Density-viscosity product of small-volume ionic liquid samples using quartz crystal impedance analysis

Quartz crystal impedance analysis has been developed as a technique to assess whether room-temperature ionic liquids are Newtonian fluids and as a small-volume method for determining the values of their viscosity-density product, rho eta. Changes in the impedance spectrum of a 5-MHz fundamental frequency quartz crystal induced by a water-miscible room-temperature ionic liquid, 1-butyl-3-methylimidazolium. trifluoromethylsulfonate ([C(4)mim][OTf]), were measured. From coupled frequency shift and bandwidth changes as the concentration was varied from 0 to 100% ionic liquid, it was determined that this liquid provided a Newtonian response. A second water-immiscible ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide [C(4)mim][NTf2], with concentration varied using methanol, was tested and also found to provide a Newtonian response. In both cases, the values of the square root of the viscosity-density product deduced from the small-volume quartz crystal technique were consistent with those measured using a viscometer and density meter. The third harmonic of the crystal was found to provide the closest agreement between the two measurement methods; the pure ionic liquids had the largest difference of similar to 10%. In addition, 18 pure ionic liquids were tested, and for 11 of these, good-quality frequency shift and bandwidth data were obtained; these 12 all had a Newtonian response. The frequency shift of the third harmonic was found to vary linearly with square root of viscosity-density product of the pure ionic liquids up to a value of root(rho eta) approximate to 18 kg m(-2) s(-1/2), but with a slope 10% smaller than that predicted by the Kanazawa and Gordon equation. It is envisaged that the quartz crystal technique could be used in a high-throughput microfluidic system for characterizing ionic liquids.

Optimization of Cement Grouts Containing Silica Fume and Viscosity Modifying Admixture

There is an increasing need to identify the effect of mix composition on the rheological properties of cementitious grouts using minislump, Marsh cone, cohesion plate, washout test, and cubes to determine the fluidity, the cohesion, and other mechanical properties of grouting applications. Mixture proportioning involves the tailoring of several parameters to achieve adequate fluidity, cohesion, washout resistance and compressive strength. This paper proposes a statistical design approach using a composite fractional factorial design which was carried out to model the influence of key parameters on the performance of cement grouts. The responses relate to performance included minislump, flow time using Marsh cone, cohesion measured by Lombardi plate meter, washout mass loss and compressive strength at 3, 7, and 28 days. The statistical models are valid for mixtures with water-to-binder ratio of 0.37–0.53, 0.4–1.8% addition of high-range water reducer (HRWR) by mass of binder, 4–12% additive of silica fume as replacement of cement by mass, and 0.02–0.8% addition of viscosity modifying admixture (VMA) by mass of binder. The models enable the identification of underlying factors and interactions that influence the modeled responses of cement grout. The comparison between the predicted and measured responses indicated good accuracy of the established models to describe the effect of the independent variables on the fluidity, cohesion, washout resistance and the compressive strength. This paper demonstrates the usefulness of the models to better understand trade-offs between parameters. The multiparametric optimization is used to establish isoresponses for a desirability function for cement grout. An increase of HRWR led to an increase of fluidity and washout, a reduction in plate cohesion value, and a reduction in the Marsh cone time. An increase of VMA demonstrated a reduction of fluidity and the washout mass loss, and an increase of Marsh cone time and plate cohesion. Results indicate that the use of silica fume increased the cohesion plate and Marsh cone, and reduced the minislump. Additionally, the silica fume improved the compressive strength and the washout resistance.

The effect of the binder size and viscosity on agglomerate growth in fluidised hot melt granulation

Fluidised hot melt granulation (FHMG) is a novel granulation technique for processing pharmaceutical powders. Several process and formulation parameters have been shown to significantly influence granulation characteristics within FHMG. In this study we have investigated the effect of the binder properties (binder particle size and binder viscosity) on agglomerate growth mechanisms within FHMG. Low-melting point co-polymers of polyoxyethylene–polyoxypropylene (Lutrol® F68 Poloxamer 188 and Lutrol® F127 Poloxamer 407) were used as meltable binders for FHMG, while standard ballotini beads were used as model fillers for this process. Standard sieve analysis was used to determine the size distribution of granules whereas we utilised fluorescence microscopy to investigate the distribution of binder within granules. This provided further insight into the growth mechanisms during FHMG. Binder particle size and viscosity were found to affect the onset time of granulation. Agglomerate growth achieved equilibrium within short time-scales and was shown to proceed by two competing processes, breakage of formed granules and re-agglomeration of fractured granules. Breakage was affected by the initial material properties (binder size and viscosity). When using binder with a small particle size (<250 µm), agglomerate growth via a distribution mechanism dominated. Increasing the binder particle size shifted the granulation mechanism such that agglomerates were formed predominantly via immersion. A critical ratio between binder diameter and filler has been calculated and this value may be useful for predicting or controlling granulation growth processes.

Dynamic grey-box modeling for online monitoring of extrusion viscosity

Melt viscosity is a key indicator of product quality in polymer extrusion processes. However, real time monitoring and control of viscosity is difficult to achieve. In this article, a novel “soft sensor” approach based on dynamic gray-box modeling is proposed. The soft sensor involves a nonlinear finite impulse response model with adaptable linear parameters for real-time prediction of the melt viscosity based on the process inputs; the model output is then used as an input of a model with a simple-fixed structure to predict the barrel pressure which can be measured online. Finally, the predicted pressure is compared to the measured value and the corresponding error is used as a feedback signal to correct the viscosity estimate. This novel feedback structure enables the online adaptability of the viscosity model in response to modeling errors and disturbances, hence producing a reliable viscosity estimate. The experimental results on different material/die/extruder confirm the effectiveness of the proposed “soft sensor” method based on dynamic gray-box modeling for real-time monitoring and control of polymer extrusion processes. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers

A Soft Sensor for Viscosity Control of Polymer Extrusion

Viscosity represents a key indicator of product quality in polymer extrusion but has traditionally been difficult to measure in-process in real-time. An innovative, yet simple, solution to this problem is proposed by a Prediction-Feedback observer mechanism. A `Prediction' model based on the operating conditions generates an open-loop estimate of the melt viscosity; this estimate is used as an input to a second, `Feedback' model to predict the pressure of the system. The pressure value is compared to the actual measured melt pressure and the error used to correct the viscosity estimate. The Prediction model captures the relationship between the operating conditions and the resulting melt viscosity and as such describes the specific material behavior. The Feedback model on the other hand describes the fundamental physical relationship between viscosity and extruder pressure and is a function of the machine geometry. The resulting system yields viscosity estimates within 1% error, shows excellent disturbance rejection properties and can be directly applied to model-based control. This is of major significance to achieving higher quality and reducing waste and set-up times in the polymer extrusion industry.

A Correlation between the Dynamic Viscosity and Crystallisation of Felodipine from its Amorphous Polymer Solid Dispersion

Purpose Previously, it has been reported that molecular mobility determines the rate of molecular approach to crystal surfaces, while entropy relates to the probability of that approaching molecule having the desirable configuration for further growth of the existing crystal; and the free energy dictates the probability of that molecule not returning to the liquid phase1. If we plot the crystal growth rate and viscosity of a supercooled liquid in a log-log format, the relationship between the two is linear, indicating the influence viscosity has upon crystal growth rate. However, such approximation has been derived from pure drug compounds and it is apparent that further understanding of crystallization from drug-polymer solid dispersion is required in order to stabilise drugs embedded within amorphous polymeric solid dispersions. Methods Mixtures of felodipine and polymer (HPMCAS-HF, PVPK15 and Soluplus®) at specified compositions were prepared using a Restch MM200 ball mill. To examine crystal growth within amorphous solid dispersions, samples were prepared by melting 5-10 mg of ball milled mixture at 150°C for 3-5 minutes on a glass slip pre-cleaned with methanol and acetone. All prepared samples were confirmed to be crystal free by visual observation using a polarised light microscope (Olympus BX50). Prepared samples were stored at 0% RH (P2O5), inside desiccators, maintained in ovens at 80°C. For the dynamic viscosity measurement, approximately 100-200mg ball milled mixture was heated on the base plate of a rotational rheometer at 150°C for 5 minutes and the top plate was lowered to a defined gap to form a good contact with the material. The sandwiched amorphous material was heated to 80°C and the viscosity was measured. Results The equation was used to probe the correlation of viscosity to crystal growth rate. In comparison to the value of xi in log-log equation reported from pure drug compound, a value of 1.63 was obtained for FD-polymer solid dispersions irrespective of the polymer involved. &#8733 Conclusion The high xi value suggests stronger viscosity dependence may exist for amorphous FD once incorporated with amorphous polymer.

The adaptive value of polyembryony.

From an evolutionary standpoint, the production of offspring is the single most important aspect of an animal's life. Offspring carry an individual's genes into the next generation and it is the differential representation of genes in a population that drives evolutionary change. There are a variety of ways in which animals create offspring, ranging from cases where parents make identical copies of themselves by budding or parthenogenesis, to the standard case in vertebrates where gametes from a male and female fuse in sexual reproduction to produce the next generation. In this article we describe an usual variant of sexual reproduction, polyembryony.

Can diagnostic triage by general practitioners or rheumatology nurses improve the positive predictive value of referrals to early arthritis clinics?

Objectives: To determine whether diagnostic triage by general practitioners (GPs) or rheumatology nurses (RNs) can improve the positive predictive value of referrals to early arthritis clinics (EACs).

Methods: Four GPs and two RNs were trained in the assessment of early in?ammatory arthritis (IA) by four visits to an EAC supervised by hospital rheumatologists. Patients referred to one of three EACs were recruited for study and assessed independently by a GP, an RN and one of six rheumatologists. Each assessor was asked to record their clinical ?ndings and whether they considered the patient to have IA. Each was then asked to judge the appropriateness of the referral according to predetermined guidelines. The rheumatologists had been shown previously to have a satisfactory level of agreement in the assessment of IA.

Results: Ninety-six patients were approached and all consented to take part in the study. In 49 cases (51%), the rheumatologist judged that the patient had IA and that the referral was appropriate. The assessments of GPs and RNs were compared with those of the rheumatologists. Levels of agreement were measured using the kappa value, where 1.0 represents total unanimity. The kappa value was
0.77 for the GPs when compared with the rheumatologists and 0.79 for the RNs. Signi?cant stiffness in the morning or after rest and objective joint swelling were the most important clinical features enabling the GPs and RNs to discriminate between IA and non-IA conditions.

Conclusion: Diagnostic triage by GPs or RNs improved the positive predictive value of referrals to an EAC with a degree of accuracy approaching that of a group of experienced rheumatologists.