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Use of phosphate magnesium material in fire protection of concrete

Conference Paper · October 2012

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 Use of phosphate magnesium material
in fire protection of concrete
Khanh-Son NGUYEN, Phuoc-Vinh NGUYEN,
Hoang NGUYEN, Thanh-Nhan NGUYEN, Thai-Hoa NGUYEN
Faculty of Materials Technology, Ho Chi Minh city University of Technology
268 Ly Thuong Kiet street, District 10, Ho Chi Minh city, Viet Nam
E-mail: ksnguyen@hcmut.edu.vn

ABSTRACT: One solution of passive fire protection consists in exploiting the characteristic of endothermic phase change of mineral
material (gypsum, portlandite, calcite, gibbsite…). Fire severity is in general modeled by temperature evolution including a major variation
at the beginning and following by the highest temperature constant at about 1100-13000C. In the strategy of protection for high-rise building
or tunnel, passive solutions follow up active actions after about first 10min of fire, serving as heat insulation barrier for structural component.
We developed a fireproofing material with phosphate magnesium binder also well-known as Sorel cement. Acid-base reaction mechanism
while mixing powdered magnesia (MgO) and dihydro phosphate (NH 4H2PO4, KH2PO4), leads to the formation crystallized products struvite
and schertelite. We control sampling product using fire test prototype in laboratory. Temperature evolution by time T(t) in sample thickness
were registered with thermocouples system. As might be expected, fire resistance of 30mm magnesium phosphate board shows promising for
fire protection of concrete structure. The conclusion of temperature insulation encourages further studies regarding thermo-physical
properties, thermal stability of dimension, nonflammable, non-toxic smoke for its practical usage.

1. INTRODUCTION KH2PO4 → K+ + PO43- + 2H+ (1)

KH2PO4 → K+ + HPO42- + H+ (2)
Portland cement (PC) is one of the most important man-made
KH2PO4 → K+ + H2PO4- (3)
materials in our civilization world. In many developing countries, H2PO4- → HPO42- + H+ (4)
the use of cement and concrete material in building and HPO42- → PO43- + H+ (5)
infrastructure construction become naturally necessary. However, Oxide base MgO dissolve partially in the solution and never be
there is a fact that manufacturing PC can make an impact on completed. MgO is slightly soluble in water, according to Eqs. (6),
environment issue. Material producing requires energy, intensive (7) and (8):
resources and increases pollution with released CO2 [1]. Finding a MgO + H2O → MgOH+ + OH- (6)
sustainable cementitious material is objective of many research. MgOH+ + 2H2O → Mg(OH)2 + H3O+ (7)
Here, our research works on the magnesium phosphate binder or Mg(OH)2 → Mg2+ + 2OH- (8)
magnesium phosphate cements (MPC), the last one belongs to group Mg2+ + 6H2O → Mg(H2O)62+ (9)
of chemically bonded ceramics. They form binder with hydration Struvite crystals are formed with the combination in solution of
reaction like as hardening cement, but their structure and their ionic products Mg(H2O)62+, PO43- and K+ [7,9]. The following figure
properties are much more similar to ceramic materials [2]. MPC can 1 explains the product development outer to inner bound of MgO
be produced at low temperatures and develop its strength rapidly grain. Forming product will envelop non-react magnesia.
after the first hour in contact with water. At this point, this kind of Mg(H2O)62+ + K+ + PO43- → KMgPO4.6H2O (10)
material can prove evidently many environmental benefits in
compared with PC.
Recent investigations [3-5] showed materials performances,
superior to the PC hardening mortar, such as high early strength,
excellent volume stability, better durability for rapid-repair
applications: deteriorated bridge decks, airport runways,
highways… In this article, we focus on its capacity of good fire
resistance applied to fireproofing material for concrete. This fire
insulation mechanism bases on latent heat of crystallized phase of
phosphate binder. Raw materials are magnesium oxide or magnesia Figure 1. Mechanism of struvite formation through solution reaction
(MgO) and mono potassium phosphate (KH2PO4) that will be used
and obtained product in panel will be exposed to heat transfer test at 3. MATERIALS AND EXPERIMENTAL METHODS
high temperature of electrical furnace. 3.1 Materials

2. ACID-BASE REACTION MECHANISM
Magnesium phosphate binder involves an acid–base reaction
between MgO and salts of phosphoric acid (monohydro phosphate,
dihydro phosphate). Bibliography study revealed different
mechanisms of material hardening. To consider the interactions
between MgO and KH2PO4, Hall et al., [6] indicated on their X-ray
diffraction spectra major peaks of struvite or K-struvite crystalline
product (MgKPO4.6H2O). The number of water molecules enclosed
in struvite crystalline is maximum. These chemical bonds waters
will be evaporated over 1000C. According to recent publication of
Soudeé & Péra [7], they divide reaction into two periods. First
period is the dissolution of acid KH2PO4 (pH<7) and a part of base
MgO, the second period is the formation of struvite and crystals
growing.
KH2PO4 acid-salt dissolve rapidly to achieve saturation point
according to Eqs. (1), (2), (3), and the fraction of PO 43-, H2PO42-,
HPO4- ions are given by Eqs. (4) and (5):
Commercial dead-burned magnesia (MgO, China) is used in this
experimental campaign. Oxide product is obtained when we
calcinate magnesium carbonate over 8000C in rotary furnace. XRF
analysis result helps us estimate magnesia content up to 70% by
mass. In the industrial product, XRD analysis detected others
crystalline mineral such as: dolomite, calcite, brucite… However,
chemical reactivity depends also on the powder finesse and surface
dislocation of magnesia crystal. Material powder is prepared
carefully in two steps: pre-grinding in planetary ball mill during 30
minutes and screening through sieve size 90μm. After that, we
conserved the obtained material in desiccators in order to avoid
inadequate reaction with environment.
Mono potassium phosphate (KH2PO4, Vietnam) 99% is used in
this research. The phosphate salt, contains mainly K, P agents, also
used as soil organic fertilizer. Its solubility is clearly better than
magnesia and depends on water solution and its temperature. Soudee
& Pera [8] also proved that dissolution of KH2PO4 provokes the
dissolution of MgO in order to maintain the stability of pH value All binder product appears solid after 7 days of curing time with
around 7. ceramic concrete seem surface (Figure 2). We analyze obtained
Borax or salt of boric acid is commonly used as a retarder product by using common XRD, IR and SEM apparatus in material
admixture in case of acid-base reaction. Literature figured out the science. Struvite and others intermediate hydrate products are
role of borax in forming waterproof layer around magnesia grain expected in this analysis.
[6]. The last one prevents dissolving in base solution. To formulate Furthermore, we analysed dehydration process by using
product sample in large dimension, we need normally avoid rapid TG/DTA apparatus. Endothermic reactions according to heat
setting and extreme exothermic of reaction between reactive evolution constituted one important thermo-physical property of
magnesia and acid phosphate. Sodium borax Na2B4O7·10H2O, used material. This phenomenon is also called latent heat during high
in this formulation step, is a laboratory compound with 99.9% temperature exposure.
purity. 3.2.2 Test of mechanical resistance
Furthermore, flying ash, fine siliceous sand, glass fibers could be
40x40x160mm3 samples at 3 and 7 days were tested for mechanical
also incorporated into binder samples to improve material
resistance. In this study, we limit the formulation work without resistance in flexion and compression. The test conforms with the
standard of resistance test ASTM for cement material. Figure 3
using these inert additives. We focus these composites results in
describes the schema of resistance test in flexion 3 points (left) and
another publication.
in compression (right). We note that bar samples were placed in
3.2 Formulation and phases analysis of product chamber before the test and we surveyed the stabilization of mass
loss during this period.
3.2.1 Mixing process
Theoretically, we note the following reaction with stoichiometry
ratio of acid-base component KH2PO4 : MgO = 50:50 (%) by mol or
77:23 (%) by mass [9].
MgO + KH2PO4 + 6H2O  KMgPO4.6H2O + Q>0 (11)
However, when we tested with small amount of 10 milligram,
violent water evaporation and quick hardening of acid-base reaction
product prevent reaction achievement. It would refer to the fact that
the core of MgO grain can not react absolutely before the mixture
hardening completely. To vary mass ratio between acid and base, we Figure 3. Schema of 3 point flexion test (left) and compression test
point out the most suitable composition with small excess of base. (right) realized on 40x40x160mm3 samples
We consider from viewpoint enough setting-time and crystallization
quality. We prepared series of sample with two mixing process: 3.2.3 1D heat transfer test throughout sample board thickness
+ Process A: KH2PO4 salt was dissolved into water first, and
MgO powders were slowly sprinkled to the solution. Material incorporated heat latent during heat evolution appeared as a
+ Process B: KH2PO4 and MgO powders were blended and good solution for fire protection product in case of accident. Hydrate
grinded into a homogeneous mixture, and then sprinkled them crystallization such as gypsum, portlandite, gibbsite, silicate calcium
slowly into water. hydrate and struvite describe important endothermic effect [11-14]
In the same way as cement hydration, water serves not only as a during water evaporation (physical and chemical) phenomenon. We
reaction component, but also improving necessary workability of conducted a prototype of heat transfer test using electrical furnace in
product. We adjusted water/solid ratio close to a constant value of laboratory scale. Dimension of sample board is fixed
0.56 for all samples. 150x150x30mm with geometry ratio thickness/height ≥ 1/5. This
Table 1. Four sample series of MgO/KH2PO4 mixture value ensures the simulation of 1D heat transfer throughout 30mm
thickness of sample. The product board was constituted as an
Sample KH2PO4 MgO Borax/Solid Water Pro entrance door of furnace. Totally, six temperature sensors
series (% wt.) (% wt.) (%wt.) /Solid cess (thermocouple TC type K, S) were disposed on the sample test.
MPC1 75 25 0 0.56 A They help us recorded thermo-diagram with 1 second interval while
MPC2 the furnace’s temperature evolved with time up to 12000C. There are
75 25 0 0.56 B
one TC on exposed side of sample and five others TC on unexposed
MPC3 75 25 2 0.56 A side in order to obtain average temperature at this position. Figure 4
MPC4 75 25 2 0.56 B shows the installation of these heat transfer tests.

After stirring solution to smooth paste during about 5 minutes, Product board 15x15x3cm3
Electrical Furnace 4kW
we poured this paste product into molds 40x40x160mm3 to form bar
sample. Mortar samples are hardened within 2 hour and were
System

unmolded after 3 hour. Unmolded samples were left keeping at

room temperature in 3 to 7 days and then follow by leaving 12 hours
at 900C of thermal chamber before product testing.
Entrance door Sensor
3.2.1 Phase analysis of product

40 Figure 4. Electrical furnace (left) and product board disposition as

an enclosed door (right)
75
50
40

50
75
150

Figure 2. 40x40x160mm3 cutting surface of a MPC2 sample, seem

ceramic material
 Figure 5. 1 TC on exposed side (right) and others 5 TCs on
unexposed side of sample board (left)
4. RESULTS AND DISCUSSIONS
Firstly, it is important to emphasize that all reactions of sample
series MPC1, MPC2 were extremely violent and exothermic. They
happen right after the contact between two reactors and water
solution. Heat generated from reaction was released very strong and
apparently it made water solution evaporate. The setting time was
consequently too fast (less than 5 minutes) and so not enough for
stirring and pour the mortars into the mold. A large amount of MgO
grits appeared unexpectedly at the end of the mixing container. We
can conclude that it is very difficult to control the reaction using this
mixing process. By comparing between the two mixing processes,
process B with pre-mixing step of material reaction proves itself
adequate. This method showed a lower amount of grit and quietly
smooth paste. It can be explained that the dissolution simultaneous a
small amount of acid and base material permit forming subsequently
reaction product little by little. This approach permitted to avoid
forming a product bound around magnesia grain which prevented
dissolving base solution.
15 20 30 40 50 60
Figure 6. XRD spectrum of MPC1 sample, CuKradiation
10 20 30 40 50
Figure 7. XRD spectrum of MPC4 product sample, CuKradiation
In case of sample series MPC3 and MPC4, we reduced the
surface activity of MgO powders in contact with borax admixture.
Reaction process appears easily to control. Workability of mortar
paste ensured pouring sample in the mold. The last one is decisive in
order to fabricate large samples for fire protection test. MgO grits
also appeared with less amount in compared to the precedent
process while we can extend mixing time. One more detail must be
noted that hydrate product could be poorly crystallized or
amorphous due to admixture excess. Admixture content 2% is
deduced from a preliminary analysis in bibliography study.
Figures 6 and 7 show respectively XRD spectrum of MPC1 and
MPC4 sample. Major peaks of struvite appear overlapping in the
range of 2 between 20-30 and 30-40. Both material reaction MgO
and KH2PO4 are revealed on the spectrum of MPC4, but apparently
they do not appear truly on the MPC1 spectrum. It is clear that acid
and base reactor did not react completely in some mixture. We can
explain by grits product existed around outer particles of magnesia.
Non-reacted magnesia is stayed within grain core.
Table 2. Resistance results at 3, 7 days of 40x40x160mm3 MPC
samples
Resistance in flexion Resistance in
Sample
(MPa) compression (MPa)
series
3days 7days 3days 7days
MPC1 1.2 2.1 4.3 5.1
MPC2 1.6 2.3 6.5 7.0
MPC3 2.3 3.1 10.2 11.8
MPC4 2.4 3.5 11.4 12.5
According to test results, resistance values in compression and
flexion are quite stable at an average value. They also evolve the
same tendency between 3 and 7 days of curing. MPC4 sample show
in the same time the highest compressive strength (12.5 MPa) and
bending strength (3.5 MPa). The compressive strength of sample
with powder premixing method (MPC2) is also higher than the
series without premixing. The result is quite logic with the solidity
of sample appearance MPC2. Both bending and compressive
strengths are also increased significantly with the quality of MgO
(material reactivity, purity, particle fineness). Using 2% borax in
mixture may affect truly on mechanical strength of 40x40x160mm
samples. We can explain with the number of contact between two
reactions components. Using borax is proved useful to control
reactions process and thus ensure reaction achievement. The mortar
paste was easier to stir and the setting-time was also about 10
minutes longer. It could be a good condition for growing and
generating struvite crystals in binder matrix.
Figure 8 illustrates the microstructure of forming binder MPC2
using a scanning electronic microscopy. Struvite crystals in this
sample (left) are large surface and coarse. They exist some positions
of non-reacting materials (white grain) on the struvite surface.
Considering grain size inferior to 10m, they could be non reacted
magnesia. Figure 8 (right) shows an zoom picture of struvite crystal
including roughness and cracking elements.
Figure 8. SEM image of MPC2 : x100 (left) and x1300 (right)
60
Figure 9. SEM image of MPC4 : x100 (left) and x1300 (right)
Furthermore, it is quite different in case of microstructure of
MPC4 sample (Figure 9); struvite crystals are small and dense.
Zoom image of this structure illustrates a good arrangement of
crystals stick body. The well controlled reaction rate could lead to
archive this crystalline state. The solidity in microstructure is
consistent with higher result of resistance compared to MPC2
sample.
 Literature study revealed that thermal decomposition of struvite
and others hydrate products in phosphate binder is a complex
process. It contains a overlapping reaction of dehydration [15] in
order to evaporate 6 molecules of water. Results of TG/DTA
realized on MPC2 and MPC4 powders are in Figures 10 and 11. We
notice a common phenomenon of a major mass loss in TG diagram
between 100 and 3000C. This mass loss takes place with an
endothermic effect in DTA diagram. The peaks of this endothermic
interval are respectively at 156 and 1710C. Up to 1000C, thermal
effect is quite small pursuing evaporation of physical water. After
3000C, we recognize some different reaction in two cases of MPC2
and MPC4 samples. These effects have connection to some
impurities in reaction material such as dolomite, brucite or calcite.
However, we can neglect these small effects in comparing with the
main dehydration reaction of struvite. To simplify, we assume that
the latent heat value is assigned to struvite. We can estimate from
DTA results this latent heat of phosphate binder about 910 J/g. The
last value is higher than gypsum latent heat, 560 J/g in the interval
of 80-2100C [16]. We can predict the stronger capacity of fire
insulating of phosphate binder than well-known gypsum board
insulating product.
KMgPO4.6H2O  KMgPO4 + 6H2O↑ + Q<0 (12)
DTA
TG
H (mV)
m (%)
Q
Temperature (0C)
Figure 10. Result of DTA/TG analysis on MPC2 sample at 7 days
DTA
TG
H (mV)
m (%)
Q
Temperature (0C)
Figure 11. Result of DTA/TG analysis on MPC4 sample at 7 days
In fact, our heat transfers test simulates in small scale of fire
resistance test proposed in ISO 834 standard [17]. ISO 834 fire
temperature evolves with time (ISO 834 curve) is according to
function T(t)=T 0+345.log(8t+1). Furnace temperature and
temperature on the unexposed sample side are recorded with time in
the Figure 7. Sample board ensures insulating condition from heat
generating in furnace. We call this principle of fire retardant in the
global strategy of fire protection.
Figure 12 displays a quite difference between temperature of
furnace () and theory ISO 834 temperature curve (○). To compare
temperature of furnace with temperature measured on exposed side
of sample board, there is also a divergence at any time. This result
can be explained by the non-homogeneity of temperature in furnace
space and/or thermal inertia. After two hours of test, temperatures at
two positions are respectively 1200 and 10200C. Average
temperature value on the unexposed side illustrates an isothermal
plateau or slight variation. Temperature recorded by 5
thermocouples at this position is very consistent. After two hour of
test, while the temperature on the exposed side is 10200C, the
temperature on the unexposed side (throughout 30mm of sample
thickness) is about 1200C. It is a promising result to ensure fire
protection for concrete structure. In the last case, we need ensure
average temperatures on concrete do not access 1400C.
Temperature (0C)
Furnace
temperature ISO 834 curve
Exposed side
TC6
TC5
TC4
TC3
TC2
2 hours
TC1
Unexposed side
times (s)
Figure 12. Temperature vs. times diagram recorded during heat
transfers test
5. CONCLUSIONS
Magnesium phosphate binder is produced in this study from reaction
between MgO base and KH2PO4 acid salt. Rapid setting and high
resistance make it high capacity of application but violent water
evaporation and poor quality of workability of solution during
mixing time could limit its usage. By using necessary borax (2% by
mass of solid) as a retarder admixture, we can ensure reaction
condition to generate struvite product in binder matrix. Material
analysis shows a large proportion of struvite well-crystallized. This
result explains important resistance both in compression and in
flexion of MPC. Fireproofing product in panel could exploit heat
latent of hydration material of struvite. The same principle is
generated in case of plaster board for fire passive protection.
We investigated two mixing processes and all results showed
that using premixing raw materials (MgO+KH2PO4) and slowly
stirring to dissolve in water may be adequate for specific board
molding. This mixing process show satisfactory when we could
blend others potential inert components such as fine sand, fly ash or
glass fiber. Mass ratio 3:1 between KH2PO4/MgO brings us the best
result of struvite obtained. It is also noted that in this experimental
condition, industrial MgO 70% is used providing a relative activity.
Borax can slow down the first setting period of MPC, it will help us
increasing time for stirring and minimize the surface reaction, which
prevents the main reaction and form unexpected grits. A small
amount 2% of borax is able to affect the compression and flexion
strength of material.
Heat resistance of this MPC sample is quite stable in contact
with high temperature up to 10200C of furnace. Fire retardant
throughout 30mm thickness of this material is better than
expectation (about 1200C after 2 hour). And it can be developed to
apply in fireproofing for concrete structure.
Acknowledgements
The authors would like to thank Nippon Sheet Glass Foundation for
Materials Science and Engineering for the financial support
(Research grant, year 2012).
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