WO2019086134A1

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(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)

(19) World Intellectual Property


Organization
International Bureau (10) International Publication Number
(43) International Publication Date WO 2019/086134 Al
09 May 2019 (09.05.2019) W 1P O PCT

(51) International Patent Classification: MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ,
A01G 24/1 7 (2018.01) A01G 24/18 (2018.01) OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA,
SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN,
(21) International Application Number:
TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW.
PCT/EP20 17/078361
(84) Designated States (unless otherwise indicated, for every
(22) International Filing Date:
kind of regional protection available): ARIPO (BW, GH,
06 November 2017 (06. 11.2017)
GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ, TZ,
(25) Filing Language: English UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ,
TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK,
(26) Publication Language: English
EE, ES, FI, FR, GB, GR, HR, HU, ΓΕ , IS, IT, LT, LU, LV,
(71) Applicant: CEMEX RESEARCH GROUP AG MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, SM,
[CH/CH]; Romerstrasse 13, 2555 BRUGG BEI BIEL (CH). TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW,
KM, ML, MR, NE, SN, TD, TG).
(72) Inventors: ZAMPINI, Davide; Ober Altstadt, 15, 6300
ZUG (CH). GUERINI, Alexandre; Rosengasse 5A, 3250
Published:
LYSS (CH). CHAPELAT, Julien; Rue du Pilate, 25,
— with international search report (Art. 21(3))
2502 BIEL/ ΒΓΕΝΝΕ (CH). LEFSRUD, Mark Gregory;
12 Westwood, HUDSO, Quebec J0P 1H0 (CA). HITTI,
Yasmeen; 1767 Theoret, BROSSARD, Quebec J4W 2K6
(CA).

(74) Agent: NOVAGRAAF TECHNOLOGIES; 2, rue Sarah


Bernhardt, CS 90017, 92665 ASNIERES SUR SEINE (FR).
(81) Designated States (unless otherwise indicated, for every
kind of national protection available) : AE, AG, AL, AM,
AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, BZ,
CA, CH, CL, CN, CO, CR, CU, CZ, DE, DJ, DK, DM, DO,
DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, HN,
HR, HU, ID, IL, IN, IR, IS, JO, JP, KE, KG, KH, KN, KP,
KR, KW, KZ, LA, LC, LK, LR, LS, LU, LY, MA, MD, ME,

(54) Title: CEMENT-FREE POROUS SUBSTRATE FOR PLANT GERMINATION AND GROWTH MADE OF ALKALI-ACTI¬
VATED POZZOLANS

0
©0
FIGURE 1
o
o (57) Abstract: The present invention concerns a Portland cement-free porous rigid mineral substrate made of alkali-activated pozzolans,
a method for preparing the same, and use of said substrate to optimize plant germination and growth.
CEMENT-FREE POROUS SUBSTRATE FOR PLANT GERMINATION AND
GROWTH MADE OF ALKALI-ACTIVATED POZZOLANS

DESCRIPTION

FIELD OF THE INVENTION

The present invention relates to a Portland cement-free porous substrate for plant
germination and growth, essentially made of alkali-activated pozzolans, with
compressive strength at 28 days between 3 MPa and 10 MPa and porosity between
25% and 40% in the hardened state. Particularly, the present invention relates to a
Portland cement-free porous substrate for plant germination and growth manufactured
with a pozzolan material, such as fly ash or slag, without using cement based products.
The invention also relates to a process for producing such a substrate.

BACKGROUND OF THE INVENTION

Plants have always played an important role in human development throughout history.
Not only are they an important ingredient in the development of medicines, but they
are also cultivated due to their beauty, fragrance and nutritional properties as they are
the basis for many diets worldwide. On top of a significant amount of the population
being exclusively vegetarian, vegetables are a main side dish for omnivores, making
seed plants a significant source of nutrients for humans. Consequently, it is not strange
that agriculture is such an old activity for mankind.

Rock wool, a lightweight hydroponic substrate, is one of the most well-known


hydroponic growing mediums. It is made by melting basaltic rock and spinning it,
forming extremely thin fibres that bunch together. Although the raw materials are
natural, the fibres are non-biodegradable and will sit in landfills for a long time. Also,
rock wool materials are a source of dust and their loose fibres can get into eyes, mouth,
skin and lungs. Furthermore, rock wool cannot be manipulated (for example, by means
of a robot) since they have no mechanical resistance, needing a frame or a substrate
to do so. Therefore, there is the need to identify a more sustainable, less harmful
material as effective as rock wool for hydroponics.

One material that could be a solid alternative to rock wool for hydroponics is permeable
concrete. Concrete releases no dust or fibres and it is safe to handle. Also, at the end
of its service life, concrete can be recycled into aggregates and re-used in fresh
concrete. But fresh concrete has a pH around 12.5, too high for seedlings and growing
vegetation. Yet, many inventions disclose cementitious materials for hydroponics,
without giving any information related to the feasibility of the actual sprouting:

TW201 100349 discloses a pervious plant-growing concrete composed of Portland


cement, blast furnace slag, silica fume, quartz sand, crushed coarse aggregate, super
plasticizer and water. The permeable concrete is poured, rolled to form a pavement
and, when hardened, soil is scattered. Consequently, a roller or paver, as well as tools
to scatter the soil are needed, which add complexity to the invention. Also, because
soil is still needed, this invention is not a real alternative to rock wool.

DE1 9822621 uses granulates made from porous concrete and mixes them with quartz
sand, lime, cement, natural gypsum, aluminium powder and water to form a product
that can be used as vegetation layer for roof greening. Although the final function is
also as a vegetation layer, the material formulation uses concrete, cement, aluminium
powder, all materials that are not necessary and are detrimental in the present
application.

US201 70044077 discloses a foamed concrete, whereby cement, water and a


pozzolanic material (called "admixture") are mixed to form a paste; after a foam agent
is added to this paste to create foamed concrete, which is then cured and crushed to

form aggregates that are added to hydrogel to form "soil concrete". Plant nutrients,
microorganisms, moisture and the like are added to the "soil concrete" by being
incorporated in the hydrogel. But hydrogel has poor mechanical strength, so it is hard
to be manipulated. Also, it is prone to bacterial growth and there are around 200 types
of bacteria that are known to cause diseases in plants.
Hwang-Hee Kim et al. (Performance Evaluation and Field Application of Porous
Vegetation Concrete Made with By-Product Materials for Ecological Restoration
Projects) uses cement porous concrete overlaid with layers of soil, which is needed for
sprouting. The present invention avoids both soil and cement, consequently it provides
a simpler substrate for plant growth and germination, which can be reused only by
rising, not needing extra materials apart from water and the seeds one wants to
germinate (for example, soil is not needed).

US201 00058957 teaches how to produce a pervious concrete from geopolymerized


pozzolanic ash but no teaching related to a process that enables the development of
seeds in such substrate. Moreover, there is no teaching regarding the aggregates'
dimensions or how to select them to attain a certain porosity of the final material, which
is an important parameter for root development when growing vegetation.

WO201 7064444 discloses a vertical element comprising a porous concrete; at least


one of the surfaces has a coating which is a render made of soil, nutrients, vegetable
or seeds of a vegetable and possibly cement and has a porosity value between 10%
and 40%. Cementitious concrete is strongly basic (pH of 12 to 13), which can affect
the sprouting and life span of the vegetation. This narrows down the vegetation that
can be planted in such a structure, which is limited to plants that thrive in dry and alkali
environments. Plant species for human consumption will die or not even germinate in
such conditions. As a result, an alternative that does not involve cement but that
renders a structure with similar properties is sought. Additionally, aggregates above 4
mm are exclusively used in this application, which results in higher pore size and
consequently low capillarity, diminishing the capability of water and nutrients to reach
the plants. Further, the paste volume claimed is higher than 150 L/m 3 which leads to a
strong matrix that hinders the roots' growth and expansion.

WO201 108651 8 discloses a module made of a concrete material or ceramic powder


which has at least one porous surface, wherein the pores are interconnected to allow
air and water to circulate, as well as to allow plant roots to develop. The interconnected
pores are thinner on the outside of the module than on the inside, where they are
larger. The module also has a substrate made of soil. There is no guidance as to how
to produce said module, apart from a reference to other publications that disclose
materials based on ceramics, neither on how to attain the porosity mentioned.

Studies were done to test the usage of cementitious materials as substrates for
agricultural purposes to substitute rock wool as a substrate for plant growing.
Nevertheless, successfully growing crops proved hard, as new plants died due to the
harsh concrete conditions. The prior art failed to reveal a product based on concrete
materials that could successfully substitute rock wool as a hydroponic or aeroponic
medium for plant growing and crop rotation, whereas the present invention can be
reused or easily recycled, which is also not the case with rock wool.

DESCRIPTION OF THE INVENTION

The inventors have discovered a process to produce a porous substrate based on


concrete materials that has the same properties as cement-based structures but
without the harmful effects of cement in plant germination, for example, the high pH
associated with cementitious mixtures. The substrate hereby disclosed has high
mechanical strength. It does not need reinforcement, neither an extra support to be
used, being sturdy on its own; it can be handled manually, reused and recycled.

High alkalinity of the final substrate, as well as low strength and poor setting times have
been common causes to dismiss alkali-activated binders as main material to produce
substrates for plant germination and growth. All these parameters have been optimized
in the present invention.

The technology behind this new product and process allows seeds to be placed inside
a porous substrate made of an alkali-activated binder to germinate hydroponically.
Water should be added to the substrate so that water is able to wet the material through
capillary action, under most cases this is approximately 1/3 to 1/2 the height of the
substrate. Enough light should be provided, wherein the amount of light needed will
depend on the species being cultivated. Proper temperature should also be
maintained; although optimal temperature also depends on the species being
cultivated, 15°C to 25°C is advisable.
Several types of plants can be cultivated according to the method, including edible
plants - tomatoes, lettuce, radish, etc. But the final application is not limited to growing
edible vegetations, but it can also be for controlled environment agriculture, sports turf
or green infrastructure (for example, green roofs, green walls, eco-restoration, etc.)
Therefore, the vegetation that can grow according to this method is not limited to
vegetables, but also grass, turf, etc.

Hereby disclosed is a Portland cement-free porous rigid mineral substrate to optimize


plant germination and growth, with a final compressive strength after hardening
between 3 MPa and 10 MPa and porosity between 25% and 35%, comprising:
- a binder composed or consisting of pozzolanic material, said pozzolanic
material representing 100% of the binder weight;
- at least one alkaline activator;
- a water-to-binder ratio between 0.2 and 0.4;
- a paste volume between 75 and 120 l/m 3;
- between 1400 kg and 1600 kg of aggregates per m3 of concrete, said
aggregates with Dmax of 4 mm;
whereas the aggregates have a D90/D1 0 comprised between 1 and 3.5,
whereas D90 is selected to be located between 3 and 3.5 mm and the D 1 0 is
equal or larger than 1.5 mm, the aggregates being characterized by the fact that
the natural packing solid is between 55% and 65% (v/v).

Preferably, the binder consists of aluminosilicate minerals, selected from natural


pozzolans or metakaolin, or industrial inorganic by-products, for example, selected
from ground granulated blast furnace slag, fly ash or any mixture thereof.

In Table 1, one can see the chemical composition of the ground granulated blast

furnace slag that can be used according to the invention; likewise in Table 2 , one can
see the chemical composition of the fly ash that can be used in the invention.

Table 1 - Chemical composition of the ground granulated blast furnace slag


according to the invention
Constituent Weight Percent (m/m %)
Lime (CaO) 30-45
Magnesia (MgO) 3-1 5

Silica (SiO 2) 30-45


Alumina (AI2O3) 5-20
Sulfur (S) 0-3
Iron Oxide (Fe2O3) 0-2
Manganese Oxide (MnO) 0-2

Table 2 - Chemical composition of the fly ash according to the inventior


Constituent Weight Percent (m/m %)
Lime (CaO) 1-40
Alumina (AI2O3) 5-35
Silica (SiO 2) 15-60
Iron Oxide (Fe2O3) 4-40
LOI (%) 0-1 5

More preferably, the binder consists of 100% ground-granulated blast-furnace slag,


100% fly ash, or a mixture thereof, said mixture comprising between 60% to 100% of
slag and 0% to 40% of fly ash.

No treatment of the binder is needed; both slag and fly ash can be used as received.

Another embodiment is the method of the invention, wherein the activator comprises
alkaline reagents selected from the group composed by sodium silicates, sodium
metasilicates, sodium hydroxide or a mixture thereof.

Preferably, if sodium metasilicates are used, these are pentahydrate sodium


metasilicates. It was observed that the activation of slags and fly ashes is more efficient
using any of the activators mentioned above or a mixture thereof.

Another embodiment is the method of the invention, wherein the ratio between the
active solid content of the activator to the total binder content is located between 2%
weight and 8% weight. This range will ensure that the binder is activated without having
the extremely alkaline environment for the growth of vegetation.

Another embodiment is the method of the invention, wherein a superplastifier is added,


in a quantity between 0.1 2 and 0.8% (m/m) of binder.

The water to binder ratio is comprised between 0.2 and 0.4 and the paste volume is
comprised between 75 and 120 l/m 3.

The paste volume, together with the water-to-binder ratio and the aggregate size,
ensures that the paste coats the aggregates, binding them together, guaranteeing that
the voids are large enough and interconnected to aerate the root system - so that they
do not asphyxiate and consequently, rot, - but small enough to guarantee water
capillarity.

Aggregates from different origins and shapes can be used, being the most common
ones natural siliceous rounded aggregates from river, lake or sea origin and limestone
based crushed angular aggregates; other sources of aggregates include construction
demolition waste and concrete demolition waste. Quartz, clay, expanded clay, glass,
expanded glass or gravel can be used. Aggregates should be added between 1400 kg
and 1600 kg per m3. The most important properties to consider when choosing
aggregates is their size and their natural packing solid percentage: aggregates should
have a Dmax below 6 mm, preferably below 4 mm ( 1 00% passing through sieve 4.75
mm (N°4)), and a natural packing solid between 55% and 65% (v/v). If a natural
packing solid between 55% and 65% (v/v) is achieved, the aggregates' shape is
negligible.

The natural packing solid is the volume occupied by the solids without compaction per
m3 .

Dmax is the maximum diameter of the aggregates used. It is defined according to EN


206 (201 3) and it is declared as the value of the coarsest fraction of aggregate actually
used in the concrete.
When choosing aggregates, ensuring that they are monogranular is another important
factor to take into account. If the aggregates used are not monogranular, then finer
aggregates will fill in the voids between the bigger aggregates and water permeability
is not secured anymore. Roots that are growing within the porous substrate will
asphyxiate in small pores. On the other hand, if pores are too big, capillarity does not
occur and water does not reach the root system.

To ensure that the aggregates are monogranular, D90/D1 0 ratio should be comprised
between 1 and 3.5. D 1 0 and D90 are granulometry data derived from particle size
distribution for the aggregates used: D90 is the sieve size [mm] at which 90% of the
particles pass through, meaning that 90% of the aggregates will have a smaller size
than D90 and 10% have a bigger size than D90.

Similarly, D 1 0 is the sieve size [mm] at which 10% of the particles pass through,
meaning that 10% of the aggregates will have a smaller size than D 1 0 and 90% have
a bigger size than D 1 0 . Consequently, D90/D1 0 is a monogranular index.

According to the present invention, D90 is located between 3 and 3.5 mm and D 1 0 is
equal or larger than 1.5 mm.

After guaranteeing a monogranular index, also D50 can be calculated, which indicates
the average size of the aggregates used. This will help us predict the size of the voids;
hence it plays an important role in determining the water permeability of the product.
D50 is also a granulometry data derived from particle size distribution for the
aggregates used, wherein D50 is the sieve size [mm] at which 50% of the particles go
through, meaning that 50% of the aggregates will have a smaller size than D50 and
50% have a bigger size than D50. D50 is the average size of the aggregates. According
to the present invention, D50 is equal or larger than 1 mm.

D90/D1 0 and D50 secure that no powders are added in the mix and guarantee that
both the final voids size and percentage of voids are ideal to carry out the present
invention.
In order to produce a Portland cement-free porous rigid mineral substrate to optimize

plant germination and growth, with a final compressive strength after hardening
between 3 MPa and 10 MPa and porosity between 25% and 35%, the following steps
should be followed:
a) Mixing:
- a binder composed or consisting of pozzolanic material, said pozzolonic
material representing 100% of the binder weight, with
- at least one alkaline activator and
- water, wherein the water-to-binder ratio is between 0.2 and 0.4, and
- between 1400 kg and 1600 kg of aggregates per m3 of concrete, said
aggregates with Dmax of 4 mm,
whereas the aggregates have a D90/D1 0 comprised between 1 and 3.5,
whereas D90 is selected to be located between 3 and 3.5 mm and the D 1 0 is
equal or larger than 1.5 mm, the aggregates being characterized by the fact that
the natural packing solid is between 55% and 65% (v/v) and ensuring that the
paste volume is between 75 and 120 l/m 3;
b) Pouring said mix a) into a mould:
The mould has no restrictions in terms of size or shape; any mould with any
size or shape can be used according to the invention, depending solely on
the final desired product. For more convenience, a hole (0.5 mm diameter
and up to ¼ to 1/8 deep of the substrate height) could be formed before
hardening, to ensure a good seeding, although this step is not compulsory;
c) Curing the cement-free porous rigid mineral substrate:
This step c) avoids water loss and cracks derived from drying. Curing is done
by spraying or sprinkling water over the substrate surface or by steam curing
(typically 60-70°C), contributing to the strength gain of the product. When
applying steam curing, this is preferably steam at atmospheric pressure;
d) Washing the cement-free porous rigid mineral substrate:
Preferably, the method to wash the substrate can be one of three methods: still cold,
hot pressure and cold pressure.
Still cold wash is performed by soaking the porous concrete in water or nutrient solution
at room temperature (20°C) for 24 hours. The soaking step is performed by introducing
the cement-free porous rigid mineral substrate in water or nutrient solution, so that the
liquid completely submerges the substrate. There should be 8 times more water than
substrates by volume.
Hot pressure wash is performed using hot water (temperature between 50°C and 60°C)
forced through the substrate at 50 PSI for 15 seconds.
Cold pressure wash is performed using room temperature (20°C) water forced through
the porous concrete at 50 PSI for 15 seconds.

The washing step has as main objective to neutralize the unreacted slag powder and
surface ions from the substrate. Furthermore, the washing decreases the pH of the
substrate from the initial value of 11 down to 8 .
e) Placing the seed on the surface of the porous rigid mineral substrate:
After the porous substrate is washed, seeds can be planted. One or two
seeds should be planted by square inch area or species spacing dependent.
When a hole has been made during the preparation of the substrates, the
seeds can be placed inside;
f) Germination:
Supplying water to the free porous rigid mineral substrate to enable
germination of the seed in water or nutrient solution. The solution level
should be maintained at 1/3 to 1/2 of the height of the substrate to ensure
liquid throughout the substrate at all times when plants are being grown.

The step f) can be done using water without nutrients (for a few days up to maximum
7 days) since germination does not require nutrient in the soaking liquid until the first
true leaf appears.
Preferably, however, the soaking step f) will be done with a nutrient solution, preferably
a hydroponic nutrient solution. Preferably the hydroponic nutrient solution should be
Hoagland solution (as in Table 3) or a modified Hoagland solution, based on the
formulation in Table 4 .

Table 3 - Formulation of the Hoagland solution


Hoagland Nutrient
Concentration
4 - General nutrient formulation that can be used in s
Nutrient Concentration
Range
M KNO3 0.063 - 2.53 g/L
1M
0.1 5 - 5.90 g/L
Ca(NO3)2'4H2O
M MgSO4'7H2O 0.06 - 2.46 g/L
M KH2PO4 (pH to
0.02 - 0.7 g/L
6.0)
H3BO3 0.36 - 14.3 mg/L
MnCI2'4H2O 0.1 5 - 5.9 mg/L

ZnSO4'7H2O 0.03 - 1 . 1 mg/L


CuSO4-5H2O 0.01 - 0.4 mg/L

Na2MoO4'2H2O 0.02 - 0.6 mg/L


NaEDTA 0.93 - 37.3 mg/L
FeSO4'7H2O 0.7 - 27.8 mg/L

The Hoagland solution is a very well-known nutrient solution developed by Hoagland


and Arnon in 1938; it provides the essential nutrients for plant growth and it is suitable
for the growth of a large variety of plant species.
The porous substrates can be reused, one just needs to clean and remove the roots
from the substrate, wash it and re-start the process at step d).

In the present invention, germination rate was measured as a ratio, by dividing the

amount of plants germinated over the total population of substrates in the tray. Any
plants that died during the experiment resulted in a reduced plant viability score.

The final growth of the substrates has been assessed by recording the fresh and dry
mass of the plants at the end of the trial period (generally 28 days). The fresh mass
corresponds to the total mass of the plant, from above the hypocotyl to the top of the
plant. After complete drying at < 100 °C for at least 48 hours in the oven, with less than
5% mass change between 6 hours of continued drying, the dry mass is also recorded
and reported.

The Portland cement-free porous rigid mineral substrate can be casted or pre-casted
horizontally or vertically, depending on the final application. Also, the Portland cement-
free porous rigid mineral substrate can be used both in interior or exterior applications,
including on-water applications, for example, wetlands.

LIST OF DEFINITIONS
Hydroponics. The cultivation of plants by placing the roots in liquid nutrient solutions
rather than in soil.

Aeroponics. Process of growing plants in air without the use of soil.

Pervious concrete, also called water permeable concrete or porous concrete. A non-
conventional concrete since it has a high number of connected pores that allow water
to go through it. Hence, it is normally used in surface applications, such as pavements,
roads and roofs, to allow water flow and prevent flooding.
Hydraulic binder. It is a material with cementing properties that sets and hardens due
to hydration even under water. Hydraulic binders produce calcium silicate hydrates
also known as CSH.

Cement. It is a binder that sets and hardens and brings materials together. The most
common cement is the ordinary Portland cement (OPC) and a series of Portland
cements blended with other cementitious materials.

Ordinary Portland cement. Hydraulic cement made from grinding clinker with gypsum.
Portland cement contains calcium silicate, calcium aluminate and calcium
ferroaluminate phases. These mineral phases react with water to produce strength.

Paste. A mixture of binders, water, air and admixtures.

Gravel (coarse aggregates). Unconsolidated rock fragments having a size from 4 to 64


mm.

Aggregates. Particulate material used in construction. Can be divided into fine and
coarse aggregates. Include sand, gravel, crushed stone, recycled concrete and
geosynthetic aggregates.

Powder. Materials with granulometry up to 64 µηη .

Hydration. It is the mechanism through which OPC or other inorganic materials react
with water to develop strength. Calcium silicate hydrates are formed and other species
like ettringite, monosulfate, Portlandite, etc.

Concrete Ingredients. Concrete is primarily a combination of hydraulic binder, sand,


fine and/or coarse aggregates, water. Admixture can also be added to provide specific
properties such as flow, lower water content, acceleration, etc.
Admixture. Chemical species used to modify or improve concrete's properties in fresh
and hardened state. These could be air entrainers, water reducers, set retarders,
superplasticizers and others.

Superplasticizers. It relates to a class of chemical admixture used in hydraulic cement


compositions such as Portland cement concrete having the ability to highly reduce the
water demand while maintaining a good dispersion of cement particles. In particular,
superplasticizers avoid particle aggregation and improve the rheological properties and
workability of cement and concrete at the different stage of the hydration reaction.

Hardened concrete. Concrete in the solid state which has developed a certain strength.
Opposite to unhardened concrete.

Strength development - setting / hardening. The setting time starts when the
construction material changes from plastic to rigid. In the rigid stage the material cannot
be poured or moved anymore. After this phase the strength development
corresponding to the hardening of the material.

Flexural strength. Measure of the tensile strength of concrete. It measures the


resistance to failure in bending. According to the norm ASTM C78, the four point
bending test is performed by loading 150 x 150 mm unreinforced concrete beams with
a span length of three times the depth. According to EN 12390, the test is done in three
points.

Flexural resistance. Resistance of a structure against external load that can induce a
bending solicitation to it.

Compressive strength. Capacity of a material or structure to withstand compressive


loads. American Society for Testing Materials ASTM C39/C39M provides Standard
Test Method for Compressive Strength of Cylindrical Concrete Specimens. Concrete
compressive strength requirements can vary from 15 MPa for pavements to 100 MPa
and higher in commercial structures.
Permeability. The capacity of a porous material to allow fluids to pass through it.

Mineral Addition. Mineral admixture (including the following powders: silica fume, fly
ash, slags) added to concrete to enhance fresh properties, compressive strength
development and improve durability.

Silica fume. Source of amorphous silicon obtained as a byproduct of the silicon and
ferrosilicon alloy production. Also known as microsilica.

Fibers. Material used to increase concrete's structural performance. Fibers include:


steel fibers, glass fibers, synthetic fibers and natural fibers.

Fly ash. Also known as Alumino silicate-by-product. Alkali reactive binder components
that together with the activator form the cementitious paste. These minerals are rich in
alumina and silica in both, amorphous and crystalline structure.

Slag. Also called Ground-granulated blast-furnace slag (GGBS or GGBFS). Produced


by quenching molten iron slag from a blast furnace in water or steam. It is produced as
a granular product which is then ground into a fine powder with pozzolanic properties.

Pozzolans. Siliceous or siliceous and aluminous materials which, when finely divided
and in the presence of water, react chemically with calcium hydroxide to form
compounds with cementitious properties. Fly ash and slag are common pozzolans.

Filler inert. Material that does alter physical properties of concrete but does not take
place in hydration reaction.

Silicate. Generic name for a series of compounds with formula Na2O.nSiO2. Fluid
reagent used as alkaline liquid when mixed with sodium hydroxide. Usually sodium
silicate but can also comprise potassium and lithium silicates. The powder version of
this reagent is known as metasilicates and could be pentahydrates or nonahydrates.
LOI. Lost on Ignition. Test used in inorganic chemistry that consists of strongly heating
("igniting") a sample of the material at a specified temperature, allowing volatile
substances to escape, until its mass ceases to change.

Water-to-binder equivalent. Also designated "water/(cement + k x addition) ratio".


Allows to take into account type II additions (such as silica fume, fly ash or blastfurnace
slag) in the water-binder ratio. The definition and k values for the additions are
described in the norm EN 206 201 3 .

Workability. The time period within which the material is not yet set and can therefore
be handled, placed, leveled and compacted.

Workability retention. It is the capability of a mix to maintain its workability during the
time. The total time required depends on the application and the transportation.

Alkali Activated cements. Low or zero clinker cements activated by the use of caustic
alkalis or alkaline salts.

Sodium Hydroxide. It is an inorganic compound with formula NaOH also known as


caustic soda or lye that is used for chemical activation. Sodium hydroxide is referred
as Activator 1 in examples in this application.

PCE. Polycarboxylic Acid Co-Polymers used as a class of cement and concrete


admixtures, and are comb type polymers that are based on: a polymer backbone made
of acrylic, methacrylic, maleic acid, and related monomers, which is grafted with
polyoxyalkylene side- chain such as EO and/or PO. The grafting could be, but is not
limited to, ester, ether, amide or imide.

Coarse Aggregates. Manufactured, natural or recycled minerals with a particle size


greater than 8 mm and a maximum size lower than 32 mm.

Fine Aggregates. Manufactured, natural or recycled minerals with a particle size


greater than 4 mm and a maximum size lower than 8 mm.
Sand (fine aggregates). Manufactured, natural or recycled granular material composed
of finely divided rock and mineral particles. Have a minimum size of 64 µηη and a
maximum size lower than 4 mm.

Particle size distribution (PSD). List of values that define the relative amount, typically
by mass, of particles present in a sample according to size.

Natural packing solid. The volume occupied by the solids without compaction per m3.

Dmax. Defined according to EN 206 (201 3). It is the declared value of the coarsest
fraction of aggregate actually used in the concrete.

Aluminosilicates. Minerals composed of aluminium, silicon, and oxygen. Metakaolin is


an example of an aluminosilicate.

Metakaolin. Formula: AI2O3.2S1O2. Dehydroxylated aluminum silicate. It is an

amorphous non-crystallized material made up of lamellar particles.

Electro conductivity (EC). The ability of a solution to conduct an electrical current.


Measuring the electrical conductivity (EC) of the water is a normal method to quantify
the concentration of salts. Excessively high salinity can affect plants, either if one
particular ion is toxic for the plant (for example, sodium), or by inducing a higher
osmotic pressure around the roots, inhibiting an efficient water absorption by the plant.

Germination rate. Measured as a ratio, by dividing the amount of plants germinated


over the total population of substrates in the tray. Any plants that died during the
experiment resulted in a reduced plant viability score.

Fresh and dry mass. The fresh mass corresponds to the total mass of the plant, from
above the hypocotyl to the top of the plant. After complete drying at < 100 °C for at
least 48 hours in the oven, with less than 5% mass change between 6 hours of
continued drying, the dry mass is also recorded and reported.
Growth rate. After a seed has gernninated, it starts to grow. Hence when germination
rate reaches a plateau, it means the plants have entered into growing phase.

BRIEF DESCRIPTION OF THE FIGURES


- Figure 1 represents the germination rate using three different washing liquids
(water, modified Hoagland solution and Hoagland solution).
- Figure 2 represents the pH profile for the three different washing liquids (water,
modified Hoagland solution and Hoagland solution).
- Figure 3 represents the electrical conductivity profile for Example 1.
- Figure 4 represents the germination rate between GGBS and Fly Ash type C .
- Figure 5 represents the evolution of pH during plant growth between GGBS and
Fly Ash type C .
- Figure 6 represents the germination rate between 2/3.2 mm and 8/1 1 mm
aggregates.
- Figure 7 represents the germination rate between GGBS and CEM based
substrates.
- Figure 8 represents the evolution of pH between GGBS and CEM based
substrates during plant growth.

EXAMPLES

EXAMPLE 1
Three porous substrates were manufactured using the same mix design:

Table 5 - Mix design for the three porous substrates


Binder (Slag) 187 kg/m 3
w/b 0.3
Activator NaOH 50% m/m 3.7% (m/m)
Activator Na 2SiO 3 40%
5.2% (m/m)
m/m
Gravel (2/3.2 mm) 1478 kg/m 3
Paste volume 20 l/m 3

- Chemical composition and fineness of ground granulated blast furnace slag


y Fluorescence

The ingredients were mixed until uniform before being poured into three different
moulds. The moulds had a cubic shape, each had 4 cm3 of volume. The samples were
steam cured at 60 to 70°C for 8 to 16 hours and placed in the curing chamber for 7
days before demoulded.
The substrates were then washed in the following 3 different solutions, as described in
step d) "Still Cold Wash":
1. one substrate was washed with Hoagland nutrient solution (treatment 1) ,
2 . the second substrate was washed with a modified Hoagland nutrient solution
with an increased concentration of KH2PO4 ( 1 . 1 mol/L) (whereas the KH2PO4
concentration in the traditional Hoagland nutrient solution is 1M) (treatment 2)
3 . and the third substrate was washed with water (treatment 3).

The substrates were then seeded according to step e) and germinated according to
step f) for a period of 28 days in their respective washing solution (substrate 1 was
soaked in Hoagland nutrient solution, substrate 2 was soaked in Modified Hoagland
solution and substrate 3 was soaked in water). For the substrate 3 , Hoagland solution
was introduced only at day 7 to guarantee sufficient nutrients. The germination rate
(Figure 1) , pH (Figure 2) and EC (Figure 3) were monitored over time.
EXAMPLE 2 - DIFFERENT BINDER: USING FLY ASH C
Porous substrates were manufactured using the following mix design:

Table 7 - Mix design for the three porous substrates

Table 8 - Chemical composition and fineness of fly ash type C by X- ray fluorescence

The ingredients were mixed until uniform before being poured into the moulds. The
moulds had a cubic shape, each had 4 cm3 of volume. The samples were steam cured
at 60 to 70°C for 8 to 16 hours and placed in the curing chamber for 7 days before
demoulded. After the porous substrate has been washed according to the procedure
described in example 1, using Hoagland solution (treatment 1) , two seeds are planted
by square inch area or species spacing dependent. The Hoagland nutrient solution
level was maintained at 1/3 of the height of the substrate to ensure solution throughout
the substrate at all times by capillarity when plants are being grown.

Germination rate as compared to the GGBS based substrates was comparable as


shown on Figure 4 below, although maximum reached was about 90%. Figure 4 shows
the germination rate after the soaking step f), wherein time 0 is the day when the seeds
were placed on the substrate.

pH also appeared to be similar than GGBS, ranging between 8 and 10 as described


on Figure 5 .

EXAMPLE 3 - AGGREGATES WITH BIGGER SIZE


Porous substrates were manufactured using the following mix design:

Table 9 - Mix design for the three porous substrates

Table 10 - Chemical composition and fineness of ground granulated blast furnace


- ray diffraction
The ingredients were mixed until uniform before being poured into the moulds. The
moulds had a cubic shape, each had 4 cm3 of volume. The samples were steam cured
at 60 to 70°C for 8 to 16 hours and placed in the curing chamber for 7 days before
demoulded. After the porous substrate has been washed according to the procedure
described in example 1 (treatment 1) , using Hoagland solution, one or two seeds are
planted by square inch area or species spacing dependent. The Hoagland nutrient
solution level was maintained to ensure solution throughout the substrate at all times
by capillarity when plants are being grown.

Germination rate with 8/1 1 mm aggregates showed a significant decrease in efficiency


(Figure 6) as compared to the use of 2/3.2 mm aggregates, which could be related to
the capillarity absorption and water retention of the substrate, as shown on Table 11.
Due to the bigger void size, the water is not retained by the porous substrate and
cannot support the germination and growth of the seeds. Only the germination can be
supported by the nutrient already provided in the seeds, but after 7 days, the plants
started to die by lack of water and nutrients in the porous structure, since capillarity
could not occur due to the big size of the pores. Such performance renders the use of
bigger size aggregates, above 4 mm, incompatible with hydroponic systems. Figure 6
shows the germination rate after the soaking step f), wherein time 0 is the day when
the seeds were placed on the substrate. Germination with 2/3.2 mm has reached a
plateau, which means that more than 95% of the seeds have not only germinated but
have continued to develop, reaching a growing stage.
Table 11 - Water absorption, retention and drained for porous substrates
(measured on 110 x 220 mm cylinder samples)

To determine "Water Absorption", "Water Retained" and "Water Drained", cylinders of


11x22 mm of the same porous material as the substrates, have been manufactured.
The substrates are first weighted when totally dry and the water absorption is
measured according to norm ASTM C 1745. After all the voids have been filled with
water, the cylinders are rapidly removed from the liquid. Water starts pouring from the
cylinder, due to its open porosity, and this water is directly collected and measured,
leading to "Water Drained". When no more water pours out, the cylinder is again
weighted. The difference between this wet cylinder and the dried cylinder leads to
"Water Retained".

EXAMPLE 4 - AGGREGATE BELOW 4 MM, BUT HAVING D90-D50-D10 OUTSIDE


THE INVENTION SCOPE
Porous substrates were manufactured using the following mix design:

Table 12 - Mix design for the three porous substrates


Table 13 - Chemical composition and fineness of ground granulated blast furnace
slag by X- ray diffraction

The ingredients were mixed until uniform before being poured into the moulds. The
moulds had a cubic shape, each had 4 cm3 of volume. The samples were steam cured
at 60 to 70 °C for 8 to 16 hours and placed in the curing chamber for 7 days before
demoulded. After the porous substrate has been washed according to the procedure
described in example 1, using Hoagland solution, one or two seeds are planted by
square inch area or species spacing dependent. The Hoagland solution level was
maintained to ensure liquid throughout the substrate at all times by capillarity when
plants are being grown.

When aggregates with a size 0.3/0.9 mm were used, germination rate proved to be
very similar to the one when 2/3.2 mm aggregates were used in the sense that all
seeds developed successfully. However, none of the roots grew through the porous
substrates and only developed from the outer layer, due to the very low size of the
voids. The growth of the plants was allowed by a higher water retention that provides
sufficient amounts of water and nutrients on the surface of the substrates (see table
14)
Table 14 - Water absorption, retention and drained for porous substrates (on 11 x 22
cm cylinder)

EXAMPLE 5 - CEMENT BASED MATERIAL


Porous substrates were manufactured using the following mix design:

Table 15 - Mix design for the three porous substrates

Table 16 - Chemical composition and fineness of CEM I 52.5R used by X- ray


diffraction
SrO (%) 0.08
Cr2O (%) 0.01
ZnO (%) 0.02
LOI 950 C (%) 3.1 0

C I (%) 0.01
Sum %) 99.75

The ingredients were mixed until uniform before being poured into the moulds. The
moulds had a cubic shape, each had 4 cm3 of volume. The samples were steam cured
at 60 to 70°C for 8 to 16 hours and placed in the curing chamber for 7 days before
demoulded. After the porous substrate has been washed according to the procedure
described in example 1, using Hoagland solution, one or two seeds are planted by
square inch area or species spacing dependent. The Hoagland solution level was
maintained to ensure liquid throughout the substrate at all times by capillarity when
plants are being grown.

Germination rate as compared to the GGBS based substrates was significantly lower
(<50%), and this due to the high pH (>1 2) released from the cement matrix rich in
calcium ions (Figures 7 and 8). Germination was much slower for the cement based
substrates and while some seed died, some other started to germinates, thus
explaining the variation of the germination curve.

EXAMPLE 6 - OPTIMIZED SUBSTRATE WITH RADISH


Porous substrates were manufactured using the following mix design:

Table 17 - Mix design for the three porous substrates


Binder (Slag) 187 kg/m 3
w/b 0.3
Activator NaOH 50% m/m 3.7% (m/m)
Activator Na 2SiO 3 40% m/m 5.2% (m/m)
Gravel (2/3.2 mm) 1478 kg/m 3
Paste volume 120 l/m 3
Table 18 - Chemical composition and fineness of ground granulated blast furnace
X- ray diffraction

The ingredients were mixed until uniform before being poured into the moulds. The
moulds had a cubic shape, each had 4 cm3 of volume. The samples were steam cured
at 60 to 70°C for 8 to 16 hours and placed in the curing chamber for 7 days before
demoulded. After the porous substrate has been washed according to the procedure
described in example 1, using a modified Hoagland solution, one or two seeds are
planted by square inch area or species spacing dependent. The Hoagland solution
level was maintained to ensure liquid throughout the substrate at all times by capillarity
when plants are being grown.

The plant growth, by means of the fresh and dry mass of the plant, was compared after
a growing period of 30 days after seeding, between the GGBS based substrates and
rockwool which is considered as the market benchmark. As it can be observed in the
table 19 below, plant growth was similar even exceeding rockwool.

Table 19 - Fresh and dry mass of the radishes


GGBS Rockwool
Substrate Benchmark

Fresh mass
(g/plant) 1.56 1.85

Dry mass
(g/plant) 0.153 0.128
CLAIMS

1. A Portland cement-free porous rigid mineral substrate, with a final compressive


strength after hardening between 3 MPa and 10 MPa and porosity between 25%
and 35%, comprising:
- a binder consisting of pozzolanic material;
- at least one alkaline activator;
- a water-to-binder ratio between 0.2 and 0.4;
- a paste volume between 75 and 120 l/m 3;
- between 1400 kg and 1600 kg of aggregates per m3 of concrete, said
aggregates with Dmax of 4 mm,
- whereas the aggregates have a D90/D1 0 comprised between 1 and 3.5,
whereas D90 is selected to be located between 3 and 3.5 mm and the D 1 0 is
equal or larger than 1.5 mm, the aggregates being characterized by the fact that
the natural packing solid is between 55% and 65% (v/v).

2 . A substrate according to claim 1, wherein the binder consists of aluminosilicate


minerals, selected from natural pozzolans or metakaolin, or industrial inorganic
by-products selected from ground granulated blast furnace slag, fly ash or any
mixture thereof.

3 . A substrate according to claim 1, wherein the binder consists of 100% ground-


granulated blast-furnace slag, 100% fly ash, or a mixture thereof, said mixture
comprising between 60% to 100% of slag and 0% to 40% of fly ash.

4 . A substrate according to claim 1, wherein the at least one activator comprises


alkaline reagents selected from the group composed by sodium silicates,
sodium metasilicates, sodium hydroxide or a mixture thereof.

5 . A substrate according to claim 1, wherein the ratio between the solid active
content of the activator and the total binder content is located between 2 weight
% and 8 weight % .
6 . A substrate according to claim 1, wherein a superplastifier is added, in a quantity
between 0.1 2 and 0.8% (m/m) of binder.

7 . Use of a Portland cement-free porous rigid mineral substrate according to claim


1 to optimize plant germination and growth.

8 . Method for preparing a Portland cement-free porous rigid mineral substrate as


defined in claim 1 to optimize plant germination and growth, comprising:
a) Mixing:
a binder consisting of pozzolanic material;
at least one alkaline activator;
a water-to-binder ratio between 0.2 and 0.4;
between 1400 kg and 1600 kg of aggregates per m3 of concrete, said
aggregates with Dmax of 4 mm;
whereas the paste volume is between 75 and 120 l/m 3;
whereas the aggregates have a D90/D1 0 comprised between 1 and 3.5,
whereas D90 is selected to be located between 3 and 3.5 mm and the D 1 0
is equal or larger than 1 .5 mm, the aggregates being characterized by the
fact that the natural packing solid is between 55% and 65% (v/v);
b) Pouring the mix obtained in step a) into a mould;
c) Curing the moulded mix;
d) Washing the cement-free porous rigid mineral substrate obtained in step c).

9 . Method according to claim 8 , further comprising a step b') of forming a hole in


the moulded mix for seeding, after step b) and before step c).

10 . Method according to claim 8 or 9 , further comprising the following steps:


e) Placing a seed on the surface of the Portland cement-free porous rigid
mineral substrate;
f) Supplying water or nutrient solution to the Portland cement-free porous rigid
mineral substrate for germination of the seed.
Method according to claim 10 , wherein the level of water or nutrient solution
supplied in step f) is maintained at 1/3 to 1/2 of the height of the substrate.
A . CLASSIFICATION O F SUBJECT MATTER
INV. A01G24/17 A01G24/18
ADD.

According to International Patent Classification (IPC) o r t o both national classification and IPC

B . FIELDS SEARCHED
Minimum documentation searched (classification system followed by classification symbols)
A01G

Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched

Electronic data base consulted during the international search (name of data base and, where practicable, search terms used)

EPO-Internal , WPI Data

C . DOCUMENTS CONSIDERED T O B E RELEVANT

Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

US 5 296 180 A (HAYES KEVIN G [US] ET AL) 1-11


22 March 1994 (1994-03-22)
col umn 3 , l i nes 45-50; f i gure 13
col umn 7 , l i ne 65 - col umn 8 , l i ne 7
col umn 10, l i ne 55 - col umn 1 1 , l i ne 15
col umn 13 , l i nes 20-25
col umn 5 1 , l i nes 40-45

US 2014/264140 Al (GONG WEI LIANG [US] ET 1-11


AL) 18 September 2014 (2014-09-18)
abstract
paragraphs [0006] - [0009]

US 2010/058957 Al (B0XLEY CHETT [US] ) 1-11


1 1 March 2010 (2010-03-11)
c i ted i n the appl i cati on
abstract; f i gure 1

-/-

X| Further documents are listed in the continuation of Box C . See patent family annex.

* Special categories of cited documents :


"T" later document published after the international filing date o r priority
date and not in conflict with the application but cited to understand
"A" document defining the general state of the art which is not considered
the principle o r theory underlying the invention
to be of particular relevance
"E" earlier application o r patent but published o n o r after the international
"X" document of particular relevance; the claimed invention cannot be
filing date considered novel o r cannot b e considered to involve a n inventive
"L" documentwhich may throw doubts o n priority claim(s) orwhich is step when the document is taken alone
cited to establish the publication date of another citation o r other
"Y" document of particular relevance; the claimed invention cannot be
special reason (as specified)
considered to involve a n inventive step when the document is
"O" document referring to a n oral disclosure, use, exhibition o r other combined with one o r more other such documents, such combination
means being obvious to a person skilled in the art
"P" document published prior to the international filing date but later than
the priority date claimed "&" document member of the same patent family

Date of the actual completion of the international search Date of mailing of the international search report

23 July 2018 31/07/2018


Name and mailing address of the ISA/ Authorized officer
European Patent Office, P.B. 5818 Patentlaan 2
N L - 2280 HV Rijswijk
Tel. (+31-70) 340-2040,
Fax: (+31-70) 340-3016 Wei nmul l er, C
C(Continuation). DOCUMENTS CONSIDERED TO BE RELEVANT

Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

US 2006/117655 Al (BODYCOMB FREDERICK M 1-11


[US] ET AL) 8 June 2006 (2006-06-08)
abstract
paragraphs [0009] , [0010]

US 2017/044077 Al (YANG KEUN-HYEOK [KR] ) 1-11


16 February 2017 (2017-02-16)
c i ted i n the appl i cati on
abstract; f i gure 1
Patent document Publication Patent family Publication
cited in search report date member(s) date

US 5296180 A 22-03-1994 NONE

US 2014264140 Al 18-09-2014 EP 2970003 A l 20-01-2016


US 2014264140 A l 18-09-2014
O 2014141051 A l 18-09-2014

US 2010058957 Al 1 1 -03 -2010 US 2010058957 A l 1 1 -03 -2010


W0 2010030560 A2 18 -03 -2010

US 2006117655 Al 08 -06 -2006 NONE

US 2017044077 Al 16 -02 -2017 CN 106414364 A 1 5 -02 -2017


KR 20160122025 A 2 1 -10 -2016
US 2017044077 Al 16 -02 -2017
W0 2016167440 Al 2 -10 -2016

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