Carbonizable Substances

Wax and petrolatum intended for certain pharmaceutical purposes are required to pass the test for carbonizable matter.
The degree of unsatura-tion (carbonizable material) is determined by reacting the wax with con-centrated sulfuric
acid. The resultant color of the acid layer must be lighter than the reference color if the wax is to qualify as
pharmaceutical grade. The melting point (ASTM D-87, IP 55) for such grades may also be required.

To determine the presence of carbonizable substances in paraffin wax (ASTM D-612) 5 ml of concentrated sulfuric
acid is placed in a graduated test tube and 5 ml of the melted wax are added. The sample is heated for 10 min at 70C
(158F). During the last 5 min the tube is shaken periodi-cally. The acid layer is compared with a standard reference
solution, and the wax sample passes if the color is not darker than the standard color.

Composition

Almost all physical and functional properties of the wax are affected by:

The molecular weight range,

Distribution of its individual components, and

The degree of branching of the carbon skeleton.

For a given melting point, a narrow-cut wax consisting almost entirely of straight-chain paraffins will be harder and
more brittle and will have a higher gloss and blocking point than a wax of broader cut or one contain-ing a higher
proportion of branched molecules.

All petroleum-derived waxes, including blends of waxes, from n-C17 to n-C44 can be separated by capillary column
chromatography (ASTM D-5442). In this method, the sample is diluted in a suitable solvent with an internal
standard, after which it is injected into a capillary column meeting a specified resolution, and the components are
detected with a flame ion-ization detector. The eluted components are identified by comparison with a standard
mixture, and the area of each straight-chain and branched-chain alkane is measured.

The polynuclear aromatic content of waxes can be estimated by the ultraviolet absorbance (ASTM D-2008) of an
extract of the sample. In this test method, the ultraviolet absorbance is determined by measuring the absorption
spectrum of the undiluted liquid in a cell of known path length under specified conditions. The ultraviolet
absorptivity is determined by measuring the absorbance, at specified wavelengths, of a solution of the liquid or
solid at known concentration in a cell of known path length.

The composition of wax is available through alternate procedures that involve solvent extraction (ASTM D-721,
ASTM D-3235, IP 158), and the refractive index (ASTM D-1747) can also give an indication of composi-tion, but
mainly purity.

The solvent-extractable constituents of a wax may have significant effects on several of its properties such as
strength, hardness, flexibility, scuff resist-ance, coefficient of friction, coefficient of expansion, and melting point.
In the test method (ASTM D-3235), the sample is dissolved in a mixture of 50% v/v methyl ethyl ketone and 50%
v/v toluene. The solution is cooled to 32C (25F) to precipitate the wax and then filtered. The yield of solvent-
extractable constituents is determined by evaporating the solvent from the filtrate and weighing the residue.
 Hardness

Hardness is a measure of resistance to deformation or damage; hence it is an important criterion for many wax
applications. It is indirectly related to blocking tendency and gloss. Hard, narrow-cut waxes have higher blocking
points and better gloss than waxes of the same average molecular weight but wider molecular weight range.
The measurement of the needle penetration of petroleum wax (ASTM D1321, IP 376) gives an indication of the
hardness or consistency of wax. This method uses a penetrometer applying a load of 100g for 5s to a stan-dard needle
with a truncated cone tip. The sample is heated to 17C (30F) above its congealing point, poured into a small brass
cylinder, cooled, and placed in a water bath at the test temperature for 1h. The sample is then positioned under the
penetrometer needle, which when released penetrates into the sample. The depth of penetration in tenths of millimeters
is reported as the test value. This method is not applicable to oily materials or petrolatum, which have penetrations
greater than 250.
The method for the determination of the cone penetration of petrola-tum (ASTM D937, IP 179) is used for soft
wax and petrolatum. It is similar to the method for determining the needle penetration (ASTM D-132l) except that a
much larger sample mould is used and a cone replaces the needle. The method requires that a 150-g load be applied
for 5s at the desired temperature.

Molecular Weight

The molecular weight of various waxes may differ according to (1) the source of the wax (whether it originated in
lighter- or heavier-grade lubri-cating oils) and (2) the processing of the wax (the closeness of the distilla-tion cut or
the fractionation by crystallization). Thus the average molecular weight of a wax may represent an average of a
narrow or a wide band of distribution.

Generally, for any series of similar waxes, an increase in molecular weight increases viscosity and melting point.
However, many of the other physical and functional properties are more related to the hydrocarbon types and
distribution than to the average molecular weight.

In the test method for molecular weight (ASTM D-2503) a small sample of wax is dissolved in a suitable solvent,
and a droplet of the wax solution is placed on a thermistor in a closed chamber in close proximity to a sus-pended
drop of the pure solvent on a second thermistor. The difference in vapor pressure between the two positions
results in solvent transport and condensation onto the wax solution, with a resultant change in temperature.
Through suitable calibration, the observed effect can be expressed in terms of molecular weight of the wax
specimen as a number average molecular weight.

Oil Content
The oil content of paraffin waxes is an indication of the degree of refine-ment, and fully refined wax usually has an
oil content of less than 0.5%. Wax containing more than this amount of oil is referred to as scale wax, although an
intermediate grade known as semirefined wax is sometimes recognized for wax having an oil content of about 1%.

Excess oil tends to exude from paraffin wax, giving it a dull appearance and a greasy feel. Such a wax would
obviously be unsuitable for many applications, particularly the manufacture of food wrappings. A high oil content
tends to plasticize the wax and has an adverse effect on sealing strength, tensile strength, hardness, odor, taste,
color, and particularly color stability.

During wax refining increasing amounts of oil are removed, and this process must be controlled. Also, the oil
content of slack waxes, petrolatum, and waxes must be assessed for end user specification. For high-oil-content
waxes (i.e., greater than 15% w/w), the method (ASTM D-3235) involves dissolving a weighed amount of wax in a
mixture of methyl ethyl ketone (MEK) and toluene, followed by cooling to 32C (27F) to precipitate the wax.
The oil and solvent are removed; then the solvent is evaporated off to produce a weighable amount of oil. Gas-
liquid chromatographic

(GLC) analysis of the solvent-extracted material has shown that the deter-mined oil contains a small amount of
additional wax, n-C17 to n-C22 alkanes, thereby producing a small error.

For wax containing less than 15% oil, the method (ASTM D-721, IP 158) is similar to that for high-oil-content waxes
(ASTM D-3235) but uses only methyl ethyl ketone as the solvent. The concept that the oil is much more soluble
than wax in methyl ethyl ketone at low temperatures is utilized in this procedure. A weighed sample of wax is
dissolved in warm methyl ethyl ketone in a test tube and chilled to -32C (-25F) to precipitate the wax. The
solvent-oil solution is separated from the wax by pressure filtration through a sintered glass filter stick. The solvent
is evaporated, and the residue is weighed.

Microcrystalline waxes have a greater affinity for oil than paraffin waxes because of their smaller crystal structure.
The permissible amount depends on the type of wax and its intended use.

The oil content of microcrystalline wax is, in general, much greater than that of paraffin wax and could be as high
as 20%. Waxes containing more than 20% oil would usually be classed as petrolatum, but this line of demar-cation
is by no means precise.

Slip Properties
Friction is an indication of the resistance to sliding exhibited by two surfaces in contact with one another. The
intended application determines the degree of slip desired. Coatings for packages that require stacking should
have a high coefficient of friction to prevent slippage in the stacks. Folding box coatings should have a low
coefficient of friction to allow the boxes to slide easily from a stack of blanks being fed to the forming and

filling equipment.

The coefficient of kinetic friction for wax coatings (ASTM D-2534) is determined by fastening a wax-coated paper
to a horizontal plate attached to the lower, movable cross arm of an electronic load cell-type tensile tester. A
second paper is taped to a 180-g sled that is placed on the first sample. The sled is attached to the load cell by a
nylon monofilament passing around a frictionless pulley. The kinematic coefficient of friction is calculated from the
average force required to move the sled at 35 in./min divided by the sled weight.

In this same vein, the abrasion resistance of wax is also an important property and can be determined by a
standard test method (ASTMD-3234).

Strength
Another popular test for wax is the tensile strength (ASTM D-1320), which is considered to be a useful guide in
controlling the quality of the wax, although the actual significance of the results obtained is not clear.
The method for determining the tensile strength of paraffin wax (ASTM D-1320) is an empirical evaluation of the
tensile strength of waxes that do not elongate more than 1/18th of an inch under the test conditions. Six dumbbell-
shaped specimens, with a specified cross-sectional area are cast. The specimens are broken on a testing machine under
a load that increases at the rate of 20 lb/s along the longitudinal axis of the sample. Values are reported as pounds per
square inch.
To determine the modulus of rupture (breaking force in pounds per square inch) of petroleum wax (ASTM D-
2004), a wax slab, 8 4 0.l5in., is cast over hot water. Small strips, about 3 1in., are cut from the center of the
slab. The strips are placed lengthwise on the support beams of the apparatus, and a breaking beam is placed across the
specimen parallel to the support beams. A steadily increasing load is applied by water delivered to a bucket suspended
from the breaking beam. The modulus of rupture is calculated from an equation relating the thickness and width of
the test specimen to the total weight required to break it.

Viscosity

Viscosity of molten wax (ASTM D-3236) is of importance in applications involving coating or dipping processes
because it influences the quality of coating obtained. Examples of such applications are paper converting, hot-dip
anticorrosion coatings, and taper manufacturing.

Paraffin waxes do not differ much in viscosity, a typical viscosity being 3 0.5 cSt at 99C (210F).
Microcrystalline wax is considerably more viscous and varies over a wide range, 1020 cSt at 99C (210F). Some
hot melt vis-cosities exceed 20,000 cSt at 177C (350F).

Kinematic viscosity is measured by timing the flow of a fixed volume of material through a calibrated capillary at a
selected temperature (ASTM D-445, IP 71). The unit of kinematic viscosity is the stokes, and kinematic viscosities of
waxes are usually reported in centistokes. Saybolt Universal seconds can be derived from centistokes (ASTM D-
2161):

Saybolt seconds @ 37.8C (100F) = cSt X 4.635

Saybolt seconds @ 98.9C (210F) = cSt X 4.667

Another method (ASTM D-2669) is suitable for blends of wax and addi-tives with apparent viscosities up to
20,000cP at 177C (350F). Apparent viscosity is the measurement of drag produced on a rotating spindle
immersed in the test liquid. A suitable viscometer is equipped to use inter-changeable spindles and adjustable
rates of rotation. The wax blend is heated by means of a heating mantle in an 800-ml beaker and continuously
stirred until the test temperature is slightly exceeded. The sample is cooled to the test temperature, the stirring is
discontinued, and the viscosity is measured. Viscosities over a range of temperatures are recorded and plotted on
semilog paper to determine the apparent viscosity at any tem-perature in the particular region of interest.