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0022–2461
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of duplicate measurements with a typical error of and molecular mass spectral data by bombarding the
±5%. sample surface with a primary ion beam and analysing
For each sample analysis, a total primary-ion dose of the masses of the sputtered secondary ions emitted from
less than 1 × 10−12 ions cm−2 was used, well below the surface. The experiment is performed under ultra-
the threshold of 1 × 1013 ions cm−2 for static SIMS. high vacuum in order to allow the efficient passage of
Both positive and negative ion spectra were acquired the ions through the Time-of-Flight mass spectral anal-
from an area of 250 µm × 250 µm in the mass range yser. Thus both positive and negative ion mode data can
m/z = 0–1000. be obtained. The control non-softened paper showed a
relatively high intensity ToF-SIMS positive ion spec-
2.3. Kawabata evaluation system for fabrics trum in the m/z = 0–100 range, typical of the fragmenta-
(KES-F) (7) tion of organic material. No ion intensity was observed
The samples, 20 × 20 cm, were conditioned at 65% in the m/z = 450–700+ region.
R.H. and 20◦ C for 24 hrs prior to testing. Although Examination of the positive ion ToF-SIMS spectrum
the KES-F system measures bending, shear, tensile, of the cationic dialkyl dimethyl quaternary ammonium
compression and surface properties only the surface Softener A film and treated paper showed three strong
analyser was utilized. The test conditions for the paper signals at m/z = 494+ , 522+ , 550+ , Figs 1 and 2. These
were 10 gf pressure for the surface roughness probe and signals confirm that the softener is a mixture of C18
50 gf for the friction probe. The data presented were an and C16 derivatives with the molecular ion structures
average of ten measurements per sample. The statisti- shown, Scheme 1. Both stearyl and oleyl C18 derivatives
cal analyses were performed using the Microsoft Excel are evident from the ToF-SIMS spectrum.
package and the Student t-Test values determined. Quantification of ToF-SIMS data can present diffi-
culties due to the relatively high proportion of neutral
secondary particles produced in comparison to positive
3. Results and discussion and negative secondary ions. However, previous ToF-
The subjective perception of smoothness of textiles is SIMS studies have successfully monitored the relative
closely related to softness, with the MMD value be- surface changes on a number of organic systems using
ing strongly correlated to the subjective perception of the formula IA /(IA + IB ), where IA and IB are mea-
smoothness [8]. With paper, smoothness/softness has sured intensities of ions A and B, respectively [11–13].
been correlated with surface roughness, SMD [9], al- For the calculations IA corresponds to the peak inten-
though the perception of smoothness will also be in- sity of the softener ion of interest and IB to the peak
fluenced by the slip/stick effect of the variation in the intensity of the signal at m/z = 41+ (C3 H+ 5 ), a non-
coefficient of friction, MMD. Therefore the effect of specific ion characteristic of organic surfaces. Analy-
softeners will be important in subjective analysis by sis of the softened paper under identical experimental
lubricating the surface and enhancing surface deforma- conditions has shown that the softener A ion intensity,
tion to create the impression of smoothness/softness. m/z = 550+ , similarly increases as the softener addi-
ToF-SIMS is an excellent technique for character- tion to the pulp increases, Fig. 3. In addition to the
izing surface chemistry and in particular fibre surface cationic species the negative ion ToF-SIMS spectra of
absorbates [7, 10]. The surface sensitive technique, with the softener film and paper also indicate the presence
its sampling depth of 1–2 nm, provides both elemental of the fatty palmitic (C15 H31 CO− −
2 ), oleic (C17 H33 CO2 ),
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Figure 2 Positive ion ToF-SIMS spectrum of softener A treated (0.4% wt/w) paper.
Scheme 1 Ion assignments in positive ion ToF-SIMS spectrum of softener A (dialkyl dimethyl quaternary ammonium ion).
Figure 3 Effect of application concentration of softener A on ToF-SIMS intensity ratio (IA , m/z = 550+ ).
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T A B L E I KES-F analysis of the mean deviation of coefficient of friction, MMD, of paper
MMD value
0.1% 0.2% 0.3% 0.4%
Control softener A softener A softener A softener A
MD CD MD CD MD CD MD CD MD CD
Mean 0.0271 0.0326 0.0230 0.0258 0.0197 0.0216 0.0168 0.0176 0.0143 0.015
SD 0.0027 0.0018 0.0020 0.0037 0.0051 0.0042 0.0040 0.0034 0.0010 0.0010
Figure 4 Student t-test analysis of effect of softener concentration on paper smoothness, MMD.
Figure 6 Positive ion ToF-SIMS spectrum of 0.4% (wt/wt) softener B treated (0.4% wt/wt) paper.
Figure 7 Effect of application concentration of softener B on ToF-SIMS intensity ratio at paper/surface (IA , m/z = 642+ ).
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Figure 8 Positive ion ToF-SIMS spectrum of softener C treated (0.4% wt/wt) paper.
Scheme 3 Proposed structure of softener C, a cationic mainly C18 /C16 diester dialkyl type quaternary ammonium softener.
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3. S . K A W A B A T A , “The Standardization and Analysis of Hand 9. J . J . K I M , I . S H A L E V and R . L . B A R K E R , Tappi J. 77(10)
Evaluation,” 2nd ed., (The Hand Evaluation and Standardization (1994) 83.
Committee, The Textile Machinery Society of Japan, July, 1980). 10. S . V O L O O J , C . M . C A R R , R . M I T C H E L L and J . C .
4. J . S . B R I N E N , Nordic Pulp Paper Res. J. 8(1) (1993) 123. V I C K E R M A N , Surf. Interface Anal. 29 (2000) 422.
5. Y . O Z A K I , ibid. 12(4) (1997) 260. 11. M . C . D A V I E S , S . R . L E A D L E Y and N . M . F R A N S O N ,
6. R . J . K U L I C K and J . S . B R I N E N , Tappi J. 81(2) (1998) Polym. Adv. Technol. 3 (1992) 293.
152. 12. G . N . B A T T S and A . J . P A U L , Langmuir 10 (1994) 218.
7. J . C . V I C K E R M A N and A . J . S W I F T , “Surface Analysis— 13. M . R . A L E X A N D E R and F . R . J O N E S , Carbon 33 (1995)
The Principal Techniques,” edited by J. C. Vickerman (J. Wiley and 569.
Sons, 1997).
8. E . F I N N I M O R E and A . K O N I G , Melliand Textilberichte 67(7) Received 2 August
(1986) 516. and accepted 11 November 2002
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