International Journal of Eco-Innovation in Science and Engineering (IJEISE) Vol 3 .
, 2022 .
https://ijeise.
id/ E-ISSN: 2721-8775 Article Synthesis and Modification of Nano-Precipitated Calcium Carbonate (PCC) with Addition of Ethylene Glycol Sani1*.
Mega Rosilina1 .
Mochamad Titus Maulana1.
Yelvia Sunarti1.
Srie Muljani1, and Dwi Hery Astuti1.
Ini Utami1 1 Department of Chemical Engineering.
Faculty of Engineering.
Universitas Pembangunan Nasional AuVeteranAy Jawa Timur.
Surabaya 60294.
Indonesia *Corresponding author: sanisjamsu@gmail.
com |Phone number: 62813 32452800 Received: 21st February 2022.
Revised: 22nd April 2022.
Accepted: 18th May 2022.
Available online: 19th May 2021.
Published regularly: May and November.
Abstract ZA fertilizer waste (Ammonium sulfat.
is waste generated from the industrial process of producing ZA The waste contains very high calcium and has the potential to be used as a raw material in the manufacture of Precipitated Calcium Carbonate (PCC).
PCC with certain qualities can be developed in the field of advanced materials, with size modification into nanoparticles.
One method to produce nanoparticles is using the coprecipitation method, with the help of a polymer solution.
This study aims to produce Nano-PCC by finding the best conditions of CaCl2: Ethylene Glycol mole ratio and stirring Nano-PCC is synthesized by reacting fertilizer waste with HCl to form a CaCl2 solution.
Then, the solution is mixed with ethylene glycol to prevent particle agglomeration so that the size obtained will be smaller.
The mixture is then reacted with Na2CO3 to form precipitated calcium carbonate (PCC).
this study, the variables were the mole ratio of CaCl2: ethylene glycol .
:12, 1:14, 1:18, 1:.
and stirring speed .
, 500, 650, 800, and 950 rp.
Based on PSA analysis, the Nano-PCC obtained at the smallest CaCl2: ethylene glycol ratio 1:12, stirring speed 950 rpm was 51.
83 nm.
Based on ScherrerAos calculations with XRD, the particle size obtained was 48.
25 nm.
SEM analysis showed that the crystals formed were dominated by vaterite crystals, with a size range of 55.
79 nm.
Keywords: ZA fertilize waste.
Nano Precipitated Calcium Carbonate (PCC).
Coprecipitation.
Ethylene Glycol Introduction ZA fertilizer waste (Ammonium Sulfat.
is waste generated from the industrial process of producing ZA fertilizer.
The amount of ZA fertilizer waste increases along with the increase in ZA fertilizer production in Indonesia.
From several studies.
ZA waste produced is known to contain high calcium, amounting to 92.
Therefore.
ZA fertilizer waste has the potential as raw material for Precipitated Calcium Carbonate (PCC) manufacture.
Precipitated Calcium Carbonate (PCC) is a widely studied material.
The versatility and design of CaCO3 particles have aroused considerable interest in both the scientist and the industrial community due to their wide field of applications and biocompatibility.
PCC is widely used as filler in paints, pigments, plastics, fibres and cement, according to its characteristics, such as morphology and size .
PCC has been widely used in various fields of health, food, and industry.
Generally.
PCC has a particle size from 0.
1 to 3 m.
PCC with certain qualities can be developed as an advanced material, by turning it into nanoparticles.
The synthesis of nanoparticles can change the properties and functions of a material.
The research of .
stated that the addition of Nano PCC can increase the tensile strength and DOI: https://doi.
org/10.
33005/ijeise.
International Journal of Eco-Innovation in Science and Engineering (IJEISE) Vol 3 .
, 2022 resilience of a composite.
Research by .
states that the use of nano PCC in the manufacture of PVC is proven to increase hardness, density, tensile strength, resistance to heat, and temperature onset, but decrease elongation at Synthesis of nanoparticles can be processed The coprecipitation method is a bottom-up synthesis method that can be used in the manufacture of Various ways to control the morphology, structure, and size of nano PCC have been developed, one of which is by using organic compounds, such as surfactants and polymers.
Surfactants and polymers can control the size and morphology of PCC by preventing particle agglomeration .
One of the polymers that can be used is ethylene glycol.
The ethylene glycol molecule is small and can form network hydrogen bonds similar in nature to water, but differ greatly in structural details.
Ethylene glycol also has a fairly high cohesive energy and dielectric constant .
In the research of .
have conducted research on the synthesis of Nano CaO using several polymer solutions such as water.
PEG 400, ethylene glycol, diethylene glycol, and glycerol, the smallest size obtained using ethylene glycol is 59 nm.
Based on the research of .
on the synthesis of CaCO3 with the addition of PEG 1:16 and stirring for 12 hours at room temperature was able to reduce the particle size to 15 nm.
The study showed that the greater the polymer concentration, the smaller the particle size.
In shortening the synthesis time, it can be done by using a higher variation of stirring speed.
stated that the higher the stirring speed, the smaller the particle size.
This is because collisions between particles will often occur so that the agglomeration process will be avoided.
If the agglomeration process can be avoided or stopped, the particle size can be maintained at the nanometer scale.
This study aims to find the best polymer concentration and stirring speed that can produce nano PCC.
Material and Method Material In this research, the main raw material is ZA fertilizer waste obtained from PT.
Petrokimia Gresik.
Equipment 1 = Statives and Clamps 2 = Magnetic stirrer 3 = Beaker Glass 4 = Thermometer 5 = Burette Fig.
The equipment of Nano-PCC synthesis Nano-PCC Synthesis ZA fertilizer waste was reacted with 2M HCl for 30 minutes.
After filtering, the filtrate CaCl 2 was mixed with ethylene glycol with a mole ratio 1:12, 1:14, 1:16, 1:18, and 1:20 for 8 hours and stirring speed 350, 500, 650, 800, and 950 rpm.
Subsequently, the pH was adjusted to 7.
5 using NaOH.
Then a precipitation process was carried out to obtain PCC by adding 1.
5 M Na2CO3.
The precipitate was allowed to stand for 12 hours and then dried in an oven to remove other substances and other solvents.
The nano-PCC will be analyzed using Particcle Size Analyzer (PSA).
XRay Diffraction (XRD), and Scanning Electron Microscopy (SEM).
Results and Discussion PCC is a modern paper and plastic industry.
reports the effect of various organic and inorganic additives used in the synthesis of the different polymorph of calcium carbonate.
The use of precipitated calcium carbonate fillers is the recommended choice in enhancing optical properties, durability, smoothness and ink adsorption in papermaking and improving the mechanical properties of plastic.
PCC can best be synthesized using solidAeliquid route or the gasAe solidAeliquid carbonation route, which consists of bubbling gaseous CO2 through a concentrated calcium hydroxide (Ca(OH).
and/or calcium magnesium hydroxide (CaMg(OH).
slurry with suitable organic additives.
DOI: https://doi.
org/10.
33005/ijeise.
International Journal of Eco-Innovation in Science and Engineering (IJEISE) Vol 3 .
, 2022 1 PSA Analysis (Particle Size Analyze.
In the research of the synthesis and modification on nano-PCC particle size from ZA fertilizer industry waste using a polymer solution, with the variable mole ratio of CaCl2: ethylene glycol and stirring speed, the results of PSA (Particle Size Analyze.
analysis were obtained as shown in Figure 2.
Size particle .
350 rpm
800 rpm
500 rpm
950 rpm
650 rpm
01:09
01:12
01:14
01:17
Mole ratio CaCl2:Etilen Glikol
01:20
that with high cohesive energy and dielectric constant, the electrostatic force on the bound ions is greater, this causes aggregation of PCC particles which causes If the concentration is too high, the particle size obtained will be even greater.
Figure 2 shows that at a stirring speed of 350 to 950 rpm, the particle size decreased in all It is because, with increasing stirring speed, the intensity of the molecules colliding with each other will occur more often to prevent particle agglomeration.
The length of the stirring time also affects the particle size, because as the stirring time increases, the smaller the particle size This is due to the increasing number of particles that are split into nano-sized particles.
In this study, the best PCC nanoparticle size was obtained at a mole ratio of CaCl2: Ethylene glycol 1:12 and stirring speed 950 rpm is 51.
83 nm, with a yield is 70.
The result of the PSA analysis is shown in Figure 3.
Fig.
Effect of CaCl2 : ethylene glycol mole ratio on nanoparticle size at various stirring Figure 2 shows that the higher the ethylene glycol concentration, the larger the particle size of the PCC produced will also tend to be.
The higher the stirring speed, the smaller the PCC particle These results are not under the research of .
which states that the higher the polymer concentration, obtained smaller the particle size.
In the study of .
using PEG polymer with mole ratios of 1:4, 1:8, 1:12, and 1:16 the sizes were 39, 30, 21, and 15 nm.
While in this study using ethylene glycol polymer at a stirring speed of 950 rpm, the smallest size was obtained with a mole ratio of CaCl2: ethylene glycol 1:12, 1:14, 1:16, 1:18, and 1:20, the sizes were 51.
83, 198.
7, 256.
4, and 348.
7 nm.
It can be seen that the use of different types of polymer can also affect particle size.
PEG polymer requires a high concentration to get a small particle size, while ethylene glycol requires a concentration that is not too high or tends to be lower.
According to the research of .
, stated that the formation of nanoparticles is only possible in certain ratios between polymers and crosslinkers (CaCl.
Too high a polymer concentration maybe also not be good for forming nanoparticles.
The higher the polymer concentration, the higher the particle This can make the particles stick together, causing agglomeration and larger particle size .
In addition, ethylene glycol has a fairly high cohesive energy and dielectric constant .
, so Fig.
PSA analysis of nano-PCC at the ratio of moles of CaCl2: ethylene glycol 1:12 and stirring speed 950 rpm 2 X-Ray Diffraction (XRD) Analysis XRD analysis is used to determine the structure and size of the crystals contained in the XRD analysis on the best result of nanoPCC is at a size 51.
83 nm.
The result of the XRD analysis are shown in Figure 4 DOI: https://doi.
org/10.
33005/ijeise.
International Journal of Eco-Innovation in Science and Engineering (IJEISE) Vol 3 .
, 2022 Counts CaCO3 Vaterite, syn Calcite, syn 100.
Position [A2Thet.
(Copper (C.
) Fig.
XRD analysis of nano-PCC at the ratio of moles of CaCl2: ethylene glycol 1:12 and stirring speed 950 rpm Based on Figure 4, it can be seen that the types of crystals formed are vaterite with a hexagonal morphology and calcite with a rhombohedral From Figure 4, it can be seen that the vaterite dominates about 93.
7% and calcite by From the XRD characterization data, the crystal size can be estimated using the formula of the Scherrer equation.
yaA ya= .
A cos(A) Using equation .
, the crystal size can be calculated and obtained D = 48.
25 nm.
The results of calculations using the Scherrer method are not much different from the results of PSA analysis, which is around 51.
83 nm.
So, it can be concluded that the particle size obtained is appropriate in the nanoparticle size range of 1-100 nm.
3 Scanning Electron Microscopy (SEM) Analysis SEM analysis aims to determine the shape and uniformity of the crystals of nano-PCC and their SEM analysis is shown in Figure 5.
Fig.
SEM analysis of nano-PCC at the ratio of moles of CaCl2: ethylene glycol 1:12 and stirring speed 950 rpm Based on the results of the SEM analysis in Figure 5, shows that the crystals formed are dominated by vaterite crystals because vaterite crystals have a hexagonal crystal system, where these crystals tend to be spherical.
In addition to vaterite, there are small amounts of calcite crystals, this can happen because of the metasable nature of vaterite crystals where when vaterite crystals are expoed to water and at low temperatures, they can change shape into calcite crystals.
Meanwhile, at high temperatures, vaterite crystals will turn into aragonite crystals.
In the research of .
, it was stated that the formation of the vaterite phase was influenced by many parameters, such as pH, temperature, and reactant concentration.
It was also explained that vaterite forms calcite crystals for several hours and aragonite forms calcite forms several months at room temperature.
Higher temperatures speed up the transformation.
Vaterite can be transformed into calcite by solvent mediation .
The results of the SEM analysis are by the previous XRD results, vaterite crystals equally dominate in the The results of the particle size range from the SEM analysis are shown in Figure 6.
DOI: https://doi.
org/10.
33005/ijeise.
Amount particle International Journal of Eco-Innovation in Science and Engineering (IJEISE) Vol 3 .
, 2022 obtained at a mole ratio of CaCl2: ethylene glycol 1:12, with stirring speed 950 rpm to produce a nano-PCC size on PSA analysis of 51.
83 nm and using Scherrer equation is 48.
25 nm.
The yield obtained is 70.
For further research, it is recommended to do pretreatment on raw materials and use a smaller variable mole ratio of CaCl2: ethylene glycol.
Acknowledgement Particle size .
The authors would like to grateful to Universitas Pembangunan Nasional AuVeteranAy Jawa Timur for support.
Fig.
Particle size Range of SEM analysis References