Introduction The interest in high performance cements has been growing in the last years, as a natural consequences of high

performance concrete production. Cement producers are requested to offer in the market hydraulic binders with high early strengths, and this can be obtained by optimizing several parameters, ranging from clinker chemistry and reactivity to cement particle size distribution. The production of such high performing cements at a reasonable cost (from the point of view of clinker content and energy requirement for high fineness grinding) can be challenging and the use of suitable cement additives becomes mandatory. everal types of products can be found on the market. !hatever is the additive used (pure grinding aids, specifically designed to increase production and fineness, or performance enhancers with effect on cement hydration), the choice of the most appropriate relies on a detailed investigation that should consider all the characteristics of the cement. Grinding aids for high performance cements "rinding aids are organic compounds that are added to the mill during cement grinding. Their main purpose is to reduce the energy required to grind the clinker into a given fineness. #n addition, some products (usually referred to as performance enhancers) provide positive effect on cement hydration improving strength development $%&. #n this paper we present a typical e'ample of full investigation about the possibility of producing high early strength type # cement, using an appropriate cement additive. !e were approached by a grinding plant with the target to produce a (ortland cement (C)* # according to )uropean standard )+ %,-.%) with early strengths as high as possible. The grinding plant has, for the production of high.performance cements, four different clinker sources available, here indicated as clinker %, /, 0 and 1. #n our lab a detailed investigation was performed, consisting in the following main points2 %. clinkers characterization3 /. investigation about clinkers4 grindability and reactivity3 0. optimum cement composition3 1. choice of the most appropriate cement additive, on the basis of the data collected. Clinkers characterization The four clinkers were characterized using the following techniques2 . 5.6ay fluorescence (567)3

. determination of loss on ignition and chemical analysis of free lime3 . 5.6ay diffraction (568) with 6ietveld refinement. 6esults are reported in the table % (chemical composition) and table / (mineralogical composition). Cement Additives Division 2 Clinker 1 Clinker 2 Clinker 3 Clinker 4 Loss on ignition 9,%: ; 9,/% ; 9,%< ; 9,%1 ; SiO2 /9,=- ; /%,9- ; /9,1, ; /9,1% ; Al 2O3 :,/= ; :,0: ; =,0< ; :,=% ; e2O3 0,%< ; 0,<: ; /,%< ; /,<, ; CaO =:,%/ ; =1,:% ; =1,1= ; =:,10 ; !gO /,%9 ; %,=% ; 0,9,; %,/: ; "2O 9,=< ; 9,-% ; 9,1< ; 9,,0 ; #a2O 9,%/ ; 9,%0 ; 9,1< ; 9,%% ; SO3 %,,= ; %,%0 ; 9,:= ; %,:1 ; ree CaO 9,:% ; 9,-< ; %,9: ; %,0- ; $a%le 1& chemical composition of clinkers according to 567 analysis Clinker 1 Clinker 2 Clinker 3 Clinker 4 $ricalcium aluminate C3A 1,/ ; -,- ; %9,< ; :,- ; $etracalcium aluminoferrite C4A %9,0 ; %%,- ; :,< ; <,, ; Alite C3S =-,, ; =%,% ; -9,, ; -0,1 ; 'elite C2S %-,0 ; %1,1 ; %/,1 ; %/,9 ; $a%le 2& mineralogical composition of clinkers according to 568 analysis with 6ietveld refinement Grinda%ilit( everal parameters affect difficulty or ease of clinker grinding. >ll of them should be taken into account, since it is not always possible to find a single correlation. #n details, the main factors directly related to clinker grindability are the following2 . amount of belite (C/ ) and alite (C0 )2 clinkers with high amount of C/ usually present more difficulties in grinding, while as the C 0 increases the grindability increases $/&3 . dimension of alite and belite crystals2 bigger crystals (especially of belite) increase clinker hardness $0&3 . impurities, such as magnesium (*g?), sulphate ( ? 0) and potassium (@/?), are reported to influence grindability, probably through a modification of crystalline structure of alite3 . tendency to pack.set and coating of grinding media and mill lining3 Cement Additives Division 3 . porosity of clinker. ince energy requirement for high fineness grinding is crucial in developing high performance cements, a preliminary investigation on clinker grindability were carried out.

The grindability of clinkers is usually compared on a lab scale by using a lab ball mill. Ay grinding several clinkers using the same procedure (same amount of material and identical grinding time), harder clinkers reach lower fineness (e'pressed as Alaine specific surface or residual on sieve) than softer. )ven though such lab tests hardly allow to forecast the energy requirement for cement production in industrial mills, a general indication of difficulties in grinding different clinkers in the same mill can be obtained. The clinkers received were compared according to the following protocol2 . >ll the clinkers were crushed to a particle size totally passing through a 0 mm sieve3 . : kg of each clinker were ground in a lab ball mill3 . Alaine specific surface and air Bet residual (>lpine) of ground material were checked. "raph % reports the 19 Cm air Bet residual and the belite content of each clinker. The grindability of clinkers %, / and 1 is directly related to the C/ amount, while clinker 0 resulted more difficult to grind, without direct correlation to C/ content. >nyway it has to be pointed out that this clinker has the highest content of *g? and the lowest content of ? 0, both factors influencing the formation of specific polymorphic modifications of alite $1&. Graph 1 Clinker grinda%ilit(& air )et residual *ersus %elite content
9,9; /,9; 1,9; =,9; <,9; %9,9; %/,9; %1,9; %=,9; %<,9; /9,9; Clinker % Clinker / Clinker 0 Clinker 1 >ir Bet residual 19 Cm Aelite content

Sulphate optimisation #t is known that gypsum in cement affects not only setting time, but also strengths development. 7or each clinker, depending on its chemical and mineralogical composition there is a ?0 content that ma'imize compressive strengths. Cement Additives Division 4 >fter grinding the clinkers were mi'ed with different amounts of ground gypsum in order to

reproduce samples of C)* #. Compressive strengths in mortar were tested according to )uropean standard )+ %,=.%. 6esults are summarized in "raph /. Graph 2 G(psum optimisation& compressi*e strengths *s g(psum content
9,9 :,9 %9,9 %:,9 /9,9 /:,9 09,9 0:,9 /; 1; =; + g(psum 24 h compressi*e strengths ,!-a. Clinker % Clinker / Clinker 0 Clinker 1

?ptimum gypsum was close to 1; for clinker / and 1, while for clinkers % and 0 was close to /; and =; respectively. There was a quite evident correlation between optimum gypsum, tricalcium aluminate and ?0 content of clinkers (graph 0)2 as C0> increases and ?0 decreases, the clinker needs more gypsum for better hydration and strengths development. Graph 3 Comparison of optimum g(psum and C3A/SO3 content of clinker
9,99; /,99; 1,99; =,99; <,99; %9,99; %/,99; Clinker % Clinker / Clinker 0 Clinker 1 C0> content ; ?ptimum "ypsum ?0 content

Cement Additives Division 5 #n table 0 the compressive strengths of cements at optimum gypsum content are summarized and compared to alite content and fineness. >s e'pected, clinker 1 (characterized by the highest C0 content and best grindability) developed ma'imum strength levels. Clinker /, due to the lowest C0 content, reached poor strengths despite the good grindability. Clinker 0 presented the opposite situation2 high level of C0 , but lower strength due to difficult in grinding. ?n the basis of the data collected, the most promising cement was identified as made with clinker 1 with the addition of 1; gypsum, ground at the highest fineness possible with acceptable mill output and water demand. 24 h strength at

optimum g(psum C3S content 0esidual 41 2m 'laine ,m2/kg. Clinker 1 /0,< *(a =-,, ; <,< ; 0,1 Clinker 2 /%,1 *(a =%,% ; :,: ; 119 Clinker 3 /%,1 *(a -9,, ; ,,/ ; 0-= Clinker 4 /<,< *(a -0,1 ; 1,/ ; 10= $a%le 3& compressive strengths at optimum gypsum, fineness and C 0 content Choice of cement additi*e The fineness levels needed for early strength increase can be reached at a reasonable cost only through the use of a specific grinding aid. #n addition, a suitable formulated product able to accelerate the clinker hydration can contribute to strength development allowing to boost cement performances. !e tested in lab some formulations by concentrating on the chemical effect on hydration and we identified the most promising as a performance enhancer belonging to the *>.(.).D series. The final step of this work was the optimization of sulphate content in presence of chemical additive. >ccording to our e'perience, the optimum gypsum can be very different if a grinding aid is used during cement production $:&. The reason of this lies in the fact that hydration of cement is modified by the presence of chemical addition. Cement Additives Division 6 Graph 4 G(psum optimisation 3ith cement additi*e
%:,9 %-,9 %,,9 /%,9 /0,9 /:,9 /-,9 /,,9 0%,9 00,9 0:,9 /; 1; :; =; + g(psum 24 h compressi*e strengths ,!-a. C)* #DClinker 1 . Alank C)* #DClinker 1 . 9,/; *>.(.).D

everal cements have been reproduced by mi'ing ground clinker 1 with different amounts of gypsum. >ll cement samples were hydrated without any cement additive (blank test) and with the addition of 9,/; *>.(.).D . The results (reported in graph 1) showed a slight shift of optimum

gypsum towards higher values. This is quite coherent with the fact that some grinding aids accelerate the hydration of aluminate phases, thus requiring the supply of higher amount of sulphates $=&. Industrial test The data collected during this complete lab investigation were used during industrial trial in the grinding plant. The results confirmed what e'pected and it was possible to produce a C)* # with high early strengths (higher than 09 *(a at /1 h) at a reasonable cost and with interesting mill output. Conclusions The use of grinding aids is of e'treme importance during production of high performance cements needed for top quality concrete. Aeside the positive effects on reduction of agglomeration and improvement of mill efficiency, grinding aids have a strong chemical effect on cement hydration. #n order to optimize cement performances, several parameters should be taken into account. Chemical and mineralogical composition, grindability of clinker, amount of gypsum and cement finenenss are probably the most important. The optimum gypsum can be very different if a grinding aid is used during cement production. This allows interesting results to be obtained, in terms of higher compressive strengths and better performances. 0eferences $%& E. ottili, 8. (adovani2 F)ffect of grinding aids in the cement industryG H (etrocem, t. (etersburg, /99/ Cement Additives Division 7 $/& !.I. 8uda2 FCement data book, Jol. %G H 0rd )dition, Aauverlag "mbI, %,-= $0& E.*. Iills2 FClinker microstructure and grindability2 updated literature reviewG H (ortland Cement >ssociation, /99$1& I.7.!. Taylor2 FCement ChemistryG . >cademic (ress, Eondon, %,,9 $:& 8. (adovani, *. *agistri2 F#mprovement of mechanical strengths by the use of grinding aids2 optimisation of sulphate content in cementG H %: th >rab #nternational Cement Conference and )'hibition, Cairo, /99< $=& *. *agistri, >. Eo (resti2 F#nfluence of grinding aids on cement hydrationG H !orld Cement, Kune /99-