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The Performance Builder For A Bright Future SKS - 6

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The document discusses SKS-6, a sodium silicate builder material that can be used as an alternative to sodium tripolyphosphate in detergents. It describes the manufacturing process of SKS-6 and its various properties and applications in laundry and automatic dishwashing detergents.

The document discusses various types of laundry detergents including basic, compact, laundry tablets, regular, color and fine-fabric detergents. It also discusses automatic dishwashing detergents.

SKS-6 is manufactured by converting sand and caustic soda to water glass, which is then spray dried. This amorphous sodium disilicate crystallizes to a layered silicate through special temperature control. Further process steps such as grinding and compacting lead to the commercial SKS-6 products.

The performance builder

for a bright future


SKS®- 6
SKS®-6
contents

IntroDuCtIon 4 Physical and chemical properties 12

Manufacturing 6 Water softening properties 14


SKS-6 characterisation 7 Alkalinity and reserve alkalinity 18
Product range, particle structure and morphology 10 Dispersed particle size, solubility and 20
dispersing properties
Storage properties 22
Water uptake 23
Surfactant uptake 24
Compatibility with other detergent ingredients 26
Precipitation and inorganic incrustations 28
Heavy metal binding capacity 31
EnvIronmEntal anD SafEty aSPECtS 32

Life cycle inventory 34


Solubility in waste water 35
Exposure modelling 37
Toxicology of SKS-6 and SKS-6 based 38
detergent formulations

2 SKS®- 6
launDry DEtErgEntS 40 aPPEnDIx 60

Basic detergent effects 42 Glossary 62


Compact detergents 44 Patents 64
Laundry tablets 47 Abbreviations 65
Regular detergents 48 Literature 66
Color detergents 50 Product range 67
Fine-fabric detergents and water softeners 51
automatIC DIShwaShIng DEtErgEntS 52
Automatic dishwashing detergents 54
Cleansing performance 56
Formation of deposits in the dishwasher 57

3
SKS-6
IntroDuCtIon

4 SKS®- 6
SKS-6 – The performance
builder for a bright future
Washing is something that is done throughout
the world, on every continent. However,
modern detergent formulations must also cater
individually for a wide range of requirements in
various countries to enable optimum results to
be obtained. Particularly in the area of builders,
detergent formulations have undergone a change
in last decades.

For years, sodium tripolyphosphate was used as the universally


preferred builder. Concerns about the possible eutrophication
of rivers and lakes have led to a decline in the use of this builder,
which differs from region to region.

The need to have an alternative to sodium tripolyphosphate


initiated an intensive worldwide search for suitable substitutes.
Combinations of zeolite A with polycarboxylate and soda ash
were developed as a phosphate substitute. Although soluble and
insoluble builders have been used for many years, so far no
builder has been available whose advantages as a whole combine
to meet the varied requirements of a modern builder.

Intensive research has resulted in the development of a certain


type of layered sodium silicate. The SKS-6 type has proved to
be the most promising one in terms of its positive properties for
use in detergents.

5
SKS-6
Manufacturing

For the manufacture of SKS-6, sand and caustic


soda are converted to water glass and this is then
spray-dried (Fig. 1). This powdery amorphous
sodium disilicate crystallises to layered silicate
through special temperature control. Other
process steps such as grinding and compacting
lead to the individual commercial products.

Figure 1: Manufacturing of SKS-6

Sand Soda ash or caustic soda

Water glass solution

Spray drying

Amorphous disilicate

Crystallisation

SKS-6

Compaction,
Milling Compaction Agglomeration,
Additives

SKS-6 powder SKS-6 granular SKS-6 cogranular

6 SKS®- 6
SKS-6
CharaCtErISatIon

SKS-6 belongs to the chemical group of sodium disilicates with the


molecular formula Na2Si2O5. These demonstrate the phenomenon
of polymorphism, i.e. the ions can be linked together, with the same
total composition in different space arrangements, different lattice
structures. Four forms occur most frequently: alpha-, beta-, delta-
and epsilon-sodium disilicate. Common to the structures is that
silicon and oxygen ions unfold two-dimensional layers, in the form
of linked tetrahedra. Sodium ions situated between the layers
ensure charge equalisation.

Figure 2: Crystal structures of sodium disilicate

Alpha-sodium disilicate Beta-sodium disilicate Delta-sodium disilicate

The different polymorphous phases differ essentially in the angles


Figure 3: Reactions of delta-sodium disilicate
in which the individual tetrahedra are arranged to one another
(Fig. 2). Ion exchange with proton/Providing alkalinity

As a technical product, SKS-6 is composed mainly of the delta Na2Si2O5 + 4 H2O NaHSi2O5 · 3 H2O + Na+ + OH–
phase with small shares of the alpha and beta phases.
Ion exchange with Ca2+ and Mg2+ (Me2+)/ Water softening

SKS-6, primarily the delta phase, can undergo some varying


2 Na2Si2O5 + Me2+ »Me (NaSi2O5)2«+ 2 Na+
reactions in tap water. These are then the basis for the multifunc-
2 NaHSi2O5 · 3 H2O + Me2+ »Me (HSi2O5 · 3 H2O)2« + 2 Na+
tional application profile. First, water molecules that come into
contact with SKS-6 on the solid’s surface are deprotonised. This Hydrolysis/Providing water glass
leads to the formation of hydroxide ions in the solution and is the
>> 20 H2O
cause of the high alkalinity supply of SKS-6 (Fig. 3). At the same Na2Si2O5 + 2 OH– 2 SiO32- + H2O + 2 Na+
time, a sodium hydrogendisilicate, kanemite, is formed. As a result NaHSi2O5 · 3 H2O + 3 OH– 2 SiO32- + 5 H2O + Na+
of the uptake of water of crystallisation in kanemite the layered
silicate separates and the crystal framework expands. As this
cannot be without an influence on the solubility and dispersing
capability, a very rapid disintegration of the disilicate granules in
the water is observed.

7
Delta-sodium disilicate and kanemite can undergo an exchange with various cations.
In particular these are the hardness-forming calcium and magnesium ions. But
heavy metal ions or ammonium salts can also thus be bound through ion exchange.

Both reactions, water softening and the supply of alkali, are similarly rapid.

An excess of water dissolves a part of the layered silicate and forms Nowadays, modern detergents are usually dry-mixed instead of
a water glass-like solution. being spray-dried, this is a more economical process. It is necessary
to have a carrier substance for this, such as SKS-6 powder, that can
These simultaneous reactions make up the diverse property profile take up liquids such as surfactants, copolymers etc.
of SKS-6. This is particularly advantageous for modern detergent
formulations and can be used in many ways. The final products thus Particularly, modern compact detergents and detergent tablets
manufactured with SKS-6 meet the highest demands on activity and require highly effective raw materials that can simultaneously
low dosage and do not cause any adverse effects after application. undertake several functions, so as to lower the dosage or to create
a degree of freedom for innovative formulations (Fig. 5).
For some time there has been a demand for compact and multi-
functional builders (Fig. 4). SKS-6 is non-eutrophic and leaves no Especially when used in dishwasher detergents, SKS-6 demon-
water-insoluble residue in waste water treatment plants that would strates its multifunctional character. It supplies the alkalinity
otherwise require a lot of resources to be separated and deposited. necessary for the cleaning process, it binds hardness in water and
from food residues, it is compatible with the carriers of active
oxygen sodium perborate and sodium percarbonate and it is
markedly effective against the consequences of glass corrosion.
This is dealt with separately in the section “Automatic dishwasher
detergents”.

8 SKS®- 6
Figure 4: Why use layered silicate SKS-6? Figure 5: Why use layered silicate SKS-6?

Why use layered silicate SKS-6? 20


· General demand for environmentally compatible and compact builders
· Modern detergents: dry mixed instead of spray dried
· Compact detergents, tablets: few ingredients, high stability Content in formula [%]
· Multifunctionality in HDP’s
· Favourable ecological profile
· Contributing to cleaning ability in ADD’s. 10
Provides additional benefit due to its anticorrosive properties
SKS-6 can totally or partially replace
· Zeolite for water softening
· Water glass for alkalinity and protection from corrosion
· Soda ash for alkalinity and washing performance 0
SKS-6 can partially replace Ingredients replaced Formula including SKS-6

· Polycarboxylate cobuilder n Polycarboxylate n Amorphous disilicate n Soda n Zeolite n SKS-6


· Surfactants, due to its detergency boosting effect

9
SKS-6
Product range, particle structure
and morphology

Today’s range of SKS-6 types comprises


SKS-6 powder, SKS-6 granular, SKS-6 HD
and SKS-6 HD-D (Fig. 6).

Figure 6: Product range of SKS-6 types

Type Silicate content Additive Mean particle size Properties/Benefits Application


[%] [µm]

SKS-6 powder > 99 – 90 -150 Liquid uptake HDPR, HDPC, HDDT

SKS-6 granular > 96 – 500 -700 Flowability, kinetics, HDPC, ADW, WS


low residue

SKS-6 HD 67-79 Polycarboxylic, 450 -700 Surfactant uptake, ADW, HDPC, WS


acid soln. flowability, dispersibility

SKS-6 HD-D 58 -73 Polycarboxylic, 450 -700 Glass care, ADW


acid soln., Zn-salt décor protection

SKS-6 powder is a powder with medium-sized particles. The micro-


scopic photograph shows that the surface is more fissured than that
of a spray-dried disilicate (Fig. 7). Therefore it is suitable to be used
as a base material for compounds with surfactants and polymers
and for heavy-duty detergents, especially regular detergents. It is
also suitable for water softeners.

SKS-6 granular is a pressed granulate with high bulk density and


is generally post-blended in a dry mixing process in detergent
production. The main applications are compact heavy-duty
detergents and automatic dishwasher detergents, but also fine-
fabric detergents and color detergents.

10 SKS®- 6
SKS-6 HD is an agglomerate of SKS-6 and a special acid copolymer.
In automatic dishwasher detergents it results in an increased
cleaning effect and offers protection from the consequences of glass
corrosion. In general, it is suitable because of its porous structure
(Fig. 7) for taking up liquid components, e.g. nonionic surfactants.
This is convenient for example with heavy-duty detergents.
It is particularly suitable for fine-fabric detergents because of its Figure 7: Morphology of various solid detergent builders

reduced alkalinity, which is achieved by conversion with acid


Amorphous disilicate 200 x
co-polymer.

In water softening formulations it can act as carrier for the higher


dosed copolymer solutions.

SKS-6 HD-D contains in addition to the special acid copolymer


a zinc salt and is especially for use in automatic dishwasher
detergents in which it provides additional glass care and décor
protection.
SKS-6 powder 200 x

SKS-6 HD 100 x

11
SKS-6
PhySICal anD
ChEmICal ProPErtIES

12 SKS®- 6
13
SKS-6
watEr SoftEnIng ProPErtIES

The layered silicate SKS-6 softens water by exchange of its sodium


Figure 8: Water softening at low water hardness
ions with the hardness-forming calcium and magnesium ions in (T = 25 °C, pH = 11, t = 10 min, 50 ppm water hardness)
tap water. When added to tap water supplied to washing machines,
60
SKS-6 powder or granules rapidly break down into very small
Remaining (Ca, Mg) CO3 [mg/l]

particles and softening takes place. SKS-6 not required for softening
dissolves in the wash water. Amorphous silicates, on the other
40
hand, work via a precipitation mechanism and exploit the solubility
(law of mass action) of calcium and magnesium silicate.
20
In the tests carried out to determine the combined calcium and
magnesium binding capacity, a defined amount of builder substance
is added to synthetic hard water (see information), which is held 0
at the specified pH during the test by continual addition of acid or 0 0.5 1
alkali. After a reaction time of 10 minutes, the solution is filtered Builder concentration [ g/l]

and the residual hardness of the filtrate is determined. n SKS-6 n Amorphous disilicate

SKS-6 reduces the hardness of tap water already at room tempera-


ture and with low initial hardness values (Fig. 8). The curves show Figure 9: Water softening at low water hardness
the residual total hardness. Amorphous silicates have only limited (T = 25 °C, pH = 11, t = 10 min, 100 ppm water hardness)

effect as a result of their residual solubility. Residual hardness with 120


Remaining (Ca, Mg) CO3 [mg/l]

amorphous silicates is considerably higher than with SKS-6.

One application with low initial water hardness conditions is for 80


example automatic dishwashing. The ion exchanger in the dish-
washing machine produces very soft water for the dishwasher liquor.
The residual hardness and the hardness from the food residue must, 40
however, be removed.

0
0 1 2

Builder concentration [ g/l]

n SKS-6 n Amorphous disilicate

14 SKS®- 6
Even in the case of low water hardness, Figure 10: Water softening at low water hardness
e.g. in Japan, further water-softening is (T = 50 °C, pH = 11, t = 10 min, 100 ppm water hardness)

recommendable. 120

Remaining (Ca, Mg) CO3 [mg/l]


80

At the upper end of the soft water range (Fig. 9-10), SKS-6 also shows
40
exceptional softening action. Even with low additions of SKS-6,
residual water hardness is reduced to less than 1° German hardness.
SKS-6 combines good calcium with very good magnesium bind-
0
ing capacity and effectively reduces total hardness. Compared with 0 1 2
amorphous silicates, only one-third of the amount of SKS-6 is re- Builder concentration [ g/l]
quired to achieve the same water softness under the specified test
n SKS-6 n Amorphous disilicate
conditions. SKS-6 is thus three times more efficient.

Figure 11: Water softening at medium water hardness


(T = 25 °C, pH = 11, t = 10 min, 200 ppm water hardness)

250

Remaining (Ca, Mg) CO3 [mg/l]


200

150

100

50

0
0 2 4
Builder concentration [ g/l]

n SKS-6 n Amorphous disilicate

Figure 12: Water softening at medium water hardness


(T = 50 °C, pH = 11, t = 10 min, 200 ppm water hardness)

250
Remaining (Ca, Mg) CO3 [mg/l]

200

The favourable properties of SKS-6 continue in the medium water


150
hardness range (Fig. 11-12). The water softening capacity of amor-
phous disilicates drops at higher temperatures because of the higher
100
solubility of the silicates.
50

0
0 2 4

Builder concentration [ g/l]

n SKS-6 n Amorphous disilicate

15
In the hard water
range SKS-6 again
demonstrates
its good water
softening capability.
(Fig. 13)

At higher wash temperatures, the degree of softening increases Through a broad pH range, SKS-6 shows very good softening capa-
further (Fig. 14). Although the water softening capability of SKS-6 bility. It already has an optimum performance at pH 9.5 (Fig. 15),
is fully available at room temperature, the exchange processes on the pH value which fine-fabric detergents require. It performs very
the silicate framework are accelerated at higher temperatures and well between pH 10 and 11, the pH range that heavy-duty detergents
increase the binding capacity of the builder. In case of amorphous require.
disilicates, the remaining water hardness is higher at increased
temperatures.

Figure 13: Water softening at high water hardness Figure 14: Water softening at high water hardness
(T = 25 °C, pH = 11, t = 10 min, 400 ppm water hardness) (T = 50 °C, pH = 11, t = 10 min, 400 ppm water hardness)

500 500
Remaining (Ca, Mg) CO3 [mg/l]
Remaining (Ca, Mg) CO3 [mg/l]

400 400

300 300

200 200

100 100

0 0
0 2 4 0 2 4
Builder concentration [ g/l] Builder concentration [ g/l]

n SKS-6 n Amorphous disilicate n SKS-6 n Amorphous disilicate

16 SKS®- 6
Comparative tests provide information about the kinetic behaviour Test Conditions Conditions for figs. 8-14:
of detergent builders. Water softening with zeolite A and with lay- Synthetic calcium- and magnesium-containing
ered silicate SKS-6 (Fig. 16) is considerably more effective than with hard water with
amorphous disilicate. Because of their smaller primary particle size · 50 (German hardness range 1)
· 100 (hardness range 1)
SKS-6 granulate has a greater surface that actively participates in · 200 (hardness range 2)
the chemical process than SKS-6 powder, and therefore they have · 400 ppm (hardness range 3)
advantages in kinetics. water hardness (Ca/Mg ratio = 39/11, 78/22, 156/44,
312/88 ppm, calculated as MCO3)
T = 25 °C, 50 °C
Particularly with builders for water softeners good magnesium
pH = 11 held constant by acid addition
binding is very important. In this domain, SKS-6 yields particularly
t = 10 min
good results compared to the example with zeolite (Fig. 17). If only
After filtration, the residual water hardness was
short application times are possible, SKS-6 granular can be used to determined by titration against EDTA.
advantage because of its very good kinetics.

Conversions of the hardness data are shown in Fig. 18.

Figure 15: Remaining calcium and magnesium concentrations at various ph values Figure 17: Magnesium binding capacity vs time
(c = 1 g/l, T = 60 °C, t = 30 min, water hardness: 225 ppm CaCO3, 56 ppm MgCO3) (c = 1 g/l, T = 30 °C, pH = 10.5, water hardness 17 °d, Mg-sensitive electrode)

400 250
Remaining Ca resp. Ca+Mg

200
MgBC [mg MgCO3/g]
[mg MgCO3/l]

150
200
100

50

0 0
8 10 12 0 5 10
pH value Time [min]

n Ca n Ca + Mg n SKS-6 powder n SKS-6 granular n Zeolite A

Figure 16: Calcium binding capacity of different builders Figure 18: Water hardness calculation diagram
(c = 1 g/l, T = 30 °C, pH = 10.5, water hardness 17 °d, Ca-sensitive electrode) (German hardness range 1: <7 °d, h.r. 2: 7–14 °d, h.r. 3: 14–21 °d, h.r. 4: >21 °d)

30
Degrees German water hardness [°d]

240
CBC [mg CaCO3/g]

180
20

120

10
60

0 0
0 5 10 0 200 400 600
Time [min] [ppm]

n SKS-6 powder n SKS-6 granular n SKS-6 HD n Ca n CaO n CaCO3 n Mg n MgO n MgCO3


n Amorphous disilicate n Zeolite A

17
Alkalinity and
reserve alkalinity

As SKS-6 dissolves, sodium ions from the silicate framework are


Figure 19: pH value vs time
exchanged with protons of the water. In this way the pH of the (c = 1 g/l, T = 25 °C, deionized water)
solution is increased. With SKS-6 it is possible to achieve higher
12
pH values than with the same amount of an amorphous disilicate
(Fig. 19).

The pH increase is essentially dependent on the temperature and


pH value

the water hardness. As a rule, a higher pH value can be achieved at 10

a lower temperature because then the silicate hydrolysis reaction


which uses alkalinity begins only slowly (Fig. 20). In tap water the
pH increase is somewhat delayed compared with pure water,
because the exchanged alkaline earth ions stabilise the layer lattice 8
and thus slightly delay the disintegration of the silicate. 0 5 10 15
Time [ min ]

The silicate lattice counteracts a decrease of the pH value, as can n SKS-6 granular n Amorphous disilicate granular
be seen when acid is added (Fig. 21). Of all tested builders, SKS-6
has the greatest buffer range of pH values higher than 8, followed
by amorphous silicate mr 2.65. Because of their molecular structure,
amorphous disilicates cannot make equal quantities of alkali avail-
able. The silicate structure is also not able to counter pH reduction
as SKS-6 does. As a compound of SKS-6 and acid copolymer SKS-6
HD deliberately contains a lower buffering effect. Phosphate and
zeolite show only a low buffering effect.

18 SKS®- 6
Figure 20: pH value of SKS-6 vs time and water hardness
(c = 10 g/l, tap water 17 °d)

13

pH value
11

9
0 5 10 15

Time [ min ]

n Deionised water 20 °C n Tap water 20 °C


n Deionised water 60 °C n Tap water 60 °C

Figure 21: Reserve alkalinity of detergent builders


(c = 1 g/l, T = 20 °C, deionized water, titration with 0.1 N HCl solution)

12

8
pH value

If one then compares the amount of alkali that the builder in effect 4
makes available with the two pH values of 10 and 9.5 (Fig. 22) it
becomes apparent that zeolite is not effective. Disilicate has a
noticeable buffering effect. In the soda/ disilicate compound it is 0
0 6 12
particularly the soda that is effective. In comparison SKS-6 is the
best alkali supplier. NaOH equivalent [ mmol ]

n SKS-6 powder n Zeolite A


n SKS-6 granular n Amorphous silicate mr 2.65
Besides others, the pH of the wash liquor is a crucial factor affecting
n SKS-6 HD n Sodium tripolyphosphate
the efficiency of the washing process. A builder with reserve alka-
linity has advantages here, since it can counter the effect of acid soil
particles and enhance soil removal. Furthermore, acid components Figure 22: Reserve alkalinity of various detergent builders
(c = 0.02 %, T = 20 °C, t = 20 min, titration with 0.1N HCl, r.a. calculated as NaOH,
added in the detergent manufacturing process can be neutralised. corresponding to the amount of acid required to set a pH value of 10.0 resp. 9.5)
Especially in compact detergents, SKS-6 can therefore be used as a
replacement for a part of the soda and the amorphous silicate. 40

SKS-6 acts as a pH regulator and buffer, even in low amounts. This


Alkali equivalent [ % ]

30
is of particular interest in regions where detergents are traditionally
used in low concentrations or, for example, in dishwashing agents. 20

10

0
SKS-6 SKS-6 HD Amorphous Soda/ Zeolite A
disilicate disilicate
cpd.
pH = 10 n pH = 9.5

19
Dispersed Figure 23: Dispersed particle size of different SKS-6 types
vs time and water hardness

particle size,
(T = 20 °C)

80

solubility
Mean particle size [μm]

and dispersing
properties
40

0
0 5 10

Time [ min ]
When SKS-6 is added to water, it breaks down into very fine par-
ticles due to chemical reactions previously described in chapter n SKS-6 granular 0 °d n SKS-6 powder 0 °d
n SKS-6 granular 17 °d n SKS-6 powder 17 °d
»SKS-6 characterisation«. The exchange of sodium ions for calcium
and magnesium ions on the newly created surface begins immedi-
ately. The process is so quick, that within several minutes SKS-6 has
dispersed into microscopically small particles of the size of about
five to fifteen microns, according to the relevant water hardness
(Fig. 23). Because of the grinding action during the compaction Figure 24: SKS-6 solubility vs time
process, SKS-6 granular contains smaller primary particles, so the (c = 2 g/l, deionized water)

process here is even faster. 100

Parallel to the disintegration of the disilicate particles, the alka-


line environment can slowly attack the silicate framework. There-
Solubility [%]

by small fragments of the silicate layers dissolve as water glass type


50
chemical species. According to the hardness of the water used the
speed of the process varies (Fig. 24-25). Important is the stabilising
influence of the hardness ions on the silicate structure. The alkaline
earth ions remain bound, they cannot cause any carbonate precipi-
tation. Ideally, the silicate share is dissolved which is not needed 0
0 15 30 45
for softening.
Time [min]

n SKS-6 granular 20 °C n SKS-6 powder 20 °C


n SKS-6 granular 60 °C n SKS-6 powder 60 °C

20 SKS®- 6
Figure 25: SKS-6 solubility vs time
(c = 2 g/l, tapwater 17 °d)

100

Solubility [ % ]
50

0
0 15 30 45
Time [ min ]
The influence of temperature n SKS-6 granular 20 °C n SKS-6 powder 20 °C
is also significant (Fig. 26). n SKS-6 granular 60 °C n SKS-6 powder 60 °C

Hydrolysis increases with the


temperature. Figure 26: Solubility of SKS-6 vs temperature
(c = 10 g/l, T = 15 min, water hardness 17 °d)

100
Solubility [ % ]

50

Traditionally, liquid or spray-dried water glass is added to deter-


gents to support the dispersing of dirt particles in the wash liquor
and to achieve a certain effect of protection against corrosion. 0
This function can be taken over by the parts formed through the 20 60 100

hydrolysis of SKS-6 that are similar to water glass (Fig. 27). Temperature [ °C ]

Figure 27: Dispersing effect of silicate builders


(c = 0.5 %, T = 20 °C, t = 2 h, pH = 10, water hardness 23 °d,
0.5 % pigment Bayferrox 130, “Schwarzband” filtration paper)

80
Dispersing effect [ % ]

40

0
SKS-6 HD SKS-6 granular Amorphous disilicate
mr 2.65

21
Storage properties
Among the most important properties of detergent raw materials are the storage
properties. These include the storage stability of the product itself, i.e. the tendency
to form lumps, caking etc. as well as the deterioration of the properties of other
detergent ingredients.

The storage stability in silos for example can be characterised by


means of ring shear measurements according to Dr. Schulze, a
modification of the Jenicke principle. Essentially a material sample
is compacted in a ring-type measuring cell (consolidation stress).
Then the sample is released and sheared by means of an applied
force, i.e. it is brought to a flowing movement. The flowability of a
sample under applied pressure, here the ffc value, is the unconfined
yield strength in relation to the consolidation stress.

In a time-dependent study, one finds that SKS-6 granular and


SKS-6 HD are still easily flowing even after being stored under
pressure for one week (Fig. 28). This is an advantage for silo
storage. Zeolite is already in the cohesive range at the start and
hardens even more after a certain time. SKS-6 powder shows a
certain storage consolidation, but it is better than zeolite.

22 SKS®- 6
Water uptake Figure 28: Storage behaviour of various builder types
(flowability ring shear test at a consolidation strength sigma1 = 22 kPa;
10 < ffc: free flowing, 4 < ffc < 10: easily flowing, 2 < ffc < 4: cohesive)
With modern detergents high demands are made on the perfor- 40

mance of the bleaching system and on the handling capability.


Free moisture in powder-type products interferes with the handling
properties and destabilises the bleaching system in particular.

ffc value
Detergent raw materials, that do not contain any moisture them- 20
selves, but can bind moisture, have a great advantage.

As a comparison shows, SKS-6 in powder form as well as in granu-


late or compound form can take up high amounts of humidity
0
(Fig. 29). The uptake depends on the partial pressure of water 0 4 8
vapour. If the relative humidity is low at lower temperatures, less Storage time [ d ]
water is taken up, if a lot of water is available then correspondingly n SKS-6 HD n SKS-6 powder
more moisture is absorbed (Fig. 30). n SKS-6 granular n Zeolite A

Figure 29: Water content of SKS-6 types vs time


(T = 20 °C, 95 % rH)

10
Absorbed mass water [ % ]

0
0 50 100 150 200

Time [ h ]

n SKS-6 powder n SKS-6 HD n SKS-6 granular

Figure 30: Water uptake of SKS-6 powder


(stop period: 3.8 d, ambient temperature)

8
Absorbed mass water [ % ]

2
0 50 100
Relative humidity [ % ]

23
Surfactant uptake In the modern detergent
production process, the
components are mixed in
a free-flowing state. This
is energy-saving since,
in contrast to the slurry
method of manufacture,
no water is evaporated.

Through suitable process control, detergents with high bulk density


Figure 31: Surfactant uptake of SKS-6 powder vs flowability
(10 < ffc: free flowing, 4 < ffc < 10: easily flowing, 2 < ffc < 4: cohesive) are obtained, which satisfy today’s requirements for compactness.
The product should have a very good appearance and be free-flow-
ing. Since individual components (e.g. surfactants) are liquid or
8
hydrous, constituents are required that have high absorption
capacity. Substances that not only act as carriers but are multifunc-
tional offer a particular advantage. SKS-6 is such a substance and
combines high calcium binding capacity and pH buffering with high
ffc value

4 absorption capacity for liquid components, e.g. surfactants.

The high surfactant absorption capability of SKS-6 can be demon-


strated. For this purpose, SKS-6, a number of other silicates and
0 zeolite were sprayed with various surfactants in different mixer
0 10 20 systems.
Nonionic surfactant content in compound [ % ]

With SKS-6 powder, compounds can be manufactured with non-


ionic surfactants that are still easily flowing. This can be shown with
Figure 32: Surfactant uptake of various detergent builders the help of shear measurements based on the Jenicke principle
(Genapol OA 080, gravity-flow mixer) (Fig. 31).

If other builders are also sprayed with surfactant at a predeter-


Nonionic surfactant content

20
mined flowability (free-flowing properties according to DIN 53916)
in a gravity-flow mixer, the amounts of surfactant taken up vary con-
in compound [ % ]

siderably (Fig. 32). Genapol OA 080 is an alkyl ethoxylate based on


C14/C15-oxoalcohol. It contains eight units of ethylene oxide and is
10 frequently used as a nonionic surfactant in detergent formulations.

0
SKS-6 Amorphous Zeolite A SKS-6 Soda/
powder disilicate powder granular disilicate cpd.
powder granule

24 SKS®- 6
Figure 33: Surfactant uptake of various detergent builders
(laS, ploughshare mixer)

30

nonionic surfactant content


in compound [ % ]
20

10

0
SKS-6 Zeolite A Sodium triphos-
powder powder phate powder

Figure 34: Surfactant uptake and flowability


(Compounds of 30 % laS with different particle size fractions of 70 % SKS-6
powder, flowability tests in ring shear tester; 10 < ffc: free flowing, 4 < ffc < 10:
easily flowing, 2 < ffc < 4: cohesive)
12

ffc value 8

0
0 500 1000

All material through sieve size [ μm ]

Figure 35: Surfactant uptake of SKS-6 hD vs flowability


(10 < ffc: free flowable, 4 < ffc < 10: easily flowable, 2 < ffc < 4: cohesive)

Among the favourites of the investigated products are powder- 60


type SKS-6 and amorphous disilicate, whereas zeolite powder has
a markedly poorer result. Because of the more porous morphology
of builder powder, its absorption capacity is in general higher than 40
that of builder granules. These have a more compact surface and
ffc value

a denser internal structure. SKS-6 granules, however, can absorb


more surfactant than soda/disilicate granules. 20

In the detergent manufacturing process, the use of ploughshare


mixers is also typical. In these mixers, high shear stresses act on 0
SKS-6 hD SKS-6 HD SKS-6 HD
the components. Under these conditions, SKS-6 powder absorbs + 25 % nonionic + 30 % nonionic
much more LAS – linear alkyl benzene sulfonate – than zeolite A surfactant surfactant

powder and sodium tripolyphosphate (Fig. 33). When SKS-6 is


used, a uniform, granulated, free-flowing product according to
DIN 53916 is obtained without lumps or caking.

The flowability of compounds with LAS can be further improved Surfactant compounds of SKS-6 HD, the granulate made from
by the use of SKS-6 powder with a smaller particle size (Fig. 34). SKS-6 and acid copolymer (Fig. 35) are particularly easy to handle.
It is possible to add e.g. 30 % alkylethoxylate without affecting the
good flowability.

25
Compatibility with other
detergent ingredients

A detergency builder must not


only achieve good water softening,
it has to be compatible with the
sensitive detergent additives.

Best known is the destruction of the bleaching system caused by the


Figure 36: Active oxygen stability of SKS-6 based detergent formulas
release of humidity. Such an effect is best demonstrated by practical
1 [%] 2 [%] 3 [%] 4 [%] formulations (Fig. 36) that are stored under forced ambient condi-
tions. These include elevated temperature and increased air humid-
SKS-6 granular* 44.3 27.2 – –
ity. The characteristic factor for the bleaching system is the active
Zeolite A – 17.1 44.3 –
oxygen content.
Zeolite P – – – 44.3

Percarbonate 25.7, Soda 22.9, Peractive AN* 7.1 %


Zeolite A used as sole builder effects a complete decomposition
* Clariant product brand names of the bleaching system after only a short storage time (Fig. 37).
Because it is water free and due to its humidity buffering property
SKS-6 in a binary zeolite/SKS-6 builder system can have a stabilis-
ing effect. Zeolite P has a lesser water of crystallisation share
Figure 37: Active oxygen stability of SKS-6 based detergent formulas
(T = 37 °C, 67 % rH, in open plastic bottles) than zeolite A and has better results. SKS-6 used alone has the
best results; the bleaching system is attacked only very slowly.
100
Active oxygen decay [ % ]

50

0
0 5 10 15
Time [ d ]
  

n 1 SKS-6 n 2 Zeolite A + SKS-6 n 3 Zeolite A n 4 Zeolite P

26 SKS®- 6
Figure 38: Active oxygen stability of SKS-6 based detergent formulas Figure 39: Active oxygen stability of SKS-6 based detergent formulas
(T = 37 °C, 67 % rh, in open plastic bottles)
5 [%] 6 [%] 7 [%] 8 [%]
100
SKS-6 granular* 30 12 – –

Active oxygen decay [ % ]


Zeolite A – 20 30 –

Zeolite P – – – 30
50
Soda 15 4 15 15

Sulfate 9 18 9 9

Percarbonate 20, LAS 12, Genapol OA 3070* 7, Peractive AN* 4,


Polycarboxylate 3 %
* Clariant product brand names 0
0 5 10 15
Time [ d ]

n 5 SKS-6 n 6 Zeolite A + SKS-6 n 7 Zeolite A n 8 Zeolite P


The same picture is obtained when complete basic heavy-duty
formulations are investigated (Fig. 38). The order of stability in
the bleaching system remains unchanged (Fig. 39). The most rapid Figure 40: Active oxygen stability of SKS-6 based detergent formulas

decomposition is achieved with Zeolite A. In combination with


9 [%] 10 [%] 11 [%]
SKS-6 a certain improvement is possible. Zeolite P has moderate
results and SKS-6 shows in comparison the best compatibility with SKS-6 granular* 40 25 –

the bleaching system. SKS-6 HD* – 20 –

Zeolite A – – 40
Of interest is also a comparison of SKS-6, SKS-6 HD and zeolite.
In one study, the three builders were integrated in heavy-duty Polycarboxylate 5 – 5

formulations (Fig. 40) and exposed to elevated temperature alone Percarbonate 20, LAS 9, Genapol OA 080* 8, Peractive AN* 5,
as well as in combination with increased humidity. Enzyme 2, Antifoam 1, Sulfate to 100 %
* Clariant product brand names

Zeolite A already shows a noticeable decrease of the bleaching


system without exposure to humidity (Fig. 41).
Figure 41: Active oxygen stability of SKS-6 HD based detergent formulas
This is a clear indication of the mobility of the zeolite water of (closed storage: glass bottle, 30 °C; open storage: wax carton, 30 °C, 70 % rh)
crystallisation. Exposure to humidity increases the decomposition
100
of the percarbonate.
Active oxygen decay [%]

50

0
9 SKS-6 granular 10 SKS-6 granular 11 Zeolite A
+ SKS-6 HD

n 7d closed 7d open

27
Precipitation and
inorganic incrustations

It was recognized early on that silicates in the form of water glass Figure 42: Morphology of precipitates of various builders
could bind the hardness-forming calcium and magnesium ions (water hardness: 400 ppm CaCo3, magnification 50 x)
of tap water. In this process, the hardness salts are removed as a
SKS-6
precipitate. The disadvantage is that the precipitate is flocculent
and bulky and forms incrustations on the laundry fabrics. These
make the laundry feel hard, cause fibre wear and lead to rapid
greying of light-coloured textiles.

Softening with amorphous disilicates in powder or granule form


employs this precipitation mechanism. First of all, the solid silicate
dissolves and forms flocculent, white precipitates. The water
hardness is thus removed from the wash liquor. If the precipitate
is filtered and dried, hard and solid compounds are obtained
Amorphous disilicate
(Fig. 42).

Another possible way of precipitating calcium and magnesium ions


is the reaction with soda. This accelerates what also happens in
tap water through reaction of the constituents on heating: calcium
carbonate – lime – is precipitated. Silicate can be added with the
intention to influence crystallisation and keep the precipitate in
suspension. In dried form, this precipitate is also hard and solid.

SKS-6, on the other hand, binds the hardness of tap water by ex- Zeolite A
changing calcium and magnesium ions for sodium ions. SKS-6
powder or granules rapidly break down in the water into microscop-
ically small particles on which the softening process takes place.
The silicate particles saturated with hardness ions have a self-
dispersing effect and remain in suspension until the wash liquor is
rinsed out.

Zeolite A also softens water by ion exchange. The insoluble zeolite


is uniformly suspended in the wash liquor and takes up the hardness
Soda/disilicate compound
ions as solids. To prevent its depositing on the fibres or in the wash-
ing machine, polycarboxylate-based dispersants must be added.

28 SKS®- 6
Figure 43: Precipitates on heating coils
(c = 1 g/l builder, 0.1 g/l Sokalan CP 5; T = 60 °C, 30 min per heating cycle,
water hardness: 80 mg/l Ca, 15 mg/l mg and 0.02 % Co2)

0.4

Weight increase [g]


0.2

0
0 10 20

Heating cycles

n SKS-6 n Zeolite A
In practice, such incrustations of lime from the water hardness and n Amorphous disilicate n Soda/disilicate cpd.

from residue of insoluble builders appear especially on the heating


coils of washing machines or on textiles. If repeated heating cycles
in washing machines are simulated (Fig. 43-44), noticeable residue Figure 44: Precipitates on heating coils
is found already after several washing cycles. After a longer, repeat-
ed use soda/disilicate compound leaves the most noticeable residue Soda/disilicate Amorphous SKS-6
followed by amorphous disilicate and zeolite. The least deposits compound disilicate

result from the use of SKS-6. In the case of soda/ disilicate


compound, the deposits are mainly precipitated lime (Fig. 45).
Apart from precipitated magnesium silicate and lime, amorphous
disilicate seems also to be subject to hydrolysis to silicic acid.
Above all, SKS-6 shows small quantities of not completely bound
calcium carbonates.

Figure 45: Composition of precipitates on heating coils

1.2
Composition [%]

0.8

0.4

0
Soda ash/ Amorphous SKS-6
disilicate cpd. disilicate

MgSi2o5 n CaCO3 n SiO2

29
Incrustations also appear on the washed fabrics (Fig. 46). With
the pure silicates rather even incrustations occur, like a covering,
whereas crystal-like deposits develop with soda/disilicate com-
pound.

If one compares zeolite and zeolite/SKS-6 systems (Fig. 47), it


becomes obvious that the main residue of the zeolite-based systems
consists of zeolite itself (Fig. 48). A combined zeolite/SKS-6 system
shows a markedly lower zeolite residue.

Figure 46: Comparison of the morphologies of residues of various builders Figure 47: Detergent formula for evaluation of inorganic incrustations composition
on fabrics (magnification 2000 x)
1 [%] 2 [%]

SKS-6 Zeolite A 31 19

SKS-6 granular* – 12

Amorphous disilicate 3 –

Soda 13 16

Polycarboxylate 5, Perborate · H2O 18, Peractive AN* 5,


LAS 10, Genapol OA 080* 8, Soap 2, Antifoam 1, Enzymes 3,
Optical brightener 0.5, Phosphonate 0.5 %
* Clariant product brand names

Amorphous disilicate

Soda/disilicate compound

Figure 48: Composition of inorganic incrustations on fabrics

6
Composition [%]

0
1 Zeolite 2 Zeolite Commercial brand
+ SKS-6

CaCO3 n CaSiO3 n Zeolite

30 SKS®- 6
Heavy metal
binding capacity

Because of their negative influence on the stability of bleaching Figure 49: Heavy metal binding capacity vs artificial water hardness
systems and their damaging effect on textile material, one endeav- (T = 25 °C, t = 10 min, pH = 10)
ours to bind heavy metal traces in detergents. Besides chelating
100
agents such as EDTA or phosphonates, SKS-6 can also take over the
function of a heavy metal scavenger. SKS-6 binds the interfering
heavy metal ions in the wash liquor by means of the same ion
exchange mechanism as the hardness ions.
hmBC [%] 50

Ion exchange is more effective than just a precipitation, as the


following comparison of SKS-6, amorphous disilicate and soda/
disilicate compound shows. For this the binding capability of
manganese and copper in soft, medium hard and hard water is 0
determined. In soft water the heavy metal binding capacity of 0 200 400

SKS-6 is higher than that of amorphous disilicate. Both show a water hardness [ppm]

preference for manganese (Fig. 49). The soda/disilicate compound n SKS-6: Cu n Amorphous disilicate: Mn
has the poorest heavy metal binding capacity. n SKS-6: Mn n Soda/disilicate cpd.: Cu
n Amorphous disilicate: Cu n Soda/disilicate cpd.: Mn

In medium hard water SKS-6 binds heavy metal ions almost com-
pletely. Here amorphous disilicate is markedly better than in soft
water. The soda/disilicate compound gives the poorest results.
The good effect of SKS-6 and the behaviour of amorphous disilicate
and soda/disilicate compound can be explained by the fact that with
SKS-6 the heavy metal traces are removed by ion exchange, whereas
with amorphous disilicate and soda/disilicate compound there has
to be a precipitation of heavy metal and silicate. In soft as well as in
medium hard water the solubility products heavy metal/carbonate
or heavy metal/silicate have not yet been exceeded, for this reason
there is no precipitation.
Test Conditions

In hard water conditions SKS-6 eliminates heavy metals almost Heavy metal concentration:
0.02 ppm Mn, 3 ppm Cu
completely, and amorphous disilicate and soda/disilicate compound
Addition of builder and water hardness:
also perform better than in less hard water. · 0.5 g/l and 0 ppm water hardness
· 0.5 g/l and 100 ppm water hardness
(78 ppm CaCO3 plus 22 ppm MgCO3)
· 1 g/l and 400 ppm water hardness
(312 ppm CaCO3 plus 88 ppm MgCO3)
· Ca and Mg used as chlorides
pH value: 10.0
Trial period: 10 min
Temperature: 25 °C

31
SKS-6
EnvIronmEntal anD
SafEty aSPECtS

32 SKS®- 6
33
Life cycle
inventory

Apart from many other attempts to judge detergent ingredients Based on data from the production of amorphous sodium disilicates,
from an ecological point of view, in recent times the process of the SKS-6 production was inventoried. This was done in the
ecological inventory (life cycle inventory) has entered the discus- sense of a »cradle to factory gate« study, i.e. the use of SKS-6 in
sion. This involves the compilation of environmental influences detergents and their disposal was not included (Fig. 50).
of the manufacture of a product in the form of material and energy
balances.

Figure 50: Selected data from the SKS-6 life cycle inventory
(data per t anhydrous material)

0
Total raw material Total water Total delivered energy Emissions Co2 Emissions inorg. salts Solid waste
consumption [t/t] consumption [m3/t] [10 gJ/t] [t/t] + acids [kg/t] [10 kg/t]

34 SKS®- 6
Solubility
in waste water

Test Conditions
Washing machine: Miele Novotronic W 917
Washing programme: single wash cycle
Wash temperatures: 30 °C, 60 °C
Water hardness: 18 °
German hardness = hardness range 3
(Ca : Mg = 3 mol : 1 mol)
Laundry: 4.5 kg (clean)
Detergent: dosage 100 g
Content of SKS-6 = 40.8 %

Modern detergents should not only offer good performance properties,


Figure 51: Dilution of household waste water in sewerage system
they must also have as less of impact on the environment as possible.
Besides economical use of energy in raw material manufacture,
formulation, production, distribution and washing processes, the Washing machine
behaviour of the detergent components in waste water treatment
plants and in rivers and lakes is particularly important. Wash liquor
+ 1st rinsing water
In the washing process, SKS-6 breaks down into numerous, micro-
scopically small particles, which bind the hardness ions. These
saturated silicate particles remain dispersed in the wash liquor. Any
SKS-6 not required for water softening dissolves in the wash liquor. Initial conc.
This wash liquor is diluted in time to a ratio of about 10 : 1 by the Additional household
washing machine rinsing water and other quantities of household waste water
water prior to discharge into the sewerage system (Fig. 51). As this
water then makes its way to the sewage treatment plant, it is calcu-
lated that further dilution to a ratio of about 40 : 1 takes place. On Additional
the way to the treatment plant, the layered silicate particles loaded Dilution 10 : 1 water
with calcium and magnesium break down into their basic chemical on way to
constituents, which remain dissolved in the water. In the treatment treatment
station
plant, the original solution is finally diluted to about 100 : 1.

In our own study of this process, laundering trials were carried


out at wash temperatures of 30 °C and 60 °C and dissolving behav- Dilution 40 : 1
iour was studied. The resulting wash liquor and first rinsing water
together were diluted 10 times and 40 times. This process simulates
the dilution in municipal sewerage systems which takes place
between the household and the treatment plant. Measurements
were carried out after one and six hours according to the average
residence times in the sewerage system in order to identify any Treatment plant
time-dependency of solubility behaviour.

At 30 °C wash temperature, the dissolved silicate content in the


mixture of wash liquor and first rinsing water is 30 % after one
hour (Fig. 52).

35
When the wash liquor and rinsing water are diluted with additional
Figure 52: Solubility of SKS-6 in waste water
water to a ratio of 10 : 1, the dissolved content increases to 50 % as
100
a result of the dilution alone. The effect of the residence time can
be seen after 6 hours – then 75 % of the silicate is dissolved. When
Dissolved contents [%]

the mixture of wash liquor and rinsing water is diluted to 40 : 1,


the dissolved silicate content is 90 % after one hour and 100 % after
a residence time of six hours. 50

The influence of temperature on solubility can be seen at 60 °C


wash temperature. The soluble silicate content in the wash liquor
and first rinsing water after one hour is 60 %. This means that the 0
hydrolytic degradation is higher at 60 °C wash temperature. 1 20 40

Dilution [Initial conc., 1 : 10, 1 : 40]


On dilution with water to a ratio of 10 : 1, the soluble silicate content n 30 °C, 1 h n 60 °C, 1 h
increases after one hour to 75 %. Residence time at this wash n 30 °C, 6 h n 60 °C, 6 h

temperature has a less pronounced effect. After six hours, the


soluble content increases to 80 %.
In a 40 : 1 solution, silicate solubility after one hour has increased
to 90 %. After six hours, all the silicate (100 %) is dissolved. The
chemical breakdown of SKS-6 into a soluble form is influenced by
three parameters: wash temperature, dilution and residence time.

As a detergent builder, SKS-6 appears to have very good performance


properties and also good ecological properties. The results of this
model study show that SKS-6 dissolves after washing before it
reaches the municipal waste-water treatment plant. Thus it behaves
ecologically like water glass, which has been used in detergents
for many decades. Through hydrolytic degradation SKS-6 also loses,
along with its ion binding power, a potential capacity to mobilise
heavy metals from sediments. To the best of our present knowledge,
the entry of soluble silicates into surface waters does not contribute
to eutrophication.

36 SKS®- 6
Exposure
modelling

With the help of model calculations it is possible to estimate the


Figure 53: Silicate input depending on SKS-6 based detergent market share fm
change of silicate concentrations in the waste water system as well (SKS-6 in det. 15 %, det. consumption 16 g/cap·day,
as in rivers that are the result of the market share of detergents typical dilution values: big river: 0.00016, river: 0.014, stream: 0.11)
containing SKS-6. 4
Sio2 conc. by det. [ppm]

The study begins with the basic concentration of silicate in tap


water. During the washing process in the household the detergent
is mixed with tap water. The waste water is passed into the sewer-
2
age system and then into the waste water treatment plant.

The water of the treatment plant is diluted with additional river


water when it is passed into the rivers. On the assumption of an
equal and ideal distribution of the silicates originated from the 0
0 0.2 0.4
detergent, the concentration of the silicate is shown as a function
Dilution in river
of the dilution. This calculation is made for two different SKS-6
n fm = 0 n fm = 0.4 n fm = 0.8
concentrations in detergents (15 and 40 %) and for different market
n fm = 0.2 n fm = 0.6 n fm = 1
shares of the relevant SKS-6-containing detergents (0 % market
share corresponds to fm = 0 and 100 % corresponds to fm = 1).

The concentration effects that occur are small in the case of high Figure 54: Silicate input depending on SKS-6 based detergent market share fm
dilution (big or normal river respectively) (Fig. 53–54), and even (SKS-6 in det. 40 %, det. consumption 14 g/cap·day,
typical dilution values: big river: 0.00016, river: 0.014, stream: 0.11)
in the case of a stream with a dilution of one to ten and with 100 %
market share of SKS-6-containing detergents, the silicate concen- 8

tration does not increase very noticeably.


Sio2 conc. by det. [ppm]

0
0 0.2 0.4

Dilution in river

n fm = 0 n fm = 0.4 n fm = 0.8
n fm = 0.2 n fm = 0.6 n fm = 1

37
Toxicology of sks-6
and sks-6 based
detergent formulations

The usual toxicological data were established for SKS-6. Only the Investigations were carried out on three ultracompact detergents
eye irritation test gives cause for classification Eye damage 1 as with builder components SKS-6, soda and bicarbonate as well
there is a risk of serious eye damage (Fig. 55). Therefore it is recom- as SKS-6, zeolite, soda and citric acid, a regular detergent with
mended on principle to use safety glasses, face protection and builder components SKS-6 and bicarbonate and two branded
rubber gloves when handling SKS-6 and to also wear a dust mask detergents (Fig. 56).
as protection in the case of exposure to dust.
Formulations with SKS-6, soda and bicarbonate did not cause
Beside the properties of SKS-6 on its own it is of interest to study any eye irritation. Despite the known alkaline effect of SKS-6 the
the properties of SKS-6 containing products as well. Their results tested ultracompact and regular formulations were shown to be as
may well differ from those that are reached with the mathematic advantageous with regard to skin irritation as recognised branded
evaluation according to the Dangerous Substances Directive. detergents, despite the fact that they contain a very high concentra-
tion of SKS-6.
The skin compatibility tests were carried out as Human Single
Patch Test using a one percent aqueous dispersion of the detergent,
and skin redness was evaluated after 24, 48 and 72 hours.
Investigations of eye irritation were carried out as Low Volume
Eye Test with 10 μl detergent, and the eye irritation was evaluated
after 1, 24, 48 and 72 hours.

38 SKS®- 6
Figure 55: Toxicology data and classification of SKS-6

Investigation Procedure Result Classification

AMES test – not mutagenic –

Algae toxicity OECD 201 NOEC 18 mg/l –

Bacteria toxicity OECD 209 Na-form: EC50 720 mg/l –

Daphnia toxicity OECD 202 EC50 491 mg/l –

Eye irritation, rabbit OECD 405 irritant Eye dam. 1, H318

Fish toxicity OECD 203 LC50 > 500 mg/l –

Inhalation tox. (rat, acute) OECD 403 > 3510 mg/m3 –

Oral toxicity (rat, acute) OECD 401 LD50 > 2000 mg/kg –

Plant growth – EC0 200 kg/ha –

Sensitization OECD 429 non sensitizing –

Skin irritation, rabbit OECD 404 non irritant –

Figure 56: Toxicology of SKS-6 based detergent formulas

Constituents SKS-6 based formulas [%] Commercial detergent

Ultracompact Regular

SKS-6 50 30 15 21.3

Zeolite A – – 15 –

Soda 1.3 21.3 11.5 –

Bicarbonate 15 15 – 6.7

Citric acid – – 6 – Nr. 1 Nr. 1

Percarbonate 20 20 20 25

TAED – – 5 2.2

Anionics – – 8 –

Nonionics 9.5 9.5 9 4.4

Polycarboxylates 2.5 2.5 4.5 –

Others 1.7 1.7 6 40.4

Low Vol. Eye Test non irritant non irritant not det. not det. not det. not det.

Skin irritations (24 h) 0 not det. 2 1 3 6

39
SKS-6
Laundry detergents

40 SKS®- 6
41
Basic detergent effects
SKS-6 removes the water hardness ions during washing and
SKS-6 is a modern builder assists the action of the surfactants. Owing to its reserve
and can perform numerous alkalinity, SKS-6 assists detergency by providing alkalinity and
functions in detergent compensating for fluctuations in pH value. Because of its silicate
formulations. We therefore components, SKS-6 can also have a corrosion- inhibiting action
and dispersing properties.
call it a multifunctional
builder. When dissolved in water SKS-6 breaks down into microscopically
small layered silicate particles, which have self-dispersing proper-
ties in the wash liquor. The particles charged with water hardness
ions remain suspended in the wash liquor. As a detergent builder,
SKS-6 therefore basically requires less dispersing additives.
The addition of polycarboxylates (PCA) to detergents formulated
with SKS-6 is therefore reduced.

42 SKS®- 6
Figure 58: Wash effect, bleach effect, enzyme effect and inorganic incrustations
in model wash test

1.2

Coefficient, standardised
0.6
Test Conditions
Miele W 917, main wash programme,
60 °C, 18 °d, dosage 75 g, 25 wash cycles 0

Wash effect: test fabrics EMPA 104, WFK 10D


Bleach effect: test fabrics WFK CFT BC-1, -0.6
WFK CFT BC-4, WFK CFT CS-3
Enzyme effect: test fabrics EMPA 112, EMPA 116,
-1.2
WFK CFT AS-10
Wash effect Bleach effect Enzyme effect Inorganic
Inorganic incrustations: test fabrics EMPA cotton, incrustations
Vossen terry towel, WFK 10A, WFK 16A, WFK 20A
SKS-6 n Polycarboxylate n Zeolite n Bicarbonate

Sodium percarbonate is used as a bleaching agent in modern The mathematical model then evaluates the different results and
detergents. The storage stability of unprotected percarbonate does interprets increasing or decreasing influences as coefficients. The
however suffer – even if atmospheric moisture is excluded – if it detergency was, as is usual, determined as delta remission of the
comes into contact with aqueous substances. SKS-6 is anhydrous soiled fabrics prior to and after one wash. The resulting coefficients
and gives advantages in storage stability because it does not intro- were standardised.
duce any additional stability- reducing water into the detergent.
If type A zeolite is used together with SKS-6 and sodium percar- As a supplier of alkalinity, SKS-6 increases detergency (Fig. 58).
bonate, specially coated percarbonate should be used. Because of its chelating and soil dispersing properties the poly-
carboxylate also increases detergency. As zeolite only functions
Using mathematical methods it is possible to put the results of as a water softener it cannot support the effect of the surfactant
washing tests into a mathematical model. In the course of a study, system. Bicarbonate, which lowers the pH, reduced the detergency.
formulations for compact detergents were systematically varied The influence of builder and cobuilder on the efficacy of enzymes is
and the influence was determined of the builder/cobuilder somehow similar to the influence of the builder on the surfactants.
system on wash effect, bleach effect, enzyme effect and inorganic Whereas SKS-6 and polycarboxylate increase the enzyme effect,
incrustations. The main builder SKS-6 and zeolite formed the zeolite and bicarbonate weaken it.
varied components, polycarboxylate was used as cobuilder and
bicarbonate as pH control. The other components such as SKS-6 boosts the bleaching effect. The positive effect can be due as
surfactant system, bleaching system and additives were not varied much to effective pH buffering as to stabilisation of the bleach sys-
(Fig. 57). tem. The chelating properties of the polycarboxylate can reinforce
bleaching in two ways. Firstly, as it leaches alkaline earths it gives
peroxide molecules access to bleachable soil and secondly, it keeps
heavy metal traces masked in solution, thus avoiding their adverse
effects.

The inorganic incrustations were determined after 25 wash cycles


Figure 57: Model wash test formulas
as ash content. While SKS-6 helps to reduce incrustation, zeolite
[%] results in noticeably higher ash values. As is shown in earlier analyt-
ical investigations of incrustations, the effect of zeolite is not to be
SKS-6 powder* 0-40
attributed to insufficient softening of the water but probably to an
Zeolite A 0-40
insufficient dispersion of the zeolite. Polycarboxylates do their job
Bicarbonate 0-15 and reduce the inorganic incrustations. As expected bicarbonate,
Polycarboxylate 0-6
because of its high carbonate ion content, demonstrates a noticeable
influence that tends to result in higher ash values.
Percarbonate 15, Genapol OA 080* 8, Anionic 6,
Citric acid 6, Peractive AN* 3, Enzyme 2.5, Anti-
foam 1, Soap 1, Opt. brightener 0.5, Perfume 0.5,
Phosphonate 0.5, Sulphate to 100 %
* Clariant product brand names

43
Compact detergents

Since the multifunctional builder SKS-6 combines various func-


Figure 59: SKS-6 based compact and supercompact detergent formulas
tions, new formulations for highly compact detergents can be
produced. SKS-6 can be used as a stand-alone builder or combined 1 [%] 2 [%] 3 [%]
with others, e.g. with zeolite or phosphate. Builder mixtures of
SKS-6 granular* 48 15 15
SKS-6 and Zeolite A exhibit an optimised price/performance ratio.
SKS-6 can be processed by the modern mixing methods for deter- Zeolite A – 15 30

gent production. It can be used as a carrier for liquid components, Soda or bicarbonate 15 12 13
e.g. surfactants. Citric acid – 6 –

Perborate · H2O – – 15
Suggestions for formulations of heavy-duty powder detergents with
SKS-6 are given (Fig. 59). The formulations differ in compactness Percarbonate 15 20 –
and dosage in the wash cycle. Peractive AN* 5 5 6

Phosphonate 0.5 0.5 0.5


Formulation 1 based on SKS-6 is technologically easy to manu-
facture as SKS-6 facilitates incorporation of the surfactants. Anionic – 8 6
The other components are mixed in. Only readily biodegradable Genapol OA 080* 10 9 4
surfactants are used and polycarboxylate can be omitted. Both are
Polycarboxylate – 4.5 6
ecologically beneficial measures. Percarbonate can be used as a
bleach and does not need to be protected against attack by water. Enzymes 2.5 2.5 2.5

Being based solely on easily dispersable components, this formula- Optical brightener 0.5 0.5 0.5
tion meets the requirements of modern detergents.
Perfume 0.5 0.5 0.5

Antifoam 1 1 1
Formulation 2 is based on SKS-6 and type A zeolite in equal
amounts. Citric acid and soda/bicarbonate supplement the builder Sulphate to 100 to 100 –
block. Polycarboxylates are used for dispersion. Because of the Dosage g/wash 60 60 75
zeolite component it is advisable to employ coated sodium percar-
* Clariant product brand names
bonate. Formulations 1 and 2 are aimed at low dosage, compactness
and very high detergent performance.

Formulation 3 is a low-cost alternative, in which a higher amount of Test Conditions

zeolite is used and citric acid is omitted. The higher zeolite content Miele W 917, main wash programme,
60 °C, 18 °d, 15 wash cycles
requires a higher addition of polycarboxylate.
Wash effect: test fabrics WFK 10C, WFK 10D,
WFK 20D
Model washing tests show that all formulations give satisfactory Bleach effect: test fabrics WFK CFT BC-1,
results with regard to inorganic incrustations and well-balanced WFK CFT BC-4, WFK CFT CS-3
detergency as well as bleaching effect (Fig. 60). Inorganic incrustations: test fabrics EMPA cotton,
WFK 20A

44 SKS®- 6
Figure 60: Wash effect, bleach effect and inorganic incrustations of
SKS-6 based compact detergent formulas

30 3

A, B delta R [%]

C Ash [%]
20 2

10 1
1 SKS-6 2 SKS-6 3 SKS-6
+ Zeolite + Zeolite 1 : 2

A Wash effect n B Bleach effect n C Inorganic incrustations

Figure 61: SKS-6 based compact detergent formulas

Formulation 1, which contains only SKS-6 as builder, is particularly 4 [%] 5 [%]

efficient. Formulations 2 and 3 with zeolite/SKS-6 combinations SKS-6 granular* 45 15


also show very good washing results with all fabrics and types of
Zeolite A – 15
soil. The modern formulation 2 containing citric acid, boosted by a
higher surfactant content, has the same primary washing effect as Soda – 3.8

formulation 3, which is richer in zeolite, but higher in dosage. Bicarbonate 11.7 –

Citric acid – 6.2


All formulations have roughly Percarbonate 20 25
the same bleaching performance. Peractive AN* 5 5

Anionic – 8
Studies of inorganic fabric incrustations after 15 washes show that
Genapol OA 080* 10 9
the secondary detergent power of all SKS-6 formulations meets
the current standard. The SKS-6 stand-alone formulation 1 does Polycarboxylate – 4.5
this without the addition of polycarboxylate. To obtain comparable Enzymes 4 4
ash values it is necessary to add polymers to the formulations
Others 4.3 4.5
containing zeolite. Polycarboxylates as dispersing agents have a very
marked influence on the secondary washing effect. * Clariant product brand names

A high measure of performance and multifunctionality is also


Test Conditions
realised in two other formulations (Fig. 61).
Single wash cycle, wash and wear test, 60 °C,
approx. 14 °d, dosage 72 g/wash
Formulation 4 – like formulation 1 – uses SKS-6 in combination Degree of whiteness: 15 wash cycles,
with sodium bicarbonate as builder system. Percarbonate and averages of 3 fabric types

bleach activator TAED (e.g. Peractive AN) are used for the bleach- Stain removal: averages of 13 stain types,
each 1 cycle, 5 repetitions
ing process. This lies in the general trend towards lower washing
Inorganic incrustations: standard cotton fabric,
temperatures. The surfactant system is composed exclusively of 15 wash cycles
nonionic surfactants and no polymers are used for soil dispersion.
As is generally practised, enzymes, foam regulators, optical
brighteners and fragrance are included in the formulation.

45
A builder system comprising SKS-6, zeolite A, soda ash and citric
Test Conditions
acid is used in formulation 5. The bleaching system is made up of
Miele W 917, main wash programme, 60 °C,
percarbonate and Peractive and the surfactant system comprises 18 °d, dosage 75 g/wash
anionic and nonionic surfactants. Because of the zeolite content, Inorganic incrustations: after 25 wash cycles,
polymers are used for dispersing. The same other additives that test fabric Vossen terry towel
are used in formulation 1 complete this formulation.

In a wash-and-wear test in an independent test institute, the degree Figure 62: Degree of whiteness, stain removal and inorganic incrustations
of SKS-6 based compact detergent formulas
of whiteness (according to Ganz/Griesser), stain removal (here
the fabrics were visually checked and the stain removal graded) 100 4
and inorganic incrustations (ash) were tested on specific test

B [Scores], C Ash [%]


fabrics. In all three tests these test detergents achieved the same
performance level as leading detergent brands (Fig. 62).

A [%]
90 2
The use of SKS-6 HD in heavy-duty detergents was tested in model
washing tests (Fig. 63).

Formulation 6 serves as comparison and contains a combination


80 0
of SKS-6, zeolite A and polycarboxylate. 4 SKS-6 5 SKS-6 + Zeolite

A Degree of whiteness (Ganz/Griesser)


In formulation 7 SKS-6 HD, SKS-6 and zeolite were used. It n B Stain removal
contains so much SKS-6 HD that a polymer content of 4 % results. n C Inorganic incrustations

Formulation 8 contains a mixture of SKS-6 HD and SKS-6, which Figure 63: SKS-6 HD based compact detergent formulas
results in an SKS-6 content of 40 % and a polymer content of 4 %.
In total this is a lesser polymer content than is usual for example 6 [%] 7 [%] 8 [%]
with zeolite formulations. The remaining components – comprising SKS-6 powder* 20 7.3 27.3
anionic and nonionic surfactants, percarbonate, Peractive, enzyme
SKS-6 HD* – 18.2 18.2
and antifoaming agent – were kept constant, and sulphate made up
the remainder of the 100 %. Zeolite A 25 25 –

Polycarboxylate 4 – –
Finally the formation of inorganic incrustations was investigated
Percarbonate 20, Anionic 9, Genapol OA 080* 8, Peractive AN* 5,
(Fig. 64). Normally these increase in the course of repeated Enzyme 2, Antifoam 1, Sulfate to 100 %
washing. It is apparent that the zeolite-containing formulation * Clariant product brand names
without SKS-6 HD results in the most incrustations. The ternary
system SKS-6/SKS-6 HD/zeolite is more advantageous (i.e. less
incrustations than with the above), the best results are obtained Figure 64: Inorganic incrustations of SKS-6 HD based
compact detergent formulas
with the formulation combining SKS-6 HD and SKS-6.
2.5
Ash [%]

1.5

0.5
6 SKS-6 + Zeolite 7 SKS-6 + SKS-6 HD 8 SKS-6
+ Zeolite + SKS-6 HD

46 SKS®- 6
Laundry tablets

Disintegration Test Conditions


30 °C, 15 °d, 950 ml water, tablet in sieve basket
with mesh size 5 mm
Wash test conditions: main wash programme, 60 °C,
18 °d, dosage: 2 tabs 40 g each via drawer dispenser,
15 wash cycles
Wash effect: test fabrics EMPA 104, WFK 10C,
WFK 10D, WFK 20D
Bleach effect: test fabrics WFK CFT BC-1,
WFK CFT BC-4, WFK CS-3
Inorganic incrustations: test fabrics EMPA cotton,
Vossen terry towel, WFK 10A, WFK 16A, WFK 20A

The formulations for laundry tablets are similar to those for deter- Figure 65: SKS-6 based laundry tablet formulas
gent powders. To solve the specific problems of tablet shape and the
higher density and the resulting more difficult decomposition on 1 [%] 2 [%]
introduction into the wash liquor, basically three types of »tabs« SKS-6 granular* 20 10
have evolved. The first type uses phosphate as an easily soluble
Zeolite A 10 15
builder. The second type is phosphate free, only slightly compacted,
coated with a layer of e.g. fatty acid which stabilises the shape, Soda 13 12
and laced with bicarbonate and citric acid to give an effervescent Anionics 10 8
effect. Type 3 is compacted sufficiently to keep its shape, and
Nonionic 7 7
contains a disintegrant, e.g. cellulose, microcrystalline cellulose,
polyacrylic acid and other ingredients. Dissolving agents in the Cellulose 5 –
form of easily soluble salts are also utilised. Acetate · 3 H2O – 10

Percarbonate 15, Citric acid 5, Polycarboxylate 4,


SKS-6 can of course be used together with different disintegrants Peractive AN* 4, Additives and Sulphate to 100 %
or dissolving agents. Formulation 1 is based on cellulose as disinte- * Clariant product brand names
gration additive. Formulation 2 for example can be considered a
basic formulation using easily soluble salts as disintegrant (Fig. 65).
Figure 66: Disintegration, wash effect, bleach effect and inorganic incrustations
In a model wash test, (Fig. 66) formulation 1 is shown to have good
of SKS-6 based laundry detergent tablet formulas
disintegration properties, good detergency and low tendency to
form inorganic incrustations. 40 4
A [s]; B, C delta R [%]

D Ash [%]
20 2

0 0
1 SKS-6 Commercial premium brand

A Disintegration n C Bleach effect


n B Wash effect n D Inorganic incrustations

47
Regular detergents

Test Conditions
Miele W 917, main wash programme, 60 °C, 18 °d,
dosage 135 g/wash, 15 wash cycles
Wash effect: test fabrics WFK 10C, WFK 10D,
WFK 20D
Bleach effect: test fabrics WFK CFT BC-1,
WFK CFT BC-4, WFK CFT CS-3
Inorganic incrustations: test fabrics EMPA cotton,
WFK 16A

Formulations 1 to 3 (Fig. 67) are similar to current conventional Figure 67: SKS-6 based regular detergent formulas
ones. Sodium perborate tetrahydrate is used in all cases as oxygen
donor. A corresponding amount of sodium sulphate is used to 1 [%] 2 [%] 3 [%]
achieve the recommended dosage. The contents of sodium car-
SKS-6 powder* 21.3 8.3 7.4
bonate and sodium sulphate can be substituted for each other
Zeolite A – 8.3 –
within certain limits.
Sodium tripolyphosphate – – 22.2
The third standard formulation is designed for all regions where Soda or bicarbonate 6.7 6.7 –
phosphate is used as detergent builder. The polycarboxylate
Perborate · 4 H2O 25 25 25
content is reduced and TAED is omitted.
Peractive AN* 2.2 2.5 –
The individual components of the detergent formulations are Phosphonate 0.2 0.3 0.2
listed here as general substance designations. The sequence follows
Anionics – 4.4 6.7
from the context and does not correspond to a manufacturing
specification. We will gladly answer your questions on manufactur- Genapol OA 080* 4.4 5 2.2

ing specifications and precise grade designations. Polycarboxylate – 2.5 1.5

Enzyme 1.1 1.4 1.4


The efficiency of the formulations is indicated below by means
of washing tests in which the detergent action on washable and Optical brightener 0.2 0.3 0.3

bleachable soil and the tendency towards inorganic incrustation Perfume 0.2 0.3 0.3
was tested (Fig. 68). Antifoam 0.4 0.6 0.6

Sulphate to 100 to 100 to 100


Both phosphate free formulations have roughly the same washing
results and bleaching performance. In the formulation containing * Clariant product brand names
phosphate the addition of TAED is omitted, and therefore
the bleaching efficiency is somewhat lower.
Another formulation demonstrates the further use of SKS-6 HD
Formulation 2 also demonstrates clearly that polycarboxylates with zeolite (Fig. 69). The polymer compound makes the addition
have to be used with detergent formulations containing zeolite to of other polymers unnecessary and it can serve as carrier base for
obtain acceptable incrustation values. Formulation 3, which the nonionic surfactants. Test washing shows good detergency,
contains phosphate, naturally shows the best secondary detergent good bleaching effect and a low tendency to incrustations (Fig. 70).
power of all the detergent formulations. Of interest is also the high compatibility with enzymes, as is demon-
strated by their good washing results.

48 SKS®- 6
Test Conditions
Miele Novotronic 927 WPS, main wash programme,
60 °C, 18 °d, dosage 150 g/wash, 15 wash cycles
Wash effect: test fabrics: EMPA 104, WFK 10C,
WFK 10D, WFK 20D, WFK 30D
Bleach effect: test fabrics: WFK CFT BC-1,
WFK CFT BC-4, WFK CFT CS-3
Enzyme effect: test fabrics: EMPA 112, EMPA 116,
WFK CFT AS-10
Inorganic incrustations: test fabrics: EMPA cotton,
Vossen terry towel, WFK 10A, WFK 16A, WFK 20A

Figure 68: Wash effect, bleach effect and inorganic incrustations of Figure 69: SKS-6 HD based regular detergent
SKS-6 based regular detergent formulas formula

30 3
4 [%]

SKS-6 HD* 8
A, B delta R [%]

Zeolite A 12
C Ash [%]

20 2 Soda 15

Perborate · 4H2O 20

Peractive AN* 2

Anionic 7
10 1
1 SKS-6 2 SKS-6 3 SKS-6 Genapol OA 080* 5
+ Zeolite + Sodium tripoly-
phosphate Antifoam 0.4
A Wash effect n B Bleach effect n C Inorganic incrustations
Enzymes 1.4

Sulphate 29.2

* Clariant product brand names

Figure 70: Wash effect, bleach effect, enzyme effect and inorganic incrustations
of SKS-6 HD based regular detergent formula

40 4
A, B, C delta R [%]

30 3
D Ash [%]

20 2

10 1
1 SKS-6 HD + Zeolite

A Wash effect n C Enzyme effect


n B Bleach effect n D Inorganic incrustations

49
Color detergents
Color detergents are supposed to be the gentle-on-color alternative to heavy-duty
detergents. Color detergents are used wherever it is not necessary to remove stains
and heavy soiling.

Test Conditions
Miele Novotronic 927 WPS, main wash cycle, 60 °C,
18 °d, dosage 65 g/wash, 15 wash cycles
Wash effect: test fabrics EMPA 104, WFK 10C,
WFK 10D, WFK 30D
Enzyme effect: test fabrics EMPA 112, EMPA 116,
WFK CFT AS-10
Inorganic incrustations: test fabrics EMPA cotton,
Vossen terry towel, WFK 10A, WFK 16A, WFK 20A

Figure 71: SKS-6 based color detergent formulas

1 [%] 2 [%]

SKS-6 granular* 10 17

SKS-6 HD* – 25

Zeolite A 33 –

Citrate 9 2
These detergents for colored textiles therefore do not contain a
bleaching system, instead, they contain a special color protection Polycarboxylate 7 –
in the form of poly vinyl pyrrolidone and poly-4-vinyl pyridine-N- Soda 12 –
oxide as dye-transfer inhibitors and soil-release polymer for easier
Bicarbonate – 8
soil removal on union fabric. With enzymes often cellulase is uti-
lised as an agent against felting and as softener and color improver, Soap 2 1.5
because it removes the diffuse discolored fibre surfaces and reveals Genapol OA 080* 10, Anionic 8, Poly vinyl pyrrolidone 3,
the brilliant original color. Generally color detergents are used in

Enzymes 2, Antifoam 1, Soil-release polymer 1, Carboxymethyl-
cellulose 1, Sulphate to 100 %
the same dosage as heavy-duty detergents.
* Clariant product brand names

SKS-6 and SKS-6 HD are also particularly suitable for these special
detergents (Fig. 71). SKS-6 is then used to advantage together with Figure 72: Wash effect, enzyme effect and inorganic incrustations of SKS-6
zeolite and citrate. SKS-6 HD simplifies the use of polymer and can and SKS-6 HD based color detergent formulas
serve as carrier for special surfactants. In a practice test (Fig. 72) 30 3
these formulations are shown to have low incrustations, good deter-
gency and a low adverse effect on the effectiveness of enzymes.
A, B delta R [%]

20 2
C Ash [%]

10 1

0 0
1 SKS-6 2 SKS-6 + SKS-6 HD

A Wash effect n B Enzyme effect n C Inorganic incrustations

50 SKS®- 6
Fine-fabric detergents
and water softeners

Figure 73: SKS-6 based fine-fabric detergents

1 [%] 2 [%] 3 [%] 4 [%] 5 [%]

SKS-6 granular* 5 12 3 – –

SKS-6 HD* – – – 25 15

Zeolite A 20-25 12 – – 10

Sodium tripoly- – – 25 – –
phosphate

Citric acid – 6 – 3 3

laS/faS 15 15 15 15 15

Genapol OA 080* 3 3 3 3 3

Soap 1-3 1-3 1-3 1-3 1-3

Polycarboxylate 2-3 3 1 – –

Carboxymethyl- – 1 – 1 1
cellulose
Fine-fabric detergents are used for domestic washing of delicate
Phosphonate – 1 – 1 1
fabrics such as wool. They are therefore of low alkalinity and con-
tain special surfactants and additives for protecting fibres and Poly vinyl pyrrolidon 1 – 1 – –
colors. As alkalinity has an adverse effect on fine fabrics, it must Sulphate to 100 to 100 to 100 to 100 to 100
not be too high. Therefore, a lower amount of SKS-6 is general-
* Clariant product brand names
ly used. If preferred SKS-6 HD can also be used. Fig. 73 gives guide
formulations for special detergents with SKS-6 and SKS-6 HD.
Figure 74: SKS-6 based water softener formulas

Especially in regions with very hard 6 [%] 7 [%]

water, water softeners are important SKS-6 granular* 10-40 –


complements to heavy-duty detergents. SKS-6 HD* – 15-50

Zeolite A 20-60 20-60


During the washing process a softener can be added to the deter-
gent, this helps to counter the formation of deposits and incrusta- Soda or Bicarbonate 0-20 0-20
tions on heating coils and internal surfaces of washing machines. Polycarboxylate 5-15 –
In accordance with this main task, water softeners are principally
Citrate 0-40 0-40
made up of builder and cobuilder components (Fig. 74). Here too,
SKS-6 acts as alkali supplier and water softener in one. Above all it Sulphate 0-30 0-30

protects effectively against the deposits of mixtures from calcium Surfactant 0-5 0-5
carbonate and magnesium carbonate. Standard formulations also
* Clariant product brand names
contain zeolite for removing calcium, soda as alkali supplier and to
increase cleansing, polycarboxylate to disperse soil and to soften
water immediately at the beginning of the washing cycle. Small
amounts of nonionic surfactants may also be included as required.

51
SKS-6
Automatic dishwasher
detergents

52 SKS®- 6
53
Automatic dishwashing
detergents

Modern dishwashing detergents are balanced blends of various Figure 75: SKS-6 based phosphate free automatic dishwashing detergents
components: builder, cobuilder, alkalis, oxidising agents, enzymes,
surfactants, bleach activators, fillers, and, if required, fragrance. 1 [%] 2 [%] 3 [%]
Their interaction in the dishwashing machine is the prerequisite
SKS-6 granular* 10 20 –
for transforming used dirty dishes into clean and hygienic dishes
SKS-6 HD* – – 31
with the least possible use of energy and water while being as gentle
on the items in the dishwasher as possible. Amorphous disilicate 12 – –

Soda 22.2 24.2 20.7


The most important tasks of a dishwashing detergent are the
Polycarboxylate 7.5 7.5 –
removal of soil from the items in the dishwasher, dispersion of the
soil in the liquor and the chelating of residual water hardness and Citrate 30, Percarbonate 10, Peractive AC* 5, Enzymes 1.5,
Genapol EP 2584* 1.5, Perfume 0.3 %
hardness ions from food residues in order to prevent deposits on
* Clariant product brand names
the items in the dishwasher and on the dishwasher interior. In
addition to this it must also have foam-regulating properties, so
as not to impair the cleaning effect of the dishwasher liquid. Figure 76: SKS-6 based automatic dishwashing detergents containing phosphate

Today, however, the excellent cleaning effect of a dishwashing 4 [%] 5 [%] 6 [%] 7 [%] 8 [%]
detergent no longer is enough for it to be called an optimum deter- SKS-6 granular* 5.2 10 15 – –
gent. In addition to this it must prevent corrosion on the items
SKS-6 HD* – – – 7.1 10
in the dishwasher. This includes glass corrosion or tarnishing of
silver cutlery. Sodium tripoly- 48 45 25 48 45
phosphate

Today dishwashing detergents are offered in phosphate containing Soda 29 27.4 30 29.6 29.7
and phosphate free formulations, either as solids or liquids. Sulphate – – 9.2 – –
They are used most frequently in the form of tablets and granules;
Polycarboxylate 2.5 2.3 5 – –
particularly tablets ensure easy use and represent the ideal form
of a compact cleaner. Enzymes 1.5 1.5 2 1.5 1.5

Perborate · H2O 10, Peractive CB* 2, Genapol EP 2584* 1.5,


Liquid dishwashing detergents, despite a lower concentration of Perfume 0.3 %
* Clariant product brand names
the materials have the advantage that they are already in liquid form
and can become effective as soon as they have been added to the
dishwasher liquor.

SKS-6 and SKS-6 HD are the preferred raw materials for this
application.

54 SKS®- 6
Figure 77: SKS-6 HD based liquid automatic
dishwashing detergent

9 [%]

SKS-6 powder* 5.5

Sodium tripolyphosphate 22.2

Water glass mr 2.0 37

Soda 4

Sodium hypochlorite 9

Polycarboxylate 1.5

Hostapur SAS 60* 1.5


Their good washing and cleaning properties are: an excellent Hordaphos 158* 0.4
capability to bind calcium and magnesium, good cleaning ability
Sodium hydroxide 1
because of a high reserve alkalinity, particularly with regard to
deposits containing starch on the items in the dishwasher and a Phosphonic acid 0.6
very good storage stability, particularly when exposed to oxidising Water 17.3
agents. Especially the unique protection against corrosion
Dosage [g] 40
damage to glassware and deposits on glasses enables the manu-
facture of high quality detergents for automatic dishwashing, * Clariant product brand names
preferably for automatic household dishwashers.

Figure 78: Cleaning efficiency of phosphate free SKS-6 and SKS-6 HD


These advantageous properties are achieved by using dishwashing
formulations (margarine, egg and normal meat: cleaning efficiency of all
detergents of a suitable composition (Fig. 75-76). detergents = 100 %, dosage 20 g)

100
Although all components of the formula contribute to the cleaning
performance of the dishwashing formulation, the most important
Cleaning efficiency [%]

of these is the builder and cobuilder system. It must disperse the


80
soil as well as chelate the water hardness out of the rinsing water
and food residues, and thereby prevent the development of insol-
uble deposits, e.g. in the form of lime deposits on the items in the 60
dishwasher and on machine parts.

Liquid formulations, with regard to their ingredients, have similar 40


compositions to powder detergents. However, the stabilising of the Rolled oats Meat, Spinach Tea Milk
intensive
solid particles in the detergent suspension requires the formulation
1 SKS-6 + disilicate n 2 SKS-6 n 3 SKS-6 HD
to be specially adapted (Fig. 77).

SKS-6 powder not only offers an increased cleaning ability but also
a stable dispersion, which even after a longer storage time does not
tend to form sediment or separate into different phases.

If the dishwasher’s built-in water softener ensures the water is


softened, a dosage of 18-25 g dishwashing detergent per cleaning
cycle in the case of granule-type or tablet dishwashing detergents
or a dosage of about 40 g of liquid detergents in the dishwasher are
sufficient to achieve a good to very good detergency.

55
Cleansing performance

Remains of food particles that have dried on and are difficult to


remove (starch, denatured protein) undergo a swelling stage during
the washing-up process and are only subsequently removed from
the surface. Because of their high reserve alkalinity, SKS-6 or SKS-
6 HD are the optimum structural elements for dishwashing deter-
gents (Fig. 78-79) for this swelling process and complete removal.

The bleaching system of the dishwashing detergents – e.g. sodium


percarbonate or sodium perborate as oxygen carriers and Peractive
as activator – are actively supported by SKS-6 HD, in that the so-
called »tea scale« (tea deposits), is easily removed. This »tea scale«
or »tea skin« is the deposit that is formed on the inside of the tea
cup when tea brewed with hard water has been allowed to stand for
a while. These very good cleansing results of SKS-6 HD, the inte-
grated builder/ cobuilder system, far exceed those achieved with a
purely physical mixture of SKS-6 and polycarboxylate (Fig. 80).

Figure 79: Cleaning efficiency of SKS-6 and SKS-6 HD formulations


containing phosphate (margarine, egg and normal meat: cleaning efficiency of
all detergents = 100 %, dosage 20 g)

100
Cleaning efficiency [%]

80

60

40
Rolled oats Meat, Tea Milk
intensive

n 4 5.2 % SKS-6 n 5 10 % SKS-6 n 6 15 % SKS-6 Figure 80: Tea removal test
n 7 7.1 % SKS-6 HD n 8 10 % SKS-6 HD (tea scale, phys. mixture, SKS-6 HD)

56 SKS®- 6
Formation of deposits
in the dishwasher

Tap water contains more or less water


hardness. If the water for the dishwasher
is not softened deposits of lime can form
on cutlery and tableware.

The dishwasher’s own softening system now has the task of


softening the tap water. The builder and cobuilder system binds
the residual water hardness and the hardness ions from the food
residues and thus prevents the formation of deposits on the items
in the dishwasher.

One of the outstanding properties of SKS-6 is its ability to bind the


calcium and magnesium ions of water even under low water hard-
ness conditions typical for automatic dishwashers. The silicate part
of SKS-6 that does not serve to soften water can disperse soil and
protect metal surfaces from corrosion.

This ensures that dishwashing detergents formulated with SKS-6,


particularly phosphate free formulations, do not show any forma-
tion of deposits in the form of lime deposits on glasses, cutlery and
machine parts (Fig. 81).

Deposits in the form of thin layers of food residues can create


iridescent colors on stainless steel surfaces, particularly on stainless
steel pots and pans. Impurities such as titanium can create, under
certain conditions, temper colors on stainless steel alloys. Particu-
larly SKS-6 HD in dishwashing detergents prevents the formation
of such deposits.

57
Glassware in dishwashers
Very different types of crockery and tableware are in daily household use.
Included are such different materials as glass, porcelain, stoneware, stainless
steel, plastic, silver, wood or also aluminium.

Figure 81: Damage and scale on glasses

New glass

From the quantity point of view, glass is the most frequent item in
the automatic dishwasher. It is defined as an inorganic product of
Glass cleaned fusion, which has been cooled without crystallising. All glassware
with detergent
used in the household is silicate glass. Their main components are
based on SKS-6 HD
quartz sand and lime, soda, potash and alumina. Boron and lead
compounds give the glass such chemical and physical properties as
refraction of light, transparency, scratch hardness, resistance to
temperature change and chemical resistance. The expert differenti-
ates between sodium/lime/silicate glass (most standard glass),
potassium/lime/silicate glass (»potassium crystal glass«), sodium/
potassium/lime glass (»Thuringian glass«), boron/alumina glass
Symmetrical clou- (»Jena glass«) and potassium/lead glass (»lead crystal glass«).
ding

Despite its chemical resistance, glass in the dishwasher is vulnerable


to softened water and dishwasher liquor. After having been washed
several times, masked defects occur in the glass, such as clouding
and iridescence.

Here, the manufacturing process of the glass plays a decisive role.


If an irregular distribution of temperature over the glass surface
Lime scale occurs during manufacture or subsequent cooling of the glass,
this can cause the diffusion of alkaline ions from the warmer to the
colder areas of the glass surface. Although these glass surfaces look
optically perfect, in places where there is a high alkaline concentra-
tion these can be leached out during washing in the dishwasher and
result in the characteristic overall or symmetrical clouding (Fig. 81).

58 SKS®- 6
The phenomenon of iridescence can be caused either by the
Figure 82: Chemical glass polish effect (potassium crystal glass)
leaching of glass components from the surface, or by the formation
6 of thin layers with different light refractions properties.

The low alkaline automatic dishwashing detergents introduced


Loss in weight [‰]

on the market in the last few years on the basis of citric acid or
3 phosphate and containing greater quantities of amorphous silicates,
especially disilicates, cause the above mentioned irreversible
damage to glassware after only a few washing cycles. In the past,
there was no satisfactory solution to this problem that would ensure
the high cleaning performance demanded by the customer while
0
0 200 400 protecting décor and glass.
Wash cycles

n SKS-6 HD n SKS-6 n Commercial brand


By using SKS-6 – particularly SKS-6 HD – instead of amorphous
silicates or blended with these, phosphate containing or phosphate
free dishwashing detergents can be manufactured that do not dam-
age glasses or decorated porcelain even after frequent washing
(Fig. 81).

The high brilliance of glasses after even several hundred washing


cycles is achieved thanks to a continual chemical polishing of
the glass surface by microscopically small particles of SKS-6 or
especially SKS-6 HD (Fig. 82).

59
SKS-6
Appendix

60 SKS®- 6
61
SKS-6
Glossary

Agglomerates For the manufacture of agglomerates powdery basic material is Color transfer inhibitors Color transfer inhibitors such as poly-4-vinyl
blended with a binder in a mixer. Thereby the grains increase in pyridine-N-oxide or polyvinyl pyrrolidone counteract the bleeding of colors from
size and become granules. heavily dyed fabrics onto light-colored fabrics.
Amorphous sodium silicate Amorphous sodium silicates are composed non- Copolymer, polycarboxylate Homopolymeric or binary, ternary or quaternary
stoichiometrically in contrast to metasilicate and the di-, tri- and higher silicates, copolymer of acrylic acid, maleic acid, vinyl acetate and methallyl sulphonic acid.
which crystallize in layered structure. This refers mainly to water glass in liquid, The main application is in the dispersion of soil and builder particles in washing
spray-dried, hydrated or anhydrous form (solid water glass). liquor and rinsing water and in the chelating of metal ions.
Basic degree of brightness Unless mentioned otherwise, difference in Degree of whiteness according to Ganz/Griesser The degree of whiteness of
reflectance (delta R) is the difference of the basic whiteness values of soiled fabrics is determined according to the formula of Ganz/Griesser. The value of the
pieces of fabric prior to and after washing while UV components are filtered out. degree of whiteness represents the impression of whiteness that is perceived by
Builders Zeolite, phosphate and SKS-6 are brought together under this the human eye.
definition in the stricter sense. They soften the water during the washing process Wash effect, bleach effect, enzyme effect In order to determine these factors,
and thus prevent the formation of inorganic incrustations, support and improve differences in reflectance (delta R) of artificially soiled pieces of fabric are deter-
the detergency of surfactants. In the broader sense soda, citric acid or other mined. Different test fabrics are particularly sensitive to wash effect, bleach effect
substances that react with calcium and magnesium are also part of this definition. or enzyme effect of detergents.
Cobuilders Cobuilders comprise in particular: copolymers, phosphonates, etc. DIN 53916 This standard, which corresponds to ISO 4324 »Surfactants –
Cobuilders are generally good chelating agents and supplement and boost the Powders and Granules – Determination of the Angle of Repose«, describes a
builder’s effect. method for the determination of the angle of repose of surfactants in powder
or granule form as well as of detergents. This is a process for determining the
flowability of detergent powders or detergent granules.
Disintegrants These are materials that swell in water by volume expansion,
e. g. special kinds of cellulose, polyacrylic acid and other polymers. They help
with the disintegration of detergent tablets.

62 SKS®- 6
ffc value The ffc value is a measure for the flowability of a bulk material. Poly-4-vinyl pyridine-N-oxide (Pvno) PVNO prevents colored fabrics from
The higher the value the better the flowability of the bulk material. It is defined staining.
as the ratio of consolidation stress divided by unconfined yield strength. Pressed granulates Contrary to agglomerates, pressed granulates are
Genapol® types These are Clariant alcohol ethoxylates. manufactured by roller compaction. The grinding effect decreases the size of the
Greying inhibitors They counteract fabric greying by forming a protective grains. In the case of e. g. SKS-6 this is advantageous for the dissolution kinetics
cover around the fabric fibre, thereby allowing soil to be removed more easily and dispersion.
and preventing soil from being redeposited. Carboxymethylcellulose is an Primary detergency In the stricter sense of the term, this refers to the effect of
example of a greying inhibitor. the surfactants and the builder’s properties in assisting the washing process. It is
Heavy metal ions Heavy metal ions can decrease the stability of the bleaching determined by the degree of whiteness obtained
system in a detergent during storage, can reduce bleach efficiency during after washing specially soiled pieces of fabric.
the washing process and are able to damage fabrics during the bleaching process. Silanol groups These are OH groups that are bound fast to silicon atoms. They
The permissible quantities in drinking water are regulated in Europe by the do not contribute to a partial pressure of water vapour. Analytically they can be
EU Regulation for Drinking Water. determined together with the water of crystallisation as loss on ignition. The
Inorganic incrustations These are inorganic residues in fabrics comprising silanol groups are dehydrated during ignition, i.e. water molecules are eliminated.
calcium deposits and undissolved detergent residues. The inorganic incrustations Soil release polyesters These are nonionic or anionic polyesters, which make it
are the percentage of a fabric that remains unburned after ashing. easier for soil to be removed from synthetic fibres.
Peractive® types These are Clariant TAED bleach activators. Water of crystallisation These are the water molecules that are intercalated in
the crystal lattice. Contrary to silanol groups they can effect the formation of a
partial pressure of water vapour on the crystal’s surface. In many cases materials
containing water of crystallisation can take up water and release it again.

63
SKS-6
Patents

EP 0849355  ompound of SKS-6 and copolymer


C
for use in laundry detergents
EP 0799798 Heavy metal binding of SKS-6
EP 0753568 Cogranular of SKS-6 and sodium hydrogencarbonate
(US 5874397)
EP 0695860 Detergent based on a compound of kanemite and percarbonate
EP 0650926 Manufacturing of SKS-6 compacted granules using a hardening aid
(US 5520860)
EP 0640683  pplication of silicon rich crystalline sheet silicates (magadiite, kenyaite) as inhibitor of
A
chemical textile fibre damage (heavy metal binding)
EP 0622448 Detergent based on SKS-6, a surfactant and polyglycol acid
EP 0614695 Light duty detergent based on kanemites
EP 0563631 Compacted cogranulates of alumino-silicates and sodium silicates, a process for their
(US 5814289) preparation and their use
EP 0444415 Detergent based on amorphous disilicates
(US 5229095)
EP 0426366 Dishwashing agent based on SKS-6 and a proton donor
(US 5066415)
EP 0337217 Laundry washing agent with storage-stabilized bleach system (TAED)
(US 5078895)
EP 0337219 Storage-stabilized washing agent with boosted bleach action
EP 0294753 Alkylammonium salts of SKS-6
EP 0267371 Phosphate containing machine dish­washing detergent based on SKS-6 and a
(US 4959170) copolymeric carboxylic acid cobuilder
EP 0168726 Shaped body made from SKS-types
(US 4703029)
EP 0164514 Basic patent, use of SKS-types for softening water and a process for softening water
(US 4820439)

64 SKS®- 6
SKS-6
Abbreviations

°d Degree German water hardness


ADW Automatic dishwashing detergent
CBC Calcium binding capacity
CFT Centre for Test Material B.V., Vlaardingen, Netherlands
delta R Difference in reflectance
DIN DIN Deutsches Institut für Normung e.V., Burggrafenstraße 6, 10787 Berlin,
Germany, http://www.din.de; German committee on industrial standardisation;
DIN standards are available from Beuth Verlag GmbH, 10772 Berlin, Germany,
http://www.beuth.de
EC0 Effective Concentration 0 %; Specified concentration causes no effects
EC50 Effective Concentration 50 %; Specified concentration causes effects
in 50 % of the animals employed
EDTA Ethylene diamine tetraacetic acid
EMPA Eidgenössische Materialprüfungs- und Forschungsanstalt,
Lerchenfeldstrasse 5, CH-9014 St. Gallen, http://www.empa.ch;
Supplier of soiled test swatches
FAS Fatty acid sulfate
ffc Characteristic number for the flowability of bulk material
fm Detergent market share
HCl Hydrochloric acid
HDDT Heavy duty detergent tablet
HDPC Heavy duty detergent compact
HDPR Heavy duty detergent regular
ISO International Organization for Standardization (ISO), 1, rue de Varembé,
Case postale 56, CH-1211 Genève 20, Switzerland, http://www.iso.ch
LAS Linear alkylbenzene sulphonate
LC50 Lethal concentration 50 %; Specified concentration causes lethal effects
in 50 % of the animals employed (i.e. EC50 where »effect« is defined to be
»lethal effect«)
LD50 Lethal dose 50 %; Specified dose causes lethal effects in 50 %
of the animals employed
mr Molar ratio of SiO2 to Na2O in silicates
NaOH Sodium hydroxide
NOEC No observed effect concentration
OECD Organisation for Economic Co-Operation and Development
PCA Polycarboxylic acid
PVNO Poly-4-vinyl pyridine-N-oxide
rH Relative humidity
SKS Schichtkieselsäure; Layered sodium silicate
TAED Tetraacetyl ethylene diamine
WFK wfk-Testgewebe GmbH,
Christenfeld 10, 41379 Brueggen, Germany, http://www.wfk.de;
Supplier of soiled test swatches
WS Water softener

65
SKS-6
Literature

1 V. Kahlenberg, M. Wendschuh-Josties, R. X. Fischer, H. Bauer, J. Holz, 24 J. Himmrich, W. Gohla: Schichtsilikate als Waschmittelinhaltsstoff,
G. Schimmel, A. Tapper: X-ray powder diffraction data for delta-Na2Si2O5, SÖFW-Journal 120 (1994) 784-792
Powder diffraction 15 (2000) 139-141 25 D. Schulze: Aufbereitungstechnik 35 (1994) 524-535
2 V. Kahlenberg, G. Dörsam, M. Wendschuh-Josties, R. X. Fischer: 26 H.-P. Rieck: SKS-6: The Multi-Benefit Builder, 84th AOCS Annual Meeting,
The crystal structure of delta-Na2Si2O5, J. Solid State Chem. 146 (1999) 380-386 1993, Anaheim, CA, 1993
3 H. Bauer, G. Schimmel, P. Jürges: The evolution of detergent builders from 27 D. Heidemann, C. Hübert, W. Schwieger, P. Grabner, K.-H. Bergk:
phosphates to zeolites to silicates, Tenside Surf. Det. 36 (1999) 4, 225-229 9Si- und 23Na-Festkörper-MAS-NMR-Untersuchungen an Modifikationenen des
4 H. Bauer, G. Schimmel, P. Jürges: The evolution of detergent builders from Na2Si2O5, Z. anorg. allg. Chem. 617 (1992) 169-177
phosphates to zeolites to silicates, Tensidtage Kiew – TKK ’98 28 G. Schimmel: Natrium-Schichtsilicat als Waschmittelbuilder,
Days of Surfactants, Kiev, 1998 Dechema-Tagung, Frankfurt, 1992
5 H. Bauer: Schwermetallbindevermögen silikatischer Waschmittel­builder, 29 H. Jakobsen: Neue Untersuchungen an Natriumdisilikat, Diplomarbeit,
SÖFW-Journal, 124 (1998) 698-701 Universität Hannover, 1991
6 Glasklare Sache: Process (1998) 158-159 30 F.-J. Dany, W. Gohla. J. Kandler, H.-P. Rieck, G. Schimmel:
7 H. Bauer, Th. Müller: SKS-6 HD – Ein neues Builder-Cobuilder-System, Kristallines Schichtsilikat – ein neuer Builder, Seifen-Öle-Fette-Wachse 20 (1990)
Proceedings of 38th International Detergency Conference (1998) 181 805-808
8 H.-P. Rieck: The Backbone of Powdered Detergents, in: Michael S. Showell 31 F.-J. Dany, W. Gohla. J. Kandler, H.-P. Rieck, G. Schimmel:
(ed.), Powdered Detergents, 1998, Marcel Dekker, New York Kristallines Schichtsilikat – ein neuer Builder, 36. Sepawa Jahrestagung, Bad
9 W. Wieker, C. Hübert, D. Heidemann, R. Ebert: Alkalien – Dauerplage für die Dürkheim, 1989
Betonherstellung?, GDCh-Tagung Bauchemie, München, 1997 32 W. Hoffmann, H.-J. Scheel: Über die gamma- und delta-Modifikationen
10 W. Wieker, C. Hübert, D. Heidemann: Recent Results of Solid-State NMR des Natriumdi­silikates, Na2Si2O5, Zeitschrift für Kristallographie 129 (1969)
Investigations and their Possibilities of Use in Cement Industry, Proceedings 10th 396-404A.
Int. Congr. on Chemistry of Cement, Gothenburg (Sweden), 1997 33 K. Pant , D. W. J. Cruickshank: The Crystal Structure of alpha-Na2Si2O5, Acta
11 H. Bauer, G. Schimmel: Neue Aspekte bei der Anwendung des Builder- Cryst. (1968) B24, 13-19
Silikates SKS-6, Tenside Surf. Det. 34 (1997) 625-629 34 A. K. Pant: A Reconsideration of the Crystal Structure of beta-Na2Si2O5, Acta
12 H. Bauer, G. Schimmel: Neue Aspekte bei der Anwendung des Builder- Cryst. (1968) B24, 1077-1083
Silikates SKS-6, Tagung der GDCh Fachgruppe Waschmittelchemie, Saarbrücken, 35 J. Williamson, F. P. Glasser: The crystallisation of Na2O · 2 SiO2 – SiO2 glasses,
1997 Phys. Chem. Glasses 7 (1966) 127-138
13 G. Schimmel: Layered sodium disilicate – a new builder for detergents, 36 A. Willgallis, K. J. Range: Zur Polymorphie des Na2Si2O5, Glastechnische
ZMPC ’97, Tokyo, 1997 Berichte 37 (1963) 194-200
14 T. Takeda, H. Okamoto, S. Yamamura: Enhancement of Detergency of Soaps 37 F. Liebau: Untersuchungen an Schichtsilikaten des Formeltyps Am(Si2O5)n. II.
by Addition of Layered Sodium Silicate, Kagaku to Kogyo (Osaka) 71 (1997) 88-92 Über die Kristallstruktur des alpha-Na2Si2O5, Acta Cryst. 14 (1961) 395-398
15 H.-P. Rieck: Natriumschichtsilicate und Schichtkieselsäuren, 38 W. Wieker, C. Hübert, D. Heidemann, R. Ebert: Alkali-Silica Reaction
Nachr. Chem. Tech. Lab. 44 (1996) 699-704 – A problem of the insufficient fundamental knowledge of its chemical base,
16 H. Bauer: Einflüsse bei der Bestimmung des Calcium- und Magnesium- Materials Science of Concrete – The Sydney Diamond Symposium 395-408
Bindevermögens von kristallinem Natriumdisilikat, SÖFW-Journal 121 (1995) 39 H.-P. Rieck: Builders: Ecology, Cost and Performance, in: A. Cahn (ed.),
168-170 Proceedings of the 3rd World Conference on Detergents: Global Perspectives,
17 K. Beneke, P. Thiesen, G. Lagaly: Synthesis and Properties of the Sodium AOCS Press, Champaign, IL
Lithium Silicate Silinaite, Inorganic Chemistry 34 (1995) 900-907 40 W. Wieker, C. Hübert, R. Ebert: Contribution to the Chemical Reaction
18 D. Schulze: Chem. Ing. Techn. 67 (1995) 60-68 Mechanism of the Alkali-Aggregate-Reaction
19 J. Wilkens: Structure – property relationships of sodium disilicates, 41 Henkel informiert: Maschinelles Geschirrspülen und Somat, Bände 1-5,
Tenside Surf. Det. 32 (1995) 475-481 Henkel KGaA, Beratung Anwendungstechnik, Postfach 10 11 00, 4000 Düsseldorf 1
20 H.-P. Rieck: A New and Promising Chapter in the Sodium Silicate Story,
Proceedings of the New Horizons ’95 Conference, AOCS Press, Champaign, IL
21 H.-P. Rieck : Trends in Detergent Builders, 86th AOCS Annual Meeting, 1995
22 H. G. Hauthal: 42. Sepawa Jahrestagung 1995 in Bad Dürkheim,
SÖFW-Journal 121 (1995) 945-946
23 J. Himmrich, W. Gohla: Schichtsilikate als Waschmittelinhaltsstoff,
40. Sepawa Jahrestagung, 1995, Bad Dürkheim, 1995

66 SKS®- 6
SKS-6
Product range

Chemical name: disodium disilicate


CAS number: 13870-28-5
EINECS number: 237-623-4

Type SKS-6 powder SKS-6 granular SKS-6 HD SKS-6 HD-D

Appearance white powder white granules white granules white granules


Process grinding compacting agglomeration agglomeration
Silicate content [ % ] > 99 > 96 67-79 58-73
Additive – water polycarboxylic acid solution polycarboxylic acid solution,
Zn salt
Mean particle size 90-150 500-700 450-700 450-700
[ µm ]
Loss on ignition at 1h, 720 °C [ % ] < 0.7 < 4 ~ 26 ~ 26
Bulk density [ g/ l] 500-670 >840 450-650 480-680
Ca-binding capacity [ mg Ca/g ] > 731) > 731) ~ 722) ~ 662)
Application HDPR, HDPC HDPC, ADW, WS ADW, HDPC, WS ADW

1) 30 °d, 20 °C
2) 17 °d, 30 °C

HDPC = heavy duty powder compact


HDPR = heavy duty powder regular
ADW = automatic dishwashing detergents
WS = water softener

67
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Switzerland

Emulsions, Detergents and


Intermediates
Email detergents@clariant.com

www.Detergents.clariant.com
www.clariant.com

This information corresponds to the present state of our knowledge and is intended as a general
description of our products and their possible applications. Clariant makes no warranties, express or
implied, as to the information’s accuracy, adequacy, sufficiency or freedom from defect and assumes
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changes in our products and applicable national and international regulations and laws, the status of our
products could change. Material Safety Data Sheets providing safety precautions, that should be observed
when handling or storing Clariant products, are available upon request and are provided in compliance
05.2013

with applicable law. You should obtain and review the applicable Material Safety Data Sheet information
before handling any of these products. For additional information, please contact Clariant.

* For sales to customers located within the United States and Canada the following applies in addition:
NO EXPRESS OR IMPLIED WARRANTY IS MADE OF THE MERCHANTABILITY, SUITABILITY,
FITNESS FOR A PARTICULAR PURPOSE OR OTHERWISE OF ANY PRODUCT OR SERVICE.

® Trademark of Clariant registered in many countries.


© 2013 Clariant International Ltd

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