Abstract Basically, a setting is a process of


Alcohol amines have been
used as grinding aids in cement grinding processes for many years. Milling aids
are predominantly developed to increase the performance or grinding capacity of
the cement product.  The setting points
of cement produced with grinding aids are mostly changing. In this study,  the effect of boron compounds to setting
points of the cements which are produced with addition of grinding aids of alkanolamines
and boron compounds in different mixing amounts is searched. Triethanolamine (TEA)
and triisopropanolamine   (TIPA) are used
as alkanoamines and boric acid (BA) and anhydrous borax (AHB) are used as boron
compounds. It is seen that BA with TEA has a small effect on cement setting
points and BA decreases the retarding effect of TEA but has no effect with TIPA
on setting times. AHB decreased the retarding effect of TEA but has no effect with TIPA on setting times. When the
boron compounds added to TEA, they accelerate the initial setting of cement 15
to 20 minutes and the final setting of cement 25 to 30 minutes according to TEA
used itself.  

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Keywords: Grinding Aid, Alkanoamines, Boric Acid, Anhydrous Borax, Initial Setting,
Final Setting


1. Introduction

Hydration reaction starts directly when
water is mixed with cement to form a paste. The paste first begins to lose its
plasticity and stiffens, and then hardens 1. Main phases, C3A, C3S,
C2S, and C4AF reacts quickly with water to produce a
jelly-like compound which starts solidifying. The action of changing from a
fluid state to a solid state is called ‘setting’. Basically, a setting is a process of transformation from an
initial state, a scattered concentrated suspension, to a final state, a
connected and strengthened system of particles. This transformation in the
practice of cement and concrete is obtained by chemical reactions between
cement particles and water (i.e., cement hydration) 2. Normal setting of
cement is associated with the hydration of Alite (C3S) and formation
of the calcium silicate hydrate (CSH) phase 3.

as a slurry has fluidity just after mixed with water and can easily flow into a
mold. The sulfoaluminates create interlocking crystals and the C-S-H starts to
form, the created network of solids causes the cement to set. The cement
paste  has no strength at this hydration stage
and also it is very friable. The  required time length for initial setting can
be determined by the amount of gypsum present in the cement. Hardening of the
cement paste ;in other words the beginning of strength gain  occurs after the formation of C-S-H, which
starts some hours after mixing.

chemical aids causes cement set acceleration according to one or more of
following mechanisms:

(1)   Ability to accelerate compound to flocculate
hydrophilic colloids, resulting in a more permeable C-S-H surface layer,
through which water and ions can diffuse faster 4.

(2)   Accelerating the participation of compound ions in aluminates
reactions, forming some aluminate ion phases mostly when there is not enough sulfate
to react with C3A. Monosulfate conversion of ettringite will not ocur
 if free ions are available 5.

(3)   An increased calcium concentration cause a quicker
super-saturation of the liquid with respect to calcium hydroxide, Ca(OH)2,
meantime a lower sulfate concentration will cause slower formation of
ettringite which will shorten the initiation of aluminate, C3A,
hydration 6.

Retarding admixture is an
admixture that retards the setting of concrete 7. A retarding admixture
causes cement set retardation by one or more of following mechanisms:

(1) Adsorption of the
retarding compound on the surface of cement particles, forming a protective thin
layer which slows down hydration;

(2) Adsorption of the
retarding admixture on to nuclei of calcium hydroxide causes of their growth poisoning,
which is essential for continued hydration of cement after the end of induction

(3) Formation of
complexes with calcium ions in solution, increasing their solubility and
discouraging the formation of the nuclei of calcium hydroxide referred to in
(2) above; and

(4) Precipitation around
cement particles of insoluble derivatives of the retarding compounds formed by
reaction with the highly alkaline aqueous solution, forming a protective skin 8.

are amines containing a single, double or triple hydroxy alkyl group. Alkanolamines
which are frequently used as concrete admixtures is used as grinding aids. The
action of TEA in the hydration of cement is not described clearly in the
literature. It is not still concluded whether it is an accelerator or a
retarder. Dodson 1 claimed that “the most popular addition rate of TEA is in
the range of 0.010 % to 0.25 % on the weight of cement. The
conclusions show that at a dosage of 0.02 %, TEA acts as an accelerator, at
0.25 % as a retarder, at 0.5 % as a severe retarder and at 1.0 % as a flash-set
accelerator. Similar behavior was found by Ramachandran 2 when measuring the
initial and final setting characteristics of Portland cement mortar mixed with
0 – 0.5 % TEA. Other studies showed that the most prominent feature of TEA is
its ability to act as both a set retarder and a set accelerator depending on
its dosage. TEA accelerates C3A hydration as well as delays C3S
hydration 2,3. Jolicoeur et al. (2007) used TEA amounts ranging from 0.02% to
0.15% in their study. When TEA 0.1% was used, a strong accelerator effect was
observed due to rapid hydration of C3A (false setting). Heren and
Olmez (1996) investigated the hydration and mechanical effects of ethanolamine
oligomers which they added to the consistency water in varying amounts of 0.1
to 1%. They compared MEA, DEA, and TEA at dosages 0.1 to 1.0 % in white
Portland cement and found no significant effect on the initial setting times at
low dosages, but significant retardation at higher dosages for all three types.
TEA is a weak base and in an aqueous phase, it is mostly in the molecular state.
TEA has the ability to chelate with certain metallicions such as Fe3+
in highly alkaline media 11.

is a tertiary amine and TIPA is used in the cement industry as a grinding aid,
and it is also used in concrete formulas. The addition of small amounts of TIPA
can result in a signi?cant increase in the strength of cement pastes at early
and late ages 12. Aggoun (2008) investigated the early strength and setting
effects of TIPA/TEA/ calcium nitrate mixture combinations in normal portland
cement and obtained important and promising results for both the setting and
curing accelerator effects of the amine/calcium nitrate composition. Aggoun has
found that TIPA’s curing accelerator performance is higher than TEA regardless
of cement type 13.

and others make a research work for the evaluation of six commercial grinding
additives, which were used for the production of Portland cement (ground in a
ball mill at a laboratory stage). They tested all cement mixtures for initial
and ?nal setting times, consistency of standard paste, ?ow of normal mortar and
compressive strengths after 2, 7 and 28 days. They found the slightly
decreasing of the initial and final setting times in case of triethanolamine
containing grinding aids that was based on the C3A reaction acceleration.
However, they also found that the presence of triisopropanolamine as a grinding
aid in the cement mixture increases the initial and ?nal setting times about
15%, acting as a retarder of hydration at early stages 14. The aim of another
research work made by Allahverdi and Babasafari is to interpret the
effectiveness of TEA on grindability, set and strength behavior of Portland
cement in laboratory ball and vibrating disk mills when added 0.06 % amount of by
the weight of the cement. It is concluded that an addition of TEA increases
both initial and final setting times and decreases compressive strengths at 3,
7 and 28day curing ages in both ball and vibrating disk mills 15.

sugars. sugar acids and salts. borax and boric acid are known as set retarders
16. But
in the study of Koyuncu (2004) and others 12 sodium borax pentahydrate (Na2B407.5H20)
was used in concrete as replacement materials in a certain ratio instead of
Portland Cement. In the concrete specimens it was observed from the experiments
that while the amount of borax ratio increases the compressive strength,
flexural strength, setting time, unit weight, and workability decreased. Additionally,
it was observed in the studies that the cement paste made with boron containing
cement had an increased  setting point
both beginning and final 18,19.  Davraz
20 used boron modified active belite cement, calcium aluminate cement and Portland
cement as a binder material in the mortar mixtures. Their aim was to research the
effects of the boron compounds into hydration reactions of the different cement
types and  these effects controllability.
Boric acid (BA) was used in the studies at the ratios of 0.25–1.00% of the weight
of cement in mortar mixtures with Portland cement. It was found that by
increasing the usage portion of B2O3 the redarding effect
was increased, this could be controlled by adding accelerator aids to the
mixture. The best results were taken from sodium aluminate and 1 % Boric acid
mixture. The formation of calcium diborate (CBH6)
barrier layers on particle surfaces should be delayed to reach to optimum
setting times and the strength in convenient B2O3
concentration 20.

and friends 21 used NMR spectroscopy to study the complex formation behaviors
between  TEA and boric acid in aqueous
solutions and to determine the stoichiometric compositions, stability, and
structures of boron complexes. They concluded formation of two kinds of 1:1
complexes in aqueous solutions. They were TEA-B and its hydrolysis product with
a bicyclo 3,3,0 structure. Both of them had tetrahedral structure around
boron atom, having a boron-nitrogen bond 21.

the concentration range of grinding aids added is from 50 to 500 ppm. After the
grinding process, the additives might not be any longer in their original
chemical form. Moreover, grinding aid composition might not only consist of
mixtures of pure compounds but also rather more complex raw materials 22.

aim in this study is to determine the contribution of the boron compounds with alkanolamines type
grinding aids to the cement settings. Also making a command about way of
setting mechanism can be helpful for further studies. Most of the boron
compound studies with cement were focusing on a higher concentration of boron
compound in past. It will be helpful for further studies to see the result of
lower boron compound containing cement experiments.  


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