Viscosity detector

The most widely used molecular weight characterization method has been GPC, which separates compounds based on hydrodynamic volume. State-of-the-art GPC instruments are equipped with a concentration detector (e.g., differential refractometer, UV, and/or IR) in combination with viscosity or light scattering. A viscosity detector provides in-line solution viscosity data at each elution volume, which in combination with a concentration measurement can be converted to specific viscosity. Since the polymer concentration at each elution volume is quite dilute, the specific viscosity is considered a reasonable approximation for the dilute solution s intrinsic viscosity. The plot of log[r]]M versus elution volume (where [) ] is the intrinsic viscosity) provides a universal calibration curve from which absolute molecular weights of a variety of polymers can be obtained. Unfortunately, many reported analyses for phenolic oligomers and resins are simply based on polystyrene standards and only provide relative molecular weights instead of absolute numbers. 

Virial coefficients (GC) 5 Viscosity detector (SEC) 452 Viscous fingering (SEC) 447 Visualization techniques (TLC) (see derivatization (TLC)] Void volume, column (LC) 371 measurement 372 Volman trap (GC) 211 Volume of a theoretical plate 49... 

Haney, M. A., The differential viscometer. II. On-line viscosity detector for size-exclusion chromatography, /. Appl. Polym. Sci., 30, 3037, 1985. 

DP (1) Differential pressure (viscosity detector) (2) Density profiling... 

A viscosity online detector in a size exclusion chromatography (SEC) instrument allows for a universal calibration for polymers with known K- and a-values. For polymers that are only soluble at high temperature, e.g., polyolefines, high-temperature detectors are available, which can be operated up to 200°C. In addition to molar mass measurements, viscosity detectors have also been employed successfully to obtain structural information of branched polymers [28]. 

Development of a Continuous Gel Permeation Chromatography Viscosity Detector... 

A continuous capillary viscosity detector has been developed for use in High Performance Gel Permeation Chromatography (HPGPC). This detector has been used in conjunction with a concentration detector (DRI) to provide information on the absolute molecular weight, Mark-Houwink parameters and bulk intrinsic viscosity of polymers down to a molecular weight of about 4000. The detector was tested and used with a Waters Associates Model 150 C ALC/GPC. The combined GPC/Viscometer instrumentation was automated by means of a micro/mini-computer system which permits data acquisition/reduction for each analysis. 

This work describes the design, operation and application of the continuous GPC viscosity detector for the characterization of the molecular weight distribution of polymers. Details of the design and factors affecting the precision and accuracy of results are discussed along with selected examples of polymers with narrow and broad molecular weight distribution. 

The automation of the HPGPC/Viscometer system is achieved by interfacing the differential refractometer (DRI) and viscosity detector to a microcomputer for data acquisition. The raw data subsequently, are transferred to a minicomputer (DEC PDP-ll/HiI) for storage and data analysis. Details of the instrument automation are given elsewhere.(6)... 

Details of the data analysis for the GPC/Viscometer system have been reviewed by Ouano.(T ) The data reduction scheme is summarized in Figure 2 and briefly will be discussed here. The intrinsic viscosity of the effluent at a given retention volume [n](v) is determined from the DRI and continuous viscosity detector responses according to the following equation... 

The high sensitivity of the viscosity detector to the high molecular weight fractions is demonstrated in the analysis of a sample of very high molecular weight polyCmethyl methacrylate) shown in Figure 8. A shoulder at 3,000,000 molecular weight detected by the DRI becomes a peak when detected by the viscometer detector. 

The use of a continuous GPC viscosity detector in conjunction with a DRI detector permits the quantitative determination of absolute molecular weight distribution in polymers. Furthermore, from this combination one can obtain Mark-Houwink parameters and the bulk intrinsic viscosity of a given polymer with a GPC calibration curve based only on polystyrene standards. Coupling these two detectors with ultraviolet and infrared detectors then will permit the concurrent determination of polymer composition as a function of molecular weight and... 

A universal calibration is therefore possible for SEC by plotting log ([q] M) vs. Vg when a viscosity detector is used. Absolute molar masses can be obtained using a light-scattering detector. 

FIGURE 16.16 Schematic representation of the fonr capillary viscosity detector [284]. PTl and PT2 are the pressnre transdncers. A is the hold-np reservoir. It decelerates the polymer solution so that the capillary which follows is still flushed with pure mobile phase when the sample solution has already entered the other capillaries. 

When the total polymer response, is known as a function of retention volume, the molecular weight distributlon can be obtained in the usual manner with the appropriate molecular weight calibration curve. The molecular weight calibration curve can be obtained (a) by using the Runyon (65) copolymer molecular weight scale approach, or (b) by using a hydrodynamic volume approach if the Mark-Houwink constants for the polymer of interest are known or can be determined, or (c) by using a hydrodynamic volume approach in conjunction with an on-line viscosity detector. 

The sample fluid could be any neat liquid or a sample of polymer solution. Under favorable conditions, a single viscosity determination on a polymer solution at high dilution can provide a direct measure of the polymer intrinsic viscosity, without the need of polymer concentration extrapolation. With this viscometer used as a continuous viscosity detector for SEC, it is possible to achieve SEC molecluar weight calibration by way of the universal SEC calibration methodology without the need of molecular weight standards for the unknown polymers. 

Figures 8 and 10 illustrate two different configurations of the viscometer used as an on-line SEC viscosity detector.

Figure 11 illustrates an SEC separation of a sample of 3-conponent polystyrene mixture with the dual concentration and viscosity detectors of Figure 10. The top trace shows the concentration elution profile of the SEC separation as detected by a uv-photometer. The bottom trace records the same SEC separation, except with the viscometer signal from the log-amplifier output.

The high viscosity of some high MW samples is known to cause flow rate upsets as the sample passes through the SEC column frits. Such flow rate upsets often occur at the time of elution of the sample. While the flow rate upsets like this are likely to cause viscosity detection errors in most other SEC viscosity detectors, the signal of the present viscosity detector, however, will remain true, cind unaffected by the high sample viscosity problem. 

DIFFERENTIAL PRESSURE CAPILLARY VISCOHETER AS AN IN-t INE VISCOSITY DETECTOR... 

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