International Journal of Multidisciplinary Sciences and Advanced Technology Vol 2 No 3 (2021) 19–25

Contents lists available at Crown Academic Publishing

International Journal of Multidisciplinary Sciences

and Advanced Technology
Journal home page: http://www.ijmsat.com

Some Mechanical Properties of Polyurehane Foams From Polyols and

Castor Oil Blends

Moses Tara Langkuk1, Moorey Bimbut Dalen2, Adedirin Oluwaseye1, Elkanah Micah
Dawes2
1
Chemistry Advanced Research Center (CARC), Sheda science and technology complex (SHESTCO), Km 10
Gwalgwalada-Abuja-Lokoja Road, Sheda, FCT, P.M.B 186, Garki, Abuja, Nigeria.
2
Chemistry Department, University of Jos, P. M. B 2084, Jos, Plateau State, Nigeria

Corresponding Author: Langkuk M. T. (langkukmr9@gmail.com)

Original article Received 1 January 2021, Accepted 23 January 2021, Available online 1 March 2021

ABSTRACT

Polyurethane (PU) foams—products that have many applications due to their unique advantages—are traditionally made
from fossil-based polyols and isocyanates. Because of the problems associated with fossil resources such as expected
depletion, environmental pollution, and global warming, biomass resources are being researched as sustainable, green and
cost-effective alternatives. In this study, Castor oil (CO) is investigated as an alternative raw material for the production
of flexible PU foams. One-short method of foam production was employed to produce flexible PU foams from blends of
raw CO and petroleum-based polyols (conventional polyol, CP and polymer polyol, PP). The density, and some
mechanical properties: Young modulus, elongation at break, tensile strength, and creep recovery of the foams produced
were studied and compared with the properties of foams produced from pure polyols (i.e. 100% CP, 100% PP and 100%
CO). The results obtained showed that the density (0.0161) and tensile strength (2.45) of the pure CO foam are the least
but the creep recovery (48.34%) and elongation at break (89.95) are the highest, and that the density and the mechanical
properties of the polyol/CO foams are largely affected by the quantity of CO, thus by varying the quantity of CO
polyurethane foams having wide range of mechanical properties could be obtained.

Key Words: castor oil, mechanical properties, polyurethane foams, green manufacturing.

2020 The Authors. Production and hosting by Crown Academic Publishing (CAP) on behalf of International Journal of
Multidisciplinary Sciences and Advanced Technology (IJMSAT). This is an open access article under the CC BY-NC-
ND license (http;//creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction
Polyurethane (PU) is any polymer consisting of a chain of organic units joined by urethane linkage (-NH-
COO-) (Polyurethane, 2019; Hans-George, 1988) whose synthesis can be carried out by a variety of methods, although
the most widely used production method is the reaction of di- or polyfunctional hydroxy compounds (colloquially
referred to as polyols) with a di- or polyfunctional isocyanate (Polyurethane, 2019).

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Over three quarter of the global consumption of PU products is in the form of foams, which are produced
through one of three general processes which include one-shot process, prepolymer process, and quasi prepolymer
process, with flexible and rigid types being roughly equal in market size (Polyurethane, 2019).
The application of flexible foams generally has been predominantly in comfort cushioning, packaging and
wearing apparel; this has resulted in emphasis on a different set of mechanical properties than for rigid foams. The
compressive nature of the material is the most important single property for most uses (Kirk, 1966). Also important are
tensile strength, tear strength, and compression set or creep recovery.
Currently, most of the isocyanates and polyols used in the manufacture of PUs are derived from the petroleum
industry (Wang, Blocck & Rogers, 2014). Due to the problems associated with fossil resources-expected depletion of
fossil resources, ozone layer depletion, ecosystem degradation, concern over greenhouse emissions (Wang et al., 2014),
attention of researchers, scientists, industrialists and governments is being turned to green manufacturing where
biomass resources are used as sustainable, green and cost-effective alternative feedstock for the production of fuels and
for manufacturing. A wide variety of biomass resources are available on our planet for conversion into bio-products
(Howard, Abotsi, Jansen van Rensburg, & S Howard, 2003). These may include whole plants, plant parts, plant
constituents, processing bio-products, materials of marine origin and animal byproducts, municipal and industrial
wastes, wood and wood waste (Wang et al., 2014; Howard et al., 2003).

Castor (Ricinus communis L.) is one of the oldest cultivated crops—mainly in Africa, South America, and
India (Thomas, Mathaus, & Fiebig, 2015; Hong & Blackmore, 2015) —which occurs in practically tropical and
subtropical regions where it grows wild as perennial and also widely found in temperate zones (Kirk, 1964). It is
considered to be one of the most promising nonedible oil crops, due to its high annual seed production and yield, and
since it can be grown on marginal land and in semiarid climate (Patel, Dumancas, Viswanath, Maples, & Subong,
2016). The castor bean is made up of approximately 75% kernel and 25% husk, and about two-thirds of the weight of
the kernel is oil (Kirk, 1964).
Castor oil (CO), a viscous, pale yellow nonvolatile and nondrying vegetable oil (Kirk, 1964) which can be
obtained from the seed of castor plant by expression, solvent extraction or a combination of both (Kirk, 1964; Akpan,
JImoh & Mohammed, 2006), is considered to be of importance to the global specialty chemical industry because it is
the only commercial source of a hydroxylated fatty acid (Severino, Auld, Baldanzi, et al., 2012) and has long been used
commercially as a highly renewable resource for the chemical industry (Ogunniyi, 2006; Mutlu & Meier, 2010). CO is
one of the few naturally occurring glycerides that approximates being a pure compound since the fatty acid portion is
nearly nine-tenth (up to 90%) hydroxyl acid-ricinoleic acid (RA) (Kirk, 1966; Kirk, 1964; Patel et al., 2016). it is this
high content of RA that makes CO valuable in the chemical industry (Dunford, 2012).
Due to the presence of different functional groups CO can undergo a number of reactions (Naughton, 1978).
The unique structure of CO offers interesting properties, making it appropriate for various industrial applications. CO is
used in the production of several important products such as improved solid propellant binders (Jain, Sekkar &
Krishnamurthy, 1993); paints, protective coatings (Kirk, 1964; Severino, et al., 2012); urethane coatings, foams,
plastics, (Kirk, 1964; Dole & Kesker, 1950; Dunford, 2012); and chemicals (e.g. sebacic acid, capryl alcohol, plasticizer
and nylon) (Dole & Kesker, 1950).
The hydroxyl functionality of RA makes the castor oil a natural polyol thus, CO and its derivatives can be used
in the synthesis of renewable monomers and polymers (Mutlu & Meier, 2010). In this regard, CO was polymerized in
one study and cross-linked with sulfur or diisocyanates to form the vulcanized and urethane derivatives, respectively
(Yenwo, Manson, Pulido, Sperling, Conde & Devia, 1977). Yi-Chun Chen and Wei Tai in another study have used CO-
base PU resin to produce low-density composites with bamboo charcoal (Chen & Tai, 2018) while Salisu and Said have
used CO as a flame retardant in PU Foam (Salisu & Said, 2012). In yet another study, full-interpenetrating polymer
networks (IPNs) were prepared from epoxy and castor oil-based PU, by sequential mode of synthesis (Raymond & Bui,
1998). Similar to the above study, a series of two-component IPN of modified CO-based PU and polystyrene were
prepared by the sequential method (Dave & Patel, 2017). The bifunctionality of RA fatty acids and the additional
functionality provided by the 12-hydroxy group has been explored for the preparation of biodegradable polyesters or
polyester-anhydrides (Patel et al., 2016).

The literature revealed that many researchers have used CO as a bio-resource alternative to fossil resources to
develop PU products. In most of these research studies, multiple fossil-based chemicals were used to modify CO, such
as in Jain et al. (1993), Dave & Patel (2017), Mutlu & Meier (2010), Mosiewicki, Dell’Arciprete, Aranguren, &
Marcovich (2009), and some of those treatments were not environmental friendly. In this study, flexible polyurethane
foams from blends of raw CO and fossil-based polyols (polymer polyol, PP, and conventional polyol, CP) were
produced using one-shot method and their densities and some mechanical properties compared with those of foams
produced using pure polyols (i.e. 100 part PP, 100 part CP and 100 part CO).
2. Material and Method

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2. 1. Sample Collection
Castor oil was obtained at NARIT chemical research center, Kaduna state-Nigeria, the polyols (PP and CP)
and other additives (products of Guanzhou Zhonglian Building Materials Ltd, GuangZou, Gaungdong, China) were
obtained from the market.
2. 2. Sample Characterization
The PP, CP, and CO were characterized both physically and chemically. The physical parameters determined
are the relative viscosity, specific gravity, refractive index and pH while chemical parameters determined include acid
value (AV), hydroxyl value (HV), iodine value (IV), and saponification value (SV). All the parameters, except, relative
viscosity were determined according to the methods of Omari, Mgani, Mubofu (2015). Relative viscosity was
determined at 25oC using Ubbelohde viscometer in which acetone was used as the solvent.
2. 3. Foam Formulation
The ingredients were measured accurately using micro syringes and measuring cylinders (quantities and order,
and blending ratios are shown is tables 1 and 2 respectively) into moulds of dimensions 21.5cm x 13.7cm x 14.5cm, the
components thoroughly stirred and toluene diisocyanate (TDI) added with continuous stirring until the systems
creamed. The foams were then allowed to rise undisturbed and left to cure overnight.

Table 1. quantities of ingredients and order of addition

Components Qty (g/hpr)

Polyol/blend 100

CaCO3 11

Surfactant (Silicon fluid) 1.02

Amine catalyst (triethylenediamine) 0.13

Stannous octanoate catalyst 2

Distilled water 4.27

TDI 50

Qty=Quantity, hpr=hundred part resin

Table 2. Blends of polyol (CP and PP) and CO in g/hpr

Polyol Castor oil (CO)

100 0.00

75.50 2.50

95.00 5.00

92.50 7.50

90.00 10.00

0.00 100.00

2. 4. Determination of Density of Foams

The foam rise, h, and the weights, w, of the foams were measured and the volume and density calculated using
the expressions (1) and (2) respectively.
(1)
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Where
(2)

2. 5. Determination of Young Modulus and Elongation at Break

Each foam was trimmed and cut into three pieces using band knife splitter Cv-02. From each of the pieces,
three test samples measuring 7.5cm x 1cm x 5cm were cut randomly using a knife and their extensions in mm with load
were read from computer coupled Universal Tensile Testing (USTROM) with a cell load of 5000N, at a speed of
60mm/min using constant rate of extension method and the tensile strain and tensile stress calculated using equations
(4) and (5) respectively. The extensions (ΔL) in mm at break and load (N) were noted and used to calculate tensile
strength and elongation (e) using equations (7) and (5) respectively.

(3)

(5)

Where
The Young modulus of the foams were then calculated using equation (6) shown below.

(6)

(7)

Where ,
2. 6. Determination of Creep recovery
From the trimmed samples, test samples measuring 7.5cm x 1cm x 5cm were cut and subjected to a computer
coupled Universal Tensile Testing (USTROM) machine with a cell load of 250N at a speed of 60mm/min under
ambient conditions (67±2% and 270C) using the method of constant rate of extension. The total extension (mm) on
application of load (20N) and the relaxation (mm) on removal of load after 5 seconds of each test piece were noted and
the recovery in mm and percentage creep recovery of each calculated using the expressions (8) and (9) respectively.

– (8)

(9)

3. Result and Discussion

3.1. Physical and chemical characteristics of CO, CP and PP
Table 3. Results of physical and chemical characterizations of samples

Characteristic CO CP PP

Specific gravity 0.9618 1.0190 1.0311

Refractive index 1.4650 1.4400 -

Relative viscosity 5.7017 10.9737 11.6579

pH 6.5500 10.2500 5.520

Acid value 3.1631 1.1164 2.2328

Hydroxyl value 161.4212 187.2001 169.1864

Iodine value 83.7540 66.9398 60.5948

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Saponification value 181.2465 129.2123 107.5605

The result obtained shows that the specific gravity of CO (0.9618) is in agreement with the values reported in
literature (Kirk, 1966, Patel et al., 2016; Omari et al., 2015) but less than the specific gravity of PP and CP (1.0311 and
1.1090 respectively).
Table 3 shows that the refractive index of CP is less than that of CO. The refractive index value of CO falls
within the ASTM range of 1.476-1.479 (Omari et al., 2015) and agrees with results from literature (Kirk, 1966; Patel et
al., 2016; Omari et al., 2015). PP does not have refractive index, this is attributable to its white color.
The pH values of the samples as seen in table 3 indicates that CO is more acidic than CP but less acidic than
PP. The acid value, iodine value, and saponification value of CO all fall within the ASTM specifications of 0.4-4.0, 82-
88, and 175-187 respectively (Kirk, 1966, Omari et al., 2015).
The hydroxyl value (the most important parameter in this work) of the CO (161.4212) fall within the ASTM
range of 160-168 (Kirk, 1966, Omari et al., 2015) and is close to that of PP (169.1864) but less than that of CP
(187.2001). This support the assertion that CO can serve as an alternative feedstock for urethane foam (Hans-George,
1988).

3. 2. Densities and Mechanical properties of CP/CO foams

Table 4. Densities and the mechanical properties of CP/CO foams

Foam Description Density, ρ Elongation at Tensile Strength Young Creep Recovery

(g/cm3) Break, e (%) (N/cm) Modulus (%)
(Ncm-2)

100.0 CP/0.0 CO 0.0340 68.57 6.74 6.81 39.73

97.5 CP/2.5 CO 0.0560 40.58 5.61 11.22 22.02

95.0 CP/5.0 CO 0.0460 39.29 2.47 1.15 19.74

92.5 CP/7.5 CO 0.0347 54.27 4.13 5.74 12.39

90.0 CP/10.0 CO 0.0622 51.08 7.41 11.06 30.21

0.0 CP/100.0 CO 0.0161 78.82 2.45 2.04 48.34

The changes in density, elongation at break, tensile strength and Young modulus of the Pure CP, CP/CO
blends and Pure CO foams (shown in table 4) do not show any particular order with changes in the composition of CO,
but all the CP/CO foams have higher densities than the pure CP and pure CO foams with the 90% CP/10% CO foam
having the highest density followed by 97.5% CP/2.5% CO foam.
The pure CO foam has the highest elongation at break of 89.95 (which agrees with the hydroxyl values of the
CO and CP) followed by the pure CP foam. However, the moduli of all the CP/CO foams and pure CP foam are greater
than that of the pure CO foam, meaning there is low degree of cross linking in the pure CO foam than in the pure CP
and CP/CO foams. The moduli of the 97.5% and 90% CP foams are higher than that of the pure foam.
As seen in table 4, the creep recovery unlike the density, tensile modulus, and the elongation at break, shows a
decreasing trend with increasing quantity of CO but begins to increase with increasing quantity of CO at 90% PP
(which has a resilience of 30.21 that is even greater than that of the pure CP foam and those of all other CP/CO foams).
Pure CO foam has the highest creep recovery of 48.34% which is greater than those of the pure CP foam and all the
CP/CO foams.
3. 2. Densities and Mechanical properties of CP/CO foams
Table 5. Densities and the mechanical properties of PP/CO foams

Foam Description Density, ρ Elongation at Tensile Strength Yong Creep Recovery

Modulus

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(g/cm3) Break, e (%) (N/cm2) (Ncm-2) (% )

100.0 PP/0.0 CO 0.0368 46.792 3.62 6.03 14.78

97.5 PP/2.5 CO 0.0322 43.213 6.67 12.35 23.49

95.0 PP/5.0 CO 0.0353 50.577 3.94 5.97 21.93

92.5 PP/7.5 CO 0.0337 49.964 5.14 7.91 23.14

90.0 PP/10.0 CO 0.0334 40.146 4.65 9.49 25.49

0.0 PP/100.0 CO 0.0161 78.815 2.45 2.04 48.34

Similarly, for PP/CO, pure PP, and pure CO foams, the changes in density, elongation at break, tensile strength
and modulus with the composition of CO does not show any particular trend but the results show that the pure PP foam
has the highest density compare to the densities of the PP/CO foams and the pure CO foam, with the pure CO foam
having the least density.
The pure CO foam has the highest elongation at break of 78.815% followed by the 95% PP foam which has a
value of 50.577%. Comparing the moduli and the tensile strengths of the PP/CO foams with the pure polyol foams, it
can be seen that all the PP/CO foams have higher moduli and tensile strengths than the pure polyol foams with the
97.5% foam having the highest modulus of 12.35N/cm2 and tensile strength of 6.67N/cm2 and the pure CO foam having
the least modulus of 2.04Ncm-2 and least tensile strength of 2.45N/cm2, which are in agreement with the hydroxyl
values of the PP and CO.
The creep recovery values of pure PP, PP/CO and pure CO foams show that the creep recovery of the pure PP
foam is less than those of all the PP/CO foams and that of the pure CO foam. This could be attributed to higher cross-
linking in the pure PP form due to its higher HV. The results show an increasing trend with increasing quantity of CO,
but that of 97.5% PP foam is higher than the resiliencies of the 95% PP and 92.5% PP foams.
Comparing the values of the creep recovery of the pure polyol foams, it can be seen that the value for pure CO
foam is the highest (48.34%) followed by that of pure CP which has a creep recovery of 39.73% and pure PP has the
least. It can also be noticed that the 10% PP foam has a smaller creep recovery than the 10% CP foam but the 97.5% PP,
95% PP and 92.5% PP foams have higher creep recovery values than their corresponding CP/CO foams.
4. Conclusion and Recommendation
The results of the creep recovery, density, modulus and elongation at break as seen on tables 4.2 and 4.5 agree
with the results of the hydroxyl values of the samples as seen in table 4.1
Although there is no any particular order in the change in some properties (density, modulus, and elongation at
break) of the foams with composition of CO, the mechanical properties are largely affected by the composition of CO,
and by varying the composition of CO, it is possible to produce a variety of PU foams having a wide range of
mechanical properties.
Other methods of PU foam production (i.e. prepolymer and quasi prepolymer processes) and the
biodegradability of the polyol/CO and 100% CO foams should be investigated.
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