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Volume 253 July 1975 Number 7
Polymer Science • Polymere
Twente University of Technology, Enschede (The Netherlands), andMiddle East Technical Universify, Ankara (Turkey)
A preparation technique for examination of wet-spun polymer fibersin a scanning electron microscope
D. M. Koenhen, M. A. deJongh, C. A. Smolders
N. Yiicesoy*)With 8 figures
(Received November 29, 1973)
1. Introduction
In the investigation of morphological struc-tures by a scanning electron microscope(SEM) the factors which effect the resolutionpower and magnification can be derided intotwo groups. Those factors connected withthe design of the instrument will depend onthe specification provided by the manufac-turer. On the other hand, sample properties,sample preparation and conditions during ex-amination in the microscope form a group ofvery important variables. Therefore with theinstrument available, much attention should bepaid to the last group of variables.In our laboratory we are studying coagula-tion phenomena of polymer solutions incontact with non-solvents.Especially the changes in morphologyduring coagulation of the polymer phaseare relevant to polymer membrane and fiberstructure and properties.In order to study the morphology during allstages of coagulation of a spinning fiber, wetried to use the freeze-shock and freeze-etching technique in combination with trans-mission electron microscopy (1). Difficultiesin obtaining a satisfactory cleavage surface
*) Research Associate at Twente University duringthe academic year 1971--1972.
with the freeze ultramicrotome for severalpolymer species, forced us to look for adifferent method. The present study of morph-ological structures makes use of the largedepth of field of the SEM. Sample preparationconsists essentially of cryogenic breaking of awet-spun fiber, followed by a low temperatureand low pressure freeze drying (or etching)treatment.To prevent charging up of the sample in themicroscope a coating is given with a chargeconducting layer.
2. Sample preparation
Previously (2, 3, 4) methods have beendeveloped for the examination of externalfiber surfaces and fatigue broken fiber ends byscanning electron microscopy. Attention waspaid to coating techniques, by vapour deposi-tion of carbon and metals like Ag, Au and Pt.A cryogenic breaking technique has alsobeen employed earlier, for the investigation ofdry polymer membranes (5) and biologicalmaterials (6).In the present work excellent fracture sur-faces Of freshly coagulated wet-spun fibershave been obtained through breaking underliquid nitrogen or liquid propane. To revealthe coagulation structure of the polymer, thespecimen is then freeze-dried (or etched) at low
M 930
Colloid and Polymer Science, Vol. 253 • No. 7
temperature and pressure in special equipment(Leybold Hereaus EPA--100). Either thewhole specimen or only a part of it can befreed from solvents in this way. We willdescribe here procedures for preparing sampleswhich are completely coagulated during wet-spinning, or which are only partly coagulated.Coating and further handling of these smallfiber samples is described also.
A. Completely coagulated fibers
The morphological structure of wet spunfibers depends strongly on the composition ofthe polymer solution (polymer content) and ofthe coagulation bath (solvent/non-solventratio).To prevent modifications of the finalstructure which has been obtained in thecoagulation bath (e.g. after 24 hours equilibra-tion) the remaining solvent in the fiber shouldbe exchanged for non-solvent as completely aspossible. This procedure is necessary sinceduring drying of the fiber the relative contentof a high boiling solvent could increase, withthe result that the polymer might redissolveand the structure might be distorted or evencollapse.In the case of polyurethane/DMF solutionsspun to equilibrium in coagulation baths ofdifferent ratios of DMF/water, the fiber wasequilibrated during successive periods of 24hrs. in mixtures of DMF/water with increasingwater content, up to pure water.The fiber was then cooled rapidly in liquidnitrogen and cryofractured with the help oftwo tweezers. Two alternative ways of dryingthese samples completely have been followed.
A 1. Low temperature drying
The frozen fiber sample is transferreddirectly to the freeze-drying apparatus (EPA--100), then at --50 °C and at a pressure of 10 -5Torr the specimen is dried completely, whichtakes several hours.The fiber is then coated with a thin charge-conducting layer and subsequently placed, atnormal T, on a SEM-disk (see section C).
A 2. Room temperature drying
The fiber specimen is brought to roomtemperature, placed on a SEM-disk (section C)and transferred to the freeze-drying apparatus,where at normal temperatures and at mode-rately lowered pressures the fiber is dried.This takes only several minutes. Subse-quently the fiber is coated with carbon andgold.It is clear that this last method can only beapplied for fibers which have enough mechan-ical strength, to withstand the capillary forcesoperative in porous structures during drying.For the fibers investigated in this study(polyurethane and nylon-6) both drying pro-cedures gave identical structures.After breaking and drying, the specimen hasto be coated with a thin (200-300 A) chargeconducting layer. Carbon and gold are hereapplied by vapour deposition. During coating,the samples were kept at low temperature(cooling finger of the EPA--100) in order toprevent heat damage to the fiber structure.
B. Intermediate stages of coagulation
In order to study early stages in coagulationthe spinning fiber was picked up from thecoagulation bath using two tweezers coupledat fixed distance and the sample was put intoliquid nitrogen immediately.Knowing the spinning speed (cma/sec), thediameter of the fiber and taking samples atdifferent distances from the spinneret, the timeof coagulation can be varied. The fiber isbroken under liquid nitrogen, put in a specialclip and transferred directly at low temperatureto the EPA-100.Since solvent is always present in this caseand since (like for DMF/water) the solventmay have a higher sublimation point than thenon-solvent, it is not possible here to dry thespecimen completely.In the case of DMF, with a freezing point of--60°C one should stay at a low enoughtemperature during etching to prevent redis-solution of the polymer in the eutectic melt ofthe DMF/water system. Therefore the spec-imen was freeze-etched for a limited time(a few hours) at --100 ° C and at a pressure of10 -5 Torr, so that enough solvent/non-solvent could have sublimated to reveal thestructure of a sufficiently deep surface layerat the cleavage plane.Subsequently the deeply cooled sample wascoated with a relatively thick (about 400 ~t)layer of carbon, to preserve the morphological
Koenhen et al., A preparation technique or examination of wet-spun polymer fibers
structure features of the etched surface. A thinlayer of gold was applied to provide surfaceconductance.The sample was then brought at roomtemperature and normal pressure and theremaining DMF and water in the fiber werecarefully removed in the EPA--100 apparatusat moderately lowered pressures, or thepolymer was coagulated completely by placingthe fiber in DMF/water mixtures of increasingwater content up to pure water and driedthereafter.The fiber specimen could then be placedon a SEM-disk (section C).
C. Fiber handling or microscopy
Examination of fracture surfaces of fibersin the SEM raises the question how to keepthe fiber vertically under the electron beam.A simple solution was found to this by ad-hering the fiber specimen at one end in avertical position to a disk of the SEM, usinga charge conducting paint (Dotite silverpaint).The intimate contact between the coatedfiber and the silver provides a better meansof charge flow than squeezing the fiber be-tween stages manipulated with a screw.Good results are obtained when the fiberspecimen is not longer than about 3 ram. Withlonger fibers bending over of the fiber mightgive problems and also possible discon-tinuities in the coating layer might accumulateto give limited charge dissipation.
The microscope used in this study was aJEOL-JSM.U3 scanning electron microscope,operated at an acceleration voltage of 25 kV.The fibers were spun from spinnerets withdiameters of 0.2--0.5 mm. This producesrelatively thick fibers, which facilitates thehandling of the fiber.Fig. 1 shows a fiber which was spun froma 25% polyurethane solution in DMF in purewater. The fiber was prepared further with thetechnique described under A J, (low tem-perature drying). A similar fiber prepared asdescribed under A2, (room temperaturedrying) is shown in fig. 2.
Fig. 1. Wet spun polyurethane fiber: 25{~o PU in DMFspun in pure water; sample preparation by low tem-perature dryingFig. 2. Wet spun polyurethane fiber: 25c~ PU inDMF, spun in pure water; sample preparation byroom temperature drying
In fig. 3 a fiber is shown, wNch was spunin a coagulation bath of 20% DMF/80%H20 from a 25% polyurethane solution inDMF. The preparation technique used aftercomplete exchange of DMF for water wasaccording to A2.

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