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10. Assessment of various pretreatment processes

10.4 Degradation of cotton during alkaline scouring

Although cotton is stable in dilute alkalis at high temperatures in absence of air, presence of air causes serious degradation. This
mainly results in oxy-cellulose formation, during which some hydroxyl groups on glucosidic units get oxidized to keto and carboxylic
groups.

Assessment of the degradation can be done by either assessing the aldehyde/carboxylic group content of cellulose, measurement of
fluidity or loss in tensile strength.

Following are some of the methods for assessment of cotton cellulose degradation:

1. Copper number, a measure of the reducing groups present in cellulose.

2. Carboxyl group content by methylene blue absorption

3. C uprammonium fluidity, which is a measure of molecular chain length of cellulose.

4. Tensile strength of the cotton material before and after scouring.

1. Copper number

The first stage of cellulose oxidation during cotton souring results in formation of –CHO groups from –OH groups. These aldehyde
groups have a reducing tendency and can reduce alkaline solution of copper sulphate, resulting in formation of insoluble cuprous
oxide which precipitates on the cotton cellulose. The amount of cuprous oxide formed is proportional to the amount of reducing
groups which is expressed as Copper Number.

The test is carried out as under-

A solution is prepared by dissolving 100g copper sulphate in 1 litre of water. Another solution is prepared by dissolving 350 g sodium
carbonate and 50 g sodium bi carbonate in another 1 litre of water. These two solutions are mixed just before use to form Fehling’s
solution.

Three groups of cotton cellulose is boiled in a solution containing 100 ml of Fehling’s solution and 200 ml of water under reflux for 15
min. during the boiling process some copper sulphate is reduced to cuprous oxide which gets deposited on cellulose.

This mass of cellulose is filtered & washed with water. The cellulose is then transferred to a beaker containing 1-2 gm fabric alum
dissolved in dilute sulphuric acid. The cuprous oxide present in cellulose reduces ferric sulphate and forms equivalent amount of
ferrous sulphate. This is titrated against N/100 ceric sulphate solution by dissolving the ferrous sulphate in sulphuric acid. Ortho
ferrous phenathroline is used as an indicator.

Thus copper number is defined as grams of cupric copper reduced to cuprous oxide by 100 g of cellulose under standard treatment
conditions.

The copper number is determined by the following formula:

Where V = ml of ceric solution - blank reading

N is the normality of ceric sulphate solution

W is the weight of the bone dry cellulose sample (it depends on type of sample; for normal samples it is 0.25 g and for highly
degraded samples 0.1 g is taken

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Copper number for pure cellulose is 0.5, for scoured & bleached cotton below 0.3 & for viscose less than 1.2.

2. Methylene blue absorption method

Normal cellulose generally has no affinity for methylene blue, a basic dye. When cellulose in oxidized, -OH groups convert to
aldehyde group. But when the oxidation is more severe, these aldehyde groups can oxidize to carboxylic groups. In degraded
cellulose, both –CHO & -COOH groups may be present. Hence there is a need to determine the degree of cellulose oxidation in
terms of –COOH groups content.

Methylene blue absorption method is based on the principle that the carboxyl groups present in cellulose are able to absorb
methylene blue dye cations quantitatively from a solution of methylene blue dye. The scheme is shown below:

The amount of dye absorbed can be determined by analyzing the drop in concentration of methylene blue in treatment solution
using calorimetric methods.

3. Cuprammonium fluidity

The degradation of a polymer results in reduction of degree of polymerization. At same concentration, the degree of polymerization
is related to the viscosity of its solution. Fluidity (ease of flow) is a property inversely related to viscosity (resistance to flow). Thus
the degradation resulting in reduction of the DP can also be assessed by measuring fluidity. In case of cotton the fluidity
measurements are made on solution of cotton material in cuprammonium hydroxide solution. In the table given below, fluidity
values of various forms of cellulosic textiles are given.

Type of cellulose Fluidity values

Unbleached cotton ~2
Bleached cotton <5
Degraded cotton showing loss in
>10
tensile strength
standard unbleached viscose ~10

Physical testing

Tensile strength, bursting strength and abrasion resistance, Tear strength can be measured

The results are influenced by both fabric structure and chemical damage.

Tear strength is also influenced by residual natural lubricants.

Staining tests

Carboxyl groups in oxidized cellulose resist staining with C.I. Direct Blue 1 or give increased uptake of C.I. Basic Blue 9.

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Harrison test

The oxycellulose test sample is immersed in a boiling alkaline silver nitrate solution.

Brown to black deposits of silver are produced on the substrate where there are reducing aldehyde groups.

Barium Activity Number

Mercerized cotton fibre is highly absorptive. It absorbs more iodine, dyes, moisture and alkalis and undergoes oxidation or
hydrolysis at increased rates compared to unmercerized cotton.

BAN method is based on preferential absorption of barium hydroxide from its dilute solution by mercerized cotton as compared to
unmercerized cotton under the same conditions.

Barium activity number is determined by expressing this ratio as percentage.

BAN of

Unmercerized cotton - 100

Semi-mercerized cotton - 115 to 130

Completely mercerized cotton ~ 155 .

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