^S 1101 .Li2 TS U®^ .L-78 CopV ^ REPORT OF ARTHUR D. LITTLE Official Chemist OF THE American Paper and Pulp Association READ AT THE ANNUAL MEETING February 6th, 1908 Gin .. Author Report of ARTHUR D. LITTLE Official Chemist of the American Paper and Pulp Association The most significant development of the year in paper making- has been the serious and general inquiry all over the world for new sources of paper stock. Wood is undoubtedly destined to maintain a position as one of the chief sources of supply for an indefinite number of years, and no possible substitute for ground wood is even in sight. There are, nevertheless, for those who will read them, plenty of signs that we are en the eve of a readjust- ment in paper making methods. For a considerable number of years the makers of many sorts of paper have found themselves in a position where' it was wood fibre or nothing else as their raw material. This general use of wood fibre as the only available basis for many branches of the industry has made for a greatly increased production, but has not always made for improvement in the quality of product. To the growing scarcity of pulp wood, the continually rising price and longer haul with which paper makers using this material are now contending, will, in a few years, be added the competition of new and better stocks which even now can be produced more cheaply than any bleached wood fibre. The time is rapidly approaching when we shall see upon the market many new paper stocks as bleached and unbleached pulp and half-stufifs. and these will be as readily available for immediate use as bleached sulphite is today. This means, of course, a gradual displacement of wood fibre from its present position of supremacy. It means also a far wider range in the quality and characteristics of available raw materials, as a result of which variety will come a broader scope for the exercise of a critical judgment and a greater skill on the part of the paper maker in the selection and manipulation of his materials. This condition is bound to react to the advantage of the industry gen- erally, and especially to the advantage of the smaller mills in the hands of expert and progressive manufacturers. There should follow a decided rise in the standard of quality, particularly in bag and wrapping papers and in those papers which may be expected to replace the cheaper grades of book, wood writing and envelope as now manufactured. At the same time the range of possible production in many mills will be extended. As these expectations will hardly be accepted on their face, it is well to inquire into the basis upon which they rest. Wood, as a raw material, has proved so available, convenient, compact, easily handled, and heretofore so cheap, that we have been led to overlook or ignore the immense sources of other and better paper stocks which lie easily within our reach. It is, there- fore, proposed to devote the major portion of this report to indi- cating what these other materials are, together with a brief state- ment as to their character and limitations, and what may reason- ably be expected of them. This statement will serve its purpose if it convinces you that we are not dealing with the perennial sug- gestions of visionaries who see a paper stock in everything which has a fibre, but are instead concerned with the serious proposals of capable technologists whose conclusions are based on careful stpdy. Let us consider first the material available in our own country and now wasted with our characteristic national miprovidence. The first in importance of these is undoubtedly the waste flax straw of our Northwest. The total area grown to flax for seed runs as high in some years as 3,700,000 acres, which means roughly a strip a mile wide and over 5,700 miles long. A ton and a half of straw to the acre is said to be a moderate yield, upon which basis we have over 5,000,000 tons of straw a year. This straw contains more than 20 per cent, of linen fibre, so that, disre- garding the inconsiderable amount of the fibre which is >vorked into tow, binder twine, and a few other similar coarse uses, there is here available more than 1,000,000 tons a year of the finest paper stock, equally suitable for the highest grades of paper as well as for bag and wrapping papers of a quality not now approached. It would be hard to find another country in which such a waste would be permitted. Flax is pre-eminently a crop for new lands, and is often the first crop sowed after such lands are turned over. Great crops of flax for seed are therefore naturally raised in Canada, particularly in Manitoba and the Canadian Northwest. ' Up to this time little or nothing has been done in the way of utilizing the fibre, although the Canadian flax should prove more valuable than our own by reason of the greater care taken in harvesting, the flax being cut or pulled and kept straight in sheaves while the seed is being separated. Within the last year at least three machines have been per- fected for separating the- short fibre which adheres to our South- ern cotton seed after the cotton has been ginned. An average cotton crop may be counted on to yield at least 600,000 tons of this short fibre, which now goes into cattle feed, to. the detriment of the latter. One meets occasionally with paper makers who have tried the fibre, but who almost invariablv condemn it as un-' worthy of serious consideration. Within the hist few weeks a writer in an Enghsh jovirnal stated with much positiveness that this cotton hull fibre was "only suitable for browns and wrap- pings." The real fact is that tnis hDre is easily reduced to a pure white stock wholly free Irom any sign of hull, and a failure to secure as good results from this neglected fibre as from a good grade of cotton rags is a reflection upon the skill of the man who tries to handle it rather than upon the quality of the fibre itself. In my report of last year I referred to the fact that on the average 22.750,000 toiis of cotton stalks are each year burned or plowed under, or otherwise wasted. These stalks have a woody structure which, lends itself readily to treatment by the sulphite process, yielding a fair proportion of fibre well suited for the pro- duction of paper of the lower grades. It is, of course, not teasiole to attempt the removal of the bark, but this is so broken up and distributed through the sheet as to be unobjectionable in papers for a wide variety of use. There are, however, undoubted difificul- ties in the way of the preliminary handling, transport and storage of the material by reason of its bulk. Somewhat the same difficulties are encountered in any large scale attempt to utilize the first class fibre which in almost unlim- ited amount has been shown to exist in the outer shell of the corn stalk. The exceptionally high tides which occur in the Gulf of Cali- fornia during the full moon of May each year, acting together with the melting snows from the mountains, cause the Colorado River to overflow its banks along its lower reaches, which are thus built up of rich, alluvial soil. The climate is almost tropical, the temperature often reaching 135 degrees in the sun. Great stretches of this country are covered with wild hemp, which, under these favoring conditions, grows luxuriantly. Many tracts are over 100,000 acres in extent. No data is available as to the yield of fibre, but hemp is known to grow to a height of 15 feet in eighty days, and to yield 1,500 to 2,000 pounds of actual fibre per acre. I need not tell you that this fibre is of the very highest grade for any of the purposes of paper making. The so called marsh hay, which is said to closely reseml^le esparto in structure and the paper making quality of its fibre, grows wild in great abundance over large areas in Canada, while the American wild rice, Zizana aquatica, also grows in such pro- fusion that 100,000 tons a year are available on the shores of the Canadian lakes alone. Paper making tests made in England rank this fibre also with esparto. Especially noteworthy in the developments of the year is the seri- ous and general revival of interest in bamboo as a source of paper stock. Its superlative value for this purpose was urged, you will remember, by Routledge in 1875 after his introduction of esparto into England. You may also remember that my report of last year refers to the very favorable conclusions as to bamboo reached by R. W. Sindall in his report to the British Government on avail- able sources of supply of paper stock in the British Colonies. These conclusions are now amply confirmed by Raitt, who has recently published the results of numerous experiments of his own on the mill scale in Burmah, Bengal, Malabar and Straits Settle- ments, and by Richmond in the laboratory of the Bureau of Science at Manila. Raitt finds in bamboo a really inexhaustible raw material. He recommends the establishment of bamboo plan- tations so arranged that one-third of the whole plantation shall be cut over every year. This will secure absolute permanence of growth, and, in fact, such systematic cropping will increase pro- duction. Raitt finds the yields of bamboo to be ii tons per acre where the growth was poor, i8 tons with moderate growth, and 44 tons per acre with luxurious growth. The best yields of fibre, 44 per cent., and the best results in treatment were secured with three year old- shoots. The internodal pieces alone were digested, the rejected nodes amounting to 8 per cent! of the total weight. The stems were cooked at 6o pounds pressure for ten hours, with 30 pounds of 76 per cent, caustic per hundredweight of dry bamboo. The fibre bleached to good color, with 20 pounds of bleach per hundredweight. Raitt further finds that the stems were easily reduced by the sulphite process, giving a yield of 51 per cent, and bleaching to a brilliant white, with 16 pounds to the hundredweight. He esti- mates that in a 200 ton sulphite plant at Rangoon the cost of bamboo fibre will be $24.30 a ton. Richmond, whose excellent work in the Philippines deserves the highest credit, finds that it is quite unnecessary to- remove the nodes prior to cooking, provided the stems are first passed through crushing rolls and afterwards, for convenience of pack- ing in the digester, cut to 3 or 4 inch lengths. He obtains from the difi^erent varieties of bamboo yields of 40 to 43.7 per cent, of bleached fibre by the soda process. The sulphite process gives 43.5 bleached fibre, which puts bamboo on about the same basis as wood in this regard. The unbleached sulphite was nearly as white as the thoroughly bleached pulp. The importance of these figures becomes evident when we consider that we have in bamboo a raw material directly com- parable to wood in many fespects, but with no bark to remove, and much more easily reduced to pulp by either the sulphite or soda process. Bamboo requires a weaker liquor and much less of it, and is reduced in less time with far less fuel consumption. A properly situated mill is assured of a regular supplv. with a yield per acre everv third year greater than that resulting from the cutting over of well grown spruce lands of good stand. Bamboo, in fact, has been known to grow 2 feet in three days in the Phil- inpines. It is interesting to- calculate from Raitt's figures for moderate growth that only about sixteen square miles is required to maintain indefinitely the supply of bamboo for a too ton mill. Two other raw materials for paper stock among those studied by Richmond demand special mention. These are Cogon grass and Abaca or manila waste. Cogon grass grows from 2 to 4 feet high in even stands on open lands, foot hills, and mountains in the I'hilippines. In content of cellulose, as well as in general com- position, Cogon closely resembles esparto and yields with equal ease to treatment. It gives a very fine, clean paper, stronger and with more snap than esparto. It "does not, however, bulk as well, but for many uses should prove even more valuable. The hand cleaning of manila fibre involves the production of much waste, while all of the several fibre stripping machines now on trial in the Philippines produce waste in nuich larger propor- tion. For every ton of merchantable manila fibre produced in the Philippines, more than a ton of fibrous waste is made in the process of hand stripping, while nearly four times as much waste is now lost by the methods of machine stripping. This Abaca waste constitutes one of the most intrinsically valuable raw materials anywhere available for paper makers, and will not be treated as a waste much longer. Richmond and others have shown conclusively that the Abaca waste is very easily reduced by alkaline treatments, and further that it bleaches readily and is suitable for paper of the very highest grades. The more general introduction of fibre cleaning machines is certain to extend the manila hemp industry and to greatly increase the already large quantity of this waste available for treatment on the spot or for export. The yields of fibre on the hand stripped waste are about 42 per cent., and on the machine stripped about one-quarter less. It is obvious that the fibrous raw materials which we have been considering require somewhat dififerent treatments to meet their individual requirements, and that they are in most instances too bulky for profitable transportation. The natural line of their development is, therefore, the manufacture of pulp and half-stuff upon the spot for trans-shipment to the mills of paper consuming countries. The methods required are for the most part simple and well adapted for introduction into small local plants. For lack of time this report must pass by the numerous pro- posals made during the year for the utilization of other less prom- ising fibres and fibrous wastes. Mention should, however, be made of Perini fibre (Canhamo Braziliensis Perini) recently discov- ered by Dr. V. A. de Perini, of Rio de Janeiro, and now attract- ing considerable attention. In its essential features Perini resem- bles jute. Coming now to the narrower questions of detail in the chemi- cal technology of paper making, we find that the vear has been marked by no development of the first importance. Under an arrangement with the American Chemical Society, your chemist and his assistants have abstracted all articles appearing in our own or foreign journals relating to cellulose and paper makii A few of these call for mention in this report. ms. The discovery of a cellulose peroxide has been announced by Cross & Uevan, but the existence of the compound has been doubted, and is in fact doubtful on good chemical grounds. The Cross & Bevan method of analysis of fibrous substances has been materially improved by Dean, in so far as it relates to- the deter- mination of cellulose. Berge has proposed as a new test for ground wood a solution of 2 grams of Para Nitraniline in 100 cc. of hydrochloric acid, of specific gravity, 1.06. It stains lignified fibres a brilliant orange, passing in extreme cases into brick red. The reagent has the advantage of being much more permanent than phloroglucin. Ebert has studied the process of wood grinding and finds that a small amount of chamical change is induced by the action of water and the heat of friction. In hot grinding this action is materially increased. Steaming and boiling render a still larger proportion af the encrusting matter soluble. He has developed a process by which he claims to convert ground wood into a chemi- cally clean pulp resembling sulphite. Kirchner reports the following advantages from the use of hot grinding. The pulp, after being pressed to 50 per cent, air dry, can be preserved for a year or more without deterioration. The heat of grinding probably produces a temperature between the wood and stone sufficiently high to kill all micro-organisms. The pulp is whiter than cold ground pulp, and finally there is no trouble from clogging of the screens with rosin. Sulphate pulp and Kraft paper are now being made by the Brompton Pulp and Paper Company, at East Angus, P. 0. Interesting results of Canadian practice in making soda fibre are given by De Cew, with percentage yields and details of treatment, in case of spruce, hemlock and five of the more com- mon deciduous woods. The latter can now be reduced in about four hours. The shortening of time has been found to increase the yield and give a sounder and stronger fibre. There is comparatively little to report regarding the sulphite process, although it has been demonstrated that unusually resinous woods may be satisfactorily reduced by the use of liquors espe- cially high in free acid. The so-called turpentine recovered during the sulphite cook is now said to be not turpentine, but cymene. A t-eview of the history of the recovery of the turpentine and of modern practice in the sulphate process is given by Knpsel in the Wochenblatt. Bender has published in Papier Zeitung an interesting report on diseases caused by handling rags, and the means taken to avoid the danger and discomfort from the rag dust. Eichhorn. in the Wochenblatt, gives valuable data on the cause and loss of weight in cooking, beating and bleaching rags. The losses of weight found in practice in making the following materials into bleached half-stuff were: I'd- Cent. New white linen and cotton 25 Russian linen 29 New calico 25 Swedish linen 29 Strong- half linen 37.5 Half bleached linen 29 Bleached excelsior cellulose 5 Colored calico 33-5 to 36 . 5 Jwte C 50 Bleached No. i cellulose 5 "Half wool" 47 Half bleached No. 2 cellulose 6.6 Nussbauin and Ebert find, as the result of experimental study, that bleaching with alkaline solutions is very slow, and that in acid solutions the speed increases as the square of the acidity of the solution. Within the usual limits the speed of bleaching doubles for each 7° C. increase in temperature. Be- tween relatively wide limits the effect of bleaching is independent of the concentration of the hypochlorite solution. With an equal consumption of chlorine the samples bleached at higher tempera- tures are whiter. The more acid the solution the more chlorine is required to produce the same white, and, finally, the more acid the solutiou the greater the loss of fibre substance. As to rosin sizing, the only novelty of note is the preparation of dry rosin size, which in appearance closely resembles ordinary rosin, and which dissolves readily in hot water for use in the ordi- nary way. Weingaertner has patented (U. S. Patent 828,004) a moist- ure and grease proof paper prepared by saturating paper with a solution of casein dissolved in sulphurous acid to which a soluble fluoride has been added. The paper thus treated is then coated on one side with paraffin. A very flexible and tenacious paper has been brought out in France (French Patent 845.386), where it is made by superficially parchmentizing the sheet by a method which precludes action on the central layers, which remain in their original fibrous condition. Dalen, of the Koniglichen Materialpriifungsamt. has pub- lished the interesting and important results of a study of the properties, sources and tests for many kinds of spots and dirt appearing in paper, and outlines a scheme of procedure which in most cases enables the origin of the dirt or spot to be determined. The German authoritv. Herzberg, has made during the year sev- eral notable publications bearing upon the durability of paper. The Materialpriifuno-samt is now testing samples frotri about 400 books and periodicals furnished bv the Librarv of the University of Berlin. One conspicuous instance is given of a work published in 1 88 1, which is now falling to pieces. T^e fibre composition was : 7 Per Ceil I. Linen 40 Cotton 30 Wood fibre 25 Straw pulp 5 The ash was 21 per cent. This example shows clearly that the fibre composition is not the only important consideration, for this paper was 70 per cent, rag and contained no lignified fibre. The physical tests are therefore shown to be quite as important as the composition, because the best of fibre can be so handled as to make the poorest of paper. In this connection it is interesting to note that the requirements as to the ash in "normal" papers laid down by the German Government in 1881 were dropped from the specifications of 1904. As to the propriety of this change, Herz- berg states that there is no^ reason why a paper containing mineral fillers should deteriorate any faster than one without fillers, if they have initially the same physical properties. In another communication Herzberg presents the results of strength and elongation tests of 162 papers of Class i, all rag without fillers ; 224 of Class 2, rag with not over 25 per cent, other pulp and not over 5 per cent, ash ; and 255 of Class 3, any pulp except lignified fibre and not over 15 per cent. ash. These papers had been lying open to the air and to a little light for twelve years. About 80 per cent, of all classes are found to have decreased about 5 per cent, in strength and about 10 per cent, in elongation. The small increases noted are believed to be due to variations in the samples and the testing machines. It is signifi- cant that there is no very marked difiference seen in the deteriora- tion of the three classes of paper, and upon the whole the results secured are very satisfactory as bearing upon the probable life of papers generally. With reference to this same important subject it is gratifying to note that the Committee of the Society of Arts, London, which made its classic report upon the deterioration of paper in 1898, has now been reappointed with the changes and additions suggested or made necessary by time, and will extend its study of the subject with a view to possible recommendations. The year has seen an unusual number of new books relating to paper and paper making. Among these should be mentioned : "The Treatment of Paper for Special Purposes," translated from the German by Andes. "The Paper Mill Chemist," by Stevens. Vols. Ill and IV of Beadle's "Chapters on Paper Making." The third and enlarged edition of Herzberg's well known "Papier Priifung." The interestina: .chronicle of the development of paper mak- ing in England entitled "The Paper Trade," by A. Dykes Spicer. and "The Encyclopedia of the Paper Industry," by J. S. Jensen, appearing in the Danish journal, Papier Tidende. 8 LIBRARY OF CONGRESS illlilliiliiill 018 371 468 5 ♦ LIBRftRY OF CONGRESS 1 018 371 468 5 «