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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
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.
3
APPLICATIONS FOR STANDARD GRADE OF CMC
4
CHEMISTRY
5
GRADES AND TYPES
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.
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
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.
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
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
9
Figure 4
Typical Installation of Eductor-Type Mixing Device
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
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
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
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
Tumbling
Film Sag
Blendor
Pouring
Waring
Gravity
Under
Home
Mixer
or
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.
Figure 18 100
1 2 3 4 5
Effect of pH on Viscosity of
Storage Time at 25C, months
Aqualon CMC Solutions
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
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.
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
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.
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
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
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.