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Construction and Building

Construction and Building Materials 19 (2005) 265274

MATERIALS
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Density and exural strength of phosphogypsumpolymer composites


C.J.R. Verbeek
a

a,*

, B.J.G.W. du Plessis

Department of Materials and Process Engineering, University of Waikato, Private Bag 3105, Hamilton, New Zealand b Department of Chemical Engineering, University of Pretoria, Lynwood Road, Pretoria, 0002, South Africa Received 31 August 2003; received in revised form 20 July 2004; accepted 21 July 2004 Available online 8 September 2004

Abstract The objective of this research was to characterize the mechanical properties of phosphogypsumpolymer composites as aected by the amount of resin, the amount of vermiculite and the particle size distribution of the vermiculite. Using 50% resin and a high ratio of coarse to ne particles resulted in the lowest density and highest strength composites. Better packing of particles in the composite improves the strength of the composite, but increases its density. It was found that the use of CaSO4 1 H O is inecient in 2 2 these composites and it yielded consistently lower strengths than its hydrated phosphogypsum counterpart. It was concluded that only 10% resin can be tolerated in the hydrated CaSO4 1 H O matrix because the resin interferes with the curing. The phosphogyp2 2 sumpolymer composites, produced in this study, had exural strengths above those of standard hydrated gypsum products and had slightly lower densities. Taking into account the expense of converting and cleaning the phosphogypsum to the hemi-hydrate form, this result is therefore positive in light of producing cheap light weight alternative gypsum-based building products. 2004 Elsevier Ltd. All rights reserved.
Keywords: A: Particle-reinforced composites; Structural materials; Polymermatrix composites; B: Strength

1. Introduction The building industry utilizes a lot of materials in large buildings as well as for smaller constructions, such as houses. In these projects the need for ame resistant, light weight and high strength materials is common. Applications of such materials range from wall panels, door skins and door cores to roof tiles and ceiling boards. A vast variety of conventional materials exist, each with unique applications and properties. These would include wood, wood composites and various gypsum products. As we strive towards a cleaner environment, we are continuously faced with the challenge to re-use materials as well as converting waste materials into more useful materials [1]. Alternative materials

Corresponding author. Tel.: +64 7 838 4947; fax: +64 7 8384835. E-mail address: jverbeek@waikato.ac.nz (C.J.R. Verbeek).

may include polymer composites of waste materials such as magnetite, phlogopite, vermiculite (not a waste, but cheap) and calcium phosphate di-hydrate [14]. These materials are successful because they can be manufactured to be lightweight as well as relatively strong, while utilizing waste materials from other industries. Vast quantities of phosphogypsum are available as a by-product from the phosphate fertilizer industry. Phosphogypsum is in the di-hydrate form and is contaminated with phosphoric acid and some other substances. It is a costly process to clean-up this gypsum and to calcine the di-hydrate to the hemi-hydrate form. The hemi-hydrate form is used in known products such as Plaster of Paris. It has been shown that some thermoplastic and thermosetting polymers can be used as binder for various inorganic, particulate materials, such as minerals [57]. Costly calcining of phosphogypsum can therefore be avoided by this alternative binding mechanism. The only drawback, using phosphogypsum is problems associated with radioactivity. This causes

0950-0618/$ - see front matter 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.conbuildmat.2004.07.011

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C.J.R. Verbeek, B.J.G.W. du Plessis / Construction and Building Materials 19 (2005) 265274

harmful radon emissions and therefore precludes indoor use of phosphogypsum in counties like the United States. These materials would therefore target outdoor or well ventilated applications. A vast amount of literature describes the factors that inuence the behaviour of particulate lled polymer composites [3,4,8]. The most important factors are the amount of binder, the surface properties of the inorganic particles and the particle size or aspect ratio thereof. The density of phosphogypsum is often too high for building applications and it has a relatively low exural strength [9]. To overcome this, exfoliated vermiculite can be used to lower the density of the composite. Vermiculite is a siliceous mineral, consisting of several crystal layers. The layers are weakly bound and can therefore be exfoliated, resulting in a very low density product. The objectives of this study are:  to produce phosphogypsumpolymer composites of similar strength to that of cured Plaster of Paris, but with lower density and  to characterize the mechanical properties of these composites, as aected by the amount of resin, amount of vermiculite and the particle size distribution of the vermiculite. Thermosetting polymers are most attractive for use in such composites for their ease of processing with the gypsum and vermiculite. At room temperature, phenolformaldehyde cures with in three minutes, which makes it an attractive binder in this study. Although the cost of polymers is high, cheaper alternatives may be considered and studies have shown that cheaper phenol formaldehyde resins can be manufactured from waste materials [10]. Phenol can also be substituted by cashew-nut-shell oil, which will render the composites more water resistant. Factors not considered in this study include the ammability of the material, but this can be addressed by judicious use of ame retardant additives.

Factors that can aect the strength of the phosphogypsum composite are:  the percentage resin used (%R),  the ratio coarse to ne vermiculite particles (dp), and  the ratio gypsum to vermiculite in the composite (GV). For comparative purposes, commercial calcium sulphate hemi-hydrate and phosphogypsum were used in separate experiments. Fig. 1 illustrates the various experiments performed to characterise the inuence of these factors on the composite performance. Preliminary experiments were performed to establish the eect of binary mixtures of the resin, gypsum and vermiculite. These are numbered Experiments 15 and are listed in Table 1. When hemi-hydrate gypsum is used, water is also needed for hydration and was included as an additional variable in those experiments. Experiments 6 and 7 were designed to investigate the combined eect of the resin, gypsum and vermiculite. For Experiment 6 phosphogypsum was used, whereas for Experiment 7 calcium sulphate hemi-hydrate was used. For both these experiments a fractional factorial experiment was designed according to the Taguchi method [12], using a L8 orthogonal array. The designs for these two experiments are shown in Tables 2 and 3, respectively. 2.1. Sample preparation and testing All samples were prepared by homogenising gypsum/ vermiculite mixtures in a high-speed mixer, after which the appropriate amount of resin, catalyst and water were added. This mixture was then homogenised in a planar mixer. The amount of resin reported always includes the RESOL and the appropriate amount of catalyst.

2. Materials and methods In accordance to the set objectives, four materials were selected for their specic properties and intended contribution to the properties of the nal composite. These were: phosphogypsum (obtained from Foskor Ltds mining operation in Phalaborwa, South Africa [11]), phenol formaldehyde resin (commercial resol and activator supplied by HA Falchem, South Africa), vermiculite (Phalaborwa, South Africa, supplied by Mandoval Ltd.) and commercially available calcium phosphate hemi-hydrate. The vermiculite was supplied at 300 lm (coarse particles) and 100 lm (ne particles).
3

CaSO4 H2O
2 7 5 6 4

CaSO4 2H2O
No binder

Fig. 1. Summary of experimental layout.

C.J.R. Verbeek, B.J.G.W. du Plessis / Construction and Building Materials 19 (2005) 265274 Table 1 Preliminary experiments Exp. # 1.1 1.2 1.3 2.1 2.2 2.3 2.4 3.1 3.2 3.3 4.1 4.2 4.3 5.1 5.2 5.3 5.4
*

267

% Resin

% Gypsum 100 100 100 25 50 25 50

Coarse: ne vermiculite

%Verm.

Gypsum:H2O 1:0.8 1:0.6 1:0.3

1:3 1:3 3:1 3:1

75 50 75 50

1:0.6

10 30 50 10 30 50 25 50 25 50 Phosphogypsum.

90 70 50 90* 70* 50*


*

1:0.6

1:3 1:3 3:1 3:1

50 75 50

Table 2 L8 orthogonal array [1] for phosphogypsum composites


Level 2

Table 3 L8 orthogonal array [1] for phosphogypsum composites


Level 2

1 : 0.8 1 : 0.6

50%

3:1

50%

3:1

3:2

Level 1

25%

1:3

Level 1

25%

1:3

N/A

N/A

N/A

4:1

3:2
N/A

N/A

Ratio Coarse to fine vermiculite

Ratio Coarse to fine vermiculite

Ratio gypsum to vermiculite

CaSO4H2O : H 2O

Ratio gypsum to vermiculite

Variable description

Variable description

4:1

Interaction: Column 1 x 2

Interaction: Column 2 x 3

Interaction: Column 1 x 2

Interaction: Column 2 x 3

Interaction: Column 1 x 3

% Resin

* Composite broke under own weight

% Resin

Exp # 1 2 3 4 5 6 7 8

1 1 1 1 1 2 2 2 2

2 1 1 2 2 2 2 1 1

Column 3 4 1 2 2 1 2 1 1 2 1 1 2 2 1 1 2 2

5 1 2 1 2 1 2 1 2

6 1 2 2 1 1 2 2 1

Results Density Strength (kg/m3) (MPa) 1000 0.00* 1023 2.09 1294 4.34 1221 2.04 807 2.86 1056 5.42 986 3.04 737 1.28

Exp #

1 1 1 1 1 2 2 2 2

2 1 1 2 2 2 2 1 1

3 1 2 1 2 2 1 2 1

Column 4 1 2 2 1 2 1 1 2

Interaction: Column 1 x 3

N/A

5 1 1 2 2 1 1 2 2

6 1 2 1 2 1 2 1 2

7 1 2 2 1 1 2 2 1

1 2 3 4 5 6 7 8

Results Density Strength 3 (kg/m ) (MPa) 977 2.00 885 0.99 1088 2.68 833 2.19 864 0.71 822 1.31 879 1.83 751 0.62

Samples of 400 g each were then compressed in a 150 mm 200 mm mould at a standard pressure of 1 MPa. Composites were left to cure at room temperature for 24 h. Samples of 30 mm 150 mm were then cut from these sheets for exural testing, using a Lloyd instrument LRX-Plus. All four-point bending tests were performed according to ASTM D790-81, with a crosshead speed of 10 mm/min.

3. Results and discussion Each of the selected variables aects the performance of the composite dierently. The resin is primarily used as binder for the particulate vermiculite and gypsum and it can therefore be suspected that it will inuence the strength of the composites to a large extent. Without resin, however, no mechanical properties can be observed

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due to the absence of a continuous structure in the particulate phosphogypsum. If calcium sulphate hemi-hydrate is used, the hydration process will yield a continuous structure, in which case the resin could act as a strength enhancement. Exfoliated vermiculite will reduce the density of the composite. Although it is known that most volumetric extenders tend to reduce the strength of lled polymers, the extent to which the strength is reduced may depend on the particle size distribution of the vermiculite. Each factor will be evaluated in terms of its main effect on the materials: (a) density, which should be as low as possible and (b) exural strength, which should be as high as possible. These two requirements are conicting and often the same factor or factor level that will increase the density may, at the same time, decrease the exural strength.

3.1. Phosphogypsumpolymer composites The specic results on strength and density for the trials in Experiment 6, are presented in Table 2. The interaction and main eects are shown in Figs. 2 and 3. The analysis of variance (ANOVA), shown in Table 4, revealed that all the main parameters contributed significantly to the density of the composite and that the interaction between the particle size distribution and the gypsum to vermiculite ratio is negligible. In Table 5 it can also be seen that the ratio of gypsum to vermiculite did not contribute signicantly to the exural strength of the material, but its interaction with the amount of resin did. It was also found that all other interactions were negligible at a 90% level of condence. 3.1.1. Percentage resin In Fig. 2, the main eect of the percentage resin indicates that an increase in resin content resulted in a decrease in density. This is perceived as a positive eect

1200 1100
Density (Kg/m3)

1000 900 800 700 600


1 2 1 2 1 2 1 2 1 2 1 2 % Resin (%R) Ratio coarse to fine vermiculite (dp) Ratio gypsum to vermiculite (GV) interaction %R x dp interaction dp x GV interaction %R x GV

Parameter and level


Fig. 2. Main and interaction eects of parameters tested with respect to density of phosphogypsumpolymer composites.

4 3.5

Strength (MPa)

3 2.5 2 1.5 1 0.5 0 1 2 1 2 1 2 1 2 1 2 1 2


% Resin (%R) Ratio coarse to fine vermiculite (dp) Ratio gypsum to vermiculite (GV) interaction %R x dp interaction dp x GV interaction %R x GV

Parameter level
Fig. 3. Main and interaction eects of parameters tested with respect to exural strength of phosphogypsumpolymer composites.

C.J.R. Verbeek, B.J.G.W. du Plessis / Construction and Building Materials 19 (2005) 265274 Table 4 ANOVA table for density (phosphogypsumpolymer composites) Factor % Resin (%R) Ratio coarse: ne vermiculite (dp) Ratio gypsum to vermiculite (GV) Interaction %R dp Interaction dp GV Interaction %R GV Error DOF F Percentage contribution 46.3 20.3 8.2 6.2 18.0 1.0

269

1 352 1 155 1 63 1 48 Factor pooled 1 138 2

error R x GV

R x dp

%R

GV

dp
Total 7 100 F1,2 = 8.53

Table 5 ANOVA table for strength (phosphogypsumpolymer composites) DOF % Resin (%R) Ratio coarse: ne vermiculite (dp) Ratio gypsum to vermiculite (GV) Interaction %R dp Interaction dp GV Interaction %R GV Error F Percentage contribution 10.3 41.6

1 46 1 183 Factor pooled Factor pooled Factor pooled 1 204 4

error

%R

46.5 1.6

R x GV dp

Total

100

F1,4 = 4.54

in terms of producing low density composites. ANOVA also revealed that the percentage resin is the most important factor, contributing 46.3% to the density of the composite. The density of the resin is considerably less than that of phosphogypsum. It therefore might seem logical to simply increase the amount of resin in order to decrease the density. Although this strategy will result in lower densities, the aim is to maximise phosphogypsum utilization. The amount of resin used also strongly inuences the exural strength of the composite. This is, however, not the most important factor inuencing exural strength. The interaction of the amount of resin with the ratio gypsum to vermiculite is more prominent than the percentage resin alone. This is due to the vermiculite acting only as a volumetric extender, i.e. when more vermiculite is used there is more porosity in the composite and hence the strength will decrease. The advantage of a

lower density is therefore compromised by the lower exural strength. The eect of the amount of resin was also investigated in Experiment 4 and is presented in Fig. 4. It
1600 1400 1200 1000 800 600 400 200 0 20 30 40 % Resin 50 16 14 12 10 8 6 4 2 0

Fig. 4. The eect of percentage resin on the density and exural strength of phosphogypsumpolymer composites (Experiment 4).

Density (Kg/m )

Strength (MPa)

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C.J.R. Verbeek, B.J.G.W. du Plessis / Construction and Building Materials 19 (2005) 265274

can clearly be seen that more resin binds the gypsum more eciently thereby increasing the exural strength. In this case the change in density is only due to the difference between the density of phosphogypsum and the resin and is much less pronounced than the change in exural strength. 3.1.2. Ratio coarse to ne vermiculite particles The ratio in which particles of dierent sizes are mixed, determines the packing eciency thereof and hence the density and the strength of the composite. ANOVA (Table 4) revealed that the ratio coarse to ne particles contributed 20% to the change in density of the composites. Fig. 2 shows that a high ratio of coarse to ne particles resulted in a higher density. When a high ratio is used the ner vermiculite as well as phosphogypsum particles can occupy the spaces between the larger particles. Improved packing eciency will also result in improved exural strength. The main eect of the ratio coarse to ne vermiculite was dominant and contributed 42% towards the change in exural strength (Table 5). This is, however, misleading and only true for the range in which these composites were tested. Normally larger particles would rather act as a point on discontinuity, which leads to stress concentrations and hence lower exural strengths. The fact that phosphogypsum also took up the voids between the larger vermiculite particles overshadowed the negative eect of larger particles. For the same reason the interaction between the ratio coarse to ne particles and the ratio gypsum to vermiculite is negligible for both density and strength. The density and strength of composites prepared by only vermiculite and resin (Experiment 5), are shown in Fig. 5. In this case the resin is denser than exfoliated vermiculite. The decrease in density when using more resin is therefore most likely due to some of the resin being absorbed into the exfoliated vermiculite. Un-exfoliated vermiculite has a much higher density than the resin and therefore the composite density will decrease when using more resin. The smaller particles will also tend to absorb more resin and therefore using a high ratio coarse to ne particle will result in a lower density.

The strength of these composites is inuenced in a similar manner. When resin is absorbed into the vermiculite it facilitates better stress transfer. Therefore, when the amount of polymer is increased the composite strength is increased. In the case of the high ratio coarse to ne vermiculite particles, less resin is absorbed and by increasing the amount of resin the strength of the composite is not increased, due to the reduced density of the composite. 3.1.3. Ratio phosphogypsum to vermiculite Exfoliated vermiculite has a considerably lower density than phosphogypsum. Using a lower ratio phosphogypsum to vermiculite will therefore result in a lower density. This factor, however, contributes only 8% to the change in density and was found to be insignicant in terms of exural strength. This factor does however shows major interaction eects, as evident from Figs. 2 and 3. The interaction with the percentage resin contributed 18% with respect to density and 46% in terms of the exural strength. This interaction eect can be expected to be very prominent. When using a low amount of resin, little binder is available and this results in low strength. When combined with a high ratio of coarse to ne particles the eect is amplied because of the reduction in density (higher porosity) and the fact that vermiculite cannot contribute to the strength of the composite. Optimal performance is therefore achieved by using as little as possible vermiculite and enough resin to ensure proper binding of all particles. 3.2. CaSO4 1 H Opolymer composites 2 2 In this section the performance of composites manufactured from CaSO4 1 H O was evaluated. It was 2 2 found that generally weaker composites formed as compared to similar formulations, using phosphogypsum. It is suspected that this lower strength material is due to the incompatibility between water and the resin. The large quantity of water necessary for hydration causes phase separation before and during curing and therefore, low strength composites are formed. It was found that the factors inuencing composite properties the most are the percentage resin and the interaction between the particle size distribution and the ratio gypsum to vermiculite. Each of these factors will be discussed separately in subsequent paragraphs. To explain the behaviour of these composites and to establish a reference, it was decided to also prepare hydrated gypsum sheets with no additives. The amount of water used for hydration was varied and the results of Experiment 1 are shown in Fig. 6. By using more than the stoichiometric amount of water, the density and strength of the gypsum sheets are reduced. By using too little water, the workability of the gypsum paste be-

1000

800 600 400 200 0 20

25% Coarse 75% Coarse

(a)

30 40 % Resin

50

2800 2400 2000 1600 1200 800 400 0

Density (Kg/m3)

Strength (kPa)

25% Coarse

75% Coarse

20

(b)

30 40 % Resin

50

Fig. 5. Eect of percentage resin and particle size distribution on the density (a) and strength (b) of vermiculite/resin composites.

C.J.R. Verbeek, B.J.G.W. du Plessis / Construction and Building Materials 19 (2005) 265274

271

1600 1400 1200 1000 800 600 400 200 0


0.3 0.6 0.8

4 3.5 3 2.5 2 1.5 1 0.5 0 water content (g/g)

Fig. 6. Density and exural strength of hydrated CaSO4 1 H O using 2 2 various quantities of water.

ANOVA (Table 6) revealed that the percentage resin and the amount of water used contributed signicantly to the change in density. The interaction of the percentage resin with the particle size distribution was found to be insignicant. For exural strength, ANOVA (Table 7) revealed that the percentage resin and the ratio gypsum to vermiculite were the only factors that contributed signicantly at a 80% level of condence. The signicant interaction parameters were found to be the interaction of particle size distribution with the percentage resin as well as with the ratio gypsum to vermiculite. 3.2.1. Percentage resin The percentage resin contributed 35.5% to the change in density of these composites. However, the interaction between the particle size distribution and the ratio gypsum to vermiculite was more important. The resin has a lower density than gypsum and therefore, an increase in resin content leads to a decrease in density. In contradiction with what was found with the phosphogypsum composites, the strength of these composites decreased when more resin was used. This result is most likely due to the resin interfering with the crystal formation

Density (Kg/m )

comes problematic, and the strength often decreases, as can be seen from the graph. The behaviour of the composites containing resin and vermiculite is much more complex and each factor warrants its own discussion. The results of each trial in Experiment 7 are presented in Table 3. The main eects of each factor, with respect to density are shown in Fig. 7, while that of exural strength are presented in Fig. 8.

1000 950

Density (Kg/m3)

900 850 800 750 700 650


1 2 1 2 1 2 1 2 1 2 1 2 1 2
% Resin (%R) Ratio coarse to fine vermiculite (dp) % H20 Ratio gypsum to vermiculite (GV) interaction %R x dp interaction dp x GV interaction %R x GV

Fig. 7. Main and interaction eects of parameters tested with respect to density of CaSO4 1 H Opolymer composites. 2 2

2.5 2

Strength (Mpa)

1.5 1 0.5 0
1 2 1 2 1 2 1 2 1 2 1 2 1 2
Ratio coarse to fine vermiculite (dp) interaction %R x dp interaction dp x GV interaction %R x GV

% Resin (%R)

Strength (MPa)

% H20

Ratio gypsum to vermiculite (GV)

Parameter and level


Fig. 8. Main and interaction eects of parameters tested with respect to exural strength of CaSO4 1 H Opolymer composites. 2 2

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Table 6 ANOVA table for density (CaSO4 1 H Opolymer composites) 2 2 Factor % Resin (%R) Ratio coarse: ne vermiculite (dp) % Water for hydration Ratio gypsum to vermiculite (GV) Interaction %R dp Interaction dp GV Interaction %R GV Error DOF 1 Factor pooled 1 Factor pooled Factor pooled 1 1 3 F 75 11 Percentage contribution 35.5 4.2

error %R x GV %R

92 21

43.7 9.3 7.3

dp x GV
Total 7 100 F1,2 = 3.56

% Water

Table 7 H Opolymer composites) ANOVA table for strength (CaSO4 1 2 2 Factor % Resin (%R) Ratio coarse: ne vermiculite (dp) % Water for hydration Ratio gypsum to vermiculite (GV) Interaction %R dp Interaction dp GV Interaction %R GV Error DOF 1 Factor pooled Factor pooled 1 1 1 Factor pooled 3 F 8 Percentage contribution 32.0

4 4 3

12.6 12.2 9.5 33.7

error

%R

dp x GV R x dp
Total 7 100 F1,3 = 2.68

GV

of the CaSO4. ANOVA also revealed that the percentage resin had the largest contribution to the exural strength of these composites. To verify this, composites of only resin, CaSO4 1 H O and the required amount of 2 2 water for hydration was prepared (Experiment 2), the results of which are shown in Fig. 9. The results presented in this gure conrm what was found in Experiment 7. It can be seen from the gure that a maximum of 10% resin can be tolerated by the gypsum matrix before the strength drops signicantly. At 50% resin the composite failed under its own weight. It is likely that above 10% resin the formation of a crystal structure is very dicult and due to the presence of a large amount of water, the resin is unable to bind the CaSO4 particles. Two possible interactions with the percentage resin exist. These are the interaction with the ratio gypsum to vermiculite (%R GV) and the interaction with the

1200
Density (Kg/m3)

6.00 4.00 3.00 2.00 1.00 0.00 0 10 20 % Resin 30


Strength (MPa)

1000 800 600 400 200 0

5.00

Fig. 9. Density of strength of hydrated CaSO4 1 H O using various 2 2 H O. quantities of resin and 0.6 g water/g CaSO4 1 2 2

particle size distribution (%R dp). Of these, the former was only signicant with respect to density and the latter with respect to strength. The interaction of the percentage resin with the ratio gypsum to vermiculite contributed 9.3% to the change in

C.J.R. Verbeek, B.J.G.W. du Plessis / Construction and Building Materials 19 (2005) 265274

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density. In light of earlier discussions, this interaction seems correct. Using more resin and more vermiculite, will result in a composite with lower density. Although this combination of factors seemingly results in a composite with low strength, this interaction eect was found to be negligible with respect to exural strength. With respect to exural strength it was found (Table 7) that the interaction of percentage resin with the particle size distribution contributed 12.2% towards the main eect. It is also evident that using more coarse particles (dp level 2) and more resin (% resin level 2) results in a composite with highest strength. Better packing can be achieved with a high ratio coarse to ne particles and hence the binder is more ecient which results in a higher strength. 3.2.2. Particle size distribution This factor was found to be insignicant towards both density and exural strength, but its interactions not. The interaction of the particle size distribution with the ratio gypsum to vermiculite was found to be the most important aspect of the composite with respect to density, contributing 44% to the main eect. By using more vermiculite, with a smaller average particle size, a lower density composite is produced. At the same time, however, the weakest composite is produced. For optimal exural strength more gypsum should be used (i.e., high gypsum to vermiculite ratio). This result is similar to that of Experiment 6, since vermiculite is not a reinforcement, but a volumetric extender. 3.2.3. Gypsum to vermiculite ratio This factor on its own showed an insignicant eect on density, and only a small eect on exural strength. This was also the case with the phosphogypsum composites. The interactions of this factor, however, are more pronounced. The interaction with the particle size distribution was discussed earlier, but some further insight can be gained by examining the results of Experiment 3 presented in Fig. 10. In this experiment vermiculite, at dierent particle sizes, was used as volumetric extender to cured CaSO4 1 H O, without any resin. 2 2

The most important observations from these graphs are that the particle size distribution has very little eect on either density or strength and that the density and strength of the composites are higher when more vermiculite is present. This behaviour is slightly dierent to what is expected. It is known that exfoliated vermiculite can absorb a large amount of liquid. If the porosity of the vermiculite is therefore lled by the slurry of gypsum and water, prior to hydration, it is possible that the low density of the vermiculite is lost. By increasing the amount of vermiculite will, therefore, lead to higher densities. In this case, the vermiculite may act as a reinforcement. The extent to which this eect is present in the other composites is negligible in terms of density and the reverse is true in terms of strength when a resin binder is also included. 3.2.4. Percentage water used for hydration Although this parameter proved to be very important for hydrating CaSO4 1 H O (Experiment 1), the eect 2 2 thereof on the exural strength of the composites produced in Experiment 7 was negligible. It also only had a minor eect on the composites density. Other eects, such as the packing density and possible phase separation over shadows the eects introduced by varying the amount of water used for hydration.

4. Conclusions The exural strength and density of calcium phosphate composites are inuenced by several factors. These were the amount of phenol formaldehyde used as binder, the particle size distribution of the vermiculite used and the amount gypsum in the nal product. It was found that as far as the phosphogypsum composites are concerned, using more resin and a high ratio of coarse to ne particles result in the lowest density and highest strength composites. It was also found that not all factors mentioned above contribute directly to the performance of the composites, but that the interactions between them are often more important. This was the case with the ratio gypsum to vermiculite where the factor alone was insignicant, but its interaction with the amount of resin used was. It was also found that the properties of the composite are strongly dependent on the particle size distribution (ratio coarse to ne particles) of the vermiculite. This relates primarily to the packing density that can be achieved and it was found, in all cases, that a better packing density improves the strength of the composite, but increases its density. In addition to the importance of these factors the exural strength of the phosphogypsum composites was increased by increasing the resin content. The hemi-hydrate composites showed opposite behaviour

1000

2000
Strength (kPa)
25% Coarse 75% Coarse

Density (Kg/m3)

800 600 400 200 0 20

1600 1200 800


25% Coarse 75% Coarse

400 0 20 30 40 50 % Vermiculite

(a)

30 40 50 % Vermiculite

(b)

Fig. 10. Density (a) and exural strength (b) of hydrated CaSO4/ vermiculite composites.

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and it was concluded that the resin interferes with the curing of the gypsum and only 10% resin can be tolerated in the gypsum matrix. It was found that the use of hemi-hydrate calcium phosphate is inecient in these composites and it yielded consistently lower strengths than its di-hydrate counterpart. Composites produced in this study had exural strengths above that of standard hydrated gypsum products with slightly lower densities. Taking into account the expense of converting di-hydrate to the hemi-hydrate form, this result is therefore positive in light of producing cheap light weight alternatives for gypsum-based building products. References
[1] Savastano H et al. Plant bre reinforced cement components for roong. Constr Build Mater 1999;13:4338. [2] Hernandez-Olivares F et al. Development of corkgyspum composites for building applications. Constr Build Mater 1999;13: 17986.