6.

GEORGE KAUFFMAN
products of chemistry California State Univenihl.Fresno
Fresno, CA 93740

Rayon
The First Semi-synthetic Fiber Product
George B. Kauffman
California State University, Fresno, Fresno, CA 93740
The use of natural fibers (flax,wool, hemp,
cotton, etc.) for textiles (woven materials) Table 1. World Fiber Production in Billions of Pounds (1,3a)
predates recorded history. However, from
the introduction in the late 19th century of Rayon
"Chardonnet silk'-the fust type of rayon to Year Rayon Noncellulosic Total Natural Total %of %oftotal
be marketed, synthetic fibers have chal- manmade Man- manmade
lenged the long-standing monopoly of natu- made
ral fibers for textile and industrial use and
have exerted a large and growing economic 1969 7.87 8.29 16.16 39.12 55.28 48.45 14.1
impact throughout the world. By 1938 U. S. 1978 7.31 21.94 29.25 32.15 61.40 24.99 11.9
rayon consumption was 300 million pounds
and exceeded wool consumption for the first of the Forthe month of December 1990the total U. S. production of rayon was 36.9million pounds or5.42%
total synthetic fiber production of 681 4 milllan pounds (36).
time. However, i t still only amounted to
about 10% of the total cotton consumption.
Between 1950 and 1970 total world fiber production in- dacron (polyester), which the chemist synthesizes from
creased from 35 billion to 55 billion pounds. About one- low-molecular weight compounds by polymerization
third of this increase was due to natural fibers, while two- (chain-building) re-
thirds was due to synthetic fiber production, which actions. Reactions for
increased fourfold during this period-from 13 percent of producing artificial
total fiber production in 1951 to 19 percent in 1969 (1,2). fibers were discov-
Before World War I1 the production of manmade fibers ered during the 19th
consisted almost entirely of rayon, but following the war century, but these ii-
new types of mmpletely synthetic fibers, such as nylon, bers did not become "'.H.~
polyesters, acrylics, and polyolefins, with specificdesirable commercially signifi-
properties have assumed an increasing proportion of both cant until the 20th
the synthetic fiber and total fiber market (3)(Table 1).Yet,
century, when pro- ....
during the early 1970's the annual world production of
rayon was still greater than that of any other fiber except cesses for their man-
cotton, and rayon continues to supplement the use of silk ufacture were ex-
and other natural fibers in a number of textile fields. ploited, along with
those for plastics and
Rayon other polymers to
Rayon i s a generic term for an artificial textile material which they are
composed of reconstituted, regenerated, and purified plant closely related. De-
substance, viz., cellulose or cellulose compounds. Because veloped as a substi-
its long-chain polymer structure is already provided by na- tute for silk, rayon is
ture and is only modified and partially degraded by chem- sometimes called " a r
ical processes, it is called a semi-synthetic fiber in contrast titicid silk" or "wood
to completely synthetic fibers such as nylon (polyamide)or silk," but this i s a
misnomer since its
chemical composi-
tion is completely dif-
ferent from t h a t of
silk. In 1924 this first
semi-synthetic fiber
was given the mined
name rayon, espe-
cially in the United Figure 2. Puckered sheet structure of cel-
S t a t e s and Great lulose chains (the dots denote hydrogen
Figure 1. Chair foml d cellobiose unit in cellulose (Ila), Britain (2,4a, 5). bonding) ($2).

Volume 70 Number 11 November 1993 887

Cellulose
Cellulose, the basic structural component of most plants,
is widely distributed in nature, comprising more than one-
third of all vegetable matter (6-10). As the world's most
abundant organic compound, it is the principal constituent
of cotton, kapok, flax, hemp, jute, wood, and ramie (an
Asian urticaceous shrub). Land plants annually produce
about 50 billion tons of this renewable resource by photo-
synthesis.
Cellulose is a polydisperse polymer, i.e., it consists of
many different molecular homologues, varying from 1,750
to 18,000repeating cellobiose units, each ofwhich contains
three reactive hydroxyl groups ( I l a ) (Fig. 1). Celluloses are
often largely linear polymers, but they are insoluble in
water because of their strong intermolecular hydrogen
- -
bondine and their small amount of cross-linkine (12) (Fie.
2). Most linear celluloses can be dissolved in solvents capa-
"

ble of breaking these strong hydrogen bonds, such as aque-

ous inorganic acids, calcium thiocyanate, zinc or lithium
chlorides. dimethvldibenzvlammonium hvdroxide. ammo-
niwal chmium hydroxide, and ammoGacal copper hy-
-
droxide ~Schweizrrkreaeent . Onlv -
" hieh-mdecular
native cellulose, which is insoluble in 17.5% aqueous so-
-
wrieht

dium hydroxide and which is called a-cellulose, can be

used in producing rayon. The only materials containing a
high enough percentage of a-cellulose for making rayon
are cotton (plants of the genus Gossypium) and some types
of wood pulp (13a).

Early Artificial Silk

In 1665 (14) the English physicist Robert Hooke (1635-
1703) suggested that (4a, 15, 16) "there might be a way

Figure 4. Louis-Marie-Hilaire Bernigaud, Comte de Chardonnet

(183!&1924)(31).

found out to make a n artificial glutinous composition much

resembling, if not fully as good, maybe better, than that
excrement or whatever other substance it be out of which
the silkworm [Bombyx moril wire-draws his clew." In 1734
the French naturalist and technologist Ren6-Antoine de
FZaumur (1683-1757) asked (4a,136,17),"Silk being noth-
ing but dried-up liquid gum, why cannot we make silk with
gum and resin?'
He reported how he tried to produce silk-like fiber by
forcing different kinds of varnish through tiny holes in the
bottoms of sheet-iron cans or tin cans to form glutinous
filaments that hardened in the air. His fibers were of no
practical importance, but his process formed the basis for
all future attempts to produce artificial silk. In 1740 a
Frenchman named Bon reported to the Ro.yal Society that
he had woven <tockmgsand gloves of yam made h ispr-
drr web filaments (41,. and in 1770 a Frenchman named
Dubet produced filaments from the silky gum extracted
from dead silkworms (18). A silk manufacturer named
Schwabe. a t a meetine of the British Association for the
~dvancementof science held a t Manchester in 1842, sug-
-
eested extrudine solutions throueh fine holes as a method
Tor producing figers (4a).

Figure 3. Christian Friedrich Schonbein (1 799-1868).
Nitrocellulose Rayon
The first practical progress toward producing a synthetic
fiber was made in Basel, Switzerland by Christian
Friedrich Schonbein (1799-1868) (Fig. 31, who in 1846 ac-
cidentally treated cellulose with a mixture of sulfuric and
nitric acids and produced a cellulose derivative that he
called guncotton (SehiesswoUe) and proposed as an explo-

888 Journal of Chemical Education

sive (19-23). Guncotton was misnamed nitrocellulose, but
it is actually cellulose nitrate because the nitrogen is pres-
ent as the nitrate (-ONOz) rather than the nitro (-NO21
group. Although cellulose is insoluble in water and most
organic solvents, the bulky nitrate group in cellulose ni-
trate tends to senarate adiacent wlvmer chains. reduce
crystallinity, a n d promote"solubiiit$ In 1855 the Swiss
chemist George Audemars (or Audhemar) of Lausanne re-
ceived the first English patent for producing artificial silk
by drawing out threads from an ethanol-ether solution of
cellulose nitrate (collodion)with a steel pointer and reeling
the threads (4a, 24).
I t was only in 1883, however, that while searching for a
better carbon filament for his electric lieht bulb. which he
invented nlmo~tsirnultnncously with, but independently
of. Thomas Alva I.:dison, the Endish phv.;~cistand rhcmist
S& Joseph Wilson swan (1828I-191@ patented a process
for squeezing an acetic acid solution of cellulose nitrate
through holes to form fibers (4a, 136, 25). Swan realized
that these filaments could be used to produce a n artificial
silk, andin 1884 and 1885he exhibited fabrics made of this
fiber in London (26). The first practical fiber made from
cellulose nitrate was produced by the French chemist and
technologist Louis-Marie-Hilaire Bernigaud, Comte de
Chardonnet (1839-1924) (Fig. 4j, who is therefore consid-
ered the founder of the rayon industry (27). Chardonnet
was a uunil of Louis Pasteur. whose work on silkworm dis-
eases iedhis student to begin research on artificial silk in
. . for his first uatent and submitted
1878. In 1884 he auulied
a memoir titled "Cne matiere textile artificiclle ressrmhl- Figure 5. Eduard Schweizer (1818-1860)(33).
ant a la soie' to the Acadtmie des Sricncrs in la84 !,la.. lib..
13b, 28,29). At the Exposition Universelle held in Paris in
1889 he was awarded the mand urize for the first pown Schweizer is uiually credited with discovering the solvcnt
made ofcellulo6r nitrate fib 130;. and in 1891 he digan action of ammoniacnl copper 11 solutions on cellulose. Ed-
to produce .Chardonnet silk" ("soic Chardonnet" in ;I far- ward Andrew Parnell &med that John Mercer (1791-
tori that he had established in his hometown of Besan~on.
1866) had earlier observed this action and had recovered
The new fiber, prepared by extruding collodion through
fine glass capillaries to form continuous filaments that cellulose from these solutions by acidification with sulfuric
harden in the air as the solvent evaporates, had the disad- acid (4a, 34).
vantage of being flammable and explosive. Chardonnet Schweizer's study of copper(I1)-amminesbegan with his
overcame this disadvantage by denitrification (removal of synthesis of unterschwefelsaure Kupferoxyd-Ammoniak
the nitrate groups by hydrolysis with nitric acid and later modern, tctranmmincc1~pperr1Ii dithionatc, ICulNHz~rl-
with sodium hydrosulfide solution which regenerate the S&j
- - by - .- . - with
. the metathesis of ICu NH~.lSOa.H.,O
cellulose) (31).Nevertheless, "Chardonnet silk" was BaSzOsin warm aqueous solution (35).In his second paper
largely superseded in the early 20th century by the more onthe subject (36)Schweizer attempted to prepare the free
inexpensive viscose rayon. base Kupferoxyd-Ammoniak (modern, tetraammine-
The cellulose nitrates (nitrocelluloses)cannot be sharolv copper(I1)hydroxide) by dissolving freshly prepared basic
defined like the esters of aliphatic alcohols such as glyc&l copper(I1) dithionate in concentrated aqueous ammonia.
trinitrate (nitroelvcerin).
-" Thev still retain their fibrous Along with the main product ([Cu(NHa)alSzOs), he ob-
structure and behave as colloids. Variation in the condi- tained a dark blue solution ([Cu(NH3)JOH)2), which "pos-
tions of nitration (time, temperature, composition of ni- sesses to an extraordinary degree the power to dissolve
trating mixture), a reaction accompanied by numerous plant fiber a t ordinary temperature." He reported (36)
side reactions, produces substances containing different
percentages of nitrogen up to the maximum of 14.17 per- I f the filtered solution [of punfied corron in thrs solutionl is
cent (for cellulose trinitrate). Those with a nitrogen con- ruprrsoturated w i t h hydrnchlonc scld, n volurnmous white
tent of 11.3-12.5 percent (consisting of mixtures of mono-, pr*cipttnte 1s fmmrd, whrch, collected on a filler,has the exact
~ ~

appearance of moist aluminum hydroxide.

di-, and trinitrates) are soluble in ether-alcohol mixtures
and were used in preparing nitrocellulose rayon by this
largely obsolete process ( 4 ~ ) .
Cuprammonium Rayon
A second type of rayon is based on a discovery by the
Swiss chemist (Matthias) Eduard Schweizer (1818-18601,
Extraordinarius (Associate)Professor of Chemistry at the
Universitat Ziirich (32, 33). Schweizer's most important
contribution to science and technology, which made his
name known throughout the chemical world. was his dis-
covery that cellulos~dissolves in a n ammoniacal solution
of copper(I1) hydroxide, now known universally a s
Schweizer's reagent or Schweizer's solution. Although
This substance unorganized, to be sure, but not changed es-
sentially in its ehemieol nature, appears to be cellulose.
Schweizer found that the solution also dissolved uauer
and linen (somewhat more slowly than cotton), silk ?mire
auicklv than cotton). and wool (onlv on warmine).
-.
I n his third article on tetraamminecopper(I1) (37)
Schweizer extended his study to other salts of the cation
and reported that a saturated ammoniacal solution of
basic copper carbonate was an excellent solvent for cellu-
lose. He attributed the solvent power to pure, uncombined
Kupferozyd-Ammoniak (modern, [CU(NH~)~I(OH)~) be-
cause the blue solution obtained by treating finely divided
copper with aqueous ammonia in the presence of air pos-

Volume 70 Number 11 November 1993 889

 Cellulose Steeping
sheets pressing
Ripening
Fiber production
Regeneration Stretching
Figure 6. The viscose process (51)
sesses this solvent power, a n observation made the year
before by Peligot (38,391.
Schweizer's last publication on the subject (40) was a let-
ter to Otto Lime Erdmann (1804-1869), editor of the Jour-
nal fur praktische Chemie. He disagreed with Erdmann's
view that "cellulose is not really dissolved in Kupferoryd-
Ammoniak but only strongly swollen" (41) and asserted
that the cellulose is actually dissolved. Reihlen later found
that cellulose dissolved in Schweizer's reagent because of
the formation of complex compounds between Cu2+and
(C6H805)Zions (42). The equilibrium reaction
is pH dependent: cellul~~se ions are present in appreciable
concentration only in a rather strongly alkaline solution. If
the hydroxide Ion concentration is lowered, the cellulose is
reprecipitated. If it is increased by addition of NaOH solu-
tlon. the crllulosc redissolves 1421.The phvsical prooerties
andchemical reactions of Schweizer's reagent have been
investigated extensively (43).
Several investigators recommended t h e u s e of
Schweizer's reagent to dissolve cellulose, but i t was not
until 1890 that the Frenchman Louis-Henri Despeissis de-
veloped and patented a n industrial process for makingtex-
tile fibers of artificial silk using cellulose dissolved in this
solution(4a, 13b, 30,4446). Unfortunately, he diedin 1892
without having utilized his patent on an industrial scale,
and his process entered the public domain. However, Max
Fremery, a German chemist from Cologne, and Johan
Urban, a n Austrian engineer, who had worked together in
1885 on the manufacture of carbon fdaments in a n electric
light factory in Rotterdam, collaborated in improving
Despeissis' process. I n 1892 they founded the Rheinische
Gliihlampen Fabrik, Dr. Max Fremery & Co. to manufac-
ture electric light bulbs. They established a factory in an
old paper-making plant at Oberbmch near Aachen. They
obtained a bank credit i n 1895 from t h e Bergische-
Markische Bank, a condition of which was that they con-
tinue their research to produce textile filaments of artifi-
cial silk.
Fremery and Urban faced considerable difficulties in
complying with this condition. An industry for manufac-
turing artificial silk from collodion already existed, and its
890 Journal of Chemical Education
Shredding Aging Xanthation
Filtration Dissolving I
&
Cutting Finishing
Drying
AAA,A
a N \\/, \\ I \\
\\
Opening
L - - - - - + & h n
r\ u u u u
fabrication processes were well kept secrets, forcing them
to carry out their own research and to solve numerous
chemical and mechanical problems (45).Aiter two years of
experimenting, Fremery and Urban fded their first patent
under the name of Herman Pauly, director of a technical
school a t Munich Gladbach, intended to avoid both compe-
tition and attracting the attention of other researchers
(47).
I t is sometimes claimed that this first practical patent
for cuprammonium silk was merely a repetition of
Despeissis' patent of a dozen years earlier. However, unlike
the earlier patent, i t described a technical method for spin-
ning the product and is truly the fundamental basis for the
cuprammonium silk industry. With their additional subse-
quent patents, as well a s those of the German Emil
Bronnert, Fremery and Urban began to manufacture a
cuprammonium artifical silk called "GlanzstofP' at their
Oberbruch works, beginning in 1898.
In 1908 Emil Thiele of J.-P. Bemberg, .. a prominent
. Ger-
man tcxtile firm, perfected the process hy usingas starting
material cotton linters (short fibers that stick to thccotton-
seeds aRer a first ginning), which were more economical
and which imparted to the thread more resistance as well
as a softer feel. This so-called "Bemberg silk" was used in
the hosiery industry for making stockings. The prosperity
of the cuprammonium process was relatively short-lived. I t
w a s generally abandoned around 1910, except by
Bemberg. However, cuprammonium rayon, prepared by
dissolving cellulose in Schweizer's reagent, extruding the
resulting solution through spinnerets (nozzles),regenerat-
ing the cellulose in dilute sulfuric acid, and washing the
fiber in acetic acid (48,49), is still used to produce the most
expensive rayon-me most resembling silk. Its extra fme-
ness and strength, attractive hand (fabric properties that
can be sensed by touching the material, such as resilience,
smoothness, body, etc.), subdued luster, and excellent
draping properties justify its added cost. It is used for sat-
ins, sheer fabrics (chiffons, nets, and ninons), underwear,
dress fabrics, linings, dresswear, sportswear, curtains,
suitings, upholstery fabrics, bedsheets, and other fabrics
(2). Almost all artificial kidney dialysis units now use
membranes prepared from films and hollow fibers of
cuprammonium rayon (50,511.
Viscose (or Xanthate) Rayon
A third type of rayon is produced by the viscose or xan-
thate process (2, 4c, 13b, 44, 51-53). "Viscose" was the
name given by British chemists Charles F. Cross ( 1 8 8 5
1935). Edward J. Bevan (185G1921). and Clavton Beadle
(186g1917) to the syrupy, yellow liqkd that they discov-
ered in 1891 bv the action of cellulose xanthate (a product
of the reaction" between carbon disulfide and alkaiine cel-
lulose) on dilute sodium hvdroxide solution 154).Althoueh
produkion of viscose rayon involved great technical diffi-
culties, these were overcome gradually by research and de-
velopment such as Charles F. Topham's invention in 1900
of the Topham spinning box, a device for centrifugally coil-
ing twisted fdaments from cellulose solution (55). By 1905
Courtaulds, the British silk company, had built a plant for
manufacturing viscose rayon in Coventry, and in 1910 the
American Viscose Company, established by Courtaulds a t
Marcus Hook, Pennsylvania, began production in the
United States. Today the viscose process accounts for most
- .
of the world's total ravon production (13b).
Viscose rayon products have widely varying properties
because ofthe versatilitvof the process, which results from
~~~
the numerous steps and s p i n k g changes that can be
made (51).This versatilitv has proven to be a mixed bless-
ing, for each step requires careful attention to assure the
. .
desired properties of the product, making the viscose pro-
cess one that needs continuous,year-ro;nd operation to
prevent gelling and to yield high quality of the product
(Fig. 6).
The raw material may be cottonlinters or soft wood pulp
from northern spruce; western hemlock, eucalyptus, or
southern slash pine, that yields the cellulose which is pu-
rified, steeped in caustic soda (sodium hydroxide solution),
and then shredded to form powdery crumbs (2,4, llb, 52,
53). The terminal hydroxyl and aldehyde gmups that are
present in cellobiose also are present in cellulose (Fig. 11,
-
but thev are not sienificant since thev are present on a
very long-chain polymeric molecule. Representing cellu-
lose bv the semiempirical formula CcH7OdOH)a. one of the
threepotentially reactive hydroxyl groups on each repeat
unit in the chain is replaced by the sodium ion:
[C6H702(0H)d + nNaOH + [C,HP,(OH)20-, Natln + n H 2 0
soda cellulose
Soda Cellulose
The aged crumbs of soda cellulose are mixed with carbon
disulfide in a revolving drum, forming cellulose xanthate,
and are then treated with dilute caustic soda solution,
yielding a thick orange-brown colloidal solution of sodium
cellulose xanthate (viscose):
-
[c,yo2(otl)p,
Na+ln+ n- fCeWz(oH)&+C-s, Na*ln
II
s that onlv three hvdroxvl e r o u ~ per
Soda cellulose Cellulose xanthate (wsmse)
The unstable viscose solution is allowed to "ripen" for
several days a t carefully controlled temperatures; during
this period i t undergoes repeated filtrations, and it in-
creases in viscosity. It is then extruded through holes in a
spinneret, and the resulting jet of viscose next enters a co-
agulating bath of NaHS03, ZnS04, and dilute HzS04, in
which it is reconverted into cellulose, which coagulates to
form a solid fdament:
Cellulose Xanthate
The tensile strength of the regenerated cellulose (viscose
rayon) is increased by stretching, which reorients the mol-
ecules so that the amorphous polymer becomes more crys-
talline. Tenasco and Cordura are among the trade names
for such high-tenacity viscose rayons (tenacity of 3.0-5.0
gtdenier compared to 1.5-2.4 for ordinary rayon). If the vis-
cose solution is passed through a slit dye into an acid bath,
ir emerges as sheets or filmsof cellophane. The rayon fila-
ment ran he manipulnted and modified during spinning to
produce cross-sectional shape variations. to increase wv-
ering power, to permit solution dyeing, or to introduce
crimp. Control of the regeneration conditions coupled with
spec&c additives can be used to produce various-modified
fibers for specialized purposes.
Viscose rayoncond&tsheat better than silk, has a cooler
feel -
-~ ~- aeainst the skin. and is hiehlv
" absorbent (it absorbs UD
to 13k of its weight in moisture), which enhances its value
- -
a s a comfortable material for clothine (2).Althoueh most
rayons lose strength when wet, modern resin finishes are
- - -
solvine this oroblem. High-wet-streneth (~olvnosic)fibers
L "
are high-tenacity viscose rayons in which the molecular
structure has been modified to give high strength, espe-
cially when wet, and good dimensional stability and firm-
ness. High-strength rayon was used increasingly in tires,
conveyor and transmission belts, hosepipes, and similar
products during World War 11. Rayon staple can be blended
with other natural and synthetic staple fibers to add mois-
ture absorption and other characteristics of cellulose to
blends of s;ronger and less absorbent fibers, among them
most of the synthetics. Rayon and acrylic fiber blends are
especially popular for knitted goods.
Viscose rayons are highly versatile, being used in all
areas of the textile industry, including men's, women's, and
children's outerwear and underwear; furnishings; carpets;
household textiles; and medical fabrics. Crimped rayons
are used in tufted carpets, rugs, and chenilles; curtains;
upholstery; and nonwoven fabrics for surgical use. Spun-
dyed rayon, in which color is incorporated during the solu-
tion phase, provides excellent stability in textiles exposed
to light, as in curtains and car upholstery. Certain rayon
fibers are used to make carbon fibers and are the only ma-
terial acceptable for the NASA space program's rocket mo-
tors.
Cellulose Acetate
A fourth type of rayon is based on the acetylation of cel-
lulose (cotton)by acetic anhydride achieved by the French
chemists Paul Schiitzenberger (1829-1927) (also spelled
Schutzenberger) and Charles Naudin (1315-1899) in 1869
(56).For many years there was considerable confusion wn-
cerning the number of acetyl groups that could be intro-
duced into the cellulose molecule; however, it is now clear
s cellulose unit can be
esterifiei, and the existenee oihiiher acetates must be at-
tributed to degradation or acetolysis of the cellulose, which
yields lower carbohydrates with more hydroxyl groups. In
1894 viscose develooers Cross and Bevan patented the
first industrial process for the manufacture of cellulose
triacetate, which was soluble in chloroform. In 1903 the
American chemi~tGeorge Miles (18611-19391 succeeded in
dissolvina panlallv hydrolyzed cellulose acetate in ace-
tone. ~ o w e i e rthebricess
, was not used a s the basis for a
textile fiber until 1907, when it was so applied by Prince
Guido Henkel von Donnersmark in Germany (13b).
Durine., World War I the British Cellulose & Manufactur-
ing Co. began manufacturing at its large Spondon. Eng-
land plant an acetone-soluble cellulose acetate developed
by the Swiss chemist Henn Dreyfus, one of the company's
heads. The product was used as a dope (fabric coating, for
Volume 70 Number 11 November 1993 891
 Table 2. Some Rayon Products (110) oriate solvent is forced throueh sninnerets into warm air,
&here the filaments are coagkatkd by evaporation of the
Trade or Product Manufacturer solvent. The filaments do not reauire a finishing treat-
brand name ment, and because two-thirds ormore of the hidroxyl
Acelon Cellulose Acetate May & Baker Plastics - .
croups are esterified.. thev
viscose rayon. However, the smaller number of hydroxyl
- than
" have a higher wet strenah
Ltd.
Agro Rayon fibers Beaunit Mills Corp. -moups . makes direct dveing difficult, and special fiber-re-
active dyes are required. &ch dyes consist essentially of
Amerith Cellulose nitrate Celanese Cop. of colored acid chlorides or vinyl sulfones that read with the
America hydroxyl groups of cellulose to form ester or ether linkages,
Arnel Cellulose triacetate Celanese Corp. of respectively. Alternatively, the dye may be incorporated in
America the spinning solution to yield colored thread. Unlike all the
Avron Rayon fibers American Viscose Corp. other commercially important types of rayon, acetate fiber
Bemberg Rayon fibers Beaunit Mills Corp. is not solvent-insoluble regenerated cellulose but is cellu-
Regenerated cellulose E. I. du Pont de lose acetate, which is still soluble in acetone, methylene
Cordura chloride, or chloroform.
Nemours & Co.
In the early manufacture of cellulose acetate, before dye-
Cowal Rayon fibers Courtaulds ing, the fiber was oRen treated with caustic soda (NaOH),
C~ystalon Rayon fibers American Enka Corp. which partially converts it back to cellulose (2). With the
Cycloset Cellulose acetate fiber E. I. du Pont de advent of newer methods for dyeing, this saponification
Nemours & Co. process was eliminated. However, it was revived for appli-
Dexel Cellulose acetate British Celanese Ltd. cation in the stretching process, when it deacetylizes the
Estron Cellulose acetate Eastman Chemical substance, producing a very fine, strong fiber that is no
filament Products longer cellulose acetate hut has been converted to a highly
oriented filament of regenerated cellulose. Saponified
Floranier Cellulose Rayonier, Inc. ravon varns ..
are ideal for applications reauirina a high
Forticel Cellulose propionate Celanese Corp. of
America
" "
ratio of strength to volume and excellent dimensional
hilitv. e.e.. in parachute ropes and fabrics, tire cords, helt-
sea-
Herwcei Cellulose acetate Hercules Powder Co. ing,"hos&, and balloon fabrics. They also have replaced
Herwse Cellulose acetate- Hercules Powder Co. natural silk in electrical insulation materials, e.g., in hear-
propionate ing aid equipment. Acetate rayon, in which not less than
Kolorbon Rayon fiber American Enka Corp. 92% of the hydroxyl gmups are acetylated, is fast drying,
supple, shrink resistant, and has a wide range of dyeahil-
Lumarith Cellulose acetate Celanese Corp. of ity (llc). Under tradenames such as Estron (Eastman) and
America
ck~aneseAcetate (Celanese), it is used for dresses, shirts,
Parfe Rayon fiber Beaunit Mills Corp. slacks, draperies, upholstery, and cigarette filters. Triace-
Silbon Rayon paper Kohjin Co. tate rayonis easily-washed and is resistant to shrinking,
Tempra Rayon fiber American Enka Corp. wrinkling, and fading, and it is used for skirts, dresses,
Courtaulds and sportswear. Some of the different brands, types, and
Topel Rayon fiber
forms of rayon are shown in Table 2.
Tusson Rayon fiber Beaunit Mills Corp.
Uvex Cellulose acetate. Eastman Kodak Co. Ecological
- and Pollution Considerations
butyrate The cuprammonium and viscose processes consume
Viscalon Rayon fiber American Enka Corp. huge amounts of water; -420-750 L (110-200 gallons) of
Zantrsl Ravon fibet American Enka Corm waterkg of rayon is required for processing,and 8-10
times that volume must be used to provide the plant sup-
plementary-service facilities (50, 51).However, in the sol-
airplane wings, and after the war Henri and his brother vent spinning process all recovery and recycle stages are
and fellow chemist Camille Edouard Dreyfus (1878-1956) closed cycles with essentially none of the expensive solvent
developed a t the plant a cellulose acetate textile fiber mar- being lost. Since rayon is made from trees, no petroleum is
keted in ~ n ~ l a n d u n dthe
e r name "Celanese," beginning in used in manufacturing the polymer, and much of the en-
1921. Great technical difficulties,including the resistance ergy used for separation and purification of cellulose is de-
of the fabric to ordinary dyes, had to he; and were sur- rived from pulping by-products as energy sources. These
mounted. By 1924 an affiliatedcompany,now the Celanese last two factors give rayon a favorable position compared
Corporation, was producing and marketing the fiber in the to completely synthetic fibers with regard to the total en-
United States. In 1929 E. I. du Pont de Nemoun & Co., ergy required for fiber production.
which had acquired the process and rights from French
manufacturers, b e g a n to produce the fiber a t i t s Literature Cited
Wavnesboro. Vireinia plant. In 1950 Courtaulds La., Lon- 1. Weigmann,H-0. "naturalFihres:'In T h N e w Eneyelo~dioBdrifaffim,15th d.;
Encyclopaedia Btit-i~a: Chicago, IL,1918: Vol. I, pp 211-289.
don, began to d&elop cellulose triacetate fibers (2). To- 2. Cook. J. G. "Man-Made Fibres;" hi Th. New E"cye11pedio Blltn""ic.. 15th 4.:
gether with British Celanese LM.,Coventry, Courtaulds Encyclopaedia Btifannica: Chicago, IL, 1918:Vol.7. pp 257-271.
later produced a triacetate fiber, under the trademark 3. Tatlie Orgonon 1979 (June], 50(61; (hl Fiber Organon 1991 IJanuaryI, 5U11, 1.
4. Wheeler, E. T h Monufmture ofhtificial Silk vith SraiolRofpronce to the Vismse
Tricel. In 1954 the Celanese Corporation began to produce Process:0.Van Noshand Co.: New York, 1928; (a1Chap. 1:(h) p 34: (4Chep. 2.
a triacetate fiber under the trademark Arnel. 5. Letcher.T. M.; Lutseke. N. S. J. Cham Educ. 1990,67,361.
The acetylation of cellulose by acetic anhydride or acetic 6. Berseh, J. Cdlulose, Cellulose Praluctn and Anifieio1Rubb.r; Henry Carey Beird:
Philadebhis, PA. 19C4
acid occurs readily in the presence of dehydrating cata- I. at,E.lnd. E n s Chrm. 1940.32.1641.
lysts, such as ZnClz and H2SO4,yielding the chlomform- or 8. Haynes, W. Cdiulae, The Chmlml T h l Gmws; DoubI&y: N e w Y o h 1953.
methylene chloride-soluble triacetate or the acetone-solu- 9 Ott. E.: Sourlh. H.M.: Gr&. M.W. Cellulose and Cellulose Lkriuafiras: Intersei-

ble diacetate, depending on the readion conditions, which

are carefully controlled (4b, 53). The solution in the appro-

892 Journal of Chemical Education

11. Seymour, R. B.; Camher, Jr.. C. E. Pd-r Chomisby:An Inlmducfion, 2nd ed.: 33. 75 J e h r e chemiseher Forsehung an der Univeraitat Zhrieh: Festschrift m r
Marcel DeWter: New Ymk, 1968; la) pp 18C~182:lbl pp 182-183; (c) p 185: Id) EMfmung dea "even Chemiachen Instituts, velfasat "on den Studierenden der
A ~ m n d i xB. Chemie:n.d., n.p. [ Zurich, 1909 1;pp 14-16.
12. ~ey&our,R. B.: C m a h q C. E. Ciont Mokcules: Essmfhl Materidsfor Ew&y 34. Pamell, E.A.LJo o n d h b o u r s of John M w w ; Longmsns, Creen : London, 1686
LivinpandProbkm Soluing; Wiley: New York, 1990; pp 6 6 8 5 . 35. Schweizer, E. J.pmkf. Chom. l855,67, 430.
13. Darhy, W D. Rayon ond Other Synfhrfie Fibers: hy Ooods Eeonomiaf: New York, 36. Schweizer, E. J.prvkt Chem. 1851.72, 1W.
1929:1elp34;1h)Chap. 1. 37. Schweieer, E. J.pmkt Chem. 1859.76.344,
14. Bragg W. "Old h d e s and New Knowldke;" six lectures before the Royal Institu- 38. P6lign, E. Compt nnd. 1668,47.1034.
tion. London. Christmas. 1925. 39. PBigot, E. Pogg Ann. 1860.58.83: 1861,63,343.
15. Hmke, R. ~ & m p h i o : o ~ s o m PhysialogrmlDe~cnptiomofMinue B d b a modo 40. Schweizer, E. J p m k t . Chem. 1859. 76,370.
bvM*if"ingGlmses: WifhObseruofionaondlnquin~~
Thenupon; J. Mart,", and 41. Erdmann, 0.L. J pmkt. Chem. 1859.76.387,
J.Allestw: London. 1665. 42. Rethlen. H. Z onorg Chem. 1848,257,340,
16. Cham. ondlnd. 1926.45.221: Tim8MifIcidSilA S u p p b m n f , April 2,1927. 43. G m l i m Hondbuch der anorgvnbchen Chemip, 7th ed.; SystemNr 60, Kqfer, Tell
17. de Reaumur, R-A. F Mdmoirepavr w u i r a I'hisfoim des i ~ m t e s 6; ~ 0 1 s Im. ; B, Liderungl: Verlag Chemie: Weinheiderastrasse, 1958; pp 11&132 and ref.
~ t i m e r i eb y a l e . Patis. 17361742. erences therein.
44. Reinthder, F. (Rowe,F. M., Trsnal.)Anifleiil Silk; Chapman & Hall: London, 1928:
Intmdubion.
45. Fauquet, L. G. Histoire & lo myonno et dez fertika synikdf~ues; Libraitie h a n d
Colin: peris, 1960: Chap. 1.
46. Despeissis, L-H. French Pat. No. 203,741 (May 9, 1890).
47. Pauiy, H. German Pat. No. 96,642 (December 1, 1897).
48. Fmvles, 0 . Leelurp E q r i m o n t s in ChomisW, 4th rev ed.; G. Bell & Sons: London,
1957: pp 232-233.617,
49. Kauffuffn,G. B.; Karbassi, M. J Chem Ed=. 1884.62.878
50.Lundberg. J.;W h a k , A. %yon."InKirh~.Xhmr C o n c k E n e y e l o ~ d i oofCkmieol
T~chnology;Wiley: New York, 1985; pp 998-999.
28. Morgan, P . W .In Hish31 0 f P 0 1 y m ~ S ~ i e - a n d Tkhnology Seymour, R. B., Ed.; 51. Turbak, A In C o n c h Emyncvlopedia ofPoly-r SciDMp andEngineoring; h e h w i t p ,
Marcel Dekker: New York, 1982; pp 4 9 4 7 . J. I., Ed.; Wiley: New York. 1990; pp 960-962.
29. Chardonnet, L-M.-H:B., Compte de. FrenchPat No. 165,349(1865): Ger. P a t . No 52. Hawsman, J. A. 'Vismse." In The E n c / ~ l o p d i oofCha-fry, 2nd ed.; ClarL, G. L.;
36.36611685). Hawley, G. G., Eda.: Van Noswand Reinhold: New York, 1968; pp 1081-1082,
53. Noller. C. R. Chemimy of Owganie Campaunda, 3rd d . ; W. B. Saundere: Philadel-

"---.
32. Kaufhm, 0. B.J Chem. Edue. 1984,61,1095

Volume 70 Number 11 November 1993 893