era! new projects proposed for new nitrogen fixation plants, b u t there seems no possibility t h a t a n y of them will come into production in 1948-49 Several existing commercial a m m o n i a plants have increased their capacity or are in t h e process thereof. T h e Army-controlled plant at E t t e r , Tex., operated now by the Phillips Chemical Co., a subsidiary of t h e Phillips Petroleum Co., is in process of installing an additional unit which will increase capacity by 60,000 tons ( N ) a year. The Army has an option on the entire production from this plant for several more years. T h e Army is installing at San Jacinto Ordnance Works near Houston, Tex., two fixation units formerly in the Missouri Ordnance plant a t Louisiana, Mo. T h e o u t p u t of this plant is expected likewise to go to occupied areas abroad. T h e increased production in certain of the commercial plants may not all go into agricultural channels. There is an increasing demand for anhydrous ammonia and its compounds for industrial use in t h e production of plastics and synthetic fibers and for refrigeration. There is an ever-growing demand -also for methanol, which can be produced with the same equipment t h a t is used for anhydrous. Several new plants for the production of urea have been rumored. Such plants would use a n h y d r o u s ammonia as tiieir base material. Some of the urea produced would no d o u b t go into fertilizers, but animal feeds a n d plastics likewise are calling for urea. Distribution of Not Uniform
Increase
Although estimates indicate t h a t the total agricultural nitrogen available will be some 7 % more t h a n last year, they are based on almost perfect uninterrupted
T
Nitrogen (N ) Available phosphoric acid (P2O&) Potash (K2O)
Textile
Chemical
operation of all plants. Labor or transportation difficulties or major breakdowns in any of the large producing p l a n t s could alter t h e situation overnight. I t m u s t also be pointed out t h a t this over-all increase will, in all probability, not be evenly distributed into all consuming areas. I t now seems quite certain that some heavily consuming areas, particularly the southeastern states and New Knglanri, will receive notably less nitrogen t h a n last year. T h e distribution pattern will be different because of geographic and economic factors which constantly change. Phosphoric
Acid
A number of new plants for t h e production of normal superphosphate have been p u t into operation during the past year and at least four plants for the production of concentrated superphosphates are under construction or just completed. Projects are also under way for producing ammonium phosphate. Several of these normal plants, two of the concentrated plants, and one ammonium phosphate plant are in the newly expanding fertilizer-using territory in the West. Last year production of superphosphate's for home use of all grades reached a total equivalent of 2 million tons (P 2 0 5 ). Production for 1948-49 is estimated at a somewhat higher figure. Since exports a n d imports are expected to remain about the same, it would seem t h a t some 100,000 t o n s additional (P20&) would be available for domestic use in the form of superphosphate. Production of normal superphosphate in a number of plants has been materially curtailed because of the delay in t h e delivery of ammonia solutions which are necessary in order that the superphosphate may be utilized to absorb these solutions and in turn be moved from bulk storage. Even
Consumption, 1947-48, Short Tons 888.000 2,000,000 920,000
Estimated Supplies. 1948-49, Short Tons 955,000 2,100,000 1,020,000
and Fiber Developments
Increase,
%
7.5 5.0 11.0
with t h i s record production, the capacity of existing superphosphate plants is not y e t nearly r e a c h e d . Unless t h e soil conservation program, of the U S D A is materially increased, there would seem to be enough superphosphate to m e e t all needs. Potash No n e w domestic sources of potash h a v e come i n t o production this year, b u t nearly every o n e of* the existing operations has expanded somewhat. T h e result is t h a t a n all-time peak of potash is in sight. Consumption of potash in the United States i n 1SM7-48 (continental and offshore) a m o u n t e d to 920,000 tons ( K 2 0 ) . Production f o r 1948—49 is expected to exceed l a s t year's by 105,000 tons (K2O), b u t exports a r e to be 5,000 tons higher leaving a net increase for use in this count r y of. 100,000 tons, making a total of 1,020,000 t o n s (lv 2 0). I t is expected t h a t irntports will remain about the same a t 25,000 t o n s (K 2 0). Most of this import t o n n a g e will come from France. Such excess a s Spain may have for export will p r o b a b l y remain in Europe. Frequent r u m o r s are heard concerning offerings of potash from the Russianoccupied a r e a of G e r m a n y . So far, it would seem t h a t the prices asked and the transportation difficulties involved would preclude any probability of its being used here in a n y quantity. The s u p p l y picture as it now shapes u p seems t o be a b o u t a s set forth in the table below w h e r e i n the estimates for 1948-49 supplies are compared with 1947—48 consumption figures. It m u s t be remembered, however, t h a t these a p p a r e n t increases are over-all figures a n d tfiey do not mean t h a t every consumer c a n expect to get more plant food t h a n Last year. Also, labor and transportation difficulties might seriously curtail production a s to any of the commodities. T hese estimates are made with no anticipation of adverse conditions of production. May t h e y be fulfilled and even exceeded!
in MOtU \
Textile Research Pays Dividends ROBERT
E.
WRIGHT AND MILTON HARRIS,
IIarris Research Laboratories, Washington, D. C.
Much fundamental research i n textiles, carried on for years previous, has come to fruition in 1948. Also typical of t h e year's accomplishments arc alterations in the actual c o n struction of fabrics to fit t h e m for protective finishes J . H E trend in textile developments during 1948, as in recent preceding years, gives evidence t h a t textile research is emerging from t h e " i n v e n t o r ' s " stage, with its
VOLUME
2 7,
NO.
relatively slow one-man attack on a problem, to the era of the research team, in which a b a t t e r y of skills is brought to bear on a project a n d t h e intensity of effort is
1 » » .JANUARY
3, 1 9 4 9
greatly increased. I t is this shift in a p proach which, is primarily responsible for t h e major gains in textile products a n d processes over the past few years a n d which promises early solutions to some of t h e i n d u s t r y ' s most important problems. In a d d i t i o n to t h e numerous research activities by private companies in the textile a n d textile chemical fields, a substantial amount of work is being under-
S3
taken or sponsored by government agencies and industry associations. Typical of these projects are those announced by the American Wool Council, t h e International Wool Secretariat, a n d t h e Textile Research Institute, which a r e joint sponsors of a four-year program of fundamental research into the physical a n d chemical characteristics of wool; b y the D e p a r t ment of Agriculture, which is sponsoring research by several agencies in both wool a n d cotton; and b y t h e National Cotton Council in the utilization of cotton. Chemical
Developments
Results of work reported during the year b y groups in the United States and abroad showed continued interest in investigations into the molecular structure and chemical reactions of cellulose, fibrous proteins, and synthetic polypeptides, and a wide range of man-made materials t h e fiberforming potentialities of which are under investigation. Information obtained in these studies contains t h e seeds of new methods of modifying n a t u r a l fibers (as in theacetylation of cotton a n d the reduction a n d rebuilding of cross-linkages in wool), improved dyeing procedures, and new synthetic fibers the properties of which may be custom-made for specific e n d uses. Several papers were concerned with the crystalHnity of cellulose, while other groups reported on t h e 8f»id n a t u r e of cotton a n d jute. An investigation of the properties of phosphorylated cotton cellulose showed it to h a v e a high cation-exchange capacity of possible industrial value. I n t h e protein fiber field t h e nature of the felting p h e nomenon in wool continues t o receive attention, together with methods of controlling it. Also noteworthy were reports of studies on the combination of casein with formaldehyde and of the phenomena associated with water absorption of proteins. Reports of industrial research showed considerable activity in the area of scouring, bleaching, dyeing, a n d other wet processing of textiles. Synthetic detergents have received attention for wool scouring and are rapidly replacing the classical soap-soda ash systems. Studies of the use of fluorescent dyes for the "optical bleaching*' of various textile m a terials have shown much promise and m a y change some of the older approaches to this problem. One paper described the use of a sulfuric acid steep for increasing the efficiency of cotton desizing operations. Continuing efforts to produce improved tire cords were reflected in reports of investigations into elastic properties of cotton, rayon, a n d nylon cords, a n d into the effects of heat on rayon cord in various atmospheres. A new vinyl resin coating combining flame, weather, a n d abrasion resistance with reduced application cost is expected t o compete with t h e most economical coating materials in a field heretofore dominated by the urea-formaldehyde a n d
24
melamine-formaldehyde rerins. Interest in t h e latter materials continued a t a high level, however, as shown fc>y the a n n o u n c e m e n t s of several new finishes in which t h e y are utilized to impart crease resistance, water repellency, and altered h a n d a n d appearance to fabrics m a d e from a variety of fibers. I n the field of warp sizing materials t w o newcomers are polymetfiacrylic acid, for use on nylon warps, and sodium carboxymethylcellulose, which has a l s o been recommended for use as a thickener a n d carrier for textile printing; pastes, a s a d y e ing assistant, and as a builder f o r detergents. N e w dyeing and printing techniques a n d reagents announced in 1948 included a caprolactam composition for printing on nylon, procedures for metachrome dyeing using cationic a n d nonionic agents, a n d methods for obtaining illuminated discharge effects on cellulose acetate- Special interest was shown in processes for v a t dyeing of wool which will make available m a n y shades of great fastness heretofore restricted t o cellulosic materials. New
Fibers
Karly in 1948 Vicara, a new regenerated protein fiber, was made available t o the industry. I t has found immediate application in the hat industry a n d in blends with other fibers. T h e new material is extruded from a solution of zein, coagulated, and subjected to after-treatments which yield a fiber the mechanical properties of which are believed to be satisfactory for a wide range of applications. The stability of this fiber during scouring a n d dyeing processes is far superior -to that o f protein fibers which have appeared on t h e market previously. Announcements of limited commercial production of Vinyon N a n d of l a b o r a t o r y scale pilot plant production of Orion were accompanied by release o f considerable information concerning -the composition, production, and properties of t h e s e new synthetics, although experimental development of both had b e e n previously reported. Vinyon N , an acrylonitrile-vinyl
Tablc I .
Consumption
and Price
Trends
D u r i n g t h e p a r t of 1948 for which d a t a are available, consumption of textile fibers was generally higher t h a n for t h e corre-
(In millions of pounds) IImport? m p o r t ? for Change,
%
42^>.8 177.8 604.6
454. 8 236. 6 691.4
+ 6.6 + 33.1 + 14.4
\\\Z£ . y
151 . i 71.2 222. 3 913.7
+ + + +
47.1 18O.0 784.6
Fiber
U. S. T e x t i l e F i b e r C o n s u m p t i o n , 1947-48
Oomestic deliveries0 194S 1947 R a y o n filament y a r n V i s c o s e 4- cupra Acetate Total R a y o n staple Viscose Acetate Total R a y o n total Wool A p p a r e l class Carpet class Total Co.tton Silk
chloride copolymer, is manufactured in several different types which v a r y in properties according t o whether or n o t the filaments h a v e been oriented a n d s u b jected to different kinds of after-treatm e n t s . Although t h e area of application of Vinyon N is still under investigation, most promising uses appear t o be for filter fabrics and d u s t fume bags in t h e industrial field, for rugs, draperies, a n d u p holstery materials, a n d in some apparel applications such as neckties, b a t h i n g suits, men's hose, football p a n t s , and ski suits. Orion, t h e t r a d e n a m e recently a d o p t e d for t h e polyacrylonitrile p r o d u c t p r e viously known as Fiber A, is said to h a v e excellent resistance t o chemical a t t a c k , particularly b y acids, and t o w i t h s t a n d degradation b y sunlight and elevated t e m peratures. Some Orion has already been used as sewing thread for canvas awnings; additional applications will probably include filter fabrics, chemically-resistant cordage, a n d a n u m b e r of household a n d • clothing fabrics. Polyethylene monofilaments, t h e s u b ject of experimental work several years ago, again claimed attention in 1948 when small-scale production was announced. Polyethylene filaments, in addition to u n usually low specific gravity (less t h a n 1), possess good resistance to sunlight, water, and chemical a t t a c k : they a r e being used initially for automobile seat covers. Among the polyamide fibers, evidence of the continuing search for improved properties was revealed b y p a t e n t s a n d research papers concerned with introduction of nitrogen-containing groups t o effect greater elasticity. N e w nylon products include a crimped staple fiber and an elastic y a r n of coiled s t r u c t u r e , b o t h of which, are expected t o find application in apparel items. U n u s u a l durability h a s been demonstrated in a n u m b e r of t y p e s of woolnylon blends.
13.7 51.2 23.5 16.5
consumption & 1947 1948
Change,
%
8.5
28.7 28.7
27.2 35.7
-5.2 +24.4
Total consumption6 1947 1948
Change,
%
477.9
557.6
+ 16.7
165.3 643.2
204.7 762.3
+ 23.8 + 18.5
363.5 110.6 474.1 3,594.2 1.5
351.4 135.6 487.0 3,51i 7 5.7
-3.3 + 22.6 -4-2.7 -2.3 +280.0
Source: Rayon Organon, a First 10 months. t> First 8 months. c First 8 months for rayoxi and wool; first 9 months for cotton and silk.
CHEMICAL
AND
ENGINEERING
NEWS
sponding period in 1947, as shown in Table I. Among the rayons, substantial increases in domestic deliveries were supplemented by imports which, in the case of filament yarn, exceeded in eight months the greatest annual total for any year since 1929, and in the case of staple fibers were only 2 % below the eight months' figure for the record year of 1939. Total eight month's consumption of wool was up slightly while cotton consumption during the first nine months was 2.3% less than for the same period in 1947. Although the estimated consumption of silk for the first nine months of the year reflected a large percentage increase over that used during the first nine months of 1947, the actual amount consumed, about 5.7 million pounds, was still very small. Synthetic fibers (nylon, Vinyon, saran, and others), among which nylon is by far the leader in volume, are not included in the table but account for only about 1% of total fiber consumption. The price shifts in major textile fibers and yarns during the period in 1948 for which data are available are shown in Table II, together with the prices in the last corresponding months in 1947 and the percentage changes since those months. Greatest net percentage changes during the 12 months occurred in scoured wool, with an increase from 122 to 180 cents a pound; in viscose rayon staple, with an increase from 32 to 37 cents a pound; and in viscose rayon yarn, which rose from 67 to 77 cents a pound. Among the materials under consideration, the only net drop in price from the latest comparable 1947 figure took place in cotton, although
Surface
Coatings
in M040
Table II.
U. S. Textile Fiber and Yarn Prices, 1947-48 (In cents per pound) 194S M a y June
July Aug. Sept. Jan. Feb. Mar. Apr. Fibers Viscose rayon 36.0 36.0 36.0 36.0 36.0 36.0 36.0 36.8 37.0 staple Cotton, 10 mkt. 35.2 32.8 34.2 37.2 37.6 37.0 34.0 31.3 31.2 average Wool, scoured 125.5 125.5 125.5 129.1 151.1 177.5 177.5 177.5 1 8 0 . 0 basis Yarns Viscose rayon. 24.0 7 4 . 0 7 4 . 0 7 4 . 0 7 4 . 0 7 4 . 0 7 4 . 0 7 6 . 3 7 7 . 0 150 den. Spun rayon, 93.1 93.1 9 3 . 1 9 3 . 1 9 3 . 1 9 3 . 1 9 3 . 1 03.1 8 3 . 3 30/1's Cotton, combed. 101.8 102.9 9 9 . 5 100.4 100.4 100.4 98..) 95 4 91 .4 30/1's Source: Rayon Organon.
prices of both spun rayon yarns and combed cotton yarns were lower in September 1948 than in January. The Time Factor in Textile Progress It is typical of the relationship of research to industry that most of the significant "developments of 1948" were conceived and carried through the experimental stages in prior years. For example, although Orion has been under investigation for several years, actual plant const ruction for its production in volume is not scheduled to begin until the spring of 1949. Similarly, a long time may elapse before a new finishing treatment can be applied t o fabrics on a commercial scale, for alterations in established methods and machinery of processing are frequently necessary in order to take advantage of the new treatment. An even more important factor which tends to retard immediate
Oct.
1947 Same Change last taontli % + 15.6
37.0
32.0
31.2
31.7
179.6
122.1
-f-47.1
77.0
G7.0
+ 14.9
-
0
83.3 87.7
1.6
+
4 2
utilization of many new finishes in the textile industry is the necessity for adjusting fabric constructions so that they may accept the benefits of the new treatment. This is exemplified in the case of water-repellent finishes by the finding that an improperly constructed fabric treated with the best available finish may offer less protection than an untreated fabric the construction of which has been designed to provide a high degree of water repellency. A further example is provided by shrink-resistant treatments for wool; it has been found that firm, balanced constructions may greatly enhance the effectiveness of the treatment. Thus, new developments in one field not only stimulate fruitful investigations in related areas, but their commercial application may actually depend upon such corollary developments, and the final results may far transcend the original limited objectives.
1
New Vehicles Mark Surface Coatings Developments H A R R Y BURRELL,, Finishes Division, Interchemical Corp., Newark, N. J., AND C. P . N E I D I G , Chemical Products Division, Atlantic Refining Co., Philadelphia, P a .
T h e i n t r o d u c t i o n of n e w resins t o i m p r o v e p a i n t products a n d combat raw material shortages has helped the paint, varnish, a n d lacquer industry to set n e w sales records surp a s s i n g t h o s e o f 1 9 4 7 , t h e i n d u s t r y ' s first b i l l i o n - d o l l a r y e a r Jt ERHAPS the most significant development in the coatings industry in 1948 was the use of oleoresinous vehicles modified by copolymerization with unsaturated monomers. Several major producers of drying oils and alkyd resins came out with "styrenated" materials. Certainly the availability of cheap styrene, cK-methyl styrene, cyclopentadiene, and butadiene at approximately half the cost of drying oils was a powerful stimulus for the development of methods to utilize them. VOLUME
2 7,
NO.
As might be expected, the copolymers differ in their properties from the parent materials. Those from drying oils with styrene or cyclopentadiene resemble varnishes, whereas the styrenated alkyds are more nearly akin to lacquers. Both are supplied as solutions, and, depending on the ratio and nature of the monomer, the products dry mainly by solvent evaporation. Drying speeds are rapid, and the Sims obtained are hard, tough, light in color, and have a high gloss with
1 » » .JANUARY
3,
1949
good apparent depth. Adhesion is generally good, as is resistance to water, alkalies and acids; outdoor durability tests are reported to show excellent results, but actual applications must still prove the point. Criticisms of the materials seem to be focused on odor, lack of gasoline and solvent resistance, incompatibility with other film formers, and on poor pigment wetting; some difficulty has also been experienced in formulating spray coatings. The content of styrene usually varies from 30 to 6b%. Production methods consist in adding the monomer, containing arelatively large amount of peroxide catalyst, slowly to the hot oil or resin. Care must be taken to ensure a true copolymer because a polymer solely or largely of styrene 25
