Materials Letters

Manuscript Draft

Manuscript Number: MLBLUE-D-17-04636R1

Title: Study on the mechanical properties of potassium sodium hydroxide

borate hydrate (KSB) single crystals by using Vickers microhardness
tester

Article Type: Short Communication

Keywords: Crystal growth, Indentation and hardness, Deformation and

fracture, Elastic properties

Abstract: The mechanical properties of solution grown potassium sodium

hydroxide borate hydrate single crystal (KSB) have been obtained by using
Vickers microhardness studies in the load range from 10 to 70 g. The
variation of microhardness with load represents the load independent
value of hardness (Indentation size effect). The Meyer's index number
'n' is calculated as 1.81 and it belongs to soft material category.
Various mechanical parameters such as yield strength, elastic stiffness
constant, fracture toughness, brittleness index, hardness contour and
crack propagation of KSB single crystal are discussed in detail.
Response to Reviewers

Response to the reviewers

Thank you very much for reviewing our paper and offering the critical comments. The

response to the reviewer comment is given below and the corrections are highlighted in red

colour in the revised manuscript.

Reviewer:

The authors have given the mechanical properties of solution grown potassium sodium

hydroxide borate hydrate single crystal. Vickers microhardness studies in the load range

from 10 to 70 g. The variation of microhardness with load represents the load independent.

They presented in very well and neatly. In my opinion, this manuscript contains good

scientific content and has many mechanical parameters. The paper should be improve with

taking into account the below remarks and corrections to meet journal standard.

Question 1: What is the solvent have been used for synthesis the potassium sodium

hydroxide borate hydrate? The authors have mentioned in introduction part "the crystal

surface was cleaned with methanol". What is the purpose to use methanol for cleaning

purpose because solvent have some kind of the effect on the surface of the crystal. In your

previous paper ref [7], author didn't mention about the solvent. The author should explain

and give reason.

Answer : Potassium sodium hydroxide borate hydrate single crystal was synthesized by slow

evaporation method using Millipore water as a solvent. The crystal surface was cleaned by

means of Millipore water as solvent and not methanol as mentioned in the manuscript. We

made use of acetone and methanol for only cleaning the shaft unit of the instrument. The

authors apologize for providing a wrong statement on the solvent which was used for
cleaning purpose. We have rectified the same and this has been included in the revised

manuscript.

Question 2: What is the relationship between the chemical bonds in compound and

hardness? The author should give proper explanation.

Answer : The hardness of the material depends on the strength of the chemical bonding

between the molecules which is responsible for its distinct hardness. The hardness of a

material increases proportionally with the strength of the chemical bonds.

The indentations were made on the prominent plane of the grown KSB single crystal for a

varying load from 10 to 70g. It is observed that the hardness value got decreased when the

load was increased to 60g because these loads are sufficient to soften the bonding in the

molecules. From the result, we concluded that the hardness of the material got increased as

the strength of the chemical bonding consequently increased (Yongjun Tian et al.,)

Yongjun Tian, Bo Xu, Zhisheng Zhao, Microscopic theory of hardness and design of

novel super hard crystals, Int. Journal of Refractory Metals and Hard materials, 33

(2012) 93-106

Question 3: In abstract part 4th line have mention "Mayer index number" but in the

manuscript page no.4 line no.12 "work hardening coefficient (n) was calculated by using

“Meyer’s law". Maintain the uniformity in the whole manuscript.

Answer : As per the reviewer suggestions, the Meyer’s index number has been maintained

uniformly in the revised manuscript.

Question 4: What is the effect of the temperature in microhardness measurements?

Answer : The role of temperature in the microhardness measurement has significant impact

on hardness of the material. As the temperature increases, the hardness of the material
decreases due to the effect of temperature on the bonding between the molecules.

If the temperature increases, the molecules start vibrating which results in weakening of the

chemical bond between the molecules. So the strength of the bond decreases in the material

which eases the indenter to penetrate through the material. As a result of this diagonal length

of the indenter increases which decreases the hardness of the material (Wolfgang kollenberg).

Wolfgang Kollenberg, Microhardness measurement on haematite crystals at

temperature up to 900°C, J. Mater. Sci 21 (1986) 4310-4314.

Question 5: What is the relationship between structure, hardness and thermal stability?

Answer : The hardness and melting point of a crystal increase proportionally with the

strength of the structure (Bonding between the molecules).

1. When the strength of the chemical bonding between the molecules is strong, the

hardness of the material increases.

2. The melting point of the material tends to be high, when the strength of bonding

between the molecules is strong (It requires more energy to break the bonds between

the molecules)

Question 6: What is the plane author have used for the microhardness measurement?

Hardness is the directionally dependent [anisotropic in nature] so each plane has different

kind of hardness value. The authors mention plane or morphology of the crystal.

Answer : The indentations were made on the prominent smooth place surface of the KSB

single crystal of (6 x 4 x 2) mm3 has been chosen for the microhardness measurement.
Question 7: In Figure no 1. Page no .4. (a) (load P vs Depth ) the caption in vertical scale

"load P in (g)" but in Figure no 1. (c) the caption in vertical scale "load P (P in g). Use

uniform caption for all figures.

Answer : As per the reviewer suggestions, the figure caption has been uniformly changed for

all the figures in the revised manuscript.

Question 8: In the same Figure no.1. [Check in the figures page no.1]. The figure captions

have given wrongly. "Figure 1(a) Load P vs Depth (b) Log P vs Log d (c) Load P vs

Hardness Hv" but it is not in the correct order. Captions are not coincident with figures.

Kindly check and give proper order.

Answer : As per the reviewer suggestions, the order of the figure caption is corrected in the

revised manuscript. The Authors apologize for the mistake.

Question 9: Page no .5. In figure caption 2. 60 only have given "g" is missing. This need to

be correct.

Answer : As per the reviewer suggestions, the error is rectified and the same has been

included in the revised manuscript. The Authors apologize for the mistake.
*Highlights (for review)

Highlights

 The variation of microhardness with load shows the load independent value of

hardness.

 The meyer index number ‘n’ is calculated as 1.81 and it belongs to soft material

category

 The fracture toughness and brittleness index for the grown crystal are found to be

0.3105 (g/μm3/2) and 194.52 (μm-1/2)

 The nature of the crack is found as palmqvist

 The hardness contour and histogram shows the stress distribution and effect of defects

region in the material.

*Manuscript

Study on the mechanical properties sof potassium sodium hydroxide borate hydrate
1
2 (KSB) single crystals by using Vickers microhardness tester
3
4
5
6 C. Ramki and R. Ezhil Vizhi*
7
8
9 Materials Research Laboratory, Department of Physics,
10
11
12 VIT University, Vellore- 632014, India
13
14
15
16 rezhilvizhi@vit.ac.in, revizhi@gmail.com
17
18
19 Abstract
20
21
22 The mechanical properties of solution grown potassium sodium hydroxide borate hydrate
23
24
25 single crystal (KSB) have been obtained by using Vickers microhardness studies in the load
26
27 range from 10 to 70 g. The variation of microhardness with load represents the load
28
29
30 independent value of hardness (Indentation size effect). The mayer index number ‘n’ is
31
32 calculated as 1.81 and it belongs to soft material category. Various mechanical parameters
33
34
35
such as yield strength, elastic stiffness constant, fracture toughness, brittleness index,
36
37 hardness contour and crack propagation of KSB single crystal are discussed in detail.
38
39
40 Keywords: Crystal growth, Indentation and hardness, Deformation and fracture, Elastic
41
42
43 properties
44
45
46 1. Introduction
47
48
49 In the past few decades, inorganic nonlinear optical materials have a significant impact
50
51
52 because they have potential practical applications in the field of optics and laser technology
53
54 which includes frequency conversion, optical limiting, optical computing and optical storage
55
56
57 devices [1]. Purely inorganic materials exhibit excellent mechanical, thermal properties and
58
59 have a high degree of chemical inertness than the organic compounds. On the basis of this
60
61
62 1
63
64
65
 idea, several alkali metal borates have been widely investigated because it generally
1
2 possesses chemical stability, high damage threshold and high optical quality as well as high
3
4
5 transparency in the UV region. Usually, borate compounds are formed by helix network of
6
7 planar BO3 and BO4 tetrahedral group and these network links together by oxygen atoms to
8
9
10 form rings into infinite chains like structures [2]. Until now numerous borate complexes with
11
12 high nonlinearity, large laser damage threshold were identified such as LiB3O5, β-BaB2O4 and
13
14
15 CsB3O5 [3-5]. In such a way we have synthesized an inorganic potassium sodium hydroxide
16
17 borate hydrate (KSB) single crystal which was grown by slow evaporation method. The
18
19
crystal structure of potassium sodium hydroxide borate hydrate was reported by Cornelia
20
21
22 Smykalla and Helmut Behm [6] and recently we have investigated on the property studies on
23
24 KSB single crystal [7]. However, the relationship between the fracture nature and hardness of
25
26
27 KSB single crystal has not yet been investigated. As a continuation of the above, KSB single
28
29 crystal grown in our laboratory is taken for the analysis to perform mechanical related
30
31
32 properties.
33
34
35 Hardness measurement is a mechanical material property which is strongly influenced on the
36
37 structure and composition of solids. The interest in hardness measurement does not depend
38
39
40 on the technical point of view but it also has an opportunity to analyse the degree of lattice
41
42 order of single crystalline materials. The microhardness is basically depends on the following
43
44
45 factors (a) effect of solid solution is being connected with the chemical nature of the atoms
46
47 (b) point defects which hinders the motion of dislocation and (c) defects aggregates and
48
49
50 amorphous region.The above mentioned points suggested that the hardness is a strength
51
52 microprobe [8]. To the best of our knowledge, there was no report on the mechanical
53
54
properties of KSB single crystal. Hence in this paper we deeply investigated the hardness
55
56
57 related parameters such as fracture toughness, elastic stiffness constant, brittleness index,
58
59 hardness contour and yield strength of KSB single crystal.
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61
62 2
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 2. Materials and methods
1
2
3 The single crystal of potassium sodium hydroxide borate hydrate (KSB) was synthesized by
4
5
6 using slow evaporation method. The grown crystal was subjected to single crystal XRD
7
8 which confirms that the crystal structure belongs to hexagonal system with space group P 2c.
9
10
11 The unit cell parameter was determined by direct method and the refinement is done by full
12
13 matrix least square technique using SHELXL program. In conventional testing, hardness of
14
15
16 the material is determined as the ratio between the applied load P and corresponding contact
17
18 area between the material and the indenter. The mechanical characterization of the grown
19
20 KSB crystal was done by Vickers microhardness tester ( Mitutoyo HM 210 B with AVPAK –
21
22
23 20 V2.0 software Part No. 11AAC666) at room temperature in which the indenter has
24
25 pyramidal with square base shape with a semi-apex angle θ equal to 68°. The crystal with flat
26
27
28 and visibly free from scratches was chosen and the load ranging from 10g to 70g were used
29
30 for indentation. Initially, the crystal surface was cleaned with Millipore water and placed
31
32
33 properly on the indenter shaft unit. The load was given gently by pressing the indenter at 90°
34
35 to the surface and the diagonals of Vickers indenter were parallel to the edges of intersection
36
37
38
on the plane. The diagonal length of each load was recorded and the average diagonal length
39
40 was used for calculation.
41
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43 3. Results and discussion
44
45
46 3.1 Effect of indentation on load
47
48
49 Figure 1(a) shows the dissimilarity in the penetration of indenter with respect to the applied
50
51 load. At first, 10g of load was impressed on the surface of the crystal and the penetration
52
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54 depth was calculated as 8.8μm. At low loads, the indenter penetrates the surface which is
55
56
nearer to the indentation and the stressed area is comparatively very small. At high load like
57
58
59 40, 50 and 60g, the penetration depth was calculated as 25.1, 26 and 27.6 μm which denotes
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62 3
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 that the effect of inner layers becomes more prominent and larger volume are stressed on the
1
2 crystal surface (figure 1(a)). When the load reaches 70 g, the applied stress is more enough to
3
4
5 break the crystal and the propagation of crack on the crystal surface was observed.
6
7
8 3.2 Load independent Hardness Hv
9
10
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12
The variation of microhardness values with load is shown in the figure 1(b). The indentations
13
14 were made on the prominent plane of the grown KSB single crystal for a varying load from
15
16 10 to 70g. It is observed that the hardness value got decreased when the load was increased to
17
18
19 60g because these loads are sufficient to soften the bonding in the molecules which indicates
20
21 the indentation size effect (ISE) of the material. The microhardness value was determined
22
23
24 using the formula [9]
25
26
27
28 = = = kg/mm2 (1)
29
30
31
32 Where P is the applied load (g) and d is the diagonal length (μm). The Meyer’s index number
33
34
35 ‘n’ was calculated by using Meyer’s law which relates the diagonal length and load as
36
37 P = kdn
38
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Log P = log k + n log d (2)
42
43
44 n- Meyer’s index and k- is a material constant. To calculate the value of ‘n’, a graph is plotted
45
46 between log P and log d which gives a straight line (figure 1(c)). The value of ‘n’ was
47
48
49 calculated using the least –square fitting method as 1.81. According to onitsch [10], n value
50
51 lies between 1 and 1.6 for harder materials and above 1.6 for softer materials. The KSB
52
53
54 single crystal comes under soft material category.
55
56
57 Figure 1(a) Load P vs Depth (b) Load P vs Hardness Hv (c) Log P vs Log d
58
59
60 3.3 Fracture mechanics
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62 4
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 In order to find the connection between hardness, bond nature and microstructural properties
1
2 of the fractured surface of KSB single crystals by using the relation
3
4
5
6 (3)
7
8
9
10 Where P is load, C is crack length, d is diagonal length of the indenter and β0 is taken as 7 for
11
12 Vickers indenter [11].
13
14
15
16 S. No Load P Yield strength Elastic stiffness Fracture Brittleness c/a Nature of
17
18 (g) σy ( kg/mm2 ) constant toughness index (Bi) crack
19
20
21
C11 ( x1014 Pa ) Kc (g/μm3/2) (μm-1/2)
22
23
24
1 10 20.933 4.3416 - - -
25
26 2 20 19.866 3.9619 - - -
27
28
29 3 30 19.733 3.915 - - -
30
31 4 40 18.066 3.355 - - -
32
33
34 5 50 17.766 3.258 - - -
35
36 6 60 15.466 2.556 - - -
37
38
39 7 70 - - 0.3105 194.52 2.0004 Palmqvist
40
41
42 Table 1 Microhardness parameters
43
44
45 From the equation (3), the nucleation of the cracks is due to the stress field formed during the
46
47
48
course of indentation (figure 2). Based on the analysis of nihara et al.[12] reported that the
49
50 reliable value of the fracture toughness only if c/a ≥ 2.5 (medium crack) whereas c/a ≤ 2.5
51
52 (palmqvist). The fracture toughness is calculated for higher load (70g) where c/a ≤ 2.5 so it is
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54
55 seen that the crack is palmqvist.
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57
58 Figure 2. Indentation photos for the load varying from 10g, 20g, 30g, 40g, 50g, 60g and 70g
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60
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62 5
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 3.4 Brittleness index (Bi)
1
2
3 The crack which is obtained around the indentation gives a relative measure of material
4
5
6 brittleness. The mathematical value of Bi can be calculated using the relation (4) and it is
7
8 found as 194.52 μm-1/2
9
10
11
12 = (4)
13
14
15
16 The yield strength σy can be calculated using the formula σy = Hv/3 (if n < 2). The values of
17
18 yield strength for different load are given in the table 1. The elastic stiffness constant (C11)
19
20
21 was calculated using Wooster’s empirical formula C11 = (Hv)7/4 [13]. The calculated stiffness
22
23 constant values for various loads are presented in table 1. The hardness of the material
24
25
26
depends on the strength of the chemical bonding between the molecules which is responsible
27
28 for its distinct hardness. From the result, we concluded that the hardness of the material got
29
30 increased as the strength of the chemical bonding consequently increased. From the stress
31
32
33 contour, it can be seen that maximum stress took place at the inner core of the crystal. Stress
34
35 distribution in the crystal for 70 g is shown in figure 3(a) and it has been concluded that the
36
37
38 stress value (717.5 Hv) for 70 g is higher than stress value in the lower loads. Figure 3(b)
39
40 shows the histogram of microhardness values obtained for the grown crystal KSB. The
41
42
43
histogram figure reflects the effect of point defects, impurities, non-uniform chemical
44
45 distribution and dislocation density within grains which beneath the indented location [14].
46
47
48 Figure 3(a) Hardness contour (b) Hardness histogram
49
50
51
52 4. Conclusion
53
54
55 Inorganic potassium sodium hydroxide borate hydrate (KSB) single crystal has been grown
56
57 by slow evaporation method. The Vickers microhardness study for the grown crystal reveals
58
59
60 that the hardness value decreases with increase in load which indicates the indentation size
61
62 6
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65
 effect (ISE). Using Meyer’s law, the ‘n’ value is calculated as 1.81 and it belongs to soft
1
2 material category. The fracture toughness and brittleness index for the grown crystal are
3
4
5 found to be 0.3105 (g/μm3/2) and 194.52 (μm-1/2). When the applied stress reaches 70g, the
6
7 material undergoes deformation so the material can have a low resistance power to oppose
8
9
10 the given stress. The value C11gives an idea about the tightness and bonding between the
11
12 neighbouring ions and the nature of the crack is found as palmqvist. The hardness contour
13
14
15 and histogram help us to find the stress distribution and effect of defects region in the
16
17 material.
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19
20
21
Acknowledgements
22
23
24 The authors are thankful to the management, VIT, Vellore for their constant support and
25
26 encouragement. Thanks to DST-SERB (SR/FTP/PS-122/2012) for the financial support to
27
28
29 carry out this work.
30
31
32 References
33
34
35 [1] A. H. Reshak, Xuean Chen, S. Auluck, H. Kamarudin, Jan Chysky A. Wojciechowski and
36
37
I. V. Kityk, J. Phys. Chem. B 2013; 117; 14141
38 [2] Chuangtian Chen, J. Cryst. Growth 1990; 99; 790
39 [3] C. T. Chen, B. C. Wu, A. D. Jiang, G. M. You, R. Li and S. Lin, J. Opt. Soc. Am. 1989;
40 B6; 616
41 [4] C. T. Chen, B. C. Wu, A. D. Jiang and G. M. You, Sci. Sin. 1985; B18; 235
42
43 [5] Y. C. Wu, T. Sasaki, S. Nakai, A. Yokotani, H. Tany and C. Chen, CsB3O5, Appl. Phy.
44 Lett. 1993; 62; 2614
45 [6] Cornelia Smykalla and Helmut Behm, Z. Kristallogr. 1988; 183; 51
46 [7] C. Ramki and R. Ezhil Vizhi, Mater. Lett. 2017; 188; 156
47
48
[8] K. K. Bamzai, P. N. Kotru and B. M. Wanklyn, J. Mater. Sci. Technol. 2000; 16; 405
49 [9] K. Sangwal, Mater. Chem. Phys. 2000; 63(2); 145
50 [10] E. M. Onitsch, Mikroskopie 1956; 95(15); 12
51 [11] R. Ezhil Vizhi, M. Vijayalakshmi, J. Cryst. Growth, 2016; 452; 204
52 [12] K. Nihara, R. Morena and D. P. H. Hasselma, J. Mater. Sci. Lett. 1982; 1; 13
53
54 [13] W. A. Wooster, Rep. Prog. Phys. 1953; 16; 16
55 [14] G. Cheng, K. S. Choi, X. Hu and X. Sun, Mater. Sci. Engg. A, 2016; 652; 384
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Figure 30

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Click here to download Figure: Revised Figure.docx
(b) 25 (a)

Depth in (m)
62
20

60 15

58

Hv (kg/mm2)
10

56 5
10 20 30 40 50 60
1.8
Experimental Load P in (g)
54

Log P (P in g)
Linear fit
1.6
(c)
52 1.4

50 1.2

48 1.0

1.2 1.3 1.4 1.5 1.6 1.7

As grown crystal
46 Log d (d in m)
10 20 30 40 50 60
Load P in (g)
Figure 1(a) Load P vs Depth (b) Load P vs Hardness Hv (c) Log P vs Log d

Figure 2. Indentation photo for 10g, 20g, 30g, 40g, 50g, 60g and 70g
(a)
Hv
22

20

18

16
(b)
14
Fr
12
eq 10
ue 8

nc 6

4
y
2

0
0 50 100 200 300 400 450 550 650

Hardness Hv

Figure 3(a) Hardness contour for 70g (b) Hardness histogram for 70g