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Osman, A.F.;  Fauzi, A.A.A.;  Alrashdi, A.A.;  Mustafa, Z.;  Halim, K.A.A. Dolomite as a Filler in a Polymer Composite. Encyclopedia. Available online: https://encyclopedia.pub/entry/25835 (accessed on 26 April 2024).
Osman AF,  Fauzi AAA,  Alrashdi AA,  Mustafa Z,  Halim KAA. Dolomite as a Filler in a Polymer Composite. Encyclopedia. Available at: https://encyclopedia.pub/entry/25835. Accessed April 26, 2024.
Osman, Azlin Fazlina, Asfa Amalia Ahmad Fauzi, Awad A. Alrashdi, Zaleha Mustafa, Khairul Anwar Abdul Halim. "Dolomite as a Filler in a Polymer Composite" Encyclopedia, https://encyclopedia.pub/entry/25835 (accessed April 26, 2024).
Osman, A.F.,  Fauzi, A.A.A.,  Alrashdi, A.A.,  Mustafa, Z., & Halim, K.A.A. (2022, August 04). Dolomite as a Filler in a Polymer Composite. In Encyclopedia. https://encyclopedia.pub/entry/25835
Osman, Azlin Fazlina, et al. "Dolomite as a Filler in a Polymer Composite." Encyclopedia. Web. 04 August, 2022.
Dolomite as a Filler in a Polymer Composite
Edit
This entry is adapted from the peer-reviewed paper 10.3390/polym14142843

Polymers are being used in many applications all around the world. However, there are some drawbacks in the properties of polymers that could hamper their usage in certain applications. Therefore, a new material polymer composite was introduced. A polymer composite is a polymer-based material with the addition of a filler. Many researchers have reported the improvement in the properties of a polymer when a filler was introduced. This helps minimize the disadvantages of using a polymer. Fillers are materials added to resins or binders (polymer/concrete/metal/ceramic) to improve their specific properties as they are turned into a new form of material called a “composite.” Dolomite is a type of sedimentary carbonate rock that consists mainly of dolomite mineral. The use of dolomite in a polymer composite system has gained increasing attention in recent years after researchers successfully proved that it is capable of improving mechanical and physical properties of various polymeric materials. 

dolomite polymer composite mechanical properties chemical modification hybrid filler

1. Dolomite

Dolomite was originally known as Dolomieu; it was named after a French geologist, Deodat Guy Dolomieu. Dolomite can be referred to as dolomite mineral and dolomite rock. Dolostone is another name for dolomite rock. Dolomite comes from a variety of origins. It may be present in lakes or beneath shallow seafloors, in early to late burial settings [1]. Dolomite can occur via two possible mechanisms, direct precipitation and through the dolomitization process, in which calcite dissolves, supplying Ca2+ ions, followed by the precipitation of dolomite from a solution rich in Mg2+ ions [1][2][3]. Some dolomites come from the replacement of the pre-existing limestone through the dolomitization process [1].
Dolomite is one of the most abundant carbonate rocks after calcite. Dolomite is widely spread in nature and can be found in Nigeria, Canada, Malaysia, and many other countries [4][5][6]. In Malaysia, dolomite can be found abundantly in the states of Perlis and Perak. There are several large quarries, thus placing them as a major producer of Malaysian dolomite [7][8][9]. Figure 1 shows one of dolomite’s quarry sites in Perlis. Dolomite that is found in Perlis is also known as “Batu reput” by the locals and is a source of quality mineral rocks [3].
Polymers 14 02843 g002 550
Figure 1. Dolomite quarry site in Perlis, Malaysia (own photograph).
Dolomite is known to be a derivative of calcite. Therefore, dolomite mineral has a similar chemical composition to calcite mineral. Calcite minerals consist of calcium and carbonate (CaCO3) layers only, while dolomite mineral consists of three layers, made up of alternating calcium (Ca) and magnesium (Mg) layers separated by a carbonate (CO3) layer. Thus, the structure of dolomite is not exactly in ordered form as in calcite, because some of the magnesium may be present in the calcium layer, while some of the calcium may be present in the magnesium layer [10]. The chemical structure of dolomite is presented in Figure 2. Hydrochloric acid is used to distinguish between calcite and dolomite. Adding HCl to calcite will cause a fuzzy reaction, while adding it to dolomite will only cause a bubbly reaction. Figure 3 shows the XRD diffraction peak of raw dolomite that was obtained from Perlis Dolomite Industries Sdn. Bhd., Malaysia. There is a sharp peak observed at 31.04°, which indicates the presence of dolomite mineral. This is in good agreement with the findings of Gregg et al. and Abdul Samad and Abd Rashid [11][12]. Dolomite from the Perlis Dolomite Industries also contains 41.4% CaCO3, which is said to be of great quality [13].
Polymers 14 02843 g003 550
Figure 2. Structure of dolomite.
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Figure 3. XRD diffraction graph of raw dolomite.
Dolomite in the form of gravel stone may have different colors, for example, white, colorless, pink, gray, and brown, but when it is transformed into fine powder, its color turns to yellowish. Researchers have collected some dolomite samples from Perlis Dolomite Industries Sdn. Bhd. and performed SEM and TEM analyses. Figure 4 shows the different particle sizes of dolomite. Figure 4a,b present dolomite in the form of gravel and granules, respectively. Figure 4c shows the powder form of dolomite. D1 represents dolomite with a particle size of 150 µm, while D2 represents dolomite with an average particle size of 63 µm. D1 has rougher texture, while D2 has smoother and soft texture. Table 1 summarizes a comparison of the physical properties of dolomite and calcite. Dolomite has a rhombohedral cleavage and a hexagonal crystal system, while calcite has a rhombohedral and trigonal system. It has Mohs hardness of 3.5–4 and specific gravity of 2.8–2.9. Figure 5 displays the SEM images of dolomite, suggesting the smooth surface of this mineral’s particles. Furthermore, the morphology of the dolomite indicates that it has an irregular shape and a rhombohedral structure. The TEM image in Figure 6 suggests that raw dolomite’s particle morphology possesses a Moire fringe pattern. This is due to the overlap of two different phases in the structure of dolomite, which are Mg and Ca [14].
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Figure 4. (a) Dolomite in gravel form, (b) dolomite in smaller granule form, and (c) dolomite in fine powder form.
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Figure 5. SEM image of raw dolomite particles.
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Figure 6. TEM image of raw dolomite particles.
Table 1. The physical properties of dolomite and calcite.
Physical Properties Dolomite [15] Calcite [16]
Chemical composition (CaMg(CO3)2) CaCO3
Color Colorless, white, pink, gray, brown, black White, colorless, gray, red, green, blue, yellow, orange, brown
Streak White White
Cleavage Perfect, rhombohedral, three directions Perfect, rhombohedral, three directions
Mohs hardness 3.5–4 3
Specific gravity 2.8–2.9 2.7
Diagnostic properties Rhombohedral cleavage Rhombohedral cleavage
Crystal system Hexagonal Trigonal
Dolomite was extensively used in many fields and industries many years ago, in the form of either raw dolomite or calcined dolomite. For example, in agriculture, dolomite was used in the form of raw material for soil stabilization and fertilizer [17]. Figure 7 shows the image of packed dolomite ready to be used as fertilizer. Dolomite was also used for decreasing the acidity of soil and the adjustment in magnesium concentration in soil. In addition, dolomite that was used for construction was also in raw dolomite form. Dolomite also has the ability to absorb poisonous and toxic substances [18][19][20]. Table 2 summarizes the use of dolomite in different industries.
Polymers 14 02843 g008 550
Figure 7. Packed dolomite for use as fertilizer (own photograph).
Table 2. Summary of dolomite usage.
Field Purpose
Agriculture As fertilizer [17]
To decrease the acidity of soil [19]
To adjust magnesium concentration in soil [19]
Aquaculture To reduce phosphorus [21]
Ceramics As a source of lime [9]
In kiln control [17]
Chemical To make salts, e.g., magnesia [22]
Construction In cement and concrete manufacturing [17][20][23]
As flooring material [3][24]
As road construction material [24][25]
Plastic for structural application As a filler [4]
Paint As a filler [26]
As an aid in pigmentation [27]
Wastewater treatment For copper ion adsorption [5]
Membrane application As low-cost membranes or substrates [28]
Plastics As a filler to improve the mechanical properties [29][30]
Pharmaceutical As a supplementary source of calcium and magnesium [31]
As an osmotic oral laxative [31]

2. Dolomite as a Hybrid Filler in a Polymer Composite

Over the years, the use of more than one filler or hybrid filler in a polymer composite system has become trending research because it can provide greater opportunity to obtain improvement in the polymer composite properties. Many researchers have proved that the use of a combined filler has further improved the mechanical, thermal, and physical properties of the polymer composite [32][33][34][35]. Often, the properties of the two fillers used as hybrid fillers are different and are able to have different effects on the polymer matrix used. Thus, this combination of fillers can result in the achievement of a variety of qualities that cannot be obtained by a single filler. According to Jaafar, the use of hybrid fillers will also affect the cost of composites, assist in acquiring specific properties of composites, and in turn improve the properties of the composites [36]. A cost reduction can be obtained when cheap and expensive materials are combined and used as a hybrid filler. However, there are still a limited number of studies involving dolomite as a co-filler in the hybrid filler system. Table 3 summarizes the use of dolomite as a co-filler/hybrid filler in the polymer composite system.
Table 3. Summary of literature studies reporting the use of dolomite as a co-filler/hybrid filler in polymer composites.
Polymer Matrix Primary Filler Secondary Filler Processing Method Filler Loading Tensile Elongation at Break (%) Impact Strength Hardness Flexural Ref.
Strength (MPa) Modulus Stress (MPa) Strength (MPa) Modulus (MPa)
Epoxy resin Carbon nanotubes (CNTs) Dolomite Mechanical stirrer Chemical vapor deposition                 [37]
0% 20.89 961.31 (MPa) N/A N/A N/A N/A N/A N/A
1% 28.52 1152.87 (MPa) N/A N/A N/A N/A N/A N/A
3% 33.83 1188.1 (MPa) N/A N/A N/A N/A N/A N/A
5% 4.93 1216.5 (MPa) N/A N/A N/A N/A N/A N/A
Physically hybrid                
0% 20.89 961.31 (MPa) N/A N/A N/A N/A N/A N/A
1% 26.71 1139 (MPa) N/A N/A N/A N/A N/A N/A
3% 29.97 1159.8 (MPa) N/A N/A N/A N/A N/A N/A
5% 27.94 1148.7 (MPa) N/A N/A N/A N/A N/A N/A
Epoxy resin Glass fiber Dolomite Hand layup 0% 59.8 N/A N/A N/A 2.4 (J) 102.12 (HRL) 72.3 N/A [38]
5% 52 N/A N/A N/A 2.7 (J) 107.27 (HRL) 62.8 N/A
10% 45.9 N/A N/A N/A 3.4 (J) 109.60 (HRL) 54.3 N/A
15% 42.8 N/A N/A N/A 3.8 (J) 112.26 (HRL) 48..8 N/A
Epoxy resin Glass fiber Dolomite Hand layup 0% 282.58 ± 12.96 2.32 ± 0.14 (GPa) N/A N/A 6.1 ± 0.37 (J) 101.32 ± 3.08 (HV) 285.3 ± 13.12 N/A [39]
5% 268.59 ± 9.43 2.94 ± 0.l5 (GPa) N/A N/A 7.2 ± 0.36 (J) 103.76 ± 2.89 (HV) 273 ± 9.65 N/A
10% 244.69 ± 7.80 3.26 ± 0.13 (GPa) N/A N/A 8.8 ± 0.35 (J) 105.64 ± 3.23 (HV) 262.8 ± 7.12 N/A
15% 227.6 ± 7.10 2.44 ± 0.10 (GPa) N/A N/A 10.2 ± 0.41 (J) 108.22 ± 2.3 (HV) 249.9 ± 7.24 N/A
VTRM 0% 374.46 ± 17.80 3.54 ± 0.21 (GPa) N/A N/A 8.1 ± 0.46 (J) 102.94 ± 3.18 (HV) 337.4 ± 14.25 N/A
5% 337.33 ± 10.80 4.15 ± 0.17 (GPa) N/A N/A 9.2 ± 0.37 (J) 106.3 ± 225 (HV) 331.8 ± 10.12 N/A
10% 293.05 ± 11.65 4.33 ± 0.22 (GPa) N/A N/A 10.6 ± 0.48 (J) 109.06 ± 3.08 (HV) 327.6 ± 12.38 N/A
15% 270.43 ± 7.12 4.02 ± 0.12 (GPa) N/A N/A 13.4 ± 0.39 (J) 112.08 ± 2.38 (HV) 319.9 ± 7.60 N/A
Low-density polyethylene (LDPE) Kenaf core fiber (KCF) Dolomite Internal mixer 0% N/A 109.37 (MPa) 1.47 N/A 3.52 (kJ/m2) N/A N/A N/A [40]
3% N/A 116.72 (MPa) 1.50 N/A 3.73 (kJ/m2) N/A N/A N/A
6% N/A 122.52 (MPa) 1.53 N/A 3.82 (kJ/m2) N/A N/A N/A
9% N/A 123.48 (MPa) 1.60 N/A 4.03 (kJ/m2) N/A N/A N/A
12% N/A 124.50 (MPa) 1.81 N/A 4.11 (kJ/m2) N/A N/A N/A
15% N/A 131.30 (MPa) 1.86 N/A 4.69 (kJ/m2) N/A N/A N/A
18% N/A 143.46 (MPa) 1.91 N/A 5.29 (kJ/m2) N/A N/A N/A
Phenolic Dolomite Multiwalled carbon nanotubes (MWCNTs) Ball milling machine 0% N/A N/A N/A N/A N/A 25(HR) N/A N/A [41]
1% N/A N/A N/A N/A N/A 36(HR) N/A N/A
3% N/A N/A N/A N/A N/A 45(HR) N/A N/A
5% N/A N/A N/A N/A N/A 52(HR) N/A N/A
Phenolic Dolomite Carbon nanotubes (CNTs) Mechanical stirrer Chemical vapor deposition                 [42]
0 N/A N/A N/A N/A N/A 25 N/A N/A
1 N/A N/A N/A N/A N/A 39 N/A N/A
3 N/A N/A N/A N/A N/A 46 N/A N/A
5 N/A N/A N/A N/A N/A 50 N/A N/A
Physically hybrid                
0 N/A N/A N/A N/A N/A 25 N/A N/A
1 N/A N/A N/A N/A N/A 30 N/A N/A
3 N/A N/A N/A N/A N/A 37 N/A N/A
5 N/A N/A N/A N/A N/A 38 N/A N/A
Waterborne polyurethane (WPU) Fibrous palygorskite (PAL) Dolomite Mechanical stirring 0% 4.9 N/A N/A 9.4 N/A N/A N/A N/A [10]
WPU/PAL10% 3.5 N/A N/A 8.8 N/A N/A N/A N/A
WPU/DOL 10% 4. N/A N/A 9.5 N/A N/A N/A N/A
WPU/MIX 10% 8. N/A N/A 8.1 N/A N/A N/A N/A
Polypropylene (PP) Wood flour Dolomite High-intensity mixer and single-screw extruder 0% 27.1 474 (MPa) N/A 29.4 N/A N/A 37.1 1013 [43]
3% 24.8 615 (MPa) N/A 20.1 N/A N/A 42.4 1592
6% 24.4 620 (MPa) N/A 22.2 N/A N/A 41.0 1617
9% 22.8 627 (MPa) N/A 19.4 N/A N/A 41.8 1673
Saleh et al. proved that the use of dolomite as a co-filler in the epoxy resin can improve the properties of the epoxy/CNT composite [37]. They combined the organic (CNT) and inorganic filler (dolomite) in order to solve the problem of high agglomeration of the CNT. Therefore, the CNT and dolomite fillers were chemically attached using the chemical vapor deposition (CVD) method to allow the de-agglomeration of the CNT and assist in the dispersion of the hybrid filler in the epoxy matrix. They also used the physically hybrid method (PHY) for comparison with the CVD method. It is interesting to report that the epoxy with 5 wt% CNT/dolomite (CVD) composites is capable of increasing the tensile strength and tensile modulus of the epoxy by 67% and 28%, respectively, when compared to the virgin epoxy [37]. When using the PHY method, the tensile strength and tensile modulus of the epoxy/CNT/dolomite composite increased when the filler was added at 3% only. This shows that the CVD method performed better than the physically hybrid method. This was because the CNTs produced by the CVD method developed a preferable load transfer effect between the filler and the matrix with the presence of CNTs on the surface of dolomite, while in the physically hybrid method, the excess or unattached CNTs agglomerated and weakened the filler and matrix interfacial strength. This was proved by the image of the fractured surface of the epoxy/CNT/dolomite at 5% filler loading, where a homogenous dispersion was seen when using the CVD method, whereas the CNT agglomeration can be spotted when using the PHY method.
The work by Verma et al. involved the use of dolomite as a co-filler in the epoxy composite containing a natural fiber (Grewia optiva)/glass fiber hybrid filler. The epoxy composite had a fixed amount of Grewia optiva and glass fiber but with varying composition of the dolomite filler (0, 5, 10, and 15 wt%). Their findings indicate that the void content, density, hardness, and impact energy increase, while tensile and flexural strength decreases with the increase in the dolomite content [38][39]. At high loading, the dolomite agglomerated. This agglomeration is prone to intrinsic structural discontinuities that eventually deteriorate the tensile and flexural strength of the composite [38]. On the contrary, the hardness and impact strength of this epoxy hybrid composite system is reported to be increased. This might be attributed to the enhanced micro-packing of the ingredients in the polymer matrix. The stiffness properties of dolomite also helped to reduce the deformation characteristic of the epoxy matrix [39]. In another study, Verna et al. studied the effect of two different processing methods to produce an epoxy composite with hybrid fillers, which were hand layup and the VTRM technique. They found out that the use of both techniques may result in a decrement in the tensile strength of the epoxy, especially at high dolomite loading (15 wt%) [39]. However, by using the hand layup method, the tensile modulus, impact strength, and hardness of the epoxy can be increased even when the dolomite is added at 15 wt%.
Shamsuri et. al. investigated the mechanical and thermal properties of a low-density polyethylene/kenaf core fiber biocomposite with the addition of dolomite as a co-filler. They revealed that there is improvement in the tensile stress, tensile modulus, and impact strength of the low-density polyethylene (LDPE)/kenaf core fiber (KCF) composite as dolomite is added as the hybrid filler [40]. A significant increase in the tensile modulus and tensile stress of the LDPE/KCF was observed as the dolomite was added at 12 wt% to 18 wt%. The sliding effect of the KCF in the structure of LDPE might be hindered due to the rigid property of the dolomite, which can provide mechanical interlocking [40]. The impact strength of the LDPE/KCF/dolomite hybrid composite also increased with increasing of dolomite loading. At 18% of dolomite loading, the increment was reported to be 50.3% when compared to the virgin LDPE. In addition, the thermal properties of the LDPE were improved when a lower amount of dolomite was used (lower than 20%).
Md Saleh et al. have investigated the efficiency of the MWCNT/dolomite hybrid filler in enhancing the thermal conductivity of the phenolic resin. It was clearly observed that the hybrid MWCNT/dolomite filler assists the phenolic to achieve a higher thermal conductivity. The thermal conductivity value increased by 7.21% compared to that of the composite with a single filler [41]. The improvement of thermal conductivity was due to the synergistic effect of the dolomite and MWCNTs, which provides an additional channel for the heat flow to bypass the polymer matrix. Interestingly, the use of the hybrid filler also resulted in the improvement of the micro-hardness of the phenolic. The micro-hardness is also improved with increasing of dolomite loading. When added at 5%, the increment was reported to be the highest (+108%) [41]. In another study by Md Saleh et al. (2016), carbon nanotubes (CNTs) and dolomite were used as a hybrid filler in the phenolic composite [42]. Again, they studied the thermal conductivity and micro-hardness of the phenolic composite with a hybrid filler with a different preparation method (CVD and PHY method). In agreement to the previous study, the thermal conductivity and micro-hardness of the phenolic was successfully improved with the addition of dolomite and CNT as a hybrid filler. The improvement in hardness might be due to the decrease in inter-particle spacing with the presence of stiffer dolomite particles [44]. Good distribution of CNTs and dolomite in the phenolic composite also contributed to this enhancement [42]. Thus, a better conductivity pathway was created, while the hardness of the dolomite improved the micro-hardness of the phenolic composite [42].
Recently, Ni et al. performed a study on the use of a fibrous palygorskite (PAL)/dolomite (DOL) hybrid filler in the waterborne polyurethane (WPU) composite and its effect on the physical and mechanical properties of the WPU [10]. The results indicated that the addition of both fillers enhanced the mechanical and thermal properties of the WPU, but this was not happening when only a single filler (either one of the fillers) was used. The tensile strength of the WPU was at the highest value when a single filler of PAL and DOL was at 4% and 6% weight loading [10]. Interestingly, at 10% hybrid filler loading, the tensile strength could still be increased dramatically, by 178%, when compared to the neat WPU. This improvement was achieved because of the synergistic reinforcement effect of the two fillers used in the waterborne polyurethane polymer. Commonly, at higher filler loading, the tensile strength would decrease due to the agglomeration of the filler. Ni et al. proved through their SEM analysis that the hybrid fillers could be better dispersed inside the matrix when compared to the single filler. Obviously, when added in single form, both fillers are separated from the WPU matrix. This is one of the factors that contributed to the enhancement in the mechanical and thermal properties of the WPU composite.
Research by Özdemir et al. focused on the use of wood flour and dolomite as a hybrid filler in the polypropylene composite [43]. The composite samples were prepared by using a single-screw extruder. The research indicates that improvement in the tensile and flexural modulus of the PP can be realized when wood flour and dolomite are used as a hybrid filler. The addition of dolomite allowed an efficient stress transfer from the polymer matrix to the filler. The improvement in the tensile modulus can also be explained by the fact that the dolomite is much more rigid than the polymers and, thus, will stiffen the polymer matrix when it is embedded in the matrix structure [25].
Lastly, the work by Amiri et al. indicates the benefit of using a hybrid filler in enhancing the flame-retardant property of the polymer composite. They found out that the addition of a nanoclay and dolomite hybrid filler to polyurethane (PU) had a positive effect by way of reducing the flammability of the PU. Dolomite has a flame-retardant property, while the exfoliated nanoclay contains clay plates that act as a heat barrier and control the flame spread. The combination of both fillers resulted in a greater flame retardancy effect in the host polymer [45].
Based on the literature studies summarized in Table 3, it is worth mentioning that dolomite can play an important role in further improving the properties of the composite when used as a co-filler. It can help improve certain properties of the polymers that may not be achievable if only a single filler is used, properties such as hardness, impact strength, thermal stability, and flame-retardancy. In addition, dolomite is frequently used as a co-filler with carbon nanotubes and fibers, such as glass fiber and natural fiber. The differences in the physical and chemical characteristics between dolomite and those fillers can bring a more significant synergistic effect in enhancing the performance of the polymeric matrices.
Other than the above-explained research, there is also a study that indicated that the performance of a polymer is not necessarily improved through the addition of dolomite as a co-filler/hybrid filler. Vijayaraghavan et al. found out that the properties of polyurethane-based concrete did not improve with the addition of dolomite and kaolin as a hybrid filler [46]. This was due to the weak bond strength between the polymer and the hybrid filler. According to the results, the authors suggested that the ratio between the two fillers should be controlled and optimized. This is because the use of a hybrid filler will involve not only a matrix–matrix network, a matrix–filler network, and a filler–filler network but also a co-filler–co-filler network, a filler–co-filler network, and a filler–co-filler–matrix network. Sufficient network interactions between the matrix phase and both fillers (hybrid fillers) may attribute to the synergistic effect of fillers and the matrix, therefore leading to significant reinforcement of the polymer matrix.

References

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Subjects: Materials Science, Composites
Contributors MDPI registered users' name will be linked to their SciProfiles pages. To register with us, please refer to https://encyclopedia.pub/register :
Azlin Fazlina Osman
,
Asfa Amalia Ahmad Fauzi
,
Awad A. Alrashdi
,
Zaleha Mustafa
,
Khairul Anwar Abdul Halim
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Update Date: 09 Aug 2022
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