Polym. Bull.

(2013) 70:1303–1312
DOI 10.1007/s00289-012-0855-2

ORIGINAL PAPER

Hansen solubility parameters of cellulose acetate

butyrate–poly(caprolactone) diol blend by inverse
gas chromatography

S. Ramanaiah • A. Sudharshan Reddy • K. S. Reddy

Received: 14 May 2012 / Revised: 22 July 2012 / Accepted: 12 September 2012 /

Published online: 22 September 2012
Ó Springer-Verlag Berlin Heidelberg 2012

Abstract The specific retention volumes, Vg0 , for adsorption of 21 solute probes on
the solid surface of cellulose acetate butyrate (CAB)–poly(caprolactone) diol
(PCLD) blend determined in the temperature range by inverse gas chromatography
were used to evaluate Hansen solubility parameters (HSP). The effect of plasticizer,
PCLD, on the HSP of CAB was investigated. The three components of HSP namely
dispersive dd2 , polar dp2 , and hydrogen bonding dh2 of the blend surface were com-
pared with the CAB surface. The dh2 of CAB was increased due to the addition of
PCLD, while the change in the dispersive and polar components was found to be
insignificant. The three HSP were decreasing linearly with increase of temperature
for the blend as well as for pure CAB. The variation of HSP with weight fraction of
CAB shown that the dp2 was positively deviating from linearity whereas dd2 and dh2
were negatively deviating from linearity.

Keywords Cellulose acetate butyrate–poly(caprolactone) diol blend 

Inverse gas chromatography  Hansen solubility parameters

Introduction

Inverse gas chromatography (IGC) technique has been demonstrated as an effective

tool for the determination HSP for the solid surfaces [1–7]. The total solubility
parameter is related to the total cohesive energy of a material that holds the atoms
and molecules of that material together. The HSP are derived by subdividing the
total solubility parameter into three components which expresses the contribution
from the three types of intermolecular forces viz. dispersive, polar, and hydrogen

S. Ramanaiah  A. S. Reddy  K. S. Reddy (&)

Department of Chemistry, Sri Venkateswara University, Tirupati 517 502, India
e-mail: ksreddy01@rediffmail.com

123
1304 Polym. Bull. (2013) 70:1303–1312

bonding of the material. HSP provide insight into the balance of dispersive, polar,
and hydrogen bonding forces operating between the material surface and adjacent
molecules. HSP can be used for estimating various physicochemical parameters of
materials. A thorough knowledge of HSP of drugs and excipients can enhance our
awareness of how pharmaceutical materials can behave when processed or dosed
into the human body [8]. HSP of solid surfaces can be applied to evaluate its
interaction with the solvents and analytes. In the solid phase extraction a knowledge
of HSP of polymers, eluents, and analytes can help in the suitable selection of
sorbent–eluent system for extraction of a particular analyte [9]. Number of polymers
can be reduced by using polymer blends as sorbents, since the HSP of polymer
blend may be different from the two pure polymers applied to form the blend.
The wide ranges of applications of cellulose esters have been thoroughly
discussed in a recent review [10]. Cellulose esters have received a great deal of
attention in the pharmaceutical industry as they possess excellent properties as
membrane materials. The properties of cellulose esters can be varied by controlling
the type and number of ester substituents, thus increasing the applications of
cellulose esters. The physiochemical properties of cellulose esters can also be
altered to suit the desired applications by addition of a plasticizer. The CAB is a
widely used biodegradable adsorbent material, particularly in waste water treatment,
as membrane material in controlled drug delivery process and in medication
adsorption, etc. [11]. The poly(caprolactone) diol can be used as a plasticizer to
biodegradable polymers in order to modify the morphology and properties
biodegradable polymers. A plasticizer usually decreases the intermolecular forces
between the polymer chain resulting in the formation of a softened and flexible
polymeric matrix. The addition of PCLD will change the HSP of CAB. The change
in solubility parameters and surface energy of CAB due to addition of PCLD will
enhance the applicability of CAB–PCLD blend in the industrial field.
The determination of HSP for the solid surface using IGC data has been proposed by
Voelkel et al. [1] based on the adsorption model described by Karger et al. [2]. The
purpose of this paper is to characterize the solid surface of CAB–PCLD blend using
HSP and compare with the solid surface of pure CAB. The variation of HSP with the
composition of CAB in the CAB–PCLD binary system has been investigated. A
survey of literature revealed that HSP for the CAB–PCLD surface has not been studied
earlier. Therefore, the specific retention volumes for 21 solute probes were determined
at seven temperatures and applied in the calculation of HSP.

IGC theory

The specific retention volumes for 21 solute probes are calculated using the
following relation.
 
0 273:15 P0  Pw
Vg ¼ ðtR t0 ÞJF ð1Þ
wT P0
where tR is the retention time of the probe solute, t0 is the retention time of methane,
F is the flow rate of the carrier gas, T is the column temperature, w is the mass of the

123
Polym. Bull. (2013) 70:1303–1312 1305

stationary phase, Pw is the water vapour pressure at room temperature, P0 is the

atmospheric pressure and J is the James and Martin pressure correction factor.
According to Hansen theory [12] the total cohesive energy, Ecoh, is approximated
as a sum of three independent contributions arising from dispersive Ed, polar Ep, and
hydrogen bonding Eh interactions.
Ecoh ¼ Ed þ Ep þ Eh ð2Þ
Therefore the total solubility parameter dT, is derived as follows. By dividing
Eq. (2) with molar volume V, we get
Ecoh Ed Ep Eh
¼ þ þ ð3Þ
V V V V
d2T ¼ d2d þ d2p þ d2h ð4Þ

where dd, dp, and dh are the Hansen solubility parameters (HSP) representing dis-
persive, polar, and hydrogen bonding components, respectively. Determination of
HSP by IGC for materials which are in the liquid state at the temperature of the
experiment have been reported extensively in the literature. However, the studies
relating to the determination of HSP for solid materials by IGC are scanty. Voelkel
et al. [1] developed a method for the determination of HSP for a solid surface by
IGC following the Snyder–Karger adsorption model [2]. Accordingly, the energy of
adsorption of test solute ‘1’ on the blend ‘2’ is given by the energy balance
expression

DEA ¼ E12 ¼ ðE11 Þ1=2 ðE22 Þ1=2 ¼ V1 ðd1 d2 Þ ð5Þ

where DEA is the energy of adsorption, V1 is the molar volume of the test solute, E11
and E22 are the cohesive energies for the test solute ‘1’ and the blend ‘2’, and E12 is
the energy of cohesion for the interaction between ‘1’ and ‘2’. d1 and d2 are
solubility parameters of solute ‘1’ and the blend ‘2’. Introducing Eq. (2) in Eq. (5)
gives:
DEA ¼ V1 ðdd1 dd2 þ dp1 dp2 þ dh1 dh2 Þ ð6Þ
The energy of adsorption DEA is related to the specific retention volume by the
following equation.
DEA ¼ RT ln Vg0 þ const ð7Þ

From Eqs. (6) and (7) one can derive the following relation.
RT ln Vg0 ¼ V1 dd1 dd2 þ V1 dp1 dp2 þ V1 dh1 dh2 þ const ð8Þ

where dd2 , dp2 , and dh2 are the dispersive, polar component, and hydrogen bonding
component of Hansen solubility parameters for the blend. Using the Vg0 and HSP of
solutes at each temperature linear multiple regression on Eq. (8) has been performed
with aid of the software OriginPro 7.0.

123
1306 Polym. Bull. (2013) 70:1303–1312

Table 1 The specific retention volumes Vg0 cm3/g, of solutes on CAB–PCLD blend in the temperature
range 343.15–403.15 K
Solute 343.15 353.15 363.15 373.15 383.15 393.15 403.15

n-Pentane 15.70 13.83 12.31 11.59 10.54 9.65 8.19

n-Hexane 23.01 19.31 16.63 15.19 12.51 10.04 9.36
n-Heptane 40.46 32.30 25.26 22.59 17.42 15.54 13.66
n-Octane 79.24 58.69 44.08 37.38 31.56 25.75 21.08
Acetone 65.23 47.73 34.28 27.98 23.31 19.86 16.00
Ether 108.26 76.96 55.46 43.18 32.74 26.93 21.86
Methanol 79.03 55.85 40.55 33.58 25.67 20.64 14.05
Ethanol 120.44 83.46 59.38 45.58 35.10 27.71 23.03
1-Propanol 243.86 164.65 114.3 87.95 64.17 48.92 39.43
1-Butanol 522.37 340.86 227.26 183.9 117.6 88.19 68.33
Benzene 127.75 97.26 71.15 59.17 46.88 39.49 33.57
Toluene 278.78 201.19 141.75 112.74 83.82 66.20 53.10
2-Propanol 131.00 93.20 63.30 49.57 36.67 29.28 24.20
2-Butanol 270.66 184.95 122.93 92.75 65.74 49.71 39.82
Dichloromethane 68.48 52.60 38.20 34.38 31.95 23.79 17.95
Trichloromethane 136.68 99.70 72.72 57.57 47.67 34.00 30.45
Methyl acetate 66.04 50.98 38.99 32.78 28.03 23.79 14.83
Ethyl acetate 103.39 76.96 57.03 45.58 37.46 30.07 25.76
1-Butyl acetate 402.20 279.15 191.96 147.92 108.96 83.48 65.59
1,4-Dioxane 394.08 275.09 193.53 145.52 106.6 82.69 64.81
THF – 81.02 57.03 45.58 35.88 28.50 24.20

Experimental

The details of the gas chromatograph and the measurement of retention times were
described earlier [13]. The retention times were measured at constant oven
temperatures at intervals of 10 °C in the temperature range from 343.15 to
393.15 K. The analytical grade CAB and PCLD are purchased from Sigma-Aldrich
Pvt. Ltd. and used directly for the preparation of column packing. The chromosorb
G/AW-DMCS with particle diameter 150–180 lm purchased from Fluka was used
as inert support material in the preparation of the column packing. The probe solutes
are analytical grade compounds purchased from SD fine and Merck. Equal amounts
of CAB and PCLD were weighed (±1 mg) separately and dissolved in the common
solvent acetone to obtain 3 % solution. For the preparation of column packing an
exact amount of the support (weighed with a precision of ±0.01 g) was wetted with
the acetone solution. The evaporation of the solvent was established in a rota
evaporator initially at 323.15–333.15 K and then under a slow stream of N2 in a
slowly rotating cylindrical evaporator at 413.15 K. The percentage of the blend in
the column packing has been found to be 15.37 % and the weight fraction of CAB

123
Polym. Bull. (2013) 70:1303–1312 1307

0 5
ln V g

0.0025 0.0026 0.0027 0.0028 0.0029

-1
1/T(K )

Fig. 1 Retention diagram of some selected solute probes: n-pentane (filled square), dichloromethane
(open square), diethylether (filled triangle), benzene (open circle), 1-propanol (filled circle), n-butyl
acetate (open triangle) in the temperature range 343.15–403.15 K for the CAB–PCLD blend

Table 2 The Hansen solubility parameters for solid surface of CAB–PCLD blend calculated using
Eq. (8), at seven temperatures: dispersive, dd2 , polar, dp2 , hydrogen bonding, dh2 ; dT2 is total solubility
parameter and r is the correlation coefficient of the regression
T (K) dd2 (MPa)1/2 dp2 (MPa)1/2 dh2 (MPa)1/2 dT2 (MPa)1/2 r

298.15a 20.49 6.67 6.65 22.22

343.15 16.59 ± 3.14 5.85 ± 2.98 5.55 ± 1.11 18.45 ± 3.08 0.952
353.15 15.82 ± 2.98 5.65 ± 1.99 5.24 ± 1.09 17.60 ± 3.75 0.950
363.15 14.64 ± 2.87 5.20 ± 1.97 5.03 ± 1.08 16.33 ± 3.64 0.945
373.15 13.87 ± 2.83 5.16 ± 2.00 4.80 ± 1.11 15.56 ± 3.64 0.939
383.15 13.22 ± 2.78 5.55 ± 2.00 4.18 ± 1.13 14.93 ± 3.61 0.932
393.15 12.91 ± 1.84 5.65 ± 2.11 4.30 ± 1.20 14.73 ± 3.05 0.928
403.15 11.44 ± 2.25 4.03 ± 1.78 4.09 ± 1.03 12.80 ± 3.05 0.930
a
Extrapolated data

in the blend was 50 %. The stainless steel column of 3 mm internal diameter and
2 m length obtained from NUCON was cleaned with methanol and acetone and then
dried in the oven. The column was weighed before and after packing. The packing
was done using mechanical vibrator and applying vacuum. Both ends of the column
were closely plugged with glass wool and conditioned at 413.15 K for 10 h with N2
flow rate maintained at 20 mL/min. 0.1 lL of the sample is injected using Hamilton
syringe. Each solute is injected three times and the average of the three retention
times was used in the calculation of Vg0 .

123
1308 Polym. Bull. (2013) 70:1303–1312

24

22

20

18

16
1/2
δ (MPa)

14

12

10

300 320 340 360 380 400

T (K)

Fig. 2 The variation of Hansen solubility parameters with temperature: dispersive dd2 (filled square),
polar dp2 (open circle), hydrogen bonding dh2 (filled triangle), total solubility parameters dT2 (times). The
plots are drawn using the data given in Table 2 and extrapolated to 298.15 K

Results and discussion

The specific retention volumes for 21 solute probes are determined in the
temperature range 343.15–403.15 K on CAB–PCLD blend and are given in
Table 1. The Vg0 values are decreasing with increase of temperature for all the
solutes. The retention diagrams drawn between lnVg0 versus 1/T are shown in Fig. 1
for some typical solutes. The retention diagrams are linear which indicate that in the
temperature range studied there is no phase change in the blend. Therefore, the
retention of the solute probes is mainly due to adsorption of the solute on the solid
surface of CAB–PCLD blend.
The HSP of all the solutes at 363.15 K and their temperature gradients are
evaluated following the relations proposed by Hansen and Beerbower [14] and are
given in our earlier paper [13] The three components of the Hansen solubility
parameters, dd1 , dp1 , and dh1 , of the 21 solutes were fitted as a function of the left hand
side of the Eq. (8) by multiple regression analysis at each temperature. The
coefficients of the multiple regression were used to obtain the dispersive component
dd2 , polar component dp2 , and hydrogen bonding component dh2 .
The three components dd2 , dp2 , and dh2 were used in Eq. (4) to calculate the total
solubility parameter dT2 , the solubility parameter values along with the errors in
these components are included in Table 2. The three components dd2 , dp2 , and dh2 are
decreasing with increase of temperature and this variation is shown in Fig. 2. The
variation of the HSP with temperature is linear in the temperature range studied. dd2
values are decreasing rapidly with increase of temperature compared to dp2 and dh2 .

123
Polym. Bull. (2013) 70:1303–1312 1309

Table 3 Dispersive component of Hansen solubility parameter dd2 (MPa)1/2 for CAB, CAB–PCLD, and
PCLD in the temperature range 343.15–403.15 K
T (K) CAB [3] CAB–PCLD PCLD [13]

298.15 22.09 20.49 18.09

343.15 17.37 ± 1.98 16.59 ± 3.14 15.70 ± 2.71
353.15 16.99 ± 1.96 15.82 ± 2.98 15.27 ± 2.57
363.15 15.86 ± 1.93 14.64 ± 2.87 14.66 ± 2.51
373.15 14.32 ± 1.94 13.87 ± 2.83 14.22 ± 2.37
383.15 13.51 ± 1.92 13.22 ± 2.78 13.78 ± 2.23
393.15 12.55 ± 1.84 12.91 ± 1.84 13.17 ± 2.141
403.15 11.82 ± 1.77 11.44 ± 2.25 12.54 ± 1.99

18

17

16
1/2
δ d2 (MPa)

15

14

13

12

11
0.0 0.5 1.0
weight fraction of CAB

Fig. 3 The variation of dd2 with the weight fraction of CAB for the CAB–PCLD blend system: 343.15 K
(filled square), 373.15 K (open square), and 403.15 K (filled triangle)

Table 4 Polar component of Hansen solubility parameter dp2 (MPa)1/2 for CAB, CAB–PCLD, and PCLD
in the temperature range 343.15–403.15 K
T (K) CAB [3] CAB–PCLD PCLD [13]

298.15 6.73 6.67 3.89

343.15 6.07 ± 1.29 5.85 ± 2.98 3.45 ± 1.77
353.15 6.43 ± 1.27 5.65 ± 1.99 3.20 ± 1.72
363.15 6.25 ± 1.32 5.20 ± 1.97 3.20 ± 1.72
373.15 5.77 ± 1.35 5.16 ± 2.00 3.13 ± 1.67
383.15 5.87 ± 1.40 5.55 ± 2.00 3.20 ± 1.62
393.15 5.68 ± 1.39 5.65 ± 2.11 2.94 ± 1.63
403.15 5.75 ± 1.40 4.03 ± 1.78 2.66 ± 1.58

123
1310 Polym. Bull. (2013) 70:1303–1312

Table 5 Hydrogen bonding component of Hansen solubility parameter dh2 (MPa)1/2 for CAB, CAB–
PCLD, and PCLD in the temperature range 343.15–403.15 K
T (K) CAB [3] CAB–PCLD PCLD [13]

298.15 5.22 6.65 9.74

343.15 4.17 ± 0.70 5.55 ± 1.11 9.13 ± 0.96
353.15 3.84 ± 0.69 5.24 ± 1.09 9.19 ± 0.94
363.15 3.51 ± 0.73 5.03 ± 1.08 9.07 ± 0.95
373.15 3.36 ± 0.75 4.80 ± 1.11 8.92 ± 0.93
383.15 3.10 ± 0.79 4.18 ± 1.13 8.71 ± 0.92
393.15 2.88 ± 0.79 4.30 ± 1.20 8.65 ± 0.93
403.15 2.64 ± 0.81 4.09 ± 1.03 8.55 ± 0.91

6
δ 2p (MPa)1/2

2
0.0 0.5 1.0
weight fractionof CAB

Fig. 4 The variation of dp2 with the weight fraction of CAB for the CAB–PCLD blend system: 343.15 K
(filled square), 373.15 K (open square), and 403.15 K (filled triangle)

The temperature gradients in dd2 , dp2 , and dh2 are -0.085, -0.018, and -0.025,
respectively. The values of the Hansen solubility parameters are in the following
order:
dd2  dp2 [ dh2

The higher value of dd2 is due to the presence of aliphatic groups, particularly the
butyl groups, in the CAB molecule which are causing the predominant dispersive
interactions. The values of correlation coefficients, r, given in Table 2 indicate that
the regression model is better at lower temperatures than at higher temperatures. A
comparison of relative errors in the three components indicates that they are in the
following order.

123
Polym. Bull. (2013) 70:1303–1312 1311

10

8
1/2
δ 2h (MPa)
6

2
0.0 0.5 1.0
weight fraction of CAB

Fig. 5 The variation of dh2 with the weight fraction of CAB for the CAB–PCLD blend system: 343.15 K
(filled square), 373.15 K (open square), and 403.15 K (filled triangle)

dd2 \dh2 \dp2

Further, the variation of the solubility parameters with temperature plots is used
to extrapolate the data to 298.15 K. The extrapolated results are also included in
Table 2. During the application of CAB–PCLD blend in the design of membrane
materials, in the coating formulations and as adsorbent materials [11], the Hansen
solubility parameters are often required at room temperature or at 298.15 K.
Therefore the extrapolated HSP given in Table 2 can be utilized to understand the
behaviour of CAB–PCLD blend in presence of different materials at ambient
temperatures. The HSP of polymers and polymer blend surfaces are particularly
useful in the solid phase extraction for selection of a suitable eluent [9].
The dd2 values as a function of temperature for CAB, PCLD, and CAB–PCLD
blend at seven temperature are given in Table 3. dd2 values as a function of weight
fraction of CAB are shown in Fig. 3 for three temperatures. The dd2 values for the
blend are lower compared to the two pure polymers. A negative deviation from
linearity is observed at all temperatures. Similarly dp2 and dh2 values for CAB, PCLD,
and CAB–PCLD blend are given in Tables 4 and 5, respectively. The variation of dp2
with the weight fraction of CAB is shown in Fig. 4. dp2 values for the blend are
slightly higher compared to the two pure polymers. In this case, a positive deviation
at higher temperature and negative deviation at lower temperature from linearity has
been observed. The variation of dh2 with weight fraction of CAB is shown in Fig. 5.
dh2 values are lower in case of blend compared to the two pure polymers and exhibit
negative deviation from linearity at all temperature. Based on the results shown in
Figs. 3, 4, 5 we can conclude that the CAB–PCLD blend surface exhibit lower
propensity for dispersive and hydrogen bonding interactions and higher propensity
for polar interactions compared to the pure polymers CAB and PCLD.

123
1312 Polym. Bull. (2013) 70:1303–1312

Conclusion

Specific retention volumes Vg0 , of 21 solute probes on the blend formed by mixing
CAB with PCLD each 50 % by weight have been measured by IGC technique. The
effect of PCLD on the solid surface of CAB has been investigated using the three
components of HSP. The three components dd2 , dp2 and dh2 of the blend are decreasing
linearly with increase of temperature. The dispersive component dd2 , and polar
component, dp2 are found to be lower in the blend compared to the pure CAB. On the
other hand, the hydrogen bonding component dh2 is slightly increased in the blend
compared to pure CAB.

Acknowledgments One of the authors S. Ramanaiah is grateful to University Grants Commission,

Basic Scientific Research (UGC-BSR) and Govt. of. India, New Delhi for the award of Meritorious
Research Fellowship.

References

1. Voelkel A, Adamska K, Strzemiecka B, Batko K (2008) Determination of Hansen solubility

parameters of solid materials by inverse gas chromatography. Acta Chromatogr 20:1–14
2. Karger BL, Snyder LR, Eon C (1978) Expanded solubility parameter treatment for classification and
use of chromatographic solvents and adsorbents. Anal Chem 50:2126–2136
3. Ramanaiah S, Reddi Rani P, Reddy KS (2011) Determination of Hansen solubility parameters for the
solid surface of cellulose acetate butyrate by inverse gas chromatography. J Macromol Sci, Phys
50:1–12
4. Ramanaiah S, Reddi Rani P, Reddy K S (2012) Hansen solubility parameters for the solid surface of
cellulose acetate propionate by Inverse gas chromatography. J Macromol Sci Phys (ID: 669681). doi:
10.1080/00222348.2012.669681
5. Zhao S, Zhang W, Zhang F, Li B (2008) Determination of Hansen solubility parameters for cellulose
acrylate by inverse gas chromatography. Polym Bull 61:189–196
6. Jia L, Wang Y, Wang B, He M, Zhang Q, Shi B (2008) Relationship between Hansen solubility
parameters and Lewis acid–base parameters of polymers. J Macromol Sci, Phys 47:378–383
7. Huang JC (2004) Methods to determine solubility parameters of polymers of using inverse gas
chromatography. J Appl Polym Sci 91:2894–2902
8. Hancock BC, York P, Rowe RC (1997) The use of solubility parameters in pharmaceutical dosage
form design. Int J Pharmaceut 148:1–21
9. Bielicka-Daszkiewicz K, Voelkel A, Pietrzynska M, Heberger K (2010) Role of Hansen solubility
parameters in solid phase extraction. J Chromatogr A 1217:5564–5570
10. Edgar KJ, Buchanan CM, Debenham JS, Rundquist PA, Seiler BD, Shelton MC, Tindall D (2001)
Advances in cellulose ester performance and application. Prog Polym Sci 26:1605–1688
11. Anant S, Brian B, Joanna K, Padmaja S (2007) Application of cellulose acetate butyrate-based
membrane for osmotic drug delivery. Cellulose 14:65–71
12. Hansen CM (2000) Hansen solubility parameters: a user’s handbook. CRC Press, Boca Raton
13. Sreekanth TVM, Ramanaiah S, Rani Reddi, Reddy KS (2009) Thermodynamic characterization of
poly(caprolactonediol) by inverse gas chromatography. Polym Bull 63:547–563
14. Hansen CM, Beerbower A (1971) In: Encyclopedia of chem technology, Suppl vol 2. Wiley,
New York

123