Fusion behavior of plastisols of PVC studied by ATR-FTIR

The behavior of PVC plastisols during gelation and fusion was studied by the ATR-FTIR technique (Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy). DBP, DOP, and DIDP, three common phthalate plasticizers for PVC, were used in plastisols formulations. Three heating rates—5, 10 and 15°C/min—and formulations with different plasticizer concentrations were studied. The IR spectra of a plastisol coincides with the IR spectra of the plasticizer except for the bands at 1435 and 613 cm^?1 from the PVC (CH₂ wagging and C—Cl stretching, respectively). When the plastisol is heated, a progressive decrease of the plasticizer bands areas can be observed, while bands from PVC increase their intensity, probably because of the adsorption of the plasticizer by the resin. On cooling, the area of all bands follows the same path as when heating, but the paths separate at a certain temperature, showing the irreversible nature of this process. The analysis of the band at 1280 cm^?1 (C(O)—O from plasticizer) during heating and cooling, shows that the temperature of separation areas (T_s) takes place at temperatures coherent with plasticizer compatibility. Studies at different heating rates and different plasticizer content are in good agreement with results using other techniques, available in the literature.     

Thermal and mechanical properties of plasticized poly(L‐lactic acid)

Acetyl tri‐n‐butyl citrate (ATBC) and poly(ethyleneglycol)s (PEGs) with different molecular weights (from 400 to 10000) were used in this study to plasticize poly(L‐lactic acid) (PLA). The thermal and mechanical properties of the plasticized polymer are reported. Both ATBC and PEG are effective in lowering the glass transition (T_g) of PLA up to a given concentration, where the plasticizer reaches its solubility limit in the polymer (50 wt % in the case of ATBC; 15–30 wt %, depending on molecular weight, in the case of PEG). The range of applicability of PEGs as PLA plasticizers is given in terms of PEG molecular weight and concentration. The mechanical properties of plasticized PLA change with increasing plasticizer concentration. In all PLA/plasticizer systems investigated, when the blend T_g approaches room temperature, a stepwise change in the mechanical properties of the system is observed. The elongation at break drastically increases, whereas tensile strength and modulus decrease. This behavior occurs at a plasticizer concentration that depends on the T_g‐depressing efficiency of the plasticizer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1731–1738, 2003     

Thulium Oxide Nanopowders Obtained by Precipitation

The aim of this work was to investigate the influence of precipitation parameters on the morphology of obtained thulium oxide powders. Tm₂O₃ precursor powders were synthesized by precipitation method using 0.1–0.25M water solutions of thulium nitrate and 1.5M ammonium hydrogen carbonate water solution as a precipitation agent. The processes were conducted at different temperatures (25–50°C). The result showed that the morphology of the obtained thulium oxide (Tm₂O₃) powders depends both on the molar concentration of thulium nitrate and the temperature of precipitation. Small, round, loosely agglomerated Tm₂O₃ nanoparticles were obtained after air calcination of precursor precipitated at room temperature with the use of 0.1M thulium nitrate solution.     

Luminescence Properties and Energy‐Transfer Behavior of a Novel and Color‐Tunable LaMgAl11O19:Tm3+, Dy3+ Phosphor for White Light‐Emitting Diodes

Novel LaMgAl₁₁O₁₉:Tm³⁺, Dy³⁺ phosphors were prepared utilizing a high‐temperature solid‐state reaction method. The phase formation, luminescence properties, energy‐transfer mechanism from the Tm³⁺ to the Dy³⁺ ions, the thermal stability, and CIE coordinates were investigated. When excited at 359 nm, the LaMgAl₁₁O₁₉: xTm³⁺ phosphors exhibit strong blue emission bands at 455 nm. After codoping with Dy³⁺ and excitation at 359 nm, the LaMgAl₁₁O₁₉:0.03Tm³⁺, yDy³⁺ phosphors emitted white light consisting of the characteristic emission peaks of Tm³⁺ and Dy³⁺. The Dy³⁺ emission intensity increased with the Dy³⁺ concentration due to the energy transfer from Tm³⁺ to Dy³⁺, and concentration quenching due to the high Dy³⁺ doping concentration (y = 0.1 mol) did not occur. The calculation of the CIE coordinates of the LaMgAl₁₁O₁₉:Tm³⁺, yDy³⁺ phosphors revealed the tunability of the emission color from blue to bluish‐white and to white by changing the excitation wavelength and the doping concentration. An energy transfer from Tm³⁺ to Dy³⁺ by dipole–dipole interaction was confirmed by the decay curve, lifetime, and energy‐transfer efficiency measurements. When excited at 359 nm, the LaMgAl₁₁O₁₉:Tm³⁺, Dy³⁺ phosphor also showed good thermal stability, suggesting that it can be used in white LEDs excited by a GaN‐based ultraviolet LED.     

Mechanistic investigation of nonisothermal suspension polymerization of vinyl chloride

Vinyl chloride suspension polymerization using different temperature trajectories was carried out in a pilot scale batch reactor. Detailed understanding of the conversion at which the primary particles become motionless (X_m) and the key effects of X_m on morphology development of PVC grains were provided. Motionless conversion is estimated for poly(vinyl chloride) (PVC) grains prepared with different temperature trajectories by cold plasticizer absorption measurements. The porosity of PVC grains (prepared isothermally and nonisothermally) shows a maximum at a certain conversion that is considered motionless conversion. With increasing monomer conversion, the cold plasticizer uptake decreases dramatically with conversions greater than motionless conversion until the monomer phase is completely exhausted (X_f) and continues to slightly decrease after X_f. The decrease in cold plasticizer absorption is more pronounced for PVC grains produced nonisothermally by lower initial temperature. The results obtained by scanning electron microscopy and Brabender^® plastography showed that the changes in internal structure and fusion behavior of PVC grains after X_m would be much lower when early aggregates of primary particles are formed. Scanning electron microscopy photographs indicate that applying the variable temperature with negative slope accelerates networking between the primary particles inside the polymerizing monomer droplets. The Brabender^® plastograph measurements indicate a lower time and temperature of fusion and a higher degree of gelation for nonisothermally produced resin in which the temperature trajectory follows a greater negative slope. J. VINYL ADDIT. TECHNOL., 24:84–92, 2018. © 2015 Society of Plastics Engineers     

Films of chitosan and N‐carboxymethylchitosan. Part II: effect of plasticizers on their physiochemical properties

Chitosan (Ch) and N‐carboxymethylchitosan (N‐CMCh) films were prepared by the casting method at concentrations of 1% and 2% of polymer, with or without plasticizer: polyethylene glycol (PEG‐400) and glycerol (G), at 15% (w/w). The influence of composition on mechanical properties, water vapour transmission rate (WVTR), water saturation, and aqueous dissolution of the films was analysed. The thermal stability of the mixture (polymer:plasticizer, 1:1) was evaluated by thermogravimetric analysis (TGA). In general, all the properties were affected by the plasticizers. The plasticized films showed lower strength and a higher percentage of elongation (%E), in the following order: G > PEG‐400 > unplasticized film. The total WVTR increased with Ch concentration, with a different WVTR profile for Ch and N‐CMCh. While the PEG‐400 addition did not significantly modify the WVTR profile of films, the glycerol enhanced the transport of water vapour through both polymers. The plasticizer addition increased the time of water film saturation, in the following order: G > PEG‐400 > unplasticized film; this was more pronounced in the N‐CMCh films, probably due to the formation of hydrogen bonds. The solubility of the films was also affected by their composition. Copyright © 2006 Society of Chemical Industry     

Diffusion Properties of Tm3+ in Congruent LiNbO3 Crystal

Diffusion properties of Tm³⁺ in congruent LiNbO₃ crystal have been investigated, together with other two related issues, i.e., Tm³⁺‐doping contribution to refractive index of LiNbO₃ substrate and Li out‐diffusion. Four X‐cut and four Z‐cut congruent LiNbO₃ substrates locally coated with 15–31 nm‐thick Tm‐metal films were annealed in surrounding air under different temperatures of 1030°C–1130°C for different durations of 20–70 h. After anneal, refractive index at Tm³⁺‐doped and Tm³⁺‐free parts of crystal surface was measured at the wavelengths of 1311 and 1553 nm and surface Li₂O contents were evaluated from measured refractive index. The results show that Tm³⁺ doping has a weak effect on substrate index and a small contribution to index increment in waveguide layer in comparison with Ti⁴⁺‐ or Zn²⁺ doping. The Li₂O content at the Tm³⁺‐doped surface equals that at the Tm³⁺‐free surface. The Li out‐diffusion depends mainly on the diffusion temperature. Below 1100°C, the Li out‐diffusion is not measurable. At 1130°C, a 30‐h diffusion procedure may cause 0.2–0.3 mol% slight loss of Li₂O content. Secondary ion mass spectrometry was used to study the Tm³⁺ diffusion properties. The results show that the diffused Tm³⁺ ions in all samples follow a complementary error function profile. From measured Tm³⁺ profiles, characteristic diffusion parameters such as diffusivity, diffusion constant, activation energy, solubility, solubility constant, and heat of solution were obtained and discussed in comparison with the case of Er³⁺ diffusion. In comparison with Er³⁺ diffusion, the Tm³⁺ diffusion shows similar anisotropy and temperature dependence of solubility. In the aspect of diffusivity, under lower temperature the Tm³⁺ has a lower diffusivity than the Er³⁺, and their diffusivity difference reduces with the increased temperature and becomes null at 1130°C.     

The preparation of Yttrium Aluminosilicate (YAS) Glass Fiber with heavy doping of Tm3+ from Polycrystalline YAG ceramics

Yttrium aluminosilicate (YAS) glass core fibers with different doping concentration of Tm³⁺ were fabricated by a “Melt‐in‐Tube” method from YAG polycrystalline ceramics. The effect of Tm³⁺ concentration on the spectroscopy of YAG ceramics and laser performance of YAS fibers were discussed. A homemade linear all‐fiber laser based on the obtained 15% Tm³⁺‐doped YAS fiber shows an optimized slope efficiency of 12.8%. The YAS fibers have been proven to be practical to achieve extremely high Tm³⁺ doping concentration and are a promising option for the 2.0 μm laser.     

Color-tunable and white emission of Tm3+ doped transparent zinc silicate glass-ceramics embedding ZnO nanocrystals

Tm³⁺ doped zinc silicate glass-ceramics composed of SiO₂-Al₂O₃-ZnO-K₂O-Tm₂O₃ embedded with ZnO nanocrystals were successfully fabricated by melt-quenching method with subsequent heat treatment. Tm³⁺ ions and ZnO nanocrystals were introduced as blue and yellow luminescence centers, respectively. The effects of heat treatment, excitation wavelength and Tm³⁺ doping concentration on the photoluminescence behaviors of these glass-ceramics were studied. Short-time (5 minutes) heat treatment was considered as the optimal heat treatment time, which facilitates simultaneously emitting narrow blue peak located at 453 nm and a broad yellow band centered at 580 nm. Blue and yellow emissions could be attributed to the ¹D₂ → ³F₄ transition of Tm³⁺ and Zn_i/O_i-related defect emission of ZnO nanocrystals, respectively. The combination of these two emissions allows the realization of white light emitting in the glass-ceramic samples. Furthermore, tunable luminescent color and chromaticity coordinates, including yellow, white and blue, can be realized by varying the pumping wavelengths as well as the content of Tm³⁺ dopant in the glass matrix. Nearly perfect white light emission with Commission Internationale de l'Eclairage coordinate (x = 0.33, y = 0.32) was achieved for the 0.05 mol% Tm³⁺ doped glass-ceramic embedding ZnO nanocrystals by heat treatment at 750°C for 5 minutes under the excitation of 360 nm. These luminescent glass-ceramics doped with Tm³⁺ ion and ZnO nanocrystals could be a promising candidate for white light emitting devices under near-ultraviolet excitation.     

Curing characteristics of glycidyl azide polymer‐based binders

The curing of a glycidyl azide polymer (GAP) with a triisocyanate, Desmodur N‐100, was followed by measuring the hardness and viscosity. The thermal behavior of the cured samples were investigated by a differential scanning calorimeter (DSC) and thermal gravimetric analysis (TGA). Curing causes an increase in the glass transition temperature of GAP. The T_g of gumstocks also increases with an increasing NCO/OH ratio while the decomposition temperature remains practically unchanged. The ultimate hardness of the cured samples increases with an increasing NCO/OH ratio. The binder with a NCO/OH ratio of 0.8 was found to provide the most suitable thermal and physical characteristics for composite propellant applications. The increase in the glass transition temperature of gumstocks upon curing can be compensated by using a 1:1 mixture of bis‐2,2‐dinitropropyl acetal and formal as the plasticizer. The T_g value of gumstocks can be decreased to −46.7°C by adding 25% b.w. of a plasticizer which does not have any significant effect on the decomposition properties of the gumstocks. Furthermore, a remarkable decrease in the ultimate hardness of the gumstocks is achieved upon addition of a plasticizer, while the curing time remains almost unaffected. The addition of dibuthyltin dilaurate as a catalyst reduces the curing time of the gumstocks from 3 weeks to 5–6 days at 60°C. Use of the curing catalyst also results in the hardening of the gumstocks. The decomposition properties of the gumstocks remain practically unchanged while a noticeable increase is observed in the glass transition temperature with an increasing concentration of the catalyst. This can also be compensated by a reverse effect of the plasticizer. The gel time, an important parameter which determines the pot life of a propellant material, can be measured by monitoring the viscosity of the mixture, which shows a sharp increase when gelation starts. The addition of a curing catalyst shortens the gel time remarkably. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 65–70, 2001     

The rate of plasticizer uptake by suspension PVC

A microscopic technique employing image analysis was developed to measure the rate of swell of suspension PVC particles in both excess and finite amounts of plasticizer at temperatures below the crystalline melting point. The rates of plasticizer uptake derived from these swell measurements were found to be dependent upon the concentration of plasticizer and the rate of heating. A high value for the activation energy for plasticizer uptake was observed (60–100 kcal/mol) in agreement with earlier work. Each resin was also characterized by a total capacity for plasticizer (TC) which was found to be dependent on the resin type, the plasticizer type, and the maximum temperature achieved. An expression was derived for the rate of plasticizer uptake in a Brabender powder mix experiment. In this case the dry time is controlled by a single rate up to the maximum capacity for plasticizer of the resin (G_max). Values of G_max and TC were found to correlate on a one-to-one basis when measured at the same temperature. In all the cases investigated the rate of plasticizer uptake in the Brabender was found to correspond to a rate derived from image analysis swell at a plasticizer level of 0.25 cc/g. This behavior was in apparent contradiction to the concentration dependence generally observed and was demonstrated to be due to the large thermal gradients which exist in the Brabender powder mix head during the experiment. This work illustrates that Brabender powder mix times may have no relationship to dry times in a high speed mixer where heating is both even and higher temperatures are achieved.     

Er3+/Tm3+ Co‐diffusion Characteristics in LiNbO3 Crystal

Co‐diffusion characteristics of Er³⁺ and Tm³⁺ ions in LiNbO₃ crystal have been studied, together with two other properties: doping effect on refractive index of substrate, and Li out‐diffusion. Er³⁺/Tm³⁺‐codoped LiNbO₃ single‐crystals were prepared by co‐diffusion of stacked Er‐ and Tm‐metal thin films, coated onto parts of the surfaces of X‐ and Z‐cut congruent LiNbO₃ crystal plates, at different temperatures and different durations in air. After diffusion, the surface refractive indices of the doped and undoped parts were measured by prism coupling technique, and the surface composition was evaluated from the measured indices. The results show that the dopings have negligible effect on the substrate index and the Li out‐diffusion depends mainly on the diffusion temperature. The Er³⁺ and Tm³⁺ profiles were studied using secondary ion mass spectrometry, and a co‐diffusion dynamical model is proposed and verified experimentally. From the measured profiles, the temperature‐dependent Er³⁺/Tm³⁺ diffusivity and solubility were obtained together with other relevant parameters, such as diffusion constant, activation energy, solubility constant and heat of solution. The Er³⁺ and Tm³⁺ co‐diffusion exhibits similar temperature dependent diffusivity, and the dependence is similar to that of single‐diffusion. In the co‐diffusion case, the total solubility consists of two parts: Er³⁺ and Tm³⁺ parts, there is no anisotropy, and the value is equal to that of single‐diffusion case, in which both ions have the similar solubility. The Er³⁺ and Tm³⁺ parts of solubility change relatively with the initial metal film thicknesses and hence have different temperature dependences. Nevertheless, their sum, i.e., the co‐diffusion solubility, remains a constant at a given temperature.     

Performance relationships in PVC–plasticizer dry blending

The phenomenon of plasticizer acceptance by poly(vinyl chloride) (PVC) in hotprocess dry blending is examined via scanning electron microscopy, mercury intrusion porosimetry, and torque rheometer measurements. The effects of granule porosity, resin molecular weight, and synthesis recipe in PVC manufacture by the suspension process are related to the rate of plasticizer acceptance. For a PVC resin to dry blend, i.e., to become a free-flowing powder when mixed with plasticizer under hot-processing conditions, the resin granules must be porous. Porosity arises from interstices between primary PVC particles. At a given granule porosity, an increase in primary particle agglomeration adversely affects dry blend performance. At constant molecular weight and for resins manufactured by a given recipe, dry-blend performance is quantitatively described by granule porosity. With an increase in resin molecular weight, a greater granule porosity is required to maintain an equivalent dry-blend time (DBT). Accordingly, for most suspending agent recipes, DBT is dependent directly upon granule porosity and inversely upon molecular weight. However, if the suspending agent used in resin manufacture is an excessively rapid film former, dry-blend performance with molecular weight variation is dependent upon the suspending agent's concentration, not upon granule porosity, which must be adequate, nor upon the resin's molecular weight. An interfacial film-forming suspending agent enhances fusion of primary PVC particles at the suspension granule—water interface, increasing the granule's “pericellular membrane” thickness. This membrane, a PVC skin, does not significantly influence dry-blend performance with low- or intermediate-viscosity plasticizers. The particle skin does impede dry-blend rates with high-viscosity, poorly solvating plasticizers, but this effect can be negated in part by increasing the diameter of pore openings in the topographical skin. Dry blending occurs below the glass transition temperature (T_g) of PVC with low-viscosity plasticizers and above the T_g with high-viscosity, poorly solvating modifiers. The influence of resin and plasticizer variables indicates the dry-blend phenomenon to be a diffusion-controlled process. The rate of dry blending is dependent upon two mechanisms: (1) the rate of pore penetration—which exposes the plasticizer to a much greater surface area than if it remained exterior, encapsulating the granule—and (2) the rate of plasticizer diffusion into the PVC matrix.     

Efficiency of plasticization of PVC by higher-order di-alkyl phthalates and survey of mathematical models for prediction of polymer/diluent blend Tg's

Presently, a suitable theory to predict the T_g vs. composition relationship for a given polymer-plasticizer blend, based on detailed molecular structure and molecular energitics considerations, is not available. In particular, the plasticizer efficiency parameter, k, which is uniquely defined at low-to-moderate diluent concentrations, and is an essential variable in the Mauritz-Storey theory of the diffusion of large molecules in amorphous polymers in the rubbery state, must always be determined by experiment. In this work, k was determined by DSC for PVC that was plasticized over a range of concentrations with a number of higher branched and linear di-alkyl phthalates. The results will be used in our plasticizer diffusion theory as well as provide guidance in the future development of a general mathematical model for predicting k. It was seen that k decreased with increasing molecular weight for both the linear and branched phthalates. For a given molecular weight, the branched phthalates have higher k values than the linear structures. These results have been rationalized in terms of the additional free volume created by the inefficiency of packing polymer chains about these large penetrant molecules. The DSC scans also implied an increasing degree of microstructural heterogeneity with increasing plasticizer concentration. Finally, relationships between plasticizer diffusion coefficient in the rubbery state and the plasticized T_g were established for low-to-moderate diluent concentration for three of the plasticizers studied by utilizing experimental diffusion data from our earlier work on these systems.     

Effects of plasticizer on structures,non‐isothermal crystallization,and rheological properties of polyarylates

We herein report the effects of plasticizer content (1–5 wt %) on the structure, non‐isothermal crystallization kinetics, thermal stability, and rheological property of a new type of multicomponent polyarylate (PAR). Fourier transform infrared spectra reveal the presence of a specific interaction between plasticizer and PAR chains, indicating the good dispersion of the plasticizer at the molecular level. The plasticizer influences on the non‐isothermal crystallization behavior of the PAR in two different ways: a mobility enhancer of PAR chains and an impurity to the crystallization of PAR. The melt‐crystallization temperature (T_mc) and enthalpy (ΔH_mc) of the plasticized PARs at cooling runs are higher than those of the neat PAR, which is owing to the enhanced mobility of PAR chains by the plasticizer. On the other hand, the non‐isothermal crystallization rates at different cooling rates of 5–40 °C/min are slower for the PARs with higher plasticizer contents, which is due to the impurity effect of the plasticizer on the melt‐crystallization of PARs. Although the PARs with 1–5 wt % plasticizer have lowered thermal decomposition temperatures, compared to the neat PAR, they are thermally stable up to ～400 °C. The complex melt viscosity of PAR with only 1 wt % plasticizer is far lower than that of the neat PAR. Overall, it is found that only 1 wt % plasticizer is quite effective to facilitate the melt‐processibility and to increase the crystallinity of PAR. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45704.     

The role of the Tm3+ concentration on CaMoO4 properties processed by microwave hydrothermal under stirring condition

The compounds based on calcium molybdate (CaMoO₄) are the subject of extensive research due to their excellent optical properties and a broad range of potential technological applications. In this work, we report a systematic study of CaMoO₄:Tm³⁺ phosphors synthesized by coprecipitation and processed in a microwave-hydrothermal system at low temperature (100°C) and stirring. The effect of the Tm³⁺ doping content (0%–12%) is studied in full detail to understand their role in the CaMoO₄:Tm³⁺ morphological, structural, and luminescent properties. The X-ray diffraction, Raman, and Fourier Transform Infrared spectroscopic techniques revealed that all the prepared powders have a tetragonal crystal structure with a distinct density of cation vacancies and structural disorders. The band gap remains almost constant for doping levels lower than 8%, but it narrows strongly for powders doped with 12% Tm³⁺ ions. The designed phosphors have shown two emission bands in which intensity depends on the Tm³⁺ ions doping level. For doping levels lower than 2%, the photoluminescence profile displays a broad emission band peaking at 543 nm (green). For concentrations higher than 4%, the band centered at 543 nm decreases in intensity and the near-infrared emission band at around 800 nm, assigned to ³F₃, ³H₄ → ³H₆ transitions from Tm³⁺ ion, become more intense. The outcomes of this work reveal that appropriated Tm³⁺ ions doping levels can be applied to suppress the PL emission in the visible range and improve that in the near-infrared region in CaMoO₄-based materials.     

Plasticizer migration from plasticized into unplasticized poly(vinyl chloride)

There exist important industrial applications, such as hoses or plastic windows, dealing with closely combining plasticized and rigid poly(vinyl chloride). Nevertheless, migration of plasticizer causes severe variation of the mechanical performance of the end-products. This work comprises an effort to investigate and understand these phenomena, also as an extension of previous work of ours in migration to liquid environments. The common system plasticized PVC/dioctylphthalate/unplasticized PVC was studied under two-sided diffusion conditions, i.e., from a thin sheet of plasticized sheet. The whole assembly was placed between two glass plates and then was held in an oven at 64°C to simulate accelerated test conditions. Some pressure was also applied to ensure perfect contact between the plastic sheets. Three different levels of initial plasticizer concentration (48, 66, and 100 phr) have been considered for a period of about five months, until equilibrium was reached. During this period the migration process was monitored by weight changes. Plots of M_t/M_∞ vs. t^½, where M_∞ the amount migrated at equilibrium and M_t the amount lost at time t, resulted in evident linear relationship. Therefore, it was proved that the Fick's law approximation for short times can be used to describe the migration kinetics for this solid/solid system. On the other hand, macroscopic observations revealed that no plasticizer was accumulated at the interface, i.e. all plasticizer leaving the plasticized sheet entered the rigid ones. Finally, it seems that the controlling stage is the diffusion inside plasticized PVC while possible annealing of the plasticized polymer structure cannot be excluded.     

Interaction between polyvinylchloride resins and di-2-ethylhexylphthalate

The interaction of two polyvinylchloride (PVC) resins, having different morphology, with di-2-ethylhexylphthalate plasticizer has been studied in a Brabender plastograph. Isothermal interaction occurring as a function of time, has been followed by recording the mixing resistance (torque) and determining, by means of a differential calorimeter, the fraction of the plasticizer free and interacted with the resin, on samples drawn out of the Brabender cell at different times. The interaction between PVC resins and di-2-ethylhexylphthalate X plasticizer in the temperature range of 63.7 to 74.3°C and with resin/plasticizer ratios varying from 1.11 to 3.33, has been determined to be:

• described formally by the first order kinetic law as it concerns the resin interacted as a function of time;
• dependent, as far as speed is concerned, on the morphology of resins namely on the specific surface area of the resin and depending whether or not there is a skin on the surface of the particles;
• independent of the resin/plasticizer ratio, at least in the examined range of ratios;
• affected by temperature according to an activation energy of 73 Kcal/mole for both the examined resins.

The mixing torque recorded during the interaction kinetics of the plasticizer with the resins, has been found to be mainly affected by the outer surface state of the resin particles, namely by the concentration (which varies with the time) of the plasticizer in the surface layer of the particles. Systems constituted by PVC resins and di-2-ethylhexylphthalate, with the same resin/plasticizer ratio, interacting at different temperatures, show mixing torques coincident when plotted versus the concentration of the plasticizer in the surface layer of the particles.     

Fatigue crack propagation behavior of cellulose esters

The effect of plasticizer concentration on fatigue crack propagation (FCP) rate in cellulose acetate-propionate (CAP) was determined. Compact tension specimens were machined from 6.2 mm-thick injection molded plaques and tested on an MTS servohydraulic testing machine using a sinusoidal waveform with a frequency of 1 Hz. Two FCP mechanisms were identified: a crazing mechanism, which dominated at low values of stress intensity factor range, ΔK, and a shear yielding mechanism, which dominated at high values of ΔK. The value of ΔK at the onset of the transition from the crazing mechanism to the shear yielding mechanism was a function of plasticizer concentration, and therefore yield strength of the CAP. The transition in crack propagation mechanism created a V-shaped feature on the fracture surface, which could be used to weight the contributions from the two crack propagation mechanisms to the overall FCP rate.     

Strong Influences of Melting Time and Tm3+ Concentration on Blue Up-Conversion Photoluminescence for Tm3+/Yb3+ Co-Doped TeO2–TlO0.5–ZnO Glass

In this study, by a conventional melt quenching method, we synthesized novel up-conversion phosphors of 60TeO₂–30TlO_0.5–(9−x)ZnO–xTm₂O₃–1Yb₂O₃ (x = 0.1–0.5) glasses, whose system was recently developed in our collaborative group, and their blue up-conversion photoluminescence (UCPL) of Tm³⁺ ions via three-step energy transfer from near-infrared (NIR) sensitizer of Yb³⁺ ions was observed. In particular, the substantial rate of the energy transfer <γ_d5> in the third step from Yb³⁺ to Tm³⁺ under excitation at 975 nm, which determined the final blue UCPL intensity, was estimated as a function of the rare-earth concentration. With an aid of analytical methods of PL lifetime and Judd–Ofelt theory, it was revealed that the highest energy transfer rate <γ_d5> was achieved to be 2.07 × 10⁻¹⁷ cm³/s for x = 0.2, and further increasing Tm₂O₃ content x in the fixed Yb₂O₃ resulted in the decrease in the energy transfer rate <γ_d5>. One of the plausible causes was concentration quenching of Yb³⁺ ions. The other was back-transfer from Tm³⁺ to Yb³⁺ ions. The influence of the condition of glass synthesis and the melting time on <γ_d5> was also discussed.