Manipulation of thick-walled PEEK bushing crystallinity and modulus via instrumented compression molding

An instrumented hot compression molding apparatus was fabricated to allow real-time monitoring and precise temperature control during the compaction and consolidation of large polyether ether ketone (PEEK) products. The objective was to determine the impact of controlled variables on the properties of the molded article. Four different strategies were designed to control the mold thermal profiles. The average crystallinity in a commercial molding process is restricted due to large thermal masses with low thermal conductivity. In contrast, this research was able to reduce the crystallinity range from 33% to 6% by developing a special controlled apparatus and implementing new processing methodologies. In this study, PEEK showed a significant increase in the modulus compared to typical values measured on commercially produced analogs, and a higher degree of property uniformity. In a single commercially molded PEEK billet, compressive modulus variability was 13% at room temperature, and 21% at 225°C. Properties of billets produced using the laboratory apparatus showed a reduction in variability to 2%.     

A re-examination of the elastic modulus dependence on crystallinity in semi-crystalline polymers

The elastic modulus versus crystallinity linear relationship in Polyethylene (PE) is re-examined via meticulous measurements over a wide set of PE. First, large discrepancies to linearity are observed; moreover, Raman spectroscopy revealed that the content of the so-called interphase exhibits considerable variations over the set of PE. Therefore a novel strategy based on DMA is developed for a better identification of the modulus of each phase along the temperature.On the one hand, below the α and β relaxations, the young modulus proved to be linearly dependant on the sum of the crystal and interphase content. On the other hand, between the α and β relaxations, the interphase appears surprisingly as stiff as the crystal. In addition, the quenched samples exhibit a particular behavior. A simple model has lead to the conclusion that their mechanical coupling and/or amorphous modulus are significantly different as compared with all others materials.     

Effect of the melt flow index and melt flow rate on the thermal degradation kinetics of commercial polyolefins

In this study, several polyolefins, including different grades of polypropylene (PP), high‐density polyethylene, linear low‐density polyethylene, and low‐density polyethylene, were tested by thermogravimetric analysis (TGA), and the relationships of their melt flow index (MFI) and melt flow ratio (MFR) values to the thermogravimetry (TG) curves, differential thermogravimetry (DTG) curves, and activation energy of thermal degradation were investigated. Kinetic evaluations were performed by Friedman and Kissinger analysis methods, and the apparent activation energy values for the overall degradation of different grades of polyethylenes (PEs) and PPs were determined. We found that for the samples with lower MFIs, the thermograms shifted to higher temperatures. Meanwhile, a higher activation energy was needed for their thermal degradation. Also, for samples with higher values of MFR, as a means of molecular weight distribution, a lower activation energy was needed for their thermal degradation, and their TGA thermograms shifted to lower temperatures. The breadth of the DTG curves depended on the MFR in the PEs, although MFR had little effect on the DTG curves in the studied PP grades. Among all of the samples studied, the injection‐molding grades with medium MFIs and low MFRs degraded at higher temperatures and showed better thermal stability. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2012     

Nonisothermal crystallization kinetics of poly(etheretherketone) (PEEK)

Analysis of the crystallization kinetics of poly(etheretherketone) (PEEK) was achieved with dynamic differential scanning calorimetry results. A new kinetic model for the nonisothermal crystallization was derived and the possibility of its application was investigated. By evaluating the parameters in the model, the crystallization behavior of PEEK was analyzed. The experimental and predicted crystallinity change showed good agreement, which indicated that the model equation was appropriate to describe the nonisothermal crystallization kinetics of PEEK. As the melt temperature was increased the number of heterogeneous nuclei decreased, hence the crystallization was delayed.     

Some aspects of nonisothermal crystallization of polymers. I. Relationship between crystallization temperature,crystallinity, and cooling conditions

The changes in temperature and crystallinity of polymer during nonisothermal crystallization were theoretically analyzed assuming a cooling condition under which heat transfer occurs at a rate proportional to the difference in temperature between polymer and the environment. When a plateau appears in the temperature change during crystallization, crystallization temperature can be predicted by a simple method. This method gives nearly the same value as that obtained by successive calculations of temperature and crystallinity throughout the whole process. In addition, a graphic method is presented to predict crystallization temperature. By using the plateau temperature observed in melt-spinning experiments, the crystallization rate under molecular orientation is evaluated. Furthermore, a method applicable to estimating the ultimate crystallinity is proposed. A rough estimation of the increase in the rate of crystallization under molecular orientation was carried out for very high-speed spinning of poly(ethylene terephthalate).     

Effect of crystallization temperature on crystal modifications and crystallization kinetics of poly(L‐lactide)

The crystalline structure of poly(L ‐lactide) (PLLA) have been found to quite depend on the crystallization temperatures (T_cs), especially in the range of 100?120°C, which is usually used as the crystallization temperature for the industrial process of PLLA. The analysis of wide‐angle X‐ray diffraction and Fourier transformed infrared spectroscopy revealed that 110°C is a critical temperature for PLLA crystallization. At T_c < 110°C and T_c ≥ 110°C, the α′ and α crystals were mainly produced, respectively. Besides, the structural feature of the α′‐form was illustrated, and it was found that the α′‐form has the larger unit cell dimension than that of the α‐form. Moreover, the crystallization kinetics of the α′ and α crystals are different, resulting in the discontinuousness of the curves of spherulite radius growth rate (G) versus T_c and the half time in the melt‐crystallization (t_1/2) versus T_c investigated by Polarized optical microscope and Differential scanning calorimetry, respectively. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of temperature and age on the relationship between dynamic and static elastic modulus of concrete

This study investigates the effects of cement type, curing temperature, and age on the relationships between dynamic and static elastic moduli or compressive strength. Based on the investigation, new relationship equations are proposed. The impact-echo method is used to measure the resonant frequency of specimens from which the dynamic elastic modulus is calculated. Types I and V cement concrete specimens with water-cement ratios of 0.40 and 0.50 are cured isothermally at 10, 23, and 50 °C and tested at 1, 3, 7, and 28 days.Cement type and age do not have a significant influence on the relationship between dynamic and static elastic moduli, but the ratio of static to dynamic elastic modulus approaches 1 as temperature increases. The initial chord elastic modulus, which is measured at low strain level, is similar to the dynamic elastic modulus. The relationship between dynamic elastic modulus and compressive strength has the same tendency as the relationship between dynamic and static elastic moduli for various cement types, temperatures, and ages.     

Morphology and properties of foamed high crystallinity PEEK prepared by high temperature thermally induced phase separation

Polyetheretherketone (PEEK) is a high-performance semi-crystalline thermoplastic polymer with outstanding mechanical properties, high thermal stability, resistance to most common solvents, and good biocompatibility. A high temperature thermally induced phase separation technique was used to produce PEEK foams with controlled foam density from PEEK in 4-phenylphenol (4PPH) solutions. Physical and mechanical properties, foam and bulk density, surface area, and pore morphology of foamed PEEK were characterized and the role of PEEK concentration and cooling rate was investigated. Porous PEEK with densities ranging from 110 to 360 kg/m³ with elastic moduli and crush strength ranging from 13 to 125 MPa and 0.8 to 7 MPa, respectively, was produced.     

Effect of monomeric unit length on crystallinity and Young's modulus for highly oriented fibers

Summary Crystallinity and Young's modulus for ultra-drawn fibers in relation to the crystallographic monomeric unit length (d) are studied. Unique relationships with the logarithm of d are found in the ultimate crystallinity and the ultimate Young's modulus. For producing ultra-high modulus fibers from flexible or rigid polymers, the shorter the unit length is better or the higher the thermal characteristic temperature such as glass transition temperature is preferred.     

Dynamic-mechanical and dielectric characterization of PEEK crystallization

Dynamic-mechanical and dielectric characterization of the cold crystallization of PEEK has been performed in order to develop a non-destructive evaluation method of crystallinity in thermoplastic matrices. The Avrami approach is applied here to describe the Poly(ether ether ketone) (PEEK) crystallization kinetics after an appropriate reduction of dynamic-mechanical and dielectric parameters. Avrami exponents obtained from dielectric characterization are comparable with those obtained with DSC measurements reported in literature, while the exponents obtained from the dynamic-mechanical characterization are higher, reflecting also changes in the aspect ratio of the growing crystals. Variations in the glass transition temperature detected during cold crystallization are analyzed and analogies between PEEK and PET are discussed.     

Quantification of the Young's modulus for polypropylene: Influence of initial crystallinity and service temperature

In this study, the mechanical properties of isotactic polypropylene (iPP) materials with different crystallinities at room and elevated temperatures were investigated. In order to obtain samples with a certain range of crystallinity, and to ensure a uniform microstructure of these samples, the iPP samples obtained by injection molding required melt compression molding and controlled annealing. In the macromechanical studies, the experimental results showed that the storage modulus and Young's modulus of polypropylene were sensitive to the service temperature. The crystallinity also had a great influence on this relationship. A function was proposed to evaluate the dependence of the Young's modulus of polypropylene on initial crystallinity and service temperature, and tested based on experimental data. The Young's modulus of iPP is reduced by about 90% when the service temperature rises from 25 to 125 °C. Moreover, the reduced value in Young's modulus between polypropylene having the highest and lowest crystallinity was reduced from 214.55 to 56.75 MPa. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48581.     

Y型分子筛结晶度和晶胞常数随温度变化规律

选取1种NaY分子筛和3种Si Cl4气相超稳法制得的DY分子筛作为研究对象,通过X荧光光谱(XRF)、N2吸附-脱附、热重(TG-DSC)和场发射扫描电镜(SEM),考察4种Y型分子筛物化性质的差异,利用原位升温粉末X射线衍射(in-situ XRD)考察相对结晶度(室温升至1 000℃)和晶胞常数(室温升至600℃)随温度变化的规律。结果表明,升温过程中4种Y型分子筛相对结晶度均表现为先升后降,NaY型分子筛在900℃时晶体结构完全消失,硅铝比较高的DY分子筛在1 000℃时,相对结晶度仅15%~35%;随着温度升高,NaY分子筛晶胞常数先减后增,而DY-1和DY-2分子筛晶胞常数先增后减,DY-3分子筛晶胞常数一直减少。(555)晶面衍射峰的偏移也随温度和骨架硅铝比变化呈规律性改变。     

Effect of copolymerization on crystallization kinetics of semicrystalline polyimides

Isothermal melt crystallization kinetics and nonisothermal cold crystallization kinetics of co‐PI based on 3, 3′, 4, 4′‐biphenyltetracarboxylic dianhydride (s‐BPDA)/1, 3‐bis‐(4‐aminophenoxy) benzene (TPER)/4, 4′‐oxydianiline(4, 4′‐ODA), and TPER PI (s‐BPDA/TPER) have been investigated. Avrami equation was used to analyze isothermal melt crystallization progress of TPER PI and co‐PI, primary crystallization processes was found to be changed as the introduction of 4, 4′‐ODA. Total activation energy ΔE for TPER PI and co‐PI were found to be ?404 and ?86 kJ mol^?1 by Arrhenius equation. Jeziorny's analysis, Ozawa's analysis, and Mo's approach were used to investigate nonisothermal cold crystallization progress of TPER PI and co‐PI. Activation energy ΔE_non for TPER PI and co‐PI were found to be 247 and 193 kJ mol^?1 by Kissinger equation. The result indicated that co‐PI exhibited lower crystallization rate than TPER PI when isothermally crystallized from melt, but higher crystallization rate under cold nonisothermal crystallization progress. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of isotacticity distribution on crystallization kinetics of polypropylene

The crystallization kinetics of isotactic polypropylene (iPP) depends not only on the undercooling but also on its microstructure characteristics. In this paper the effect of isotacticity distribution on the isothermal kinetics of iPPs in the crystallization regime III was examined by differential scanning calorimetry. The microstructure features of two commercial film grade iPPs were characterized with temperature rising elution fractionation and size exclusion chromatography. The results indicated that, although the overall isotacticities and molecular weights of two iPPs were similar, their isothermal crystallization kinetics displayed marked differences due to the disparity in isotacticity distributions. With increasing molecular weight of components containing crystallizable units, the isothermal crystallization rate exhibited a higher temperature dependence. When the isotactic defects in polypropylene chains increase with the molecular weight of components, both the fold surface free energy σ_e and the work of chain folding q decreases, in spite of the higher molecular weight. © 2002 Society of Chemical Industry     

Isothermal crystallization kinetics and effect of crystallinity on the optical properties of nanosized CeO2 powder

The isothermal crystallization kinetics and effect of crystallinity on the optical properties of cerium dioxide (CeO₂) nanopowders synthesized using a coprecipitation route at 293 K and pH 9 were investigated using X-ray diffraction, transmission electron microscopy, selected area electron diffraction, and ultraviolet–visible absorption spectrophotometry. The activation energy of CeO₂ crystallization from dried cerium dioxide precursor powders by isothermal method of 64.1±3.24 kJ/mol was obtained. The average value of the growth morphology parameter (n) is 1.94, meaning that two-dimensional growth with plate-like morphology was the primary mechanism of CeO₂ crystallization from cerium dioxide precursor powders. The indirect band gap energy (E_i) of CeO₂ decreased from 3.03 eV to 2.83 eV when the crystallinity increased from 18% to 82%, and the direct band gap energy (E_d) of CeO₂ also decreased from 3.76 eV to 3.64 eV.     

Effect of flow rate on temperature in a Bi-P-O catalyst bed: Global enhancement by forced flow rate cycling

Effects of flow rate on reactivity of oxidative coupling of propylene with Bi₂O₃-P₂O₅ were investigated by reaction experiments and by model calculations. Although the conversion is lower at the higher flow rate because of the shorter contact time, there may be a case that when the temperature in the catalyst bed increases and it causes the reaction rate to accelerate. It is thought that the heat was accumulated in the catalyst bed when heat generation rate was much faster than the heat removal rate. The simple calculation based on the assumption of the pseudo-homogeneous phase indicated that the heat was not accumulated at the higher flow rate by the steady-state operation. However, heat wave emerged and accelerated the reaction after the flow rate was changed from the lower flow rate to the higher flow rate. Forced flow rate cycling, an operation where flow rate is changed periodically, was experimentally conducted. The time averaged conversion was slightly enhanced compared with the result from the steady-state operation at the flow rate of . In addition, even in the steady-state operation under the condition where a non-adiabatic reactor packed with only catalyst was used, the conversion and the yield of benzene became higher at the higher flow rate because of the temperature increase in the catalyst bed.     

Effect of surface nucleation on isothermal crystallization kinetics: Theory, simulation and experiment

Surface nucleation of poly(l/d-lactide) at the interface with aluminum was studied by performing isothermal DSC analysis of amorphous samples of varying thickness between 100 °C and 130 °C. To ensure complete wetting of the aluminum surface, a hot melt laminating process was used to prepare the samples. Theoretical aspects of surface crystallization kinetics were explored and the resulting model was compared with the results of Monte-Carlo simulations. Three stages of surface crystallization were identified depending on the growth geometry: (1) impingement-free growth, (2) increasingly laterally-constrained transverse growth, and (3) interstitial growth. By fitting the Monte-Carlo simulation to the experimental half-times of crystallization the surface nucleation concentration and the bulk nucleation rate was estimated at 4 different temperatures. It was found that both surface nucleation concentration and the bulk nucleation concentration decrease with increasing crystallization temperature.     

Permeability and elastic modulus of cement paste as a function of curing temperature

The permeability and elastic modulus of mature cement paste cured at temperatures between 8 °C and 60 °C were measured using a previously described beam bending method. The permeability increases by two orders of magnitude over this range, with most of the increase occurring when the curing temperature increases from 40 °C to 60 °C. The elastic modulus varies much less, decreasing by about 20% as the curing temperature increases from 20 °C to 60 °C. All specimens had very low permeability, k < 0.1 nm², despite having relatively high porosity, ? ~ 40%. Concomitant investigations of the microstructure using small angle neutron scattering and thermoporometry indicate that the porosity is characterized by nanometric pores, and that the characteristic size of pores controlling transport increases with curing temperature. The variation of the microstructure with curing temperature is attributed to changes in the pore structure of the calcium–silicate–hydrate reaction product. Both the empirical Carmen–Kozeny, and modified Carmen–Kozeny permeability models suggest that the tortuosity is very high regardless of curing temperature, ξ ~ 1000.