Nutrition & Biosciences

Pharma Solutions

Chemistry of METHOCEL™
Cellulose Ethers - A Technical Review
 Nutrition & Biosciences

Chemistry of METHOCEL™ Cellulose Ethers Regulated Uses

METHOCEL™ cellulose ether products are available in
two basic types: methylcellulose and hydroxypropyl Pharmaceuticals
methylcellulose.
Premium grades of METHOCEL™ products meet the
Both types of METHOCEL™ have the polymeric backbone specifications of the United States Pharmacopoeia (USP
of cellulose, a natural carbohydrate that contains a basic XXIII), European Pharmacopoeia (EP) and Japanese
repeating structure of anhydroglucose units. Pharmacopoeia (JP) and are listed as methylcellulose and
hypromellose1. In addition, methylcellulose (METHOCEL™
A products) is Generally Recognized As Safe (GRAS) by the
U.S. Food and Drug Administration.
To support new drug applications in the United States,
drug master files (DMFs) for these products are on
file at the Bureau of Drugs of the U.S. Food and Drug
Administration.

Comparison of METHOCEL™ Grades for Pharmaceutical Applications

Comparison of METHOCEL™ Grades for Pharmaceutical Applications
METHOCEL™
K3 LV K100 LV K4M K15M K100M E3 LV E5 LV E6 LV E15 LV E50 LV E4M E10M VLV A15 LV A4C A15C A4M
Premium Products:

Viscosity 2,663- 13,275- 75,000- 2,663- 9,525- 1,298- 2,663-

2.4-3.6 80-120 2.4-3.6 4.0-6.0 4.8-7.2 12-18 40-60 2.3-3.3 12-18 320-480
(mPa.s 2% in water at 20C) 4,970 24,780 140,000 4,970 17,780 2,422 4,970

19.0- 19.0- 19.0- 19.0- 19.0- 28.0- 28.0- 28.0- 28.0- 28.0- 28.0- 27.0- 27.5- 27.5- 27.5- 27.5-
Methoxyl substitution N/A
24.0% 24.0% 24.0% 24.0% 24.0% 30.0 30.0 v30.0 30.0 30.0 30.0% 30.0% 31.5% 31.5% 31.5% 31.5%

If CR designation, 22.0- 22.0- 22.0- 22.0- 28.0- 28.0-

N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A
methoxyl substitution 24.0% 24.0% 24.0% 24.0% 30.0% 30.0%

Hydroxypropoxyl 7.0- 7.0- 7.0- 7.0- 7.0- 7.0- 4.2-

7.0-12.0 7.0-12.0 7.0-12.0 7.0-12.0 7.0-12.0 N/A N/A N/A N/A N/A
substitution 12.0% 12.0% 12.0% 12.0% 12.0% 12.0% 7.5%

If CR designation,
7.5- 7.5- 8.5- 9.5- 8.5- 8.5-
hydroxypropoxyl N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A
9.5% 9.5% 10.5% 11.5% 10.5% 10.5%
substitution

Loss on Drying 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% 5.0% 5.0%
(weight %) Max Max Max Max Max Max Max Max Max Max Max Max Max Max Max Max Max

If CR designation,
Particle size, N/A ≥ 99.0% ≥ 99.0% ≥ 99.0% ≥ 99.0% N/A N/A N/A N/A N/A ≥ 99.0% ≥ 99.0% N/A N/A N/A N/A N/A
% thru 40 mesh

If CR designation,
Particle size, N/A ≥ 90.0% ≥ 90.0% ≥ 90.0% ≥ 90.0% N/A N/A N/A N/A N/A ≥ 90.0% ≥ 90.0% N/A N/A N/A N/A N/A
% thru 100 mesh

If CR designation,
50.0- 50.0- 50.0- 50.0- 50.0- 50.0-
Particle size, N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A
80.0% 80.0% 80.0% 80.0% 80.0% 80.0%
% thru 230 mesh

(These are typical properties, not to be construed as specifications)

1 The former official monograph name of hypromellose was “hydroxypropyl

methylcellulose” or “HPMC”.

2
How to Prepare Aqueous Solutions of This “time delay” of hydration or viscosity build is a
METHOCEL™ Cellullose Ethers function of the level of surface treatment as well as
temperature, pH of the system, and concentration of
METHOCEL™ cellulose ether products are carbohydrate the METHOCEL™ product. Normally, the concentration
polymers which dissolve in cold water (and in some of METHOCEL™ in the system does not become a factor
instances in certain organic solvents) by swelling and until the concentration exceeds 5% by weight (relative to
subsequent hydration. There is no sharp solubility limit water in the system). At higher concentrations, the time
such as occurs in the dissolution of ionizing salts. The of hydration (referred to as delay time) is reduced. The
concentration of METHOCEL™ in solution is usually limited delay time is generally reduced as temperature is raised.
by the viscosity that a manufacturer is equipped to handle. In many cases it is desirable to “trigger” viscosity build
It also depends on the viscosity and chemical type of immediately following dispersion. Aqueous slurries can
METHOCEL™ product used. Solutions of low-viscosity be held for 45 minutes and still remain usable in neutral
products can be made at 10% to 15% concentration while systems. A trigger can be conveniently initiated by adding
high-viscosity products have a normal limit at 2% to 3% a small amount of a base, such as ammonium hydroxide,
concentration. sodium bicarbonate, etc. If METHOCEL™ is dispersed in
The form of METHOCEL™ cellulose ether product chosen neutral water (pH approximately 7), there is adequate time
(powder, surface-treated powder or granules) influences for thorough dispersion. Addition of base to raise the pH to
the techniques used to make solutions. Surface-treated approximately 9 causes the hydration to be completed in
and granular products can be added directly to aqueous just a few minutes.
systems. They disperse readily with mild agitation For best results and to achieve maximum hydration,
and dissolve (build viscosity) gradually under neutral surface-treated powders should be added with good
conditions. The dissolution rate of surface-treated products agitation to a neutral pH system. The system should be
can be increased by adjusting to an alkaline pH after agitated thoroughly for a few minutes, followed by an
dispersing the powder in water. Although untreated adjustment of pH to 8.5 to 9.0 with continued agitation,
METHOCEL™ powders are soluble in cold water, they until full viscosity is reached (usually 10 to 30 minutes).
must first be thoroughly dispersed in the water to prevent Once the pH has been shifted to the alkaline side (pH 8.5
lumping. to 9.0), allowing full and rapid solubilization of the surface-
Working with Surface-Treated Dispersible Powders treated product, solutions will be stable over the pH range
of 3 to 11.
In many applications, the combination of easy dispersion
in cold water and rapid hydration (viscosity build) is The addition of a slurry to an alkaline pigment grind
desirable. or filler dispersion, or the addition of a slurry to a basic
pigment-latex formulation, provides rapid solubilization
Surface-treated METHOCEL™ powders are chemically
and uniform viscosity development. The addition of dry,
treated so that they become temporarily insoluble in cold
alkaline pigments or fillers to a slurry on high-speed
water. This allows the METHOCEL™ product to be added
or low-speed mixing equipment also results in rapid
to a formulation and dispersed at relatively low shear
solubilization and viscosity development.
without any significant initial increase in viscosity.

3
 Nutrition & Biosciences

Working With Untreated Powders Dispersion Techniques

Although METHOCEL™ powders are soluble in cold water, 1. Add the surface-treated METHOCEL™
they must first be thoroughly dispersed in the water to powder to the water. Begin agitation.
prevent lumping. In some applications, dispersion can be
accomplished at ambient temperatures or in cold water 2. Continue agitation and add sufficient
by using an eductor funnel or high-shear mixer. However, ammonium hydroxide, sodium bicarbonate,
if untreated powders are added directly to cold water or other alkaline material (e.g., pigment
without sufficient agitation, a lumpy solution may result. grind) to the dispersion to obtain a pH of
Lumping results from incomplete wetting of the individual 8.5 to 9.0. This will result in rapid viscosity
powder particles. Only part of the powder dissolves, and development. Continue agitation until
a gelatinous membrane shields the remaining powder sufficient hydration has been achieved.
from complete hydration. Several dispersion techniques
are commonly used and are described below. Each has
advantages in certain applications. 1. Add the METHOCELTM cellulose ether to the
non-solvent. A ratio of 5-8 parts non-solvent
Dispersion in Hot Water
to 1 part METHOCEL™ is recommended to
Often called the “hot/cold” technique, this method takes obtain a liquid slurry.
advantage of the insolubility of METHOCEL™ cellulose
ethers in hot water. The powder is first dispersed by mixing 2. Agitate the mixture and METHOCEL™
thoroughly with 1/5 to 1/3 of the total required volume of powder until the particles of METHOCEL™
water that has been heated to above 90°C (194°F). Mixing cellulose ether are evenly dispersed.
continues until all particles are thoroughly wetted.
3. The dispersion of METHOCEL™ in a
For complete solubilization, the remainder of the water is nonsolvent medium may be added to cold
then added as cold water or ice to lower the temperature water, or cold water may be added to the
of the dispersion. Once the dispersion reaches the dispersion.
temperature at which that particular METHOCEL™ product
becomes water soluble, the powder begins to hydrate and 4. Continue mixing until the METHOCEL™
viscosity increases. powder is completely hydrated and the
In some applications, it may be desirable to heat the entire solution is smooth. You can now add the
volume of water, disperse the METHOCEL™ powder, and remaining ingredients in your formulation.
then cool the mixture while agitating until hydration is
complete. It is very important, however, to have adequate
cooling after wetting with hot water to ensure complete
hydration and viscosity development.
Dispersion in Concentrated Salt Solutions
Both untreated and surface-treated METHOCEL™ cellulose
ethers can be dispersed in concentrated salt solutions.
Dissolution occurs when the brine is diluted with cold
water.
Dispersion by Dry-Blending
Dry-blending involves mixing METHOCEL™ powder with
other dry ingredients before adding the water component.
Dry-blending separates the particles of METHOCEL™
cellulose ethers to allow thorough wet-out and complete
hydration when water is added. The minimum ratio of
other dry, powdered ingredients to METHOCEL™ powder
varies from 7:1 to 3:1.

4
How to Prepare Solutions of METHOCEL™
Celulose Ethers in Non-Aqueous Solvents and
Non-solvent Media

Solvents
The solubility of METHOCEL™ cellulose ethers in non-
aqueous media varies according to the nature and quantity
of substituent groups on the anhydroglucose chain. When
using a water-miscible, organic solvent, such as an alcohol
or glycol, use a ratio of at least 5 to 8 parts solvent to 1 part
METHOCEL™.
Dispersion in Non-solvent Media
Untreated METHOCEL™ cellulose ethers may also be
dispersed in non-solvent media such as vegetable oil,
propylene glycol, polyethylene glycol, glycerine, corn
syrup, and high-fructose corn syrup. A ratio of 5 to 8 parts
nonsolvent to 1 part METHOCEL™ is recommended to
obtain a fluid slurry. The dispersion of METHOCEL™ in a
non-solvent medium may then be added to cold water, or
the cold water may be added to the dispersion.

5
 Nutrition & Biosciences

Equilibrium Moisture Content Versus Percent Relative

Properties of METHOCEL™ Celulose Ethers in Equilibrium
EquilibriumMoisture Content
Moisture Content
Humidity (25°C)
Versus
Versus Percent
Percent Relative
Relative
Humidity(25°C)
Humidity (25°C)
Powder Form
METHOCEL™ cellulose ether products are white to slightly 40
off-white powders which are essentially odorless and 40
tasteless. The apparent density of the powders ranges
from 0.25 to 0.70 g/cm3 (250–700 kg/m3).
30
30
Moisture Sorption

25°C
O,O,25°C
METHOCEL™ products sealed in their original shipping
containers absorb little to no atmospheric moisture. Once 20

2 2
%%HH
20
a container is opened, however, there is pickup of moisture
from the air. When “exposed” METHOCEL™ cellulose ether
is weighed, a portion of the total weight, therefore, may be 10
water. Such weight must be corrected for moisture content 10
to ensure that the proper weight of METHOCEL™ is used to
give the desired viscosity. The moisture sorption rates for
the various METHOCEL™ grades are very similar to one
another. 0 20 40 60 80 100
0 20 40 60 80 100
Percentage relative humidity, mean average value,
Resistance to Microorganisms Percentage relative humidity, mean average value,
+95% probability
+95% probability
An important property of METHOCEL™ cellulose
ether products is their high resistance to attack by
microorganisms. METHOCEL™ products with higher
Molecular Weight/Viscosity
Molecular Weight/Viscosity Correlation, 20°C20°C
Correlation,
degrees of substitution are especially resistant to enzymes. Molecular Weight/Viscosity Correlation, 20°C
The fact that virtually all METHOCEL™ ethers pass through
the intestinal tract essentially unchanged attests to the 100 000
20°C

100 000
mPa•s20°C

stability of these products to a wide range of biochemical

and enzymatic systems.
solution,mPa•s

10 000
10 000
As the cellulose is modified by substitution with various
radicals, such as alkyl and hydroxyalkyl groups, resistance
aqueoussolution,

1 000
to microbial attack increases. Several researchers have 1 000
reported that the degree of substitution (D.S.) of water
soluble cellulose derivatives was a primary factor, with a 100
anaqueous

100
threshold D.S. value of 1.0 required for protection. Because
METHOCEL™ cellulose ether products have excellent 10
uniformity of substitution, with a D.S. much higher than 1.0, 10
Viscosityofofan

they possess excellent resistance to microbial attack.

Viscosity

1 000 10 000 100 000 1 000 000

1 000 10 000 100 000 1 000 000

Molecular weight
Molecular weight
Mn Mw
Mn Mw

6
Properties of Solutions of METHOCEL™ Effect of Concentration on Viscosity
Cellulose Ethers Most formulations require a predetermined product
viscosity of METHOCEL™ cellulose ether. The figure on
page 8 shows how the concentration of METHOCEL™
Molecular Weight/Viscosity Relationships
products of varying viscosity affects the aqueous solution
The viscosity of an aqueous solution of METHOCEL™ viscosity at 20°C. The measurements were made using an
cellulose ether is proportional to the molecular weight Ubbelohde viscometer (ASTM D2363). Data for both low
or chain length of the specific METHOCEL™ product and high molecular weight METHOCEL™ products are
used. Commercial designations of METHOCEL™ products shown and represent the average material found within a
are based on viscosity values determined in water at viscosity specification.
20°C, with a concentration of 2% METHOCEL™. The
This figure is plotted on an 8th root scale, not a logarithmic
measurement methods used are described in the current
scale. The 8th root of the viscosity is a roughly linear
product specifications.
function of the concentration. The equation which
The table below provides further information regarding expresses the illustrated approximate relationship
the correlation of number average molecular weight with between solution viscosity and polymer concentration
the commercial viscosity designation. One characteristic is α¹/₈ = (C·α) + 1, where α is the solution viscosity in
of polymers is their molar weight distribution. Different millipascal-seconds, C is the polymer concentration in
methods of calculating average molecular weight solution (expressed in percent), and α is a constant specific
numbers are available. The common technology for to the molecular weight. The value of α may be calculated
determining these values is size exclusion chromatography by substitution and may then be used to calculate the
(SEC) coupled with multi-angle-laser-light-scattering approximate viscosity at the desired concentration.
(MALLS). The number average molecular weight (Mn) is
For example, for a 4,000 mPa·s product, (4,000)¹/₈ = (C·α)
the total weight of the sample divided by the number of
+ 1. Solving for α yields a value of 0.910. For a 1,500 mPa·s
molecules in the sample. The weight average molecular
product, (1,500)¹/₈ = (C·α) + 1. Solving for α yields a value
weight (Mw) also takes the weight of each molecule into
of 0.747. Having calculated α for a particular METHOCEL™
account. Mw will generally be 3 to 10 times the Mn.
product, this value can be used to calculate viscosity at
The intrinsic viscosity [h] (also known as Staudinger other concentrations.
Index) represents the hydrodynamic volume for each
To find the line for any intermediate grade, locate the
gram of the polymer and is determined by viscosimetry.
desired 2% viscosity above 2% on the abscissa and draw a
Here the specific viscosity divided by the concentration is
straight line to the point of origin.
extrapolated to infinite dilution.

Viscosity of Methylcellulose of Various Molecular Weights

Number average degree Number average

Viscosity grade, 2%, 20°C, mPa•s Intrinsic viscosity (h), dL/g
of polymerization molecular weight (Mn)

5 53 10,000 1.2
10 70 13,000 1.4

40 110 20,000 2.0

100 140 26,000 2.6

400 220 41,000 3.9

1,500 340 63,000 5.7

4,000 460 86,000 7.5

8,000 580 110,000 9.3
15,000 650 120,000 11.0
19,000 750 140,000 12.1
40,000 950 180,000 15.0
75,000 1,160 220,000 18.4

7
 Nutrition & Biosciences

Viscosity / Concentration
Viscosity Relationships
/ Concentration Relationships The relationship may be expressed mathematically as:
(ηB)^¹/₈ = x1*(η1)^¹/₈+x2*(η2)^¹/₈ , where x1 and x2 are the
100 000
15 000 weight fractions of components one and two, respectively.
4 000 1 500
40 000 400
The example on the chart shows that 60% of 15,000 mPa·s
75 000 100 000
material and 40% of the 400 mPa·s material are needed
to make a blend having a viscosity of 4,000 mPa·sº.
50 000
Effect of pH on Viscosity
100 Because METHOCEL™ products are nonionic, the
viscosities of their solutions are generally stable over a
15 000
wider pH range than are the viscosities of gums that are
Viscosity mPa•s (at 20°C)

10 000 ionic in nature. Outside the range of pH 3 to 11, however,

50
there may be a gradual loss of viscosity at higher
temperatures or after long periods of standing, especially
4 000 with high-viscosity solutions. Solutions of METHOCEL™
cellulose ethers in acids or in strong caustic solutions will
1 500
15
decrease in viscosity. This factor should be considered
1 000 when determining the shelf life of products.

400
250
Blending
BlendingChart
Chart
100 5
50 100 000
25

15

10

0 1 2 3 4 5 6 7
15 000
% METHOCELTM cellulose ether

10 000
Viscosity, mPa•s 20°C

Blending for Intermediate Viscosity

4 000
METHOCEL™ products of the same substitution type, but
of different viscosity grades, can be blended to obtain an
intermediate viscosity grade. The figure to the right is a
blending chart that can be used for this purpose. To use
the chart, mark the viscosity of one material along the left 1 000
axis (Scale A) and the viscosity of the other material along
the right axis (Scale B). Connect the two points in a straight 400
line that crosses the graph. In the example shown, the
viscosities of the starting materials are 400 mPa·s on the
left and 15,000 mPa·s on the right. Now find the desired
100
final viscosity on either axis and draw a horizontal line that
intersects with the first line. From this intersection point,
draw a vertical line down to the bottom scale. The number
of that scale shows the percentage of Scale B Material 10

needed in the blend. In this example 4,000 mPa·s is the

desired final viscosity. So the required blend is 60% of
the 15,000 mPa·s (Scale B) material and 40% of the 400 0 20 40 60 80 100
mPa·s (Scale A) material.
Percent of scale B material in blend

8
Properties of METHOCEL™ Celulose Ethers in Preservatives for Aqueous Solutions
Powder Form METHOCEL™ cellulose ethers normally do not require
preservatives. They are not, however, antimicrobial agents.
If contamination occurs, microorganism growth will not be
Effect of Additives on Viscosity
inhibited.
In the preparation of formulations, viscosities may
To preserve solutions of METHOCEL™, addition of 0.05%
occasionally result which are considerably higher than
to 0.15% of DOWICIDE™ A antimicrobial or DOWICIL™
expected. This phenomenon can be caused by the
75 preservative is suggested. More information on these
interaction of METHOCEL™ with one or more of the
products is available upon request. For regulated uses, the
formula ingredients. As a result, it may be possible to use
appropriate permitted preservative should be used .
less thickener and still have adequate viscosity.
Compatibility of Aqueous Solutions
This effect usually passes through a maximum that
is dependent on the concentration of the interacting The methylcellulose and hypromellose molecules are
materials and on the presence of other ingredients such as nonionic and are not precipitated as insoluble salts
pigments, latex particles, or preservatives. by multivalent metal ions. However, METHOCEL™
cellulose ethers can be salted out of solution when the
Effect of Freezing on Solutions
concentration of electrolytes or other dissolved materials
Solutions of METHOCEL™ cellulose ether products do exceeds certain limits. This is caused by competition of the
not undergo separation into phases upon freezing. There electrolytes for water and results in reduced hydration of
is no separation of fluid layers (syneresis) or formation the cellulose ether.
of insoluble precipitates or haze. This lack of phase
Water-insoluble materials such as pigments, fillers, etc.
separation on freezing is particularly important in frozen
will not adversely affect METHOCEL™ cellulose ethers.
food items. As solutions of METHOCEL™ cellulose ether
Actually, solutions of METHOCEL™ often serve as excellent
products are cooled, solubilization increases, as evidenced
dispersing media for such materials. Other water-soluble
by increasing viscosity and improved clarity of solutions.
substances, such as starches, glues, and resins, may or may
When the solutions freeze, part of the water is held in the
not be compatible with METHOCEL™. Tests should be run
latent supercooled state and does not freeze. The heat
on these materials to determine compatibility. Because
normally released on freezing (heat of fusion) is decreased
METHOCEL™ cellulose ether products are not soluble in
by the amount of the super cooling.
concentrated salt solutions, these media can be used as
Defoamers for Aqueous Solutions non-solvent dispersing media for METHOCEL™ products.
The foaming of solutions of METHOCEL™ cellulose Subsequent dilution reduces the salt concentration to a
ethers is easily controlled by using foam stabilizers and level that allows dissolution of the METHOCEL™ product.
defoamers.
Defoamer concentrations should be kept to the minimum
required because these materials are generally low in
water solubility. The choice of a defoamer depends on the
type of other ingredients in the system. For defoaming
complex systems, consultation with the supplier of
defoamers is suggested.
Antifoam agents are extremely efficient surface-active
compositions which displace other surface-active
substances at the air/water interface. Their use, therefore,
might interfere with the performance of METHOCEL™
products in applications where the mechanical properties
of solution surface films is critical.

9
 Nutrition & Biosciences

Controlling Gel Temperature Gel Strength and Texture

The specific temperature at which thermal gelation The texture and strength of gels produced by heating
occurs (the incipient gelation temperature or IGT) and solutions of METHOCEL™ cellulose ethers varies with
the firmness of the gel are governed by the nature the product type, viscosity grade, and concentration of
and quantity of the substituent groups attached to the METHOCEL™ used. In general, the strength of the gel
anhydroglucose ring. Thus, gelation and the gel firmness increases sharply as molecular weight increases and
vary with each type of cellulose ether. The molecular gradually becomes constant at or above a viscosity of
weight of the particular METHOCEL™ product selected 400 mPa·s. Gel strength also increases with increasing
has little effect on the gel temperature. However, concentration.
increasing the concentration of the solution lowers the gel Interfacial Gelation
temperature.
In addition to bulk-phase gelation, METHOCEL™ cellulose
ethers also exhibit interfacial or surface gelation
Gelation Temperature as a Function of Concentration phenomena as a result of their surfactant nature.
Gelation Temperature as a Function of Concentration Interfacial gelation plays an important role in many
applications where a protective colloid, emulsification,
60
or surfactant function is desirable. Examples include:
55
suspension polymerization of vinyl chloride; aqueous
foam stabilization in shampoos, bubble baths; and the
Gelation Temperature, °C

50 stabilization of non-dairy whipped toppings and salad

dressings.
45
To achieve thermal gelation, concentrations of 1.5 wt %
40 are generally necessary. However, even at concentrations
as low as 0.001 wt %, many METHOCEL™ products exhibit
35 surface thermal gelation due to the migration of polymer
molecules to the air/water interface.
30
The equilibrium concentration of METHOCEL™ products
25 at any given interface depends upon the nature of the
interface, presence of other solvents, temperature, and
potential for formation of associative structures with other
0 2 4 6 8 10 12 surfactants. However, the concentration of METHOCEL™
Wt.% Concentration at an interface can be orders of magnitude greater than
METHOCELTM E Slope = -1 METHOCELTM A Slope = -2.33 that presumed to be present in the bulk phase. As a result,
METHOCEL F Slope = -1.77
TM surface film formation (surface gelation) occurs.
Surface gelation (filming) occurs very rapidly in many
solutions of METHOCEL™ products whether dilute
The Effects of Heating Rate and Agitation on Gelation or concentrated. This effect is most evident (and
Accurate measurement of gelation temperature requires troublesome) when one employs du Nouy tensiometry to
care because it is a function of the rate of heating and the determine surface tension.
rate of shear. Both a high rate of shear and a fast heating Generally speaking, increasing the molecular weight,
rate result in an apparently high gel temperature. concentration, or temperature of a solution of
Agitation also affects the strength of the gel. Continued METHOCEL™ will promote the onset of surface gelation
rapid agitation during gelation may break down the gel just as in thermal gelation.
structure and alter both the texture and strength of the
gel. For maximum development of gel strength, heat
the solution well above the gelation temperature under
quiescent conditions.

10
Properties of Unplasticized Films of METHOCEL™ Cellulose Ethers

PROPERTIES* METHOCEL™ A15 LV METHOCEL™ E15 LV

Specific gravity 1.39 1.29

Area factor 24 000 in2 / lb / mil 25 860 in2 / lb / mil

Moisture vapor transmission rate,
67,5g / 100in2 / 24h / mil 65g / 100in2 / 24h / mil
100°F (38°C), 50% RH
Oxygen transmission rate, 75°F (24°C) 25cm3 / 100in2 / 24h / mil 70cm3 / 100in2 / 24h / mil
Tensile strength, 75°F (24°C), 50% RH 9 000 lb /in2 (62MPa)±10% 10 000 lb /in2 (69MPa)±10%
Elongation, 75°F (24°C), 50% RH 5-15% 5-15%
Stability to ultra violet light, 500h,
Excellent Excellent
Fadeometer exposure
Resistance to oils and most solvent Excellent Excellent
Ultraviolet transmission (2 mil film)
55% 82%
400nm
49% 34%
290nm
26% 6%
210nm
*Typical properties, not to be construed as sales specifications. Data based on a mil dry film

Effect of Additives on Thermal Gelation Effect of Additives on Film Solubility

Additives may either increase or decrease thermal- The water solubility of films and coatings of METHOCEL™
gelation temperature, depending on whether the cellulose ethers can be altered by the use of cross-linking
additive exhibits a coagulant or a solubilizing effect on compounds and resins. The degree of insolubility can be
the METHOCEL™ product. For example, solutes such controlled by the choice and quantity of a cross-linking
as ethanol, PEG 400, and propylene glycol all raise the reagent. All urea formaldehyde, melamine formaldehyde,
gel points of METHOCEL™ products, which is due to the and resorcinol formaldehyde resins can be used.
solubilizing effect the solutes impart. Additives such Dialdehydes such as glyoxal are also effective. Supplier
as glycerin, sorbitol, and most salts lower gel points by literature should be consulted for selection of catalysts
lowering the solvency of the aqueous system, resulting in and curing compounds.
a more rapid dehydration of the METHOCEL™ product. Resistance of Films to Solvents
Properties of Films of METHOCEL™ Cellulose Ethers Films and coatings of METHOCEL™ are unaffected by
High-strength, water-soluble films, supported or animal and vegetable oils, greases, and petroleum
unsupported, may be rolled, cast, or extruded from hydrocarbons.
formulations of METHOCEL™ cellulose ether products.
These clear, smooth films or coatings are impervious to
oils, greases, and most solvents. They are also effective
binders, even when loaded with inert materials. The need
for a plasticizer may be more pertinent when using low
viscosity 5 mPa·s METHOCEL™ cellulose ethers because of
lower film elongation properties. This can be more acute if
drying temperatures are too high.

11
 Nutrition & Biosciences

Analytical Methods Safety Considerations

METHOCEL™ cellulose ether products resemble the
Measuring Viscosity naturally occurring plant in many of their chemical,
physical, and functional properties. All of these materials
Certain precautions must be observed for the accurate possess a basic carbohydrate structure.
measurement of the viscosity of solutions of METHOCEL™
cellulose ethers because they exhibit a nonlinear METHOCEL™ products have had extensive evaluation and
shear stress/shear rate relationship, which results in testing in both acute and long-term feeding studies in a
pseudoplastic viscosity behavior at most shear rates. number of species, including humans. Their many years of
use in a wide variety of food items attests to the safety of
DuPont employs the ASTM reference method (D1347 and METHOCEL™ Premium products.
D2363) as its standard procedure for non-pharmaceutical
grades while pharmaceutical grades are measured in Although dust from METHOCEL™ cellulose ether products
compliance with the USP. This method involves the use of could conceivably cause temporary mechanical irritation
Ubbelohde viscometers, one type for low viscosities and to the skin and eyes under extreme conditions and may
another for high viscosities. The Ubbelohde viscometer is a be considered a nuisance dust if inhaled, the products
precision device which requires only a small test sample. are considered to present no significant health hazard in
handling. Please review the handling precautions within
For measuring low viscosity, the appropriate capillary tube the Material Safety Data Sheet/Safety Data Sheet for more
size is chosen to obtain a flow time of 50 to 150 seconds information.
(see table to the right). The viscometer is placed in a 20°C
bath, and the length of time required to deliver a given
volume through the capillary tube is measured. The
Capillary Tubes for Measuring Viscosity
time in seconds is then converted to millipascalseconds
(mPa·s). Detailed procedures are given in current ASTM Size of Heavy Wall Tubing,
standards D1347 and D2363. The most reproducible Viscosity mPa•s
inside diameter
viscosities are obtained by cooling to 4°C and holding for
at least one-half hour before testing at 20°C. Low viscosity
15 1.5 mm
Viscosity may also be determined using a rotational
viscometer such as the Brookfield model LVF† viscometer. 25 1.8 mm
When the viscosity of a solution is less than 500 mPa·s, 100 2.4mm
the viscosity is less dependent on shear, and the solution
may be regarded as near-Newtonian. The apparent 400 3.2mm
viscosity of a solution of higher viscosity will be highly
dependent on the rate of shear, decreasing as the rate of High viscosity
shear is increased.
1,500 5.0 mm
The rotational instrument should be calibrated against
4,000 6.0 mm
standard oils. It’s important to note, however, that there is
no direct correlation between Ubbelohde and Brookfield 8,000 7.5 mm
measurements for non-Newtonian liquids. For details 15,000 10.0mm
regarding analysis methods, please contact your local
50,000 15.0 mm
salesperson for METHOCEL™ cellulose ethers.
75,000 15.0 mm
Handling Considerations
Material Safety Data Sheets/Safety Data Sheets for
METHOCEL™ products are available from The DuPont
to help you further satisfy your own handling, disposal,
and safety needs and those that may be required by
government regulations. Such information should
be requested prior to handling or use. The following
comments are general and are not a substitute for the
detailed safety information found in the Material Safety
Data Sheet/Safety Data Sheet.

12
Flammability Because METHOCEL™ cellulose ether products and
Cellulose ether products are organic polymers that will their aqueous solutions present no significant ecological
burn when exposed to heat and a sufficient oxygen problems, they can be disposed of by industrial
supply. Fires can be extinguished by conventional means, incineration or in an approved landfill, providing
avoiding any raising of dust by strong water jets. DuPont regulations are observed. Incineration should be done
recommends the use of water spray, carbon dioxide, or under carefully controlled conditions to avoid the
powder extinguishers. possibility of a dust explosion. Customers are advised to
review their local, state, provincial or national regulations
Storage governing the disposal of waste materials to determine
Caution: A fine dust of this material is capable of forming appropriate means of disposal in their area.
an explosive mixture with air. Powder samples should Customer Notice
not be exposed to temperatures above 135° to 145°C.
Samples may decompose and lead to a possible dust DuPont strongly encourages its customers to review both
explosion. As in storage of any dusts or fine powders, their manufacturing processes and their applications of
good housekeeping is required to prevent dusts in air DuPont products from the standpoint of human health and
from reaching possibly explosive levels. When handling environmental quality to ensure that DuPont products are
in large quantities or in bulk, the general precautions not used in ways for which they are not intended or tested.
outlined in NFPA 63, “Prevention of Dust Explosions in DuPont personnel are available to answer your questions
Industrial Plants,” and in NFPA bulletins 68, 69, and 654 and to provide reasonable technical support. DuPont
are recommended. product literature, including safety data sheets, should be
consulted prior to use of DuPont products. Current safety
With METHOCEL™ cellulose ether products with particle data sheets are available from DuPont.
sizes of 74 µm or less (finer than 200 mesh), critical levels
are reached at concentrations of 28 g/m3 (0.03 oz/ft3). Chemical Inventory
The minimum ignition energy required to cause a dust METHOCEL™ products, methylcellulose and hydroxypropyl
explosion is 28mJ. Static from a human body has about methylcellulose, comply with all applicable rules and
25mJ. This is normally not enough energy to ignite the orders under Toxic Substances Control Act PL94-469. The
powder. Chemical Abstracts Services Registry No. (CAS) is 9004-
As with any organic chemical material, METHOCEL™ 67-5 for methylcellulose and 9904-65-3 for hydroxypropyl
cellulose ethers should not be stored next to peroxides or methylcellulose.
other oxidizing agents. METHOCEL™ products have also been reported for the
Accidental Spills and Housekeeping following inventories:
Solutions of METHOCEL™ cellulose ethers are slippery. • European Inventory of Existing Chemical Substances
To prevent employee falls and injury, floor spills of dry (EINECS)
powder should be thoroughly vacuumed or swept up. • Australia Inventory of Chemical Substances (AICS)
Any slight residual product on the walls or floor can then
• Ministry of International Trade and Industry Inventory
be flushed with water into a sewer. If the spill is a viscous
(MITI, the Japanese inventory)
solution, it should be further diluted with cold water
before disposal. Likewise, accumulation of dust should be • Canadian Domestics Substances List (DSL)
avoided to control this hazard. Many countries are in the midst of creating new chemical
Disposal inventories.
Despite the very slow rate of biodegradation, cellulose
ether products should not present any hazard in the
waste/soil compartment. Their behavior is similar to wheat
flour or sawdust. Although DuPont studies using standard
procedures showed no 5-day, 10-day, or 20-day BOD
values, activated sludge studies with (14C) methylcellulose
showed that methylcellulose was 96% degraded or
otherwise removed from solution in 20 days. Thus,
METHOCEL™ cellulose ethers should present no ecological
hazard to aquatic life.

13
 The information contained herein is based on data known to DuPont or its affiliates at the time of preparation of the information and believed by them to be reliable.
This is business-to-business information intended for food, beverage and supplement producers, and is not intended for the final consumer of a finished food,
beverage or supplement product. The information is provided “as is” and its use is at the recipient’s sole discretion and risk. It is the recipient’s sole responsibility to
determine the suitability and legality of its proposed use of DuPont products for its specific purposes. Information and statements herein shall not be construed as
licenses to practice, or recommendations to infringe, any patents or other intellectual property rights of DuPont or others.

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