Вы находитесь на странице: 1из 32

C C

M
C C
M
C C
M
C C
M
C C
M
C C
M
C C
M
C C
M
C C
M
C C
M
C C
M
C C
M
C C
M
C C
M
C C
M
C C
M
C C
M
C C
M
C

AQUALON

Sodium
Carboxymethylcellulose

Physical
and
Chemical
Properties

AQUALON CMC
An Anionic Water-Soluble Polymer

CONTENTS

PAGE
Effect of Temperature . . . . . . . . . . . . . . .
Effect of pH . . . . . . . . . . . . . . . . . . . . . . .
Effect of Mixed Solvents . . . . . . . . . . . . .
Stability . . . . . . . . . . . . . . . . . . . . . . . . . . .
Microbiological Attack . . . . . . . . . . . . . . .
Chemical Degradation . . . . . . . . . . . . . . .
Compatibility . . . . . . . . . . . . . . . . . . . . . . . .
Effect With Salts . . . . . . . . . . . . . . . . . . .
Monovalent Cations . . . . . . . . . . . . . . .
Polyvalent Cations . . . . . . . . . . . . . . . .
Gelation of Solutions . . . . . . . . . . . . . . . . . .
Effect With Water-Soluble Nonionic Gums . .
PROPERTIES OF CMC FILMS . . . . . . . . . . . .
PACKAGING AND SHIPPING . . . . . . . . . . . . .
MICROBIOLOGICAL INFORMATION AND
REGULATORY STATUS FOR USE IN FOODS,
DRUGS, COSMETICS, AND TOILETRIES . . .
Microbiological Information . . . . . . . . . . . . .
Food Status . . . . . . . . . . . . . . . . . . . . . . . .
Food Labeling . . . . . . . . . . . . . . . . . . . . . . .
Pharmaceutical Use . . . . . . . . . . . . . . . . . .
Cosmetics and Toiletries . . . . . . . . . . . . . . .
APPENDIXMETHODS OF ANALYSIS . . . . .
Viscosity of Solution . . . . . . . . . . . . . . . . . .
Moisture Determination . . . . . . . . . . . . . .
Solution Preparation . . . . . . . . . . . . . . . .
Viscosity Measurement . . . . . . . . . . . . . .

AQUALON CMC AN ANIONIC


WATER-SOLUBLE POLYMER . . . . . . . . . . . . . . 2
APPLICATIONS . . . . . . . . . . . . . . . . . . . . . . . . . . 3
CHEMISTRY . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
GRADES AND TYPES . . . . . . . . . . . . . . . . . . . . 6
Grades . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Degree of Substitution . . . . . . . . . . . . . . . . . . . 6
Viscosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Particle Size . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Product Coding . . . . . . . . . . . . . . . . . . . . . . . . 7
PROPERTIES . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Moisture Absorption . . . . . . . . . . . . . . . . . . . . . 8
Physiological Properties . . . . . . . . . . . . . . . . . . 8
DISPERSION AND DISSOLUTION OF CMC . . . . 9
Solvent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Type of CMC . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Shear Rate . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Dispersion Methods . . . . . . . . . . . . . . . . . . . . . 9
Theory of Polymer Dissolution . . . . . . . . . . . . . 11
PROPERTIES OF CMC SOLUTIONS . . . . . . . . . 13
Viscosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Effect of Concentration . . . . . . . . . . . . . . . . 13
Effect of Blending . . . . . . . . . . . . . . . . . . . . 13
Blending Chart . . . . . . . . . . . . . . . . . . . . . . 13
Effect of Shear . . . . . . . . . . . . . . . . . . . . . . 16
Pseudoplasticity . . . . . . . . . . . . . . . . . . . 16
Thixotropy . . . . . . . . . . . . . . . . . . . . . . . . 17

Hercules Incorporated, 1999.

.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.
.
.
.

20
20
20
21
21
21
22
22
22
23
23
23
24
25

.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.
.
.
.

25
25
25
26
26
26
27
27
27
27
28

AQUALON CMC
AN ANIONIC WATER-SOLUBLE POLYMER

Aqualon sodium carboxymethylcellulose (CMC) has a


minimum purity of 99.5%. An anionic water-soluble polymer
derived from cellulose, it has the following functions
and properties:
It acts as a thickener, binder, stabilizer, protective colloid,
suspending agent, and rheology, or flow control agent.
It forms films that are resistant to oils, greases, and
organic solvents.
It dissolves rapidly in cold or hot water.
It is suitable for use in food systems.
It is physiologically inert.
It is an anionic polyelectrolyte.
These properties and functions make it suitable for use in
a broad range of applications in the food, pharmaceutical,
cosmetic, paper, and other industries. To serve these diverse
industries, the polymer is available in three grades: food,
pharmaceutical, and standard, and in many types based
on carboxymethyl substitution, viscosity, particle size, and
other parameters.
This booklet describes basic chemical and physical properties
of Aqualon CMC in all its forms. The wide variety of types
produced and the typical uses for this versatile polymer are
also discussed. The contents page will guide the reader to
subjects of special interest.
Technical or semi-refined grades of sodium carboxymethylcellulose are also available and are described in Booklet
250-3, available from Aqualon by request.

APPLICATIONS

Since its commercial introduction in the United States by


Hercules Incorporated in 1946, sodium carboxymethylcellulose has found use in an ever-increasing number of
applications. The many important functions provided by
this polymer make it a preferred thickener, suspending aid,
stabilizer, binder, and film-former in a wide variety of uses.

A representative listing of the many applications for sodium


carboxymethylcellulose is given below and on the following
page. Many of these applications do not require the use of
the highly purified grade, and a technical grade of CMC is
available for certain applications. Aqualons chemists and
engineers continue to tailor-make various grades and types
to meet the needs of specific customers and industries
requiring water-soluble polymers.

The wide range of viscosity and substitution types available


from Aqualon for the highly purified grades and the less
highly purified technical grades of CMC continues to expand
the uses for this product line.

APPLICATIONS FOR PURIFIED CMC(1)


Types of Uses

Specific Applications

Properties Utilized

Cosmetics

Toothpaste

Thickener; flavor stabilizer; suspending aid; binder

Shampoos; foamed products

Suspending aid; thickener; foam stabilizer;


high water-binding capacity

Creams; lotions

Emulsion stabilizer; film-former; thickener

Foods

Pharmaceuticals

Gelled products

Thickener; gelling agent; film-former

Denture adhesives

Wet tack; long-lasting adhesion

Frozen desserts; soft-serve

Controls ice crystal growth; improves mouthfeel, body,


and texture

Pet food

Water binder; gravy thickener; extrusion aid; binder


of fines

Protein foods

Retains water; improves mouthfeel

Baked goods

Batter viscosifier; improves moisture retention


and texture

Beverages

Suspending aid; rapid viscosifier; improves mouthfeel


and body; protein stabilizer in acidified drinks

Desserts; icings; toppings

Odorless and tasteless; thickens; controls sugar crystal


size; improves texture; inhibits syneresis

Low-calorie foods

No caloric value(2); thickens; imparts body and mouthfeel

Syrups

Clear; thickens; imparts favorable mouthfeel and body

Dressings; sauces

Thickener and suspending aid; imparts mouthfeel

Animal feed;
extrusion products

Lubricant; binder; film-former

Ointments; creams; lotions

Stabilizer; thickener; film-former

Jellies; salves

Thickener; gelling agent; protective colloid, film-former

Tablet binder; granulation aid

High-strength binder

Bulk laxatives

Physiologically inert; high water-binding capacity

Syrups

Thickener

Suspensions

Thickener; suspending aid

(1)For

these applications, food grades (designated F) or pharmaceutical grades (designated PH) are used.
These types may be referred to as cellulose gum.
(2)Depends on test method.

APPLICATIONS FOR STANDARD GRADE OF CMC


Types of Uses

Specific Applications

Properties Utilized

Adhesives

Wallpaper paste

Water-binding aid; adhesion; good open time;


nonstaining

Starch-corrugating adhesive

Thickener; water-binding and -suspending aid

Latex adhesives

Thickener; water-binding aid

Insecticides

Thickener; binder; suspending aid

Drift-control agent

Thickener

Glazes
Porcelain slips
Vitreous enamels
Refractory mortars

Binder for green strength; thickener; suspending aid

Welding rod coatings

Binder; thickener; lubricant

Foundry core wash

Binder; thickener; suspending aid

Latex paints; paper coatings

Rheology control; suspending aid; protective colloid

Detergents

Laundry

Whiteness retention through soil suspension

Lithography

Fountain and gumming


solutions

Hydrophilic protective film

Water-based inks

Binder; rheology control; suspending aid

Internal addition

High-strength binder; improves dry strength of paper

Surface addition

High-strength binder; oil-resistant film-former; provides


control of curl and porosity and resistance to oils
and greases

Pigmented coatings

Thickener; rheology control; water-retention aid

Laundry and fabric sizes

Film-former

Latex adhesives; backing


compounds
Printing pastes and dyes

Rheology control; thickener; water binding and holdout

Warp sizing

High film strength; good adhesion to fiber; low


BOD value

Cigar and cigarette adhesive

Good wet tack; high film strength

Reconstituted sheet

High-strength binder and suspending aid

Aerial-drop fluids

Ceramics

Coatings

Paper and paper


products

Textiles

Tobacco

CHEMISTRY

CMC is a cellulose ether, produced by reacting alkali


cellulose with sodium monochloroacetate under rigidly
controlled conditions.

Figure 1
Structure of Cellulose

Figure 1 shows the structure of the cellulose molecule; it is


visualized as a polymer chain composed of repeating cellobiose units (in brackets). These, in turn, are composed of
two anhydroglucose units (-glucopyranose residues). In
this structure, n is the number of anhydroglucose units
(which are joined through 1,4 glucosidic linkages), or the
degree of polymerization, of cellulose.

OH

OH

CH2OH

OH

OH

CH2OH

O
HO
H

H
O

OH

OH

H
O

O
CH2OH

OH

OH

OH

O
CH2OH

n-2
2

Figure 2
Idealized Unit Structure of CMC, With a DS of 1.0

Each anhydroglucose unit contains three hydroxyl groups,


shown in white. By substituting carboxymethyl groups for
some of the hydrogens of these hydroxyls, as shown in
Figure 2, sodium carboxymethylcellulose is obtained. The
average number of hydroxyl groups substituted per anhydroglucose unit is known as the degree of substitution, or
DS. If all three hydroxyls are replaced, the maximum theoretical DS of 3.0 (impossible in practice) results.

CH2OCH2COONa

OH

OH

O
H

CASRN:
9004-32-4
CAS Name: Cellulose, carboxymethyl ether,
sodium salt

OH

OH

H
O

H
O

Optimum water solubility and other desirable physical properties of CMC are obtained at a much lower degree of substitution than 3. The most widely used types of Aqualon
CMC have a DS of 0.7, or an average of 7 carboxymethyl
groups per 10 anhydroglucose units. Higher degrees of
substitution result in CMC products having improved
compatibility with other soluble components.

CH2OCH2COONa

Table I Typical Molecular Weights for Representative


Viscosity Types of Aqualon CMC
(DS = 0.7 in All Cases)

Cellulose ethers, such as CMC, are long-chain polymers.


Their solution characteristics depend on the average chain
length or degree of polymerization (DP) as well as the degree
of substitution. Average chain length and degree of substitution determine molecular weight of the polymer. As
molecular weight increases, the viscosity of CMC solutions
increases rapidly. Approximate values (weight averages) for
the degree of polymerization and molecular weight of several viscosity types of Aqualon CMC are given in Table I.
The degree of neutralization of carboxymethyl groups also
impacts viscosity. In solution, the degree of neutralization is
controlled by the pH.
At the end of the carboxymethylation, the reaction mixture
contains a slight excess of sodium hydroxide, which is usually neutralized. Although the neutral point of CMC is pH
8.25, the pH is generally adjusted to about 7-7.5. If the pH
to which the CMC is neutralized is 6.0 or less, the dried
product does not have good solubility in water; solutions
are hazy and contain insoluble gel particles. If the pH is
4 or below, the dried product is insoluble in water.

Viscosity
Type

Degree of
Polymerization

Molecular
Weight

High
Medium
Low

3,200
1,100
400

700,000
250,000
90,000

GRADES AND TYPES

DEGREE OF SUBSTITUTION

To serve its diverse markets, Aqualon produces CMC in


several grades and in a wide variety of types, based on
the degree of substitution, viscosity, particle size, and
other parameters.

Aqualon CMC is produced with the following degrees


of substitution:

GRADES

Type

Aqualon CMC is available in the three grades outlined below.

Grade

Designation

Food

7
9
12

Intended Use

F
P*

Food, cosmetic,
pharmaceutical

Pharmaceutical

PH**

Cosmetic,
pharmaceutical

Standard

None

Industrial

Substitution
Range(a)

Sodium
Content, %

0.65-0.90(b)
0.80-0.95
1.15-1.45

7.0-8.9
8.1-9.2
10.5-12.0

(a)Ranges

shown in this table are not necessarily current


specifications.
(b)ln 7S types, the upper limit of substitution is 0.95.

Higher degrees of substitution give improved compatibility


with other soluble components such as salts and nonsolvents. Generally, the number given in the product designation is approximately 10 times the DS.

*P (1.2 D.S. types and CMC 7L2P)


**PH (0.7 and 0.9 D.S. types)

Table II Some Types of Aqualon CMC


Designations for Indicated Substitution Types
7
9
12

Viscosity Range at 25C,(c) cps (mPas)


Highat 1% Concentration
2,500-6,000
1,000-2,800
1,500-3,000

7H4
7H3S, 7HOF
7H

Mediumat 2% Concentration
800-3,100
1,500-3,100
400-800
200-800
100-200

12M31
7M
7M8S
7M2

Low(d)at 2% Concentration
25-50

7L

at 4% Concentration
50-200

7L2

(c)Ranges
(d)Some

9H4

9M31
9M8

shown in this table are not necessarily current specifications.


even lower viscosity types are available. Contact your technical representative for additional information.

12M8

VISCOSITY

PARTICLE SIZE

CMC is manufactured in a wide range of viscosities. Highviscosity types are prepared from high viscosity cotton linters. Medium-viscosity types are prepared from wood pulp
of specified viscosity. Low-viscosity types are prepared by
aging the shredded alkali cellulose and by using chemical
oxidants. The foregoing methods of regulating the viscosity
are based on controlling the DP. It is also possible to attain
high viscosity by decreasing the solubility so that the product
is highly swollen but not completely dispersed. This can be
accomplished by decreasing the uniformity of the reaction
and lowering the DS. For example, products at DS 1.2 do
not have solution viscosities as high as products of DS 0.7
prepared in substantially the same way. However, the solutions of the higher-substituted products are much smoother.

Aqualon CMC is available in several different particle sizes


to facilitate handling and use in processing operations such
as solution preparation and dry-blending. Screen analysis is
given here for three of the types. Other types are available.

Designation Description

The viscosity ranges of some types are listed in Table II.


Others are available to meet specific needs. Regular viscosity types with a DS of 0.7 meet most needs and are designated by the number 7, followed by the letter H (high), M
(medium), or L (low). All other types are designated by an
additional number following the letter which, when multiplied
by a factor, gives the approximate upper viscosity limit. The
factor and applicable concentration appear below.

Viscosity Type

Factor

Concentration, %

High
Medium
Low

1,000
100
10

1
2
2

Particle Size(e)

None

Regular

On U.S. 30, %, max


On U.S. 40, %, max

1
5

Coarse

On U.S. 20, %, max


Through U.S. 40,
%, max
Through U.S. 80,
%, max

(e)AII

Fine

On U.S. 60, %, max


Through U.S. 200,
%, min

55
5
0.5
80

screens are U.S. Bureau of Standards sieve series.

PRODUCT CODING
An example of the coding used for ordering Aqualon CMC
follows:
For cellulose gum Type 7H3SCF:
7 means that the typical degree of substitution is
approximately 0.7.
H means high viscosity.
3 means that the viscosity of a 1% solution is in the
range of 3,000 cps.
S means smooth solution characteristics.
C means coarse particle size.
F means food grade.

Solutions of all CMC types display pseudoplastic behavior.


(See page 16.) Some types, particularly those of higher
molecular weight and lower substitution, also show thixotropic behavior in solution. (See page 17.) These thixotropic
solutions will possess varying amounts of gel strength and
are used where suspension of solids is required. The S, 9,
and 12 types produce solutions with little or no thixotropy,
and are utilized where smooth solutions without structure
are required.

Aqualon can tailor the chemical and physical properties of


CMC to meet special requirements. Users are encouraged
to discuss their needs with their technical representative,
or to call the 800 number shown on the back cover for
product information.

Specific properties are available in certain other types. For


example, the O type, 7HOF, provides the best solubility
and storage stability in acid media.

PROPERTIES

Typical properties of Aqualon CMC polymer and in solution


and film form are shown in Table III. These are not necessarily specifications.

Figure 3
Effect of Relative Humidity on Equilibrium Moisture
Content of Aqualon CMC at 25C

Table IIITypical Properties of Aqualon CMC


Equilibrium Moisture Content, %

Polymer
Sodium carboxymethylcellulose
dry basis, %, min . . . . . . . . . . . . . . . . . . . . 99.5
Moisture content (as packed), %, max . . . . . . . 8.0
Browning temperature, C . . . . . . . . . . . . . . . . 227
Charring temperature, C . . . . . . . . . . . . . . . . . 252
Bulk density, g/ml . . . . . . . . . . . . . . . . . . . . . .0.75
Biological oxygen demand (BOD)(f), ppm
7H type . . . . . . . . . . . . . . . . . . . . . . . . . 11,000
7L type . . . . . . . . . . . . . . . . . . . . . . . . . . 17,300
Solutions
pH, 2% solution . . . . . . . . . . . . . . . . . . . . . . . . 7.5
Surface tension, 1% solution,
dynes/cm at 25C. . . . . . . . . . . . . . . . . . . . . . 71
Specific gravity, 2% solution . . . . . . . . . . . . 1.0068
Refractive index, 2% solution . . . . . . . . . . . . 1.336

40
12M31P
7HF

30

20

10

0
0

Typical Films (Air-Dried)


Density, g/ml . . . . . . . . . . . . . . . . . . . . . . . . . 1.59
Refractive index . . . . . . . . . . . . . . . . . . . . . . 1.515
Thermal conductivity, W/mK. . . . . . . . . . . . . . 0.238

20

40
60
Relative Humidity, %

80

PHYSIOLOGICAL PROPERTIES
Dermatological and toxicological studies by independent
laboratories demonstrate conclusively that sodium carboxymethylcellulose shows no evidence of being toxic to white
rats, dogs, guinea pigs, or human beings. Feeding, metabolism, and topical use studies also show that CMC is physiologically inert. Patch tests on human skin demonstrated that
sodium carboxymethylcellulose was neither a primary irritant
nor a sensitizing agent. Additional information is available
from Hercules Incorporated.

(f)After

5 days incubation. Under these conditions, cornstarch has


a BOD of over 800,000 ppm.

MOISTURE ABSORPTION
CMC absorbs moisture from the air. The amount absorbed
and the rate of absorption depend on the initial moisture
content and on the relative humidity and temperature of
the surrounding air. Figure 3 shows the effect of relative
humidity on equilibrium moisture content of three types
of Aqualon CMC.
As Aqualon CMC is packed, its moisture content does not
exceed 8% by weight. Because of varying storage and shipping conditions, there is a possibility of some moisture
pickup from the as-packed value.

DISPERSION AND DISSOLUTION


OF CMC

A number of factors such as solvent, choice of polymer, and


shear rate affect dispersion and dissolution of CMC.

DISPERSION METHODS

SOLVENT

CMC particles have a tendency to agglomerate, or lump,


when first added to water. To obtain good solutions easily,
the dissolving process should be considered a two-step
operation:

Aqualon CMC is soluble in either hot or cold water. The


gum is insoluble in organic solvents, but dissolves in suitable mixtures of water and water-miscible solvents, such as
ethanol or acetone. Solutions of low concentration can be
made with up to 50% ethanol or 40% acetone. Aqueous
solutions of CMC tolerate addition of even higher proportions of acetone or ethanol, the low-viscosity types being
considerably more tolerant than the high-viscosity types,
as shown below.

1. Dispersing the dry powder in water. Individual particles should be wet and the dispersion should not
contain lumps.
2. Dissolving the wetted particles.
When the proper technique is used, good dispersion is
obtained, and CMC goes into solution rapidly. To prepare
lumpfree, clear solutions, a variety of methods can be used:

Tolerance of Aqualon CMC Solutions for Ethanol

Method 1
Add CMC to the vortex of vigorously agitated water. The rate
of addition must be slow enough to permit the particles to
separate and their surfaces to become individually wetted,
but it should be fast enough to minimize viscosity buildup of
the aqueous phase while the gum is being added.

Volume Ratio of Ethanol


to CMC Solution, 1%
CMC
Type

First Evident
Haze

First Distinct
Precipitate

7L
7M
7H

2.4 to 1
2.1 to 1
1.6 to 1

3.6 to 1
2.7 to 1
1.6 to 1

Method 2
Prior to addition to water, wet the powder with a watermiscible liquid such as alcohol, glycol, or glycerol that will
not cause CMC to swell. Two to three parts of liquid per part
of CMC should be sufficient.

Note: In these tests, ethanol (95%) was added slowly at room


temperature to the vigorously stirred 1% CMC solution.

Method 3
Dry-blend the CMC with any dry, nonpolymeric material
used in the formulation. Preferably, the CMC should be
less than 20% of the total blend.

TYPE OF CMC
The higher the degree of substitution, the more rapidly
CMC dissolves. The lower the molecular weight, the faster
the rate of solution.

Method 4
Use a water eductor (Figure 4) to wet out the polymer particles rapidly. The polymer is fed into a water-jet eductor,
where a high-velocity waterflow instantly wets out each
particle, thus preventing lumping. This procedure speeds
solution preparation and is particularly useful where large
volumes of solutions are required. For users wishing the
convenience of an automatic system, a polymer solution
preparation system (PSP), which is used in conjunction
with a water eductor, is shown in Figure 5.

Particle size has a pronounced effect on the ease of dispersing and dissolving CMC. C, or coarse, types were
developed to improve dispersibility of the granules when
agitation is inadequate to produce a vortex on the liquid
surface. Solution time, on the other hand, is extended
considerably with a coarse material.
For applications requiring a rapid solution time, CMC of
fine particle size (X grind) is best. However, special dissolving techniques, such as prewetting the powder with a
nonswelling liquid, mixing it with other dry materials, or
using an eductor-type mixing device, are necessary to
obtain dispersion.

Special, fast-dissolving fluidized polymer suspensions of


CMC are available to give very rapid dissolution where it is
required or where agitation is substandard.
Users are encouraged to contact their technical representative for information on PSP units or fluidized suspensions
of CMC.

SHEAR RATE
Preparing solutions by extremely low shear agitation, such
as shaking by hand, is generally not recommended. Properties of the resulting solution are quite different from those
prepared by higher shear methods. The effect of shear on
solution properties is discussed in more detail on pages 11
and 16.

Figure 4
Typical Installation of Eductor-Type Mixing Device

Lightnin Mixer

Funnel

Polymer Feed

Mix Tank

Mixing Device

Air BleedHoles

Makeup Water
Workman
Platform

Water
Inlet

Eductor

Discharge
Special Mixing Device
This inexpensive equipment is
most effective for quickly preparing uniform solutions of CMC.

Figure 5
Automated Polymer Solution Preparation (PSP) System

Dust
Collector
Polymer Hopper
Polymer
Eductor

Screw
Drive
Motor

Water

Helical Screw Feeder

Air
Eductor
PSP Unit

10

Preparation Tank

THEORY OF POLYMER DISSOLUTION

time-dependent phenomenon, if CMC/salt solutions are


allowed to stand, it is very possible that the final stage of
disaggregation will be Stage 2 and the equilibrated viscosity
will be higher than that of CMC in distilled water. Hence, one
cannot assume that addition of salt will lower equilibrated
solution viscosity, only that it will inhibit polymer disaggregation. With Types 9 and 12, the slight viscosity increase in
saturated salt is caused by the viscosity bonus effect discussed on page 20.

When a polymer is dispersed in a solvent, the degree of


disaggregationi.e., separation of polymer molecules
is affected by the:

Chemical composition of the polymer.


Solvating power of the solvent.
Shear history of the resulting solution.

Figure 6 shows how these states of disaggregation may


affect viscosity of the liquid. If CMC is added to a liquid
and its degree of disaggregation reaches equilibrium, the
polymer may:

Figure 6
Idealized Curve Showing Effect of Degree
of Disaggregation on Viscosity of Polymer Solution

Remain as a suspended powder, neither swelling


nor dissolving (1).
Swell to a point of maximum viscosity without completely dissolving (2).
Reach maximum disaggregation (3).
Exist in an intermediate state (1a, 1b, 2a).

Depending on choice of polymer, solvent, and mechanical


means of preparing the solution, the user of CMC can alter
its state of disaggregation to suit his needs. Table IV shows
the effect of these factors on the disaggregation of CMC as
measured by solution viscosity.

2a

Viscosity

1b

Increasing DS makes CMC more hydrophilic, or waterloving; hence, types having high DS are more readily disaggregated in water. Plotting solution viscosity at constant
shear against increasing DS (Types 7 through 12) produces
a curve similar in shape to that shown in Figure 6.

3
1a

Increasing electrolyte concentration reduces disaggregation, as evidenced by the lower viscosity in saltwater of
Type 7. The viscosities listed in Table IV were measured
under quality control conditionsthat is, two hours after
solution was complete. At this point, CMC dissolved in an
electrolyte solution is probably in the Stage 1 section of the
disaggregation curve. CMC dissolved in distilled water
under quality control conditions is at Stage 3 of the curve.
Viscosities of CMC/salt solutions measured at this point will
be lower than the viscosities of corresponding CMC solutions prepared in distilled water. Since disaggregation is a

Degree of Disaggregation

Table IV Factors Affecting Disaggregation of Aqualon CMC


(This table shows the effect of polymer composition, solvent strength, and mechanical shear on disaggregation, as
measured by solution viscosity. All data are at 25C. Cellulose gum was added dry to the solvents listed.)
Viscosity, cps (mPas)
Anchor Stirrer

Waring Blendor

Cellulose
Gum Type

Distilled
Water

4% NaCl

Saturated
NaCl

Distilled
Water

4% NaCl

Saturated
NaCl

7HF

1,680

140

45

760

1,040

2,440

7H3SF

1,680

570

165

760

750

1,720

9M31F

215

160

225

125

95

235

12M31P

175

80

180

100

55

140

11

In many cases, the high shear imparted by the Waring blendor


can enhance viscosity development or disaggregation.

Figure 7
Effect of Solvent Strength on Disaggregation
of Aqualon CMC
(1.75% CMC in Glycerin-Water)

The effect of solvent strength (polarity in binary solvent mixtures) on the disaggregation of CMC is shown in Figure 7.
Note the similarity of these curves to the curve in Figure 6.
The data in Figure 7 and in Table IV show that an increase
in solvating power or an increase in mechanical shear
breaks internal associations of gel centers and promotes
disaggregation.

100,000

The effect of solutes such as salts or polar nonsolvents on


the viscosity of CMC solutions also depends on the order of
addition of the gum and solute. This is shown in Figure 8. If
CMC is thoroughly dissolved in water and the solute is then
added, it has only a small effect on viscosity. However, if the
solute is dissolved before the CMC is added (as is the case
with Table IV data), it inhibits breaking up of crystalline
areas, and lower viscosities are obtained. This effect of
solutes is less apparent with more uniformly substituted
material containing fewer crystalline areas.

Viscosity, cps

9M8F

10,000

7MF

12M8P

1,000
300
0

20
40
60
80 100
Water in Solvent, weight %

Figure 8
Effect of Solutes on Viscosity of CMC Solutions

Solute Added After CMC

300
200

Apparent Viscosity, cps

Solute Added
Before CMC
100
80
60

40
30
20

10
0.02

Solutes Used:
NaCl
NaCl + NaOH (pH 10.1)
Na2So4
Na4P2O7 10H2O (pH 9.5-9.8)
KCl or LiCl

0.04
0.08 0.1
0.2
0.4
Molal Concentration of Cation, moles/1,000 g solvent
12

0.8 1.0

PROPERTIES OF CMC SOLUTIONS

Viscosity is the single most important property of CMC solutions. Aqualon has acquired considerable information on
factors affecting viscosity, and these data are given here.
Stability of CMC solutions to microbiological attack and
chemical deterioration is also discussed in this section.

Equation: Because the viscosity-concentration relationship is


an exponential function, the viscosity resulting from blending
is not an arithmetic mean. The viscosity of a blend can, however, be approximated by use of the equation below, which
is derived from the Arrhenius equation that relates viscosity
with polymer concentration.

VISCOSITY

n log V1 + (100-n) log V2


Log Vs =
100
where Vs = Viscosity sought
n = Percent (by weight) of the first component of the
blend having a viscosity of V1
V2 = Viscosity of the second component of the blend

Solutions of CMC can be prepared in a wide range of viscosities. Such solutions are non-Newtonian because they
change in viscosity with change in shear rate. Consequently,
it is essential to standardize viscosity determination methods.
This standardization must include the type and extent of
agitation used to dissolve the CMC, as well as precise control of temperature, conditions of shear, and method of viscosity measurement. The procedure used in the Aqualon
control laboratory is described in detail in the Appendix,
page 27.

Note: All viscosities must be expressed at the same polymer


concentration and in the same units.
Use of the chart itself is simple. For example, suppose one
wishes to obtain a solution with a viscosity of 900 cps at 3%
concentration. The water-soluble polymer is available as
Material A with a viscosity of 1,800 cps at 3% concentration,
and Material B with a viscosity of 700 cps at 3% concentration. A line is drawn connecting these two viscosities on the
chart. The point at which this line intersects the desired viscosity line is then determined, and the percentage it represents is read from the bottom of the chart. Thus, in this
example, 28% of Material A and 72% of Material B are
needed to yield the desired viscosity of 900 cps at a total
polymer concentration of 3%.

Effect of Concentration
The viscosity of aqueous CMC solutions increases rapidly
with concentration. This is shown in Figure 10. The bands
show the range of viscosity obtainable with standard
viscosity types.

Effect of Blending
Two viscosity types of CMC can be blended to obtain an intermediate viscosity. Because viscosity is an exponential
function, the viscosity resulting from blending is not an
arithmetic mean.

Limitations of Blending: The relationship between viscosity


and concentration can vary significantly, depending on the
chemical composition as well as the molecular weight (viscosity type) of the polymers involved. The greatest accuracy
is obtained from use of the equation or the blending chart of
Figure 9 if the following conditions are met. Departure from
these conditions can result in deviation from the predicted
value of viscosity.

A blending chart (VC-440), available from Aqualon, can be


used to determine the result of blending various amounts of
two viscosity types of CMC. It can also be used to determine
the amount of CMC required to achieve a desired viscosity
when blending two types of known viscosity.

Blending Chart
The blending technique outlined in this bulletin can be
used eqully well for Aqualon cellulose gum (sodium
carboxymethylcellulose), Natrosol hydroxyethylcellulose,
Culminal methylcellulose and methyl hydroxypropylcellulose
and Klucel hydroxypropylcellulose. This technique is useful
when it is desirable to blend two viscosity types of the same
water-soluble polymer in order to obtain a solution having a
predetermined viscosity and solids concentration.
Blends can be calculated directly from the equation that follows; or, more conveniently, the blending chart in Figure 9
can be used. From this chart, one can determine, without
calculations, the percentage of any two viscosities that must
be blended to secure a desired intermediate viscosity.
Likewise, it is possible to determine the viscosity that will
result from utilizing any blend.

13

The chemical composition of the polymers must be similar


i.e., the type and level of chemical substitution must be
the same.

The solution viscosities of the polymers should be as


close together as possible.

Figure 9
Chart for Blending Aqualon Water-Soluble Polymers

5,000
4,000
3,000
Viscosity of
Available
Material A

2,000

Solution Viscosity at 25C, cps

Viscosity of
Available
Material B
1,000
900
800
700
600

Desired
Viscosity
in Example

500
400
300

200

100
90
80
70
60
50

Blend Needed
for Desired
Viscosity

40
30

Material A, %
Material B, %

20
100
0

90

80

70

60

50

40

30

20

10

10

20

30

40

50

60

70

80

90

100

14

Figure 10
Effect of Concentration on Viscosity of Aqueous Solutions of Aqualon CMC
(Bands approximate the viscosity range for the types shown.)

30,000

7H4, 9H4
7H

20,000

7H3S, 7HOF
10,000
9M31, 12M31
7L

7M, 9M8, 12M8

Solution Viscosity at 25C, cps

7M2
7L2
1,000

100

10
5
0

CMC, weight %

15

10

Effect of Shear

Figure 11
Shear Stress vs. Shear Rate for Newtonian
and Pseudoplastic Liquids

Shear Stress

CMC is often used to thicken, suspend, stabilize, gel, or


otherwise modify the flow characteristics of aqueous solutions or suspensions. Preparation and use of its solutions
involve a wide range of shearing conditions. It is therefore
important that the user understand how rheological behavior
can affect the system.

PseudoplasticitySmall amounts of CMC dissolved in


water greatly modify its properties. The most obvious immediate change is an increase in viscosity. Interestingly, a single
CMC solution will appear to have a different viscosity when
different physical forces are imposed on it.

tic

las

op
eud

Ps

nia

wto
Ne

These physical forces may be conveniently referred to as


high, intermediate, or low shear stress. For example, rolling
or spreading a liquid as if it were an ointment or lotion would
be high shear stress. After the liquid has been applied, gravity and surface tension control flow. These forces are conditions of low stress. Intermediate stress is typified by pouring
a liquid out of a bottle.

Shear Rate

Figure 12
Viscosity vs. Shear Rate

If a solution of high-viscosity CMC appears to be a viscous


syrup as it is poured from a bottle, it will behave as a thin
liquid when applied as a lotion, and yet when high shear
stress is removed it will instantly revert to its original highly
viscous state. This type of flow behavior is referred to as
pseudoplasticity or time-independent shear-thinninga form
of non-Newtonian flow. It differs from the time-dependent
viscosity change called thixotropy.

When viscosity (shear stress divided by shear rate) is


plotted against shear rate, a Newtonian system gives a
horizontal line. If viscosity decreases as shear rate is
increased, the flow is pseudoplastic.

Apparent Viscosity

If shear stress is plotted vs. shear rate, as in Figure 11, a


Newtonian fluid will produce a straight line passing through
the origin. A pseudoplastic liquid, such as a CMC solution,
will give a curved line. Plotting apparent viscosity against
shear rate, as in Figure 12, produces a horizontal straight
line for a Newtonian fluid and a curved line for a pseudoplastic liquid.
Solutions of some medium- and high-viscosity types of
CMC exhibit pseudoplastic behavior because their longchain molecules tend to orient themselves in the direction
of flow; as the applied force (shear stress) is increased, the
resistance to flow (viscosity) is decreased. When a lower
stress is imposed on the same solution, the apparent
viscosity is higher because random orientation of molecules presents increased resistance to flow.

Newtonian
Pseu

dopla

Shear Rate

16

stic

Rheograms are helpful to illustrate the effect of thixotropy.


A thixotropic solution will form a hysteresis loop when shear
stress is plotted against shear rate, as shown in Figure 14A.
The increased shear stress required to break the thixotropic
structure has reduced the resistance to flow, or viscosity. If
a solution has gel strength, a spur forms in the hysteresis
loop; this is shown in Figure 14B. It is an indication of the
stress necessary to break the gel structure and cause the
solution to revert to its normal apparent viscosity.

Generally, solutions of the medium- and high-viscosity


types with a high DS (i.e., 0.9 and 1.2) and S types are
pseudoplastic rather than thixotropic. In contrast to this,
regular high- and medium-viscosity gums of DS 0.7 (slightly
less uniformly substituted) show thixotropic behavior in
solution. (See Thixotropy, below.)
Solutions of low-molecular-weight CMC i.e., low-viscosity
typesare less pseudoplastic than those of high-molecularweight gum. However, at very low shear rate, all CMC
solutions approach Newtonian flow. Figure 13 shows
these relationships.

Figure 14A
Thixotropic Flow

Shear Stress

10,000
1,000

7.3% 7L

100

Shear Rate
1% 7H3S

Figure 14B
Extremely Thixotropic Flow With Gel Strength

Waring
Blendor

Home
Mixer

Tumbling
or
Pouring

0.1
1
10
100 1,000 10,000
Shear Rate (Reciprocal sec)
Brookfield
Viscometer

10
0.01

Film Sag
Under
Gravity

Apparent Viscosity, cps

Figure 13
Effect of Shear Rate on Apparent Viscosity of
Aqualon CMC Solutions

Shear Stress

ThixotropyIf long-chain polymers have a considerable


amount of interaction, they will tend to develop a threedimensional structure and exhibit a phenomenon known
as thixotropy.
Thixotropy is a time-dependent viscosity change. It is characterized by an increase in apparent viscosity when a solution remains at rest for a period of time after shearing. In
certain cases, the solution may develop some gel strength,
or even set to an almost solid gel. If sufficient force (shear
stress) is exerted on a thixotropic solution, the structure
can be broken and the apparent viscosity reduced.

Shear Rate

17

Figure 15 illustrates thixotropy in another manner. At a


constant shear rate (D = K), viscosity decreases with time.
When shear is removed (D = zero), viscosity increases significantly with time.

Figure 15
Thixotropic Flow Is a Time-Dependent
Change in Viscosity

Thixotropic solutions are desirable, or even essential, for


certain uses of CMC, such as suspension of solids. Highand medium-viscosity types of regular Aqualon CMC
(0.7 DS) generally exhibit thixotropic behavior. S types
and high-DS types in medium and high viscosity have been
developed for uses requiring clear, smooth solutions of
little or no thixotropy. Figure 16 illustrates the difference
in appearance between solutions of regular and S-type
Aqualon CMC. S and high-DS types show the typical
pseudoplasticity of long-chain molecules.

Apparent Viscosity

D = Zero

D=K

Figure 16
Thixotropic and Nonthixotropic Solutions of CMC
The solution of regular Aqualon CMC, left, is thixotropic; S-type Aqualon CMC, right, is essentially nonthixotropic.

18

Figure 17
Effect of Temperature on Viscosity of Aqualon CMC Solutions

10,000

1% 7H

2% 9M8

Viscosity, cps

1,000

2% 7M

1% 9M31
1% 12M31

100

2% 7L

10
0

10

20
30
40
Temperature, C

19

50

60

70

80

Effect of Temperature

Figure 19
Stability of Aqualon Cellulose Gum in
Organic Acids1% Solution of Type 7HOF

Viscosity of CMC solutions depends on temperature, as


shown in Figure 17. Under normal conditions, the effect of
temperature is reversible, so temperature variation has no
permanent effect on viscosity. However, long periods of heating at high temperatures will degrade CMC and permanently
reduce viscosity. For example, a 7L type held for 48 hours at
180F lost 64% of its original viscosity.

Viscosity at 25C, cps

10,000

Effect of pH
CMC solutions maintain their normal viscosity over a wide
pH range. In general, solutions exhibit their maximum viscosity and best stability at pH 7 to 9. Above pH 10, a slight
decrease in viscosity is observed. Below pH 4.0, the less
soluble free acid carboxymethylcellulose predominates
and viscosity may increase significantly. Figure 18 shows
the effect of pH on the viscosity of typical Aqualon
CMC grades.

1.0% Lactic Acid


1,000

1.0% Citric Acid

0.3% Fumaric Acid

100

Figure 18
Effect of pH on Viscosity of
Aqualon CMC Solutions

1
2
3
4
5
Storage Time at 25C, months
Effect of Mixed Solvents

5,000
Brookfield Viscosity, cps

5.0% Acetic Acid

The behavior of highly substituted CMC in mixed-solvent


systems, such as glycerin-water, is similar to its effect in
water alone. In mixed systems, however, viscosity of the solvent affects viscosity of the solution. For example, if a 60:40
mixture of glycerin and water (which is 10 times as viscous
as water alone) is used as the solvent, the resulting solution
of well-dispersed CMC will be 10 times as viscous as the
comparable solution in water alone. This behavior is shown
in Figure 19 and is commonly referred to as the viscosity
bonus effect.

2.0% 9M31
1.0% 7H

1,000
500

2.0% 7H

Figure 20
Effect of Mixed Solvents on Viscosity of
Aqualon CMC Solutions1% Type 12M31

100
2

6
pH

10

12

10,000
Tests with Aqualon CMC Type 7M have shown that very little
polymer degradation takes place if solutions are allowed to
stand overnight at room temperature at a pH as low as 2.
However, at pH values of 4-5 and temperatures of 150F,
most of the viscosity is lost in 24 hrs.

1% CMC in Glycerin-Water
1,000
Apparent Viscosity, cps

In acidic systems, the order in which CMC is added to the


solvent is also important. If a CMC solution is prepared prior
to the addition of acid, a higher viscosity is obtained than
when dry CMC is dissolved in an acidic solution.
Aqualon cellulose gum Type 7HOF is a particularly efficient
thickener for acidic systems. Clear, viscous solutions are
obtained when it is dissolved in water and then acidified. Its
stability in several organic acids, typical of those used in
low-pH foods, is shown in Figure 19.

100
1% CMC in Water
10
Glycerin in Water
1
Water
10 -1
10

100

1,000

Shear Rate,

20

sec-1

10,000

STABILITY

Chemical Degradation
Under certain conditions, solutions of CMC are susceptible
to chemical degradation. Permanent loss of viscosity can
occur resulting from scission of the long-chain molecules.
Such viscosity loss is accelerated by increasing the temperature and/or lowering the pH. Aqualon cellulose gum Type
7HOF provides improved resistance to viscosity degradation
and precipitation in low-pH systems.

CMC is subject to microbiological attack and chemical


degradation. However, corrective measures can be taken
to prevent both from occurring.

Microbiological Attack
Although CMC is more resistant to microbiological attack
than many other water-soluble gums, its solutions are not
immune. Heat treatment can be used to destroy many
microorganisms while having little effect on CMC properties. Heating for 30 min at 80C, or for 1 min at 100C,
is generally sufficient.

An oxidative type of degradation occurs under alkaline conditions in the presence of oxygen. The rate of viscosity loss
is also increased by heat and/or ultraviolet light. Inclusion of
an antioxidant, exclusion of oxygen, and avoidance of highly
alkaline conditions are obvious preventive measures.

When solutions are stored, a preservative should be added


to prevent viscosity degradation. If cellulases (hydrolytic,
viscosity-destroying enzymes) have been introduced by
microbial action, even in trace amounts, addition of most
preservatives will not prevent degradation; therefore, it
is important to preserve solutions as soon as possible
after preparation.

To obtain the best stability during prolonged storage of CMC


solutions, users should:

The preservatives shown below have proved effective for


solutions of Aqualon CMC. The preservative manufacturer should be consulted regarding the kind and amount
to be added.

Protect against microbiological attack.


Maintain solution pH as nearly neutral as possible
(7.0 to 9.0).
Avoid prolonged exposure to elevated temperatures.
Exclude oxygen and sunlight.

Preservatives for Aqualon CMC

Busan 11M1, 85(g)


Dowicide A(h)
Dowicil 75, 200(h)
Formaldehyde
Methyl- and propylparabens(i)

Phenol
Proxel GXL(j)
Sodium benzoate(i)
Sodium propionate(i)
Sorbates (Na and K salts)(i)

(g)Buckman

Laboratories International, Inc.


Chemical Co.
(i)Preservatives cleared by the Food and Drug Administration for food, cosmetic, and pharmaceutical products. Pertinent regulations indicate
maximum use levels (tolerances) in some cases.
(j)Zeneca Biocides
(h)Dow

21

COMPATIBILITY

Table V Compatibility of Aqualon CMC With


Inorganic Salt Solutions

Aqualon CMC is compatible in solution with most watersoluble nonionic and anionic polymers and gums. Its
compatibility with salts depends on factors discussed in
this section.

Salt

Effect With Salts


Compatibility of CMC with inorganic salt solutions depends
largely on the ability of the added cation to form a soluble
salt of carboxymethylcellulose. For example, the potassium
salt of carboxymethylcellulose is as soluble in water as the
sodium salt; consequently, if potassium ion is added in moderate amounts to a CMC solution, it has little effect on solution viscosity, clarity, or other properties. On the other hand,
the zirconium salt of carboxymethylcellulose is insoluble in
water; therefore, if zirconium ion is added to a CMC solution,
precipitation results.

Aluminum nitrate
Aluminum sulfate
Ammonium chloride
Ammonium nitrate
Ammonium sulfate
Calcium chloride
Calcium nitrate
Chromic nitrate
Disodium phosphate
Ferric chloride
Ferric sulfate
Ferrous chloride
Magnesium chloride
Magnesium nitrate
Magnesium sulfate
Potassium ferricyanide
Potassium ferrocyanide
Silver nitrate
Sodium carbonate
Sodium chloride
Sodium dichromate
Sodium metaborate
Sodium nitrate
Sodium perborate
Sodium sulfate
Sodium sulfite
Sodium thiosulfate
Stannic chloride
Zinc chloride
Zinc nitrate
Zinc sulfate

As a general rule, monovalent cations from soluble salts of


carboxymethylcellulose, divalent cations are borderline, and
trivalent cations form insoluble salts. Some exceptions to this
rule are given in the following pages.
The effect of salts varies with the particular salt, its concentration, pH of the solution, degree of substitution of the CMC,
and manner in which the salt and CMC come in contact.
Highly substituted CMC (i.e., DS 0.9 and 1.2) has a greater
tolerance for most salts. Increased salt tolerance can also
be obtained by dissolving the CMC before adding the salt.
Adding dry CMC to a salt solution or dissolving the salt and
gum simultaneously will reduce compatibility.
Compatibility of Aqualon CMC with some inorganic salt solutions is shown in Table V. Solutions of 1% CMC Type 7H
were prepared in distilled water. Aqueous solutions of salts
were prepared at concentrations of 10% and either 50% or
saturated. Then, 1 g of gum solution was added to 15 g of
each salt solution, and the effect was observed.
Monovalent CationsAs previously stated, monovalent
cations usually interact with carboxymethylcellulose to form
soluble salts. In aqueous systems containing these cations,
viscosity depends primarily on the order of addition of gum
and salt. If CMC is thoroughly dissolved in water prior to
addition of such a salt, the latter has little effect on solution
viscosity. However, the viscosity imparted by CMC will be
depressed if the gum is added dry to a salt solution. (See
Figure 8, page 12.) The effect of polymer composition, salt
concentration, and shear history is shown in Table IV, page
11. Viscosity developed by S types of Aqualon CMC is less
affected by salts of monovalent cations than that developed
by other types, regardless of the order of addition.

10%
Solution

50% or
Saturated
Solution

P
P
C
C
C
C
C
P
C
P
P
P
C
C
C
C
C
P
C
C
C
C
C
C
C
C
C
P
P
P
P

P
P
C
C
P
P
P
P
C
P
P
P
C
C
C
C
C
P
C
C
C
C
C
C
P
C
C
P
P
P
P

C = Compatible P = Precipitate
Note: 1 g of a 1% solution of CMC Type 7H was added to 15 g
of salt solution.

22

EFFECT WITH WATER-SOLUBLE


NONIONIC GUMS

Polyvalent CationsGenerally, divalent cations will not


form crosslinked gels with CMC. Viscosity reduction occurs,
however, when divalent cations are added to a CMC solution, and it may be accompanied by the formation of a haze.
Calcium, barium, cobalt, magnesium, ferrous, and manganous cations will perform this way. S types of Aqualon
CMC are only slightly affected by moderate concentrations
of divalent cations if the cation is added to the CMC solution.

CMC is compatible with most water-soluble nonionic gums


over a wide range of concentrations. In many instances, the
low-viscosity types are compatible over a broader range than
the high-viscosity types.
When a solution of anionic CMC is blended with a solution
of nonionic polymer such as NATROSOL hydroxyethylcellulose or KLUCEL hydroxypropylcellulose, a synergistic effect
on viscosity is observed. Such a polymer mixture produces
solution viscosities considerably higher than would ordinarily
be expected, as shown in Table Vl. The polymers can be
blended dry, then dissolved; or solutions can be prepared
first, then blended. If other electrolytes are present in the
system, the effect is reduced.

Trivalent salts form insoluble precipitates with CMC. Trace


amounts of heavy metal cations of lesser valence also form
precipitates. Precipitation occurs by crosslinking, ionic bonding, or complex formation. Included in this classification are
cuprous, cupric, silver, ferrous, uranium, chromous, stannous, plumbous, and zirconium cations.

GELATION OF SOLUTIONS

Table Vl Synergistic Effect on Viscosity When


a Nonionic Polymer Is Blended With
Aqualon CMC

The effect of trivalent cations on CMC solutions can be


controlled and used to advantage where gelation is desired.
Gels of varying texture can be produced by careful addition
of certain salts of trivalent metals, such as aluminum.
Gradual release of aluminum ions to a CMC solution will
result in uniform crosslinking of the polymer molecules
between carboxymethyl groups. Gradual release of aluminum ions can be accomplished by using a slowly soluble
aluminum salt such as monobasic aluminum acetate,
AIOH (C2H3O2)2; soluble salts such as aluminum sulfate, Al2
(SO4)3, in combination with appropriate chelating agents; or
insoluble salts such as dihydroxyaluminum sodium carbonate (DASC), Al(OH)2OCOONa, followed by in situ formation
of the soluble acid form of DASC.

Polymer

Properties of CMC gels depend on many factors. In general,


the stiffness of a CMC gel increases with:

An increase in CMC concentration.


An increase in CMC molecular weight.
An increase in the concentration of trivalent metal ion.
A decrease in solution pH.

Cellulose gum,
Type 7H3SF
Natrosol 250 HR

1,500
1,800

1,650

3,200

Cellulose gum,
Type 7H3SF
Klucel H

1,500
1,640

1,570

3,280

(k)From

Techniques for producing CMC gels by crosslinking with


trivalent metals are discussed in more detail in Aqualon
Bulletin VC-521 and Bulletin VC-522.

23

Viscosity Viscosity of a Blend


of a 1%
of Equal Parts
Solution at at 25C, cps (mPas)
25C, cps
(mPas)
Expected(k) Actual

blending chart, VC-440.

PROPERTIES OF CMC FILMS

CMC is seldom used to prepare free or unsupported films.


However, its ability to form strong, oil-resistant films is of
great importance in many applications.
Clear films can be obtained by evaporating the water from
CMC solutions. These fairly flexible films are unaffected by
oils, greases, or organic solvents. Their typical properties
are given in Table Vll. The films were 2 mils thick and contained about 18% moisture.
Where improved flexibility and elongation are desired, plasticizer is added to the casting solution. By including 10 to
30% glycerol in a formulation, elongation can be improved
by 40 to 50%, and folding endurance can be increased to
10,000 MIT double folds. Plasticizers that have proved
effective with CMC are:

Ethanolamines
Ethylene glycol
Glycerol
1,2,6-hexanetriol
Mono-, di-, and triacetin

1,5-pentanediol
Polyethylene glycol
(mol wt 600 or less)
Propylene glycol
Trimethylolpropane

Table VllTypical Properties of Films Prepared From Aqualon CMC


CMC
Property

Type 7L

Type 7M

Type 7H

8,000 (563)

13,000 (915)

15,000 (1,056)

Elongation at break, %

8.3

14.3

14.3

Flexibility, MIT double folds

93

131

513

Negative

Negative

Negative

Refractive index

1.515

1.515

1.515

Specific gravity

1.59

1.59

1.59

Tensile strength, psi (kg/cm2)

Electrostatic charge

24

PACKAGING AND SHIPPING

Aqualon CMC is packed at a moisture content no higher


than 8%. Because of varying storage and shipping conditions, there is a possibility of some moisture pickup from
the as-packed value. The standard package is a 50-lb-net,
3-ply, polyethylene-lined multiwall kraft paper bag. The type,
lot number, and bag number are stenciled on the bottom of
each bag.

Truckload shipments originate from Hopewell, Virginia.


Less-than-truckload quantities are also available from
Hopewell or from warehouse stocks conveniently located
near industrial centers.
Read and understand the Material Safety Data Sheet
(MSDS) before using this product.

MICROBIOLOGICAL INFORMATION AND


REGULATORY STATUS FOR USE IN FOODS,
DRUGS, COSMETICS, AND TOILETRIES
lulose gum) meet standards set by the U.S. Code of Federal
Regulations, Title 21, Section 182.1745Substances that
are generally recognized as safe (GRAS). The FDA defines
this GRAS substance as the sodium salt of carboxymethylcellulose, not less than 99.5% on a dry-weight basis, with
maximum substitution of 0.95 carboxymethyl groups per
anhydroglucose unit, and with a minimum viscosity of 25 cps
for 2% (by weight) aqueous solution at 25C. Aqualon foodgrade (F) cellulose gum meets these requirements. Aqualon
cellulose gum is also certified to be kosher.

MICROBIOLOGICAL INFORMATION
Aqualon production facilities for carboxymethylcellulose
(CMC) are operated in compliance with Current Good
Manufacturing Practice Regulations (CGMPRs) as promulgated in the U.S. Code of Federal Regulations. While
extreme care is exercised at every process step and the
product is of excellent microbiological quality, CMC is not
marketed as a sterile material.
Aqualon CMC is routinely sampled and subjected to microbiological testing by an independent laboratory and data are
tabulated to provide an ongoing indicator of control in production. The data generated are not intended to be used to
provide product specifications, but typical results using our
standard protocol, are shown below.

Both the Food Chemicals Codex and the Food and


Agriculture Organization of the United Nations World Health
Organization (FAO/WHO) have established specifications for
identity and purity of sodium carboxymethylcellulose, which
are also met by Aqualon food-grade cellulose gum.

Aerobic plate count, cfu/g . . . . . . . . . . . . . . . . . . . . . . <100


Mold, cfu/g . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . <100
Yeast, cfu/g . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . <100
Coliforms, MPN/g . . . . . . . . . . . . . . . . . . . . . . . . . . . . <30
E. coli/10 g . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . negative
Staphylococcus aureus/10 g . . . . . . . . . . . . . . . . . negative
Salmonella/25 g . . . . . . . . . . . . . . . . . . . . . . . . . . negative
Pseudomonas/10 g . . . . . . . . . . . . . . . . . . . . . . . . negative

FOOD STATUS
Title 9, Chapter III, of the Code of Federal Regulations lists
ingredients acceptable by the U.S. Department of Agriculture
for use in meat and poultry food products, subject to labeling
requirements, under the following Sections:

Aqualon utilizes officially approved methods to determine


the above microbial parameters, but recommends that users
of Aqualon CMC assure themselves of compliance with any
microbiological criterion by testing each lot.
The typical values above allow for the fact that some
microorganisms may be present in CMC. We therefore
recommend that our customers control the microbiological
quality of their finished product through appropriate process
and formulation expertise.

318.7

Binder, extender, or stabilizer for meat type


baked pies when used in an amount sufficient for the purpose in accordance with
21CFR172.5

381.147

Binder, extender, or stabilizer in various


poultry products when used in an amount
sufficient for the purpose

FDA Definitions and Standards for Food


Cellulose gum may be used in a wide variety of standardized
foods, subject to Title 21 of the Code of Federal Regulations.
Within each of the following parts of Subchapter BFood

Certain types of purified sodium carboxymethylcellulose (cel-

25

FOOD LABELING

and Food Products are several definitions and standards


permitting use of cellulose gum. Further details on individual sections of the standards are available by request.
131
Milk and cream products
133
Cheese and related cheese products
135
Frozen desserts
150
Fruit butters, jellies, and preserves
169
Food dressings and flavorings

Cellulose gum, accepted as a common, or usual, name for


Aqualon purified sodium carboxymethylcellulose, may be
used in food-label ingredient statements. The food manufacturer or processor is permitted to use either sodium carboxymethylcellulose or the shorter and more common
term, cellulose gum. The Food Chemicals Codex, which
describes in detail the standards required of food-grade
additive materials uses cellulose gum as the primary
name, in addition to the more technical term, sodium
carboxymethylcellulose.

In addition, the use of cellulose gum is permitted under the


following Sections:
146.121
Frozen concentrate for artificially sweetened lemonade
152.126(a)
Frozen cherry pie
165.175
Soda water
168.180
Table syrup

Establishment of cellulose gum as an accepted common


name for sodium carboxymethylcellulose resulted from an
Aqualon petition granted by order of the Deputy Commissioner of Food and Drugs, effective June 26, 1963.

PHARMACEUTICAL USE

Cellulose gum, including CMC standard grades, is permitted


for use in boiler water additives and food-packaging applications under the following Sections:
173.310
Boiler water additives
174.5
General provisions applicable to indirect
food additives
175.105
Adhesives
175.300
Resinous and polymeric coatings
176.170
Components of paper and paperboard in
contact with aqueous and fatty foods
176.180
Components of paper and paperboard in
contact with dry food
177.1210
Closures with sealing gaskets for food
containers
182.70
Substances migrating to food from
cotton and cotton fabrics used in dry
food packaging

Sodium carboxymethylcellulose is listed in the current U.S.


Pharmacopoeia. Its applications may be both therapeutic
and excipient. Therapeutic uses include bulk-forming laxatives in which sodium carboxymethylcellulose may be the
primary ingredient. Excipient uses include those of suspending, tablet binding, or viscosity increasing.
Sodium carboxymethylcellulose 12 (degree of substitution
1.15-1.45 min) is listed in the National Formulary for use
as a pharmaceutic aid. The same excipient uses just given
are applicable.
Aqualon CMC meeting the requirements of the U.S.
Pharmacopoeia or the National Formulary can be supplied
by request.

COSMETICS AND TOILETRIES


Cellulose gum is the accepted term used by the Cosmetic,
Toiletry and Fragrance Association, Inc., for sodium carboxymethylcellulose. The product is so listed in the Associations CTFA International Cosmetic Ingredient Dictionary
and Handbook.

Note: A communication from the Food and Drug Administration to Hercules Incorporated, Aqualon Division, defines
as suitable for use in packaging materials sodium carboxymethylcellulose of purity not less than 90% on a dryweight basis.

26

APPENDIX
METHODS OF ANALYSIS

General principles for analysis of CMC and details of several


procedures are contained in Aqualon Bulletin VC-472,
Analytical Procedures for Assay of CMC and Its Determination in Formulations. Copies may be obtained by request.

3. Return the samples to the oven for 45 minutes; cool and


weigh as before. If the second dried weight is not within
0.005 g of the first, repeat the 45-minute oven periods
until two subsequent weighings are in agreement. Then,
using the lowest dried weight obtained, calculate percent
moisture as follows:

Several analytical procedures are contained in ASTM D1439,


Standard Test Methods for Sodium Carboxymethylcellulose.
Copies are available directly from ASTM, 100 Barr Harbor
Drive, West Conshohocken, PA 19428.

Original sample wt dry sample wt


100 = % moisture.
Original sample wt

Solution Preparation

VISCOSITY OF SOLUTION

Immediately after weighing CMC samples for moisture determination, the same undried gum should be weighed for solution preparation. Moisture and solution sample weighings
should be made closely together to ensure that the moisture
content of both is the same at time of weighings.

An accurate determination of the viscosity of a CMC solution


is frequently needed. As explained on page 13, the apparent
viscosity of such a solution depends on a number of factors,
and if reproducible results are to be obtained, a closely standardized method of solution preparation and viscosity determination must be followed.

1. Quickly weigh the required amounts of CMC (see Table


VlII), to the nearest 0.005 g, into clean weighing dishes.

The standardized Aqualon method for determining viscosity


of CMC solutions specifies the Brookfield viscometer(3). The
spindle guard supplied with this instrument should be used
for all determinations.

2. From the determined percent moisture, calculate the


weight of distilled water to be added as follows:
a. For 1% viscosity solution:
Weight of undried CMC (99 percent moisture)
= Weight of water.

Solution volumes specified should not be less or they may


not cover the appropriate Brookfield spindle.

b. For 2% viscosity solution:


Weight of undried CMC
(98 Percent moisture)
= Weight of water.
2

Preparation of the solution is critical, in that the CMC must


be completely dissolved to obtain a significant measurement. To determine the proper amount of gum, a moisture
correction must be included to place the viscosity measurement on a dry CMC basis.

c. For 4% viscosity solution:


Weight of undried CMC
(96 Percent moisture)
= Weight of water.
4

The viscosity-measurement test must be rigidly standardized because the viscosity reading obtained depends on rate
of shear, temperature, amount of agitation prior to measurement, and elapsed time between agitation and measurement. The method used in Aqualon laboratories is given
here in detail.

3. Add the calculated amount of distilled water to the


respective 12-oz. bottles. Use 12-oz. bottles with an
ID of 212 in.
4. Stir the water with a mechanical agitator to create a vortex. An anchor-shaped stirrer turned by compressed air
is satisfactory. Carefully sift the sample into the water,
avoiding the center of the vortex, and be sure that all the
material is transferred. Lower the bottle into a constanttemperature bath (25 6 0.5C).

Moisture Determination
1. Weigh duplicate samples of 5 g, to the nearest 0.001 g,
into previously dried and weighed moisture cans with
covers. The samples for solution preparation (see next
section) should be weighed right after these moisture
samples.

5. Increase stirring speed and stir vigorously until solution


is complete. (Usually 1 to 3 hrs is required.) When solution is complete, measure viscosity as described in the
next section.

2. Place the samples in a gravity convection oven maintained at 105 6 0.5C and heat for three hours. Cool in
a desiccator and weigh.
(3)Brookfield

Synchro-Lectric Model LVF, 4 speeds, 4 spindles, range


0 to 100,000 cps, Brookfield Engineering Laboratories, Middleboro,
Massachusetts.

27

If the solution cannot be kept at constant temperature


during preparation, follow Steps 6 and 7.

Viscosity Measurement
1. Select from Table IX, below, the Brookfield spindlespeed combination for the viscosity type of gum being
tested. Attach the selected spindle to the instrument,
then set the instrument for the corresponding speed.

6. When the solution is complete, remove the stirrer, place


a sheet of cellophane over the mouth of the bottle, and
cap it.

2. If the solution was prepared in a constant-temperature


bath, immediately insert the spindle (with the guard
attached) into the solution. Start the spindle rotating
and allow it to rotate for three minutes before taking
the reading.

7. Place the bottle in a constant-temperature bath for at least


30 minutes, but no more than two hours. (If the sample
stands longer than two hours, return it to the stirrer for
10 minutes.)

Table VllI Approximate Undried CMC Weights


for Solution Preparation
Aqualon
CMC
Viscosity Type

Sample
Weight, g

Add Distilled Water


to Give This Exact
Percent Solids
Content

L2
L&M
H

10.5
5.2
2.3

4.0
2.0
1.0

3. If Steps 6 and 7 of the solution preparation procedure


were followed, remove the bottle from the constanttemperature bath and shake it vigorously for 10 seconds.
Then remove the cap and proceed with Steps 1 and
2 of the viscosity measurement.
4. Stop the instrument, read the dial, and multiply the dial
reading by the factor shown in Table IX. The result is the
solution viscosity in centipoises (mPas).

Table IX Brookfield Spindle-Speed Combinations for


Determination of Solution Viscosity

Aqualon CMC Type


7L2
7L
7M2
7M, 7M8S, 9M8, 12M8
9M31, 12M31
7H, 7H3S, 7HOF
7H4, 9H4

Concentration,
%

Spindle
Number

Spindle
Speed,
rpm

Factor

Maximum Reading,
cps (mPas)

4
2
2
2
2
1
1

2
1
2
2
3
3
4

60
60
60
30
30
30
30

5
1
5
10
40
40
200

500
100
500
1,000
4,000
4,000
20,000

28

HERCULES INCORPORATED
Aqualon Division
Hercules Plaza
1313 North Market Street
Wilmington, DE 19894-0001
(800) 345-0447
www.aqualon.com

The products and related information provided by Hercules are for manufacturing use only. Hercules makes no express, implied, or other representation, warranty, or guarantee concerning (i) the handling, use, or application of such products, whether alone, in combination with other products, or
otherwise, (ii) the completeness, definitiveness, or adequacy of such information for users or other purposes, (iii) the quality of such products, except
that such products are of Hercules standard quality. Users are advised to make their own tests to determine the safety and suitability of each product
or product combination for their own purposes. Read and understand the Material Safety Data Sheet (MSDS) before using this product. Hercules does
not recommend any use of its products that would violate any patent or other rights.

250-10H REV. 4-02

Supersedes all previous editions.

PRINTED IN U.S.A.

Brenntag Specialties, Inc. Local Offices


Northeast:
1000 Coolidge Street
South Plainfield, NJ 07080
800-732-0562
800-833-8139 (Fax-General)

Southeast:
6525 The Corners Parkway
Suite 208
Norcross, GA 30092
800-833-8142
800-833-8143 (Fax)

Southwest:
15710 JFK Boulevard
Suite 260
Houston, TX 77032
800-627-2436
877-796-7257 (Fax)

Mid-Atlantic:
5700 Tacony Street
Philadelphia, PA 19135
800-423-7423
800-864-9824 (Fax)

Midwest:
24119 W. Riverwalk Court
Unit 145
Plainfield, IL 60544
800-833-8140
800-833-8141 (Fax)

West:
One Camino Sobrante
Suite 215
Orinda, CA 94563
800-227-1345
925-253-9601 (Fax)

www.brenntagspecialties.com
E-Mail:
specialties@brenntag.com

Authorized Distributor:

Вам также может понравиться