Professional Documents
Culture Documents
and materials*
J. W. S. Hearle
Department of Textile Technology, University of Manchester
Institute of Science and Technology, Manchester M60 1QD, UK
and S. C. Simmens
Shirley Institute, Didsbury, Manchester, UK
(Received 1 December 1972)
Table 2 Common techniques and applications of scanning luminescence can also be used, though care is needed in
electron microscopy to fibres, yarns and fabrics interpretation of results on complicated surfaces, because
the contrast arises both from differential light emission
Techniques Applications
and direction (topographical contrast).
Basic specimen : Low magnification
Direct observation of Assembly structure--arrangement
sample* of fibres in yarns or non-woven SOME SPECIAL TECHNIQUES
fabrics, and yarns in woven or
Cut end (plate method)* knitted fabrics as produced or Swelling and staining
modified The central problem in the use of electron microscopy
Section, moderately
thick (>1/zm)*
to help in understanding fibre structure is to find a
Presence of soil or foreign objects means of showing up structural elements which may be
Disintegration of fibres Identification of fibres in structure present.
(blend distribution, faulty fibres) It has been common practice to stain fibre sections to
Peeling of fibres Observation of damage in textile enhance contrast, e.g. heavy-metal containing substances
products
Thin section such as osmium tetroxide are taken up differentially by
Examination of original, Medium magnification: wool fibres depending on variations in protein composi-
cut or ruptured Fibre shape and form tion. However, the range of techniques is steadily being
surfaces* Fibre surface structure, roughness, expanded. For example, Swift 9 has developed specific
Other features: defects or damage
Reduction of charging Particles on fibre surface stains for particular amino acid residues in hair fibres.
by metal-coating, or Fracture morphology Stains can also be used to show up differences in accessi-
soaking or spraying Gross internal features (cell struc- bility, and for this purpose a mild swelling treatment
with antistat* ture in wool, voids, macrofibrils, etc) may first be given. Ingrain1°, 11 treats cellulose fibres,
Distribution of resins or finishes
Choice of viewing angle (external or internal) location of
such as Ramie, with caustic soda and then phosphotung-
conditions and variations in composition stic acid in order to show up a fibrillar structure.
magnification* A further development has been reported by Billica
Analysis of X-ray et al. 12. A synthetic fibre is swollen in the vapour of
emission High magnification: boiling methyl methacrylate (or some other vinyl mono-
Imaging in X-ray mode Fracture detail
Contribution to elucidation of fibre mer) for about 3 h; polymerization of the monomer
fine structure then occurs over a few days and, finally, the reactive
polymer, which now impregnates the fibre, is stained
* In frequent use at UMIST with osmium tetroxide. In addition to opening up the
then allow it to dry before examination. The Duron material slightly in order to clarify the structure, the
may be sprayed on, but this has the disadvantage of impregnation also helps to support the fibre and preserve
giving droplets on the specimen. structure during sectioning.
It should also be noted that it is often possible to Another swelling and staining technique is described
examine specimens as received without any antistatic by Sotton et al. 13-15. Fibres are first exposed to hydrogen
treatment, if the viewing conditions are carefully chosen. sulphide under pressure and then reacted with silver
In general, the choice of viewing conditions involves a nitrate. Some examples are shown in Figure 9.
compromise and, in any except the easy specimens,
effort spent in securing the best compromise in relation Dark-field (diffraction contrast)
to the type of specimen and the needs of the investigation Where a specimen contains crystalline regions, contrast
will do much to improve the results. The parameters can be generated by dark-field viewing. By selecting one
available for variation are accelerating voltage, beam part of the diffraction pattern, and using it to form the
current, lens currents, aperture sizes, viewing distance, image, crystallites with a particular orientation show up
astigmatism correction, and exposure time: these interact as bright patches. Ingram10,11 has used this method to
together to influence resolution, contrast, depth of focus, show up continuity of orientation over lengths of about
penetration and spread in specimen, charging troubles, 40 nm in fibrils in cellulose fibres; but he points out that
specimen damage, and specimen movement or vibration it is difficult to get good results because cellulose is very
error. These problems and, in particular, the advantage susceptible to electron damage, and so it is necessary to
of using relatively low voltages for fibre examination are use a low beam intensity, which with weak diffraction
discussed by Hearle et al.8. gives a very weak signal.
The plate method is an easy method for examining Earlier, Peterlin et al. 16 applied the technique more
fibre cross-sections. The individual fibres, or the yarn, successfully on laboratory-prepared specimens of poly-
are surrounded with a bundle of packing yarn, and then ethylene, but it is a technique which might be explored
pulled through a hole in the stub with a wire or strong more in studying synthetic fibre structure.
yarn. The surface is then cut flush and coated. It is
necessary to ensure that the yarns are tightly packed Disintegration
before cutting. Another way of studying fine structure is to break up
Comments on disintegration, peeling and sectioning of the fibre. The classical methods are well-known and
fibres have already been made in connection with direct have already been mentioned. A comparatively new
electron microscopy. method, utilizing the X-press equipment of Biotec,
Some examples selected from our studies at UMIST involves forcing a frozen mixture of water and fibres
using these methods are shown in Figure 8. through an orifice under high pressure. The principles
The X-ray emission mode is being used for identifica- were described by Edebo 17. At -25°C and 2x 105kg/
tion of location of finishes, soil particles etc. Cathodo- mm 2, ice undergoes a crystal lattice transition. At the
Figure8 Examples of scanning electron microscope studies of textiles. (a) Cross-sectional shape of cellulose acetate fibres by the plate
method; (b) wool fibre; (c) internal surface of nylon-6 filament revealed by peeling; (d) bonded-fibre fabric; (e) conventional (ring-frame)
cotton yarns; (f) comparative study of break-spun yarn; (g) cotton-polyester blend fabric, showing general structure and singed fibre
ends; (h) used cotton-nylon sheets showing fibre damage. [From work of B. Lomas, B. H. Bhutta and K. L. Ghandi (UMIST)]
Figure9 Use of staining methods by SottonZ3-zS--treatment with HzS followed by AgNO3 to show structural differences. (a), (b) stained
acrylic fibres; (c), (d) surface region of polyester fibres. (Pictures by courtesy of M. Sotton, Institut Textile de France)
Figure 10 Use of X-press method on fibres. (a) Nylon, after 10 passes, showing little change apart from distortion due to buckling (s.e.m.);
(b) fibre B, after 10 passes (s.e.m.); (c) fibre B, after 10 passes (s.e.m. higher magnification); (d) fibre B, after 10 passes (direct electron
microscope); (e) fibre B, after 10 passes (direct electron microscope, higher magnification); (f) viscose rayon, after 10 passes; (g) cotton,
after 2 passes; (h) resin crosslinked cotton after 2 passes. [Pictures by B. Lomas and J. T. Sparrow (UMIST) and S.C.S.)]
Figure 11 (a) High-voltage transmission electron microscope view of a fractured carbon fibre; (b) s.e.m, view of fibre. (Pictures by courtesy
of d. V. Sharp, AERE, Harwell)
/
II
Figure 12 Fibril of cotton (65 000×) (S.C.S.). Short sections, located on the line diagram, are shown to allow adequate magnification in
the print
can interpret the difference between fibres which are electron microscope pictures is not easy or unambiguous,
formed by direct crystallization (precipitation) from and Preston 2s argues strongly that the basic fibrillar
solution, followed by stretching, and those which are units are thicker. Evidence from other sources (X-ray
formed by crystallization in the oriented solid state as diffraction, chemistry, biosynthesis) is inconclusive or
being a difference between a micellar and a fibrillar conflicting.
texture. In wool, fibrillar disintegration does not easily occur,
In natural cellulose fibres, there is clearly a coarse but the staining of sections shows micro fibrils about
fibrillar structure, and this breaks down into separate 70A in diameter spaced 100A apart in a matrix (Figure
fibrils. The problem of the identity of the ultimate micro- 14). A wealth of circumstantial evidence identifies the
fibril is well illustrated by Figures 7 and 12, which show microfibrils with helical crystalline material made of
cotton mechanically disintegrated in a blendor. In low-sulphur protein and the matrix with amorphous
Figure 12, there is an enormous length of a fibril, about material of high-sulphur (cystine crosslinked) protein.
7/~m, with lateral dimensions of about 120A; but at There is believed to be a continuity between the helical
the end, it splits into finer fibrils. The question is whether segments of chains in the microfibril and their tails in
these represent a smaller basic unit (a protofibril), or the matrix. In the stained cross-sections, the eye of faith,
whether they are merely the result of cleavage between looking with some reason for double or triple helices,
the molecules in the coarser fibrillar crystallite. Examina- can see indications of a protofibrillar internal structure
tion of the residue left on evaporation of the liquor of the microfibrils; but interpretation of the electron
shows globular particles which may well be single micrographs at this level is difficult, though Fraser et
molecules resulting from the ultimate splitting of the aL 24 have shown that it can be helped by optical filtering.
crystals. Thus there is doubt about evidence from disinte- More convincing evidence came with the apparent
gration studies, even if one can accept the measurements isolation of protofibrils by disintegration of wool. How-
of the size of the protofibrils, near the limit of resolution. ever, Millward ~5 and Fraser et aL ~6 have shown that the
Fibrils can be shown up in thin sections, or disintegrated 'protofibrils' can arise from contamination of the
lamellar fragments, by developing contrast by the staining specimen with cellulose--providing, incidentally, in their
methods mentioned earlier, as shown in Figure 13. studies of disintegrated Kleenex tissue some of the best
ingraml0, zl states that this suggests that the secondary pictures of finer cellulose fibrils. Dobb and Sikorski 27, 28
walls in cotton are lamellae consisting of partly coalesced do not accept that the observed protofibrils always arise
fibrils of about 50A in lateral width. Manley 22 has in this way. They show by selected area electron diffraction
proposed very specific crystallographic modes of fibre that fragments from a disintegrated Merino wool fibre
formation, and finds support in his electron microscope were indeed keratin; however, these were relatively
studies. However, the detailed interpretation of the large sheets not isolated protofibrils and, as in other
Fibre fractography
The advent of scanning electron microscopy has
opened up the subject of fibre fractography, and has
been the most important aspect of our s.e.m, work at
UMIST. Because it shows the whole specimen in focus
(as compared with the very limited depth of focus in an
optical microscope) the general features of fibre fracture
are clearly visible in s.e.m, views and, in addition, much
fine detail can be examined at higher magnification.
The work is important for several reasons: (a) for its
general scientific interest; (b) for the insight into mecha-
Figure 14 Stainedsection of wool. [Reproducedfrom d. Textile nisms of failure in fibres, and thus as a guide to the
Inst. (1969,60, 498) by permission of the Textile Institute]
possibility of improvement of fibre properties by the
fibre producer; (c) for the insight into the causes of
such specimens, the evidence that they were composed failure in use and processing and thus as a guide to
of 2 n m filaments does not seem conclusive. At the improvement in processing methods or into construction
moment, it is difficult to avoid taking the view that while of yarns, fabrics and garments; (d) as a means of diagnosis
protofibrils may exist in wool, there is no convincing of causes by failure.
evidence for their existence. The results can be briefly summarized by a classifica-
The main evidence against a fibrillar fine structure in tion of the forms of fracture which have been observed.
polyamide and polyester fibres is the difficulty of pro- There are, however, many variants and combinations of
ducing fibrils by fibre disintegration or fracture--in the basic forms, and a full account of the work is, or
comparison, for example, with the ease with which will be, contained in other papers, including a continuing
fibrillation occurs in cotton or wet-spun acrylic fibres. Atlas of pictures al.
This would suggest that the structure is a partially The fibre fractures, so far observed, can be divided
ordered network of shorter elements or a micellar into the following classes.
REFERENCES
1 Chapman, J. A. and Menter, J. W. Proc. R. Soc. (A) 1954, 226,
400
2 Chapman, J. A., Pascoe, M. W. and Tabor, D. J. Text. Inst.
1955, 46, 3
3 Dlugosz, J. Proc. 1st Eur. Reg. Conf. Electron Microsc., Stockholm
1956, p 283
4 Ramanthan, N., Sikorski, J. and Woods, H. J. Proc. Int. Conj.
Electron Microsc., London 1954, p. 482
5 Scott, R. G, A S T M Spec. Tech. Publ. No. 257 1959, p 121
6 Byrne, G. A. and Brown, K. C. J. Soc. Dyers Colour. 1972, 88,
113
7 Chippendale, P. J. Text. Inst. 1960, 5 (11), T392
8 Hearle, J. W. S., Lomas, B. and Sparrow, J. T. J. Microsc.
1970, 92, 205
9 Swift, J. A. J. Text. Inst. 1972, 63, 64, 129
10 Ingram, P. Papers of SIRTEC, Institute Textile de France, 1969,
Figure 17 Fatigue failure of nylon. [Picture by A. R. Bunsell and p 519
L. Konopasek (UMIST)] 11 Peterlin, A. and Ingrain, P. Text. Res. J. 1970, 40, 345
12 Billica, H. R., van Veld, R. D. and Davis, H. A. 7th Int. Electron
Microsc. Congr. Grenoble 1970, p 335
13 Sotton, M. C.R. Acad. Sci. Paris 1970, 270, 1261
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1381
15 Sotton, M. and Vialard, A-M. Text. Res. J. 1971, 41, 834
16 Peterlin, A., lngram, P. and Kiho, H. Makromol. Chem. 1965,
86, 291,
17 Edebo, L., J. Biochem. Microbiol. TechnoL Eng. 1960, 2, 453
18 Sharp, J. V. and Burnay, S. (3. Proc. 25th Anniv. Meet. E M A G
Inst. Physics, London, 1971, p 28
19 Hearle, J. W. S., Clarke, D. J., Lomas, B., Reeves, D. A. and
Sparrow, J. T. Proc. 25th Anniv. Meet. E M A G Inst. Physics,
London, 1961, p 210
20 Lipson, H. and Lipson, S, G. J. Appl. Cryst. 1972, 5, 239
21 University of Leeds, Textile Industries Department, exhibit at
EMCON 1972
22 Manley, R, St. J. J. Polym. Sci. (A-2) 1971, 9, 1025
23 Preston, R. D. J. Microsc. 1971, 93, 7
24 Fraser, R. D. B., MacRae, T. P. and Millward, G. R. J. Text.
Inst. 1969, 60, 343
25 Millward, G. R . J . CellBiol. 1969, 42, 317
26 Fraser, R. D. B., MacRae, T. P. and Millward, G. R. J. Text.
Inst. 1969, 60, 498
27 Dobb, M. G. and Sikorski, J. J. Text. Inst. 1969, 60, 497
28 Dobb, M. G. and Sikorski, J. Appl. Polym. Syrup. 1971, 18, 743
29 van Veld, R. D., Morris, G. and Billica, H. R. J. AppL Polym.
Sci. 1968, 12, 2709
30 Hearle, J. W. S. and Greer, R. J. Text. bzst. 1970, 61,243
Figure 18 Acrylic fibre tensile fracture. [Picture by B. Lomas 31 'An Atlas of Fibre Fracture', (continuing series) Text. Manuf.
(UMIST)] 1972 (.January), No. 1
32 Hearle, J. W. S. and Cross, P. M. J. Mater. Sci. 1970, 5, 507
fibre axis to give breaks in two or more steps. This type 33 Hearle, J. W. S, and Sparrow, J. T. Text. Res. J. 1971, 41, 736
of failure resembles, at many orders of magnitude smaller 34 Bunsell, A. R. and Hearle, J. W. S. J. Mater. Sci. 1971, 6, 1303
in scale, the fracture of fibre-reinforced composites and
is probably due to the separate rupture of fibrils within
General references
the fibre.
J. A. Chapman in 'Physical Methods of Investigating Textiles',
Failure from kink-bands. Fibres in compression, for (Eds J. W. S. Hearle and R. Meredith), Interscience, New York,
example on the inside of a bend, develop oblique bands 1959, Ch 3
'Fibre Structure', (Eds J. W. S. Hearle and R. H. Peters), Butter-
visible in polarized light. Under repeated flexing, failure
worths, London, 1963
occurs along these bands. This is an area of current study. J. W. S. Hearle and R. Greer, Text. Progr. 1970, 2, (4)
'The Use of the Scanning Electron Microscope', (Eds J. W. S.
Other breaks orfibre ends. This is a miscellaneous group Hearle, J. T. Sparrow, and P. M. Cross), Pergamon Press, Oxford,
not separately classified. It includes fibres which are cut, 1972