Construction and Building Materials 38 (2013) 407–412

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Construction and Building Materials

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Rheological behaviour of gypsum plaster pastes with polyamide powder wastes

S. Gutiérrez-González a, M.M. Alonso b, J. Gadea a, A. Rodríguez a, V. Calderón a,⇑
a
Departamento de Construcciones Arquitectónicas e Ingenierías de la Construcción y del Terreno, Universidad de Burgos, C/Villadiego s/n, 09001 Burgos, Spain
b
Instituto de Ciencias de la Construcción Eduardo Torroja (CSIC), C/Serrano Galvache 4, 28033 Madrid, Spain

h i g h l i g h t s

" The effect of polyamide powder waste on rheological properties of plaster is studied.
" Thixotropy, yield shear stress and plastic viscosity of the mixtures are analysed.
" The fluidity and viscosity of the pastes are function of the amount of polymer.
" Results justify the possibility of reusing polyamide waste in construction materials.

a r t i c l e i n f o a b s t r a c t

Article history: This study investigates the influence of polyamide powder waste on the rheological properties of plaster
Received 29 March 2012 pastes. Plaster blends are prepared using different volumetric proportions of polyamide by fixing the
Received in revised form 30 July 2012 water/conglomerate ratio. A rotational viscometer is used to determine the yield shear stress and the
Accepted 11 August 2012
plastic viscosity of the pastes. These results correlate with the data obtained with the paste fluidity test.
Available online 29 September 2012
Moreover, the effect of the polyamide on the thixotropy of the mixtures is analysed. The yield shear
stress and the viscosity of the pastes decrease and increase respectively as a function of the amount of
Keywords:
polyamide waste used in the mix. A strong correlation between the results of fluidity and plastic viscosity
Rheology
Gypsum plaster
indicates the amount of polyamide waste influences directly the fluidity of the paste. The relation
Polyamide powder between shear rate and shear stress provides insight into the effects of the polyamide on plaster paste
Wastes thixotropy.
Fluidity Ó 2012 Elsevier Ltd. All rights reserved.
Viscosity

1. Introduction
Over recent years, the use of polymeric wastes as polymer addi-
tives in the manufacture of lightweight plasters has been widely
studied with a view to improving the thermal behaviour of these
materials [1–3].
One of the most useful tools for the evaluation of the applicabil-
ity of plaster materials is the study of their rheological properties,
which are modified by various factors, such as the water/aggregate
ratio, mixing conditions and the type and concentration of addi-
tives [4,5]. These modifications are associated with the setting pro-
cess over time and play an important role in the application phase
of the rendering material.
In previous studies, the setting process and consistency values
were evaluated in the fluid state using the conventional methods
[6], which provide an approximate determination of the consis-
tency and the setting time, establishing the time that each sample
⇑ Corresponding author.
E-mail address: vcalderon@ubu.es (V. Calderón).
of plaster paste takes to reach the plastic state. However, these
methods have their limitations when evaluating the rheological
behaviour of the material, because they are unable to determine
its viscosity or its yield shear stress [7]. This limitation is even
more significative when new formulations containing additives
such as superplasticizers are evaluated, polymer resins, fibres,
and fillers, among others, which not only change the kinetic reac-
tions of the setting process, but also affect the workability of the
paste [8,9].
Rotational viscometer in the field of cement and gypsum pastes
has been used to overcome the limitations of these traditional
methods, to determine the rheological behaviour of the pastes by
means of shear stress and shear rate which are calculated from tor-
que and speed of rotation, respectively [10,11].
Although there are some studies that analyze the plaster’s rhe-
ological behaviour, there is no previous information about how the
inclusion of aggregates as recycled materials may affect the appli-
cability of this type of plaster conglomerates. On the other hand,
there are studies that examine the effect of compound mineral
powders on workability and rheological property of concrete,

0950-0618/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
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408 S. Gutiérrez-González et al. / Construction and Building Materials 38 (2013) 407–412

finding that exist a correlation between the surface characteristic 100

of each component of the compound powders [12].
90
In this regard, in view of previous investigations into the use of PAW
Gypsum
polyamide for the manufacture of lightweight plasters [13,14], re- 80

Cumulative passing (%)

search has been conducted on the way in which polyamide powder 70
waste influences on the workability and rheological property of
60
plaster pastes using rotational viscometer, in order to predict their
effects for the on-site application of these new materials. This 50
study investigates the rheological behaviour of different plasters 40
formulated with powder polyamide wastes with the intention to
analyse, in a simple way using a viscometer, the practical applica- 30
bility of these recycled materials, and the relationship of the vis- 20
cosity with its fluidity which is measured in terms of workability.
10
Besides, the advantage of using these materials and analyze
their behaviour in terms of viscosity is based on the possibility of 0
use recycling waste polymers as a part of the plaster conglomer- 0,01 0,1 1 10 100 1000 10000
ates, which could contribute to the use of fewer raw materials Particle diameter (µm)
and generate less amount of wastes in landfills. Material
10% of sample with 50% of sample with 90% of sample with
inferior size (µm) inferior size (µm) inferior size (µm)
The steps followed in this research are: characterisation of the
Gypsum 1843.42 51.30 2.51
different dosages in their fresh and hardened states, analysis of Polyamide 37.19 59.86 85.69
the rheological properties of the mixtures, correlating the plastic
viscosity value with the value obtained in the plaster paste fluidity Fig. 2. Laser granulometry and size particle classification of 10, 50, 90% in volume
of plaster and PAW.
test, and analysis of the thixotropy of the mixtures, through the
evaluation of their hysteretic cycles.
water has been adjusted based on equipment performance criteria, because low
2. Experimental water relationships involving a reduction of curing time, which could to lead the
overload of the viscometer. In addition, this parameter has been fixed to establish
2.1. Materials a comparison between the different mixtures and to determinate the influence of
the inclusion of polyamide.
The plaster used in this study is characterised as B1 according European Norm The plaster conglomerate is the total amount of plaster and polyamide powder
EN 13279-1 [15]. The substance was submitted to X-ray diffraction using a Philips contained. Table 1 shows the nomenclature of all dosages, the setting time by Vicat
PW1830, which identified the following concentrations: high for calcium sulphate needle, the results of the densities in wet and dry states which give the percentage
hemihydrate (CaSO40.5H2O); low to medium for anhydrite (CaSO4); and low for water retention of each specimen and the results of compression and flexural
quarz (SiO2), dolomite (MgCa(CO3)2) and muscovite (KAl2Si3AlO10(OH)2). The real strength at 7 days to characterise the mechanical properties.
density is 2650 kg/m3 (given in the manufacturer’s specifications).
Polyamide Powder Waste (PAW) was obtained from waste raw material gener-
2.3. Test Methods
ated in an industrial laser sintering process. Its chemical composition was obtained
through CHNS elemental analysis using a LECO CHNS-932 analyser (Fig. 1). The real
2.3.1. Determination of paste fluidity
density of the PAW is 1070 kg/m3 which was measured with the Pycnometer meth-
Reference plaster pastes and pastes with different substitutions by volume of
od, using isopropyl alcohol [16].
plaster for polyamide were mixing according to the method specified in standard
For better physical characterisation of the components, its grain size distribu-
EN-13279. When the mixture time had elapsed, the paste was introduced into a
tion was performed by laser diffraction analysis using a HELOS 12 K SYMPATEC ana-
truncated cone measuring 40 mm in height, with an upper internal diameter of
lyzer. Samples were analysed for 15 s in an isopropyl alcohol suspension (Fig. 2).
65 mm and a lower internal diameter of 75 mm supported on a glass plate. Subse-
Values of grain size corresponding at 10%, 50% and 90% by volume, are shown for
quently, the mould was removed allowing the specimen to spread out. Its diameter
both components.
was then measured in both directions perpendicular to each

2.2. Mixing and characterisation of the blends

Six blended plasters with different additions of PAW were mixed (G0, G0.5PA,
G1PA, G2PA, G3PA and G4PA). The procedure to obtain the pastes consisted of pro-
gressive additions of polyamide powder to the plaster, substituting by volume dif-
ferent proportions of plaster for PAW. The dry components are mixed until
homogenisation. After that, the water is added. The water/polyamide powder
waste + plaster (water/(PAW + p)) ratio by volume used for all dosage is 0.645, a
similar water/conglomerate ratio used by other authors [17]. Also, the amount of
2.3.2. Determination of rheological parameters through rotational viscometer
The rheological parameters of the yield shear stress and plastic viscosity of the
plaster pastes were determined by using a Haake Rheowin Pro RV1 viscometer fit-
ted with a serrated coaxial rotor.
Reference plaster pastes and pastes with different substitutions by volume of
plaster for polyamide were prepared, mixing the necessary proportions for each
dosage for 2 min in a mixer blade.
A rheological test was conducted on the pastes that consisted of pre-stirring at
100 s1 for 1 min, subsequently the rotor speed dropped to 10 s1, before increasing
again to 100 s 1 for 1.5 min, finally dropping within the same interval of time to
10 s1 [18,19] The measurements of each blend were repeated a minimum of thrice
to obtain a viscosity and yield shear stress values which have a reproducibility of
90%.

2.3.3. Thixotropy
The thixotrophy of the different mixtures tested in the rotational viscometer
Element PAW was obtained on the basis of their hysteretic cycles immediately after the mixture
of their components. This was done through a graphic representation of the up-
C 70.4 curve and the down-curve that link the shear rate parameter to the shear stress
H 11.2 parameter. Thus, the intention is to analyse the formation and destruction of the
N 7.1 internal structures within the six samples under the same measurement conditions.
S 0.1
Others 11.3
2.3.4. FSEM
Total 100.0
The microstructure of the polyamide plaster blends was observed by Fast Scan-
ning Electron Microscopy (FSEM HITACHI S-4800) using an accelerating voltage of
Fig. 1. FSEM and elemental analysis of the PAW. 20 kV and intensity of 20 lA.
 S. Gutiérrez-González et al. / Construction and Building Materials 38 (2013) 407–412 409

Table 1
Plaster samples volume ratio, setting time, and density of the fresh pastes. The compressive and flexural strength of the hardened products and water retention are presented.

Sample Volume ratio Setting time Bulk density Dry density Water retention Compressive strength Flexural strength
(plaster/PAW) (min) (kg/m3) (kg/m3)a (%) (MPa)a (MPa)a
G0 1/0 39 1434 1110 29.1 3.53 1.69
G0.5PA 1/0.5 47 1268 903 40.4 1.80 0.66
G1PA 1/1 49 1164 828 40.6 1.46 0.69
G2PA 1/2 52 1090 773 41.0 1.00 0.12
G3PA 1/3 53 1039 733 41.8 0.72 0.12
G4PA 1/4 61 1027 710 44.7 0.60 0.07
a
Cubic samples cured for 7 days (Relative Humidity = 50%, 22 °C) [6].

Table 2
Fluidity test, plastic viscosity and shear stress for each sample.

Sample Fluidity test (mm) Plastic viscosity (Pa s) Shear stress (Pa)
G0 200.15 0.0362 28.71
G0.5PA 169.65 0.0829 13.80
G1PA 125.75 0.1364 12.31
G2PA 101.40 0.2182 13.56
G3PA 98.05 0.5333 14.78
G4PA 91.70 0.6243 17.80

Fig. 3. Relationship between shear stress and plastic viscosity.

Fig. 5. FSEM of the plaster-polyamide interface (G2PA.

Fig. 4. Shear rate versus shear stress for the sample G2PA.

3. Results and discussion 30

3.1. Rheological parameters G4PA

25

As an example, Figs. 3 and 4, respectively, show the relationship

between shear stress and plastic viscosity and shear rate versus 20
Viscosity (Pa)

shear stress both for the sample G2PA. These data were obtained
from good adjustment with a straight line in accordance with Bing- 15
ham’s equation [20] and that corresponds to the drop in shear rate.
s ¼ so lc_ ð1Þ 10

where s is the shear stress applied to the paste in Pascals, c_ is the

shear rate in s1, l represents the plastic viscosity of the system 5
at any given time in Pa s and so is the yield shear stress in Pa.
In view of the results show from Table 2 for plastic viscosity, it 0
may be seen that increasingly high amounts of polyamide increase 0 20 40 60 80 100
the viscosity of the mixtures, beginning with viscosity values of Shear rate (s-¹)
0.0362 Pa s in reference mixtures (G0) and reaching values
of 0.6243 Pa s in mixtures with higher polyamide substitutions of Fig. 6. Evolution of the plastic viscosity according the time in dosage G4PA.
410 S. Gutiérrez-González et al. / Construction and Building Materials 38 (2013) 407–412
gypsum (G4PA). This effect may be explained in terms of the uni-
form distribution of the particles in the mixture prior to setting,
evenly dispersed throughout the mixture, producing a partial fill-
ing of the voids between the large gypsum crystals by the rounded
polyamide particles resulting in a thickening effect that produces
increasingly viscous mixtures. This explanation is further sup-
ported on the observation of his microstructure as revealed by
the FSEM from Fig. 5.
In view of the results for the yield shear stress (Table 2), it may
be seen that the addition of polyamide lead to a reduction in the
flow point. Thus, dosages that incorporate polyamide in their com-
position lead to reductions in the yield shear stress of between 40%
and 60% approximately with regard to the reference dosage (G0).
One explanation of this effect is due to the reduction of the inter-
action forces between particles as a result of the presence of the
rounded polyamide powder particles [21]. In other words, the
polyamide particles uniformly dispersed in the aqueous plaster
mixture place themselves in the spaces that are formed between
the plaster crystals, facilitating the shear effect in the plaster pastes
and reducing their flocculation. This effect is translated into a
reduction in the yield shear stress of all the dosages that include
PAW in their composition.
In turn, it can be seen from Fig. 6 that mixtures of plaster with
polyamide at rest have a high viscosity, which complicates the sed-
imentation of the particles, whereas under conditions of plaster
flow, for example during plaster application by projection, the vis-
cosity falls, facilitating the flow; a behaviour that is known as
shear-thinning.
3.2. Relationship between fluidity paste and plastic viscosity
Table 2 shows the results of the paste fluidity test where it may
be seen that diameter of the spread decreased as the polyamide
Fig. 7. Relationship between fluidity and plastic viscosity pastes.
Fig. 8. Evolution of the shear rate with time on the rheological test.
content increased producing a progressive loss of paste fluidity,
for the same water/conglomerate ratio. In other words, the addi-
tion of the PAW in plaster pastes reduces the shear thinning effect
more than in the reference pastes without polyamide. In this way,
mixtures with a high substitution of plaster with polyamide at rest
(G4PA) lead to a loss of the fluidity effect of approximately 54%
with regard to the reference mixtures (G0). The explanation for this
might be that, in the first place, the polyamide that is used as a
substitute absorbs some water and calcium ions during the mixing
and at the start of the setting process [22]. Thus, the result of add-
ing PAW leads to a change in the rheological properties of the
material, yielding plasters with a low segregation tendency, which
in turn facilitates their application. If these results are compared
with the plastic viscosity data obtained through rotational viscom-
etry, a correlation between both parameters may be seen, which
varies in an inversely proportional way, tracing a potential-type
line tendency, in accordance with the equation shown in Fig. 7.
With regard to the comparison between both methods, it may
be seen that the paste fluidity measurement method fails to ac-
count for the rheological changes over time with great precision,
which is essential when ascertaining information on the behaviour
of this material during its application.
On the other hand, the fluidity test provides no values for phys-
ical parameters at all. Its results cannot be expressed in physical
rheological units, although it has proved useful over the years for
the classification of different materials in terms of their workability
and ability to be cast [23].
3.3. Thixotropy
Thixotropy is defined in terms of the area enclosed between the
up-curve and the down-curve of the rheogram [24]. This area may
be expressed as:
A ¼ sc_ ð2Þ
This equation considers the degree of thixotropy, in other words
the energy that is required to break the thixotropic structure of the
material.
A manifestation of thixotropy can be observed thought their
hysteresis cycles. It consists in systematically increased and
decreasing the shear rate between zero and a maximum value. In
this case, increasing from 0 to 100 and decreasing from 100 to 0
(Fig. 8). When the transient data are plotted as shear stress versus
shear rate, a thixotropic sample will lead to less difference between
the ascending and descending curves as the microstructure has
more time to come closed to the steady state one. The area A en-
closed by the loop has been used as a characteristic for thixotropy
[25].
Fig. 9. Effect of the polyamide in the hysteresis cycles.
 S. Gutiérrez-González et al. / Construction and Building Materials 38 (2013) 407–412
Fig. 10. Variation of thixotropy and setting time of the samples.
The hysteresis cycles may be seen in Fig. 9 of the different PAW
plaster pastes as well as their area which allows us to evaluate the
thixotropy of the pastes with different polyamide concentrations
(Fig. 10). Reference dosages without polyamide (G0) in their com-
position show a rheopectic or anti-thixotropic behaviour, given
that the changes in the structure of the plaster material and its set-
ting process take place over time. This entails an irreversible break-
down in gypsum-based systems, in which as the shear rate shown
in the down-curve is reduced, the shear stress increases. However,
as larger amounts of PAW replace the plaster in the mixtures, a fall
in the anti-thixotropic effect may be observed, which leads to a
reduction of this effect of approximately 85% in samples G0.5PA.
As larger proportions of PAW are incorporated, this rheopectic ef-
fect is inverted, which gives rise to thixotropic pastes. Thus, it
may be seen from the down-curve that as the shear rate falls in
dosages G1PA, G2PA, G3PA and G4PA, the recorded shear stress
is lower than that recorded on the up-curve, as the shear rate in-
creases, leading to thixotropic behaviour that increases with larger
amounts of PAW. All the samples that incorporate PAW in their
composition presents a gradual recovery of their structure when
the shear is removed, which indicates that the pastes are partially
deflocculated. This may be due to that the large amounts of poly-
amide, which leads to higher setting time, resulting in a drop of
the shear stress with the time [26]. This can be seen from Fig. 10,
which shows that the thixotropy and the setting time vary slightly
proportional.
4. Conclusions
The inclusion of compounds such as polyamide powder waste
as a recycled and reusable material in substitution of varying
amounts of plasters is therefore of great interest in the production
of new construction materials, because would contribute to the re-
assessment of a waste product that is generated in large quantities.
It has been established that the addition of polyamide powder
waste as a gypsum substitute is a factor that encloses an important
influence on the rheological properties of these compounds.
The parameter provided by the fluidity test could be expressed
in rheological units but are traditionally used to classify the casting
ability of the materials. There is a good correlation between the flu-
idity and the plastic viscosity parameters (R = 0.964) which al-
lowed establishing a relation between both these parameters. In
any case, it is clear that the addition of PAW slows down the set-
ting time as shown by the correlation of results for fluidity test
and the initial setting time.
Concerning the most adequate samples for its application in on-
site plastering it could be the G0.5PA dosage, based on experience
411
and on EN-13279-2 which specifies that the mean of the diameters
measured at the shaker table should be 165 ± 5 mm.
The dosages of studied PAW behaved as non-newtonian fluids,
undergoing an increase in their viscosity at rest, which is reduced
when shear rate is applied.
Increasingly higher amounts of PAW lead to greater viscosity,
reaching value that were 17 times higher in mixtures with maxi-
mum substitutions of plaster for polyamide, in comparison with
the reference blends. Lower yield shear stress was detected in
the order of 40% for G4PA mixtures and 60% in G1PA pastes.
It has been confirmed that the addition of PAW modifies the
structure of the pastes, leading to a greater thixotropic effect.
In view of the results, it may be concluded that the plaster
pastes that incorporate polyamide waste significantly change their
rheological properties with regard to their application on site. This
study, together with previous investigations of characterisation
published with this type of materials, lead to justify the possibility
of reusing a type of polyamide waste, as an alternative to its dis-
posal, in a sustainable way, using the waste such as a raw material
in new lightweight construction materials.
Acknowledgements
Our thanks to VIAS S.A Company and Ministerio de Educación y
Ciencia (Proyecto YESA 2012, MICINN-CDTI) and the financial sup-
port provided by the Junta de Castilla y León (BU013A10-2).
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