Journal

J. Am. Ceram. Soc., 81 [6] 155056 (1998)

Effect of Water Content on the Structure and Mechanical Properties of MagnesiaPhosphate Cement Mortar
David A. Hall and Ronald Stevens*,
Ceramics Division, School of Materials, University of Leeds, Leeds, LS2 9JT, United Kingdom

Bayhass El Jazairi
Feb MBT, Swinton, Manchester, M27 1DT, United Kingdom

Magnesiaphosphate cement mortars, based on magnesia and ammonium dihydrogen orthophosphate, were prepared with water contents (measured as a weight fraction of the dry material) in the range 5% to 12%. It was shown by XRD that the major reaction product was magnesium ammonium phosphate hexahydrate (MgNH4PO4 6H2O), also known as the mineral struvite. Evidence was also found to suggest the presence of an amorphous or poorly crystalline phase with a lower degree of hydration in materials prepared with water contents less than 8%. For higher water contents, the excess water gradually evaporated during aging to leave an interconnected fine porous structure which exhibited poor mechanical properties. An increase in the water content from 5% to 12% also led to a significant increase in the crystallite size, from around 0.5 m to 10 m. I. Introduction

mortar based on magnesia (MgO) and ADP (ammonium dihydrogen orthophosphate, NH4H2PO4) was magnesium ammonium phosphate hexahydrate (MgNH4PO4 6H2O), also known as the mineral struvite: MgO + NH4H2PO4 + 5H2O MgNH4PO4 6H2O (1)

AGNESIAPHOSPHATE cements (MPC) are based on the chemical reaction of an aqueous acidic ammonium phosphate solution with a solid basic magnesia powder. On mixing, acidbase reactions lead to the formation of insoluble magnesium ammonium phosphate hydrates, which constitute the binding phase in the hardened cement. The commercial importance of this cement system was recognized in a patent granted in 1947.1 Subsequently, such materials have found applications as casting investment in dentistry,2,3 cold-setting refractory gunning mixes,4 and in the rapid repair of concrete paving.5,6 A number of different chemical formulations have been proposed, but in general all specify the use of a relatively unreactive fused or dead-burned magnesia powder with a watersoluble ammonium ortho- or polyphosphate. Most of the systems described in the literature have also contained a large proportion of inert filler (often silica-based) and a set-retarder in order to control the exothermic setting reactions. As a result of the current commercial applications of these materials, there has been a growing interest in the physical and chemical nature of the hardened cement, as well as the chemistry of the setting reactions.7 Abdelrazig et al.8,9 reported that the principal reaction product occurring in a commercial MPC

This compound was first reported in nature in guano deposits, where the ambient conditions and the availability of the appropriate chemical species initiated its precipitation from aqueous solution.10 Subsequently, struvite has been observed as an important constituent of human urinary and renal calculi and consequently much work has been conducted in order to clarify the various regimes of pH and chemical concentrations over which its formation is favored.11 Two other reaction products, MgNH4PO4 H2O (dittmarite) and Mg(NH4)2(HPO4)2 4H2O (schertelite), were observed to form in MPC systems either when the water content used was insufficient to ensure complete reaction of the available ADP or when the heat evolved on setting caused the evaporation of a substantial proportion of the water present. The tetrahydrate, schertelite, was reported as being the main intermediate reaction product by Kato et al.12 and by Takeda et al.,13 who carried out studies on the setting reactions in magnesia phosphate dental casting investments. Similar observations were made by Abdelrazig et al.,9 who proposed the following reaction sequence: MgO + 2NH4H2PO4 + 3H2O Mg NH4 Mg NH4
2

HPO4

4H2O

(2) (3)

HPO4

4H2O + MgO + 7H2O MgNH4PO4 6H2O

The same two reactions were identified by Miyaji et al.,14 who reported the degradation of a magnesiaphosphate casting investment by reaction with atmospheric moisture. In nature, schertelite has been observed in the drier layers of guano deposits and is known to dissolve rapidly and incongruently in the presence of water to yield struvite:15 Mg NH4
2

HPO4)2 4H2O + 2H2O + MgNH4PO4 6H2O + NH4 + H2PO4

(4)

P. W. Browncontributing editor

Manuscript No. 192086. Received January 17, 1996; approved January 21, 1997. Supported by the Engineering and Physical Sciences Research Council and Feb Ltd. *Member, American Ceramic Society. Now at the Materials Science Centre, University of Manchester, Manchester, M1 7HS, United Kingdom. Now at the Department of Materials Science, University of Bath, Bath, BA14 7LL, United Kingdom.

Popovics et al. reported that the use of low water contents or elevated aging temperatures in the preparation of MPC paste and mortar led to the formation of magnesium ammonium phosphate monohydrate, MgNH4PO4 H2O, which subsequently converted to the hexahydrate on further aging.16,17 The occurrence of such conversion reactions was not reported as causing any serious degradation of the mechanical properties of magnesiaphosphate cements. In contrast, the use of excess water in a magnesiaphosphate cement was found to lead to an increase in porosity and to a consequent reduction in the com1550

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Structure and Mechanical Properties of MagnesiaPhosphate Cement Mortar

1551

pressive strength of the hardened material, from 46 to 12 MPa.8 It is generally recommended that the magnesia should be present in a large excess; therefore, it is evident that the formation of reaction products is usually limited either by the available water or by the amount of ADP included in the dry mixture. It was concluded by Abdelrazig et al. that the chemical reactions were largely completed within the first hour after mixing, although substantial increases in compressive strength (from 25 to 55 MPa) did occur upon further aging. Similar results were reported earlier by El-Jazairi.6 It has been shown that the reaction products in magnesiaphosphate cements can display a striking crystalline morphology, which was taken as indirect evidence that the setting reactions occurred via a through-solution mechanism.18 The aim of the present work was to evaluate in detail the effects of the water content on the properties of a commercialtype MPC mortar (produced principally for the rapid repair of concrete pavements), in order to clarify the microstructure property relationships in these materials. II. Experimental Methods Materials with water contents in the range 5% to 12% (given as a weight fraction of the dry component) were prepared using a commercial MPC mortar (FEB SET-45, Feb MBT, Swinton, U.K.) which had been previously conditioned in a temperature and humidity-controlled laboratory before use (20 2C, 60% rh). The main components of this material are magnesia (MgO), ADP (ammonium dihydrogen orthophosphate, NH4H2PO4), and silica sand. The dry mixture was weighed out in either 2 or 4 kg batches and then added to the water contained in a Hobart mixer. After mixing for 2 min, the material was cast into the appropriate molds for subsequent testing, as described below. Setting generally occurred within 15 min, and the specimens were removed from the molds within 1 h. Longterm aging of the hardened test pieces was conducted within the same temperature and humidity-controlled environment. The flow of the wet mix was determined by means of a standard flow table,19 the flow test being performed by lifting off the brass mold and then operating the table five times in 5 s. The flow was then measured in terms of the radial spread along 4 diameters in standard units (where 1 unit 4 mm), using a set of callipers. Tests for final setting time were carried out using a Vicat needle, according to the procedure described in BS 4550.20 The as-mixed MPC mortar was cast into a cylindrical brass mold having a diameter of 80 mm and a height of 40 mm for this test. As a further qualitative measure of the rate of reaction, the temperature rise in a small (150 g) specimen of mortar was monitored using semi-adiabatic calorimetry.21 Two characteristic times, denoted t1 and t2, were used as a means of indicating the rate of heat evolution, t1 being the time at which the maximum rate of temperature rise occurred and t2 the time at which the maximum temperature Tmax was attained, as illustrated in Fig. 1. The plastic density of the wet mix was determined according to the procedure described in BS 4551,19 using a brass cylinder with an approximate volume of 500 mL. Bulk densities were measured both from the mass/dimensions of beam and cubeshaped specimens (prepared for mechanical testing) and by using the Archimedes method, which involved measuring the upthrust when a specimen was immersed in mercury, using a Doulton densometer. The latter test was applied to bars obtained from the flexural strength tests, yielding specimens measuring approximately 25 mm 25 mm 50 mm. The powder density was determined using a pycnometer bottle, with water, after first reducing small (50 g) specimens of the hardened mortar (aged for 30 days) to a fine powder by attrition for 20 s in a tungsten carbide shatterbox. The total porosity P of each specimen was then calculated from the measured bulk and powder densities, b and p, according to Eq. (5). XRD analysis of the powder specimens was carried out using a Philips PW 1310 X-ray diffractometer, with a scanning rate of 0.5 2 /min.

Fig. 1. Schematic illustration of results obtained from adiabatic calorimeter.

P=1

b p

(5)

The elastic modulus was found by inducing flexural vibrations in hardened MPC mortar specimens (measuring 25 mm 25 mm 285 mm) using an oscillator (Electrodynamic Materials Tester Type SCT4) together with an electromagnetic vibration generator. The method of determination of Youngs modulus E was similar to that described by Davis,22 which involved measuring the resonant frequency of the fundamental flexural resonance mode, f0, which occurred typically at a frequency of 1 kHz. Subsequently, E was calculated according to the following formula:22 E = 946.45
2 l 4 f0

h2

(6)

where l is the length of the bar (meters), h is the height of the bar (meters), is the bulk density of the material (Mg m3), and T is a correction factor, dependent on dimensions ( 1.05 in the present case). The elastic modulus was determined after aging times from 1 h to 28 days, taking an average from two specimens for each result. Typical uncertainties in these measurements were 2%. Flexural strength was determined by subjecting beamshaped specimens (measuring 25 mm 25 mm 100 mm) to a three-point load in an Instron 1185 testing machine, with a span of 75 mm. Six specimens of each composition were tested after aging for 7 days. The fracture surfaces resulting from the tests were stored for subsequent examination by SEM. Compressive strength tests were performed on cube-shaped specimens, measuring 71 mm on each side, according to BS 4551.19 Four specimens of each composition were tested to failure in a Contest Instruments type GD10 compression testing machine, after aging for 7 days. Typical uncertainties in the strength tests, expressed as the maximum/minimum values recorded, were 10%. III. Results and Discussion

(1) Setting Characteristics, Density Measurements, and XRD An increase in the water content generally led to a reduction in the viscosity of the wet mix and facilitated the mixing and casting procedures. Materials prepared with less than 6% water were difficult to process in the time available, the initial stages of setting beginning from around 8 min after mixing. This was reflected in the results obtained using the flow table, as given in Table I. The substantial decrease in viscosity obtained between water contents of 6% and 7% resulted in an unexpected

1552 Table I.

Journal of the American Ceramic SocietyHall et al. Flow of Wet MPC Mortar as a Function of Water Content
Flow along four diameters

Vol. 81, No. 6

Water content (%)

5 6 7 8 10 12

0, 0, 1, 0 10, 10, 9.5, 10 19, 20, 20, 21 Too great to measure

1 unit

4 mm.

reduction in plastic density (Fig. 2). This may be attributed to air entrained as a result of the vigorous mechanical mixing action employed during preparation. A gradual increase in plastic density was observed following further increases in the water content, which indicates that the more fluid mixes allowed some of this entrained air to escape. Variations in the water content between 5% and 12% caused noticeable changes in the setting characteristics of the mortar and in the kinetics of heat evolution, as measured by semiadiabatic calorimetry. Data illustrating these effects are presented in Figs. 3 and 4. At 5% water, the setting time was found to be around 9 min, increasing to values between 12 and 14 min for higher water contents. The rate of heat evolution was also more rapid at the lower water contents. However, it is apparent that the specimens prepared using higher water contents reached significantly higher peak temperatures (Tmax increased from 66 to 88C as the water content increased from 5% to 10%). The implication of this trend is that an increase in the water content led to an increase in the degree of hydration, at least during the first few hours of aging. The results obtained for bulk density, presented in Fig. 5, showed in general a relatively small reduction in density as the water content increased from 5% to 12%, with an anomalously high value being obtained at 10%. Although the results obtained by the different methods are not in exact agreement on the absolute values, each curve does show the anomaly at 10%. It is likely that this is a consequence of the rheological characteristics of the wet mix, i.e., that for compositions containing 8% or less water, air entrained during mixing remained until setting occurred and became a cause of porosity in the hardened material. The reduction in density observed following a further increase in water content above 10% is likely to be due to the evaporation of excess water during setting and subsequent aging, as discussed below. By assuming that the major reaction product in this system is struvite (MgNH4PO4 6H2O), the ideal water content can be calculated on the basis of the amount required to ensure complete reaction of the available ADP (according to Eq. (1)), giving a predicted value of approximately 7%. Compositions prepared with water contents higher than this should exhibit a

Fig. 3. Calorimetry curves for MPC mortar prepared with various water contents.

Fig. 4. Summary of results obtained for setting time and calorimetry as a function of water content.

Fig. 2.

Plastic density of MPC mortar as a function of water content.

weight loss during aging caused by the evaporation of excess water. This calculated figure of 7% is in good agreement with the experimental results in that specimens prepared with 7% or more water did show significant weight losses during aging (Fig. 6), with a consequent reduction in density (Fig. 7). The ultimate values obtained for weight loss in specimens prepared with 10% and 12% water were 1.2% and 2.7% respectively. These values are somewhat less than would be anticipated assuming that all of the excess water had evaporated by the time of the final measurement at 28 days. However, this is not unexpected given that some water would certainly have evaporated during the initial exothermic setting and hardening period before the first weight measurement was made (at 3 h) and that there still appeared to be some weight loss occurring (albeit at a reduced rate) toward the end of the aging period. In contrast, specimens prepared with water contents of 5% and 6% appeared to exhibit a slight increase in weight during the aging period (Fig. 6), which may be a result of continued hydration by reaction with atmospheric moisture. In view of these observations regarding the loss or gain of water, it is evident that the atmosphere (in particular humidity) could play an important role during the aging of MPC mortar. In the experiments reported here, the relative humidity was controlled

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Fig. 5. Bulk density of MPC mortar as a function of water content, determined from flexural strength test bars (Archimedes method), compressive strength test cubes (mass/dimensions), and elastic modulus bars (mass/dimensions).

Fig. 8.

Powder density of MPC mortar as a function of water content.

Fig. 6. Fractional weight change as a function of time for elastic modulus bars.

density would be nearly constant as a function of water content. In fact, a monotonic reduction in density was observed between water contents of 5% and 8%. This effect was investigated further using XRD. The proportion of the hexahydrate in the hardened MPC mortar was analyzed by scanning over the (020) and (040) reflections of the hexahydrate, struvite, at 15.8 and 31.8 2 , and the (200) reflection of MgO at 42.9 2 . The most intense peak of struvite, the (111) reflection at 20.9 2 , could not be used because of overlap with the strong reflections due to the quartz aggregate. Although a substantial amount of background noise was evident in the XRD spectra, there was a significant increase in the intensities of the struvite reflections with increasing water content. The integrated peak areas were employed to determine the intensity ratio of hexahydrate to magnesia, Ih/Im, which gives a qualitative comparison of the amount of hexahydrate present in each of the specimens. The results of this analysis exhibited a strong correlation with the powder density results (compare Figs. 8 and 9) in that the hexahydrate content increased continuously as the water content increased from 5% to 8%, then remained relatively constant. These observations may indicate that the specimens prepared using a water content below 8% contained a substantial proportion of hydrated amorphous or poorly crystalline material having a density higher than that of the crystalline phase MgNH4PO4 6H2O. Although no other crystalline magnesium ammonium phosphate hydrates were detected by XRD, their presence cannot be ruled out completely because of the relatively low proportion of cementitious material in the system, which meant that even the reflections due to the major hydrated

Fig. 7.

Time dependence of bulk density for elastic modulus bars.

at a level of 60% rh. Lower humidity levels or higher aging temperatures could well yield more rapid weight losses, dependent on the initial water content. The results obtained for the powder density, presented in Fig. 8, showed a continuous reduction in density as the water content increased from 5% to 8%, tending to a relatively constant value of around 2.44 Mg m3 upon further additions. The experimental uncertainty in these measurements was estimated as 0.01 Mg m3, weighing errors being much smaller at around 0.002 Mg m3. If the cementitious material in each sample comprised the same hydrated magnesium ammonium phosphate phase, then it might be expected that the powder

Fig. 9. Changes in ratio of XRD peak intensities of hexahydrate (struvite) to magnesia as a function of water content.

1554 Table II.

Water content (%)

Journal of the American Ceramic SocietyHall et al. Fractional Porosity of MPC Mortar as a Function of Water Content
b

Vol. 81, No. 6

(Mg m3)

(Mg m3)

5 6 7 8 10 12

2.28 0.02 2.26 2.24 2.22 2.25 2.18

2.53 0.01 2.50 2.47 2.44 2.45 2.44

0.100 0.014 0.097 0.094 0.090 0.083 0.106

phase, the hexahydrate, were relatively weak in comparison to those of quartz and MgO. There is a reasonable correlation of these X-ray results with the calculated stoichiometric water content of 7% and with earlier observations regarding the weight losses due to the evaporation of excess water in specimens prepared with water contents greater than 8% (Figs. 6 and 7). Also, there was an indication of a reduced degree of hydration in the calorimetry results (Figs. 3 and 4). The observation that the noncrystalline phase appears to exhibit a higher density than the crystalline hexahydrate phase might be explained if a reduced degree of hydration was present in this material. The fractional porosity P, as calculated from the measured bulk and powder densities (Eq. (5)), did not show a clear trend as a function of water content (Table II), although from the bulk density measurements reported above it was expected to increase as the water content increased. A possible reason for this is that the fractional uncertainty of 1.5% in the ratio b/ p was increased by an order of magnitude when the subtraction was made to yield P. The method was then not sensitive to the expected relatively small variation in P, since the powder density was reducing concurrently with the bulk density. Alternatively, if the chemical composition of the amorphous phase corresponded to that of the tetrahydrate, schertelite, then it would have been possible for a partial dissolution reaction to occur during the powder density tests, according to Eq. (4), leading to erroneously high powder density values for materials containing less than 8% water. This would tend to yield calculated porosities higher than the true values for these materials. (2) Mechanical Properties Experimental values for Youngs modulus as a function of water content are presented in Fig. 10. Each curve represents the results obtained at a given aging time, from 3 h to 28 days, while each point is an average of the values obtained from two nominally identical bars. At the earliest ages, from 3 to 24 h, the modulus appeared to decrease linearly with an increase in the water content. However, after further aging a substantial

Fig. 11. Variation in (a) Youngs modulus and (b) bulk density as a function of aging time, for various water contents.

increase in modulus at the higher water contents became apparent. An anomalously high value was evident at a water content of 10%, corresponding to the relatively high density values illustrated in Fig. 5. The late increase in modulus at the higher water contents can be more easily appreciated by plotting the values as a function of aging time, as shown in Fig. 11(a). This behavior appears to reflect the loss in density of these specimens (Fig. 11(b)), which was explained above in terms of the gradual evaporation of excess water. The late increase in modulus can be understood in terms of the precipitation of additional hydrated material within the porous structure, as the excess water evaporated and the concentrations of the relevant chemical species present within the remaining aqueous solution increased. According to Abbona and Boistelle,23 the crystallization of struvite can be reduced to bond 2+ 3 + + formation between Mg(H2O)6 PO4 NH4 or MgPO4 NH4 ions, which would all be present within the saturated aqueous pore solution. Prior to starting the flexural strength tests, a number of nominally identical bars (36 in total) were fabricated using water content of 6%. After 7 days, flexural strength tests were performed using one of three different crosshead speeds, from 0.05 to 2 mm/min, in order to establish the reproducibility of the test and to determine whether the measured flexural strength was dependent on the loading rate. The results of this investigation, presented in Table III, showed that the measured strength did show some dependence on loading rate, as is the case for OPC concrete. This strain rate dependence has been attributed to the occurrence of precritical, stable crack growth, and can be modeled using nonlinear fracture mechanics.24 Such models predict that the precritical crack growth increases with decreasing strain rate, and so the effective crack length also increases. Thus, it is found that a reduction in the loading rate leads to a reduction in the load at failure, as was observed in the present work. Subsequent tests were carried out at a loading rate of 2 mm/min in view of time considerations. The results obtained for flexural and compressive strength as a function of water content, presented in Fig. 12, show a trend which is similar to that reported by previous authors.6 An optimum water content of 6% resulted in a material having a flexural strength of around 10 MPa and a compressive strength

Table III.

Dependence of Measured Flexural Strength on Mechanical Loading Rate

f

Crosshead speed (mm min1)

(MPa)

Fig. 10. Youngs modulus as a function of water content, measured at various aging times.

0.05 0.20 2.00

7.43 0.72 8.24 0.83 8.36 1.03

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Structure and Mechanical Properties of MagnesiaPhosphate Cement Mortar

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Fig. 12. Flexural and compressive strength as a function of water content, measured after 7 days aging.

Fig. 13. Micrograph of pull-out surface in specimen prepared with water content of 12%.

of 57 MPa after aging for 7 days. These values fell to just 2.1 and 11 MPa, respectively, when the water content was increased to 12%. Thus, the strength exhibited a much greater sensitivity to water content than did the elastic modulus. The reasons for the observed reduction in strength with increasing water content are discussed further in Sections III(3) and III(4). (3) Microstructure Examination of polished specimens using SEM revealed that the coarse microstructures of materials prepared with water contents in the range 5% to 10% were quite similar. The coarse aggregate (silica sand) grains were clearly evident, while a number of relatively large (100 to 1000 m) spherical pores were also found to be present. A further increase in the water content to 12% increased the fluidity of the wet mix to such an extent that some segregation of the aggregate occurred, leaving a surface layer of the binding phase with a thickness of 1 to 3 mm. At this water content, there were no clearly evident large pores, which indicates that those observed at the lower water contents were a result of entrained air bubbles, some of which were allowed to escape before setting occurred in the more fluid mixes. This observation provides further support to the above interpretation of the plastic density results (Fig. 2). It was evident from microscopical observations that the hardened mortar is a composite material consisting of isolated aggregate grains and pores bound together by a fine cementitious matrix. The matrix itself is a composite of hydrated material, fine scale porosity, unreacted (excess) magnesia, and fine filler material. Fracture surfaces obtained from the mechanical tests showed that with reducing water content (and hence increasing strength) the fracture path changed from exclusively intergranular (with respect to the aggregate grains) to mixed interand transgranular; i.e., the fracture path was solely along the cementaggregate interface for a water content of 12%, while cleavage of the aggregate occurred at lower water contents. This was apparently caused by the presence of fine porosity within the binding phase at high water contents, which resulted in a reduction in the strength of the cementitious matrix and of the cement-to-aggregate bond. A reduction in the bond area at the higher water contents was most clearly evident on the cement pull-out surfaces, where the fracture path had been along the surfaces of the aggregate grains, as shown in Fig. 13. EDX analysis indicated that the large tabular crystals were magnesium ammonium phosphate reaction products (presumably struvite), while the spherical particles were the fine aluminosilicate filler material. The increase in fine porosity at the higher water contents,

which clearly caused a severe degradation of the mechanical properties (as described above), is a direct result of the excess (unreacted) water. Another clear trend was a pronounced increase in crystal size (from less than 0.5 m to around 10 m) and a more well-defined crystalline morphology as the water content increased from 5% to 8%. These observations provide further evidence to support the results discussed above regarding an apparent increase in the degree of crystallinity of the hydrated phase between water contents of 5% and 8%. (4) StructureProperty Relationships in MPC Mortar The major reaction product found in the MPC mortar studied in the present work was magnesium ammonium phosphate hexahydrate. As noted above, this compound has also been reported as the main binding phase in a number of previous studies on magnesiaphosphate cements. When sufficient water was included in the mix (i.e., for water contents of 8% and above), reaction (1) appeared to go to completion, consuming all of the available ADP. Although other hydrated magnesium ammonium phosphate compounds are known, struvite appears to be the favored reaction product in the presence of sufficient water and is relatively stable once formed. Any excess water included in the mix did not become chemically bound within the hardened cement and subsequently evaporated to leave a finely porous structure with very low mechanical strength. The reduction in strength can be attributed solely to the presence of the irregular fine porosity, with a size range of around 10 m, which was observed to disrupt both the cementaggregate bond and the bonding between hydrated crystal aggregates (as shown in Fig. 13). In contrast, the occasional large (1 mm) spherical pores, caused by air bubbles entrained during mixing, were clearly evident in all specimens with water contents in the range 5% to 10% and did not seem to degrade the mechanical properties significantly. This is most likely because the high volume fraction of coarse aggregate grains already provides an array of stressconcentrating flaws, which is affected only marginally by isolated pores with similar dimensions. The effect of high water contents on the structure and mechanical properties of MPC mortar provides a sharp contrast to the case of ordinary Portland cement (OPC), where the C-S-H (CaOSiO2H2O) gel can accommodate a variable water content and hydration of the calcium silicates (mainly C3S and C2S) may continue over a period of months or even years.25 Therefore, it is apparent that the strength of MPC is lost more quickly at higher water contents than would be case for OPC. The phase formation at water contents lower than 7% is more complex, since in this case it was noted that the amount of water present was less than that demanded by the stoichiometry of Eq. (1). Therefore, reaction products with a lower

1556

Journal of the American Ceramic SocietyHall et al.

Vol. 81, No. 6

degree of hydration might be expected to form if all of the ADP present in the mix reacts. The reduction in the peak temperature obtained from the calorimeter results (Figs. 3 and 4), the increase in the powder density (Fig. 8), and the reduced content of crystalline struvite for water contents less than 8% (Fig. 9) suggest the presence of an amorphous or poorly crystalline phase with a lower degree of hydration than that of struvite. The precise nature of this amorphous phase is of considerable interest, since it is evident that the materials prepared with low water contents exhibited the highest elastic modulus (Fig. 11), as well as the highest flexural and compressive strengths (Fig. 12). In general, it can be recognized that the highest strength materials are obtained by complete reaction of all the available water, since the presence of any unreacted water will inevitably result in the formation of the fine-scale porosity which has been shown to degrade the mechanical properties. The most certain means of achieving this goal is to employ a water content of approximately 6%, which is less than that required for complete reaction according to Eq. (1). It is assumed that all of the available ADP can still react by the formation of an amorphous or poorly crystalline magnesium ammonium phosphate phase with a lower water content than that of struvite. The fact that somewhat lower strengths were achieved at the stoichiometric water content of 7% suggests that inhomogeneous mixing led to some regions containing excess water, resulting in the presence of fine-scale porosity within the binding matrix. This view is supported by the observation that materials prepared with a water content of 7% exhibited a slight weight loss during aging, whereas those containing 5% and 6% water showed a slight weight gain (Fig. 6). The slight increase in weight observed for specimens prepared with low water contents indicates that a continued hydration reaction may have been occurring during the aging period, although only to a very limited extent. The water permeability of the hardened mortar would clearly be an important factor in the occurrence of such reactions. Further studies are necessary in order to clarify the nature of the hydrated phase(s) in MPC mortar at low water contents, and to establish whether there are any significant changes in the degree of hydration during aging. IV. Conclusions

ucts with a more clearly defined crystalline morphology and the presence of a significant amount of unreacted water within the hardened cement, which gradually evaporated during aging to yield a finely porous structure. The presence of this fine porosity throughout the hydrated binding phase resulted in a severe degradation of the mechanical properties. References
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The crystal structure and morphology of the hydrated binding phase in MPC mortar were found to be highly sensitive to the water content. An increase in water content from 5% to 8% led to an increase in the quantity of crystalline magnesium ammonium phosphate hexahydrate, MgNH4PO4 6H2O, with evidence also being found to suggest the presence of an amorphous or poorly crystalline phase with a lower degree of hydration. For water contents in the range 5% to 7%, the hydrated binding phase appeared to be reasonably dense, the main source of porosity being attributed to relatively large (1 mm) spherical air bubbles entrained during the mixing and casting procedures. These relatively large isolated pores did not appear to affect the mechanical strength significantly. The use of water contents greater than or equal to 8% resulted in reaction prod-