Precipitated calcium carbonate, a method for its manufacture and uses
thereof
The present invention which claims priority to European application
No. 13159828.6 filed March 18th, 2013, the whole content of this application
being incorporated herein by reference for all purposes, relates to precipitated
calcium carbonate in dry form or in the form of a slurry, a method for its
manufacture and uses thereof, especially for its use as an opacifier, notably in the
manufacture of paints, plastics or paper. The present invention also relates to a
specific method to produce paints, papers and paper coatings, and a specific
method to produce plastisols and sealants.
The use of precipitated calcium carbonate particles as a filler, for instance
in papers and paints, is known in the art, including the use of precipitated
calcium carbonate particles of specific shapes. For instance, US
patent 4,824,654 discloses a process of producing needle-shaped calcium
carbonate particles which are useful as a filler or a reinforcing material of
various materials such as rubbers, papers, plastics and paints. According to said
patent, the particles have an average length of 5-100 mih and an average diameter
of 0.2-5 mih and may confer high smoothness and gloss to the material.
Another example is given by European patent application EP-A-2 292 701
which discloses a process for preparing an aqueous suspension of dispersed
calcium carbonate, wherein the resulting coating of said suspension provides
opaque properties or has a specific light scattering coefficient S, such suspension
comprising dispersed calcium carbonate and an alkali carbonate and/or alkali
hydrogen carbonate and being especially suitable in the field of paper coatings,
paper mass fillings, paints and plastic coatings. Dry precipitated calcium
carbonate can also be used for the manufacture of plastisols and sealants.
When high opacity is sought, such as in paints which dry to give matt or
silk (i.e. mid-sheen) finishes, zinc sulphide and, most often, titanium dioxide are
used as opacifiers, as disclosed in EP0634463.
However, titanium dioxide has the disadvantage to be expensive.
Furthermore, its typical industrial manufacturing processes are not
environmentally friendly. There is thus a need for opacifiers having good
opacifying properties but with a limited cost.
The purpose of the present invention is, i.a., to provide an opacifier
showing excellent opacifying properties while being of reasonable cost
compared to known high quality opacifiers such as titanium dioxide, and being
easily applicable.
According to one aspect, the invention relates to a precipitated calcium
carbonate comprising particles which are at least partially in the form of
nanofibers or nanochain like agglomerates constituted by at least two
interconnected primary particles, and which precipitated calcium carbonate
optionally comprises scalenohedron particles.
According to another aspect, the present invention relates to a slurry of
precipitated calcium carbonate ("PCC)") particles. The slurry is preferably an
aqueous slurry.
The precipitated calcium carbonate and the respective slurry are now
described in detail.
The slurry comprises precipitated calcium carbonate preferably in an
amount of 20 to 60 % by weight.
Preferably, the content of precipitated calcium carbonate is equal to or
greater than 26 % by weight, more preferably, equal to or greater than 27 % by
weight, and still more preferably, equal to or greater than 28 % by weight.
Especially preferably, the content of precipitated calcium carbonate is equal to or
greater than 30 % by weight. Preferably, the content of precipitated calcium
carbonate is equal to or lower than 50 % by weight. A preferred range of the
content of precipitated calcium carbonate is from equal to or greater than 28 %
by weight to equal to or lower than 45 % by weight.
The primary particles of the PCC are rhomboids and scalenohedrons.
While the rhomboids form elongated entities namely nanochains or nanofibers,
by aggregation, the scalenohedrons are elongated entities per se.
Thus, the structure of the PCC particles is constituted at least partially by a
PCC entity (particles or aggregates) that show an elongated shape; i.e. they have
an aspect ratio of > 1. A specific feature of the elongated entities is that they
combine together to form microshells.
Thus, the slurry comprises elongated entities of PCC particles. The term
"elongated entities" denotes especially nanofibers and nanochainlike aggregates
and scalenohedrons. Nanofibers or nanochainlike aggregates and
scalenohedrons form microshells.
The slurry comprises particles which are in the form of nanofibers or
nanochain like agglomerates constituted by at least two interconnected primary
particles which often are rhomboids. These particles are predominant particles in
slurries having a content of precipitated calcium carbonate in the lower end of
the preferred range.
Slurries with a relatively high content of precipitated calcium carbonate,
for example, in slurries containing equal to or more than 28 % by weight, and
especially in slurries containing equal to or more than 30 % by weight of
precipitated calcium carbonate, also comprise precipitated calcium carbonate in
the form of scalenohedrons. The scalenohedrons also form microshells. The
higher the concentration of precipitated calcium carbonate in the slurry the
higher the content of scalenohedrons substituting the precipitated calcium
carbonate in the form of nanofibers.
Indeed, it has been surprisingly found that said calcium carbonate particles
exhibit improved opacifying properties while keeping a mat finish, allowing the
preparation of compositions showing an improved opacity of the composition
itself and/or of the product obtained after curing or drying of said composition,
compared to the use of other calcium carbonate grades. It is therefore possible to
prepare compositions having an improved opacity with a matt finish. It is also
possible to replace at least part of high quality opacifiers such as titanium
dioxide, without decreasing the opacity of the composition and/or of the product
obtained after curing or drying of said composition, which is of great economical
interest for high performance paints. In particular in paints, the use of PCC
according to the present invention might substitute up to 60 wt % of Ti0 2
content without affecting opacity of the resulting composition.
In the present invention, the term "opacifier" intends to denote a substance
that, when added to a material, renders it opaque or at least increases its opacity.
Opacity is linked to the light scattering coefficient S and the light absorption
coefficient K of the material, a higher S and/or a lower K corresponding to a
higher opacity. Opacity is especially important in matt paints and papers.
The term "paint" intends to denote any liquid, liquefiable, or mastic
composition, more particularly liquid or liquefiable composition, comprising
pigments, which after application to a substrate in a thin layer is converted to an
opaque solid film. Such a solid film is most commonly used to protect, to color
or to provide texture to objects, for instance, walls.
The term "particle" is understood to mean a physically and chemically
autonomous entity. The term "primary particle" refers to the elementary
particles of precipitated calcium carbonate. The predominant primary particles
are rhomboids and scalenohedrons as explained above.
In the terms "nanofibers" and "nanochain like agglomerate", the prefix
"nano" means that the nanofibers or nanochain like agglomerates have a
characteristic dimension at the nanoscale, preferably, a characteristic dimension
which is, on average, less than 500 nm, more preferably, a characteristic
dimension which is, on average, less than 250 nm, and in particular, a
characteristic dimension which is, on average, less than 200 nm. In nanofibers
or nanochain like agglomerates, said characteristic dimension is the average
diameter.
The term "nanofiber" intends to denote an elongated entity having a
characteristic dimension, i.e. average diameter, less than 500 nm, preferably an
average diameter less than 250 nm, and in particular, an average diameter less
than 200 nm. The term "nanochain like agglomerate" intends to denote an
elongated entity having a characteristic dimension, i.e. average diameter, less
than 500 nm, preferably an average diameter less than 250 nm, and in particular,
less than 200 nm. Nanofibers mainly differ from nanochain like agglomerates in
that the individual primary particles cannot be distinguished anymore and form
nanofibers which appear to be homogeneous and even, for example on electron
microscopy photographs, whatever the magnification. In nanochain like
agglomerates, the primary particles retain their individuality and remain visible,
for example on electron microscopy. Nanochain like agglomerates can also be
named "nanorosaries".
The term "scalenohedron" refers to elongated PCC primary particles which
present a primary particle size in a range of from 80 to 300 nm, and preferably of
from 100 to 200 nm. Such primary particle size is representative of the smaller
dimension of the particle.
An essential feature of the present invention resides in the fact that at least
part of the precipitated calcium carbonate particles are in the form of an
elongated entity. As already described above, the elongated entities are often of
the type of nanofibers or nanochain like agglomerates, such nanofibers or
nanochain like agglomerates being constituted by at least two interconnected
primary particles and therefore having an elongated morphology; or they are
scalenohedral elementary particles also having an elongated morphology.
In the present invention, precipitated calcium carbonate particles are
preferably present in the form of elongated entities in an amount of at least 1%
by weight of the calcium carbonate particles. Often, precipitated calcium
carbonate particles are present in the form of elongated entities in an amount of
at least 8 % by weight of the calcium carbonate particles. In the present
invention, precipitated calcium carbonate particles are typically present in the
form of elongated entities in an amount of at least 10 % by weight of the calcium
carbonate particles, more preferably in an amount of at least 15 % by weight of
the calcium carbonate. The amount of elongated entities, be they nanofibers or
nanochain like agglomerates, or scalenohedrons, has been evaluated relying
on SEM (Scanning Electron Microscopy) or TEM (Transmission Electron
Microscopy) image analysis. The obtained values correspond to the number of
elementary particles that belongs to the nanofibers in respect to the total number
of elementary nanoparticles, the measurement being performed in areas of
acceptable resolution. It is preferred to determine the amount in a homogenized
sample.
According to the invention, the primary particles are preferably in the form
of calcite crystals. The primary particles may present in a huge variety of
shapes, the most common being rhombohedral and scalenohedral morphology.
The presence of scalenohedral particles provides certain advantageous properties
as outlined below.
In the present invention, the scalohedron particles are elongated elementary
particles. As to the nanofibers or nanochain like agglomerates, without wishing
to be committed to a theoretical explanation, it is believed that the nanofibers or
the nanochain like agglomerates result from the end-to-end juxtaposition of
primary particles that are approximately spherical. Thus, contrary to the
scalenohedron particles, the nanofibers or nanochain like agglomerates are
secondary particles, formed by agglomerisation of primary particles. Therefore,
the average primary particle size (dp) is close to the smaller dimension of the
scalenohedron elementary particles and to the average diameter of the nanofibers
or nanochain like agglomerates. Advantageously, the average primary particle
size (dp) differs from the smaller dimension of the scalenohedron and from the
average diameter of the nanofibers or of the nanochain like agglomerates by less
than 50 %, preferably by less than 25 %, more preferably by less than 10 %.
These nanofibers or nanochain like agglomerates are thus secondary particles or
agglomerates of primary particles. Said nanofibers or nanochain like
agglomerates can optionally be further combined in any way. For instance, the
nanofibers or nanochain like agglomerates may be interwoven with respect to
one another in a disorganized way. The nanofibers or nanochain like
agglomerates can also be combined parallel to one another and form "faggots"
that may be composed of several tens or hundreds of similar nanofibers or
nanochain like agglomerates. The nanofibers or nanochain like agglomerates
can also be combined to form microshells. Microshells may be composed of
tens to hundreds of nanofibers or nanochain like agglomerates. In such a case,
the nanofibers or nanochain like agglomerates are usually visible at least on the
inner part of the microshell like agglomerates. In the present invention, the
nanofibers or nanochain like agglomerates are most of the time combined to
form microshells.
The scalenohedron elementary particles also form microshells.
The average diameter of the nanofibers or nanochain like agglomerates of
the present invention can thus be estimated on the basis of the average primary
particle size of the particles constituting the same (dp). As an approximation, it
is considered that the average diameter of the nanofibers or nanochain like
agglomerates is equal to the average primary particles size (dp). Said primary
particle size (dp), and the particle size of the scalenohedron elementary particles,
is in general equal to or higher than 1 nm, in particular equal to or higher
than 10 nm, more particularly equal to or higher than 20 nm, values equal to or
higher than 30 nm giving good results. An elementary particle size (dp) (as to
the scalenohedron particles) and primary particle size (dp) (as to the primary
particles forming the nanofibers or nanochain like agglomerates) of equal to or
greater than 50 nm is particularly preferred. The primary and elementary particle
size (dp) is usually equal to or lower than 500 nm, preferably, equal to or lower
than 250 nm, and in particular, equal to or lower than 200 nm. Suitable ranges
for the primary and elementary particle size (dp) of the scalenohedrons and
nanofibers or nanochain like agglomerates are usually from 10 to 500 nm,
preferably 40 to 250 nm, more preferably, 50 to 200 nm. The primary particle
size (dp) is typically measured by permeability. The average diameter of the
scalenohedron particles, nanofibers or nanochain like agglomerates of the present
invention can also be estimated relying on SEM (Scanning Electron Microscopy)
or TEM (Transmission Electron Microscopy) observations. For instance, the
diameter of scalenohedron particles and of nanofibers or nanochains can be
determined by image analysis of pictures taken by scanning electron
microscopy (SEM) or transmission electron microscopy (TEM), measuring
directly the diameter of particles or measuring the breadth of rectangles
comprising the particles, preferably measuring directly the diameter. The
average diameter is the arithmetic mean of the individual diameters of the
nanoparticles constituting a given population of nanoparticles. Said average
diameter is in general equal to or higher than 1 nm, in particular equal to or
higher than 10 nm, more particularly equal to or higher than 20 nm, values equal
to or higher than 30 nm giving good results; in particular, it is equal to or higher
than 40 nm. The average diameter is usually equal to or lower than 500 nm,
preferably, equal to or lower than 250 nm, and more preferably, equal to or lower
than 200 nm. Suitable ranges for the average diameter of the nano fibers or
nanochain like agglomerates are usually from 10 to 500 nm, preferably, from 40
to 250 nm, more preferably, from 50 to 200 nm.
The average length of the scalenohedron particles, nanofibers or nanochain
like agglomerates can be estimated relying on SEM (Scanning Electron
Microscopy) or TEM (Transmission Electron Microscopy) observations. For
instance, the length of scalenohedron particles and nanofibers or nanochain can
be determined by image analysis of pictures taken by scanning electron
microscopy (SEM) or transmission electron microscopy (TEM), measuring
directly the length of particles or measuring the length of rectangles comprising
the particles, preferably measuring directly the length. The average length is the
arithmetic mean of the individual lengths of the particles, e.g., nanoparticles
constituting a given population of nanoparticles. The nanofibers or nanochain
like agglomerates typically result from end-to-end juxtaposition of from 2 to 20
primary calcium carbonate particles, preferably 2 to 10, most preferably 2 to 8.
The average length of the nanofibers or nanochain like agglomerates typically
ranges from 20 to 2000 nm, preferably from 20 to 1000 nm, more preferably,
from 40 to 1000 nm, and most preferably from 80 to 1000 nm.
In the present invention, the nanofibers or nanochain like agglomerates,
and the scalenohedrons, respectively, may be at least partially combined in an
organized or random way to form aggregates. In a specific embodiment, these
nanofibers or nanochains may at least partially combine themselves to form
microshell-like aggregates in which the nanofibers are at least partially,
preferably mostly, visible on the inner part of the shell. Likewise, the
scalenohedron particles may at least partially combine themselves to form
microshell-like aggregates. The median size of these aggregates may be
evaluated on the basis of the aggregate median size (D50) or Stake's diameter,
determined by sedimentation analysis (see Examples). Said aggregate median
size (D50) is generally equal to or higher than 100 nm, especially equal to or
higher than 200 nm, more specifically equal to or higher than 400 nm, for
instance equal to or higher than 600 nm. The aggregate median size of the
calcium carbonate particles of the present invention is typically equal to or lower
than 5 mih, with preference equal to or lower than 4 mih, with higher preference
equal to or lower than 3 mih, for example equal to or lower than 2.5 mih. Very
suitable ranges for the aggregate median size of the aggregates are from 0.1
to 5 mih, preferably from 0.2 to 4 mih, more preferably from 0.4 to 3 mih, most
preferably from 0.8 to 2.5 mih.
In the present invention, it is advisable to limit the amount of aggregates
having a size above 10 mih. The amount of agglomerates having a size
above 10 mih is preferably less than 5 % by weight of the calcium carbonate,
typically less than 2 % by weight, especially less than 1% by weight. It has
indeed been found that aggregates with a size above 10 mih can have a
detrimental effect on the compositions comprising the same, especially resulting
in a decrease of the composition opacity.
The scalenohedron particles, the nanofibers or the nanochain like
agglomerates of the present invention have typically an aspect ratio strictly
higher than 1.0. The aspect ratio is defined as the ratio of a "higher
dimension" (L) of a particle, typically its length, on a "smaller dimension" of the
particle, usually its diameter. The aspect ratio of the particles of the present
invention is usually equal to or higher than 2, preferably equal to or higher
than 3, for instance equal to or higher than 4. The aspect ratio of the
scalenohedron particles, the nanofibers or the nanochain like agglomerates of the
present invention is often equal to or lower than 50, more often equal to or lower
than 20, values equal to or lower than 15 or equal to or lower than 10 giving
good results. The aspect ratio is generally determined by image analysis of
pictures taken by scanning electron microscopy (SEM) or transmission electron
microscopy (TEM), these techniques being used to determine the lengths and
diameters of the scalenohedron particles, the nanofibers or the nanochain like
agglomerates. In the present invention, the aspect ratio of a population of
nanofibers or the nanochain like agglomerates is the mean aspect ratio of a
population of nanofibers or the nanochain like agglomerates, i.e. the arithmetic
mean of the individual aspect ratios of the nanofibers or the nanochain like
agglomerates constituting a given population of nano fibers or the nanochain like
agglomerates. The aspect ratio of a population of scalenohedron particles is the
mean aspect ratio of a population of scalenohedron particles, i.e. the arithmetic
mean of the individual aspect ratios of scalenohedron particles constituting a
given population of scalenohedron particles. Preferred suitable ranges for the
aspect ratio varies from 2 to 50, especially from 2 to 20, more particularly 2 to 8.
In order to conduct image analysis of pictures taken by SEM or TEM,
magnification should be chosen in a reasonable way, such that the particles
would be reasonably defined and present in a sufficient number. In such
conditions, the analysis of a reasonable number of pictures, for instance
around 10 pictures, should allow accurate characterization of the particles. If
magnification is too low, the number of particles would be too high and the
resolution too low. If the magnification is too high, with for instance less
than 10 particles per picture, the number of pictures to be analyzed would be too
high and several hundreds of pictures should be analyzed to give accurate
measurements. The method must therefore be chosen to provide a good
dispersion degree of the nanoparticles into the sample.
Such precipitated calcium carbonate particles, in the form of scalenohedron
nanofibers or nanochain like agglomerates, have generally an aggregation ratio,
defined as the ratio of the aggregate median size (D50) on the average
diameter (dp), higher than 1, preferably equal to or higher than 2 , more
preferably equal to or higher than 5, most preferably equal to or higher than 10,
in particular equal to or higher than 20. The aggregation ratio of the particles is
usually equal to or lower than 300, often equal to or lower than 100, most often
equal to or lower than 50. An aggregation ratio from 5 to 300 is especially
suitable, more particularly from 10 to 100, most particularly from 20 to 50.
Calcium carbonate particles in the present invention generally have a SBET
specific surface area higher than 5 m /g, especially from 10 to 60 m g, for
example, from 24 to 36 mVg. SBET specific surface area is measured by the BET
technique described in Standard ISO 9277.
In a preferred embodiment, the precipitated calcium carbonate of the
present invention comprises a crystallization controller. The expression
"crystallization controller" is understood within the broad functional meaning.
The function of the crystallization controller is to modify the interaction between
the solid phase, liquid phase and gas phase present, during the nucleation and/or
the growth of the crystalline seeds of calcium carbonate, so as to control the
crystalline morphology obtained and thus the appearance of the resulting calcium
carbonate particles. Crystallization controllers also play an important role to
control the size of the precipitated calcium carbonate particles and may act as
growth promoters or growth inhibitors.
In an especially preferred embodiment, the crystallization controller is
selected from the group consisting of polyacrylic acid, salts thereof and mixtures
thereof. Advantageously, the crystallization controller is selected from partially
neutralized polyacrylic acid, especially polyacrylic acid wherein part of the acid
groups has been neutralized with sodium ions. For instance, around 70 % of the
acid groups are neutralized, leading to a partially neutralized compound having
a pH around 5-6. In another aspect, about 100 % of the acid groups are
neutralized, leading to a neutralized compound having a pH of about 6.5 to
about 10.
In the present invention, the crystallization controller is usually present in
an amount equal to or higher than from 0.1 wt % by weight of calcium
carbonate, preferably equal to or higher than 0.2 wt %, more preferably equal to
or higher than 0.25 wt %, for example equal to or higher than 0.5 wt %. The
crystallization controller amount is typically equal to or lower than 10 wt % by
weight of calcium carbonate, especially equal to or lower than 4 wt %,
particularly equal to or lower than 2.5 wt %, more particularly lower
than 2 wt %, values equal to or lower than 1wt % being also suitable. Ranges of
0.1 to 10 wt % by weight of calcium carbonate are often used, more often from
0.2 to 4 wt %, for instance from 0.25 to 2.5 wt % or even from 0.25 to 1wt %.
In the present invention, the crystallization controller has typically an
average molecular weight from 500 to 15000 g/mol, often from 700
to 5000 g/mol, more often from 800 to 4000 g/mol, most often from 1000
to 3500 g/mol. The crystallization controller is usually added to the reaction
medium prior to or during the calcium carbonate precipitation, typically as an
aqueous solution.
The precipitated calcium carbonate slurry of the present invention has the
advantage that it can be used as such for the intended use, for example as
opacifier in paint, plastics or paper and related materials; or any application in
which it is targeted to substitute Ti0 2 for its opacifying properties. This is
possible because of the high concentration in which the precipitated calcium
carbonate is present in the slurry. According to precipitated calcium carbonate
of the state of the art, only slurries with much lower concentration of precipitated
calcium carbonate with desired opacifying properties were produced.
According to an alternative, the slurry of the invention can be dried to
obtain dried precipitated calcium carbonate. The dried calcium carbonate still
provides the desired opacifying properties described above. The dried PCC is
especially suitable for application in plastisols and sealants or in polymers, e.g.
in polyethylene and polypropylene.
The dried precipitated calcium carbonate, obtainable or obtained from the
slurry described above, is another aspect of the present invention. It contains
elongated entities as described above. Preferably, the dried precipitated
carbonate contains scalenohedron elementary particles. The dried precipitated
calcium carbonate preferably comprises microshells formed from nanofibers or
nanochain like aggregates, and from scalenohedron elementary particles,
respectively. The dimensions of the primary particles (rhomboids) and the
scalenohedron particles are described in detail above. Preferably, the dried
precipitated calcium carbonate contains scalenohedron particles and microshells
formed from the scalenohedron particles.
The precipitated calcium carbonate particles of the present invention are
typically prepared by precipitation in the presence of a crystallization controller
preferably selected from polyacrylic acid, salts thereof and mixtures thereof.
In some cases, it may be advantageous to further coat dried particles with a
layer of organic matter such as saturated or unsaturated fatty acids having 2
to 22 carbon atoms, fatty acids with chains from 16 to 18 carbon atoms being
preferred. Such a coating of the particles is especially suitable for their
subsequent use in plastics. In paint and paper applications, the particles are
usually not coated with a layer of organic matter.
Another aspect of the present invention is to provide a process for the
manufacture of the slurry. The process for the manufacture of the slurry of
precipitated calcium carbonate of the present invention is usually performed in
water.
The process comprises
a) A step of providing CaO, which is reacted with water to form Ca(OH)2,
preferably to form dry Ca(OH)2
al) An optional step wherein the Ca(OH)2 of step a) is dried to provide
dried Ca(OH)2;
b) A step wherein the dry Ca(OH)2 of step a) or the dried Ca(OH)2 of step al)
is contacted with water to form a slurry; and
c) A step wherein the slurry of Ca(OH)2 from step b) is carbonated with C0 2.
Step a) is preferably performed at a temperature of from 10 to 95°C, and
preferably, at a temperature of from 20 to 60°C. Preferably, the amount of water
is selected such that directly in step a), a dry Ca(OH)2 is formed and step al) is
not necessary. Thus, a preferred process for the manufacture of the slurry of
precipitated calcium carbonate comprises
a) A step of providing CaO, which is reacted with water to form dry Ca(OH)2
b) A step wherein the dry Ca(OH)2 of step a) is contacted with water to form a
slurry; and
c) A step wherein the slurry of Ca(OH)2 from step b) is carbonated with C0 2.
The dry or dried Ca(OH)2 may be milled before contacting it with water to
form a slurry.
In step b), the reaction temperature is preferably kept in a range of from 10
to 95°C, preferably, in a range of from 10 to 60°C. Often, the concentration of
calcium hydroxide in the formed milk of lime is in a range of from 10 to 45 % by
weight, and more preferably, in a range of from 15 to 35 % by weight. The
concentration of calcium hydroxide in the milk of lime formed in step b) is in
particular selected such that after carbonisation, the CaC0 3 concentration is
preferably equal to or greater than 27 % by weight as indicated above. Here, it is
preferred that the concentration of Ca(OH)2 is equal to or greater than 19 % by
weight.
The viscosity of the milk of lime formed in step b) is preferably in a range
of from 20 to 4000 cP, more preferably, in a range of from 20 to 1000 cP. The
viscosity refers to the Brookfield viscosity and may be measured with a rotative
viscosimeter at 50 rpm.
In the preparation process, the milk of lime formed in step c) is carbonated
by reaction of the latter with carbon dioxide gas. Carbon dioxide gas having a
concentration of carbon dioxide varying from 3 to 100 % could be used with
success. However, it is preferable to use carbon dioxide gas for which the
concentration is from 10 to 60 % by volume, especially from 10 to 40 % by
volume, and in particular, 25 to 40 % by volume, carbon dioxide gas being
diluted with air or other inert gas.
Some additives might also be further added during the carbonation step,
such as isoascorbic acid, to reduce yellowness of the resulting calcium carbonate
particles.
The advantage of the process of the invention is that a slurry is obtainable
which has a very high content of precipitated calcium carbonate which still has
the desired opacifying effect. Of course, in the 1-step carbonization processes of
the state of the art, one could react CaO with a respectively adapted amount of
water to obtain a slurry of milk of lime with a relatively high content of Ca(OH)2
which then could be carbonated with C0 2. The main disadvantage is that control
of carbonation is decreased due to bad C0 2 absorption in the very viscous milk
of lime. Therefore, carbonation is not repeatable from one batch t o the other,
resulting in fluctuations of PCC properties such as elementary particle size and
size of the aggregates which may influence the opacity. It is assumed by the
inventors that this is due to a too high viscosity in the reaction mixture during
carbonization. It must be considered as very surprising that the simple step of
dehydrating and subsequent formation of a slurry of the formed milk of lime
provides a slurry of CaC0 3 which is highly concentrated and nevertheless has
the desired effect.
Said preparation process preferably is performed such that a precipitated
calcium carbonate slurry comprising equal to or more than 27 % by weight of
PCC by weight of slurry. Preferably, the amount is still higher as indicated
above, up to equal to or less than 60 % by weight. A very preferred range is
from 28 to 45 % by weight. As described below, the slurry may be applied as
such.
If it is desired to provide dry PCC, the precipitated calcium carbonate
particles might be filtered, for example through a planar filter, and dried, for
instance in an oven, by spraying into a stream of hot air (spray drying), or by the
action of radiation such as infrared radiation (epiradiator), preferably in an oven
or by the action of radiation such as infrared radiation. The resulting particles
might then be further milled, for instance in a pin mill apparatus with a milling
intensity ranging from 10 000 rpm to 20 000 rpm. The dried PCC is very well
suited, for example, to be used in the manufacture of plastisols, sealants and
polymers. Preferably, the slurry containing the PCC is applied as such. The
advantage, of course, is that it can be used immediately after its manufacture,
without drying and rehydration. Another advantage is that due to the high
concentration of PCC in the slurry, the size of carbonators used in the
precipitation process can be reduced. This advantage is especially useful when
precipitation is performed on site as described below.
The particles obtained in the process mainly formed from calcite. The
calcite crystals, if being pseudo-spherical or cubic, are randomly aggregated and
form nanofibers which in turn, may form microshells; if being scalenohedrons,
they may be randomly aggregated or form microshells.
The PCC slurry according to the present invention is especially suitable in
paints, paper mass fillings, paper coatings and plastic coatings, preferably in
paints, paper mass fillings and paper coatings. The slurry is especially
advantageous in aqueous paints, particularly in matt or silk (i.e. mid-sheen)
aqueous paints, more particularly in matte aqueous paints such as acrylic paints
or "latex house paints", where high opacity is sought with a mat finish. The use
of the present invention might also be of specific interest in paper fillings and
paper coatings such as in cigarette papers or rolling papers.
The slurry of the present invention is therefore typically applied to improve
opacity of paints, papers, paper coatings or plastic coatings, preferably of paints,
papers and paper coatings, more preferably of paints. The slurry can also be
applied to decrease the cost of a composition without decreasing its opacity
and/or the opacity of the product obtained after curing or drying of said
composition.
In a still further embodiment, the present invention relates to the use of the
slurry as a filler, preferably as an opacifier. This opacifier may be used to
substitute Ti0 2 (in any applications where the latter is used as an opacifier.
Advantageously, the precipitated calcium carbonate particles in the slurry
are used as an opacifier in paint, plastic ink, or paper industry, especially in
paints, paper mass fillings and paper coatings, more particularly in aqueous
paints such as in matte or silk (i.e. mid-sheen) aqueous paints, most particularly
in matte aqueous paints such as acrylic paints or "latex house paints", where high
opacity is sought with a mat finish. The slurry might also be of interest for use
in paper fillings and paper coatings such as in cigarette papers or rolling papers.
In a particular further embodiment, the specific precipitated calcium carbonate
particles in the slurry are used as a functional additive. Such functional additive
can bring some additional properties to the target object, being such as adequate
rheology characteristics for different applications. Advantageously, such
specific precipitated calcium carbonate particles after drying are used as a
functional additive in plastisol, sealant or ink.
While above, the use of the slurry containing dispersed calcium carbonate
is described, the slurry may as well be dewatered, and the resulting dried and
optionally milled calcium carbonate may be used as describe here before,
especially in plastisols, sealants and polymers. Other applications may include
cements, lubricants and healthcare.
The precipitated calcium carbonate can be used to substitute Ti0 2. It can
be, for example, applied in polyethylene plastics.
Another aspect of the present invention is to provide a process wherein
formed slurry is used "on site". The term "on site" means that the apparatus for
the formation of the PCC slurry is located at a close distance to the apparatus
wherein articles like paint, plastics or paper and related materials are produced.
The distance between the apparatus for forming the PCC slurry and the apparatus
wherein it is applied is preferably equal to or shorter than 500 m, more
preferably, equal to or shorter than 100 m. The distance can even be shorter,
e.g. equal to or lower than 50 m, and it is possible that the apparatus for PCC
slurry generation is located in close proximity of the apparatus wherein it is
applied, e.g. in a distance equal to or shorter than 10 m. Especially preferably,
the apparatus for the PCC slurry manufacture is in fluid connection to the
apparatus in which it is applied. Thus, by a fluid connection, it is avoided to
transport the PCC in tanks or bottles ; it is also avoided to provide a drying step
to transport dry PCC.
The slurry of the invention is especially suited for a production on site
because due to the higher PCC concentration, carbonators with reduced size may
be applied. The transport costs are drastically reduced because no transport on
the road or via rail is necessary. The customer gets a ready-made slurry with
reliable properties.
Should the disclosure of any patents, patent applications, and publications
which are incorporated herein by reference conflict with the description of the
present application to the extent that it might render a term unclear, the present
description shall take precedence.
The present invention is further illustrated below without limiting the
scope thereto.
Examples
Precipitated calcium carbonate (PCC) particles characterization
Average primary particle size (dp) (measured on the dried slurry)
dp is determined by permeability measured according to a method derived
from BS 4359-2. The basis of this method is the measurement of the air
permeability of a pellet, which is analogous to the "Blaine" or the "Lea & Nurse
method". The calculation of the dp derives from the Carman & Malherbe
formula : 1.05 e 2 2.88 e 2
q L d 2+ ds
( 1 - e )2 1- e
with
w
A x L x D
It can be shown that the mean particle diameter ds which is determined
according to the Carman & Malherbe formula is not absolutely independent from
the porosity of the pellet. Consequently, a correction is brought considering the
reference porosity e = 0.45 and the dp was calculated according to the formula :
dp =ds e-3.2( e -0,45)
Definitions ~ and unities are as
follows :
q = volumetric rate of air flow passed through the PCC pellet (cm /g),
e = porosity,
W = weight of PCC,
L = thickness of the pellet,
D = density of PCC (g/cm3),
A = area of the cross section of the pellet (cm2),
ds = mean particle diameter according to Carman & Malherbe (m h), and
dp = mean particle diameter according to Solvay (m h) .
Average diameter and average length (is measured on the dried slurry)
Average diameter and average length of the scalenohedron particles,
nanofibers or nanochain like agglomerates is estimated relying on scanning
electron microscope (SEM) observations. The samples are prepared from a
metallized powder and observed with a Hitachi S-4800 SEM. The samples are
directly placed on a graphite tape, then metallized with platinum for 1 minute
under a vacuum of 10 1 Pa with a beam intensity of 6 niA.
Aggregate median size (D50 or Stoke 's diameter)
D50 can be measured on the slurry or on dried particles. It is measured on
the basis of French standard ISO 13317-3, "Particle size sedimentation analysis
of a powder by variable height gravity in a liquid. Method by X-ray absorption
measurement", in which the general method and the apparatus (Sedigraph) are
described. Since the preparation of the sample influencing the results of the
measurement, such preparation method is described below.
Preparation of the samples : 2.7 g of precipitated calcium carbonate are
introduced into 50 ml of Na-hexametaphosphate (2 g/L) and the solution is
treated by magnetical stirring and ultrasound.
For the measurements, a Sedigraph 5100® equipped with an automatic
sampler Mastertech 5 1® from Micro meritics was used. The measurement was
performed between 0.1 mih (starting diameter) and 100 mih (ending diameter).
Generalprocedure for the preparation of aqueous emulsion paints
Opticalproperties
Paint test cards are prepared using an automatic coater (Erichsen,
Typ 509 MC) to coat contrast test cards (Leneta Form 09) with the paint samples
to be tested, at a feed rate of 7.5 mm/s (layer of 200 mih) . Films are then left to
dry before measurements.
Optical properties are measured using a spectrophotometer
(DataColor DC 600 and Datacolor QCX software), calibrated with a black
standard (luminance factor 0.1 %) and a white calibration standard
(serial No. 12077) before each measuring cycle. This provides the following
results : brightness (Y, DIN 53163), yellowness (DIN 6167) and opacity.
Opacity corresponds to the contrast ratio which is the ratio Y biack Y w ite
x 1 ,
where Ybiack and Y white are the brightness on respective black and white parts of
the contrast test cards.
Gloss is measured with a gloss measuring equipment such as micro-TRIgloss
from Byk-Gardner. Same cards are used as those used to measure the
optical properties. The gloss is measured at an angle of 85° for at least three
different positions on the sample surface. Gloss values are given in GU
(Gloss Unit).
General procedure to produce paint formulations : test to substitute
40 %Ti0 2
The following formulations are prepared :
- Formulation 1 : reference without PCC from the invention.
Formulation 2 : Substitution of 40 % Ti0 2 using a dry PCC prepared from
19 wt. % PCC slurry prepared according to the present invention.
Formulation 3 : Substitution of 40 % Ti0 2 using a 19 wt. % PCC slurry
prepared according to the present invention.
Formulation 4 : Substitution of 40 % Ti0 2 using a dry PCC prepared from
30 wt. % PCC slurry prepared according to the present invention.
Formulation 5 : Substitution of 40 % Ti0 2 using a 30 wt. % PCC slurry
prepared according to the present invention.
*GCC is ground calcium carbonate
Cellulose is added to the water with stirring. Ammonia is added and the
mixture was stirred again and then allowed to swell for approximately
20 minutes with repeated stirring. The wetting agent, the dispersing agent and
the defoamer are then added, followed by GCC, PCC and Ti0 2. The
composition is transferred into a dissolver and is dispersed during approximately
5 minutes at 2500±500 Rpm, then the binder and the biocide are added and the
mixture is further dispersed for approximately 2 minutes at 2000±500 Rpm. The
paint is allowed to stand for one day at room temperature before testing.
The resulting aqueous emulsion paints are characterized as follows,
according to EN- 13300 standards.
Example 1 - Preparation of a dry PCC from a milk of lime presenting a
concentration of 15 wt. %.
CaO is reacted with water such that dry Ca(OH)2 is obtained. The reaction
is controlled such that 1 molar equivalent of water is reacted per one molar
equivalent of CaO and the water content of the dry Ca(OH)2 is less than 2 %.
The dry Ca(OH)2 is contacted with water to provide a milk of lime. C0 2 is
bubbled into a milk of lime presenting a solid concentration of 15 wt. % in the
presence of a crystallization controller consisting of a mixture of polyacrylic acid
and sodium polyacrylate. The resulting PCC slurry presents a concentration
of 19 wt. % and is then filtered, dried and milled to obtain a dry PCC
(Formulation 2). The PCC contains nanochain like agglomerates, combined to
form microshell like aggregates.
Example 2 - Preparation of a PCC slurry from a milk of lime presenting a
concentration of 15 wt. %.
C0 2 is bubbled into a milk of lime presenting a solid concentration
of 15 wt. % in the presence of a crystallization controller consisting of a mixture
of polyacrylic acid and sodium polyacrylate. The resulting PCC slurry presents a
concentration of 19 wt. % (Formulation 3). The analysis of the PCC particles
recovered from the slurry shows a morphology of nanochain like agglomerates,
combined to form microshell like aggregates.
Example 3 - Tests in paints of the PCC prepared in the example 1 and 2
The obtained results show that it is possible to substitute up to 40 %
of Ti0 2 while keeping an opacity close to the reference one. Opacity of the
slurry is similar to the slurry one.
Example 4 - Preparation of a dry PCC from a milk of lime presenting a
concentration of 26 wt. %.
C0 2 is bubbled into a milk of lime presenting a solid concentration
of 26 wt. % in the presence of a crystallization controller consisting of a mixture
of polyacrylic acid and sodium polyacrylate. The resulting PCC slurry presents a
concentration of 30 wt. % and is then filtered, dried and milled to obtain a
dry PCC (Formulation 4). The analysis of the PCC particles recovered from the
slurry shows a morphology of nanochain like agglomerates, combined to form
microshell like aggregates.
Example 5 - Preparation of a PCC slurry from a milk of lime presenting a
concentration of 26 wt. %.
C0 2 is bubbled into a milk of lime presenting a solid concentration
of 26 wt. % in the presence of a crystallization controller consisting of a mixture
of polyacrylic acid and sodium polyacrylate. The resulting PCC slurry presents a
concentration of 30 wt. % (Formulation 6). The analysis of the PCC particles
recovered from the slurry shows a morphology of nanochain like agglomerates,
combined to form microshell like aggregates.
Example 6 - Tests in paints of the PCC prepared in the example 4 and 5
The obtained results show that it is possible to substitute up to 40 %
of T1O2 while keeping an opacity close to the reference one. Opacity of the
slurry is similar to the slurry one

CLAIMS
1. A precipitated calcium carbonate comprising particles which are at
least partially in the form of nanofibers or nanochain like agglomerates
constituted by at least two interconnected primary particles, and which
precipitated calcium carbonate optionally comprises scalenohedron particles.
2. The precipitated calcium carbonate according to claim 1 comprising
scalenohedron particles.
3. The precipitated calcium carbonate according to claim 1 or 2 wherein
at least a part of the nanofibers or nanochain like agglomerates, and, if present,
scalenohedron particles form microshells.
4. The precipitated calcium carbonate according to anyone of the
preceding claims wherein the primary particle size of thenano fibers or nanochain
like agglomerates is from 50 to 200 nm.
5. The precipitated calcium carbonate according to anyone of claims 2
to 4 wherein the average length of the scaleonhedron particles is in a range of
from 250 to 500 nm.
6. The precipitated calcium carbonate according to anyone of claims 2
to 4, wherein the precipitated calcium carbonate particles comprise a
crystallization controller, preferably a crystallization controller selected from
polyacrylic acid, salts thereof and mixtures thereof.
7. The precipitated calcium carbonate according to claim 5, wherein the
precipitated calcium carbonate particles comprise from 0.1 to 10 wt % of
crystallization controller by weight of calcium carbonate, preferably from 0.2
to 4 wt %, more preferably from 0.25 to 2.5 wt %, most preferably from 0.25
to 1wt %.
8. The precipitated calcium carbonate according to claim 5 or 6, wherein
the crystallization controller has an average molecular weight from 500
to 15000 g/mol, preferably from 700 to 5000 g/mol, more preferably from 800
to 4000 g/mol, most preferably from 1000 to 3500 g/mol.
9. The precipitated calcium carbonate according to anyone of the
preceding claims, wherein the nanofibers or nanochain like agglomerates have an
average diameter from 50 to 200 nm, and wherein the nanofibers or nanochain
like agglomerates have an average length from 80 to 1000 nm.
10. The precipitated calcium carbonate according to anyone of the
preceding claims, wherein the nanofibers or nanochain like agglomerates are at
least partially combined in the form of microshell like aggrs, preferably having
an aggregate median size (D50) from 0.8 to 2.5 mih.
11. The precipitated calcium carbonate according to anyone of claims 1
to 10 which is in the form of an aqueous slurry.
12. The precipitated calcium carbonate in the form of an aqueous slurry
according to claim 11 which comprises 19 to 60 % by weight of the precipitated
calcium carbonate.
13. The precipitated calcium carbonate in the form of an aqueous slurry
according to claim 12 which comprises 28 to 35 % by weight of the precipitated
calcium carbonate.
14. The precipitated calcium carbonate of anyone of claims 11 to 13,
obtainable by
a) A step of providing CaO, which is reacted with water to form Ca(OH)2,
preferably to form dry Ca(OH)2
al) An optional step wherein the Ca(OH)2 of step a) is dried to provide
dried Ca(OH)2;
b) A step wherein the dry Ca(OH)2 of step a) or the dried Ca(OH)2 of step al)
is contacted with water to form a slurry; and
c) A step wherein the slurry of Ca(OH)2 from step b) is carbonated with C0 2.
15. A process for the manufacture of precipitated calcium carbonate which
is suitable as opacifier, which process comprises
a) A step of providing CaO, which is reacted with water to form Ca(OH)2,
preferably to form dry Ca(OH)2
al) An optional step wherein the Ca(OH)2 of step a) is dried to provide
dried Ca(OH)2;
b) A step wherein the dry Ca(OH)2 of step a) or the dried Ca(OH)2 of step al)
is contacted with water to form a slurry; and
c) A step wherein the slurry of Ca(OH)2 from step b) is carbonated with C0 2.
16. The process of claim 15, which process comprises
a) A step of providing CaO, which is reacted with water to form dry Ca(OH)2;
b) A step wherein the dry Ca(OH)2 of step a) is contacted with water to form a
slurry; and
c) A step wherein the slurry of Ca(OH)2 from step c) is carbonated with C0 2.
17. The method of claim 15 or 16, wherein the concentration of Ca(OH)2
in step c) is equal to or greater than 15 % by weight.
18. A method for the manufacture of paint, plastics, paper, plastisol,
sealant or ink wherein the precipitated calcium carbonate of anyone of claims 1
to 11 is applied in a production plant to provide precipitated calcium carbonate
as filler.
19. The method of claim 18 wherein the precipitated calcium carbonate in
the form of a slurry of anyone of claims 11 to 14 is applied in a production plant
used for the manufacture of paint, plastics, paper, or ink.
20. The method of claim 19 wherein the slurry is produced on site of the
production plant.
21. The method of claim 18 comprising a step of drying the slurry to
provide dry precipitated calcium carbonate which is then applied for the
manufacture of plastisols, sealants or polymers.
22. The method of anyone of claims 18 to 2 1 wherein the precipitated
calcium carbonate is used to substitute Ti0 2.
23. The method of anyone of claims 18 to 22 wherein the precipitated
calcium carbonate is used in polyethylene plastics.