Accessed from 128.83.63.
20 by nEwp0rt1 on Tue Jun 05 03:52:14 EDT 2012
Second Supplement to USP 35–NF 30 Physical Tests / 〈912〉 Rotational Rheometer Methods 5651
Calibration and Calculation of kinematic and Newtonian
viscosities of sample fluid: Proceed as directed in Method
I.■2S (USP35)
Add the following:
〈912〉 ROTATIONAL RHEOMETER
.
■
METHODS
The principle of the method is to measure the force (torque)
acting on a rotor when it rotates at a constant angular veloc-
ity (rotational speed) in a liquid. Rotational rheometers/vis-
cometers are used for measuring the viscosity of Newtonian
fluids, i.e., a fluid having a viscosity that is independent of
the shearing stress or rate of shear, or the apparent viscosity
of non-Newtonian fluids, which may exhibit different rheo-
logical behavior, depending on shear rate, shear stress, and
temperature. The following procedures are used to determine
the viscosity of Newtonian fluids or the apparent viscosity of
non-Newtonian fluids. The calculated viscosity of Newtonian
fluids should be the same (within experimental error), regard- Figure 2. Disc-shaped spindles
less of the rate of shear (or rotational speed). Given the de-
pendence of viscosity on temperature, the temperature of the Procedure: Under these test conditions the shear rate varies
substance being measured should be controlled to within between the outer surface of the spindle and the inner sur-
±0.1°, unless otherwise specified in the individual mono- face of the beaker or cup containing the test substance. As a
graph. Unless otherwise directed in the individual mono- result, the following additional information must be de-
graph, use Method I. scribed along with the measured viscosity:
• METHOD I. SPINDLE RHEOMETERS (RELATIVE RHEOMETERS—SPIN- 1. Size and geometry of spindle
DLE VISCOMETERS) 2. Angular velocity of the spindle
Apparatus: In the spindle rheometer, the apparent viscosity 3. Inner dimensions of the test substance container
is determined by rotating a cylinder- or disc-shaped spindle, 4. Temperature of the test substance
as shown in Figures 1 and 2, respectively, immersed in a 5. Use of instrument accessories, such as a spindle guard
large volume of liquid. The preparation of the test specimen, including its tempera-
ture equilibration, is specified in each individual mono-
graph. Follow the instrument manufacturer’s recommenda-
tions regarding sample loading, spindle selection, and
rheometer operation.
Calibration: Select at least two calibration standards whose
viscosities differ by an appropriate value within the viscosity
range of the test substance under measurement for a partic-
ular rheometer configuration. Measure the apparent viscosi-
ties of each standard, as described above, at multiple rota-
tional speeds.
A rheometer is deemed to be calibrated if the measured
apparent viscosities are within ±5% of the stated values.
Generally, calibration, operation, and cleaning of rheometers
should be performed according to the recommendations of
the instrument manufacturer.
• METHOD II. CONCENTRIC CYLINDER RHEOMETERS
Apparatus: In the concentric cylinder rheometer, the appar-
ent viscosity is determined by placing the liquid in the gap
between the inner cylinder and the outer cylinder. Both con-
trolled-stress and controlled-rate rotational rheometers are
available commercially in configurations with absolute ge-
ometries (e.g., very small annular gaps between concentric
cylinders) that can provide consistent meaningful rheological
data for non-Newtonian fluids. Controlled-stress rheometers
provide controlled-stress input and measurement of the re-
sulting shear rate. Controlled-rate rheometers provide con-
trolled-shear rate input and determination of the resultant
shear stress, measured as torque, on the rotor axis. Concen-
Figure 1. Cylinder-shaped spindles
Official from December 1, 2012
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5652 〈912〉 Rotational Rheometer Methods / Physical Tests Second Supplement to USP 35–NF 30
tric cylinder rotational rheometers are sometimes referred to
as cup-and-bob rheometers. These rheometers involve an
additional design consideration depending on whether the
outer cylinder (the cup) or the inner cylinder (the bob) ro-
tates. Rotating-cup rheometers are called Couette systems,
while rotating-bob rheometers are called Searle systems, as
shown in Figures 3 and 4, respectively.
Figure 4. Searle concentric cylinder system for rotational
rheometry
Procedure: Place a sufficient quantity of a test solution or
fluid in the rheometer, and allow the sample to reach ther-
mal equilibrium, as indicated in the individual monograph.
Operate the rheometer following the procedure recom-
mended by the instrument manufacturer. For non-
Newtonian systems, the monograph indicates the type of
Figure 3. Couette concentric cylinder system for rotational rheometer that should be used and the shear rate(s) at
rheometry
Official from December 1, 2012
Copyright (c) 2012 The United States Pharmacopeial Convention. All rights reserved.
Accessed from [Link] by nEwp0rt1 on Tue Jun 05 03:52:14 EDT 2012
Second Supplement to USP 35–NF 30 Physical Tests / 〈912〉 Rotational Rheometer Methods 5653
which the measurements should be made. [NOTE—If there is Calibration: Rotational rheometers require calibration with
evidence of time-dependent (e.g., thixotropic or rheopectic) rheological standards appropriate for the shear rate or shear
rheological behavior, this should be noted as well.] As noted stress ranges and the nature of the fluid or material under
above, apparent viscosity should be determined preferably evaluation. To determine or confirm the apparatus constant,
over a range of shear rates appropriate to the material under perform the necessary tests beforehand, using fluids of
test. The procedure employed to measure the apparent vis- known viscosities of appropriate viscosity standards at the
cosity of the liquid is repeated, using a series of different required temperature.
rotational speeds or torques. From a series of such viscosity • METHOD III. CONE-AND-PLATE RHEOMETERS
measurements, the relationship between the shear rate and Apparatus: In the cone-and-plate rheometer, the liquid is
the shear stress of a non-Newtonian liquid—that is, the flow introduced into the gap between a flat disc or plate and a
characteristics of the non-Newtonian liquid—can be cone forming a defined angle. Viscosity measurement can
obtained. be performed by rotating the cone or the plate, as shown in
Calculation of shear rate, shear stress, and viscosity: For Figures 5 and 6, respectively. [NOTE—Because the volume of
non-Newtonian liquids, it is essential to specify the shear sample is small, even a small absolute loss of solvents can
stress, σ, or the shear rate , at which the viscosity is meas- cause a large percentage change in viscosity. Such a loss is
ured. Under narrow gap conditions (conditions satisfied in particularly relevant for volatile solvents but could be
absolute rheometers), the shear rate in s−1, and the shear significant even for nonvolatile solvents such as water.]
stress σ, in Pa (N · m−2 or kg · m−1 · s−2), are calculated using
Equations (1) and (2) below:
RO = radius of the outer cylinder (m)
RI = radius of the inner cylinder (m)
ω = angular velocity (radians/s)
M = torque acting on the cylinder surface (N · m)
h = height of immersion of the inner cylinder in the
liquid medium (m)
Generally, the angular velocity can be calculated using
Equation (3):
n = rotational speed, in revolutions/min (rpm)
For laminar flow, the viscosity η (or apparent viscosity ηApp),
in Pa · s , is given by the following equation:
[NOTE—1 Pa · s = 1000 mPa · s.]
k = the constant of the apparatus (radians/m3) Figure 5. Cone-and-plate rotational rheometer with rotating
cone
Official from December 1, 2012
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5654 〈912〉 Rotational Rheometer Methods / Physical Tests Second Supplement to USP 35–NF 30
α = angle between the flat plate and the cone
(radians)
R = radius of the cone (m)
ω = angular velocity (radians/s)
M = torque acting on the flat plate or cone surface
Figure 6. Cone-and-plate rotational rheometer with rotating (N · m)
plate For laminar flow, the viscosity η (or apparent viscosity ηApp),
Procedure: Proceed as directed for Method II. Concentric in Pa · s, is given by the following equation:
Cylinder Rheometers.
Calculation of shear rate, shear stress, and viscosity: The
shear rate in s−1, and the shear stress σ, in Pa, are
calculated by Equations (5) and (6).
k = constant of the apparatus (radians/m3)
Calibration: Proceed as directed for Calibration in Method II.
Concentric Cylinder Rheometers.■2S (USP35)
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Second Supplement to USP 35–NF 30 Physical Tests / 〈913〉 Rolling Ball Viscometer Method 5655
Add the following: each single measured rolling time, the resulting viscosity can
be expressed as dynamic viscosity (mPa · s) as well as kine-
matic viscosity (mm2/s) for a sample of known density.
■〈913〉 ROLLING BALL Procedure: Select a measuring system [tube (or capillary)
and ball combination] within the anticipated range of vis-
VISCOMETER METHOD cosity of the sample liquid. As necessary, heat the clean and
dry tube and ball of the viscometer to the temperature
specified in the individual monograph, and control the tem-
perature to ±0.1°, unless otherwise specified in the individ-
The following procedure is used to determine the viscosity ual monograph. Select a measuring angle to obtain a mini-
of a Newtonian fluid, i.e., a fluid having a viscosity that is mum rolling time of 20 s. Fill the tube with the sample
independent of the shearing stress or rate of shear. liquid, being careful to avoid bubble formation. Close the
Apparatus: See Figure 1. tube, and insert it in the instrument. Allow to equilibrate at
The basic design of a rolling ball viscometer consists of a the specified temperature for NLT 15 min for a rolling ball
tube (or capillary) that contains the sample liquid under test viscometer with a tube of large diameter. For a micro rolling
and a ball chosen so that it will require a minimum rolling ball viscometer, follow the instrument manufacturer’s in-
time of 20 s at the measuring angle in the sample liquid. structions regarding temperature equilibration. Release the
ball, and record the time required for the ball to roll from
the upper to the lower ring mark (or measuring sensor).
Repeat the test run at least four times.
The rolling time in the fluid under examination is the
mean of NLT four consecutive determinations. The result is
valid if the percent relative standard deviation (%RSD) for
the four readings is NMT 2.0%.
Calculation and Calibration: Calculate the Newtonian vis-
cosity, η, in mPa · s, using the formula:
η = k × (ρ1 − ρ2) × t
k = calibration constant of the instrument (mm2/s2) at a
specified measuring angle and temperature
ρ1 = density of the ball used (g/mL)
Figure 1. Basic design for rolling ball viscometer. ρ2 = density of the sample liquid (g/mL)
t = rolling time of the ball (s).
Calibrate each tube (or capillary) and ball combination at
Measuring Principle: The rolling ball measurement is the test temperature and test angle using fluids of known
based on Stokes’s Law, as influenced by the angle of inclina- viscosities and densities (viscosity standards) to determine
tion of the tube (or capillary). The Newtonian viscosity, η, in the measuring system constant, k. [NOTE—Some automated
mPa · s, is calculated using the following equation: viscometers use a polynomial function to determine the cali-
bration for different angles and temperatures.] The viscosity
η = [(ρ1 − ρ2) × g × r2 × sinθ] / v∞ values of the calibration standards should bracket the ex-
pected viscosity value of the sample liquid.
ρ1 = density of the ball used (g/mL) Calibrations are specific to the ball radius, ball density,
ρ2 = density of the sample liquid (g/mL) temperature, and test angle. Recalibration is necessary when
g = gravitational constant (mm/s2) any of these parameters is changed.
r = radius of the ball (mm) Where no reference values at the required test tempera-
θ = angle of inclination of the tube (or capillary) ture are available, follow the manufacturer’s instructions for
v∞ = terminal velocity of the ball (mm/s) mathematical corrections to the calibration function. When
Determine the viscosity of a liquid by observing the roll- the materials of the ball and tube are dissimilar, apply cor-
ing time of a solid sphere (ball) under the influence of grav- rections calculated using the linear thermal expansion coeffi-
ity in an inclined cylindrical tube filled with the sample liq- cients of the materials.■2S (USP35)
uid. Measure the time taken by the ball to travel the fixed
distance between two ring marks or measuring sensors. For
Official from December 1, 2012
Copyright (c) 2012 The United States Pharmacopeial Convention. All rights reserved.