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International Conference on Recent Advances in Mechanical Engineering and Interdisciplinary Developments [ICRAMID - 2014]

Effect of Addition of Nano Zirconia in Ceramic Glazes

G.Venkatesh

Dept. of Metallurgical Engineering, PSG College of Technology Coimbatore, India

venkih07@gmail.com

S.Manisha Vidyavathy

Dept. of Ceramic Technology, Anna University Chennai, India manisha@annauniv.edu

D.Thenmuhil

Dept. of Ceramic Technology, Anna University Chennai, India thenmuhil@annauniv.edu

R.Vinothan

Orient Bell Limited Bangalore, India vinothan.r@orientbell.com

Abstract— In this present study zirconia particles of nano metric dimensions were synthesized using sol-gel method via the starting precursors of zirconium oxy-chloride octa-hydrate (ZrOCl 2 .8H2O) and oxalic acid {(COOH) 2 .2H 2 O}. A transparent sol obtained was dried at 110° C for 12 hours and the dried gel was subjected to calcination at 1000°C respectively for 3 hours in order to obtain nano-zirconia particles. XRD characterization reveals the presence of single phase tetragonal ZrO 2 and SEM morphological characterization reveals the presence of nano size ZrO 2 particles .The particle size distribution also confirms the nano metric size range of ZrO 2 particles. The obtained nano particles was incorporated in the glaze composition which generally is defined as a thin glassy layer on a ceramic body that results by applying a special admixture on ceramic body and by fusing at high temperature. This glaze formulation is well bounded for dry tile manufacturing process .The incorporation of the prepared nano zirconia in a typical glaze composition are well established for its excellent mechanical, thermal and good resistance to chemical attack. Addition of zirconia increases the opacity of the tiles and also enhances the brightness .In this study with the comparison of standard conventional zircon it is bound to say that particle size decreases. Moreover glaze characterizations i.e.TG-DTA, Spectrophotometer, Abrasion resistance, crazing resistance tests was studied which shows the improvement of surface characteristics which has been enhanced by using the nano particles. The opacity is also increased with lower dose of usage of zirconia nanoparticles.

Keywords— Nano zirconia, glaze, surface characteristics.

I. INTRODUCTION

The prime focus upon the ceramic glaze research is drastically increasing in recent days over the white wares and sanitary wares. In general typical constituents consists mixture of several vitrified oxides and inorganic additives, termed as glaze [1]. Glazes with high gloss, reflect light strongly [2].An improvement of the mechanical properties of the ceramic glaze is observed [3] by addition of monoclinic nano zirconia. Since zirconia exists as polymorphs certainly tetragonal zirconia seems to be unstable for the firing temperature. Nanometric particle suspension was developed in the typical glaze system for innovative surface characteristics in floor and wall tile industry. So imparting of nano particle technology adheres a greater attention to ceramic products via yielding outstanding properties [4]. The major property of zirconia is basically a refractory material with a higher thermal stability confines to its commercial usage. One of the most extensive

properties of zirconia applied in glazes acts as an opacifier i.e enhances the opacity depending on the dose of usage. Ceramic particles in a colloidal state are charged to become dispersed in a repulsive manner by forces developed on the surface of particles [4,5] can be said as electrosteric stabilization[5]. Studies upon nano glazes development have a prominent interest over the industry scale. The effects conveys to its microstructural features, mechanical durability and its physio- thermal properties. Nano characteristics of the glaze are to produce a clean, bright and attractive surface, antibiotic and activate the substance present in the glaze. The constituents of the glaze consists of various kinds of raw materials in which one or more of them are converted to nano particles and are used in the glaze composition[8,9]. Zirconia has a high covalence and seven Co-ordination bonding characteristics which are rare in other transition metals [6] . ZrO 2 has three crystal forms which are closely related to the cubic fluorite structures .the practice of using nano zirconia with monoclinic phase with larger surface area yields a better catalyst and reactant. Nano- zirconia exhibits more excellent chemical and physical properties as compared to normal or coarse zirconia powder, which aims through this study. Due to the small particles diameter result in a better sintering ability pertains to more efficient coating over a tile substrate ..

II. EXPERIMENTAL PROCEDURE

A. Nano Zirconia Synthesis and Characterization

At first the sol gel method has been adopted for the synthesizing zirconia with the starting materials zirconium oxy-chloride octahydrate (ZrOCl 2 .8H 2 O) and oxalic acid ((COOH) 2 .2H 2 O) and 1 M solution were prepared using distilled water. With the aid of constant stirring upto a ratio of 1:0.7 forms a transparent sol. The formation of zirconium oxalate can be expressed as

2ZrOCl 2 .8H 2 O+(COOH) 2 H 2 O 10H 2 O (Eq. 1)

International Conference on Recent Advances in Mechanical Engineering and Interdisciplinary Developments [ICRAMID - 2014] Effect of

ZrO(COO) 2 + 2HCl +

Zirconium oxalate sol obtained was kept at room temperature for a very short time to achieve gelation. The gel was dried at 110° C for 12 hours and thus zirconia powders were obtained. The as prepared samples obtained from drying

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International Conference on Recent Advances in Mechanical Engineering and Interdisciplinary Developments [ICRAMID - 2014]

of gel is been calcined. The calcination was done at 1000 °C for 3 hours at the heating rate of 10°C/s. The crystallinity of nano ZrO 2 was observed at the temperatures higher than 800°C. Finally the fine powders obtained after calcination yields a nano metric range of ZrO 2 . The X-ray diffraction studies ( BRUKER D-2,Ni filter, CuKα radiation) were done in order to determine the phase purity , crystal structure of Powder samples ,Crystallite size using Scherer method and last In order to assess the stability behavior of crystalline behavior of zirconia .The as synthesized powder samples were characterized using TG/DTA for its thermal behavior .Further information was revealed by scanning electron microscope (SEM) for its powder morphology and its particle size determination .for the ultimate particle size determination was done by laser particle size analyser (Malvern).

B. Glaze Formulation and Characterization

The typical raw materials used in industrial grade for glaze formulation is shown in Table 1 with their weighing ratios.

TABLE I THE COMPOSITION OF GLAZE AND ENGOBE

Composition

Percentage [%]

Glaze

Engobe

Carboxy Methyl Cellulose

<0.2

<0.2

Talc Powder

<3.5

 

Sodium Tri Poly phosphate

<0.2

<0.4

Quartz Powder

<5.2

<6.4

Clay

<5.2

<54.0

Alumina

<2.3

<3.2

Calcite Powder

<14

<18.0

Feldspar

<20

 

Wollastonite

<4.3

 

Frit (Opaque + Transparent)

<23

<19.0

White Aluminium Oxide

<2.2

 

Zirconium Silicate

12.4-13.4

 

Drain Glass Scrap

<5.8

<11.0

Above composition is weighed and batched accordingly and set as a standard conventional zircon composition for a industry grade. In this above formulation Instead of using zircon the prepared nano zirconia is imparted at various ratios to study its technological benefits over the usage of conventional zirconium silicate .To proceed with the first standardization of the nano zirconia composition first optimization procedure was taken by adding 13.4, 6.7, 5.0, 3.4, 1.7 and 0.134 % ratios of nano ZrO 2 accordingly . The procedure for preparing glaze is done using weighing of raw materials and mixing it .Allowing water percentage from 45- 50% for each composition was held in porcelain jar and likewise grinding media was added milled together for 30 minutes .the completion of milling obtains the glaze slip that was eventually undersized using 240 mesh. The prepared glaze slip was stripped over the engobed tile surface for obtaining a uniform glaze coating .the tile using here is a industry grade tile manufactured from Orient Bell Ceramics Pvt. Ltd. However the current focus is on the glaze formulation not on the tile substrate. The engobe (refer Table 1) is applied on a tile before applying a glaze. Another set of emblematic industrial engobe composition is shown below.

This engobe is applied over to the dried tile surface and again pre dried before applying a glaze. The benefits of applying engobe is it acts as an interface between body and glaze followed by fast firing technology using roller kiln at 40 min cycle. The similar procedure was trailed for the second optimisation with the following ratio 0.5, 1, 1.5, 2, 5 and 10 % with reference to standard composition devises different cycle rate and firing temperature. The glaze characterisations traverse with the examination of visual appearance which reveals the surface texture, gloss and smoothness. With rid of visual quality the colour tree i.e spectrophotometer (MinoltaCM-2002spectrophotometer) divulges any single colour position of a dot or point on this form, which is recorded in the order of hue, value or Chroma (H.V.C.), and L*, a*, b* values [3]. Since every property of ceramic tile has a resistance to abrasion, the abrasion resistance of various ratios were examined. The crazing of all the tiles is tested using auto clave with 5.2 Kg/cm 2 for two hours per cycle to ensure the life of the tiles in application. Chemical resistance of the tile surface were inspected using hydrochloric acid and potassium permanganate as alkalis to confines the results. Solar reflective index of the coated tile was tested which shows the reflectance of sunlight over the tile glazed with nano materials.

III. RESULTS AND DISCUSSION

A. Powder Characterization

1) XRD Analysis : It is well known that calcination temperature has a strong influence on the morphology of the powders and the occurrence of pure single crystalline phase (Hernawan, RifkiSeptawendar et al 2011 and 2012). Fig. 1 shows the X-ray powder diffraction patterns for the calcined powders in addition to that crystallite size were determined using Scherer formula. The wavelength of X-ray source used is ( λ = 1.54 A °). It was observed that increasing temperatures to 1000 °C the crystallinity nature also increases i.e more crystalline peaks were observed. In 1000 °C only monoclinic structure are matched with standard reference pattern .Both the pattern matches with zirconia (ZrO 2 ) .thus the diffraction studies also elucidates the crystallite size behaviour due to the line broadening effect seen. The crystallite size is found to be as 50 – 60 nm by using Debye Scherer method.

International Conference on Recent Advances in Mechanical Engineering and Interdisciplinary Developments [ICRAMID - 2014] of gel

Fig. 1 XRD pattern of Zirconia synthesised at 1000°C

2)Microstructural Observation : Fig. 2 shows the SEM image of zirconia powder samples calcined at 1000°C. It can be inferred that the particle size range is in order of 50nm – 200nm .It is evident from the SEM image the particle size

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International Conference on Recent Advances in Mechanical Engineering and Interdisciplinary Developments [ICRAMID - 2014]

greatly influence the morphological characteristics and steric behavior in the glaze slip.

International Conference on Recent Advances in Mechanical Engineering and Interdisciplinary Developments [ICRAMID - 2014] greatly influence

Fig. 2 SEM image of Zirconia at 1000°C

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Fig. 4 Shows the TG-DTA curve for nano zirconia powders

3)Particle Size Analyser: The particle size distribution is in the range of 100-150 nm for nano zirconia (refer with Fig. 3 a) whereas the standard conventional zircon (refer with Fig. 3 b) is of 685 nm.

International Conference on Recent Advances in Mechanical Engineering and Interdisciplinary Developments [ICRAMID - 2014] greatly influence

Fig. 3 a Particle size distribution for nano zirconia

International Conference on Recent Advances in Mechanical Engineering and Interdisciplinary Developments [ICRAMID - 2014] greatly influence

Fig. 3 b Particle size distribution for

Conventional zircon

4)TG-DTA Analysis: A TGA and DTA of the synthesized nano zirconia powders where recorded as a graph with temperature and weight (refer Fig. 4). It was observed from the TGA curve (refer Fig. 4) the weight loss occurring over a range of temperatures with followed by reaction occurring in various temperatures. At first a substantial weight loss happens in the temperature range from 294° C to 372° C associated with evaporation of organics and volatile substances as observed on the TGA curve. The large weight loss in the 290.08–373.88 °C range has been attributed to the vaporization of the by-products of the reactions, evolution of carbon as a gas and condensation polymerization. The exothermic peaks on the DTA curve (refer Fig. 4) at same temperatures and 490° C confirm this fact. On the other hand, the exothermic peak which occurs at 490° C on the DTA curve is attributed to the decomposition of the amorphous phase into a tetragonal one. The weight losses observed in this range are due to evolution of remained carbon and tetragonal and amorphous phases both coexist in the 490–

630° C range. Suddenly, in a narrow range of temperatures, which corresponds to the endothermic peak at 630°C, all tetragonal phase starts to transform to monoclinic. Above this temperature, there are no more weight losses i.e constant.

B. Glaze Characterization

1)

Spectrophotometer: It is otherwise known as the

Colour Tree. It is cylindrical or sometimes spherical in shape, which is a representative form of any single colour (refer

Fig.5).

International Conference on Recent Advances in Mechanical Engineering and Interdisciplinary Developments [ICRAMID - 2014] greatly influence

Fig. 5 Shows the general colour

representation

in

spectrophotometer

TABLE II SPECTROPHOTOMETER RESULT FOR STANDARD ZIRCON

STD zircon

L*

a*

b*

13.4

92.3

-1.8

3.5

TABLE III SPECTROPHOTOMETER RESULT FOR FIRST SET OF OPTIMIZATION FOR NANO ZIRCONIA

Nano zirconia

L*

a*

b*

13.4

 
  • 94.6 2.1

-2.1

 

6.7

91.9

-2.0

2.0

  • 5.0 -1.7

 
  • 89.6 3.2

 
  • 3.4 -2.0

 
  • 88.6 4.4

 
  • 1.7 -1.8

 
  • 86.4 6.3

 

0.134

 
  • 85.7 6.0

-1.7

 

From the above results addition of nano zirconia in varying percent shows that less than of 6.7% gives the almost close results with the standard composition. It is observed by the texture and color appearance. Hence the first optimization confines that less than 6.7% of nano ZrO 2 matches the standard value.

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International Conference on Recent Advances in Mechanical Engineering and Interdisciplinary Developments [ICRAMID - 2014]

TABLE IV SPECTROPHOTOMETER RESULT FOR SECOND SET OF OPTIMIZATION FOR NANO ZIRCONIA

Nano zirconia

L*

a*

b*

0.5

 

5.0

  • 82.3 4.9

 

1

 
  • 83.5 4.8

5.0

 

1.5

 

5.2

  • 84.9 4.7

 

2

 
  • 86.8 4.0

4.9

 

5

 

3.6

  • 88.3 2.9

 

10

 
  • 90.5 1.8

2.9

 

STD

 
  • 86.9 3.6

5.2

 

The second set of optimization quantifies that 2 % of Nano zirconia matches the standard value . Hence from the above results it can be said that 2% of nano zirconia replaces the standard conventional zircon property. 2) Abrasion Resistance: For nano zirconia over 1500 Revolutions it is inferred that very less surface erosion and thereby increases surface hardness compared with the standard composition .comparatively for standard composition from fig infers that Surface hardness is less also surface is eroded slightly .It is also can be said as that increasing the percentage 0.5-13.6% of nano zirconia directly increases the abrasion resistance of material (refer Table 5 & Table 6).

TABLE V ABRASION RESISTANCE RESULTS FOR NANO ZIRCONIA

Nano zirconia

Grade

0.5-1%

Class II

1.5-2%

Class III (1500 revolutions)

5-10%

Class IV

TABLE VI THE STANDARD INDUSTRY ABRASION OPTIMISATION

S.No

Revolutions passed

Class

1

300

I

2

600

II

3

1500

III

4

12000

IV

5

25000

V

International Conference on Recent Advances in Mechanical Engineering and Interdisciplinary Developments [ICRAMID - 2014] TABLE IV

Fig. 6 Shows the Abraded Surface of Standard Zircon

3) Chemical Durability: With reference to standard composition the effect of hydrochloric acid and potassium permanganate (alkali) doesn’t affect the surface characteristics and its texture .hence the property does not change over the attack of acids and alkalis .So chemical durability is likely increasing when addition of nano zirconia . 4) Solar Reflective Index: Solar reflectance isn't the only property to look for in a roofing material. It should also have a high infrared emittance to help the roof shed heat by re- radiation. It is computed by solar reflectance (R) and the

thermal emittance (E) .It is observed that for the tile coated with conventional standard zircon has SRI of 96 and

comparatively the usage of nano zirconia about 2% shows the

SRI as 103 . This drastic increase in SRI elucidates that the

withstand of surface roof temperature can go more than 55-60

°C .Hence overall it can be said as the usage of nano zirconia

enhances the reflectance more than a commercial conventional

glaze and it creates a unique behaviour in tile industry.

IV. CONCLUSIONS

Thus from the above results it can be concluded that the behavior of nano zirconia addition to a typical glaze shows a promising results over industrial scale .the uniqueness of using 2% nano zirconia reduces the raw material consumption by nearly 75% and also enhances some extensive properties such as opacity i.e surface appears to be much glossy with much brightness. Lower dosage of nano zirconia enhances the surface roughness and higher the usage pertains the surface to be harder. The abrasion resistance of 2 % ZrO 2 matches the standard industry optimization. Finally obtaining a solar reflectance of 103 for 2% ZrO 2 it is obviously can be used for cool roofing purpose at a greater extent.

REFERENCES

[1]

BijanEftekhariYekta, ParvinAlizadeh, Leila Rezazadeh, Floor tile glass-ceramic glaze for improvement of glaze surface properties, J. European Ceram. Soc. 26 (2006) 3809–3812.

[2]

M. Llusara, G. Monro´sa, C.M. Rodriguesb, J.A. Labrinchac, Study of zircon or zirconia crystals addition in ceramic glazes by impedance spectroscopy, Ceramics International 31 (2005) 181–

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[3]

J.K. Nsiah, Ceramics Effect Of Different Glaze-Base Systems On Generation Of Colour, Quarterly Science Vision, Vol.9 No.1-2 (Jul - Dec, 2003) & 3-4 (Jan - Jun, 2004)

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B. EftekhariYekta, P. Alizadeh, L. Rezazadeh, Synthesis of glass-

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SiO 2 –ZrO 2 system, J. European

Ceram. Soc. 27 (2007) 2311–2315.

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K. Pekkana, B. Karasu, Zircon-free frits suitable for single fast-

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Navrotsky,Energy Crossovers in Nanocrystalline Zirconia, J. Am.

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[7] Linda Fro¨berg, LeenaHupa, Topographic characterization of

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K.J. Hong, J.M. Kim, H.S. Kim, Microstructure and properties of CaO–ZrO 2 –SiO 2 glass–ceramics prepared by sintering, J. European Ceram. Soc. 23 (2003) 2193–2202.

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M. Llusara, G. Monro´sa, C.M. Rodriguesb, J.A. Labrinchac, Study of zircon or zirconia crystals addition in ceramic glazes by impedance spectroscopy, Ceramics International 31 (2005) 181–

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[10] Robert J. Castilone, Dattaguru Sriram, and William M. Carty, Robert L. Snyder, Crystallization of Zircon in Stoneware Glazes, J. Am. Ceram.Soc. 82 [10] 2819–24 (1999).

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Processing and Technology, Volume – I ,

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