Preparationandpropertiesofporoussiliconcarbideceramicsthrough coatmixandcompositeadditivesprocess

ZHAOHongsheng,LIUZhongguo,YANGYang,LIUXiaoxue,ZHANGKaihong,LIZiqiang InstituteofNuclearandNewEnergyTechnology,TsinghuaUniversity,Beijing100084,China Received18October2010accepted29November2010

Abstract: The coreshell structure siliconresin precursor powders were synthesized through coatmix process and addition of Al2O3SiO2Y2O3 compositeadditives.Aseriesofporoussiliconcarbideceramicswereproducedaftermolding,carbonizationand sintering.Thephase,morphology,porosity,thermalconductivity,thermalexpansioncoefficient,andthermalshockresistancewere analyzed.Theresultsshowthatporoussiliconcarbideceramicscanbeproducedatlowtemperature.Thegrainsizeofporoussilicon carbideceramicissmall,andthethermalconductivityisenhancedsignificantly.Compositeadditivesalsoimprovethethermalshock resistanceofporousceramics.Thebendingstrengthlossrateafter30timesofthermalshocktestoftheporousceramicswhichwere addedAl2O3SiO2Y2O3 andsinteredat1650Cisonly6.5%.Moreover,theporeinsideofthesampleissmooth,andtheporesize distribution is uniform. Composite additives make little effect on the thermal expansion coefficient of the porous silicon carbide ceramics. Key words: siliconcarbideporousceramiccoatmixcompositeadditives

1Introduction
Porous silicon carbide ceramics are important materials, which exhibit lots of excellent properties of both porous ceramics and silicon carbide. Due to possessing a set of attractive properties, porous silicon carbide ceramics have been widely employed in many application fields, involving aerospace, energy, machinery, metallurgy, chemistry, environmental, biologicalandmedicalfields,usingasfilters,membranes, heat exchangers, thermal insulators, capacitors, soundabsorbing material, damping buffers, various sensors,catalystsandcatalystcarriers,etc[13].Porous silicon carbide ceramics have been synthesized using various methods [4], including oxidation bonding method [5], combustion synthesis, chemical vapor reaction,solgel[6]andcarbothermalreductionreaction [78], preceramic foam processing [9], and coatmix method. Coatmix method has an extensive application prospect due to the advantages of simple technology, energy saving, high efficiency, controllable process and environmental compatibility. The product of coatmix technologypossessescontrollableporesize,narrowpore

size distribution and high purity [1011]. Researches show that the porosity, strength and thermal shock resistance of porous silicon carbide ceramics could be improved by adding sintering additives such as Al2O3, Y2O3,MgO,K2O andSiO2[1213]. In this work, the siliconresin precursor powders with coreshell structure were synthesized through coatmix process, and Al2O3, Al2O3SiO2 and Al2O3SiO2Y2O3 wereintroducedassinteringadditives, respectively. Then porous silicon carbide ceramics were producedaftermolding,carbonizationandsintering.The phase, surface morphology, porosity, thermal conductivity, thermal expansion coefficient, bending strength and thermal shock resistance of porous silicon carbideceramicswereanalyzed.

2Experimental
2.1Samplepreparation Thesiliconresin precursorpowderswith coreshell structure were synthesized through coatmix process from industrial grade silicon powder and barium phenolic resin. Additives were chemically pure neutral Al2O3 withparticlesizeof75150m,chemicallypure

Foundationitem:Project(50802052)supportedbytheNationalNaturalScienceFoundationofChina Correspondingauthor:ZHAOHongshengTel:+861089796090Email:hshzhao@tsinghua.edu.cn DOI: 10.1016/S10036326(11)608613

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Y2O3 and analyticallypureSiO2, respectively.Takingthe total mass of precursor powders of 100 g, the sample batchandsinteringtemperatureofporoussiliconcarbide ceramicsareshowninTable1.
Table 1 Batch and sintering temperature of porous silicon carbideceramics Samplem(Powder)/ m(Al2O3)/m(SiO2)/ m(Y2O3)/ Temperature/ No. g g g g C S1 S2 S3 S4 S5 S6 S7 100 100 100 100 100 100 100 3 3 3 3 0 3 3 1 1 1 1 0 0 1 0.71 0.71 0.71 0.71 0 0 0 1450 1550 1650 1750 1650 1650 1650

3Resultsanddiscussion
3.1 Effectofsintering temperature Figure1 shows the XRD patterns of porous silicon carbide ceramics with Al2O3SiO2Y2O3 additives at different sintering temperatures. In Fig. 1, the peaks at 2 =36, 41, 60, 72 and 76 are assigned to (1 1 1), (2 00),(2 2 0), (3 1 1) and(2 2 2) planes of cubic SiC according to the standard JCPDS cards (291129). Itis found that no carbon peaks and silicon peaks can be observed in these patterns. The pattern of sample S1 shows that only SiC diffraction peaks appear at the sinteringtemperatureof1450C.ItisindicatedthatSiC ceramicisalreadyobtainedat1450C.Figure2shows the surface SEM images of the samples sintered at differenttemperatures.ItcanbeseenfromFig.2thatthe microstructure of sample S1 is uniform and dense, indicating that the composite additives decrease the formationtemperature ofporoussiliconceramics.

After mixing, the precursor powder and additives werepressuremoldedat50140Cand0.550MPafor 20120 min,. Then the materials were carbonized at 6001000C for 14h under argonatmosphere. After that the samples were treated by high temperature vacuumsinteringat14501750Cfor2 h,withheating rateof510 C/min. 2.2Characterizationofsamples The morphology and phase of porous silicon carbide ceramics were analyzed by S3000N type scanningelectronmicroscopeandBruker P4typeXray diffraction instrument, respectively. The porosity of the sample was measured by Autopore IV 9510 mercury porosimeter. LFA427 type laser flash apparatus, DIL402C type thermal dilatometer and STA449 type simultaneousthermalanalyzerwereusedtomeasurethe thermal diffusivity (), linear expansion coefficient and specificheatcapacity (cp).Thedensityofthesamplewas obtained through drainage method, and the thermal conductivitywascalculatedusingtheformula =cp. The products were processed to be samples of 3 mm4 mm40 mm by diamond surface grinding machine.Thenthreepointbendingstrengthmeasurement of30mmspanwastakenonthesamplesbyZwickz005 type material detection equipment. The samples were heated to 800 C and heat shock 30 times under air atmosphere.Thermalshockresistancewasperformedby bendingstrengthlossrateofmaterials [14]:

Fig. 1 XRD patterns of porous silicon carbide ceramics at differentsinteringtemperatures

h =

s 0 - s1 100 % s 0

(1)

where is bending strength loss rate s0 is bending strength before thermal shock s1 is bending strength afterthermalshock.

Figure 3 shows the bending strength and bending strength loss rate of samples, which were taken Al2O3SiO2Y2O3 as additive, and sintered at different temperatures. It can be seen from the curves that the bending strengths of all the samples before and after thermal shock gradually decrease along with increasing thesinteringtemperaturefrom1450Cupto1650C. While the strength of the samples before and after thermalshockdecreasesrapidlyfrom1650Cto1750 C.Thebendingstrengthlossrateofthesamplesintered at1 650 C(S3)isonly6.5%,whichisthelowestamong allsamples.Whenthetemperatureisbelow1650C, the bending strength loss rate of the samples gradually decreases as the sintering temperature increases. The bendingstrengthlossrateofthesamplesinteredat1750 C(S4)reaches52.8%.Theresultsshowthatthehigh

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Fig.2 SurfaceSEMimages ofporoussiliconcarbideceramicsatdifferentsintering temperatures: (a)S1(b)S2(c)S3(d)S4

Fig. 3 Thermal shock resistance of porous silicon carbide ceramicssinteredatdifferenttemperatures

Fig. 4 Thermal conductivity at RT and 800 C for porous siliconcarbide ceramicssinteredatdifferenttemperatures

sintering temperature would lead to the decrease of the thermalshockresistance. Figure 4 shows the effect of sintering temperature on the thermal conductivity of the samples. The results showthatthesamplesinteredat1650Chasthehighest thermal conductivity. It is corresponding to the data of the bending strength before and after thermal shock at 1650 C (Fig.3). Figure 5 shows the effect of sintering temperature on thelinear expansion coefficient ()of porous silicon carbide. As shown in Fig. 5, the sintering temperature hasnoobviousinfluenceonlinearexpansionofsamples. ThelinearexpansioncoefficientofthesampleS1

sintered at 1 450 C is lower at the low temperatures. While the linear expansion coefficient of sample S3 sinteredat1 650 Cishigherat thehightemperatures. Figure 6 shows the effect of sintering temperature on porosity of the samples. As shown in Fig. 6, the bendingstrengthandthermalshockresistanceofsample S3 are very good, and the porosity of sample S3 is the highest. From the surface morphology of sample S3 shown in Fig. 2, it can be seen that sample S3 has uniform pore size distribution, which can disperse thermal elastic strain energy. Besides, sample S3 has smoothporewall,whichcanrelaxthestress.Therefore,

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Fig.5Thermalexpansioncoefficientofporoussiliconcarbide ceramicssinteredatdifferenttemperatures

highest bending strength both before and after the thermalshock.Besides,thebendingstrengthlossrateof sample S3 after thermal shock is the lowest, and far lower than those of samples with other additives. As showninXRDpatterns(seeFig.7),bothsamplesS3and S7withcompositeadditivesperformthepeaksofmullite phase (3Al2O32SiO2), which has better thermal shock resistanceandmechanicalcharacteristics[15]. As shown in Fig. 7, sample S3 has more mullite phases because of the addition of Y2O3, which may promote liquid phase sintering and then result in more mullitephases.Italsocanbefoundthattheadditivesof the other two compounds reduce the bending strength before thermal shock. Particularly, the bending strength of sample S6 obtained by adding Al2O3 before thermal shock is only 1.9 MPa, which is far lower than that of othersamples.

Fig. 6 Porosity of porous silicon carbide ceramics sintered at differenttemperatures

Fig.7 XRDpatternsofsamples S3 andS7

thethermalshockresistanceofsampleS3 isimproved. 3.2 Effectofdifferentadditives Thebendingstrengthandbendingstrengthlossrate of porous silicon carbide ceramics with different additives before and after thermal shock at 800 C are showninTable2. AsshowninTable2,sampleS3(Al2O3SiO2Y2O3 asthecompositeadditive,sinteredat1650C)hasthe
Table 2 Thermal shock resistance of porous silicon carbide ceramicswithdifferentadditives Thermalshockresistance/MPa Sample Lossrate/ No. Beforethermalshock After thermalshock % S3 S5 S6 S7 13.8 11.1 1.9 9.1 12.9 3.8 1 3.7 6.5 65.8 47.4 59.3

Therefore, the formation of mullite phase is beneficialtoenhancethe bendingstrengthbeforethermal shock and thermal shock resistance of porous silicon carbide ceramics. The addition of Y2O3 decreases the formation temperature of mullite, whiletheliquid phase sintering makes the grain refinement. Table 3 exhibits theeffectofadditivesonthethermalconductivityofthe porous silicon carbide ceramics. As shown in Table 3, Al2O3SiO2Y2O3 composite additive increases the thermal conductivity obviously. It is ascribed to the second phase mullite distributed continuously around matrix grains in this system, while no continuous distribution of mullite phase appeared for the samples with the other two additives. As shown in Table 4, porous silicon carbide products keep the characteristics of high porosity after composite additives. The sample S3 (Al2O3SiO2Y2O3 as additive), which has the best thermal shock resistance, remains nearly 70% porosity. Thesample withAl2O3SiO2 additivehas higherporosity, butitsbendingstrengthandthermalshockresistanceare notideal.

ZHAOHongsheng etal/Trans.NonferrousMet.Soc.China21(2011) 13291334 Table 3 Thermal conductivity of porous silicon carbide ceramicswithdifferentadditives Sample No. S5 S6 S7 S3
1 1 Thermalconductivity/(Wm K )

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Roomtemperature 43 30 38 160

800C 21 17 14 65

Table 4 Porosity of porous silicon carbide ceramics with differentadditives SampleNo. S5 S6 S7 S3 Porosity/% 67.9 65.0 73.7 69.8

Figure8showsthethermalexpansioncoefficientof sampleswithdifferentadditivesandsinteredatdifferent temperatures. At low temperature, the sample with Al2O3SiO2Y2O3 composite additive has the lowest linear expansion coefficient, while the sample with Al2O3SiO2 composite additive has the lowest linear expansion coefficient at high temperature. Whereas, as shown in Fig. 8, composite additives make no remarkable influence on linear expansion coefficient of ceramics.

Fig. 9 SEM images of porous silicon carbide ceramics: (a) Without additives (S5) (b) With Al2O3SiO2Y2O3 additive (S3)

silicon carbide ceramics with Al2O3SiO2Y2O3 additive isenhanced.

4Conclusions
1) Based on the fabrication of coreshell structure siliconresin precursor powders by coatmix method, porous silicon carbide ceramics were prepared at lower temperature by adding a small amount of Al2O3SiO2Y2O3. 2) By adding Al2O3SiO2Y2O3, more mullite phases in the porous silicon carbide ceramics generate, thesiliconcarbidegrainsarerefined,andthewallofthe poresbecomessmoother. 3) Porous silicon carbide ceramics synthesized through composite additivehavehigh porosity both the thermalshockresistanceand the thermalconductivity are enhanced. While the composite additive performs less impact on the linear expansion coefficient of the samples.

Fig.8Thermalexpansioncoefficientofporoussiliconcarbide ceramicswithdifferentadditives

Figure 9 shows the SEM images of porous silicon carbide ceramics without additive and with Al2O3SiO2Y2O3 additives. As shown in Fig. 9, the grains of samples with Al2O3SiO2Y2O3 additives are refined. Finegrained materials generally have better strength and thermal stress resistance than coarse grain.Therefore,thethermalshockresistanceofporous

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4) Porous silicon carbideceramics with thehighest thermal conductivity, the highest porosity, and the best thermal shock resistance were synthesized by adding a proper amount of Al2O3SiO2Y2O3 and sintering at 1650 C.

[7]

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