قراءة كتاب The Dyeing of Cotton Fabrics: A Practical Handbook for the Dyer and Student
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The Dyeing of Cotton Fabrics: A Practical Handbook for the Dyer and Student
paper; unsized paper is immersed in strong acid of the proper strength for about a minute, and then immediately rinsed in water. The acid acts upon the surface of the paper and forms the cellulose-sulphuric acid which remains attached to the surface. On passing into the water this is decomposed, the acid is washed away, and the cellulose is deposited in an amorphous form on the paper, filling up its pores and rendering it waterproof and grease-proof. Such papers are now largely used for packing purposes.
ACTION OF HYDROCHLORIC ACID.
Dilute hydrochloric acid of from 1° to 2° Tw. in strength, used in the cold, has no action on cellulose. Cotton immersed in acids of the strength named and then well washed in water is not materially affected in any way, which is a feature of some value in connection with the bleaching of cotton, where the material has to be treated at two points in the process with weak acids. Boiling dilute hydrochloric acid of 10° Tw. disintegrates cellulose very rapidly. The product is a white very friable powder, which if viewed under the microscope appears to be fragments of the fibre that has been used to prepare it. The product has the composition C12H22O11, and is therefore a hydrate of cellulose, the latter having undergone hydrolysis by taking up the
elements of water according to the equation 2C6H10O5 + H2O = C12H22O11. By further digestion with the acid, the hydrocellulose, as it is called, undergoes molecular change, and is converted into dextrine. In composition hydrocellulose resembles the product formed by the addition of sulphuric acid which has received the name of amyloid. It differs from cellulose in containing free carboxyl, CO, groups, while its hydroxyl groups, HO, are much more active in their chemical reactions.
Hydrocellulose is soluble in nitric acid, 1.5 specific gravity, without undergoing oxidation. Nitrates are formed varying in composition.
The formation of hydrocellulose has a very important bearing in woollen manufacture. It is practically impossible to obtain wool free from vegetable fibres, and it is often desirable to separate these vegetable fibres. For this purpose the goods are passed into a bath of hydrochloric acid or of weak sulphuric acid. On drying the acid converts the cotton or vegetable fibre into hydrocellulose which, being friable or powdery, can be easily removed, while the wool not having been acted on by the acid remains quite intact. The process is known as "carbonising". It may not only be done by means of the acids named but also by the use of acid salts, such as aluminium chloride, which on being heated are decomposed into free acid and basic oxide. For the same reason it is important to avoid the use of these bodies, aluminium chloride and sulphate, zinc and magnesium chlorides, etc., in the treatment of cotton fabrics; as in finishing processes, where the goods are dried afterwards, there is a great liability to form hydrocellulose with the accompaniment of the tendering of the goods.
ACTION OF NITRIC ACID.
The action of nitric acid on cellulose is a variable one, depending on many factors, strength of acid, duration of
action and temperature. Naturally as nitric acid is a strong oxidising agent the action of nitric acid on cellulose is essentially in all cases that of an oxidant, but the character of the product which is obtained varies very much according to the conditions just noted. When cellulose or cotton in any form is immersed in nitric acid of 1.4 to 1.5 specific gravity for a moment, and the fibre be well washed, there is a formation of hydrate of cellulose which has a gelatinous nature. This is deposited on the rest of the material, which is not materially affected so far as regards strength and appearance, but its power of affinity for dyes is materially increased. There is some shrinkage in the size of the cotton or paper acted upon.
Nitric acid changes all kinds of cellulose into nitro products, the composition of which depends upon the strength of the acid, the duration of treatment, and one or two other factors. The nitrocelluloses are all highly inflammable bodies, the more highly nitrated burning with explosive force. They are produced commercially and are known as "gun cotton" or "pyroxyline". The most highly nitrated body forms the basis of the explosive variety; the least highly nitrated forms that of the soluble gun cotton used for making collodion for photographic and other purposes.
The products formed by the action of nitric acid are usually considered to be nitrocelluloses. It would appear that they are more correctly described as cellulose-nitrates, for analysis indicates the presence of the NO3 group, which is characteristic of nitrates, and not of the NO2 group, which is the feature of nitro bodies in general. Further, nitro compounds, when subject to the action of reducing agents, are converted into amido compounds, as is the case, for instance, with nitro-benzene, C6H5NO2, into aniline, C6H5NH2, or with nitro-naphthalene, C10H7NO2, which changes into naphthylamine,
But the nitric acid derivatives of cellulose are not capable of conversion by reducing agents into similar amido compounds. They have the following properties, which accord more closely with nitrates than with nitric bodies: alkalies remove the nitric acid; cold sulphuric acid expels the nitric acid, cellulose sulphates being formed; boiling with ferrous sulphate and hydrochloric acid causes the elimination of the nitric acid as nitric oxide (on which reaction a method for determining the degree of nitration of gun cotton is based). It is best therefore to consider them as cellulose nitrates. Several well-characterised cellulose nitrates have been prepared, but is an exceedingly difficult matter to obtain any one in a state of purity, the commercial articles being always mixtures of two or three. Those that are best known and of the most importance are the following:—
Cellulose Hexa-nitrate, C6H4O5(NO3)6. This forms the principal portion of the commercial explosive gun cotton, and is made when a mixture of strong nitric acid and strong sulphuric acid is allowed to act on cotton at from 50 to 55° F. for twenty-four hours. The longer the action is prolonged, the more completely is the cotton converted into the nitrate, with a short duration the finished product contains lower nitrates. This hexa-nitrate is insoluble in ether, alcohol, or in a mixture of those solvents, likewise in glacial acetic acid or in methyl alcohol.
Cellulose Penta-nitrate, C6H5O5(NO3)5, is found in explosive gun cotton to a small extent. When gun cotton is dissolved in nitric acid and sulphuric acid is added, the penta-nitrate is thrown down as a precipitate. It is not soluble in alcohol, but is so in a mixture of ether and alcohol, it is also slightly soluble in acetic acid. Solutions of caustic potash convert it into the di-nitrate.
Cellulose Tetra-nitrate, C6H6O5(NO3)4, and Cellulose Tri-nitrate, C6H7O5,(NO3)3, form the basis of the pyroxyline or solu
ble gun cotton of commerce. It has not been found possible to separate them owing to their behaviour to solvents being very similar. These nitrates are obtained by treating cotton with nitric acid for twenty or thirty minutes. They are characterised by being more soluble than the