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Journal of Heat and Mass Transfer 130 (2019) 431–439 Contents lists available at ScienceDirect International

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International Journal of Heat and Mass Transfer

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Transfer journal homepage: www.else vier.com/locate/ijhmt Experimental and numerical investigations on the effect of

Experimental and numerical investigations on the effect of alkaline hornification on the hydrothermal ageing of Agave natural fiber composites

Deepak Jain a , b , , Ishita Kamboj a , Tarun Kumar Bera a , Amardeep Singh Kang c , Rohit Kumar Singla a

a Mechanical Engineering Department, Thapar Institute of Engineering & Technology, Patiala 147004, India b Department of Biomedical Engineering and Mechanics, Virginia Polytechnic Institute and State University, Blacksburg, VA 24061, USA c I. K. Gujral Punjab Technical University, Kapurthala 144603, India

Gujral Punjab Technical University, Kapurthala 144603, India article info Article history: Received 1 August 2018

article info

Article history:

Received 1 August 2018 Received in revised form 23 October 2018 Accepted 25 October 2018 Available online 30 October 2018

Keywords:

Mass diffusion Natural fibers Fiber pretreatment Microstructural investigations Fick’s law Finite element analysis

abstract

Experimental and numerical investigations are performed to evaluate the mass diffusion in Agave Americana natural fiber composites considering several environmental conditions. The effect of fiber pretreatment by alkaline hornification is analyzed on the moisture uptake behavior of the Agave fiber composites. It was observed that water retention value, which is a measure of affinity towards moisture, reduces with each subsequent hornification cycle. The microstructural investigations were performed to analyze the morphological changes in fiber microfibrils. Composite specimens were subjected to acceler- ated ageing under water and humidity conditions at controlled temperatures between 0 C and 75 C. Composites were weighted periodically and mass gain curves were analyzed. A comparison is drawn between the mass gain behavior of composites fabricated using untreated and alkali hornified Agave fibers. The studies have revealed a clear influence of alkaline hornification on the improvement of the hydrothermal durability of the Agave fibers. The effective moisture diffusivity of the composites is deter- mined using edge correction factors for rectanguloid specimens. Finally, the experimental mass gain is compared with the numerical Fick’s law based finite element (FE) approximations. 2018 Elsevier Ltd. All rights reserved.

1. Introduction

With a promising range of mechanical and physical properties natural fibers have become potential alternative materials. An increase in research activities in this direction is driven by several promising features of these fibers such as reasonable mechanical strength, biodegradability, and low cost of these fibers in compar- ison to synthetic fibers. Amidst several benefits, a key barrier in the extensive deployment of natural fibers is their affinity towards the moisture and water in the service environments. The prolonged exposure in thermal and moisture service environments may result in matrix plasticization, swelling, hydrolysis, oxidation, interfacial de-cohesion between fiber and matrix [1–3] . Several fiber pre-treatment methods have been proposed in the past to reduce the moisture susceptibility of these fibers. Pretreat- ment of the fibers with different alkali concentrations improved the surface roughness and removal of non-cellulosic content such

Corresponding author. Address: Room No. CD-105, Mechanical Engineering Department, Thapar Institute of Engineering & Technology, Patiala 147004, India E-mail address: deepak.jain@thapar.edu (D. Jain).

0017-9310/ 2018 Elsevier Ltd. All rights reserved.

as lignin, hemicellulose, wax, and other water soluble components reduced the water uptake in several types of natural fibers [4–6] . The removal of the impurities and improved surface roughness also enhanced the elastic modulus of several natural fibers [7–9] . As an alternative approach, the fiber pretreatment by cyclic horni- fication can also reduce the water retention inside many naturally available fibers [10–12] . Chemical treatment of Agave fibers with maleic and acetic anhydride reduced the water uptake and improved the fiber matrix bonding [13] . Besides, alkali treatment resulted in an improved fiber-matrix adhesion, tensile and com- pressive strength of the Agave fibers [14] . The authors observe that there doesn’t exist any literature on the assessment of alkaline hornification on the properties of Agave fibers. Further, there is no literature available which consider the combined effect of temperature and humidity on the Agave fiber reinforced composites. The objective of the present work is to determine the combined effect of water, humidity and tempera- ture on both untreated and alkali hornified fiber composites. The microstructural investigations were conducted to reveal the morphology after subsequent hornification cycles. Water retention values were evaluated at the end of each hornification cycle. We

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D. Jain et al. / International Journal of Heat and Mass Transfer 130 (2019) 431–439

consider the temperatures in a range of 0–75 C with both humid- ity and water exposure conditions. The analytical investigations were done to deduce the effective diffusivity from the respective mass gain curves under different conditions. Toward the end, we perform Fick’s law based finite element analysis (FEA) and com- pare the numerical and the experimental results.

2. Experiment details

2.1. Materials

The Agave Americana fibers were used as the reinforcements. They were off-white to yellow in color with a semi-dull appear- ance. The fiber length was 2.8 m and fiber diameter was 100– 150 m m. The substantial presence of cellulose and hemicellulose content is a key reason for the high moisture susceptibility of these fibers in comparison to other natural fibers. Table 1 represents the density, moisture and typical material constituents of Agave Amer- icana fibers. The commercially available epoxy resin LY556 and hardener HY951 (Huntsman) were used as matrix materials. The extra pure sodium hydroxide pellets (Sigma Aldrich) were used for the cyclic alkali hornification.

2.2. Alkaline hornification

Fiber hornification can be considered as an accelerated ageing of the natural fibers under controlled conditions to improve their microstructural properties. The swelling of cellulose during the soaking cycle increases its dimensional stability. In addition, the formation of an irreversible hydrogen bond with the repetition of the hornification cycles reduces the water retake inside the inter- fibrillar space [11] . In the soaking cycles, the alkali treatment is known to remove lignin, wax, and other water soluble compounds. In the alkaline hornification, the fibers were soaked in a water bath with 8% (w/v) alkali concentration. In the present fiber pretreat- ment process, the temperature and time duration for the subsequent soaking and drying cycles were followed after experi- mental conditions [11,17–18]. Fig. 1 shows the experimental setup for alkali hornification of fibers. During the soaking cycles, the fibers were immersed in a water bath for 2 h under a temperature of 23 C. Each soaking cycle was followed by drying of the fibers

Table 1 Constituents of Agave Americana fibers [15, 16] .

Density

Moisture

Cellulose

Hemicellulose

Lignin

Wax

1.36 g/cm 3

7–9%

68–80%

15%

5–17%

0.26%

inside the furnace maintained at 110 C for four hours. The temper- ature was reduced gradually at the end of the drying cycle to avoid the thermal shocks. Therefore, after 4 h of continuous drying at 110 C, the temperature was reduced gradually by 5–10 C after every 5 to 10 min in the last one hour. The alternate soaking and drying together form one cycle. Four such cycles were conducted. The visual and hand evaluation of the hornified fibers revealed changes in surface texture, shape, and color of these fibers. Fig. 2 (a–e) shows the fiber textures at the end of successive drying cycles. The change in color is evident from the off-white color of unconditioned fibers to bumblebee color of conditioned fibers. Although the natural fibers do not possess a fixed diameter, the shrinkage of the hornified fiber was apparent when compared with the untreated fibers. Water retention value ( WRV ) is a standardized method to calcu- late the amount of water retained in the fibers after successive soaking cycles. It is commonly used as a measure for the quantita- tive assessment of the natural fiber’s affinity towards the moisture. It is expressed according to Eq. (1) as [11] :

WRV ¼ ðM w M d Þ

M d

ð 1Þ

Here, M w and M d are wet and dry mass measured after subse- quent Soaking and drying cycles. Table 2 shows the WRV at differ- ent stages of hornification. Fig. 3 shows a gradual reduction in water retention capacities of Agave fibers at the end of each hornification cycle. The percentile hornification measures the overall drop in WRV. The fibers condi- tioned after the 4th cycle was used in the preparation of the com- posite specimen for moisture diffusion experiments.

2.3. Microstructural investigations

The microstructural fiber morphology was studied through scanning electron microscopy (SEM). The fiber cross sections were analyzed for both untreated and alkali hornified fibers after each hornification cycle. SEM micrographs were recorded on JEOL (6510LV) series scanning electron microscope. The test samples were gold coated to avoid electrical charge accumulation. Fig. 4 shows the SEM images of the fiber cross-section at two different resolution scales of 100 and 20 m m. The untreated fiber cross sec- tions in Fig. 4 (a) shows a possible presence of non-cellulose amor- phous components such as wax, lignin and hemicellulose within the microfibrils. The partial removal of these components and other water soluble residues after the first hornification cycle and shrinkage of the fiber cells at the end of second hornification cycle is noticeable. The regions enclosed inside dashed yellow rect- angles show a shrinkage of fiber cells due to soaking followed by drying in subsequent hornification cycles. The shrinkage around

in subsequent hornification cycles. The shrinkage around Fig. 1. Cyclic Hornification (a) Soaking in the water

Fig. 1. Cyclic Hornification (a) Soaking in the water bath and (b) Drying in the furnace.

D. Jain et al. / International Journal of Heat and Mass Transfer 130 (2019) 431–439

433

(a) Untreated (b) Cycle-I (c) Cycle-II (d) Cycle-III (e) Cycle-IV
(a) Untreated
(b) Cycle-I
(c) Cycle-II
(d) Cycle-III
(e) Cycle-IV

Fig. 2. The texture of (a) Untreated, and alkali hornified fibers after (b) cycle I (c) cycle II, (d) cycle III, and (e) cycle IV.

Table 2 WRV and% hornification.

WRV for each cycle of hornification (%)

0 cycle 1 cycle 2 cycles 3 cycles 4 cycles % hornification 200 176.1 158.6
0 cycle
1 cycle
2 cycles
3 cycles
4 cycles
% hornification
200
176.1
158.6
149.1
145.3
27.4
220
200
180
160
140
01234
Hornification cycle Number
WRV (%)

Fig. 3. WRV with the number of hornification cycles.

the voids results from the collapse of fiber cell walls and formation of microcracks after 2nd, 3rd and 4th cycle of hornification. These cracks are visible in relatively higher resolution images in Fig. 4 (c2), (d2) and (e2). The crack formation is mainly because of the excessive fatigue of fiber cell walls due to soaking and drying.

2.4. Specimen fabrication and hydrothermal ageing

Thermosetting matrix was prepared by mixing resin ( LY556 ) and hardener ( HY 951 ) according to the industrial specifications in a ratio of 10:1. The composite sheets were fabricated using hand lay-up method followed by compression loading and curing under room temperature. The sheets were cured at the room temperature for 7 days. The composite sheets were finally machined into the rectanguloid strip shape specimens. The dimensions of specimens

were Length ( l ) = 76.2 mm, Width ( w ) = 24.5 mm , and Thickness ( h ) = 3 mm. These dimensions were taken according to ASTM D570-98 [19] standard test method for moisture diffusion. The specimens were placed inside a forced air circulation humidity chamber with the temperature control constancy of ±1.0 C. At a relative humidity of 70% the specimens placed under three different temperatures conditions of 25 C, 50 C & 75 C. In the water absorption experiments, we chose four different temper- atures viz. 0 C, 25 C, 50 C & 75 C. A cryostat water bath capable to maintain sub-zero temperatures was used for maintaining 0 C temperature condition inside water. A digital water bath was used for the other three temperature conditions of 25 C, 50 C & 75 C. The specimens were weighed on an electronic analytical balance having a readability of 0.1 mg. The mass gain was measured peri- odically. Before weighing, the specimens were removed securely and it was ensured that they are wiped dry to get rid of any undue surface moisture. The mass gain is measured according to the Eq.

(2):

M t ¼ W t W O W O

100%

ð 2Þ

Here, M t is the instantaneous percentile mass gain, W t is the measured weight, and W O is the initial weight of the specimen. Fig. 5 shows the mass gain profiles under the different environ- ments. Throughout the graphs, we use a nomenclature ‘X-YZ’ to define an environmental condition. Here X designates the type of fiber treatment. X as ‘UN’ means untreated, whereas ‘AH’ means alkali hornification. Y indicates exposure to water (W) or humid- ity(H) condition and Z indicates the temperature condition. As an example, AH-H50 refers to the composite specimen fabricated using alkali hornified (AH) fibers, subjected to humidity (H) condi- tion at 50 C. Fig. 5 (a) plots the mass gain for the composites subjected to humidity and temperature inside the moisture chamber. The specimens were placed inside the moisture chamber for approx- imately 400 h. A sharp rise in mass gain can be noticed initially due to the high concentration gradient between the exterior environment and a composite specimen with the dry interior. The moisture diffuses mainly through the gaps within the poly- mer chains of epoxy matrix. The sharp rise is followed by a decline in the rate of mass gain. Most of the specimens attained the moisture saturation within 350 h. After this, they didn’t show any considerable mass gain. The fiber pretreatment showed a high influence on the moisture uptake throughout the exposure duration. Under the similar environmental condi-

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D. Jain et al. / International Journal of Heat and Mass Transfer 130 (2019) 431–439

Untreated (a1) (a2) Fibers After (b1) (b2) Cycle I After (c1) (c2) Cycle II Microcrack
Untreated
(a1)
(a2)
Fibers
After
(b1)
(b2)
Cycle I
After
(c1)
(c2)
Cycle II
Microcrack
Lume
After
(d1)
(d2)
Cycle III
Microcrack
After
(e1)
(e2)
Cycle IV
Microcrack

Fig. 4. SEM micrographs of the fiber cross-section at different pretreatment stages.

tions, with a lower mass gain, alkali hornified fiber specimens has a lower mass gain in comparison to the untreated Agave fiber specimens. The moisture sorption experiments clearly quantify the effect of fiber modification on the improvement in the hydrophobicity of alkali horrified fiber specimens. The natu- ral fibers have a complex composite structure which influences the moisture diffusion mechanism. Presently, there is a limited knowledge of molecular processes and chemical kinetics on moisture diffusion. However, it is well known that during the moisture sorption, the crystalline and closely packed hydrophilic

cellulose structures allows the moisture to penetrate though the less oriented amorphous regions consisting of non-fibrous pec- tins, hemicellulose and lignin. These amorphous regions are highly susceptible to moisture as water/moisture can penetrate further through these regions only [20] . During the alkali horni- fication, the reaction with hydroxyl groups in the fibers leads to the removal of moisture susceptible hemicellulose and lignin compounds. It can be explained as:

Fiber-OH þ NaOH ! Fiber-O Na þ þ H 2 O

D. Jain et al. / International Journal of Heat and Mass Transfer 130 (2019) 431–439

435

UN-H75 (a) Humidity Chamber 1.4 UN-H50 1.2 1.0 AH-H75 0.8 AH-H50 0.6 UN-H25 0.4 AH-H25
UN-H75
(a) Humidity Chamber
1.4
UN-H50
1.2
1.0
AH-H75
0.8
AH-H50
0.6
UN-H25
0.4
AH-H25
0.2
0.0
0
100
200
300
400
Time (Hr.)
7
(b) Water Bath
UN-W75
6
5
AH-W75
UN-W50
4
AH-W50
3
UN-W25
2
AH-W25
1
0
0
50
100
150
200
250
300
350
Time (Hr.)
3.0
(c) Cryo Bath
UN-W0
2.5
2.0
AH-W0
1.5
1.0
0.5
0.0
0
100
200
300
400
500
Time (Hr.)
Mass Gain (%)
Mass Gain (%)
Mass Gain (%)

Fig. 5. Mass gain vs. time plots for environmental exposure inside (a) Environ- mental chamber at 70% R.H (b) Water bath at 25 C, 50 C & 75 C, and (c) Cryostat bath at 0 C.

The increase in crystallinity due to removal of these cementing amorphous compounds leads to a better packing of cellulose chain and improves the fiber matrix adhesion of the composite [21] . Also, the subsequent hornification cycles results in irreversible closure

7 Untreated fibers / Water exposure Alkali Hornified fibers / Water exposure Untreated fibers /
7
Untreated fibers / Water exposure
Alkali Hornified fibers / Water exposure
Untreated fibers / 70% RH
6
Alkali Hornified fibers / 70% RH
5
4
3
2
1
0
0
25
50
75
Temperature ( o C)
Mass Gain (%)

Fig. 6. Comparison of mass gain at different environmental conditions.

of fiber cell walls which results in reduced moisture permeability [10,11]. Similar observations can be made in Fig. 5 (b) and (c) plots for the exposure to the water at different temperatures. The mass gain was much lower in pre-conditioned fiber specimens. The effect of elevated temperatures on the diffusion behavior is also evident. The rate of mass gain (initial slope of the curves) and final mass gain increased with the increase in temperature. This is because of the increased diffusivity at higher temperatures. Fig. 6 compares the mass gain measured at the end of 14 days. It was the time when most of the specimens reached a saturation stage. In comparison to untreated fiber composites, the alkali hornified composites showed an average mass gain about 45%, 24%, 21% and 28% lower at 0 C, 25 C, 50 C & 75 C respectively. Similarly, under the humidity conditions the mass gain was about 30%, 27%, and 26% lower at 25 C, 50 C & 75 C.

3. Numerical investigations

The mass gain curves for most of the specimens showed a sig- nificant moisture uptake initially for several days which is followed by the pseudo saturation plateau. Such a behavior can reasonably be considered as a Fickian diffusion [22,23]. As a part of numerical investigations, first, we first evaluate the moisture diffusion coefficient of different composite specimens from their respective mass gain curves. The calculated diffusion coefficients were used in subsequent Fick’s law based finite element procedure to find the theoretical mass gain.

3.1. Evaluation of moisture diffusion coefficients

To find the moisture diffusion coefficient ð D c Þ of monolithic composite specimen, we ignore the topological effects of fiber dis- tribution and assume it as homogeneous and isotropic. Therefore, it is reasonable to assume that diffusion coefficients ð D x ; D y ; D z Þ are same in all the three directions ( X, Y, and Z ) along with a rect- anguloid model that represents a composite specimen. Fig. 7 shows the model geometry similar to experimental specimens. When a specimen is immersed in water/humidity conditions, the three- dimensional moisture uptake is assumed to follow Fick’s law of diffusion:

@

c

@

t

¼ D c

@ 2 C þ @ 2 C þ @ 2 C

@ x 2

y 2

@

z 2

@

!

ð 3Þ

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D. Jain et al. / International Journal of Heat and Mass Transfer 130 (2019) 431–439

X Y Z h
X
Y
Z
h

Fig. 7. Specimen geometry and rectangular coordinates.

The solution of Eq. (3) upon volume integration is used to calcu- late the fractional mass uptake as [24] :

M

t

M

1

¼ 1

e

h

8

P

2

3

1

X

1

X

1

X

p¼0 q¼0 r ¼0

p

2

tD

eff

2pþ1

l

2

þ

1

ðð 2p þ 1Þð2q þ 1Þð2r þ 1ÞÞ 2

2qþ1

w

2

þ

2r þ1

h

2

i

ð 4Þ

where M t is instantaneous mass and M 1 is saturation mass. Eq. (4) also states that a saturation state exists when fractional mass uptake asymptotes to unity. The rectanguloid specimens used in experiments have thickness

h 3 mm. It is much smaller than the other two dimensions ( l, w ).

For the approximation of D c , we use the procedure stated for the

thin rectanguloid shapes [25] under an initial assumption that the moisture uptake in the composite occurs only along the broader face parallel to XY plane. To compensate for the edge effects, an edge correction factor ( f ) is suggested as:

f

¼ 1 þ 0: 54 h

l

s

ffiffiffiffiffiffi

x

D

D

z

þ 0: 54 h

w

s

ffiffiffiffiffiffi

D

y

D

z

þ 0 :33

h

2

lw

s

ffiffiffiffiffiffiffiffiffiffiffi

D x D y

D

z

; D x D y D z

ð

5Þ

For a simplistic estimation of the diffusivity ð D c Þ of monolithic specimens under the assumptions that:

(i) The geometrical effects of the unidirectional fiber arrange- ment are minimal, (ii) and the diffusion coefficient in the composites is the same in all directions, as it is in the resin. i.e. D x ¼ D y ¼ D z ¼ D c , the edge correction factor becomes:

f

2

¼ 1 þ 0: 54 h þ 0: 54 w þ 0: 33 lw

l

h

h

ð

6Þ

p

ffiffiffiffiffiffiffiffiffiffi

time = length for one of

the specimen. The diffusion coefficient of the composite is calcu-

lated from the slope ( S ) of this graph. The initial mass uptake yields

a linear increase with

the initial portion of the mass uptake curve when M t = M 1 6 0 : 5.

Under an assumption of one-dimensional mass flow, Eq. (4) reduces to:

time /length . The slope is determined for

Fig. 8 plot the fractional mass gain vs.

p

ffiffiffiffiffiffiffiffiffiffi

M

t

M

1

¼ 1 8

P

1

2 X

p¼0

1

ð 2p þ 1Þ 2 e

p

2

tD ð

x

2p þ 1

l

Þ

2

ð

7Þ

For M t = M 1 6 0 : 5, Eq. (7) can be approximated as:

UN-W50 1.0 0.8 0.6 0.4 0.2 0.0 0.00 0.05 0.10 0.15 0.20 0.25 [Time(Sec.)] 1/2
UN-W50
1.0
0.8
0.6
0.4
0.2
0.0
0.00
0.05
0.10
0.15
0.20
0.25
[Time(Sec.)] 1/2 / Length
p
ffiffiffiffiffiffiffiffiffiffi
Fig. 8. M t = M 1 vs
time /length plot of UN-W50 specimen.
r
ffiffiffiffiffiffiffiffi
M t
4
D x t
¼
p
M 1
l
M
t /Mα

ð

8Þ

Using the edge correction factor for the 3-dimensional mass dif-

fusion, Eq. (8) is rewritten as:

M

t

¼

4f

ffiffiffiffiffiffiffi

r

D c t

M

1

l

p

ð 9Þ

Rearrangement of Eq. (9) gives the slope of the initial portion of the mass gain curve as:

S

¼ M t =M 1

p

ffiffi

t

= l

¼ 4f

r

ffiffiffiffiffiffi

c

D

p

ð10Þ

and finally, Eq. (10) can be rearranged as:

D c ¼ p

S

16 f

2

ð

11Þ

In this manner, the respective mass gain curves of different

specimens were analyzed to evaluate their respective moisture dif- fusion coefficients. Table 3 shows the coefficient of moisture diffu- sion for different specimens calculated using Eq. (11) .

3.2. Finite element analysis (FEA)

Evaluation of mass diffusion coefficients is followed by the finite element analysis. Fick’s law based commercial finite element code Abaqus [26] is used to model the mass diffusion inside the specimen models. To reduce the computational effort, we use the

symmetry of the rectanguloid specimens along all the three princi-

pal directions ( X, Y, and Z ) and model the moisture diffusion in 1/8th of the entire volume. Fig. 9 shows the full body model with

the 1/8th meshed region. Assuming a state of constant diffusivity, the Fick’s law is used to find the concentration C( X i ; t ) as the solu- tion variable inside the modeled volume verified by the boundary conditions:

@

c

@

t

¼ D c r 2 C

with C ð X i ; t Þ ¼ 0 at t

¼ 0 in the whole domain X m ; and

C ¼ C amb on boundary C c

ð

12Þ

ð 13Þ

Here r 2 is the Laplacian operator and C c represents all the three boundary surfaces which are exposed to the ambient moisture

D. Jain et al. / International Journal of Heat and Mass Transfer 130 (2019) 431–439

Table 3 Coefficient of moisture diffusion of different specimens.

437

Type

The coefficient of Moisture diffusion (m 2 /sec)

 

Humidity Chamber

Water Bath

25 C

50 C

75 C

0 C

25 C

50 C

75 C

Untreated

0.78 10 12 0.62 10 12

1.08 10 12 0.96 10 12

1.12 10 12 1.02 10 12

3.62 10 12 1.55 10 12

4.02 10 12 3.86 10 12

5.56 10 12 4.22 10 12

7.66 10 12 5.92 10 12

Alkali Hornified

10 1 2 5.92 10 1 2 Alkali Hornified Fig. 9. Moisture diffusion model and FE

Fig. 9. Moisture diffusion model and FE mesh.

ð C amb Þ . The other three planar surfaces of modeled volume which are opposite to moisture exposed surfaces have no mass flux either entering or leaving through them for the entire duration. Under these boundary conditions, the moisture ingresses towards the dry interior regions. Fig. 10 shows the moisture concentration pro- files for AH-W75 specimen model at different time instances. The geometry shown in Fig. 10 is the flipped image of the meshed region shown in Fig. 9 with the left, bottom and front surfaces as moisture exposed boundaries and top surface reveals the moisture evolution along the specimen interior. The mass gain, M ð X m ; t Þ ; by the specimen due to moisture ingression at time t can be calculated through the volume integral of the moisture concentration at that time. That is,

M ð X m ; t Þ ¼ Z X m c ð x; y ; z; t Þ dV

ð 14Þ

Fig. 11 (a, b) show the theoretical mass gain of different speci- mens. With the time, a steep initial mass gain is followed by an asymptotic mass gain that indicates the saturation stage. However, due to the time-bound nature of the experiments and a slower rate of mass gain, the mass saturation couldn’t be attained under humidity conditions. It is obvious that the mass gain is according to the computed diffusivities. The objective of present analytical investigations is to determine the theoretical diffusivities and com- pare the mass gains determined through FEA approximations with experimental mass gains. Fig. 12 compares the experimental and numerical results for one of the specimens.

75 hr.

10 hr. 40 hr. bottom 150 hr. 90 hr.
10 hr.
40 hr.
bottom
150 hr.
90 hr.
7 5 h r . 10 hr. 40 hr. bottom 150 hr. 90 hr.

Fig. 10. Moisture concentration profiles inside the 1/8th model.

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D. Jain et al. / International Journal of Heat and Mass Transfer 130 (2019) 431–439

8 (a) Water Exposure 7 UN-W75 6 5 AH-W75 UN-W50 4 AH-W50 UN-W25 3 AH-W25
8
(a) Water Exposure
7
UN-W75
6
5
AH-W75
UN-W50
4
AH-W50
UN-W25
3
AH-W25
UN-W0
2
AH-W0
1
0
0 100
200
300
400
500
Mass Gain (%)

Time (Hr.)

1.4 (b) Humidity Conditions UN-H75 1.2 UN-H50 1.0 AH-H75 0.8 AH-H50 0.6 0.4 UN-H25 0.2
1.4
(b) Humidity Conditions
UN-H75
1.2
UN-H50
1.0
AH-H75
0.8
AH-H50
0.6
0.4
UN-H25
0.2
AH-H25
0.0
0 100
200
300
400
500
Mass Gain (%)

Time (Hr.)

Fig. 11. Mass gain vs time under (a) Water exposure (b) Humidity conditions.

1.4 AH-W0 (Experimental) AH-W0 (Fickian FEA) 1.2 1.0 0.8 0.6 0.4 0.2 0.0 0 100
1.4
AH-W0 (Experimental)
AH-W0 (Fickian FEA)
1.2
1.0
0.8
0.6
0.4
0.2
0.0
0
100
200
300
400
Time (Hr.)
Mass Gain (%)

Fig. 12. Experimental vs Analytical results for AH-W0 specimen.

A difference of 10–15% between the instantaneous mass gain of experimental work and theoretical predictions was observed in some cases. The subtle difference between FEA based Fick’s calcu- lations and the experimental values was found especially at the

later stages of diffusion. Such deviations can be attributed to resin deterioration or morphological changes. It is understandable that the effect of such conditions is difficult to predict using the simpli- fied numerical procedures under the straightforward assumptions. Nevertheless, a close proximity was found between experimental and FEA predictions for most of the specimens. It also proves that the stated procedure results in a reasonable prediction of numeri- cal diffusivities.

4. Conclusions

A comprehensive experimental and numerical study has been

conducted to evaluate the moisture diffusion behavior of Agave fiber reinforced polymer composites. The effect of fiber pretreat- ment by alkaline hornification is evaluated on the moisture dura- bility assessment in accelerated hydrothermal ageing conditions. The experimental work was followed by an assessment of moisture diffusion coefficients of different specimens and finite element analysis. The important conclusions drawn from this study are:

1. Fiber pretreatment by alkaline hornification resulted in a signif- icant reduction of mass gain of natural fiber composites at all the temperature conditions under both humid and wet environments.

2. Several irreversible changes in fiber morphology were observed. SEM investigations revealed the reduction in lumen size and partial removal of alkali soluble lignin and water soluble con- tents of the fibers with subsequent soaking and drying cycles.

3. The change in microstructural morphology resulted in the reduced water retention in agave fibers. A drop in water reten- tion value by 27% after four cycles of hornification lead to a remarkable reduction in mass gain of composites at all the exposure conditions. The coefficient of moisture diffusion for alkali treated Agave fiber specimens reduced by 130% in com- parison to the untreated specimens at 0 C.

4. The mass diffusion appears to follow Fick’s diffusion behavior inside both conditioned and unconditioned composite specimens. The effective diffusivities were derived using edge

correction factor and implementing Fick’s law for the inverse calculation. The derived diffusivities resulted in a fair prediction

of mass gain through FEA investigations.

The present investigations clearly uncover the underlying potential of alkaline hornification for the improvement of moisture durability of Agave fibers. The effect of similar treatment on the behavior of these fibers in synergistic mechanical and hydrother- mal ageing environments is still unknown and it is a work in progress.

Conflict of Interest Statement

The authors declared that there is no conflict of interest.

Appendix A. Supplementary material

Supplementary data associated with this article can be found, in the online version, at https://doi.org/10.1016/j.ijheatmasstransfer.

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