The impact of column connection on band broadening in very high pressure liquid chromatography

A series of experiments was conducted to evaluate the degree of band broadening in very high pressure LC due to column connections. Different column manufacturers use slightly different designs for their column fittings. If the same column connections are repeatedly used to attach columns of different origins, different void volumes form between capillary tubes and column inlets. An Agilent Ultra Low Dispersion Kit (tubing id 75 μm) was installed on an Agilent Infinity 1290 ultra HPLC and used to connect successively an Agilent, a Phenomenex, and a Waters column. A series of uracil (unretained) samples were injected and eluted at a wide range of flow rates with a water/acetonitrile mixture as eluent. In order to determine the variance contribution from column connections as accurately as possible a nonretained probe compound was selected because the variance contribution from the column is the smallest for analytes, which have very low k values. Yet, this effect still has an impact on the resolution for moderately retained compounds (k > 2) for narrow-bore columns packed with fine particles, since variance contributions are additive for linear chromatographic systems. Each injection was replicated five times under the same experimental conditions. Then NanoViper column connections (tubing id 75 μm) were used and the same injections were made. This system was designed to minimize connection void volumes for any column. Band variances were calculated as the second central moment of elution peaks and used to assess the degree of band broadening due to the column connections. Band broadening may increase from 3.8 to 53.9% when conventional metal ferrules were used to join columns to connection sites. The results show that the variance contribution from improper connections can generate as much as 60.5% of the total variance observed. This demonstrates that column connections can play a larger role than the column packing with respect to band dispersion.

Very high pressure liquid chromatography using fully porous particles: Quantitative analysis of fast gradient separations without post-run times

Using a column packed with fully porous particles, four methods for controlling the flow rates at which gradient elution runs are conducted in very high pressure liquid chromatography (VHPLC) were tested to determine whether reproducible thermal conditions could be achieved, such that subsequent analyses would proceed at nearly the same initial temperature. In VHPLC high flow rates are achieved, producing fast analyses but requiring high inlet pressures. The combination of high flow rates and high inlet pressures generates local heat, leading to temperature changes in the column. Usually in this case a post-run time is input into the analytical method to allow the return of the column temperature to its initial state. An alternative strategy involves operating the column without a post-run equilibration period and maintaining constant temperature variations for subsequent analysis after conducting one or a few separations to bring the column to a reproducible starting temperature. A liquid chromatography instrument equipped with a pressure controller was used to perform constant pressure and constant flow rate VHPLC separations. Six replicate gradient separations of a nine component mixture consisting of acetophenone, propiophenone, butyrophenone, valerophenone, hexanophenone, heptanophenone, octanophenone, benzophenone, and acetanilide dissolved in water/acetonitrile (65:35, v/v) were performed under various experimental conditions: constant flow rate, two sets of constant pressure, and constant pressure operation with a programmed flow rate. The relative standard deviations of the response factors for all the analytes are lower than 5% across the methods. Programming the flow rate to maintain a fairly constant pressure instead of using instrument controlled constant pressure improves the reproducibility of the retention times by a factor of 5, when plotting the chromatograms in time.

Unilateral bicep curl hemodynamics: low-pressure continuous vs high-pressure intermittent blood flow restriction

 Light-load exercise training with blood flow restriction (BFR) increases muscle strength and size. However, the hemodynamics of BFR exercise appear elevated compared with non-BFR exercise. This questions the suitability of BFR in special/clinical populations. Nevertheless, hemodynamics of standard prescription protocols for BFR and traditional heavy-load exercise have not been compared. We investigated the hemodynamics of two common BFR exercise methods and two traditional resistance exercises. Twelve young males completed four unilateral elbow flexion exercise trials in a balanced, randomized crossover design: (a) heavy load [HL; 80% one-repetition maximum (1-RM)]; (b) light load (LL; 20% 1-RM); and two other light-load trials with BFR applied (c) continuously at 80% resting systolic blood pressure (BFR-C) or (d) intermittently at 130% resting systolic blood pressure (BFR-I). Hemodynamics were measured at baseline, during exercise, and for 60-min post-exercise. Exercising heart rate, blood pressure, cardiac output, and rate–pressure product were significantly greater for HL and BFR-I compared with LL. The magnitude of hemodynamic stress for BFR-C was between that of HL and LL. These data show reduced hemodynamics for continuous low-pressure BFR exercise compared with intermittent high-pressure BFR in young healthy populations. BFR remains a potentially viable method to improve muscle mass and strength in special/clinical populations.

Study on nanocellulose by high pressure homogenization in homogeneous isolation

Nanocellulose from cotton cellulose was prepared by high pressure homogenization (HPH) in ionic liquids (1-butyl-3-methylimidazolium chloride ([Bmim]Cl). The nanocellulose possessed narrow particle size distribution, with diameter range of 10–20 nm. Weight average molecular weight (Mw) of nanocellulose treated by HPH was lower (173.8 kDa) than the one ILs treated cellulose (344.6 kDa). X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), and Solid-state CP/MAS 13C NMR measurements were employed to study the mechanism of structural changes, which suggested that network structure between cellulose chains were destructed by the shearing forces of HPH in combination with ionic liquids. The intermolecular and intra-molecular hydrogen bonds of cellulose were further destroyed, leading to the long cellulose molecular chains being collapsed into short chains. Therefore, the nanocellulose could provide desired properties, such as lower thermal stability and strong water holding capacity. Results indicated that it had great potential in the applications for packaging, medicines, cosmetics and tissue engineering.

Strain gradient plasticity modelling of high-pressure torsion

Gradient plasticity modelling combining a micro-structure-related constitutive description of the local material behaviour with a particular gradient plasticity frame is presented. The constitutive formulation is based on a phase mixture model in which the dislocation cell walls and the cell interiors are considered as separate 'phases', the respective dislocation densities entering as internal variables. Two distinct physical mechanisms, which give rise to gradient plasticity, are considered. The first one is associated with the occurrence of geometrically necessary dislocations leading to first-order strain gradients; the second one is associated with the reaction stresses due to plastic strain incompatibilities between neighbouring grains, which lead to second-order strain gradients. These two separate variants of gradient plasticity were applied to the case of high-pressure torsion: a process known to result in a fairly uniform, ultrafine grained structure of metals. It is shown that the two complementary variants of gradient plasticity can both account for the experimental results, thus resolving a controversial issue of the occurrence of a uniform micro-structure as a result of an inherently non-uniform process. © 2007 Elsevier Ltd. All rights reserved.

Inner architecture of bonded splats under combined high pressure and shear

Micron size aluminum particles (Figure 1) are deformed into “interlocked splats” at room temperature under high pressure and shear. Sample's induced inner architecture is examined (Figure 2). Tests are carried out to characterize material's heterogeneous properties (Figure 3). Presented formulation of the test data indicates an excellent shear strength; stronger than its solid counterpart.

Numerical investigation of high and low pressure tube hydroforming

Hydroforming is one option to reduce vehicle weight while increasing component stiffness and rigidity. This typically involves using a fluid to form a component with high internal pressure. Tube hydroforming has gained increasing interest in the automotive and aerospace industries because of its many advantages such as part consolidation, good quality of the formed part etc. The main advantage is that the uniform pressure can be transferred to whole part at the same time. In low pressure hydroforming, the internal pressure is significantly and the hydroformed section length of line stays almost the same as the circumference of the blank tube. This paper details the comparison between high and low pressure hydroforming. It is shown that the internal pressure and holding force required for low pressure hydroforming process is much less than that of high pressure. Also stress and thickness distribution are more uniform and the process is highly suitable for the forming of advanced high strength steels.

FEA comparison of high and low pressure tube hydroforming of TRIP steel

The increasing application of hydroforming for the production of automotive lightweight components is mainly due to the attainable advantages regarding part properties and improving technology of the forming equipment. However, the high pressure requirements during hydroforming decreases the costs benefit and make the part expensive. Another requirement of automotive industries is weight reduction and better crash performance. Thereby steel industries developed advanced high strength steels which have high strength, good formability and better crash performance. Even though the thickness of the sheet to form the component is reduced, the pressure requirement to form the part during expansion is still high during high pressure hydroforming. This paper details the comparison between high and low pressure tube hydroforming for the square cross-section geometry. It is determined that the internal pressure and die closing force required for low pressure tube hydroforming process is much less than that of high pressure tube hydroforming process. The stress and thickness distribution of the part during tube crushing were critically analysed. Further, the stress distribution and forming mode were studied in this paper. Also friction effect on both processes was discussed.

Crash investigation of side intrusion beam during high and low pressure tube hydroforming

Advanced high strength steels (AHSS), in particular, are an attractive group materials, offering higher strength for improved energy absorption and the opportunity to reduce weight through the use of thinner gauges. High pressure tube hydroforming (HPTH) has been used to produce safety components for these steels, but it is expensive. Low pressure tube hydroforming (LPTH) is a lower cost alternative to form the safety components in the car. The side intrusion beam is the second most critical part after front rail in the car structure for passenger safety during crash. The forming as well as crash behaviour of a square side intrusion beam from both processes was investigated using numerical simulation. This paper investigated the interaction between the forming and crash response of these materials in order to evaluate their potential for use in vehicle design for crashworthiness. The energy absorption characteristics of the different tubes were calculated and the results from the numerical analyses compared for both hydroforming process.

Experimental and numerical investigation of low pressure tube hydroforming on 409 stainless steel

Tube hydroforming has been widely used to produce automotive structural components due to the superior properties of the hydroformed parts in terms of their light weight and structural rigidity. Compared to the traditional manufacturing process for a closed-section member including stamping and followed by welding, tube-hydro forming leads to cost savings due to reduced tooling and material handling. However, the high pressure pumps and high tonnage press required in hydroforming, lead to increased capital investment reducing the cost benefits. This study explores low pressure tube hydro forming which reduces the internal fluid pressure and die closing force required to produce the hydroformed part. The experimental and numerical analysis was for low pressure hydro formed stainless steel tubes. Die filling conditions and thickness distributions are measured and critically analysed.