Textile chemists make greater use of spectroscopic analytical techniques

THEORY CORRECT. Evidence devel­oped by Dr. John W. Gofman (seated) and Jason L. Minkler supports a 66-year-old theory of Dr. Theodor Boveri

a culture of malignant cells that re­sulted from a viral infection of healthy tissue. These also show the Ε16 ex­cess, both relative and absolute. They collected control information by carry­ing out similar statistical analyses of normal diploid cells, both male and female. To date, they have karyo­typed more than 2000 cells and have measured some 140,000 chromosomes.

The Lawrence Radiation Laboratory workers have set themselves a stringent set of standards. For each tissue spec­imen that they examine, they compile chromosome data for between 50 and 100 cells. "This assures us of arriving at mean values for each chromosome type that are statistically accurate to within a very small margin of error," Dr. Gofman points out. About 99% of the information accumulated has less than one chance in 10,000 of being in error, he estimates. "We generally demand a l-in-1000 level of accuracy before we accept any data," he adds.

As expected, they find that the chromosome content of all the cancer cells tested (with the exception of the RPMI-2650 cell line) is higher than the 46-chromosome level of nor­mal diploid cells. More significant is the finding that the Ε16 chromo­some count consistently tops that of the other chromosome types on a rel­ative basis. Even in the case of RPMI-2650, a nasal septum cancer in which the cells have 46 chromosomes, there are three Ε16 chromosomes in­stead of the normal two.

Dr. Gofman and Mr. Minkler plan to analyze the chromosomal content of the remaining malignant specimens in the American Type Culture Collec­tion. They will then try to determine the biochemical significance of the E16 chromosome excess and will check whether the imbalance is brought about by carcinogenic agents such as certain chemicals and atomic radiation.

With the large variety of natural and synthetic fibers used in textile manu­facturing coupled with the host of chemical treatments to which today's textiles are subjected, chemists are turning more and more to spectro­scopic techniques to analyze textiles and textile fibers. Established tech­niques such as visible, ultraviolet, and particularly infrared spectrometry are finding increased use in analyzing fab­rics and dye solutions. Newer tech­niques, too, such as atomic absorption spectroscopy for the quantitative de­termination of metals and internal re­flectance spectroscopy for fast deter­mination of infrared spectra directly on a fabric sample are also beginning to be widely used in textile analysis.

The "black art" practices of the tex­tile industry are rapidly fading from the scene. Textile producers are be­coming much more sophisticated, chemically and instrumentally. In­dustry scientists have devised ways to chemically treat natural and synthetic textiles and textile blends to impart such properties as shrink resistance, water repellency, permanent press, crease resistance, fire resistance, and rot-proof and soil-release properties. And textile companies such as Beaunit are even using computers in dyeing and color matching.

To detect and determine quantita­tively textile additives, to detect struc­tural alterations in fibers caused by chemical treatment, and to aid the tex­tile dyer in computer color match­ing, the textile chemist is turning more often to rapid spectroscopic

methods of analysis. The trend to­ward wider use of spectroscopic tech­niques in textile analysis was empha­sized by several speakers at the Sym­posium on Spectrochemical Applica­tions in the Analysis of Textiles and Textile Fibers held during the seventh national meeting of the Society for Applied Spectroscopy in Chicago.

One of the most important prob­lems of the dyehouse is: What is the fastest, least expensive way to make a textile take the apparent color of something else and obtain a color match? The material may be fiber, yarn, fabric, or even apparel. It may be composed of one fiber or blends. And the blends may range from two types of the same nature, such as two cottons varying in dyeability and di­ameter, or the blends may contain fibers chemically different such as cot­ton and polyester.

"With computerized dyeing, we have reached the point where it is pos­sible to take standardized dyestuffs, fabrics, and procedures and dye to shade in existing equipment with "zero adds" [additions of dyestuff to the dye bath]," Braham Norwick of Beaunit's textile division said at the symposium. "In one of Beaunit's dyehouses we have recent figures indicating that in 40 out of 42 new shades, we dyed and got approval without "adds" to the computed formula.

Spectrophotometry can be used to monitor dyestuff variation. Dyestuffs may leave the manufacturer with con­trolled strength and still show varia­tions, Mr. Norwick points out. Just

Dyes with the same visible spectrum may differ in the infrared spectrum 4000 3000 2000 1500 CM : 1000 900 800 700

3 4 5 6 7 8 9 10 11 12 13 14 15 Wave length in microns

Two different dyes may give identical visible spectrophotometric absorption curves in solution but not always dye a fabric similarly. Infrared curves of the two dye baths show chemical differences which can affect dye action

4t C&EN MAY 27, 1968

as wool in a heated area in winter may weigh 15% less than when exposed to humidity in summer, commercial dye-stuffs pick up or lose moisture. It is thus a waste of time to weigh to one part in a thousand material which can change by several per cent in moisture content.

Visible spectrophotometry doesn't always give assurance that commercial dyestuffs are identical, Mr. Norwick says. Two sources of the same dye in­dex number, Celanthrene Fast Pink 3B and Palacet Fast Pink FF 3B, show the same strength in their visible spec-trophotometric absorbance curves, he has found. However, they don't act alike in the dye bath. One of the reasons for this can be seen from the infrared curves which show chemical differences.

Infrared spectroscopy can be used to identify fibers and fabrics. In some cases, the technique can measure how extensively the fabric has been chemi­cally modified, says Elizabeth R. Mc­Call of the U.S. Department of Agri­culture's Southern Regional Research Laboratory (New Orleans, La.). In­frared spectroscopy offers a way to get information on the changes in chemi­cal structure which occur in cotton finishing. These structural changes are important to the chemist whose goal is to improve fabric performance, Miss McCall points out. Infrared spectroscopy gives information con­cerning these structural changes by identifying and determining new func­tional groups. Infrared spectral data also find use in evaluating changes in crystallinity and polymorphic form. In addition, the data can be used to detect and estimate the amount of cot­ton in blends with other fibers.

In using infrared data to study crys­tallinity in unmodified cellulose, the ratio of band absorbancies at 1372 and 2900 cm.*1 is independent of the sample's lattice type. The values ob­tained from this ratio correlate well with structure data obtained by x-ray diffraction, Miss McCall and her USDA coworker Nancy M. Morris have found. Chemical modification involving reaction with the cellulose molecule's OH groups causes the hy-droxyl stretching band in the 3330 cm.-1 region to shift to shorter wave lengths, Miss McCall says. These changes stem from a decrease in the extent of hydrogen bonding, she ex­plains.

Recently developed cellulose modi­fication treatments that give perma­nent-press qualities to cotton produce an intermolecular cross-link between the cellulose chains. Reagents that cause this type of change are often difunctional or polyfunctional com­pounds of the N-methylol type. Many of these are urea derivatives such as

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Chemicals for Industry

SWIFT & COMPANY Chemicals for Industry Department 115 WEST JACKSON BLVD., CHICAGO, ILLINOIS 60604 In Canada: Swift Canadian Co., Limited, Guelph, Ontario In United Kingdom: Swift's Chemicals (U. K.) Ltd. Oriel Street, Liverpool 3, England

11DA8

MAY 27, 1968 C&EN 49

Swift

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Chemicals for Industry S W I F T & C O M P A N Y Chemicals for Industry Department 115 WEST JACKSON BLVD.. CHICAGO. ILLINOIS 6 0 6 0 4 In Canada: Swift Canadian Co , Limited. Guelph, Ontario In United Kingdom: Swift 's Chemicals (U.K.) Ltd. Oriel Street, Liverpool 3, England

ϋ 1 1 D B 8

DIRECT METHOD. Paul A. Wilks, Jr., adjusts an internal reflection IR spectrophotometer that directly analyzes a fabric containing blends of two different fibers

monomethylol urea, dimethylol urea, dimethylolethylene urea, triazines, triazones, urons, and carbamates. The extensive use of these compounds, many of which are closely related chemically, has caused increased in­terest in identifying reaction products which lead to superior fabric proper­ties. Infrared spectroscopy is a unique tool for identifying these compounds, Miss McCall says.

Infrared spectra of a number of fab­rics woven from two or more types of fibers can be obtained with the use of internal reflection spectroscopy, ac­cording to Paul A. Wilks, Jr., and John W. Cassels of Wilks Scientific Corp. (South Norwalk, Conn.). An impor­tant advantage of the internal reflec­tion technique is that infrared spectra can be obtained directly from the fabric with no special treatment.

In internal reflection spectroscopy a beam of light is internally reflected from the surface of a transmitting me­dium. A portion of the energy in the beam passes outside the surface and then is returned into it during the re­flection process. When a material of lower index of refraction than the transmitting medium is brought in contact with the surface, energy will be absorbed at those wave lengths

50 C&EN MAY 27, 1968

Swift

where the material absorbs. Thus an infrared spectrum of a material that is nearly identical to a conventional transmission spectrum can be pro­duced by internal reflection.

In the analysis of blends made from two different fibers, a 60° angle of in­cidence for the radiation gives better results than the 45° angle usually used in internal reflection, Mr. Wilks says. Analyses of blended fabric woven from threads containing both nylon and cotton are more reliable than those of fabric woven from threads of pure nylon and pure cotton, he points out.

Using the internal reflection tech­nique, Mr. Wilks and Mr. Cassels have quantitatively analyzed two different nylon-cotton blends. The results of the two analyses fitted closely to a calibration curve prepared from vary­ing ratios of pure nylon to pure cotton and agreed closely with the known composition values.

Although infrared absorption spec­tra are often capable of yielding quan­titative determinations of the chemical modifying reagent or resin used in durable-press or crease-resistant treat­ments, the infrared technique lacks sensitivity in certain instances. How­ever, the modifying reagent often con­tains an organometallic compound, an inorganic salt, or an oxide. In these instances, a spectroscopic pro­cedure to determine an element, me­tallic or nonmetallic, offers a very sen­sitive, rapid, and accurate method to measure quantitatively the identified resin, Robert T. O'Connor of USDA's Southern Regional Research Labora­tory points out.

Among the elements used in these modifying reagents are aluminum, cad­mium, sulfur, selenium, and chromium, to name just a few. Aluminum occurs in the form of the oxide in the reagent for soil resistance, as the hydroxide for water repellency, and as the 8-quinolinolate for resistance to micro­organisms. Cadmium is used as the chloride in microorganism resistance, as the pentachlorophenate in rot proof­ing, and as the hydroxide in flame and weather proofing. Sulfur turns up as the sulfone in cross-linking to achieve durable press. Selenium oc­curs as cadmium selenide in mildew proofing. And chromium appears as a perfluorooctanoic acid complex for water and oil repellency, as the oxide in rot or weather resistance, mildew proofing, or protection against ultra­violet radiation, as lead chromate in weather proofing or as a flame retard-ant, and as potassium dichromate in microorganism resistance.

Among the spectroscopic tech­niques used in Mr. O'Connor's labora­tory for the analysis of these and other elements are emission spectroscopy, x-ray fluorescence, and atomic absorp-

Try this... and see how Swift's Fluid Colloids may give you a helping hand

Piece e re drop cf worr> c o l l e d en one p a l r \ Po'af: po l r - i ' c n ^ h c r No'·? the l u b n c i ! / end η-„.;1. b . '~ ; : ' , c r cf a CO^' Γ · „ Ο „ ; f,!rr>.

Extremely thin film formation. Coacervation. Encapsulation. Pro­tective colloidal action. These are basic properties of Swift's Fluid Colloids which are demonstrated in the simple test described above. How can you use them to help control uniform particle formation . . . binding, suspending, emulsifying, or dispersing other materials, or as film-formers or release aids?

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Company-

Street -

City

iP le . i se Pr in t )

State. -Zip No.

MAY 27, 1968 C&EN 51

Swift

ft doesn't matter greatly whom you call...

Unless you want a laboratory chemical made to an unusual standard of purity

If you need a reagent that is made to an unusual standard of purity, the best place to call is MCAB. If we cannot produce it for you possibly we can suggest a source. We're interested in your requirements for new items, or for familiar ones made to new standards. Write to us at 2909 Highland Ave., Norwood, Ohio 45212 or phone (513) 631-3220. We'd like to hear from you.

ινκψ Matheson, Coleman ά Bell/Manufacturing Chemists

Norwood, Ohio/Los Angeles, California/East Rutherford, N.J.

tion. Atomic absorption spectroscopy, a comparatively new technique, is be­coming increasingly valuable in the rapid, quantitative determination of a large number of elements in textiles when the particular element deter­mined is known to be present. A number of textile producers such as Dan River Mills, Cone Mills, and Beaunit are running large numbers of elemental analyses using the atomic absorption technique.

RESEARCH IN BRIEF

Gas chromatography plays the central role in a method for fast detection of infectious diseases. The method, now under research at Cornell University, is based on determining the distinctive mixture of chemicals given off by a strain of bacteria or virus. So far, the method has been applied successfully to eight species of bacteria in mice and four types of viruses causing hepa­titis, herpes, distemper, anemia, bac­teria, influenza, and other diseases in dogs and horses. Cornell research as­sociate Brij M. Mitruka told the 68th annual meeting of the American Soci­ety for Microbiology, in Detroit, that each strain of bacteria or type of virus examined so far produces two or more kinds of unique chemical products. The method is sensitive enough to determine chemical changes from a single bacterial cell in some cases, he says.

An M.S. program in forensic science has been approved by the graduate activities committee of the City Uni­versity of New York. Starting as an evening program in September 1968, it is the only one in this field offered east of California, according to Dr. Alexander Joseph, of CUNY's John Jay College of Criminal Justice. Re­quirement for admission to the pro­gram, Dr. Joseph says, is a B.S. in chemistry. The purposes of the cur­riculum are to provide further educa­tion for directors and other profes­sionals in the work of crime laborato­ries and related areas and to prepare those interested in such careers. An­nouncement of the M.S. program fol­lows by one year the launching of a B.S. program in forensic science at John Jay College of Criminal Justice. The B.S. program combines analytical chemistry and forensic science.

Azo compounds have been created naturally by microbial action in soil treated with propanil (3'4-dichloro-propionanilide), a herbicide used to destroy weeds in rice fields. Dr. David Pramer and Dr. Richard Bartha of Rutgers College of Agriculture and

52 C&EN MAY 27, 1968

We produce eleven different aluminum alkyls.

Environmental Science find that soil micro-organisms decompose propanil. The first and short-lived product of the decomposition is an aniline. The aniline then undergoes further modifi­cation and ultimately condenses with itself to form an azo compound. The two biochemists also find that the en­zyme peroxidase can serve as a cata­lyst for converting anilines to azo compounds. The fact that anilines can be converted into azo compounds by micro-organisms is unexpected and new, Dr. Pramer says. "Since ani­lines are frequently an important con­stituent of different pesticides," Dr. Pramer points out, "we plan to investi­gate others and see if azo compound formation occurs only in the case of propanil or if it is a general reaction that must be under constant surveil­lance to safeguard public health and welfare."

A study of toxicological data users has been started by Science Communi­cation, Inc., Washington, D.C. The research and consulting organization specializes in the communication and use of scientific and technical informa­tion and will study the requirements of individuals and organizations using toxicological data. Under an 18-month, $156,000 contract from the National Library of Medicine, U.S. Public Health Service, the study will seek to identify distinct sets of users, in health research and application, to determine what kinds of data or infor­mation they are most likely to require, and to determine what methods of searching and delivery of information will best serve these users. Project findings will be used as design guide­lines for a national toxicological infor­mation system, now under develop­ment by the National Library of Medi­cine.

A joint air pollution study is under way by the U.S. Public Health Service's National Center for Air Pollution Con­trol, the Chicago Department of Air Pollution Control, and the Atomic En­ergy Commission through its Argonne National Laboratory. The three agen­cies plan to develop a computer pro­gram to predict the dispersion of sulfur dioxide from coal- and oil-fired plants in Chicago. NCAPC will provide $90,000 to support the study for nine months; Argonne will receive $40,000 for the same period from AEC. Ma­jor purposes of the study are to pre­dict levels of sulfur oxides during air pollution incidents and establish an effective pollution warning system, to develop air pollution abatement plans to minimize the severity of pollution incidents, and to develop long-range city and county plans which take into account the air pollution problem in developing zoning ordinances.

Many more are available in de­velopment quantities and, upon re­quest, homologs of these alkyls can be prepared for special research. Shipments are made in ten differ­ent size ICC approved cylinders (Vit, lb. to 2650 lbs. net wt.) and tank trucks of 30,000 lbs. or tank c a r s of 6 0 , 0 0 0 lbs . m i n i m u m

weight. Another big plus — Texas Alkyls engineers are always avail­able to provide service based upon their years of experience in appli­cation, shipping, handling and safe­ty. Don't forget, too, that Stauffer makes a broad line of copolymeri-zation catalysts of vanadium and titanium.

TEXAS ALKYLS, Inc., 6910 Fannin Street, Houston, Texas 77025. Exclusive Sales Agent: Stauffer Chemical Company, Specialty Chemical Division, 299 Park Avenue, New York, N. Y. 10017.

MAY 27, 1968 C&EN 53

ROUNDUP OF TEXAS AI KM S

COMMERCIAL I'RODUTS!

• EADC ethylaluminam dkhloride

• DEAC dtethylalumimim chloride

• DEAI diethylalumimim iodide

• TEAL triethylaluminum

• EASC ethylaluminum sesquichloride

• TNPRAL tri-ft-propylaluminum

• DIBAC diisobutyl-alumioum chloride

• TIBAL triisobutylaluminum

• ISOPRENYL isoprenylaluminom

• DIBAL-H diisobutyl-aluminum hydride

B MONIBAC moooisobutylaloniinum dichloride

PLUS DEVELOPMENT QUANTITIES OF:

Diethylaluminum fluoride Methylaluminura sesquichloride Tri-n-butylaluminum Diethylaluminum bromide Tri-/i-hexylaluminum Trimethylaluminum

Triisohexylaluminum Tri-M-octylaluminum Tri-n-decylaluminum Diethylaluminum hydride Ethylaluminum diiodide Tri-/i-dodecylaluminum

Di-n-propylaluminum chloride Dimethylaluminum chloride Tri-/t-hexadecylaluminum if-Propylaluminum dichloride Diethylaluminum ethoxide