Historical of cement

Kata "cement" berasal dari bangsa Roman asli.

Bangsa Romans membuat structural concrete dari batu pecah atau sejenis

material dengan burned lime sebagai binding medium .

bentuk construction ini disebut "opus caementitium.
British engineer John Smeaton (1724-1792) menemukan clay component
as essential to hydraulic setting dan hardening behaviour .
1756, he sought a water-resisting binding medium tor the masonry of the
new Eddystone lighthouse near Plymouth.
1796 Briton, James Parker, membuat hydraulic cement. Yang disebutnya
"Roman cement
1824 Joseph Aspdin, a British bricklayer, untuk menghasilkan excellent
hydraulic lime, dg burning a mixture containing certain proportions of lime
dan clay pada high temperalure. ia menyebutnya "Portland cement".
first rorary kiln in Germany was commissioned in 1898
 Definition of cement
difinisi cement German Standard DlN1164
"Cement adalah bahan pengikat hydroulis yang digilinghalus untuk mortar dan concrete,
banyak mengandung calcium oxide dengan silicon dioxide, aluminium oxide dan ferric oxide,
yang terbentuk dg sintering atau fusion. bila dicampur dg air, cement mengeras dg air dan
udara, mencapai compressive strength at least 25 N/mm2 at 28 days.
Portland cement dibuat dari portland cement clinker dicampur dengan sulphate.
Portland blast furnace cements (slag cements) ditambah blastfurnace slag, seperti trass
cement additionally contains trass
 Raw material of cement
1. Limestone dan clay mineral (CaO,SiO2,Al2O3,Fe2O3,MgO):
pure limestone >95%,CaCO3 (by weight)
marly limestone 85-95% CaCO3, (by weight)
lime marl 70-85 % CaCO3 (by weight)
Marl 3O-70 % CaCO3. (by weight
clay marl 15-30% CaCO3. (by weight)
marly clay 5-15% CaCO3, (by weight)
Clay < 5% CaCO3. (by weight)

2. Correction material (SiO2,Fe2O3,Al2O3,MgO) :

silica sand : quartz (SiO, "sand")
ferrit sand : limonite (FeOOH), pyrite (FeS2)
Bauxite stone : Al2O3
Dolomite : CaMg(CO3)2

3. Gypsum : gypsum (CaSO4.2H2O),

Natural gypsum
Phospho gypsum
Batasan nilai chemical composition dari cement
raw material (after ignition)
 Hydraulic modulus
Hydraulic modulus :
 Lime saturation factor
LSt I : actual content CaO yg ada
didalam raw materlal (or in the clinker)
sebagai % maximum kadar CaO yang
dapat mengikat dg acidic oxides (SiO2,
Al2O3, Fe2O3.) didalam most lime-rich
clinker phases under technical
conditions of burning and cooling.
LSt = 100 repesents the optimum CaO
content
LSTIII if MgO > 2 %
For technical clinkers the value of
LSt lll is between 90 and 102
(values above 97 are to rated as
very high-quality).
 Silica modulus
Silica modulus (SM) (or silica
ratio) adalah ratio silica (SiO2)
terhadap jumlah alumina
(Al2O3) dan ferric oxide
(Fe2O3):
modulus ini merupakan ratio
solid terhadap liquid didalam
clinkering material, Karena pada
clinkering temperature SiO2
predominantly present dalam
solid phases (alire and belite),
whereas the other two oxides
occur in the liquid phase (melt).
industrial cements , silica
modulus umumnya 1 .8 and
3.0.
 Iron modulus
iron modulus (lM). Dikenal juga sebagai
alumina ratio (AR), adalah ratio alumina
terhadap ferric oxide:
bila ferric oxide content lebih tinggi,
sehingga iron modulus lebih rendah
lower.
viscosity melt berkurang.
value IM < 0.638 clinker phase disebut
tricalcium aluminate (C3A) membentuk:
C3A-free cements ars meningkatkan
sulphate resistance.
industrial cements ,modulus ini
umumnya antara 1 .3 dan 4.0 dan
kebanyakan antara 1 .8 dan 2.8.
special cements bias lebih rendah
nilainya (dibawah 0.4).
 burning process
Carbon dioxide (CO2) is driven out of the
limestone and water of hydration is driven
out of the clay, As a result, the materials
undergo a decrease in weight in the
production of cement clinker.
Furthermore, about 7% of water of
hydration is expelled lrom the clay in the
raw meal (organic constituents, etc. are
not considered).
Jadi, bila raw meal mengandung, 76%
CaCO3,dimana CaCO3 dan clay di pijarkan,
loss on ignition sekitar:
f rom CaCO3 = 0.76 x 44 = 33.44% CO2
f rom clay = 0,24 x 7 = 1 .68 % H2O
= 35.12% total
loss on ingnition,
 Ignition loss of clinker
raw meal with 76%
CaCO3 gives abut 64.9%
of clinker, for an
ignition loss of about
35.1 % (or:1 kg of raw
meal yields about 0.65
kq of clinker).
For different values of
the CaCO3 of the raw
meal the quantities ol
materials can be
calculated with the
following formulas:
Takihg account of losses
of material in the
manufacturing process,
it is generally assumed
in practice that 1,55-
1.60kg of raw material
is needed for producing
' 1 kg of clinker.
Calculation raw mix proportions
Calculation raw mix proportions
Calculation raw mix proportions
principal reactions in clinker burning
X-ray analysis methods
 Hubungan antara silica modulus dan the combining of lime in
synthetic raw meals made from pure oxides (from Sycev, 1962)
effect limestone particle size pada kadar free CaO pada
berbagai temperatures,
Compressive strengths of clinker phases (water-cement ratio = 0.5);
1=C3S; 2=C2S ; 3=C3A ; 4=C4AF (from Bogue, 1985)
 Clinker phases
Alite (tricalcium silicate)= tricalcium silicate (C3S), dibawah 1250 C,
tricalcium silicate bias dibentuk CaO dan C2S bila very slow cooling, khususnya bila
mengandung Fe2 + sebagai hasil burning dibawah kondisi reducing conditions.
Belite (dicalcium silicate)= terjadi terutama dalam bentuk padat
pd clinkering temperature dan terdapat hanya dalam porsi kecil dalam clinker
dengan high lime standard.
Perkembangan strength lambat, tetapi pada kekuatan akhir baik sbg alite.
Beta belite, yang terbentuk dominan didalam clinker, pada room
temperature berubah ke Gamma belite, yg mebentuk lebih stable , tetapi
virtually lacking in hydraulic properties (beta-gamma inversion)
Aluminate phase= ( C3A), bersama dengan alite dan belite, aluminate
phase meningkatkan early strength dalam hardening cement.
Ferrite phase=The ferrite phase does not possess a constant
chemical composition; it is in fact I member of a solid solution
series extending theoretically from C2A to C2F
Experimentally determined chemical composition of the
clinker phases of a portland cement clinker (% by weight)
Portland cement clinker: micrograph obtained light: alite: with reflected dark
grey, mostly with straight boundaries; belite : light grey, curved
boundaries;ferrite: white matrix; aluminate: dark lnclusions in white matrix
Portland cement clinker: under-burned (porous); micrograph obtained with
reflected light: free lime.: black pocket; belite: light coloured textured areas;
alite: dark textured areas; pores (here filled with resin): grey areas with
grinding scratches
Bogue's formulas for calculating the
potential composition
potential phase content selalu didapat dibawah 100 %
 materials yg digiling di finish grinding
Sulphate (Gypsum)= untuk mengontrol (retard) setting time .
retarding effect reaction sulphate dengan tricalcium aluminate, set terlalu cepat
(clinker mengandung higher content C3A memerlukan banyak sulphate.
Blastfurnace slag = granulated blastfurnace slag yg digiling dg clinker dan gypsum
menghasilkan slag cement dengan high slag content .
Pozzolanas= reaksi pada normal temperature dg calcium hydroxide dan
menghasilkan strength-developing chemical compounds (hydraulic hardening)
Fly-ash = banyak mengandung SiO2, Al2O3 and Fe2O3 . pozzolanic material ,
activated dg calcium hydroxide membentuk hydraulic hardening
Fineness and particle size distribution = digiling hingga menghasilkan cement yg
halus akan bereaksi dg air = hydration process.
Mill atmosphere : (temp > 120 C,water content CaSO4. 2 H2O keluar membentuk
hemihydrate (CaSO4.1/2 H2O) atau soluble anhydrite (CaSO4)
Grinding aids = effective grinding aids seperti glycols (e. g., ethylene glycol,
propylene glycol) dan ethanol amines (e.g., triethanol amine). Penambahan nya
kurang dari 0.005% berat
Kadar gypsum dan hemihydrate (termasuk soluble anhydrite) berfungsi sbg
mill charge temperature selama grinding
 Hydration of cement
strength of mortar (aggregate particle size < 4 mm) dan concrete (aggregate
particle size < 16 mm, < 32 mm or <163 mm) dipengaruhi banyak factors
al:
type and quality of the cement;
water-cement ratio (proportions by weight)
aggregates (type, strength, particle shape, surface, quantity, grading);
admixtures dan additives.
compaction and curing
temperature and age
Relation antara 28-day compressive strength of concrete
, water-cement,ratio dan cement strength
 Hydration clinker phases
hydration reactions can be represented as follows in a simplified
general way:

clinker phases + water hydrate phases + energy

(high in energy; (low in energy; (heat of
contain no water) contain waler) hydration)
 Aluminate
In the absence of gypsum in the cement, tricalcium aluminate reacts very quickly:
3 CaO.Al203 + 6 H2O 3 CaO.Al2O3. 6 H2O. (1)
3 CaO .Al2O3 + Ca(OH)2 + 12 H2O 4 CaO .Al2O3 + 13 H2O (2)
Both these reactions would cause excessively rapid setting of the cement
paste.Sulphate, in the form of gypsum or anhydrite-ll, is therefore added as a
retarder,interground wirt the clinker in the f inish grinding mill. The hydration
reaction in the presence of sulphate proceeds as follows:
3 CaO .Al2O3. + 3 (CaSO4. 2H2O) + 26 H2O CaO. Al2O3 .3 CaSO4. 32 H2O
C3A + 3 (Cs'2 H) +26H C3A 3Cs.32H (3)
aluminate + gypsum + water etringet/trisulphate
Hardened cement paste with acicular ettringite crystals
(scanning electron micrograph)
 Alite
Alite (tricalcium silicate) reacts with-water to form calcium silicate
hydrates (CSH phases) containing less lime, while calcium hydroxide is split
off. Belite (dicalcium silicate) shows similar behaviour. The hydration
reaction is, for example:
6 (3CaO.SiO2) + l8H2O 5CaO.6SiO2.5H2O + 13Ca(OH),.
6 CaS + 18 H C5S6H5 + 13 CH (4)
Alite +water CSH phase + Calsium hydroxide
 Calcium silicate paste (scannin g electron
hydrates (CSH phases) in hardened cement micrograph)
Heat of hydration of clinker phases (in J/g)
 Schematic diagram of the formation of the hydrate phases and the structure
development in the hydration of cement (from Locher/Richartz/Sprung, 1 976)
 Relations between chemical reactions, phase
content and strength of portland cement
Relative compressive
strengths associated
with variation of the
silica modulus
(laboratory cements;
referred to cement with
lime standard KSt : 95:
silica modulus 2.0;
alumina modulus 2.0;
2.8 % SO3, fineness
3200 cm2/g Blaine)
Relative compressive strengths associated with variation of the iron modulus
(laboratory cements; referred to cement with lime standard KStl : 95; silica
modulus 2.0; alumina modulus 2.O; 2.8 % SO3: fineness 3200cm2/g Blaine)
Relative compressive strengths associated with variation of the lime standard
(laboratory cements; referred to cement with lime standard KSt:95; silica
modulus 2.0; alumina modulus 2.0; 2.8 % SO3; fineness 3200 cm2/g Blaine)
Relative compressive strengths as a function of lime standard,silica modulus
and iron modulus, referred to the respective 2-day strengths (laboratori
cements)
 Effect of increasing MgO content on compressive strength
development and clinker phase content (laboratory cements)
Effect of K2SO4 on compressive strength development and
clinker phase content (laboratory cements)
Types, strength classes, designation and quality
control of cements
Classification and designation of cements (from
Cembureau1968)
Strength classes (DlN 1164)
 Cement testing
Fineness
Sieve residue
Specific surface
Setting times
Soundness
Strength
Heat of hydration