Macro-porous Ti2AlC MAX-phase ceramics by the foam

replication method

C.R.Bowena and T.Thomas

Department of Mechanical Engineering, University of Bath, BA2 7AY, UK

Abstract

This paper describes the fabrication of porous Ti 2AlC MAX-phase ceramics using the

foam replication technique. The influence of heat-treatment cycle and sintering time on

phase composition, microstructure and type of defect is discussed. Compression testing

indicates that strength is related to defects that are introduced during the foam

replication stage, as observed by optical and electron microscopy. The manufacturing

process is adapted by employing additional coating stages to produce electrically

conductive macro-porous ceramics with a range of strengths (0.2 – 6.3MPa) and

macrostructures. Such materials are of interest for use as a high surface area electrode

for harsh environments or microbial fuel cells.

Keyword: porosity, Ti2AlC, MAX-phase, strength, processing, defects

a
Prof C. R. Bowen, Department of Mechanical Engineering, University of Bath,
Claverton Down, BA2 7AY, Bath, England. Tel: 01225 383660, Fax: 01225 386928,
Email: c.r.bowen@bath.ac.uk.

1
1. Introduction

There is significant interest in the manufacture of porous materials with desired

properties and microstructure; one reason being the relative ease with which porous

structures can be tailored for specific applications. Porous ceramics have been

considered for water purification [1], porous hydroxyapatite bio-ceramics as a bone

graft substitute [2], filtering of high temperature molten metals and high temperature

thermal insulation [3]. The materials are of particular interest where the application

environment demands the ability to withstand high temperatures, corrosion resistance,

high stiffness, thermal insulation and wear. The manufacturing techniques developed for

creating porous ceramics include (i) foaming of an aqueous ceramic suspension, (ii)

replication of a sacrificial foam template and (iii) the use of synthetic and natural

templates [4, 5]. In this paper the fabrication of macro-porous Ti 2AlC MAX-phase

ceramics using reticulated polyurethane (PU) foam as a synthetic template is

demonstrated. As seen in figure 1, a reticulated polyurethane foam of the required

shape, pore distribution and pore size is impregnated with a Ti2AlC ceramic slip which

is subsequently dried and pyrolysed to remove the polymer foam before it is finally

sintered to obtain the Ti2AlC porous ceramic.

The final porous structure formed is a replica of the foam template used. The advantage

of the foam replication method is the ability to control the pore distribution and pore

size by simply changing the structure of the template foam used. One disadvantage of

this process is that the porous ceramic can contain defects; these can be (i) on the solid

parts of the foam struts due to shrinkage of the slip during drying or (ii) internal defects

due to the pyrolysis of the polymer foam from the centre of struts. These defects

ultimately reduce the mechanical strength.

2
The motivation for the present work is to produce an electrically conductive macro-

porous material. Applications include electrode materials for harsh chemical

environments, at high temperatures or for use in a microbial fuel cell (MFCs). The

desired typical properties for such applications include:

(i) sufficient mechanical strength to be handled and survive in-service loads,

(ii) a high level and size of open porosity for high surface area and flow of

electrolyte, gas or nutrients through the porous ceramic,

(iii) high electrical conductivity.

As an example of a potential application, previous work on porous ceramics for

microbial fuel cells used an electrically insulating ceramic that required an additional

chemical vapour deposition treatment to deposit a conductive fluorine tin oxide [6] and

provide electrical conductivity. By adopting an electrically conductive MAX-phase

material, such as Ti2AlC, the need for the additional conductive coating can be

eliminated.

The MAX-phase ceramics are a class of ductile material group with the general

molecular formula Mn+1AXn (n = 1, 2, or 3), where M is an early transition element, A is

an element from group 13 or 14 of the periodic table such as B, Al, Ga, C, Si, Ge, Sn

and Pb and X is either a carbon or nitrogen [7]. Depending on the value of n, M2AX,

M3AX2 and M4AX3 phases are referred to as 211, 312 and 413 phases respectively and

recently MAX-phases with higher values of n such as 514 and 615 [7] phases have been

reported. These materials are inherently nano-laminated ternary carbides or nitrides.

Currently there are approximately sixty known phases [8] and Nowotny et al. [9] carried

out their initial investigation and crystallographic analysis in 1960’s. The materials are

3
of interest since they exhibit both metallic and ceramic properties. Their similarities to

metals include high electrical conductivity, e.g. ~ 3 x 10 6 Ω-1m-1 [10], high thermal

conductivity, good thermal shock resistance, machinability and they exhibit a degree of

plasticity at elevated temperatures. Their ceramic properties include a refractory nature

and oxidation resistance and they can maintain their strength at high temperatures [11]

with a decomposition temperature of 15000C under vacuum [12]. Sun and Zhou [13]

reported a detailed review of the Ti-Al-C MAX-phase system and Ti2AlC and Ti3AlC2

are the two aluminium containing MAX-phases of interest due to their low density of

4.1 g/cm3 [13] along with high oxidation resistance. In the 211, 312 and 413 MAX-

phase family, 211 Ti2AlC is a frequently researched material with well-established

properties. Ti2AlC has a low density of 4.1 g/cm3 and a high electrical conductivity of

3x106 Ω-1m-1. Due to the nature of the bonding the bulk modulus of Ti 2AlC (186 GPa) is

lower than the bulk modulus of binary TiC (240 GPa) [14] and it has a brittle to ductile

transition temperature of approximately 1050oC [15]. Gilbert et al. [16] found that the

shear modulus of Ti2AlC at 1000oC is 88% of its shear modulus at room temperature. In

addition the 211 Ti2AlC materials can be readily prepared by subjecting the

stochiometrically mixed Ti, Al and C to a combustion synthesis process [17]. This novel

combination of both metallic and ceramic properties, its technical application towards

chemical resistance, high temperature, machinability and load bearing ability are the

main reasons to select Ti2AlC as an a candidate material for a porous electrically

conductive electrode material. Research on the manufacture of macro porous Ti-Al-C

MAX-phase ceramics is rather limited [18-20] and the majority of porous MAX-phase

ceramic are produced by reactive sintering which generates porosity up to 65%

throughout the sample body with a wide distribution of pore sizes [21-23]. One of the

4
disadvantages of the reactive sintering approach is the difficulty in fine control of the

pore size and pore distribution during the exothermic reactions of the elemental

reactants used to form the product, thereby leading to material inhomogeneity. However

in the foam replication technique, the pore distribution directly relates to the structure of

the synthetic template employed and offers a route to produce conductive ceramics with

controlled pore size.

With regard to the Ti2AlC MAX-phase material, the majority of research conducted to

date is based on dense material [9, 10, 15, 24-28]. Hu et al. [18] and Zhou et al [20]

reported the production of porous Ti2AlC and Ti3SiC2 respectively, prepared using NaCl

as the pore former for controlling the volume fraction of porosity and the pore size. Sun

et al. [19] reported the manufacture of a porous reticulated Ti3AlC2 ceramic that was

used as a substrate to deposit catalytic CeO2 for a gas exhaust catalyst device. This

paper aims to establish a tailorable manufacturing route to produce macro-porous

Ti2AlC ceramic by foam replication technique with isotropic material properties.

2. Experimental procedures

2.1 Slip preparation

Commercially available Ti2AlC (“Maxthal 211 engineering ceramic material”) from

Kanthal was used as the ceramic powder with a 90% particle size distribution of 20µm

particles, with the remainder being a mixture of 2µm and 8µm particles.

Poly(ethylenglycol) with an average molecular number of 380-420 from Sigma Aldrich

was used (2 wt% of the ceramic powder) as the plasticizer and binder to obtain a high

flow of the slip solution for ease of coating of the polymer foam. Dispex GA40 from

Ciba AG (1.2 wt% of the ceramic powder) was used as an anti-settling agent to suspend

5
the ceramic particles in the solution during the foam replication process. Methyl

cellulose from Sigma Aldrich (2.4 wt% of the ceramic powder) was used as a

thickening agent to increase the viscosity of the slip without affecting the solid loading

(defined in this paper as the wt% of ceramic employed). The above-mentioned

chemicals were mixed in distilled water (resistivity18.2Mcm) and ball milled for 36

hours. Polyurethane foam (“Reticulated vitreous carbon foam” from Duocel) of 10 ppi

(pores per inch) was used as the synthetic replica template in this work as applications

of macro porous ceramics, such as microbial fuel cells [29], require a high degree of

open pore channels for easy flow of media.

2.2 Slip design and viscosity measurements

To achieve the optimum composition for coating of the Ti 2AlC ceramic slip on to the

polymer foam it was necessary to produce slips with a range of viscosities. Slip

viscosity was characterized using a Brookfield DV-II+ Pro-viscometer. The viscosity

was controlled by using a range of distilled water contents while keeping the amount of

other chemical compositions described in Section 2.1 constant (see Table 1 for

compositions). Viscosity readings were taken using ‘Spindle 63’ which is specific for

the viscometer with a constant 1.5 RPM for all testing. The slip composition was milled

for 24hrs prior to the viscosity measurement.

6
2.3 Coating of foam with ceramic slip

The polyurethane foam was initially cut into a large rectangular block of 100 x 50 x

25mm for preliminary coating studies and later cut into small rectangular blocks of 25 x

25 x 25mm for microscopic analysis and mechanical testing. To impregnate the foam

with the ceramic slip, it was fully immersed into the slip to ensure that the entire foam

was coated, as shown in figure 2 (left image). Once the foam was impregnated care was

taken to ensure that excess slip was removed before the slip dried. A manual squeezing

technique, figure 2 (right image) was used to remove this excess slip. Although most of

the excess slip was eliminated at this stage, some pores in the foam remain filled with

the ceramic slip. Compressed air was used to ensure an open porous structure. Prior to

sintering the foams were left to dry for 24 hours at room temperature.

2.4 Sintering conditions

2.4.1 Dwell time

Once dried, the impregnated foams were sintered in a tube furnace using an inert Argon

atmosphere. A heating rate and cooling rate of 150 C/hour was initially employed with

a dwell time at the sintering temperature of 1400C. The sintering temperature was

based on initial sintering study of dense Ti 2AlC cold-pressed pellets with a dwell time

of 5hrs (figure 3a) and then cooling at 150 C/hour to room temperature.

2.4.2 Foam pyrolysis

Since burn-out of the polymer has the potential to create defects prior to sintering, a

pyrolysis stage was also introduced in the heat treatment cycle. This involved a 1hr

dwell at 200°C and a slower heating rate of 60°C/hr to 800°C with a 1hr dwell, as seen

in figure 3b. The decomposition temperature of polyurethane foam is approximately

7
600oC [30], hence to ensure a complete and controlled decomposition of polyurethane

foam, an upper temperature of 800oC was chosen.

2.5 Application of additional coating to reduce defects

The basic processing of impregnating foam, drying and sintering is described by Path I

in the flowchart in figure 4. To further reduce the formation of defects and increase the

ceramic strut thickness in the final ceramic foam an additional ceramic coating was

applied. This additional ceramic coating was either applied before sintering (Path II) or

after sintering (Path III). Precise details of the process and its influence on properties are

provided later in the paper.

2.6 Microstructural and phase analysis

The microstructure of the porous ceramic samples was analysed using a JEOL 6480LV

SEM equipped with an Oxford instrumentation IMLA X-act X-ray detector with

particular attention being given to the identification of defects either on or within the

individual struts of the porous ceramic using Secondary Electron Imaging (SEI). The

phases formed after sintering were analysed using XRD (Cu target, Kα).

2.7 Compression testing

Compression testing was carried out to determine mechanical strength of the sintered

ceramics. Samples of 25 x 25x 25mm dimensions were prepared and subjected to

uniform, uniaxial compressive load with a cross-head speed of 2mm/min. Rubber pads

were used on the upper and lower surfaces to distribute the load uniformly and the

maximum load at failure was recorded to determine the compressive strength. Six

samples at minimum were tested for each batch.

8
3. Results

3.1 Viscosity study

Initial investigations examined the development of the slip to coat the polymer foam.

The criteria used to establish an optimum composition of the ceramic slip were:

i. uniform coating over the polyurethane foam,

ii. easy removal of excess slip from the foam while coating,

iii. fast drying (under 24 hours) to minimise processing time,

iv. minimum loss of slip during drying process,

v. a sufficiently thick coating for mechanical strength for handling.

Each trial was conducted for 5 minutes and the maximum viscosity was recorded in

mPa.s (milliPascal-second). Table 1 below provides the complete set of data of the

measured viscosity for different quantities of distilled water. The quantity of other

components was maintained constant.

3.1.1 Effect of slip viscosity on the polymer foam coating

For the slips made with the lowest quantity of distilled water (48wt%) the slip was

highly viscous, as seen in Table 1. As a result of the high viscosity and low degree of

flow of the slip, it was difficult to achieve a uniform coating of the slurry over the

polymer foam and it tended to be of high thickness (approx. 1.13mm thick analysed

using ImageJ 1.48t), resulting in a long drying period. A number of internal pores were

blocked, as excess slip could not be squeezed out by mechanical deformation of the

foam or removed using compressed air.

9
For the slips made with 52wt% of distilled water it was possible to achieve a uniform

coating (approx. 0.77mm thick analysed using ImageJ 1.48t) over the foam and the

excess slip could be easily squeezed out during mechanical deformation since the flow

of the slip improved considerably. The slip coating on the polymer substrate dried

within 24hrs without filling the inner pores of the foam.

For the slip made with 56wt% of distilled water, due to the increase in water content,

the viscosity was lower than the slips with 52 and 48wt%. A uniform thin layer of

coating was achieved (approx. 0.57mm thick analysed using ImageJ 1.48t), but this led

to a thin coating and the ceramic body after sintering was fragile and difficult to handle

without fracture. The slip coating dried quickly and no clogging of pores was observed.

The slip made with 60wt% of distilled water had the lowest viscosity and as a result

there was poor adhesion of the slip to the foam.

From the above observations made in Table 1 the slip with 52wt% of distilled water was

used to produce the porous Ti2AlC ceramic.

3.2 XRD of sintered material

XRD of the sintered porous material using the 5hr dwell at 1400 oC is shown in Figure 5

showing the presence of Ti2AlC and TiC as a secondary phase. Wang et al. [31]

indicated that TiC and TiAl are common secondary phases since they have a lower

Gibbs free energy of formation compared to Ti 2AlC. Sintering at lower temperatures

(1300 oC) or a shorter time (3hr) led to XRD larger TiC peaks in the final material; this

observation is in agreement with work of Mei et al. [32] who noted higher TiC contents

in Ti2AlC processed at lower temperatures. On sintering above 1400C conversion of

TiC and TiAl to Ti2AlC takes place by a solution precipitation process, as reported by

10
Ge et al. [33] and Mei et al. [32] also observed that TiC reacted with Ti 2AlC to form

Ti3AlC2 at high temperatures. The final sintered material exhibited a homogeneous

colour within the porous ceramic product. Four-point probe measurement on the surface

of the Ti2AlC ceramic indicated a bulk resistivity of 0.00857Ω.cm (conductivity 1.1 x

104 Ω-1m-1).

3.3. Influence of pyrolysis stage on microstructure

Figure 6a shows a SEM image of the struts in the sample prepared using 52wt% of

distilled water using the profile of figure 3a. It can be observed that the struts contain a

number of defects in the form of cracks. The formation of cracks has been previously

reported on research related to the foam replication method [3, 34-36]. These cracks are

formed as a result of the burn-out of gases produced during the decomposition of the

polyurethane foam at elevated temperature. In addition, since the foam is burnt out it

leaves behind hollow struts throughout the material as seen in the SEM image in figure

6b, especially at the triple points. Therefore it is important that the decomposition of the

polymer replica takes place in a controlled manner that was achieved using the

temperature profile in figure 3b. The dwell and slower heating rate at lower temperature

aids in controlling the decomposition rate of the foam so there is a gradual outgassing of

the polyurethane during heat-treatment.

Figure 6c shows an SEM image of the struts in the sample prepared with 52wt% of

water with a pyrolysis stage in the heat treatment process (figure 3b). Although there

were defects in the region, the struts had comparatively less defects compared to the

samples with no pyrolysis, for example compare figure 6d and 6b.

11
3.4 Coating of foams prior to sintering

Clearly the reduction in size and number of defects in a ceramic is necessary to achieve

sufficiently strong ceramic foam. The concept of applying an additional coating of

Ti2AlC to the foam before it was sintered was considered to further reduce the number

of defects on the struts followed by subjecting the coated foam to a heat-treatment using

the thermal cycle in figure 3b.

Samples were prepared according to the processing route on Path II in figure 4, using a

slip of lower viscosity (51589 mPa.s as in Table 1) for the second stage of coating. A

lower viscosity slip was preferred since the excess slip could not be squeezed out of the

foam by mechanical deformation at the second stage, as it would damage the initial

ceramic coating of the PU foam. After the second coating there was a relatively thick

coating (approx. 2.08mm thick analysed using ImageJ 1.48t) on the pre-coated samples;

the high thickness of the struts leads to some pores filled with ceramic, even when

compressed air was applied, but this has the potential to increase strength. Efforts to use

a lower slip viscosity at the second stage resulted in poor adhesion of the ceramic slip

during the second coating stage.

Figure 6e is an SEM of the struts of the sintered porous ceramic where the foam was

coated prior to sintering. The frequency of the defects are reduced compared to those

manufactured using Path I, and the thickness of the struts are increased (approx.

2.21mm). An optical image of the structure of the sintered material is also shown in

figure 6f.

12
3.5 Coating of foams after sintering

Since it was evident that defects are formed in the centre of the ceramic struts during the

decomposition of the polyurethane foam, another approach to reduce the size and

frequency of defects was to re-coat the sintered ceramic foam after the polymer foam

had been burnt out and the ceramic has been sintered. In this method the Ti 2AlC foam

was simply used as the template.

Samples were prepared according to the processing route on Path III in figure 4. Once

the Ti2AlC foams are sintered using the thermal cycle of figure 3b, it was recoated with

a low viscosity slip (60wt% distilled water) of 51589 mPa.s viscosity. After recoating

the ceramic and using compressed air to remove any slip filling the pores, the samples

were subjected to vacuum of 1 bar pressure for 5 minutes to ensure that the slip was

absorbed into the cracks of the ceramic foam. The samples were subsequently dried and

re-sintered using temperature profile of figure 3b.

In this case the ceramic struts are thinner and the majority of the pores remain open (see

figure 6g and 6h) unlike the foam coated prior to sintering in figure 6d and 6e, which is

one advantage of re-coating the sample after sintering. As a result, depending on the

percentage of open pore channel needed it is possible to adopt the coating technique

accordingly.

3.6 Mechanical testing

3.6.1 Influence of pyrolysis stage on microstructure

Compression testing was carried out the Ti 2AlC foam blocks to measure any change in

the mechanical strength due to the introduction of a pyrolysis stage. The samples with

dimensions of 25 x 25 x 25mm were prepared using a slip made with 52wt% of distilled

13
water for the two different sintering conditions (figure 3b and 3c). From figure 7 it can

be seen that there was an increase in the compressive strength due to the introduction of

a pyrolysis stage in the heat treatment cycle, however the defects were still present

within the centre of the struts due to the burnout of the PU foam (figure 6c). Therefore

there was a need to further minimise the defects if an increase in the compressive

strength is desired.

3.6.2 Coating of foam before sintering

Coating of the foam prior to sintering was found to reduce the defects to some extent,

e.g. due to shrinkage/drying of the slip, the existence of remaining cracks resulted from

the burn out of the polyurethane foam. Nevertheless, the compressive strength has

increased significantly to an average of 6.34N/mm 2 for the foams coated before

sintering (Path II, figure 7) compared to the 0.32N/mm 2 for the Ti2AlC foams (Path I).

This high strength is also due to the higher thickness of the ceramic struts and the

existence of some filled pores.

3.6.3 Coating of foam after sintering

From the compressive test results in figure 7, the foams coated after sintering (Path III)

had an average maximum compressive strength at failure of 2.95 N/mm 2. The ceramic

prepared with this technique exhibits a higher compressive strength compared to the

Ti2AlC foams due to a reduction in defects. The reason for the lower compressive

strength compared to the foam that was coated prior to sintering, is that the majority of

the open pore channels are filled with material when the foam is coated prior to

sintering which offers a greater resistance to mechanical load. Nevertheless the foams

coated after sintering were structurally stable, could be readily handled and is a

14
candidate for a porous electrode or a microbial fuel cell substrate due to the electrical

conductivity of the Ti2AlC ceramic.

4. Conclusions

This paper has demonstrated that Ti2AlC ceramic could be used to fabricate macro-

porous MAX-phase electrically conductive ceramics as an electrode material.

Optimisation of the sintering conditions has been undertaken to form the Ti 2AlC phase

and reduce defect production during the pyrolysis of the polymer foam. A variety of

fabrication techniques were examined to improve the compressive strength and number

and size of defect within the porous ceramic. This included an additional coating that

can be applied before or after sintering the initial foam. Both the advantages and

disadvantages of each method were examined in the study and approaches to minimise

the formation of defects due to polymer burnout was developed. Such open porous

conductive ceramic materials have potential applications in electrodes for use in harsh

environments (chemical or high temperature) and microbial fuel cells. Understanding

the mechanism of defect formation and its control is fundamental to successfully

manufacture a range of MAX-phase ceramics and tailor their strength and degree of

open porosity to potential applications.

Acknowledgement

Bowen would like to acknowledge the research time provided by the Bath Aqua Sulis

Club.

15
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 Figure 1. Schematic of foam replica technique.

Figure 2. (Left) Foam immersed into the slip (Right) slip excess removed prior to treatment with

compressed air.

Figure 3. Sintering condition for Ti2AlC sintering (a) 5hr dwell (b) introduction of pyrolysis stage.

Figure 4. Processing steps for the manufacture of porous foam, coated foams prior to sintering and coated

foams after sintering.

Figure. 5 XRD data of the porous ceramic prepared using 1400oC for 5hrs

Figure 6 (a) SEM of cracks formed along struts for sintered material prepared with 52wt% distilled water

(Path I), (b) optical micrograph of hollow region in struts of sintered porous ceramic prepared with 52wt

% of distilled water due to the decomposition of the foam during sintering (Path I), (c) SEM image of the

hollow strut in sintered porous Ti2AlC with 52wt% distilled water using thermal profile in figure 3b (Path

I), (d) optical micrograph showing the surface coat quality after introducing thermal profile in figure 3b

(Path I), (e) SEM image of defects formed on struts of sintered ceramic coated prior to sintering (Path II)

(f) optical micrograph of surface coating quality of sintered ceramic coated prior to sintering (Path II), (g)

SEM image of coated foam after sintering showing individual strut surface (Path III), (h) optical

micrograph showing the surface coat quality of sample coated after sintering (Path III)

Figure 7. Summary of compression test data conducted. Six samples at minimum were tested for each

batch.

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 Table 1 Viscosity coefficient of slip measured at different distilled water content with constant spindle

speed of 1.5 RPM. The slip composition was milled for 24hrs prior to the viscosity measurement.

Quantity of Quantity of water as Maximum spindle Dynamic viscosity in

water (g) wt% of the ceramic torque (%) (mPa.s)

60 48 82.9 332000

65 52 35 146000

70 56 20.8 75184

75 60 12.9 51589

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