C&EÏM'S A N N U A L REVIEW O F DEVELOPMENTS IN cial dishwashing as well as in the household. Acceptance of liquid light-duty products may have a bearing on the fact that one well-known brand of granular light-duty syndet has been changed to an all-purpose product, sold under the same name as before. Three new syndet bars—at least one containing some so» p—have appeared for test marketing, a field where there was previously only one. They are higher in price than soap but are described as longer lasting. Indications are that people buy a detergent more on satisfactory performance than on price, providing the latter is within reason, which suggests that syndet bars may be headed toward taking some substantial portion of this half-billion-pound market. The Federal Trade Commission rendered a decision in November that the manufacturers of well-known syndets should stop claiming that these wash clothes "just as clean" without rinsing as with rinsing. Meanwhile, no-rinse has died a natural death to be replaced by claims of syndets washing clothes as clean without bleaching as soap will with bleaching. The presence of optical bleach, in use now for some years, is the answer.
Foreign Four of t h e leading granular syndets are now made in Britain on modified formulations by subsidiaries of the three leading American soap companies. Shortages of phosphates dictate modifications there. Plants for the production of syndets are in operation in many countries; one was opened in Pern in August. Theoretical Correlation of various published x-ray measurements suggests that there are three main types of micellar configuration of detergents, whether soap or synthetic in nature, and equilibrium between different types may exist in a solution. Laboratory studies continue to emphasize the difference in performance of detergents in soft and hard water. For example, sodium alkyl aryl sulfonate plus sodium sulfate only, is reported in Launderometer studies to give better detergency on wool in 300 parts per million hard water than does a commercial phosphate-built detergent. In distilled water the opposite is true. At high concentrations, 0.2% or more, commercial soap gives better detergency than either of the syndet products in distilled water, but
much poorer results than either in 300 parts per million water. Sorption studies made with use of radioactive tracers (sulfur-35 for a sulfonate, and carbon-14 for soap) show that both soap and alkyl aryl sulfonate are sorbed to a greater degree o n wool than on cotton. On wool both physical and chemical sorption occur, the former rapidly, the latter slowly. Soap is sorbed by cotton more slowly than alkyl aryl sulfonate, but is much more difficult to desorb. Builders, temperature, a n d t h e hardness of the water affect the result. In distilled water it is probably the fatty acid which is sorbed; in hard water, the calcium and magnesium soaps. These and other investigations suggest that sorption of the detergent by fabric may b e one of t h e important factors in the over-all detergent process. The effect of builders on such sorption may enter into their useful functioning, also the sorption of detergent and builders by soil. As detergency studies become a little less empirical, more and more factors are brought to light which can affect the result. (The author expresses appreciation for the editorial assistance of Cornelia T. Snell. )
ROBERT B. HOBBS and WILLIAM K. WILSON, National Bateau of Sî&rsd&rds, Washington, D, C
Pulp a n d Paper . .
•
Industry
displays
its
optimism
with a $ 6 0 0 million outlay for n e w mills and modernization in the period 1952—54 PRODUCTION in the paper and paperboard industry was again showing a definite upward trend toward the end of 1952, following a weakness that had extended from mid-summer of 1951 to July, 1952. The American Paper and Pulp Association's production ratio (production as percentage of normal capacity) had gradually declined from 100 in June, 1951 to 76 in July 1952 but recovered to a level of 91 for October. The paperboard operating ratio of the National Paperboard Association had shown a similar, but sharper, de40
cline from 103 in June 1951 to 71 in July 1952 but rose in even more decided fashion to 96 for October. This optimism in the industry is reflected in a huge volume of spending and plans for new mills and modernization in the three-year period 1952-54. Some of the larger projects, a s listed by "Paper Mill News," are summarized in the table. The total new capital for these and other projects was estimated b y the same source at $600 million. Our Canadian neighbors are experiencCHEMICAL
ing a similar trend. Prominent projects include a 300,000-ton expansion of newsprint production by Bowater in Newfoundland, a new $65-million pulp and newsprint mill by Celgar Development Co. in British Columbia, trie $21-million Elk Falls mill in British Columbia, which began operation in September 1952, St. Lawrence Corp.'s $22-million expansion program in Quebec, and Westminster Paper Co/s $25miliion bleached sulfate mill planned for British Columbia. An interesting major foreign development is a $45-million AND
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THE CHEMICAL A N D CHEMICAL PROCESS INDUSTRIES
chemical pulp and newsprint mill for the New Zealand government, to be built jointly by two American companies and a New Zealand company. Southward Shift A significant aspect of tlie new projects is the acceleration of the southward shift of the center of gravity of the pulp and paper industry. Of the 10 major projects listed, three are in Florida, three in Georgia* and two in Tennessee. Tn mr«ny cases, advantage is being taken of the more rapid growth of Southern softwoods to operate timberlands on a sustained-yield basis. The industry in the North and East is by no means stagnant, however. In addition to the major project listed for Maine, other multimillion dollar projects are scheduled or have just been completed by the Brown Co. in New Hampshire, American Box Board Co. in Michigan, Clifton Paper Board Co. in New Jersey, Container Corp. in Pennsylvania, KimberlyClark and Nekoosa-Edwards in Wisconsin, Mead Corp. in Ohio, and Minnesota and Ontario Paper Co. in Minnesota. Though the continually increasing demand for paper products, relative to the supply of softwood pulp, had not yet reached a highly critical point, foresighted persons in the industry were engaged in many development programs designed to anticipate future needs. Semichemical pulping of hardwoods was definitely expanding, and in September 1952 the Pulp and Paper Magazine of Canada published an estimate that the production of semichemical pulp for corrugated board would exceed 3500 tons per day by trie end of the year. Two new mills for the manufacture of semichemical bond, writing and printing papers, using aspen and other northern hardwoods, were reported in operation, while the successful use in VOLUME
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Canada of unbleached aspen neutral-sulike semichemical pulp for newsprint was also noted. The installation of modern instrumentation in paper mills continued its rapid growth. Since the end of the war, automatic controls for temperature, drying operations, pH, concentration of chemicals, and push-button control of machinery have become almost commonplace. An interesting recent development appearing in many plants is the beta-ray thickness gage. In one form it permits the rapid sequential measurement of substance at four locations across the moving web and allows the machine tender to detect immediately any significant variation in the substance of the paper, as well as furnishing an automatic, permanent record. Growth and forest management of southern pine were the subjects of a broad program at the North Carolina State College at Raleigh, while the utilization of this material, as well as scrub oak and other regional sources of fibers, was being investigated by the University of Florida at Gainesville, the Herty Foundation Laboratory in Savannah, and the Forest Prod-
JANUARY
5,
1953
ucts Laboratory at Madison, Wis. The Northern Regional Research Laboratory at Peoria continued to lay a solid technological foundation for eventual use of wheat straw, with a potential supply of tens of millions of tons annually. Attention was again directed toward sugarcane bagasse by a report from t h e Department of Commerce to the House Judiciary Committee, in which it was concluded that the production of newsprint from 100% bagasse was feasible. General opinion in the industry, however, was that the future of bagasse as a papermaking fiber was more likely to lie in its use in mixed pulps with other fibers, as indicated by the highly successful press rui» of 168,000 copies of the Chicago Tribune, using a bagasse-softwood newsprint developed by the Northern Regional Laboratory. This view was said to be reinforced by the fact of the relatively small annual amount of bagasse available in the continental United States and the economic problem of replacing its fuel value to sugar mills from other sources. De-inking and reclaiming of waste paper as a means of augmenting the supply of fiber continued to receive attention, particularly as a result of a seminar on the subject held by the Technical Association of the Pulp and Paper Industry in February, and the continued development and availability of equipment for the flotation process of de-inking. The possibility of tropical hardwoods as a tremendous future source of papermaking fibers was emphasized b y a symposium conducted by the Institute of Paper Chemistry late in 1951 and reported in the technical literature during 1952. Other programs of the institute that continued to be of major value to the industry were its series of publications on instrumentation .aid physical test methods and its thorough bibliographical service. The institute and the New York State College of Forestry were among the principal sources of publicly available new technological information on neutral sulfite pulping and other developments. Research on paper and pulp continued to receive an ever-increasing stimulus from fundamental research on cellulose and wood during the year. Similarly, there was maintained an important exchange of
41
C&EN'S ANNUAL REVIEW OF DEVELOPMENTS IN ideas between these fields of s t u d y a n d those of synthetic high p o l y m e r s , elec tronics, sugars, starches, a n d otheirs, F r o m these varied areas of research caznie a d d i tional know-how to solve probieims in p u l p a n d paper technology, such as improve m e n t s in pulping, instrumentation, and t h e manufacture of papers witha specific rheological properties, to m e n t i o n a few. Research in cellulose c h e m i s t r y has em phasized problems relating to R u e struc t u r e . Heterogeneous hydrolysis lias b e e n explained as a «rapid reaction in t h e amor p h o u s regions of t h e cellulose structure w i t h a much slower reaction in time crystal line areas. The hydrolysis rate levels off sharply when tlie amorphous m a t e r i a l has b e e n hydrolyze*d, a n d the a v e r a g e d e g r e e of polymerization a t this point is called the leveling-oiF DP. The levelimg-off D P values are frequently similar for n a t i v e cel lulose. Recent work indicates, howevei, that the residues obtained h a v e entirely different properties, even though the aver age DP's from viscosity data aire similar. T h e s e properties appear t o be associated w i t h fiber orieatation as measured! by linear swelling and x:-ray diffraction. T h e frag m e n t s or residimes resulting from "hydrolysis of cellulose to the leveling-off DP, are considered by some to b e f u n d a m e n t a l building units o f the cellulose firoer. More research on this problem is und-er w a y . T h e degradation of cellulose by highenergy radiation h a s attracted consider a b l e interest. "Work on t h e d e p o l y m e r i z a tion of cellulose by x-radiation sunder dif ferent atmospheric conditions h a s shown t h a t the role o£ moisture is very important, a n d that dried samples were m o s t severely depolymerized- This correlates with ear lier work on She effect of far ultraviolet light (2537 -Α.). H i g h - e n e r g y c a t h o d e rays cause a decrease in crysta-Ilinity and polymerization, of t h e cellulose a^nd decom position of the glucose a n h y d r i d e units to noncarbohydra.te materials. Studies of the kinetics of hydrolysis of the m a t e r i a l ir radiated with cathode rays h a v e shown t h a t the rateo* hydrolysis of t h e crystalline areas is greatly increased, p r e s u m a b l y b e cause of a rartdom depolymerization. This results i n an Improved ratio of sugar pro duction to sugar destruction i n acid hy drolysis. An economically feasible appli cation of this ^principle should r e s u l t in t h e efficient utilisation of waste w o o d in t h e production of sugars. Several articles have ^appeared recently o n end-group assay which m a k e use of t h e Kiiiani reaction to estimate t h ^ i aldehyde groups a t the ends of the cellulose chains. Probably the ^most sensitive m e t h o d of this t y p e is the ooie using t h e r a d i o a c t i v e C u isotope. This has been applised only to dextrans, but it should be ap»plicable to other polysaccharides, i n c l u d i n g cellulose, which a r e no* affected b y a slmghtly alka line medium. An interesting development i m the m a n u facture of specialty papers is -an all-glass paper made from very fine ;glass fibers without the aid of a binding: agent, re
42
lose were published during the year. Hy pochlorite bleaching is still the old stand by although chlorite, chlorine dioxide, and peroxide bleaching a r e becoming more popular. Chlorite and chlorine dioxide are especially popular for the final bleaching stage, and are reported to b e less degrad ing t o the cellulose t h a n hypochlorite. At the testing conference of t h e Tech nical Association of t h e Pulp a n d Paper Industry at Syracuse in September, the status of approximately 50 methods was discussed b y t h e following committees: pulp testing, nonfibrous materials testing, Statistics in Quality Control microscopy, chemical methods, packaging I n recognition of the modern trend to materials testing, paper testing, a n d wax ward the use of statistics, more and more testing. Many T A P P I standard methods articles a r e appearing on t h e use of statis are developed in cooperation with ASTM tics in quality control in t h e mill and in subcommittees o r ACS Cellulose Division design of experiments in the laboratory. subcommittees. An example of this is the A special course in statistics for the paper work on a method for disperse viscosity industry, given during the summer at the of p u l p which is being carried out at the University of Maine, presaged a growing Institute of* Paper Chemistry and financed use of statistical engineering in the indus by a TAPPI grant. try. A tangible recognition of the effect of Following t h e brilliant researches of the the polymolecularity of cellulose a n d cellu staS* of t h e Swedish Forest Products Re lose derivatives on their physical proper search Laboratory on the rheological p r o p ties is the great interest in methods for erties of papers, more thought is being the determination of chain length distri given to paper as a visco-elastic material, bution, which has culminated in a pro with the result that botli methods of m a n u posed ACS method. Also, several papers facture a n d methods of testing should be were presented at t h e ACS Atlantic City improved. This should eventually allow meeting in September on various prac a m o r e intelligent selection of raw mate tical phases of t h e determination of rials and manufacturing procedures in the molecular weight a n d molecular weight development of "tailor-made'* papers. distribution. T h e testing of dissolving pulps in* rela i n connection with t h e lignin problem, the economics of sulfite waste liquor con tion to their performance is receiving con tinues in the red although satisfactory siderable attention. It has b e e n found methods, technologically speaking, have that small amounts of impurities, such as been developed both for disposal and for pentosans or lignin, can cause consider utilization. It has been estimated that able filtering difficulty. This m a y b e an about $7 million h a s been spent o n re indication that t h e morphological structure search on sulfite waste liquor in the past of t h e cellulose has not been degraded decade. Present research may b e divided sufficiently to obtain the desired reactivity. into tour categories : ( 1 ) recovery of p u l p ing chemicals, ( 2 ) lignin fraction, ( 3 ) Instrumentation Assumes Increasing Importance sugar fraction, and ( 4 ) whole liquor. T h e whole liquor is being evaluated • Recognizing the importance of instru for use a s a road binder, although its use mentation in research, testing, a n d quality in this connection would b e seasonal. control, t h e American Paper and Pulp As Evaporation and burning appear to b e sociation maintains a program of research promising, but the capital outlay is high. on instrumentation at t h e Institute of A report from one mill which has been Paper Chemistry. Reports to t h e Ameri evaporating a n d burning calcium-base and can Paper and Pulp Association are pub ammonia-base sulfite liquors indicated that lished in Tappi, the monthly magazine of this might b e economically feasible al the Technical Association of the Pulp and though any one of several factors could Paper Industry. T h r o u g h November 10 swing t h e balance either way. Vanillin is reports have been published, including being p r o d u c e d from t h e lignin fraction, one which liscussed the status of t h e in belt the d e m a n d is rather small, and unless strumentation program, an excerpt of n e w uses are found for vanillin, this outlet which follows: "To illustrate t h e impor is definitely limited. T h e sugar fraction tance and scope of this program, there are is being investigated for the production at least 4 6 properties of paper of sufficient of yeast for use in animal feed. An obvious importance to have inspired instruments solution to t h e sugar fraction problem for their evaluation, and there are more would b e fermentation to industrial al than 72 instruments available for measur cohol, b u t competition is too keen from ing these properties. Twenty-nine of these o t h e r r a w materials, such as molasses and 46 properties have at least b e e n touched ethylene from petroleum refining. on in some report, and over 60 of t h e 72 A number of reports on typical bleach instruments h a v e b e e n studied in detail i n g operations and the deteriorating effect or used for comparison with instruments of different bleaching procedures on cellu so studied." ported by the Naval Research Laboratory and the National Bureau of Standards. This product is at present too costly for general u s e , b u t its unique filtering and electrical properties give it value for special purposes. It is now b^ing pro duced commercially, and, as an interest ing side light for the analyst, at least two companies are making filter papers from glass fibers. Experimental papers from quartz a n d ceramic fibers have been re ported, b u t these are not in commercial production.
CHEMICAL
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NEWS
