International Journal of Technical Research and Applications e-ISSN: 2320-8163,

www.ijtra.com Volume 3, Issue 4 (July-August 2015), PP. 182-184

SYNTHESIS OF ALUMINIUM TRIHYDRATE

FROM KAOLIN THROUGH ALKALI
DISSOLUTION METHOD
Pawan Rangdal, Pradeep H.N
Department of Chemical Engineering,
Dayananda Sagar College of Engineering, Kumaraswamy Layout, Bangalore - 560078. Karnataka. India.
pawan_rangdal@yahoo.co.in, hnpradeep7@yahoo.co.in

Abstract— The aim of this work was to synthesis aluminum contaminating large land areas and water bodies and nearly
trihydrate from kaolin through alkali dissolution route. 100 people were injured and 10 people were killed during this
Thermogravimetric analysis showed that the material had good accident.
thermal stability and can withstand temperatures up to 206˚C An alternate attempt has been made in this work to
without any physical deterioration. X-ray diffraction confirmed
that synthesized aluminum trihydrate had monoclinic structure
synthesize Al(OH)3 using kaolin (Bikaner clay) as a raw
and scanning electron microscopy indicated that the product had material that contains higher Al2O3 (34 - 40%), next to bauxite
a particle size range between 10 to12 μm. Aluminum tridhydrate [11,12]. Alkali dissolution method was followed to synthesize
has a unique fire retardation mechanism. When it is heated, it Al(OH)3, as no harmful byproducts were produced by this
decomposes endothermically in to Al2O3 and H2O, the oxide layer method.
forming a protective barrier which prevents the fire from
penetrating into the surface and cause further burning, and H2O II. MATERIALS AND METHODS
in the form of vapor suppresses the toxic smoke produced. A. Chemicals and equipment used
Index Terms— Aluminum trihydrate, kaolin, alkali dissolution, The following chemicals were used in the study. Kaolin
fire retardant.
(Bikaner, Rajasthan, India), sodium hydroxide [NaOH] (SD
I. INTRODUCTION Fine, Mumbai), white lime [Ca(OH)2] (AK Scientific, India),
Aluminium trihydrate [Al(OH)3] (ATH) is a white powder sodium bicarbonate [NaHCO3] (SD Fine, Mumbai),
which is commercially produced from bauxite using Bayer’s polyethylene glycol (Leo chemicals, Bangalore)
process. It is used as an additive or filler which functions as a A ball mill, hot air oven (Kemi, India), magnetic stirrer
fire retardant and smoke suppressant in electronic and (Kemi, India) and autoclave were used in the study.
electrical cables [1,2]. Most commonly polymers like
polyvinyl chlorides (PVC) and paraffins are used as insulating B. Synthesis of aluminum trihydrate
material for electrical cables. Surveys indicate that in closed or The composition of Bikaner kaolin clay used in this
compact places like tunnels, subways etc [3], whenever there experiment is given in Table 1. It was obtained from Bikaner,
is a fire, people die by inhaling toxic smokes produced by the Rajasthan, India.
burning of PVC used as cable insulation or pipes or any other
TABLE I. COMPOSITION OF BIKANER KAOLIN CLAY
construction materials rather than the fire [4]. In United States
Constituents Percentage
3,240 people died in the year 2013 in fire accidents, which is
an increase of 13.5% when compared to 2012. 15,925 peoples SiO2 53.11%
were injured and approximately property worth US $11.5 Al2O3 44.02%
billon was damaged as a result of fire in 2013 [5]. Fe2O3 0.71%
ATH is the most consumed fire retardant in the world and it CaO 0.40%
has a unique fire retardation mechanism. ATH in PVC or other MgO 0.24%
insulating polymers will decompose endothermically on K2O 0.20%
heating above 200˚C forming aluminum oxide and water Na2O 0.72%
vapor according to the reaction given below [6]:
2Al(OH)3→Al2O3+3H2O (1) The raw kaolin clay was ground in a ball mill for 120
This oxide forms a char or protective layer that stops the min and sieved in a 200 # screen. Since kaolin contained
fire from penetrating further into the material and the water higher SiO2 / Al2O3 ratio it cannot be used directly to
vapor produced will dilute the toxic gases that are produced by precipitate Al(OH)3. In order to increase the Al2O3 / SiO2 ratio,
the burning polymers [7]. the ground clay was leached with 8M NaOH solution at a
In general Bayer’s process is the commercial route for the temperature of 95˚C for 100 min. Obtained product was
production of ATH. It involves digestion of bauxite with washed with distilled water for several times and filtered using
sodium hydroxide solution at a temperature of about 250 to Whatman filter paper. The following are the possible
280˚C [8,9]. In this process, a toxic red sludge is produced as a reactions.
waste product that contains all non aluminus materials mainly 2OH- + SiO2 → H2SiO42- (2)
ferrous metal and objectionable levels of metals like mercury, OH- + Al2O3 + H2O → Al(OH)4- (3)
lead and chromium [10]. This red sludge is highly alkaline in 6H2SiO4 + 6Al(OH)4 +6Na →
nature which is a potential threat to the environment. In 2010 Na6 [AlSiO4]6.4H2O + 12OH- + 8H2O (4)
it led to AJAK alumina plant accident in Hungary. A large pit A second stage leaching is done in order to further remove
holding the red mud collapsed resulting in spreading and SiO2 and obtain a sodium aluminate solution from which ATH

182 | P a g e
 International Journal of Technical Research and Applications e-ISSN: 2320-8163,
www.ijtra.com Volume 3, Issue 4 (July-August 2015), PP. 182-184

[Al(OH)3] could be precipitated. 50 g of desilicated kaolin as Third region extends from 301˚C to 740˚C with a mass
described above is mixed with 20 g of white lime [Ca(OH)2] loss of about 8.16% due to removal of moisture formed during
and 150 ml of 20M NaOH solution in a nickel crucible and the decomposition. Thereafter the oxide has been formed and
was heated to a temperature of about 200 to 280˚C for 1 h in there is no expected mass loss.
an autoclave. The possible reactions are as follows: Fig. 2. shows TG-DSC results. Differential scanning
SiO2 + Ca(OH)2 + Na⁺ → NaCaHSiO4 + H⁺ (5) calorimetry (DSC) is a technique for the energy necessary to
Al2Si2O13 + 2Ca(OH)2 + 2Na⁺ + 8OH- + 7H2O → establish a nearly zero temperature difference between a
2NaCaHSiO4 + 6Al(OH)4- (6) substance and an inert reference material, as the two
Na[AlSiO4]6.4H2O + 6Ca(OH)2 + 6OH- + 2H2O → specimens are subjected to identical temperature regimes in an
6NaCaHSiO4 + 6Al(OH)4- (7) environment heated or cooled at a controlled rate. The
The sodium aluminate solution obtained had high Na2O / downward peak in the DSC curve refers to the endothermic
Al2O3 ratio. It was treated with Ca(OH)2 firstly and then with decomposition of ATH with a heat value of 660.5 J/g.
NaHCO3 for 120 min under continues stirring:
2Al(OH)4- + 3Ca(OH)2 + 3 H2O → 20
Ca3Al2(OH)12↓ + 2OH- (8) 0
Ca3Al2(OH)12 + 3HCO3- → 20
3CaCO3↓ + 2Al(OH)4- + OH- + 3H2O (9) 18 Area = 12560.084 mJ

Heat flow endo down (mW)

Delta H = 660.4472 J/g 40
This sodium aluminate solution with reduced Na2O / Al2O3 DSC
ratio was mixed with polyethylene glycol (PEG) and then CO2 o 60
Peak 275.35 C
gas was introduced in to the solution at room temperature 16
80
under continuous stirring. The introduction of CO2 into the

mg
100
solution was continued until the pH of the solution reached
14 120
12.5, when ATH precipitated. PEG solution was added into TGA
the solution in order to prevent the agglomeration of the 140
particles during precipitation. order to prevent the
12 160
agglomeration of the particles during precipitation.
180
100 200 300 400 500 600 700
C. Sophisticated instrumental analysis o
Thermogravimetric and differential thermal analysis (TG- Temp ( C)

DTA), differential scanning colorimetery (DSC), x-ray Fig. 2 TG-DSC of ATH

diffraction (XRD), and scanning electron microscopy (SEM)
were performed to characterize the raw material and the Fig. 3. shows the xrd patterns of raw kaolin and the
product. product of first stage of desilication. The peak at 26.35˚ with
(h k l) value of (1 0 1) indicate silica (SiO2) and the peak at
III. RESULTS AND DISCUSSION 24.58˚ with (h k l) value of (1 0 2) indicate alumina (Al2O3)
Fig. 1. shows TG-DTA results. 19.37 g of ATH was peak, according to JCPDS card number 86-1630 for silica and
heated up to 740˚C at a rate of 5˚C/min. There are three 82-1468 for alumina.
regions in the graph; the first region extending up to 212˚C
with a weight loss of about 2.84%. This mass loss is due to 8000 20000
vaporization of moisture content in the sample. The second
(1 0 1)

7000
region extends up to about 301˚C with a mass loss of about SiO2

26.12%. The downward peak of the DTA curve in this region

(0 1 2)

6000 15000
Al2O3
is indicative of an endothermic decomposition of Al(OH)3 to 5000
its oxide, Al2O3, as given by equation (1).
Kaolin
Intensity
Intensity

4000 10000

20 0.1 3000
(1 0 1)

DTA 2000 SiO2 5000

(0 1 2)

19 0.0 Al2O3
1000
18 -0.1
st
1 stage product
0 0
17 -0.2
20 40 60 80
16
mg / C

-0.3 2
mg

15
o

-0.4
14 Fig. 3 XRD patterns of kaolin and desilicated kaolin
-0.5
13 TGA Chemical analysis indicated that the Al2O3 / SiO2 ratio has
-0.6
12 212
increased to 0.94 from 0.59 after the first stage desilication.
301
-0.7 The xrd of the final product (ATH) obtained from the sodium
100 200 300 400 500 600 700
aluminate solution is given in Fig. 4.
o
Temp ( C)

Fig. 1 TG-DTA of ATH

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 International Journal of Technical Research and Applications e-ISSN: 2320-8163,
www.ijtra.com Volume 3, Issue 4 (July-August 2015), PP. 182-184

increased the Al2O3 / SiO2 ratio to 0.94 from 0.59. TG-DTA

results showed that the synthesized material was thermally

(0 0 2)
60000
Al(OH)3 (ATH) stable up to 212˚C. XRD results confirmed that monoclinic
ATH has been formed. SEM results indicated a particle size
50000
range of 1 to10 μm for the product.
40000
ACKNOWLEDGEMENT
Intensity

30000
The first author acknowledges Dr. J.U. Kennedy, Head of
the Dept. of Ceramic & Cement Technology, PDA College of
20000 Engineering, Gulbarga, Karnataka for extending laboratory
facilities to carry out the project.
10000
REFERENCES
0 [1] Shilpa Hiremath and Sukumar Roy, “Aluminium Trihydrate
(ATH) — A Versatile Material,” BHEL Journal Bangalore,
20 40 60 80 April 2007.
[2] Richard Horrocks, Gill Smart, Shonali Nazare, Baljinder
2
Kandola and Dennis, “Zinc Hydroxystannate and Stannate
Synergies in Halogen-containing, Flame-retardant Polymeric
Fig. 4 XRD of ATH Formulations,” Journal of Fire Sciences Online First, 2009.
[3] Office of Aviation Research, “Fire-Resistant Materials:
The xrd of ATH indicates that the product formed is Research Overview,” Washington, D.C. 20591, December 1997.
[4] Emina Mihajlovic, Sveta Cvetanovic, Amelija Dordevic, Ivan
pure. The major peak with an (h k l) value of (0 0 2) at 18.45˚ Krstic and Danilo Popovic, “PVC material fire retardants”,
is the characteristic of monoclinic ATH as per JCPDS card Faculty of Occupational Safety, University of Nis, Serbia, Vol 7,
number 76-1782. 2010.
Fig. 5. shows the scanning electron microscope image of the [5] J.M. HUBER CORPORATION [online], “Fire Retardant
synthesized product (ATH) at × 10000 times magnification. Additives,” Available: www.hubersmaterials.com. November
2011.
[6] Shuang Qing Su, Jing Yang, Hong Wen Ma, Fan Jiang, Yu Qin
Liu and Ge Li, “Preparation of Ultrafine Aluminum Hydroxide
from Coal Fly Ash by Alkali Dissolution Process”, School of
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Geosciences, Beijing 100083, P.R.C. Copyright © Taylor &
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[8] Andrew R,. Hind , Suresh K. Bhargava and Stephen C. Grocott,
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[9] Fathi Habashi, Laval University and Quebec City Bull. Hist.
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Fig. 5 SEM [10] www.wikipedia.com
[11] Bharatkumar Z. Dholakiya. Center for Coatings and Biobased
Particles with irregular shapes and varying particle sizes can Technology, San Marcos, Texas, USA. Accepted on 25. 5. 2009.
be seen and particles as small as 1-10 μm are observed. [12] Seyed Ali Hosseini, Aligholi Niaei and Dariush Salari,
Department of Applied Chemistry, Faculty of Chemistry,
Formation of agglomerates can also be seen at some spots.
University of Tabriz,Tabriz, Iran. Open Journal of Physical
Chemistry, vol-1, 23-27. 2011.
IV. CONCLUSIONS
Aluminium trihydarte was synthesized from Bikaner clay
through alkali dissolution method. First stage of desilication

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