THE COLOURING MATTER OF LOGWOOD.
The wood of _Hæmatoxylon campechianum_ (logwood), a native of South
America, comes into the market in small logs of a red colour; it
contains a colouring matter whose properties are fairly well known.
Before the discovery of the coal-tar dyes logwood was a most important
colouring material; by means of it red, blue, violet and black colours
can be obtained. At present it still plays an important part in dyeing.
Many varieties of logwood come into commerce. The most important are
Campeachy wood, Honduras, Jamaica and St. Domingo logwood; the first
named is the best, and the last the poorest quality. To facilitate
the extraction of the colouring matter by water logwood is frequently
sold in chips. Many dye-wood grinders moisten logwood with lime water;
this gives the powder a better colour, but diminishes the yield of
colouring matter. Since the only useful constituent of logwood can be
extracted by treatment with water, and the wood is only a carrier of
the colouring matter, which is only useful for fuel when exhausted,
logwood extracts are largely used in place of the wood. The extracts
are black resin-like masses, which easily dissolve in water; they are
very hygroscopic, and should therefore be kept in closed vessels.
=Logwood Extract.=—Solid extracts can be obtained from the majority of
dye-woods. The use of these is a great convenience to the dyer and
the colour maker; the method by which extracts are made is therefore
briefly described.
Dye-wood extracts can be made on the small scale, by washing out the
finely divided wood until soluble matters are no longer taken up by
the water, and cautiously evaporating the united extracts. When the
extract becomes concentrated the greatest care must be taken to prevent
burning on the bottom of the vessel; a burnt extract is always darkened
by the presence of products of decomposition, and its solution has a
brown colour. Apart from this, the complete extraction of the colouring
matter requires much time, and such dilute solutions are produced that
they cannot be evaporated, but at the best can be used in the place of
water to extract fresh quantities of wood.
When steam is utilised to extract dye-woods these defects are
removed. A burnt extract is not to be feared, and a small quantity of
water is sufficient to extract the colouring matter completely. The
apparatus illustrated in Fig. 37 is very suitable for the extraction
of dye-woods, and in general for obtaining vegetable extracts. The
extraction vessel is pear-shaped, its two hollow axes move in hollow
bearings. Thus it may be turned upside down, and steam and water can be
introduced into the interior through the axes, which are connected with
the pipes, E, W, and R. The opening at the pointed end of the pear is
closed by the screw, S; through it the substances to be extracted are
introduced. In the lower portion of the vessel is a sieve upon which
the materials are spread out. The opening of the pipe connected with E
and W is below the sieve.
[Illustration: FIG. 37.]
The process is commenced by introducing the materials through the
upper opening, fastening the cover down steam-tight by the lever,
B, and the screw, S, and then running in water through W until it
flows out through the lower of the two narrow pipes which are shown
somewhat paler in the shaded portion of the drawing. All the taps are
then closed with the exception of that on the upper of the two small
pipes. By opening the cock on R steam is led in. As a rule, steam at a
low pressure is used, not more than half an atmosphere. The contents
begin to boil in 15 to 30 minutes, steam then issues from the open
tap. According to the nature of the material to be extracted, boiling
is continued from 40 to 60 minutes. The side tap is then closed, and
the tap on the pipe E opened. The pressure of the steam now forces the
liquid up the pipe E; the pressure of half an atmosphere is sufficient
to raise it about 4 metres. In this way it can be forced into a tank
above. The rest of the liquid can be run off through the cock, _h_,
at the bottom of the vessel. When quite empty the cover is taken off,
the vessel turned over, and the solid residue removed. One extraction
of dye-woods is not sufficient to remove the whole of the colouring
matter; in most cases the wood is treated a second time before the
apparatus is emptied. Even then some quantity of colouring matter
remains in the wood. The twice extracted wood is brought into a tub
filled with water, and the solution resulting from the long contact
of the water with the wood is used in the next operation to extract
new quantities of wood instead of fresh water. The dimensions of the
extraction vessel vary according to the size of the works. A large
apparatus costs not much more than a smaller, since in both cases the
labour is the same, so that it is advisable to use a large apparatus.
When the copper extraction vessel is made to have its greatest diameter
about 1 metre, it can be charged with about 50 kilogrammes of rasped
wood at once.
[Illustration: FIG. 38.]
The extraction apparatus of Hänig and O. Reinhard is shown in Fig. 38.
It can be turned over by means of cog-wheels. In the cover are an air
valve, _e_, and safety valve, _f_; below the cover is a coil, _k_,
fed with cold water from _c_. In the extraction, by opening the valve
_v_, steam enters through _a_ at _l_; it is condensed by the cooled
cover, the condensed water flows through the material on the sieve,
and collects in the space B. After some time _v_ and _z_ are opened,
the liquid is then boiled by the steam in the coil, _s_. Steam rises
through the material, is condensed on the cover, and again drops down.
At the end of the operation the solution is drawn off through the cock,
_h_.
[Illustration: FIG. 39.]
=Kohlrausch’s Process for Obtaining Concentrated Extracts of Colouring
Matters and Tannins.=—When dye-wood or tan-bark is continually brought
in contact with fresh quantities of water, after some time it is
exhausted; if the solution containing a certain quantity of the soluble
matters is brought in contact with fresh material not yet extracted,
it takes up more soluble matter, and thus becomes more concentrated.
The substances contained in tan-bark are very soluble in water, so that
by the appropriate treatment of a certain quantity of bark, divided
amongst different vessels, with a certain quantity of water, on the
one hand the bark can be exhausted completely, and on the other very
concentrated solutions (”bark extracts”) obtained. The process patented
by Kohlrausch is based upon the principles just stated; it can be
used to obtain tannin extracts from tan-bark and colour extracts from
dye-wood. In this process the raw materials need not be finely ground
in order to be completely extracted; they may be used in large pieces.
It will be understood from the following description that fine bark
meal or finely-rasped dye-wood could not be worked.
[Illustration: FIG. 40.]
The apparatus consists of a number of 10 to 20 extractors connected
together, also with a water tank above, and with a boiler. A single
extractor is represented in section in Fig. 39, together with
the necessary pipes and valves by which it is connected with the
neighbouring extractors, the water tank and the boiler. Fig. 40 is a
plan of three extractors connected together.
The extractors consist of wooden or copper vessels, slightly conical
in shape, and of sufficient strength to resist the pressure of one
atmosphere. On the top is a copper dome closed by a lid, through which
the raw material is introduced, and also steam and water. Immediately
above the bottom is an opening, also closed by a screw, which serves
to remove the exhausted materials. An inclined sieve is placed at some
distance above the bottom; upon this the material rests. The extract
collects below the sieve, and may be run off by the pipe or brought
into another extractor. All the metallic portions of the apparatus
which come in contact with the liquid must be made of a metal such as
copper, which does not act upon tannic acid. Iron cannot be used; it
forms deep bluish or greenish black compounds with tannic acid, which
would cause the extract, instead of being pale and clear, to resemble
ordinary writing ink.
In a range of 10 extractors the process is carried out in the following
manner: The extractors numbered 1 to 10 are filled with bark or
dye-wood and closed; 1 is then filled with water from the tank, and
heated by steam to 50° to 70° C. After some time the contents of 1 are
forced into 2, and 1 is again filled with water, so that the material
in 2 is in contact with the solution from 1, whilst the material in 1
is warmed with a fresh quantity of water under pressure; the extract
in 2 is transferred to 3, that in 1 to 2, and 1 is again filled with
water, and so on. Finally from 10 a very strong extract of tannin
or colouring matter is obtained. The quantity of water required to
fill one extractor has come ten times in contact with fresh bark
or dye-wood. The material in 1 has been treated with ten times the
quantity of water; it is now exhausted, and is replaced by fresh
material. The sequence of the vessels is now changed. The original
extractor 2 is to be regarded as 1, and 1 as 10. After ten repetitions
the original order of the extractors re-obtains. Ninety-nine per cent.
of the tannic acid of bark is extracted in this way.
The concentrated extracts obtained in this apparatus should be mixed
with a little carbolic acid to prevent decomposition; they may then
be filled into barrels. The extracts may also be so far concentrated
by evaporation that they become syrupy. The tannins are readily
decomposed; they would be considerably altered if their solutions were
evaporated in open vessels. The extracts are therefore evaporated at a
very low temperature under diminished pressure in vacuum pans, which
are now much used for the concentration of solutions of substances,
such as sugar, which would be injured by heating above a certain
temperature. Essentially, a vacuum pan is a thick-walled copper vessel,
in which the liquid is warmed by a steam coil. It is connected with an
air pump, which exhausts the air at the commencement of an operation,
and afterwards steam. The liquid is thus constantly evaporated under
a low pressure. Extracts of tan-bark and dye-woods boil briskly
under these conditions at temperatures below 60° C., at which no
decomposition of the tannin or the colouring matter is to be feared.
When the solutions have been evaporated to the proper strength they are
run off directly into the packages in which they are to be despatched,
and in which they become syrupy or even solid masses, according to the
extent to which the evaporation has been driven.
The packages should be at once closed; the thick extract is thereby
most simply and safely prevented from decomposing, to which risk it
would be exposed by the access of mould spores. If these were already
present in the barrels or were communicated to the extract by the air,
they would either be killed by the hot liquid or would be prevented
from developing for a long time. In the closed vessels the extracts
remain completely unaltered.
The concentrated solution of colouring matter obtained by extracting
dye-woods in the above apparatus can be at once used, after dilution,
in the preparation of lakes and in dyeing, but it is not an extract in
the ordinary commercial sense of the term, _i.e._, it does not solidify
on cooling. To obtain solid extracts the concentrated solutions must
be evaporated; concentration with fire heat would be attended with
danger to the quality of the extract, steam heat is therefore used.
The liquid to be evaporated is brought into shallow steam-jacketed
pans, in which the operation is continued until the liquid solidifies
into a resin-like mass when dropped on cold stone. When sufficiently
evaporated the extract is allowed to solidify, broken into lumps,
and these packed whilst still warm into barrels lined with paper.
The lining is necessary on account of the hygroscopic nature of the
extracts; when they are exposed to the air they absorb water and form a
viscous fluid which soon becomes mouldy.
A properly prepared dye-wood extract should dissolve in water without
residue, and the solution when largely diluted should show the
characteristic colour of the wood with no brownish shade, and when the
colouring matter is precipitated from such a solution by a metallic
salt the residual solution should be almost colourless. If the extract
dissolves incompletely in water and the solution is brown after
precipitation of the colouring matter, the extract has been burnt in
the evaporation.
* * * * *
Logwood and logwood extract contain two substances of importance
in dyeing and colour making. These are hæmatoxylin and hæmateïn.
Hæmatoxylin is found in logwood in greatest amount shortly before the
wood is cut. When pure it forms colourless crystals of a peculiar sweet
taste, which are soluble in cold water with difficulty, more easily
in hot, and readily soluble in alcohol or ether. The composition of
hæmatoxylin is expressed by the formula C₁₆H₁₄O₆.
Hæmatoxylin is not a colouring matter. It is important because from it
is obtained the essential colouring matter of logwood—hæmateïn. When a
trace of ammonia is added to the colourless solution of hæmatoxylin,
the liquid at once becomes dark red owing to the formation of hæmateïn.
When a larger quantity of ammonia is added the liquid acquires a deep
red colour, and then contains only hæmateïn (its ammonia compound),
which is formed according to the following equation:—
C₁₆H₁₄O₆ + NH₃ + O = C₁₆H₉O₅.NH₄ + 2H₂O.
To obtain hæmateïn in the pure state it is then only necessary to add
sufficient acetic acid to decompose the hæmateïn ammonia compound.
Hæmateïn separates as dark violet crystals, which readily dissolve in
water and alcohol; its aqueous solution gives blue precipitates with
the majority of the metallic salts. This behaviour of hæmatoxylin
towards ammonia explains the increase in colouring power of logwood,
which has been exposed for a long time to the action of the air in the
rasped state. Through the action of the ammonia in the air a larger
quantity of the hæmateïn ammonia compound has been formed. It has
been proposed to facilitate the formation of this ammonia compound
by moistening rasped logwood with a very dilute glue solution and
allowing it to lie in the air. This process can only have the object
of utilising in the formation of hæmateïn the ammonia resulting from
the decomposition of the glue, but in this decomposition deep-seated
reactions occur, which might affect the hæmateïn itself. It thus
appears more suitable to effect the formation of hæmateïn by the direct
use of ammonia. This can be done with little cost by watering heaps of
rasped logwood with ammonia and repeatedly shovelling about the wood
so that it comes into contact with the air. The author has found that
the conversion of hæmatoxylin to hæmateïn is very complete in this
process; care should be taken not to make the layer of rasped wood too
deep, and to take its temperature frequently. In the transformation
of hæmatoxylin to hæmateïn the temperature rises, the rise might be
injurious if it proceeded too far. Thus if the temperature of the
interior of the heap is found to be high the wood should be turned over.
The solution of the logwood colouring matter produces handsome lakes,
all of which have, however, the inconvenient property of acquiring
an ugly grey colour on long standing. The finest and most durable of
the logwood lakes is known as violet lake, which is made with alumina
salts. The best result is obtained when a solution of aluminium
acetate, obtained by precipitating alum with lead acetate, is mixed
with a logwood decoction or a solution of logwood extract. The
precipitate is pale or deep violet according to the amount of aluminium
salt added. After drying to a certain point at a gentle heat it can be
mixed with gum solution to a paste, which is then completely dried.
Logwood is most valuable in dyeing and calico printing, in which it
serves to produce a fine and durable black. When potassium chromate is
added to a decoction of logwood a deep black liquid results, which can
be used as a good and cheap writing ink. If somewhat stronger solutions
are used a greenish precipitate first separates, which soon acquires a
pure black hue; it is the chromium lake of hæmateïn. This compound is
very durable and is largely used in dyeing to produce fast blacks. The
black precipitate might be dried and used as an artists’ black pigment
if the carbon blacks were not cheaper and more durable.