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C C

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C C
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AQUALON

C C
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C C
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C C Sodium
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C C Carboxymethylcellulose
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C C
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C C
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C C
M Physical
C C and
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C C Chemical
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C C Properties
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C C
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C C
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C C
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C C
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AQUALON CMC
An Anionic Water-Soluble Polymer

CONTENTS PAGE
AQUALON CMC AN ANIONIC Effect of Temperature . . . . . . . . . . . . . . . . . 20
WATER-SOLUBLE POLYMER . . . . . . . . . . . . . . 2 Effect of pH . . . . . . . . . . . . . . . . . . . . . . . . . 20
APPLICATIONS . . . . . . . . . . . . . . . . . . . . . . . . . . 3 Effect of Mixed Solvents . . . . . . . . . . . . . . . 20
CHEMISTRY . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
GRADES AND TYPES . . . . . . . . . . . . . . . . . . . . 6 Microbiological Attack . . . . . . . . . . . . . . . . . 21
Grades . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 Chemical Degradation . . . . . . . . . . . . . . . . . 21
Degree of Substitution . . . . . . . . . . . . . . . . . . . 6 Compatibility . . . . . . . . . . . . . . . . . . . . . . . . . . 22
Viscosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 Effect With Salts . . . . . . . . . . . . . . . . . . . . . 22
Particle Size . . . . . . . . . . . . . . . . . . . . . . . . . . 7 Monovalent Cations . . . . . . . . . . . . . . . . . 22
Product Coding . . . . . . . . . . . . . . . . . . . . . . . . 7 Polyvalent Cations . . . . . . . . . . . . . . . . . . 23
PROPERTIES . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 Gelation of Solutions . . . . . . . . . . . . . . . . . . . . 23
Moisture Absorption . . . . . . . . . . . . . . . . . . . . . 8 Effect With Water-Soluble Nonionic Gums . . . . 23
Physiological Properties . . . . . . . . . . . . . . . . . . 8 PROPERTIES OF CMC FILMS . . . . . . . . . . . . . . 24
DISPERSION AND DISSOLUTION OF CMC . . . . 9 PACKAGING AND SHIPPING . . . . . . . . . . . . . . . 25
Solvent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 MICROBIOLOGICAL INFORMATION AND
Type of CMC . . . . . . . . . . . . . . . . . . . . . . . . . . 9 REGULATORY STATUS FOR USE IN FOODS,
Shear Rate . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 DRUGS, COSMETICS, AND TOILETRIES . . . . . 25
Dispersion Methods . . . . . . . . . . . . . . . . . . . . . 9 Microbiological Information . . . . . . . . . . . . . . . 25
Theory of Polymer Dissolution . . . . . . . . . . . . . 11 Food Status . . . . . . . . . . . . . . . . . . . . . . . . . . 25
PROPERTIES OF CMC SOLUTIONS . . . . . . . . . 13 Food Labeling . . . . . . . . . . . . . . . . . . . . . . . . . 26
Viscosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 Pharmaceutical Use . . . . . . . . . . . . . . . . . . . . 26
Effect of Concentration . . . . . . . . . . . . . . . . 13 Cosmetics and Toiletries . . . . . . . . . . . . . . . . . 26
Effect of Blending . . . . . . . . . . . . . . . . . . . . 13 APPENDIXMETHODS OF ANALYSIS . . . . . . . 27
Blending Chart . . . . . . . . . . . . . . . . . . . . . . 13 Viscosity of Solution . . . . . . . . . . . . . . . . . . . . 27
Effect of Shear . . . . . . . . . . . . . . . . . . . . . . 16 Moisture Determination . . . . . . . . . . . . . . . . 27
Pseudoplasticity . . . . . . . . . . . . . . . . . . . 16 Solution Preparation . . . . . . . . . . . . . . . . . . 27
Thixotropy . . . . . . . . . . . . . . . . . . . . . . . . 17 Viscosity Measurement . . . . . . . . . . . . . . . . 28

Hercules Incorporated, 1999. 1


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 carboxymethyl-
cellulose are also available and are described in Booklet
250-3, available from Aqualon by request.

2
APPLICATIONS

Since its commercial introduction in the United States by A representative listing of the many applications for sodium
Hercules Incorporated in 1946, sodium carboxymethyl- carboxymethylcellulose is given below and on the following
cellulose has found use in an ever-increasing number of page. Many of these applications do not require the use of
applications. The many important functions provided by the highly purified grade, and a technical grade of CMC is
this polymer make it a preferred thickener, suspending aid, available for certain applications. Aqualons chemists and
stabilizer, binder, and film-former in a wide variety of uses. engineers continue to tailor-make various grades and types
to meet the needs of specific customers and industries
The wide range of viscosity and substitution types available requiring water-soluble polymers.
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
Gelled products Thickener; gelling agent; film-former
Denture adhesives Wet tack; long-lasting adhesion
Foods 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; Lubricant; binder; film-former
extrusion products
Pharmaceuticals 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)Forthese 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.

3
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
Aerial-drop fluids Insecticides Thickener; binder; suspending aid
Drift-control agent Thickener
Ceramics Glazes Binder for green strength; thickener; suspending aid
Porcelain slips
Vitreous enamels
Refractory mortars
Welding rod coatings Binder; thickener; lubricant
Coatings 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 Hydrophilic protective film
solutions
Water-based inks Binder; rheology control; suspending aid
Paper and paper Internal addition High-strength binder; improves dry strength of paper
products
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
Textiles Laundry and fabric sizes Film-former
Latex adhesives; backing Rheology control; thickener; water binding and holdout
compounds
Printing pastes and dyes
Warp sizing High film strength; good adhesion to fiber; low
BOD value
Tobacco Cigar and cigarette adhesive Good wet tack; high film strength
Reconstituted sheet High-strength binder and suspending aid

4
CHEMISTRY

CMC is a cellulose ether, produced by reacting alkali Figure 1


cellulose with sodium monochloroacetate under rigidly Structure of Cellulose
controlled conditions.
Figure 1 shows the structure of the cellulose molecule; it is H OH CH2OH
O
H OH CH2OH
O
visualized as a polymer chain composed of repeating cello- HO OH H H H H O OH H H H H OH

biose units (in brackets). These, in turn, are composed of H


H O OH H
H H
H O OH H H
O O
two anhydroglucose units (-glucopyranose residues). In CH2OH H OH CH2OH
n-2
H OH
this structure, n is the number of anhydroglucose units 2

(which are joined through 1,4 glucosidic linkages), or the


degree of polymerization, of cellulose.
Each anhydroglucose unit contains three hydroxyl groups, Figure 2
shown in white. By substituting carboxymethyl groups for Idealized Unit Structure of CMC, With a DS of 1.0
some of the hydrogens of these hydroxyls, as shown in
Figure 2, sodium carboxymethylcellulose is obtained. The
average number of hydroxyl groups substituted per anhy-
droglucose unit is known as the degree of substitution, or CH2OCH2COONa H OH
DS. If all three hydroxyls are replaced, the maximum theo- O
retical DS of 3.0 (impossible in practice) results. H H
H O OH H
CASRN: 9004-32-4 OH H H H H O
CAS Name: Cellulose, carboxymethyl ether, O
sodium salt H OH CH2OCH2COONa
Optimum water solubility and other desirable physical prop-
erties of CMC are obtained at a much lower degree of sub-
stitution 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 Table I Typical Molecular Weights for Representative
compatibility with other soluble components. Viscosity Types of Aqualon CMC
Cellulose ethers, such as CMC, are long-chain polymers. (DS = 0.7 in All Cases)
Their solution characteristics depend on the average chain
length or degree of polymerization (DP) as well as the degree Viscosity Degree of Molecular
of substitution. Average chain length and degree of substi- Type Polymerization Weight
tution determine molecular weight of the polymer. As
molecular weight increases, the viscosity of CMC solutions High 3,200 700,000
increases rapidly. Approximate values (weight averages) for Medium 1,100 250,000
the degree of polymerization and molecular weight of sev-
eral viscosity types of Aqualon CMC are given in Table I. Low 400 90,000

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 usu-
ally 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.

5
GRADES AND TYPES

To serve its diverse markets, Aqualon produces CMC in DEGREE OF SUBSTITUTION


several grades and in a wide variety of types, based on
the degree of substitution, viscosity, particle size, and Aqualon CMC is produced with the following degrees
other parameters. of substitution:

Substitution Sodium
GRADES Type Range(a) Content, %
Aqualon CMC is available in the three grades outlined below.
7 0.65-0.90(b) 7.0-8.9
Grade Designation Intended Use 9 0.80-0.95 8.1-9.2
Food F Food, cosmetic, 12 1.15-1.45 10.5-12.0
P* pharmaceutical (a)Ranges shown in this table are not necessarily current
Pharmaceutical PH** Cosmetic, specifications.
(b)ln 7S types, the upper limit of substitution is 0.95.
pharmaceutical
Standard None Industrial Higher degrees of substitution give improved compatibility
with other soluble components such as salts and nonsol-
*P (1.2 D.S. types and CMC 7L2P)
vents. Generally, the number given in the product desig-
**PH (0.7 and 0.9 D.S. types)
nation is approximately 10 times the DS.

Table II Some Types of Aqualon CMC

Designations for Indicated Substitution Types


Viscosity Range at 25C,(c) cps (mPas)
7 9 12

Highat 1% Concentration
2,500-6,000 7H4 9H4
1,000-2,800 7H3S, 7HOF
1,500-3,000 7H

Mediumat 2% Concentration
800-3,100 12M31
1,500-3,100 9M31
400-800 7M 9M8 12M8
200-800 7M8S
100-200 7M2

Low(d)at 2% Concentration
25-50 7L

at 4% Concentration
50-200 7L2

(c)Ranges shown in this table are not necessarily current specifications.


(d)Some even lower viscosity types are available. Contact your technical representative for additional information.

6
VISCOSITY PARTICLE SIZE
CMC is manufactured in a wide range of viscosities. High- Aqualon CMC is available in several different particle sizes
viscosity types are prepared from high viscosity cotton lin- to facilitate handling and use in processing operations such
ters. Medium-viscosity types are prepared from wood pulp as solution preparation and dry-blending. Screen analysis is
of specified viscosity. Low-viscosity types are prepared by given here for three of the types. Other types are available.
aging the shredded alkali cellulose and by using chemical
oxidants. The foregoing methods of regulating the viscosity Designation Description Particle Size(e)
are based on controlling the DP. It is also possible to attain
high viscosity by decreasing the solubility so that the product None Regular On U.S. 30, %, max 1
is highly swollen but not completely dispersed. This can be On U.S. 40, %, max 5
accomplished by decreasing the uniformity of the reaction
and lowering the DS. For example, products at DS 1.2 do C Coarse On U.S. 20, %, max 1
not have solution viscosities as high as products of DS 0.7 Through U.S. 40,
prepared in substantially the same way. However, the solu-
tions of the higher-substituted products are much smoother. %, max 55
Through U.S. 80,
The viscosity ranges of some types are listed in Table II. %, max 5
Others are available to meet specific needs. Regular viscos-
ity types with a DS of 0.7 meet most needs and are desig-
nated by the number 7, followed by the letter H (high), M X Fine On U.S. 60, %, max 0.5
(medium), or L (low). All other types are designated by an Through U.S. 200,
additional number following the letter which, when multiplied %, min 80
by a factor, gives the approximate upper viscosity limit. The
(e)AII screens are U.S. Bureau of Standards sieve series.
factor and applicable concentration appear below.

Viscosity Type Factor Concentration, %


PRODUCT CODING
High 1,000 1 An example of the coding used for ordering Aqualon CMC
Medium 100 2 follows:
Low 10 2 For cellulose gum Type 7H3SCF:
Solutions of all CMC types display pseudoplastic behavior. 7 means that the typical degree of substitution is
(See page 16.) Some types, particularly those of higher approximately 0.7.
molecular weight and lower substitution, also show thixo- H means high viscosity.
tropic behavior in solution. (See page 17.) These thixotropic 3 means that the viscosity of a 1% solution is in the
solutions will possess varying amounts of gel strength and range of 3,000 cps.
are used where suspension of solids is required. The S, 9, S means smooth solution characteristics.
and 12 types produce solutions with little or no thixotropy,
C means coarse particle size.
and are utilized where smooth solutions without structure
are required. F means food grade.

Specific properties are available in certain other types. For Aqualon can tailor the chemical and physical properties of
example, the O type, 7HOF, provides the best solubility CMC to meet special requirements. Users are encouraged
and storage stability in acid media. to discuss their needs with their technical representative,
or to call the 800 number shown on the back cover for
product information.

7
PROPERTIES

Typical properties of Aqualon CMC polymer and in solution Figure 3


and film form are shown in Table III. These are not necessar- Effect of Relative Humidity on Equilibrium Moisture
ily specifications.
Content of Aqualon CMC at 25C
Table IIITypical Properties of Aqualon CMC
Polymer 40

Equilibrium Moisture Content, %


Sodium carboxymethylcellulose 12M31P
dry basis, %, min . . . . . . . . . . . . . . . . . . . . 99.5
Moisture content (as packed), %, max . . . . . . . 8.0
Browning temperature, C . . . . . . . . . . . . . . . . 227 30 7HF
Charring temperature, C . . . . . . . . . . . . . . . . . 252
Bulk density, g/ml . . . . . . . . . . . . . . . . . . . . . .0.75
Biological oxygen demand (BOD)(f), ppm
7H type . . . . . . . . . . . . . . . . . . . . . . . . . 11,000 20
7L type . . . . . . . . . . . . . . . . . . . . . . . . . . 17,300

Solutions 10
pH, 2% solution . . . . . . . . . . . . . . . . . . . . . . . . 7.5
Surface tension, 1% solution,
dynes/cm at 25C. . . . . . . . . . . . . . . . . . . . . . 71
Specific gravity, 2% solution . . . . . . . . . . . . 1.0068 0
Refractive index, 2% solution . . . . . . . . . . . . 1.336 0 20 40 60 80
Relative Humidity, %
Typical Films (Air-Dried)
Density, g/ml . . . . . . . . . . . . . . . . . . . . . . . . . 1.59 PHYSIOLOGICAL PROPERTIES
Refractive index . . . . . . . . . . . . . . . . . . . . . . 1.515 Dermatological and toxicological studies by independent
Thermal conductivity, W/mK. . . . . . . . . . . . . . 0.238 laboratories demonstrate conclusively that sodium carboxy-
(f)After
methylcellulose shows no evidence of being toxic to white
5 days incubation. Under these conditions, cornstarch has
a BOD of over 800,000 ppm.
rats, dogs, guinea pigs, or human beings. Feeding, metabo-
lism, and topical use studies also show that CMC is physio-
logically inert. Patch tests on human skin demonstrated that
MOISTURE ABSORPTION sodium carboxymethylcellulose was neither a primary irritant
CMC absorbs moisture from the air. The amount absorbed nor a sensitizing agent. Additional information is available
and the rate of absorption depend on the initial moisture from Hercules Incorporated.
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 ship-
ping conditions, there is a possibility of some moisture
pickup from the as-packed value.

8
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,
Aqualon CMC is soluble in either hot or cold water. The

the dissolving process should be considered a two-step
gum is insoluble in organic solvents, but dissolves in suit- operation:
able mixtures of water and water-miscible solvents, such as
ethanol or acetone. Solutions of low concentration can be 1. Dispersing the dry powder in water. Individual par-
made with up to 50% ethanol or 40% acetone. Aqueous ticles should be wet and the dispersion should not
solutions of CMC tolerate addition of even higher propor- contain lumps.
tions of acetone or ethanol, the low-viscosity types being 2. Dissolving the wetted particles.
considerably more tolerant than the high-viscosity types,
as shown below. When the proper technique is used, good dispersion is
obtained, and CMC goes into solution rapidly. To prepare
Tolerance of Aqualon CMC Solutions for Ethanol lumpfree, clear solutions, a variety of methods can be used:
Volume Ratio of Ethanol Method 1
to CMC Solution, 1% Add CMC to the vortex of vigorously agitated water. The rate
of addition must be slow enough to permit the particles to
CMC First Evident First Distinct separate and their surfaces to become individually wetted,
Type Haze Precipitate but it should be fast enough to minimize viscosity buildup of
the aqueous phase while the gum is being added.
7L 2.4 to 1 3.6 to 1
7M 2.1 to 1 2.7 to 1 Method 2
7H 1.6 to 1 1.6 to 1 Prior to addition to water, wet the powder with a water-
miscible liquid such as alcohol, glycol, or glycerol that will
Note: In these tests, ethanol (95%) was added slowly at room not cause CMC to swell. Two to three parts of liquid per part
temperature to the vigorously stirred 1% CMC solution. of CMC should be sufficient.
Method 3
TYPE OF CMC Dry-blend the CMC with any dry, nonpolymeric material
The higher the degree of substitution, the more rapidly used in the formulation. Preferably, the CMC should be
CMC dissolves. The lower the molecular weight, the faster less than 20% of the total blend.
the rate of solution.
Method 4
Particle size has a pronounced effect on the ease of dis- Use a water eductor (Figure 4) to wet out the polymer par-
persing and dissolving CMC. C, or coarse, types were ticles rapidly. The polymer is fed into a water-jet eductor,
developed to improve dispersibility of the granules when where a high-velocity waterflow instantly wets out each
agitation is inadequate to produce a vortex on the liquid particle, thus preventing lumping. This procedure speeds
surface. Solution time, on the other hand, is extended solution preparation and is particularly useful where large
considerably with a coarse material. volumes of solutions are required. For users wishing the
convenience of an automatic system, a polymer solution
For applications requiring a rapid solution time, CMC of preparation system (PSP), which is used in conjunction
fine particle size (X grind) is best. However, special dis- with a water eductor, is shown in Figure 5.
solving techniques, such as prewetting the powder with a
nonswelling liquid, mixing it with other dry materials, or Special, fast-dissolving fluidized polymer suspensions of
using an eductor-type mixing device, are necessary to CMC are available to give very rapid dissolution where it is
obtain dispersion. required or where agitation is substandard.
Users are encouraged to contact their technical representa-
SHEAR RATE tive for information on PSP units or fluidized suspensions
of CMC.
Preparing solutions by extremely low shear agitation, such
as shaking by hand, is generally not recommended. Prop-
erties 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.

9
Figure 4
Typical Installation of Eductor-Type Mixing Device

Lightnin Mixer Polymer Feed

Mix Tank
Funnel Mixing Device
Air Bleed-
Makeup Water
Holes
Workman
Water Platform
Eductor
Inlet

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

Figure 5
Automated Polymer Solution Preparation (PSP) System

Dust
Collector
Polymer Hopper
Polymer Water
Eductor

Screw
Drive Helical Screw Feeder
Motor

Air
Preparation Tank
Eductor
PSP Unit

10
THEORY OF POLYMER DISSOLUTION time-dependent phenomenon, if CMC/salt solutions are
allowed to stand, it is very possible that the final stage of
When a polymer is dispersed in a solvent, the degree of disaggregation will be Stage 2 and the equilibrated viscosity
disaggregationi.e., separation of polymer molecules will be higher than that of CMC in distilled water. Hence, one
is affected by the: cannot assume that addition of salt will lower equilibrated
solution viscosity, only that it will inhibit polymer disaggre-
Chemical composition of the polymer.
gation. With Types 9 and 12, the slight viscosity increase in
Solvating power of the solvent.
saturated salt is caused by the viscosity bonus effect dis-
Shear history of the resulting solution.
cussed on page 20.
Figure 6 shows how these states of disaggregation may
affect viscosity of the liquid. If CMC is added to a liquid Figure 6
and its degree of disaggregation reaches equilibrium, the Idealized Curve Showing Effect of Degree
polymer may: of Disaggregation on Viscosity of Polymer Solution
Remain as a suspended powder, neither swelling
nor dissolving (1). 2
Swell to a point of maximum viscosity without com-
pletely dissolving (2).
Reach maximum disaggregation (3).
Exist in an intermediate state (1a, 1b, 2a).
Depending on choice of polymer, solvent, and mechanical 2a
1b
means of preparing the solution, the user of CMC can alter

Viscosity
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.
3
Increasing DS makes CMC more hydrophilic, or water-
loving; hence, types having high DS are more readily dis-
aggregated in water. Plotting solution viscosity at constant 1a
shear against increasing DS (Types 7 through 12) produces
a curve similar in shape to that shown in Figure 6.
Increasing electrolyte concentration reduces disaggre- 1
gation, as evidenced by the lower viscosity in saltwater of
Type 7. The viscosities listed in Table IV were measured
Degree of Disaggregation
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 solu-
tions prepared in distilled water. Since disaggregation is a

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 Distilled Saturated Distilled Saturated
Gum Type Water 4% NaCl NaCl Water 4% NaCl 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 Figure 7
can enhance viscosity development or disaggregation. Effect of Solvent Strength on Disaggregation
The effect of solvent strength (polarity in binary solvent mix- of Aqualon CMC
tures) on the disaggregation of CMC is shown in Figure 7. (1.75% CMC in Glycerin-Water)
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 100,000
breaks internal associations of gel centers and promotes
disaggregation.
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 9M8F 7MF
CMC is thoroughly dissolved in water and the solute is then

Viscosity, cps
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
10,000 12M8P
areas, and lower viscosities are obtained. This effect of
solutes is less apparent with more uniformly substituted
material containing fewer crystalline areas.

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
Solute Added
Before CMC
Apparent Viscosity, cps

100
80

60

40
Solutes Used:
30 NaCl
NaCl + NaOH (pH 10.1)
20 Na2So4
Na4P2O7 10H2O (pH 9.5-9.8)
KCl or LiCl

10
0.02 0.04 0.08 0.1 0.2 0.4 0.8 1.0
Molal Concentration of Cation, moles/1,000 g solvent

12
PROPERTIES OF CMC SOLUTIONS

Viscosity is the single most important property of CMC solu- Equation: Because the viscosity-concentration relationship is
tions. Aqualon has acquired considerable information on an exponential function, the viscosity resulting from blending
factors affecting viscosity, and these data are given here. is not an arithmetic mean. The viscosity of a blend can, how-
Stability of CMC solutions to microbiological attack and ever, be approximated by use of the equation below, which
chemical deterioration is also discussed in this section. is derived from the Arrhenius equation that relates viscosity
with polymer concentration.
VISCOSITY n log V1 + (100-n) log V2
Solutions of CMC can be prepared in a wide range of vis- Log Vs = 100
cosities. Such solutions are non-Newtonian because they where Vs = Viscosity sought
change in viscosity with change in shear rate. Consequently, n = Percent (by weight) of the first component of the
it is essential to standardize viscosity determination methods. blend having a viscosity of V1
This standardization must include the type and extent of V2 = Viscosity of the second component of the blend
agitation used to dissolve the CMC, as well as precise con-
trol of temperature, conditions of shear, and method of vis- Note: All viscosities must be expressed at the same polymer
cosity measurement. The procedure used in the Aqualon concentration and in the same units.
control laboratory is described in detail in the Appendix,
page 27. Use of the chart itself is simple. For example, suppose one
wishes to obtain a solution with a viscosity of 900 cps at 3%
Effect of Concentration concentration. The water-soluble polymer is available as
The viscosity of aqueous CMC solutions increases rapidly Material A with a viscosity of 1,800 cps at 3% concentration,
with concentration. This is shown in Figure 10. The bands and Material B with a viscosity of 700 cps at 3% concentra-
show the range of viscosity obtainable with standard tion. A line is drawn connecting these two viscosities on the
viscosity types. chart. The point at which this line intersects the desired vis-
cosity line is then determined, and the percentage it repre-
Effect of Blending sents is read from the bottom of the chart. Thus, in this
Two viscosity types of CMC can be blended to obtain an in- example, 28% of Material A and 72% of Material B are
termediate viscosity. Because viscosity is an exponential needed to yield the desired viscosity of 900 cps at a total
function, the viscosity resulting from blending is not an polymer concentration of 3%.
arithmetic mean.
Limitations of Blending: The relationship between viscosity
A blending chart (VC-440), available from Aqualon, can be and concentration can vary significantly, depending on the
used to determine the result of blending various amounts of chemical composition as well as the molecular weight (vis-
two viscosity types of CMC. It can also be used to determine cosity type) of the polymers involved. The greatest accuracy
the amount of CMC required to achieve a desired viscosity is obtained from use of the equation or the blending chart of
when blending two types of known viscosity. Figure 9 if the following conditions are met. Departure from
Blending Chart these conditions can result in deviation from the predicted
The blending technique outlined in this bulletin can be value of viscosity.
used eqully well for Aqualon cellulose gum (sodium
carboxymethylcellulose), Natrosol hydroxyethylcellulose,
The chemical composition of the polymers must be similar
i.e., the type and level of chemical substitution must be
Culminal methylcellulose and methyl hydroxypropylcellulose the same.
and Klucel hydroxypropylcellulose. This technique is useful
when it is desirable to blend two viscosity types of the same The solution viscosities of the polymers should be as
water-soluble polymer in order to obtain a solution having a close together as possible.
predetermined viscosity and solids concentration.
Blends can be calculated directly from the equation that fol-
lows; 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
Figure 9
Chart for Blending Aqualon Water-Soluble Polymers

5,000

4,000

3,000
Viscosity of
Available
2,000 Material A

Viscosity of
Available
Material B
1,000
900
800
700 Desired
Viscosity
Solution Viscosity at 25C, cps

600
in Example
500

400

300

200

100
90
80
70
60
50
Blend Needed
40 for Desired
Viscosity
30

20
Material A, % 100 90 80 70 60 50 40 30 20 10 0
Material B, % 0 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
20,000 7H
7H3S, 7HOF

10,000
9M31, 12M31
7L
7M, 9M8, 12M8

7M2
7L2
Solution Viscosity at 25C, cps

1,000

100

10

5
0 1 2 3 4 5 6 7 8 9 10
CMC, weight %

15
Effect of Shear Figure 11
CMC is often used to thicken, suspend, stabilize, gel, or Shear Stress vs. Shear Rate for Newtonian
otherwise modify the flow characteristics of aqueous solu- and Pseudoplastic Liquids
tions 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. tic

Shear Stress
oplas
PseudoplasticitySmall amounts of CMC dissolved in
Pseud
water greatly modify its properties. The most obvious imme-
diate change is an increase in viscosity. Interestingly, a single n
nia
CMC solution will appear to have a different viscosity when wto
different physical forces are imposed on it. 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, grav- Shear Rate
ity and surface tension control flow. These forces are condi-
tions of low stress. Intermediate stress is typified by pouring
a liquid out of a bottle.
Figure 12
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 Viscosity vs. Shear Rate
liquid when applied as a lotion, and yet when high shear When viscosity (shear stress divided by shear rate) is
stress is removed it will instantly revert to its original highly plotted against shear rate, a Newtonian system gives a
viscous state. This type of flow behavior is referred to as horizontal line. If viscosity decreases as shear rate is
pseudoplasticity or time-independent shear-thinninga form increased, the flow is pseudoplastic.
of non-Newtonian flow. It differs from the time-dependent
viscosity change called thixotropy.
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,
Apparent Viscosity

will give a curved line. Plotting apparent viscosity against


shear rate, as in Figure 12, produces a horizontal straight Newtonian
line for a Newtonian fluid and a curved line for a pseudo-
plastic liquid.
Pseu
dopla
Solutions of some medium- and high-viscosity types of stic
CMC exhibit pseudoplastic behavior because their long-
chain 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 Shear Rate
stress is imposed on the same solution, the apparent
viscosity is higher because random orientation of mole-
cules presents increased resistance to flow.

16
Generally, solutions of the medium- and high-viscosity Rheograms are helpful to illustrate the effect of thixotropy.
types with a high DS (i.e., 0.9 and 1.2) and S types are A thixotropic solution will form a hysteresis loop when shear
pseudoplastic rather than thixotropic. In contrast to this, stress is plotted against shear rate, as shown in Figure 14A.
regular high- and medium-viscosity gums of DS 0.7 (slightly The increased shear stress required to break the thixotropic
less uniformly substituted) show thixotropic behavior in structure has reduced the resistance to flow, or viscosity. If
solution. (See Thixotropy, below.) a solution has gel strength, a spur forms in the hysteresis
loop; this is shown in Figure 14B. It is an indication of the
Solutions of low-molecular-weight CMC i.e., low-viscosity stress necessary to break the gel structure and cause the
typesare less pseudoplastic than those of high-molecular- solution to revert to its normal apparent viscosity.
weight gum. However, at very low shear rate, all CMC
solutions approach Newtonian flow. Figure 13 shows Figure 14A
these relationships. Thixotropic Flow
Figure 13
Effect of Shear Rate on Apparent Viscosity of
Aqualon CMC Solutions

Shear Stress
Apparent Viscosity, cps

10,000

1,000 7.3% 7L

100 Shear Rate


1% 7H3S
10
0.01 0.1 1 10 100 1,000 10,000
Shear Rate (Reciprocal sec)
Figure 14B
Extremely Thixotropic Flow With Gel Strength
Viscometer
Brookfield

Tumbling
Film Sag

Blendor
Pouring

Waring
Gravity
Under

Home
Mixer
or

ThixotropyIf long-chain polymers have a considerable


Shear Stress

amount of interaction, they will tend to develop a three-


dimensional structure and exhibit a phenomenon known
as thixotropy.
Thixotropy is a time-dependent viscosity change. It is char-
acterized by an increase in apparent viscosity when a solu-
tion 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
Shear Rate
can be broken and the apparent viscosity reduced.

17
Figure 15 illustrates thixotropy in another manner. At a Figure 15
constant shear rate (D = K), viscosity decreases with time. Thixotropic Flow Is a Time-Dependent
When shear is removed (D = zero), viscosity increases sig-
Change in Viscosity
nificantly with time.
Thixotropic solutions are desirable, or even essential, for
certain uses of CMC, such as suspension of solids. High-
and 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 D = Zero
developed for uses requiring clear, smooth solutions of

Apparent Viscosity
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 D=K
pseudoplasticity of long-chain molecules.

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
1,000
2% 7M
Viscosity, cps

1% 9M31
1% 12M31

100

2% 7L

10
0 10 20 30 40 50 60 70 80
Temperature, C

19
Effect of Temperature Figure 19
Viscosity of CMC solutions depends on temperature, as Stability of Aqualon Cellulose Gum in
shown in Figure 17. Under normal conditions, the effect of Organic Acids1% Solution of Type 7HOF
temperature is reversible, so temperature variation has no
permanent effect on viscosity. However, long periods of heat-
ing at high temperatures will degrade CMC and permanently
10,000
reduce viscosity. For example, a 7L type held for 48 hours at
180F lost 64% of its original viscosity.

Viscosity at 25C, cps


Effect of pH 5.0% Acetic Acid
CMC solutions maintain their normal viscosity over a wide
pH range. In general, solutions exhibit their maximum vis- 1.0% Lactic Acid
cosity and best stability at pH 7 to 9. Above pH 10, a slight 1,000 1.0% Citric Acid
decrease in viscosity is observed. Below pH 4.0, the less 0.3% Fumaric Acid
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.

Figure 18 100
1 2 3 4 5
Effect of pH on Viscosity of
Storage Time at 25C, months
Aqualon CMC Solutions

5,000 Effect of Mixed Solvents


The behavior of highly substituted CMC in mixed-solvent
Brookfield Viscosity, cps

2.0% 9M31 systems, such as glycerin-water, is similar to its effect in


water alone. In mixed systems, however, viscosity of the sol-
vent affects viscosity of the solution. For example, if a 60:40
1,000 1.0% 7H 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
500 comparable solution in water alone. This behavior is shown
in Figure 19 and is commonly referred to as the viscosity
2.0% 7H bonus effect.

Figure 20
100
Effect of Mixed Solvents on Viscosity of
2 4 6 8 10 12
Aqualon CMC Solutions1% Type 12M31
pH
10,000
Tests with Aqualon CMC Type 7M have shown that very little
polymer degradation takes place if solutions are allowed to 1% CMC in Glycerin-Water
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. 1,000

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


Apparent Viscosity, cps

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. 100
Aqualon cellulose gum Type 7HOF is a particularly efficient
thickener for acidic systems. Clear, viscous solutions are 1% CMC in Water
obtained when it is dissolved in water and then acidified. Its
stability in several organic acids, typical of those used in 10
low-pH foods, is shown in Figure 19.
Glycerin in Water

Water

10 -1
10 100 1,000 10,000
Shear Rate, sec-1

20
STABILITY Chemical Degradation
Under certain conditions, solutions of CMC are susceptible
CMC is subject to microbiological attack and chemical to chemical degradation. Permanent loss of viscosity can
degradation. However, corrective measures can be taken occur resulting from scission of the long-chain molecules.
to prevent both from occurring. Such viscosity loss is accelerated by increasing the temper-
Microbiological Attack ature and/or lowering the pH. Aqualon cellulose gum Type
Although CMC is more resistant to microbiological attack 7HOF provides improved resistance to viscosity degradation
than many other water-soluble gums, its solutions are not and precipitation in low-pH systems.
immune. Heat treatment can be used to destroy many An oxidative type of degradation occurs under alkaline con-
microorganisms while having little effect on CMC prop- ditions in the presence of oxygen. The rate of viscosity loss
erties. Heating for 30 min at 80C, or for 1 min at 100C, is also increased by heat and/or ultraviolet light. Inclusion of
is generally sufficient. an antioxidant, exclusion of oxygen, and avoidance of highly
When solutions are stored, a preservative should be added alkaline conditions are obvious preventive measures.
to prevent viscosity degradation. If cellulases (hydrolytic, To obtain the best stability during prolonged storage of CMC
viscosity-destroying enzymes) have been introduced by solutions, users should:
microbial action, even in trace amounts, addition of most
preservatives will not prevent degradation; therefore, it Protect against microbiological attack.
is important to preserve solutions as soon as possible
after preparation. Maintain solution pH as nearly neutral as possible
(7.0 to 9.0).
The preservatives shown below have proved effective for
solutions of Aqualon CMC. The preservative manufac- Avoid prolonged exposure to elevated temperatures.
turer should be consulted regarding the kind and amount Exclude oxygen and sunlight.
to be added.

Preservatives for Aqualon CMC

Busan 11M1, 85(g) Phenol


Dowicide A(h) Proxel GXL(j)
Dowicil 75, 200(h) Sodium benzoate(i)
Formaldehyde Sodium propionate(i)
Methyl- and propylparabens(i) Sorbates (Na and K salts)(i)
(g)Buckman Laboratories International, Inc.
(h)Dow 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

21
COMPATIBILITY Table V Compatibility of Aqualon CMC With
Aqualon CMC is compatible in solution with most water-
Inorganic Salt Solutions
soluble nonionic and anionic polymers and gums. Its
compatibility with salts depends on factors discussed in 50% or
this section. 10% Saturated
Salt Solution Solution
Effect With Salts
Compatibility of CMC with inorganic salt solutions depends Aluminum nitrate P P
largely on the ability of the added cation to form a soluble Aluminum sulfate P P
salt of carboxymethylcellulose. For example, the potassium
salt of carboxymethylcellulose is as soluble in water as the Ammonium chloride C C
sodium salt; consequently, if potassium ion is added in mod- Ammonium nitrate C C
erate amounts to a CMC solution, it has little effect on solu- Ammonium sulfate C P
tion viscosity, clarity, or other properties. On the other hand, Calcium chloride C P
the zirconium salt of carboxymethylcellulose is insoluble in Calcium nitrate C P
water; therefore, if zirconium ion is added to a CMC solution,
precipitation results. Chromic nitrate P P
Disodium phosphate C C
As a general rule, monovalent cations from soluble salts of Ferric chloride P P
carboxymethylcellulose, divalent cations are borderline, and
trivalent cations form insoluble salts. Some exceptions to this Ferric sulfate P P
rule are given in the following pages. Ferrous chloride P P
Magnesium chloride C C
The effect of salts varies with the particular salt, its concen-
tration, pH of the solution, degree of substitution of the CMC, Magnesium nitrate C C
and manner in which the salt and CMC come in contact. Magnesium sulfate C C
Highly substituted CMC (i.e., DS 0.9 and 1.2) has a greater Potassium ferricyanide C C
tolerance for most salts. Increased salt tolerance can also Potassium ferrocyanide C C
be obtained by dissolving the CMC before adding the salt. Silver nitrate P P
Adding dry CMC to a salt solution or dissolving the salt and
gum simultaneously will reduce compatibility. Sodium carbonate C C
Sodium chloride C C
Compatibility of Aqualon CMC with some inorganic salt solu- Sodium dichromate C C
tions is shown in Table V. Solutions of 1% CMC Type 7H
were prepared in distilled water. Aqueous solutions of salts Sodium metaborate C C
were prepared at concentrations of 10% and either 50% or Sodium nitrate C C
saturated. Then, 1 g of gum solution was added to 15 g of Sodium perborate C C
each salt solution, and the effect was observed. Sodium sulfate C P
Monovalent CationsAs previously stated, monovalent Sodium sulfite C C
cations usually interact with carboxymethylcellulose to form Sodium thiosulfate C C
soluble salts. In aqueous systems containing these cations, Stannic chloride P P
viscosity depends primarily on the order of addition of gum Zinc chloride P P
and salt. If CMC is thoroughly dissolved in water prior to
addition of such a salt, the latter has little effect on solution Zinc nitrate P P
viscosity. However, the viscosity imparted by CMC will be Zinc sulfate P P
depressed if the gum is added dry to a salt solution. (See
C = Compatible P = Precipitate
Figure 8, page 12.) The effect of polymer composition, salt
Note: 1 g of a 1% solution of CMC Type 7H was added to 15 g
concentration, and shear history is shown in Table IV, page
of salt solution.
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.

22
Polyvalent CationsGenerally, divalent cations will not EFFECT WITH WATER-SOLUBLE
form crosslinked gels with CMC. Viscosity reduction occurs, NONIONIC GUMS
however, when divalent cations are added to a CMC solu-
tion, and it may be accompanied by the formation of a haze. CMC is compatible with most water-soluble nonionic gums
Calcium, barium, cobalt, magnesium, ferrous, and manga- over a wide range of concentrations. In many instances, the
nous cations will perform this way. S types of Aqualon low-viscosity types are compatible over a broader range than
CMC are only slightly affected by moderate concentrations the high-viscosity types.
of divalent cations if the cation is added to the CMC solution.
When a solution of anionic CMC is blended with a solution
Trivalent salts form insoluble precipitates with CMC. Trace of nonionic polymer such as NATROSOL hydroxyethylcellu-
amounts of heavy metal cations of lesser valence also form lose or KLUCEL hydroxypropylcellulose, a synergistic effect
precipitates. Precipitation occurs by crosslinking, ionic bond- on viscosity is observed. Such a polymer mixture produces
ing, or complex formation. Included in this classification are solution viscosities considerably higher than would ordinarily
cuprous, cupric, silver, ferrous, uranium, chromous, stan- be expected, as shown in Table Vl. The polymers can be
nous, plumbous, and zirconium cations. blended dry, then dissolved; or solutions can be prepared
first, then blended. If other electrolytes are present in the
GELATION OF SOLUTIONS system, the effect is reduced.

The effect of trivalent cations on CMC solutions can be Table Vl Synergistic Effect on Viscosity When
controlled and used to advantage where gelation is desired. a Nonionic Polymer Is Blended With
Gels of varying texture can be produced by careful addition
of certain salts of trivalent metals, such as aluminum.
Aqualon CMC
Gradual release of aluminum ions to a CMC solution will Viscosity Viscosity of a Blend
result in uniform crosslinking of the polymer molecules of a 1% of Equal Parts
between carboxymethyl groups. Gradual release of alumi- Solution at at 25C, cps (mPas)
num ions can be accomplished by using a slowly soluble
aluminum salt such as monobasic aluminum acetate,
25C, cps
AIOH (C2H3O2)2; soluble salts such as aluminum sulfate, Al2 Polymer (mPas) Expected(k) Actual
(SO4)3, in combination with appropriate chelating agents; or Cellulose gum,
insoluble salts such as dihydroxyaluminum sodium carbon-
ate (DASC), Al(OH)2OCOONa, followed by in situ formation Type 7H3SF 1,500
1,650 3,200
of the soluble acid form of DASC. Natrosol 250 HR 1,800
Properties of CMC gels depend on many factors. In general, Cellulose gum,
the stiffness of a CMC gel increases with: Type 7H3SF 1,500
1,570 3,280
An increase in CMC concentration. Klucel H 1,640
An increase in CMC molecular weight.
An increase in the concentration of trivalent metal ion. (k)From blending chart, VC-440.
A decrease in solution pH.
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
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 con-
tained about 18% moisture.
Where improved flexibility and elongation are desired, plas-
ticizer 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 1,5-pentanediol
Ethylene glycol Polyethylene glycol
Glycerol (mol wt 600 or less)
1,2,6-hexanetriol Propylene glycol
Mono-, di-, and triacetin Trimethylolpropane

Table VllTypical Properties of Films Prepared From Aqualon CMC

CMC
Property Type 7L Type 7M Type 7H
Tensile strength, psi (kg/cm2) 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
Electrostatic charge Negative Negative Negative
Refractive index 1.515 1.515 1.515
Specific gravity 1.59 1.59 1.59

24
PACKAGING AND SHIPPING

Aqualon CMC is packed at a moisture content no higher Truckload shipments originate from Hopewell, Virginia.
than 8%. Because of varying storage and shipping condi- Less-than-truckload quantities are also available from
tions, there is a possibility of some moisture pickup from Hopewell or from warehouse stocks conveniently located
the as-packed value. The standard package is a 50-lb-net, near industrial centers.
3-ply, polyethylene-lined multiwall kraft paper bag. The type,
lot number, and bag number are stenciled on the bottom of Read and understand the Material Safety Data Sheet
each bag. (MSDS) before using this product.

MICROBIOLOGICAL INFORMATION AND


REGULATORY STATUS FOR USE IN FOODS,
DRUGS, COSMETICS, AND TOILETRIES
MICROBIOLOGICAL INFORMATION lulose gum) meet standards set by the U.S. Code of Federal
Regulations, Title 21, Section 182.1745Substances that
Aqualon production facilities for carboxymethylcellulose are generally recognized as safe (GRAS). The FDA defines
(CMC) are operated in compliance with Current Good this GRAS substance as the sodium salt of carboxymethyl-
Manufacturing Practice Regulations (CGMPRs) as promul- cellulose, not less than 99.5% on a dry-weight basis, with
gated in the U.S. Code of Federal Regulations. While maximum substitution of 0.95 carboxymethyl groups per
extreme care is exercised at every process step and the anhydroglucose unit, and with a minimum viscosity of 25 cps
product is of excellent microbiological quality, CMC is not for 2% (by weight) aqueous solution at 25C. Aqualon food-
marketed as a sterile material. grade (F) cellulose gum meets these requirements. Aqualon
cellulose gum is also certified to be kosher.
Aqualon CMC is routinely sampled and subjected to microbi-
ological testing by an independent laboratory and data are Both the Food Chemicals Codex and the Food and
tabulated to provide an ongoing indicator of control in pro- Agriculture Organization of the United Nations World Health
duction. The data generated are not intended to be used to Organization (FAO/WHO) have established specifications for
provide product specifications, but typical results using our identity and purity of sodium carboxymethylcellulose, which
standard protocol, are shown below. are also met by Aqualon food-grade cellulose gum.
Aerobic plate count, cfu/g . . . . . . . . . . . . . . . . . . . . . . <100
Mold, cfu/g . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . <100 FOOD STATUS
Yeast, cfu/g . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . <100
Title 9, Chapter III, of the Code of Federal Regulations lists
Coliforms, MPN/g . . . . . . . . . . . . . . . . . . . . . . . . . . . . <30
ingredients acceptable by the U.S. Department of Agriculture
E. coli/10 g . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . negative
for use in meat and poultry food products, subject to labeling
Staphylococcus aureus/10 g . . . . . . . . . . . . . . . . . negative
requirements, under the following Sections:
Salmonella/25 g . . . . . . . . . . . . . . . . . . . . . . . . . . negative
Pseudomonas/10 g . . . . . . . . . . . . . . . . . . . . . . . . negative 318.7 Binder, extender, or stabilizer for meat type
baked pies when used in an amount suffi-
Aqualon utilizes officially approved methods to determine
cient for the purpose in accordance with
the above microbial parameters, but recommends that users
21CFR172.5
of Aqualon CMC assure themselves of compliance with any
microbiological criterion by testing each lot. 381.147 Binder, extender, or stabilizer in various
poultry products when used in an amount
The typical values above allow for the fact that some
sufficient for the purpose
microorganisms may be present in CMC. We therefore
recommend that our customers control the microbiological FDA Definitions and Standards for Food
quality of their finished product through appropriate process Cellulose gum may be used in a wide variety of standardized
and formulation expertise. foods, subject to Title 21 of the Code of Federal Regulations.
Certain types of purified sodium carboxymethylcellulose (cel- Within each of the following parts of Subchapter BFood

25
and Food Products are several definitions and standards FOOD LABELING
permitting use of cellulose gum. Further details on individ-
ual sections of the standards are available by request. Cellulose gum, accepted as a common, or usual, name for
131 Milk and cream products Aqualon purified sodium carboxymethylcellulose, may be
used in food-label ingredient statements. The food manufac-
133 Cheese and related cheese products turer or processor is permitted to use either sodium car-
135 Frozen desserts boxymethylcellulose or the shorter and more common
150 Fruit butters, jellies, and preserves term, cellulose gum. The Food Chemicals Codex, which
169 Food dressings and flavorings describes in detail the standards required of food-grade
additive materials uses cellulose gum as the primary
In addition, the use of cellulose gum is permitted under the name, in addition to the more technical term, sodium
following Sections: carboxymethylcellulose.
146.121 Frozen concentrate for artificially sweet-
ened lemonade Establishment of cellulose gum as an accepted common
name for sodium carboxymethylcellulose resulted from an
152.126(a) Frozen cherry pie Aqualon petition granted by order of the Deputy Commis-
165.175 Soda water sioner of Food and Drugs, effective June 26, 1963.
168.180 Table syrup
Cellulose gum, including CMC standard grades, is permitted PHARMACEUTICAL USE
for use in boiler water additives and food-packaging applica- Sodium carboxymethylcellulose is listed in the current U.S.
tions under the following Sections: Pharmacopoeia. Its applications may be both therapeutic
173.310 Boiler water additives and excipient. Therapeutic uses include bulk-forming laxa-
174.5 General provisions applicable to indirect tives in which sodium carboxymethylcellulose may be the
food additives primary ingredient. Excipient uses include those of suspend-
175.105 Adhesives ing, tablet binding, or viscosity increasing.
175.300 Resinous and polymeric coatings Sodium carboxymethylcellulose 12 (degree of substitution
176.170 Components of paper and paperboard in 1.15-1.45 min) is listed in the National Formulary for use
contact with aqueous and fatty foods as a pharmaceutic aid. The same excipient uses just given
176.180 Components of paper and paperboard in are applicable.
contact with dry food Aqualon CMC meeting the requirements of the U.S.
177.1210 Closures with sealing gaskets for food Pharmacopoeia or the National Formulary can be supplied
containers by request.
182.70 Substances migrating to food from
cotton and cotton fabrics used in dry COSMETICS AND TOILETRIES
food packaging
Cellulose gum is the accepted term used by the Cosmetic,
Note: A communication from the Food and Drug Adminis- Toiletry and Fragrance Association, Inc., for sodium car-
tration to Hercules Incorporated, Aqualon Division, defines boxymethylcellulose. The product is so listed in the Associ-
as suitable for use in packaging materials sodium carboxy- ations CTFA International Cosmetic Ingredient Dictionary
methylcellulose of purity not less than 90% on a dry- and Handbook.
weight basis.

26
APPENDIX
METHODS OF ANALYSIS

General principles for analysis of CMC and details of several 3. Return the samples to the oven for 45 minutes; cool and
procedures are contained in Aqualon Bulletin VC-472, weigh as before. If the second dried weight is not within
Analytical Procedures for Assay of CMC and Its Determi- 0.005 g of the first, repeat the 45-minute oven periods
nation in Formulations. Copies may be obtained by request. until two subsequent weighings are in agreement. Then,
using the lowest dried weight obtained, calculate percent
Several analytical procedures are contained in ASTM D1439, moisture as follows:
Standard Test Methods for Sodium Carboxymethylcellulose.
Copies are available directly from ASTM, 100 Barr Harbor Original sample wt dry sample wt
100 = % moisture.
Drive, West Conshohocken, PA 19428. Original sample wt

VISCOSITY OF SOLUTION Solution Preparation


Immediately after weighing CMC samples for moisture deter-
An accurate determination of the viscosity of a CMC solution mination, the same undried gum should be weighed for solu-
is frequently needed. As explained on page 13, the apparent tion preparation. Moisture and solution sample weighings
viscosity of such a solution depends on a number of factors, should be made closely together to ensure that the moisture
and if reproducible results are to be obtained, a closely stan- content of both is the same at time of weighings.
dardized method of solution preparation and viscosity deter-
mination 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 2. From the determined percent moisture, calculate the
spindle guard supplied with this instrument should be used weight of distilled water to be added as follows:
for all determinations. a. For 1% viscosity solution:
Weight of undried CMC (99 percent moisture)
Solution volumes specified should not be less or they may = Weight of water.
not cover the appropriate Brookfield spindle.
b. For 2% viscosity solution:
Preparation of the solution is critical, in that the CMC must Weight of undried CMC
be completely dissolved to obtain a significant measure- (98 Percent moisture)
= Weight of water.
ment. To determine the proper amount of gum, a moisture 2
correction must be included to place the viscosity measure-
ment on a dry CMC basis. c. For 4% viscosity solution:
Weight of undried CMC
The viscosity-measurement test must be rigidly standard- (96 Percent moisture)
ized because the viscosity reading obtained depends on rate = Weight of water.
4
of shear, temperature, amount of agitation prior to measure-
ment, and elapsed time between agitation and measure- 3. Add the calculated amount of distilled water to the
ment. The method used in Aqualon laboratories is given respective 12-oz. bottles. Use 12-oz. bottles with an
here in detail. ID of 212 in.

Moisture Determination 4. Stir the water with a mechanical agitator to create a vor-
1. Weigh duplicate samples of 5 g, to the nearest 0.001 g, tex. An anchor-shaped stirrer turned by compressed air
into previously dried and weighed moisture cans with is satisfactory. Carefully sift the sample into the water,
covers. The samples for solution preparation (see next avoiding the center of the vortex, and be sure that all the
section) should be weighed right after these moisture material is transferred. Lower the bottle into a constant-
samples. temperature bath (25 6 0.5C).

2. Place the samples in a gravity convection oven main- 5. Increase stirring speed and stir vigorously until solution
tained at 105 6 0.5C and heat for three hours. Cool in is complete. (Usually 1 to 3 hrs is required.) When solu-
a desiccator and weigh. tion is complete, measure viscosity as described in the
next section.
(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 Viscosity Measurement
during preparation, follow Steps 6 and 7. 1. Select from Table IX, below, the Brookfield spindle-
speed combination for the viscosity type of gum being
6. When the solution is complete, remove the stirrer, place
tested. Attach the selected spindle to the instrument,
a sheet of cellophane over the mouth of the bottle, and
then set the instrument for the corresponding speed.
cap it.
2. If the solution was prepared in a constant-temperature
7. Place the bottle in a constant-temperature bath for at least
bath, immediately insert the spindle (with the guard
30 minutes, but no more than two hours. (If the sample
attached) into the solution. Start the spindle rotating
stands longer than two hours, return it to the stirrer for
and allow it to rotate for three minutes before taking
10 minutes.)
the reading.
Table VllI Approximate Undried CMC Weights 3. If Steps 6 and 7 of the solution preparation procedure
for Solution Preparation were followed, remove the bottle from the constant-
temperature bath and shake it vigorously for 10 seconds.
Add Distilled Water Then remove the cap and proceed with Steps 1 and
Aqualon to Give This Exact 2 of the viscosity measurement.
CMC Sample Percent Solids 4. Stop the instrument, read the dial, and multiply the dial
Viscosity Type Weight, g Content reading by the factor shown in Table IX. The result is the
solution viscosity in centipoises (mPas).
L2 10.5 4.0
L&M 5.2 2.0
H 2.3 1.0

Table IX Brookfield Spindle-Speed Combinations for


Determination of Solution Viscosity

Spindle
Concentration, Spindle Speed, Maximum Reading,
Aqualon CMC Type % Number rpm Factor cps (mPas)
7L2 4 2 60 5 500
7L 2 1 60 1 100
7M2 2 2 60 5 500
7M, 7M8S, 9M8, 12M8 2 2 30 10 1,000
9M31, 12M31 2 3 30 40 4,000
7H, 7H3S, 7HOF 1 3 30 40 4,000
7H4, 9H4 1 4 30 200 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 represen-
tation, 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.