards of 25% were achieved through these material and process changes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008