Minerals Engineering, Vol. 12, No. I, pp.

75-91, 1999

Pergamon 0892-6875(98)00121-6

1998 Elsevier Science Ltd All rights reserved 0892--6875/99/5 - - see front matter

THE POTENTIAL USE OF GEOPOLYMERIC MATERIALS TO IMMOBILISE TOXIC METALS: PART II. MATERIAL AND LEACHING CHARACTERISTICS

J.G.S. VAN JAARSVELD ~, J.S.J. VAN DEVENTER ~ and A. SCHWARTZMAN*

Department of Chemical Engineering, The University of Melbourne, Parkville, Victoria 3052, Australia. E-mail: jsj.van_deventer@chemeng.unimelb.edu.au t School of Physics, The University of Melbourne, Parkville, Victoria 3052, Australia (Received 21 July 1998; accepted I October 1998)

ABSTRACT
The stabilisation and solidification of waste materials by the technology of geopolymerisation is fairly unknown and has not been studied in any depth. This paper presents some experimental evidence as to the physical and chemical characteristics of geopolymers manufactured from fly ash originating from two different regions. It has become apparent that these materials could be used for a wide variety of environmental and other applications such as the immobilisation of heavy metals and the fabrication of structural products. In this study compressive strength testing, specific surface area determinations, Transmission Electron Microscopy (TEM), Nuclear Magnetic Resonance (NMR) and leaching tests were used in characterising a number of geopolymer matrices. It is also shown how the inclusion of heavy metal ions, alkali metal cations and different processing conditions affect the physical and chemical characteristics of the final product. 1998 Elsevier Science Ltd. All rights reserved

Keywords Leaching; environmental; recycling; waste processing

~TRODUCTIONANDBACKGROUND
In a previous paper [1] the possible applications of geopolymers in waste processing have been discussed. These applications can be divided into two categories: (1) Structural products such as concrete replacements in various environments and (2) Immobilisation systems for heavy metal containment. Experimental evidence regarding leaching data and physical properties was also presented, although all of it considered commercially produced geopolymer cements that were mixed with waste products and allowed to set. Relatively high costs and problems relating to transferring new technology to industry prevented these commercially produced binders from becoming popular and to date only limited successes have been achieved [2]. The possibility of producing geopolymeric matrices by utilising waste materials has been proposed [1] and therefore this paper will present some experimental evidence on the physical properties and leaching characteristics of geopolymers manufactured almost entirely from waste materials. It should be kept in mind, however, that the present level of scientific knowledge with regard to geopolymers leaves much to be desired and even the evidence presented here cannot serve to fundamentally understand these products although a number of qualitative conclusions can be drawn. 75

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Various factors affect the eventual mechanical and chemical properties of the finished product. These include the thermal history of the clay used, the type and amount of alkali metal cations present, the heavy metal being immobilised as well as certain physical considerations such as particle size and ease of mixing of the various reagents. The last two aspects will not be addressed in this paper, as they were fairly similar for all examples under consideration. It was noted previously [1,3] that the mechanism by which geopolymerisation is thought to occur involves the dissolution, migration and polymerisation of AI and Si precursor species as well as a surface reaction on the remaining surface area of undissolved waste particles. Although this is a very simplistic view of the process it will take some time before sufficient experimental evidence is available to fully quantify the reaction kinetics of the synthesis reaction. Depending on the eventual application, the product from such a process should be chemically inert and physically strong in order to prevent any further leaching of immobilised metals and compounds. Physical strength is not only an advantage as far as physical encapsulation of toxic materials is concerned, but also provides for the utilisation of these products in certain building applications. Although physical properties, such as compressive strength and porosity, can be utilised in distinguishing between different matrices, leaching tests will usually provide more substantial information regarding the immobilising efficiency, chemical stability as well as mechanism and kinetics of toxic metal immobilisation in geopolymeric matrices. Apart from standard environmental leaching tests, specifically designed tests, such as those discussed in this paper, have not yet been used in characterising geopolymer matrices and remain novel to a large extent. As was mentioned previously [1] X-ray diffraction techniques are inadequate for studying the structure of geopolymers, mainly because of their fairly high amorphous content. This problem can be overcome by using a combination of analytical techniques such as Nuclear Magnetic Resonance (NMR) as well as Transmission Electron Microscopy (TEM).

EXPERIMENTAL
Materials Fly ash used in the synthesis of matrices El, E2, F1 and G1 was obtained from SASOL at Sasolburg, South Africa and that used in matrices H1 to H4 from Tarong power station in Queensland, Australia. Both fly ashes are of coal origin, with particle sizes in the order of 50% smaller than 12 larn and chemical compositions as shown in Table 1. Kaolinite, grade HR1, was obtained from Commercial Minerals, Sydney, Australia. In the preparation of matrices E1 and E2, metakaolinite was used, manufactured by calcining the above-mentioned kaolinite at 600C for 6 h as described by Madani [4]. All experiments were performed using the same batches of reagents and starting materials. Distilled water was used throughout.

TABLE 1 Composition of fly ash as determined by fusion and XRF-analysis (mass%)

Element as oxide
SiO2 A1203

SASOL fly ash 50.1 28.3 8.2

4.0

Tarong fly ash 61.4 33.0 0.6

1.1

CaO
Fe203

MgO TiO2 Na20

K20

SO3 Loss on ignition

2.0 1.5 0.5 0.9 0.4 4.1

0.3 2.0 0.1 0.1 0.0 1.4

Use of geopolymericmaterialsto immobilisetoxic metals: part II Synthesis

77

Sample preparation was performed as described previously [3] with at least a 7-day waiting period being observed before any tests were performed. In each case the samples were cast in 50mm cubes, vibrated for 5 minutes and allowed to set at 30C for 24 hours before being removed from the moulds and kept at room temperature for another 6 days. Heavy metal cations were added to the reaction mixture during mixing as a solution of Cu(NO3) 2 or Pb(NO3) 2 in water. Tables 2 and 3 summarise the compositions of the respective matrices. It could well be noted that the amount of NaOH and KOH used in producing matrices El, E2, F1, F2 and G1 was chosen such as to provide for equal molar amounts of Na and K present in the structures of all the matrices in Table 2.

TABLE 2 Compositions of matrices prepared from SASOL fly ash (mass%) Matrix
E1 E2 FI F2 G1

Contaminant
Cu Pb Cu Pb Cu 0.1 0.1 0.1 0.1 0.1

Alkali metal
K O H 5.0 K O H 5.0 NaOH 3.7 NaOH 3.7 KOH 5.0

Clay
Metakaolinite Metakaolinite Kaolinite Kaolinite Kaolinite 16.0 16.0 15.0 15.0 15.0

Water/Fly ash mass ratio

0.2 0.2 0.2 0.2 0.2

A1203/SIO2 mass ratio

0.57 0.57 0.57 0.57 0.57

TABLE 3 Compositions of matrices prepared from Tarong fly ash (mass%)

Matrix H1 H2 H3 H4 Contaminant Cu Pb Pb Cu 0.1 0.1 0.2 0.2 Alkali metal KOH KOH NaOH NaOH 5.0 5.0 6.0 6.0 Clay Kaolinite 14.0 Kaolinite 14.0 Kaolinite 14.0 Kaolinite 14.0 Water/Fly ash ratio 0.43 0.43 0.45 0.45 A1203/SIO2 ratio 0.57 0.57 0.57 0.57

An~yses

Compressive strength testing

Compressive strength testing was performed as per AS 1012.9 [5] using three 50 mm cubes of each sample and averaging the experimental values obtained. All samples were tested after 14 days. An Amsler FM 2750 compressive strength testing apparatus was used.

Leaching tests
Samples submitted to leaching tests were crushed and sieved into particle size fractions, the latter being leached until equilibrium conditions were obtained. Leaching of each particle size fraction was conducted using a modified TCLP [3, 6] procedure utilising acetic acid buffered at pH = 3.3 by analytical grade sodium acetate. The liquid/solid ratio was kept at 1:25 and the temperature controlled at 30C. Equilibrium tests on matrices El, E2, F1 and G1 were conducted by two different methods i.e. by the use of stirred vessels with overhead impellers and also by using horizontally rolled bottles. The latter technique allowed for equilibrium to be obtained after around 60 hours, with the stirred technique reaching equilibrium in around 24 hours. In the case of matrices H1 to H4 only the stirring technique was used with sampling being performed periodically over a 24-hour period. Sampling was conducted by syringe and the total sampling volume never exceeded 10% of the fluid volume, thus creating an average error of 5%. Concentrations of Cu and Pb were determined using a Perkin Elmer Optima 3000 ICP-OES, with scandium as internal standard.

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Specific surface area, infrared analysis and X-ray diffraction

BET surface areas were determined for all samples by using a Micromeritics Flowsorb ASAP 2020 with a 30/70 ratio of N 2 and He, degassing for 18 hours at 95C. Infrared spectra were recorded for matrices El, E2, F1 and G1 on a Mattson Galaxy 2020 spectrometer using the KBr pellet technique (0.5 mg powder sample mixed with 250 mg of KBr). X-ray powder diffraction data were obtained for all samples using a Phillips PW 1800 diffractometer with Cu K(x radiation.

Nuclear magnetic resonance and transmission electron microscopy

Nuclear magnetic resonance (NMR) spectra were recorded using the Magic Angle Spinning (MAS) technique. 29Si and 27A1 spectra were recorded at spinning speeds of 15 kHz (27A1) and 4 kHz (29Si) for matrices El, F1, F2 and G1. Certain samples were also submitted to investigation by transmission electron microscopy (TEM) on a JEOL CX 100 TEM fitted with an X-ray microanalysis system. The specimens were prepared by mechanically grinding the powder in ethanol, followed by ultrasonic agitation and precipitation on an amorphous carbon film.

RESULTS AND DISCUSSION

General
It is of interest to note that in synthesising the various geopolymer samples, it became very obvious that mixing will play an important role in any proposed commercial venture involving the large-scale production of geopolymer related materials. A property such as the rheology of the reacting mixture was quantitatively observed as being of importance to the properties of the final product and although it fell outside the scope of this study it will be an important factor that still needs to be investigated in any future study. The two fly ashes used differed as far as their chemical contents were concerned and especially the amounts of carbon and calcium that they contained. The main crystalline phases in both cases were mullite and quartz, although amounts of amorphous silica and alumina compounds were also present. The exact nature and quantity of these amorphous phases cannot be determined easily although it is widely accepted that they are responsible for most of the reactivity associated with a specific fly ash [7].

Compressive strength and specific surface area

It is significant to note that the inclusion of Pb instead of Cu serves to strengthen the structure in terms of compressive strengths achieved (Table 4). This is true in the case of E1 and E2, HI and H2 as well as H3 and H4. In each case the matrices contain equal mass amounts of the heavy metal although the molar amounts would differ and there would be less Pb ions present in each case than in the corresponding matrix containing Cu. Table 5 shows that Pb resulted in higher specific surface areas than Cu. However, this is not at all what would be expected from a structural point of view where the stronger sample could be expected to have less porosity. It therefore seems a reasonable assumption that although the Pb ion influences the structure in terms of causing increased porosity this effect is offset by its contribution to structural strength in another way such as through its much larger ionic radius than that of Cu. It is not clear whether these ions are finding themselves bonded into the structure or whether the surrounding matrix is just physically encapsulating them. This issue will be discussed in more detail later.

TABLE 4 Compressive strengths after 14-days (MPa)

Matrix El E2 FI GI HI 142 H3 [-[4 Contaminant Cu Pb Cu Cu Cu Pb Pb Cu Alkali metal K K Na K K K Na Na Compressive sttens~h 28.1 33.7 43.8 51.4 4.5 7.3 18.! 16.5

Use of geopolymedcmaterialsto immobilisetoxic metals: part II

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TABLE 5 BET surface areas for different matrices (m21g)

Matrix
E1 E2 F1 G1 H1 H2 H3 H4

Contaminant
Cu Pb Cu Cu Cu Pb Pb Cu

Alkali metal
K K Na K K K Na Na

Specific surface area

12.1 16.7 8.8 16.4 9.3 12.2 7.8 4.3

Referring to Table 2 it can be seen that the only difference between G1 and E1 is the use of calcined kaolinite in the case of El. This seems to adversely affect the compressive strength of E1 compared with that of G1. According to Davidovits [8] the calcining of kaolinite transforms the octahedrally co-ordinated AI layers into the more reactive tetrahedral form creating metakaolinite and increasing geopolymer reactivity. E1 would therefore be expected to have a higher compressive strength than the corresponding matrix manufactured with less reactive kaolinite. This result implies that the concept of geopolymer synthesis does not entirely depend on dissolution and migration of ions dissolved from mineral surfaces because A1 ions would find it much easier to dissolve from metakaolinite than from uncalcined kaolinite. In these results, however, this effect is not reflected in an increased compressive strength and in fact results in a weaker structure. If it is assumed that there is a reaction taking place on the surfaces of individual particles and that the layer structure of the uncalcined kaolinite remains intact while particle surfaces bind to the "bulk" geopolymer phase, these results can be explained. Significant to note is the fact that the specific surface area of the stronger matrix is again larger, implying that the thermal processing of the kaolinite results in a totally different final structure, which suggests a combination of dissolution-migrationpolymerisation as well as surface-solid state reactions taking place. In the case of F1 and G1 the exact same molar amounts of respectively NaOH and KOH were used and resulted in GI having a higher compressive strength although its specific surface area was smaller than that of F1. The proposed explanation for these contradictory observations is that Na and K form part of the final structure, effectively creating two different geopolymers. This observation is also in accordance with existing knowledge of zeolite chemistry [9]. Comparing the compressive strengths achieved for those samples manufactured from the SASOL fly ash (Table 2) and those from the Tarong fly ash (Table 3) it is evident that the first group exhibits generally much higher compressive strengths and this can be attributed to a number of factors: (a) the higher CaO content [10] of the SASOL fly ash (b) a lower water to fly ash ratio used in the samples made from the SASOL fly ash (c) different alkali metal content of the two fly ashes (d) different A1 and Si content and (e) different solubilities of the AI and Si precursors. The increased carbon content of the SASOL fly ash could be responsible for a decrease in strength as well as increased porosity although it seems to be more than compensated for by the presence of Ca and the fact that less water was used in the initial mix design (Tables 2 and 3).

X-ray diffraction (XRD) and electron microscopy

As mentioned earlier [1] the study of geopolymers using X-ray diffraction is made difficult by the fact that a large part of the structure is amorphous to x-rays. Comparing Figures 1 and 2 with Figures 3 and 4 shows the relatively large amorphous content between 20 and 40 degrees 20. This is much more pronounced in the case of E1 and E2 than in F1 and G1, mainly because of an increased amorphous contribution by unreacted metakaolinite used in the synthesis of E1 and E2. The amount of crystallinity present is caused by quartz and mullite phases present in the fly ash. It can be seen, however, that a certain amorphous content is present in all of the samples and this was further investigated by electron diffraction. As far as

80

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E1 and E2 are concerned the different contaminant metal included in each structure did not seem to make any difference to the crystalline part of the spectra and it is therefore assumed that the metal finds itself bonded into the amorphous part of the matrix. Further proof of this is supplied by the electron diffraction studies as will be discussed below.
2500 2000 1500
0

1000 500 0
I I I I I I I
I I

10

20

30

40

50

60

70

80

90

Degrees

(2-Theta)

Fig.1 X-ray diffraction spectrum of matrix El.

2500 2000 1500 1000 500 0
! I
I I I ! ! I I

IO O

10

20

30

40

50

60

70

80

90

Degrees

(2-Theta)

Fig.2 X-ray diffraction spectrum of matrix E2.

3500 3000 2500
e:S O O

2000 1500 1000 500 0

I I

10

20

I 30

I 40 Degrees

I 50 (2-Thsta)

, 60

i l0

i 80

90

Fig.3 X-ray diffraction spectrum of matrix F1.

Use of geopolymericmaterialsto immobilisetoxic metals:part II

4000 3500 3000 ,!!
: :l (,,1

81

2500 2000 1500 1000 500 0 0

I I I I ! ! ! I I

10

20

30

40

50

60

70

80

90

D e g r e e s (2-Theta)

Fig.4 X-ray diffraction spectrum of matrix G1. Results from the electron diffraction experiments are qualitatively summarised in Tables 6 to 8 for F1, G1 and E1 respectively. In each case the structure, relative abundance and constituent elements of each phase are indicated. In most cases it is possible to quantify most of these phases in terms of d-spacings and semiquantitative compositional information, although such a discussion will form part of a different study and falls outside the scope of the present paper. The electron diffraction study concentrated on newly formed phases and with reference to Figure 5 this can be explained by noting the relatively large unreacted fly ash particles surrounded by newly formed geopolymer phase. Most diffractograms were recorded avoiding obvious unreacted fly ash, kaolinite and metakaolinite particles. In every case the calculated d-spacings proved whether a phase was new or belonging to unreacted components of the initial mix, all of whose dspacings are well documented in the literature. Each phase presented in Tables 6 to 8 therefore constitutes a newly formed structure. Matrix F1 (Table 6) consisted of two main phases and a number of less-abundant phases. Although the two main phases were both amorphous and consisted of essentially the same elements, they were in fact different, containing different ratios of Si and A1. It is also significant to note that the most abundant crystalline phase does not contain any of the added Cu and in fact most of the Cu is contained in the amorphous phases. The presence of Ca in each of the amorphous phases suggests that Ca could be fulfilling a charge-balancing role together with K and Na. Although F1 was synthesised with NaOH the amorphous phases almost exclusively contain K as well, suggesting that K is favoured in a charge-balancing environment to Na and this could explain why matrices containing primarily K seem to have higher compressive strengths compared with those synthesised with primarily NaOH. In the case of G1 (Table 7) and E1 (Table 8) most new phases seem to be amorphous, especially in the case of El, where no semiamorphous or micro-crystallinity was detected. In each case the matrices were synthesised using KOH and in each case the added heavy metal appeared in the amorphous phase. The phases described here also differ from those in the traditional cement field through their fairly high AI content, because traditional cement hydration products usually consist of phases containing either Si or A1. The reason for this can be ascribed to the fact that in most geopolymer mixes an abundance of alkali-metal ions are present which enables the A1 to substitute Si without losing the electronic neutrality of the structure. TABLE 6 Qualitative electron diffraction results for F1 Structure Amorphous Amorphous Crystalline Amorphous Amorphous Amorphous Polycrystallinv Semi-Crystalline Abundance High High Medium Medium Low Low Low Low Composition A1, Si, K, Ca, Cu AI, Si, K, Ca, Cu Al, Si, Na, K, Ca, Fe Al, Cu Al, Si, Na, K, Ca Al, Si, Na, K, Ca, Cu, Fe Al, Si, Na, K, Ca, Cu Al, Si, Cu

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TABLE 7 Qualitative electron diffraction for G1

Structure Amorphous Semi-amorphous to microcrystalline Amorphous

Abundance High High Medium

Composition A1, Si, K, Ca, Cu A1, Si, K, Ca, Cu AI, Si, Na, K, Ca, Fe, Ti

TABLE 8 Qualitative electron diffraction for E1

Structure Amorphous Amorphous Amorphous

Abundance High High Medium

Composition AI, Si, Na, K, Ca, Cu, Ti Al, Si, K, Na, Ca, Cu A1, Si, K, Ca, Cu

Fig.5 TEM micrograph of matrix G1. The micrograph in Figure 6 shows what was typically found for matrices E1 and E2 where the grinding of the sample during preparation for electron microscopy resulted in the amorphous phase being dislodged from the fly ash particles. This is not the case for matrix G1 in Figure 5 where the amorphous phase seems quite securely bonded to the surface of the fly ash particles, even after sample grinding, resulting in a structure with a much higher compressive strength. Infrared (IR) and nuclear magnetic resonance (NMR) In order to gain a better structural understanding, infrared analyses were conducted on El, E2, F1 and G1 and NMR spectroscopy on El, F1, F2 and G1. The main feature of all IR spectra in Figures 7 to 10 is the central peak between 1010 and 1040 cm -~ that is attributed to the Si-O-Si or A1-O-Si asymmetric

Use of geopolymericmaterials to immobilise toxic metals: part II

83

Fig.6 TEM micrograph of matrix El. stretching mode [11]. In the case of F1 and G1 this peak can be found at exactly 1031 cm -~ and it is reasonable to assume that the presence of K or Na would not affect its locality. On the other hand in the case of E1 and E2 this peak is found at 1025 and 1012 cm -~ respectively, indicating that the contaminant metal does affect the structure and suggesting that it might be part of the structure and not just physically encapsulated. The peak found at 543 cm -~ in both Figure 9 and 10 has previously been assigned to bending of Si-O-AI where the AI is in octahedral co-ordination [4] confirming the fact that some kaolinite particles remain unreacted. E1 and E2 exhibit a peak each at 559 cm -1 that has been assigned to be originating from double-ring structures formed by Si and A1 tetrahedra [11]. In all four spectra a small broad peak can be found between 700 and 800 cm -~ although this is more pronounced in the case of E1 and E2 than for F1 and G1. The reason is found in the fact that this region is associated with bonds containing tetrahedrally co-ordinated A1 and specifically Si--O-AI. Again this agrees with the earlier conclusions that structures manufactured from metakaolinite will contain relatively more four co-ordinated A1, not only because of unreacted metakaolinite but also because of easier dissolution of A1 before and during synthesis. This also indicates that in the case of F1 and G1 a degree of dissolution takes place either during or after synthesis as this is the only way that will allow for tetrahedrally co-ordinated A1 to become part of the structure.

1.5
1025
1

u c-

467

,~ 0.5

500

1000

1500 Wavelength (era-l)

2000

25OO

30O0

Fig.7 Infrared spectrum of matrix El.

84 1.5

J.G.S. van Jaarsveld et

al.

1012
0

459

/'~

0.5

500

1000

1500
Wavelength (cm-1)

2000

2500

300O

Fig.8 Infrared spectrum of matrix E2.

2.5 2

=8 1.5
0 .Q

1010~
I ! I I I I

1031

1 0.5 0

500

1000

1500
Wavelength (cm-1)

2000

2500

3000

Fig.9 Infrared spectrum of matrix FI. 2.5 2.

1031 472

~ 1.5

1010]~

0.5
1 ! ! I

500

1000

1500
Wavelength (m-1)

2000

2500

3000

Fig.10 Infrared spectrum of matrix G1. Comparing Figures 11 to 14 and Figures 15 to 18 for matrices El, F1, F2 and G1 it is evident that both the 29Si and the 27A1 MAS NMR spectra are very similar for F1, F2 and G1. The 29Si and 27A1 spectra for E1 differ from these, mainly because of the relatively higher content of tetrahedrally co-ordinated AI. Figure 15 suggests that E1 contains considerably more tetrahedrai AI, denoted by the 58.5 ppm shift, than six coordinated AI, indicated by the 0.1 ppm shift [12]. This is in accordance with what has previously been suggested. The spectra of F1, F2 and G1 exhibit the same peak shifts of 58.5 and 2.2 ppm indicating a mixture of 4 and 6 co-ordinated A1, again confirming and supporting the earlier findings from the TEM and IR analyses. It is worth noting that different alkali and heavy metal ions do not seem to influence either the 29Si or 27A1 spectra. The 29Si spectra for E1 (Figure 11) contain two main shifts i.e. at -90 and -104.2 ppm. The latter has been attributed to Si atoms connected in four directions via oxygen linkages to 3 Si and 1 A1 atom or to only 4 Si atoms, the so called Si(1AI) or Si(1A1) sites [13]. The shift at -90 ppm is again

Use of geopolymericmaterialsto immobilisetoxic metals: part II

85

associated with Si(3A1) sites and it is apparent that not many Si(4A1) sites (-80 to - 9 0 ppm) are present in the spectra of El. This is, however, not the case with the 29Si spectra of F1, F2 and G1 where the two main shifts are -87.3 and -91.9 ppm, indicating an abundance of Si(4AI) and Si(3A1) sites. In terms of structural properties this could explain why the compressive strengths achieved with matrices F1, F2 and G1 were higher than that of E1 and E2. The classical model of a geopolymer as proposed by Davidovits [8] theoretically contains mainly Si(4A1) sites and as such F1, F2 and G1 could be regarded as resembling this model more closely than E1 and E2. The MAS NMR investigation presented here is, however, very simplistic and a more thorough investigation of geopolymers manufactured from waste materials will be necessary to fully quantify all the structural characteristics.

-90 ppm

- 100 ppm

-200

Fig.ll 29Si MAS NMR spectrum of El. -91.9 ppm

-87.3 ppm

-I00 ~m

-200

Fig.12 2aSi MAS NMR spectrum of F1.

86

J.G.S. van Jaarsveld

et al.

-91.9 ppm

-87.3 ppm

I 0

I -100

-200

ppm
Fig.13 29Si MAS NMR spectrum of F2.

-91.9 ppm

-87.3 ppm

I 0

I -100 ppm

I -200

Fig.14 29Si MAS NMR spectrum of G1.

Use of geopolymericmaterials to immobilise toxic metals: part II

87

58.5 ppm

200

0 ~m

-200

Fig.15 27A1 MAS NMR spectrum of El.

2.2 ppm

58.5 ppm

200

0 ppm

-200

Fig.16 27A1 MAS NMR spectrum of F1.

88

J . G . S . van Jaarsveld et al.

2.,' ppm

58.5 ppm

I 200

I 0 ppm

I -200

Fig.17 27A1MAS NMR spectrum ofF2.

2.2 ppm

58.5 ppm

I 200

I 0 ppm

I -200

Fig.18 27A1 MAS NMR spectrum of G1.

Use of geopolymeric materials to immobilise toxic metals: part II

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Leaching
In a previous study [3] the potential of geopolymer binders for the immobilisation of heavy metals was discussed and environmental leaching results presented. Kinetic leaching tests were conducted with sampling done periodically until equilibrium was reached. Matrices El, F1 and G1 contain identical amounts of Cu and therefore leaching results can be compared on the same basis. Figure 19 shows the leaching curves for five particle size fractions of H2 and for the sake of simplicity all other leaching tests will be summarised in terms of the equilibrium values obtained. These results are presented in Tables 9 and 10.
10 9

8
A

E Q.
Q.
v

7 6 5 4 3 2 1 0 0 200

I::

g
c Q o e,. o
0

212-600 --.m~ 600-1000 ~ 1000-1700 1700-2360 x 2360-28O0

,.Q n

400

600

800 Time (min)

1000

1200

1400

1800

Fig. 19 Leaching curve of H2. Leaching in acetic acid buffered at pH 3.3, solid/liquid ratio 1:25, 30C and mixing speed of 200 rpm.

TABLE 9 Equilibrium concentrations achieved during leaching (ppm)

Matrix Element Cu Pb Cu Cu 212/600 ~tm Stirred Rolled bottle 22 23 17 12 30 34 24 20 1700/2360 ~tm Stirred R o l l e d bottle 17 17 11 9

E1 E2 F1 G1

28 33 22 17

TABLE 10

Equilibrium concentrations for different particle size fractions using stirred leaching configuration (ppm)
Contaminantt 212/600 I.tm 60011000 gm 100011700 gm 170012360 rtm 2360/2800 gm

Matrix

H1 H2 H3 I"t4

Cu Pb Pb Cu

26.1 9.1 14.8 17.1

21.2 8.9 13.3 14.1

20.3 8.6 11.6 11.1

19.2 8.4 9.8 7.5

18.5 8.2 9.2 6.3

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J.G.S. van Jaarsveldet

al.

It is significant to note that for E1 and E2 the Pb ions always seem to leach slightly more than the Cu, regardless of the particle size and leaching method used. This fact is probably due to the larger surface area measured in E2 compared with E1 although comparison of F1 and G1 does not follow the same trend where Cu leaching from G1 is generally less than from F1, with the latter having half the specific surface area. On the other hand G1 has a higher compressive strength and one would expect a higher abrasion resistance than in the case of El, E2 or F1. The leaching of Cu from El, F1 and G1 follows the same trend as their respective compressive strengths and this suggests that abrasion plays a role in liberating some of the metal during leaching. An increase in equilibrium leaching values with decreasing particle size is a feature that is found for all matrices and this further supports the above statement that some liberation occurs form particle surfaces, whether through mechanical or chemical means. It was shown previously [3], however, that a certain amount of leaching also occurs as a result of pore diffusion and this aspect needs to be investigated further. The differences in leaching of Cu from F1 and G1 as well as differing surface areas and strengths again point to the fact that the type of alkali metal cation has an important influence on all aspects of the final structure. This is further supported by the fact that equilibrium values for the rolled bottle experiments were generally higher than those found for the stirred type method. This is most probably due to the longer leaching time (60 hours) as well as the fact that abrasion between particles and the side of the vessel is much more severe than in the case of the latter method leading to higher degree of physical breakdown. Visual observation of the solid residue from the leaching experiment also confirmed this. Table 10 shows that increased leaching from smaller particle sizes holds for the range of matrices and particle sizes investigated although certain trends appear to be different from those obtained for El, E2, FI and G1. As was previously reported [3] the immobilisation of Pb in matrices not containing metakaolinite seems to be more efficient than for Cu and this could be in part attributed to differences in ionic radius or chemical interaction with the other matrix forming components during synthesis resulting in slightly different roles played by Cu and Pb in the final product. It was mentioned earlier that Cu is present in most of the newly formed amorphous phases. Unfortunately this could not be confirmed for lead due to equipment limitations. One could safely assume, however that any matrix will have a limited capacity for the amount of heavy metal its structure can tolerate before structural failure will cause increased leaching of that metal. This point is illustrated by comparing the differences in leaching of Cu and Pb from matrices HI, H2, H3 and H4. Although H1 and H2 were synthesised with KOH, and H3 and H4 with NaOH, the latter group also contains double the amount of heavy metal introduced into the first. At smaller particle sizes H3 releases less Pb than the Cu released by H4 although this trend is reversed when the larger particle size fractions are considered. This trend is not present in the case of H1 and H2 where the Cu always leaches more than the Pb. Referring to Table 5 the specific surface area of Cu containing matrices H1 and H4 is smaller than that of their Pb-containing counterparts although the latter seem to generally have a higher immobilisation efficiency.

CONCLUSIONS The study and structural understanding of geopolymers derived from waste materials will become more essential as the number of commercial applications of these materials increases. From this study it is not only apparent that a multitude of possible applications exist but also that this technology can be applied to waste sources from different parts of the world. From a structural point of view it is possible to manufacture materials with fairly high compressive strengths and the capacity to also immobilise heavy metals. It was also shown that total dissolution of the waste materials is not necessary and that the solidified waste material consists of an amorphous phase bonded to the surfaces of unreacted waste particles. In the case where a system such as this is utilised for the immobilisation of heavy metals, the immobilisation proceeds through a combination of physical encapsulation and chemical bonding into the amorphous phase of the matrix. It does not seem as if the heavy metal influences the basic tetrahedral building blocks of the structure although it influences the structure in a physical manner such as to alter the compressive strength and specific surface area. Finally the presence of Si(4AI) sites is preferred if a strong durable product is desired although this situation can only be achieved where substantial amounts of charge balancing ions are available. K and Na usually fulfil this role although geopolymers manufactured from fly ash containing some Ca compounds have higher compressive strengths than those without. It is finally worth noting that both the physical and

Use of geopolymericmaterialsto immobilisctoxic metals:part I1

91

chemical properties of the final product will be interdependent on not only the waste materials used in synthesis but also the curing conditions as well as effects introduced by the presence of any heavy metals immobilised in the structure.

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3.

6. 7.
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10. 11. 12. 13.

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