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Synthesis, properties and applications of cordierite ceramics

Article in Interceram - International Ceramic Review · January 2007

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Ceramics in Asia >>>
Synthesis, Properties and Applications of Cordierite Ceramics, Part 2
A. Chowdhury, S. Maitra, H.S. Das, A. Sen, G.K. Samanta, P. Datta

of the finished seal and/or to lower the ther- ial pressing.Yu et al. [46] studied the influence
Anirban Chowdhury is a
post-graduate research stu- mal contraction coefficient of the composite. of different silica fume contents on the struc-
dent working in the area of • The MgO–Al2O3–SiO2 system is a very popu- ture and properties of mullite-cordierite com-
sol gel ferroelectrics for his lar one for glass-ceramics where cordierite is posites. The cordierite content increases while
PhD at the Institute for Ma- the dominant phase along with clinoenstatite mullite decreases with increasing silica fume
terials Research, University (MgO-SiO2). These materials are character- contents. The optimum formulation is as fol-
of Leeds, UK. He earned his BTech in Ceramics ized by higher temperature stability under load lows: cordierite - 66.3 %, mullite - 33.7 % and
from the College of Ceramic Technology, Uni- than lithium aluminosilicates together with bulk density - 2.69 g/cm3. Hipedinger et al. [47]
versity of Calcutta and MTech in Materials Sci- good thermal and mechanical shock resist- developed a cold-setting refractory material us-
ence from IIT Kanpur. He received the presti- ance. Their low permittivity and high resistiv- ing the magnesia-phosphate reaction.A cement
gious ORS award and a Tetley & Lupton Schol-
ity lead to a broad range of applications, e.g. paste based on alumina, silica fume, magnesia
arship for 2005–2008.
microwave component materials, radomes, etc. and orthophosphoric acid was designed to form
• A very recent application for cordierite is in cordierite-mullite during heating. This cement
making thick films. paste set at room temperature and
Abstract Interceram 56 (2007) [2] MgHPO4·3H2O (newberyite) phase was ob-
As an engineering material, cordierite has many 5.1 Applications in kilns and furnaces served.
applications in different fields exploiting its Cordierite is extensively used as a material for
unique electrical, mechanical and thermal prop- kiln furniture in whiteware industries due to its 5.3 Other composites of cordierite
erties. The synthetic aspect of cordierite is of excellent thermal shock resistance. Mohr [44] Taruta et al. [48] fabricated a machinable
constant interest to researchers. Elucidation of worked on the development of cordierite kiln cordierite-mica composite by low temperature
its structure and establishing the properties of furniture, focusing on parameters such as the sintering. 40 mass-% mica-composition glass
its structure has always been considered a fas- effect of grog addition (low expansion grog, like powder was mixed with conventional magne-
cinating subject by researchers. In the present
fused silica, can be used in special cases; gener- sia, alumina and silica powders (raw materials
paper these different aspects of cordierite are
ally, grogs with thermal expansion larger than of cordierite) and then compacted and fired in
briefly reviewed.
cordierite are preferred), the effects of time and a sealed Pt container. Mica crystallized at about
temperature, and the development of slag re- 730 °C, cordierite was suddenly formed at
Keywords:
Cordierite, processing, properties, applications sistance (good grades of kyanite and kaolin, cal- 1050–1100 °C, and densification was achieved
cined to 1580–1600 °C provide excellent grogs at 1000–1100 °C. The formation and sintering
for commercial cordierites). of cordierite were promoted by a small amount
of fluorine gas or fluorides (AlF3) which evap-
5 Applications of cordierite ceramics 5.2 Cordierite-mullite composites orated from the glass at >800 °C, and HF gas
A major field of application for cordierite lies in was formed by reaction of the fluorine with the
Cordierite is widely used in various fields of ce- the production of composites and fibre strength- water evaporated from the glass. Machinability
ramics. Its traditional applications are as fol- ening. Different attempts have been made to de- was achieved by the interlocking microstruc-
lows: velop cordierite-mullite composites with good ture of mica developed in the composite. Shi et
• Refractory products ➝ saggars, kiln furniture thermal shock resistance as well as high me- al. [49] prepared cordierite-ceria composite ce-
(widely popular in whiteware industries), gas chanical strength.Camerucci et al.[45] prepared ramics with oxygen storage capacity. Oxygen
burners, etc. cordierite and cordierite-mullite ceramics by storage capacity (OSC) is an important param-
• Electro-ceramics ➝ resistors, fusibles, flame the slip casting method. The rheological behav- eter in three-way catalysts (TWC) for the pu-
guards, etc. iour of the slip became Newtonian when the sol- rification of exhausts from automotive gasoline
• Tablewares ➝ Flameproof application devel- id content was reduced to 60 mass-% and a plas- engines. The authors prepared the composite
opments in fast-firing techniques which allow ticizer was added. This led to higher green den- using the sol-gel method so as to append the
wide temperature variations during the cool- sities (~63 %) of the body. Different firing cy- OSC to the support to which the catalyst is ap-
ing cycle have renewed interest in this type of cles were tested to improve the sintered density, plied. CeO2 particles are uniformly and sepa-
body. which ultimately reached values between 96.5 rately distributed in the cordierite matrix, their
• Cordierite is common as a refractory filler. Re- and 97.5 % of the theoretical density. In all cas- number and granularity being dependent on
fractory fillers are frequently blended with es,both the green and the sintered densities were the amount of Ce4+ addition. The cordierite and
powdered solder glass to increase the strength significantly higher than those obtained by ax- 10 mass-% CeO2 possess an apparent OSC, ap-

98 Vol. 56 (2007) [2]

Ceramics in Asia
propriate porosity, flexural strength and ther- positions. Ferraris et al. [55] synthesized crystallization of the thick film was determined
mal expansion coefficient. It will be helpful to cordierite-mullite coating to be applied on to be ~83 kcal/mol (~350 kJ/mol). In the case
enhance the OSC of the catalytic converters and SiCf/SiC composites. The composites were coat- of the 3 mass-% PbO sample fired in a nitrogen
so improve the purification effects for the ex- ed by a simple and low cost slurry technique and atmosphere at 950 °C for 30 min, the remaining
hausts. Ma et al. [50] fabricated AlN-cordierite heat treated at 1180 °C for 1 h in order to obtain glass was estimated using the parallel mixing
composites using different AlN contents and in- a uniform, pore-free and crystalline coating rule, to have a dielectric constant of 15.3 at
vestigated the effect of AlN content on the me- through the glass-ceramic method. The melt- 1 MHz. The estimated coefficient of thermal ex-
chanical, thermal and dielectric properties of ing point of the crystalline phases formed in the pansion of the remaining glass for the 3 mass-%
these materials. It was observed that there ex- coating during the coating process (cordierite, PbO sample was 19 ⫻ 10–6 / K.
ists an optimum AlN content for the mechani- 2MgO-2Al2O3-5SiO2 and mullite, 3Al2O3-2SiO2
cal and thermal properties while the dielectric rate of 3 : 1 mass-%) was measured at about 5.6 Cordierite filters
property decreases with an increase in AlN con- 1430 °C. Perham et al. [56] also worked in a Cordierite has been successfully tried in a num-
tent. Kaya et al. [51] fabricated stainless steel somewhat similar direction as they developed ber of industrial day-to-day applica-tions. Ne-
(316L) fibre-reinforced cordierite-matrix com- a method for the joining of SiC substrates us- gro et al. [59] studied the mechanical behaviour
posites of tubular shape using electrophoretic ing a cordierite glass-ceramic which, being of cordierite ceramic filters for automotive emis-
deposition and pressureless sintering. The sin- amorphous, melts the SiC substrates to form a sion control in a fired condition after thermal
tered composites, which had an internal and ex- strong bond when rapidly fired. Doping with a shock and thermal ageing. Park et al. [60] inves-
ternal deposit thickness of ~1 mm, were free of fluoride ion flux can lower the peak processing tigated the feasibility of porous cordierite in
surface cracks when a deposition time of 2.5 min temperature without significantly altering the foam type structures such as filters for dust col-
was used.Metal-fibre-reinforced cordierite com- crystallizing path.High strength can be achieved lection.Various shaped porous cordierites with
posites such as those developed here may con- through this process (σF >500 MPa). different pore sizes and with constant porosity
stitute a promising alternative for manufactur- of 80 % were prepared by the conventional me-
ing damage-tolerant tubular components for 5.5 Cordierite thick films chanical foaming method combined with gel
applications at temperatures up to ~900 °C.Shyu A more recent but highly promising application casting using water-soluble polymers. Gas per-
and Wang [52] studied the relationship of the of cordierite is the synthesis of cordierite thick meability of the membrane layers of 150 µm was
amount and viscosity of glass with the sintered films. Mei et al. [57] prepared thick films of above 200 ⫻ 10–13 m2. In the dust collection
densities of cordierite-borosilicate glass com- cordierite-based glass ceramics by aqueous tape test, the removal efficiency for particulates fin-
posites. The dielectric constant of these com- casting from suspensions containing er than 10 µm was above 99.99 %. Montanaro
posites was in the range of 4.9–5.7 at 1 MHz. cordierite/glass mass-% of 70/30 to 30/70. The [61] studied the interactions of sodium sulphite,
Sonje et al. [53] incorporated cordierite as a low suspensions with 50–60 mass-% glass showed iron oxide and cerium oxide from fuel additives
coefficient of thermal expansion (CTE) ceram- the lowest viscosity values, while the green tape with a cordierite monolith filter in the operat-
ic particulate filler into different epoxy resins to containing 30 mass-% glass showed a homoge- ing temperature range of a diesel soot filter. He
produce an isotropic low CTE polymeric com- neous microstructure at both the top and bot- concluded that the said oxides do not react sig-
posite material for electronic circuit board ap- tom surfaces. The green densities increased with nificantly with the filter, but sodium sulphite
plications. The dependence of the CTE values the glass content. The sintered tapes (1150 °C, leads to a diffuse etching starting from low op-
on the properties of the epoxy resins, the nature 2 h) containing 50–60 mass-% glass showed the erating temperatures. However, the total poros-
of interfacial bonding and the dispersion of the lowest values for the dielectric constant (simi- ity and pore size distribution were not affected
fillers in the resin matrix were also studied. lar to 5.2) and dielectric loss (similar to 0.002) by these interactions. Park et al. [62] developed
at 1 MHz. Cho et al. [58] developed a cordierite a new trap to reduce the particulate matter emis-
5.4 Cordierite coatings based thick film on an oxidized copper layer sion from diesel engines and to control the com-
Weaver et al. [54] studied the role of bulk nu- where the authors found evidence of copper dif- bustion rate of the particulate matter filtered in
cleation in the formation of crystalline cordierite fusion as it was incorporated into the cordierite the trap. Cordierite is a major component of the
coatings produced by air plasma spraying. and the remaining Cu was precipitated, which trap as it is susceptible to thermal shock.
Cordierite glasses doped with 6.3, 8.3 and 10.1 ultimately lowered the densification and crys-
mass-% TiO2 were plasma sprayed onto SiO2- tallization temperature. The authors also stud- 5.7 Cordierite substrates
based refractory concrete substrates. Only the ied the microstructure, crystallization kinetics Reznik et al. [63] utilized cordierite as substrate
cordierite powders containing 8.3 and 10.1 and properties of nonstoichiometric cordierite material and produced pyrolytic carbon de-
mass-% TiO2 produced crystalline coatings. For (2.4 MgO, 2Al2O3, 5SiO2, containing 3 mass-% posits by the CVD technique on a planar
compositions with less than 8 mass-% TiO2 the P2O5 and 3 mass-% PbO) based thick film di- cordierite substrate using methane as a source
crystallization is believed to be controlled by electrics. A stable glass ceramic thick film mi- gas. The surface morphology was characterized
surface nucleation at imperfections. Bulk nu- crostructure that was formed in a 96 % alumi- by a cell structure induced by grains elongated
cleation-controlled crystallization was observed na substrate was observed after firing at a tem- perpendicular to the substrate surface. The ma-
at compositions above 8 mass-% TiO2 and the perature of 915 °C for 30 min in nitrogen at- terial located at the interface was more amor-
presence of Al2TiO5 was detected in these com- mosphere. The activation energy for phous compared to the graphite-like materials

100 Vol. 56 (2007) [2]

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located within the cells. Chen et al. [64] studied supported on cordierite monoliths in the total temperature is raised from 850 to 900 °C. The
the potential of burying inductors in multilay- oxidation of chlorinated hydrocarbons. In the increase in the resistance of the LTCC resistors
er ceramic substrates by inserting a ferrite lay- case of monolith supported LaCoO3 perovskite, is attributed to the interruption of the conduc-
er into a low-temperature cofired cordierite sub- an irreversible catalyst deactivation was ob- tion path by platelike anorthite crystals that are
strate. Bi2O3 was doped to lower the sintering served. Orlandi et al. [71] investigated the bio- produced in the resistor-substrate interface dur-
temperature and increase the permeability of compatibility of two cordierite ceramics (DF ing co-firing.
Ni-Zn-Cu ferrite. Sohn et al. [65] investigated and Cord 1014) with similar chemical compo-
the suitability of glass-ceramics containing sition and different porosity, as a potential sup- 5.11 Electrochemical applications
cordierite as a crystal phase for application to port for cell growth in a continuous-flow, sol- Domenech-Carbo et al. [75] studied the elec-
magnetic disk substrates to achieve higher stor- id-bed reactor. They concluded that Cord 1014 trochemistry of α-, β-, and µ-cobalt containing
age capacity. Parent glasses were prepared with could be a promising support for growing CHO cordierites (Co2Al4Si5O18) attached to paraffin-
a CeO2 addition as flux, and α-cordierite was (Chinese hamster ovary) cells in great numbers impregnated graphite electrodes by linear scan
precipitated after heat treatment. The optimum and producing recombinant hepatitis B surface and cyclic voltametries in HCl + NaCl and
properties for the magnetic memory disk sub- antigens. NaOH electrolytes. Cordierite-modified elec-
strates are as follows: Bending strength - 192 MPa, trodes display a significant site-dependent cat-
Vickers hardness - 642.1 kg/mm., CTE - 5.9 Optical applications alytic effect on the electrochemical oxidation of
39 ⫻ 10–7 / K, and surface roughness - 2.7 nm. Park and Shin [72] prepared glass-ceramics con- mannitol in 0.1 (M) NaOH.
taining cordierite and a small amount of rutile
5.8 Cordierite supports as the major crystalline phases for application 5.12 Electromagnetic applications
Recent advances have been made in research on as IR reflectors. Nucleation occurred at 750 °C Wang et al. [76] synthesized cordierite by sol-
cordierite monolithic catalyst supports, partic- for 3 h and crystal growth at 1100 °C for 5 h. gel processing with the aim of using it as MLCI
ularly on honeycombs and ceramic foams. Car- This material showed over 90 % reflectance in material. It has a low dielectric coefficient (3.5)
ty and Lednor [66] reported that honeycombs the spectral range of 570 to 2500 nm. at high frequency (1.8 GHz). The sintering tem-
are used as catalyst supports for the removal of perature decreased with increasing Bi2O3 and
gaseous or particulate emissions from combus- 5.10 Electrical and electronic B2O3 additions. Luo et al. [77] also synthesized
tion engines and for reducing nitrogen oxide applications a sol-gel derived cordierite ceramic that had a
emissions from power plants. They also noted Cordierite electric ceramics have an important low dielectric constant and a low dissipation fac-
that ceramic foams are attracting attention as role in modern technology. They have been used tor and could be co-fired with highly conduc-
catalyst supports due to their high thermal sta- in electrothermics for the production of elec- tive metals such as Au,Ag, Pd, and Cu paste be-
bility, high porosity and increased tortuosity tric heater supports. Nowadays, due to its elec- low 1000 °C, suggesting that it would be a prom-
with respect to honeycombs.Yamuna et al. [67] trical, electromechanical and thermal proper- ising material for high frequency MLCIs.Wang
prepared honeycomb and pellet type carriers ties, this ceramic finds its applications in elec- et al. [78] developed cordierite-based ceramics
from kaolin-based cordierite composition, and tronics for the production of microelectronic by sintering at 950 °C a glass selected from the
their efficiency in pollution monitoring was components and in the machine-building in- MgO–Al2O3–SiO2 system with a small amount
studied in two-stroke vehicles. The convention- dustry for the manufacture of internal combus- of B2O3 and P2O5 with the aim of using the ma-
ally prepared kaolin based cordierite system re- tion components.Acimovic et al. [73] prepared terial in high frequency chip inductors. Crys-
moved 78 % of the CO and 82 % of the hydro- cordierite ceramics based on sepiolite and ex- talline phases in this sintered sample are most-
carbons from the exhaust gases under idling amined their applications in foundries, defin- ly α-cordierite (hexagonal high cordierite) with
conditions. Cordierite honeycombs are used as ing the technological parameters for the pro- trace amounts of µ-cordierite. It achieved 99 %
catalyst supports and must be coated with duction of refractory coatings for sand moulds of theoretical density, a dielectric constant of
porous alumina to increase their specific sur- and cores, and of refractory linings for use in 5.5, a dielectric loss of 0.001 and a thermal ex-
face area. Hua et al. [68] tried to prepare porous the lost loam process. Ting et al. [74] studied the pansion coefficient of 26.7 ⫻ 10–7/K. It has a
alumina with a large surface area on the inter- interactions between ruthenia-based resistors uniformly dense microstructure with granular
nal surface of cordierite honeycombs through and cordierite-glass substrates in low-temper- crystals.Yue et al. [79] prepared a series of nov-
in-situ and dip-coating methods of loading ature co-fired ceramics which are composed of el composites of NiCuZn ferrite and cordierite
γ-Al2O3 prior to its hydrolysis during the prepa- a RuO2-based resistor and a cordierite-glass crystallites by sintering the mixtures of nano-
ration of alumina sol. Seijger et al. [69] studied substrate that are sintered at temperatures of sized NiCuZn ferrite particles and MgO-Al2O3-
the in situ synthesis of binderless ferrierite coat- 850 °C and 900 °C. X-ray diffractometry re- SiO2 glass powder to be used for MLCIs. These
ings on 300 si cordierite honeycomb supports. vealed that the lead ruthenate pyrochlore composite materials have tuneable electromag-
The silica-to-alumina ratio of the synthesis mix- (Pb2Ru2O6.5) in peak-fired thick-film resistors netic properties with high resonance frequen-
ture and the development of the ferrierite coat- (TFR) disappears and the co-fired samples con- cies. In another work, Yue et al. [80] fabricated
ing as a function of time were also investigated. tain only RuO2 in the resistor film when sintered ferrite-glass-cordierite nanocomposites by mix-
Schneider et al. [70] studied the catalytic behav- at 900 °C. The overall resistance of the LTCC re- ing and sintering NiCuZn ferrite nanopowder
iour of perovskite (LaMnO3, LaCoO3, etc.) sistors is increased by a factor of ~3 when the and MgO-Al2O3-SiO2 gel powder prepared by

Vol. 56 (2007) [2] 101

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102 Vol. 56 (2007) [2]

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