EP0758308A1 - Filler for concrete and similar building material - Google Patents
Filler for concrete and similar building materialInfo
- Publication number
- EP0758308A1 EP0758308A1 EP19950913945 EP95913945A EP0758308A1 EP 0758308 A1 EP0758308 A1 EP 0758308A1 EP 19950913945 EP19950913945 EP 19950913945 EP 95913945 A EP95913945 A EP 95913945A EP 0758308 A1 EP0758308 A1 EP 0758308A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fly ash
- concrete
- ash
- particles
- filler
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000004567 concrete Substances 0.000 title claims abstract description 68
- 239000000945 filler Substances 0.000 title claims abstract description 62
- 239000004566 building material Substances 0.000 title claims abstract description 22
- 239000010881 fly ash Substances 0.000 claims abstract description 108
- 239000002245 particle Substances 0.000 claims abstract description 85
- 239000002956 ash Substances 0.000 claims abstract description 33
- 239000000446 fuel Substances 0.000 claims abstract description 9
- 239000003245 coal Substances 0.000 claims description 65
- 239000000203 mixture Substances 0.000 claims description 61
- 239000000463 material Substances 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 9
- 238000010298 pulverizing process Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000009435 building construction Methods 0.000 claims 1
- 229910021487 silica fume Inorganic materials 0.000 description 31
- 238000011161 development Methods 0.000 description 19
- 239000004568 cement Substances 0.000 description 18
- 238000005259 measurement Methods 0.000 description 18
- 239000011148 porous material Substances 0.000 description 15
- 239000011398 Portland cement Substances 0.000 description 12
- 239000012530 fluid Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000004570 mortar (masonry) Substances 0.000 description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 description 9
- 239000011707 mineral Substances 0.000 description 9
- 239000004576 sand Substances 0.000 description 9
- 101100219315 Arabidopsis thaliana CYP83A1 gene Proteins 0.000 description 7
- 101000806846 Homo sapiens DNA-(apurinic or apyrimidinic site) endonuclease Proteins 0.000 description 7
- 101000835083 Homo sapiens Tissue factor pathway inhibitor 2 Proteins 0.000 description 7
- 101100269674 Mus musculus Alyref2 gene Proteins 0.000 description 7
- 101100140580 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) REF2 gene Proteins 0.000 description 7
- 102100026134 Tissue factor pathway inhibitor 2 Human genes 0.000 description 7
- 230000000740 bleeding effect Effects 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- 230000035515 penetration Effects 0.000 description 5
- 238000002459 porosimetry Methods 0.000 description 5
- 238000010276 construction Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- UDYLZILYVRMCJW-UHFFFAOYSA-L disodium;oxido carbonate Chemical compound [Na+].[Na+].[O-]OC([O-])=O UDYLZILYVRMCJW-UHFFFAOYSA-L 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- 229920006706 PC-C Polymers 0.000 description 1
- 239000011400 blast furnace cement Substances 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012669 compression test Methods 0.000 description 1
- 238000011981 development test Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011372 high-strength concrete Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000682 polycarbomethylsilane Polymers 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
- C04B18/08—Flue dust, i.e. fly ash
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Definitions
- This invention relates to a filler for concrete and similar building material and more specifically to a filler suitable for, high performance, durable, strong and highly fluid concrete.
- Concrete is a conglomerate of sand, gravel and broken stones for example which together are called an aggregate, whereby this aggregate is embedded in a matrix such as Portland cement or blast furnace cement. Concrete is one of the most important building materials and is used in great quantities.
- Constructions which are made of high performance, durable, strong and highly fluid concrete are stronger, more stable, have a high workability and can be built more slim- lined. Such concrete offers a greater compressive strength, in the region of 80-120 Newton/mm 2 , and a greater durability compared to normal concrete.
- the present invention concerns the utilization of microminiaturized ash for the production of high perfor ⁇ mance, durable, strong and highly fluid concrete, which can be utilized on a much greater scale than presently.
- Ash such as fly ash and fuel ash, in particular coal fly ash, strongly resembles microsilica with respect to composition and qualities, with the exception of particle size.
- the particle size of coal fly ash lies mainly in the range of 10-300 ⁇ m, whilst the particle size of microsilica is mostly less than 1 ⁇ .
- Coal fly ash with a particle size within this range improves the characteristics of concrete and similar building materials when used as a filler.
- it is desirable that the coal fly ash particles are reduced in size, because the particles are too coarse in order to realize an ideal stacking of the particles and dense cement structure such as occurs with microsilica.
- the present invention provides a filler for concrete or similar building material, comprising physically comminuted ash particles, wherein the ash is, preferably, coal fly ash.
- Coal fly ash is a fine powder which substantially consists of ball shaped glass like particles.
- the powder mainly consist of Si0 2 and A1 2 0 3 .
- Coal fly ash is obtained in great quantities by means of electrostatic or mechanical separation of material particles from the waste gas of furnaces stoked with coal powder. Such coal fly ash can be roughly 100 times cheaper produced than micro-silica which is presently used as filler material for concrete and simi ⁇ lar building materials.
- the grain size of coal fly ash thus obtained lies between 10-500 ⁇ m, with a D(50) of roughly 20-50 ⁇ m and a D(90) of roughly 80-300 ⁇ m. (This means that 50 % of the particles have a diameter smaller than 20-50 ⁇ m and that 90 % of the particles have a diameter smaller than 80-200 ⁇ m.)
- Coal fly ash has puzzolane qualities. This means that the material develops hydraulic qualities when it is activated in a basic environment (pH > 12) . Under hydraulic qualities is understood the ability of a material to react with water with the formation of insoluble in water stable compounds.
- Coal fly ash also serves as filler material. This means that the material fills up the hollow cavities in the concrete (pores) . Besides this, coal fly ash improves the workability of concrete.
- coal fly ash was physically comminuted, in order to yield a super fine product (reduced coal fly ash) .
- This physically comminuted coal fly ash preferably has a grain size of between 0-5 ⁇ m, and more preferably a D(50) of between 0.5-3 ⁇ m.
- This physically communited fly ash has the advan ⁇ tage that it is more reactive since its specific surface and the puzzolanity is greater.
- the filler qualities of the reduced coal fly ash are also improved, whereby the smaller pores in the concrete can now be filled.
- the ash is preferably coal fly ash obtained from the waste gasses of an installation stoked with powder charcoal, but it will be obvious that ash can also be obtained from other processes, such as ash collected with electrostatic filters from burning municipal waste and sludge, and other fuel ashes.
- the present invention further provides, according to a second aspect, concrete or similar building material comprising as filler material, physically comminuted ash, particularly coal fly ash, particles, preferably with a diameter substantially of 5 ⁇ m or smaller; the use of physi ⁇ cally comminuted ash, particularly coal fly ash, as a filler for concrete and a method for production of concrete or similar building material comprising bringing together physically comminuted ash particles, particularly coal fly ash particles, with relatively small diameters with the basis composition of the concrete or similar building mate- rial.
- a method for the production of a filler material for concrete or similar building material can preferably occur with known mechanical mill methods, such as ball mills (dry or wet pulverization) , jet stream mills (dry pulverization) and vibration mills, and most preferably can be carried out in a pearl mill (wet pulverization) , for optimum results, in order to yield a product of physically, comminuted fly ash which can be supplied both in the form of a slurry and as a solid.
- This product is cheaper to produce than known concre ⁇ te filler materials, whereby high performance, durable, strong and highly fluid concrete, having physically comminu ⁇ ted ash as filler material, can be utilized on a larger scale than is at present.
- the present invention provides for the use of pulverizing mills for physically comminuting ash particles, particularly coal fly ash particles, and the use of concrete, or similar building materials with physically comminuted ash filler, particularly physically comminuted coal fly ash particles, in the construction industry.
- pulverizing mills for physically comminuting ash particles, particularly coal fly ash particles
- concrete, or similar building materials with physically comminuted ash filler particularly physically comminuted coal fly ash particles
- Coal fly ash was selected from a low N0 ⁇ furnace from the Maasvlakte-centrale in the Netherlands.
- the chemi ⁇ cal and physical composition of this coal fly ash is given below in table 1.
- the material was pulverized in an aqeous suspensi ⁇ on with a solid material content of 35 %.
- the average pulve- ration time for a loading of 30 kg was 5 hours.
- the particle size of the comminuted fly ash is given in figure 2.
- the comminuted ultra fine fly ash particles so obtained were characterized by the inventors in order to obtain an impression of their qualities with respect to microcilica. In this comparison, the finest fraction of fly ash particles, separated out from the start material by means of air separation, the physically comminuted in the pearl mill fly ash particles and microsilica particles were taken, the results of which are shown in Table 2.
- Table 2 start air physically micro ⁇ material separated comminuted silica
- Figure 3 shows an overview of the particle size distribution of these materials used for comparison.
- Figures 4 and 5 show electron micrographs of the coal fly ash particles obtained after comminution with the pearl mill, taken at 10 ⁇ m and 3 ⁇ m respectively.
- Figure 15 shows an electron micrograph of air separated fly ash particles taken at 10 ⁇ for comparison.
- a pre-pulverization step can be incorporated. This comminuted, ultra fine coal fly ash, obtained via the pearl mill, was used for a laboratory research program carried out into mortar and concrete compositions.
- the mortar for the strength development was produ ⁇ ced according to DIN-IN 196 part 1, and had the following composition:
- the filler material was added to the above compo ⁇ sition in a slurry form.
- the comminuted, ultra fine coal fly ash obtained by the pearl mill was used, and micro- silica, and a mixture of the comminuted, ultra fine coal fly ash obtained via the pearl mill and the microsilica were also used for comparison.
- Table 3 sample SP Hager- strength strength strength s ⁇ ength density code (g) mann 3 days 7 days 28 days 91 days kg/m J mm N/mm 2 N/mm 2 N/mm 2 N/mm 2 N/mm 2
- PC physically comminuted, ultra fine coal fly ash particles
- SP Superplastifier
- PCMS 50 weight % physically comminuted, ultra fine coal fly ash particles / 50 weight % microsilica
- cement type Portland cement A D max of tne mineral aggregates : 31,5 mm additional material : sand/river aggregate
- cement type Portland cement A D max ° - ne mineral aggregates : 16 mm additional material : sand/river aggregate
- % filler matenal weight % of the cement
- % auxiliary substance superplast weight % of the cement weight (Cugla)
- WCF water/cement ratio
- Tables 6 and 7 show the results of the slump, fluid measurement, vibration measurement and bleeding of the mixtures l and 2 respectively.
- the slump was determined according to NEN 5956, the vibration measurement according to NEN 5957 and the bleeding according to NEN-EN 480.
- the fluid measurement was determined substantially according to NEN 5957.
- Table 6 sample slump flow vibration bleeding code mm measurement measurement % mm mm
- AS air separated fly ash particles
- PC physically comminuted, ultra fine coal fly ash particles
- MS microsilica
- PC/MS mixture 50 weight % / 50 weight % physically commi ⁇ nuted, ultra fine coal fly ash particles/microsilica
- REF1/2 reference concretes
- D max mineral aggregate 31,5 mm
- the samples with a mixture of microsilica and ultra fine coal fly ash particles had the same workability as samples with physically comminuted ultra fine coal fly ash particles alone.
- Table 7 sample slump flow vibration bleeding code mm measurement measurement % mm mm
- Figure 8 and 9 graphically represent the flow measurement, (an indication of workability) for mixtures l and 2.
- NEN 5968 and concerned an average of three compression tests.
- Tables 9, 10 and 11 show the compressive strength development for the mixtures 1, 2 and 3, carried out at 1, 2 , 3, 7, 28 and 91 days respectively.
- Table 9 sample strength strength strength strength strength strength strength strength code 1 day 2 days 3 days 7 days 28 days 91 days (N/mm 2 ) (N/mm 2 ) (N/mm 2 ) (N/mm 2 ) (N/mm 2 ) (N/mm 2 ) (N/mm 2 ) (N/mm 2 ) (N/mm 2 )
- AS air separated fly ash particles
- PC physically comminuted, ultra fine coal fly ash particles
- MS microsilica
- AS air separated fly ash particles
- PC physically comminuted, ultra fine coal fly ash particles
- MS microsilica
- PC physically comminuted, ultra fine coal fly ash particles
- D max of 31.5 mm was for ultra fine fly ash, 15 %, microsilica 15 % and for PC/MS 15 %;
- Figures 10, 11 and 12 show graphically the com- pressive strength results.
- the durability of concrete is described as the resistance against environmental influence, whereby the concrete has a long life span.
- good design and a good realization are of great importance.
- the design of a concrete mixture begins with an optimal mixing of the different components in order to achieve concrete with a very closed structure.
- a number of tests were carried out by the inventors, namely - the water penetration test for determining permeability,- mercury porosimetry for determining porosity and the pore distribution of the concrete, -petrography for visualizing the components after hardening and temperature development for predicting crack formation as a result of thermal stress.
- AS air separated fly ash particles
- PC physically comminuted, ultra fine coal fly ash particles
- MS microsilica
- D (mineral aggregates) 16 mm - Mercury porosimetry
- AS air separated fly ash particles
- PC physically comminuted, ultra fine coal fly ash particles
- PC/MS mixture 50 weight % / 50 weight % physically commi ⁇ nuted, ultra fine coal fly ash particles/microsilica
- Temperature development is a measurement of the amount of heat released from cement during hydration.
- thermo couples in sample cubes.
- AS air separated fly ash particles
- PC physically comminuted, ultra fine coal fly ash
- MS microsilica
- T totat yielded information about the total amount of released heat and is a quantification of the average tempe ⁇ rature per hour.
- the start temperature of D ma ⁇ 16 mm was higher than that of D ⁇ na ⁇ 31.5 mm, because this measurement was taken in a period in which the environmental temperature was higher.
- the effect of this on the T total was on average 10 %.
- Mixture 3 had a higher temperature development and a higher heat development.
- Figures 13 and 14 graphically show the temperature development for the mixtures with a D r ⁇ a ⁇ of 31.5 mm and a D of 16 mm.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Ceramic Engineering (AREA)
- Combustion & Propulsion (AREA)
- Civil Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to a filler for concrete or similar building material comprising: physically comminuted particles of ash, such as fly ash and or fuel ash.
Description
FILLER FOR CONCRETE AND SIMILAR BUILDING MATERIAL
This invention relates to a filler for concrete and similar building material and more specifically to a filler suitable for, high performance, durable, strong and highly fluid concrete. Concrete is a conglomerate of sand, gravel and broken stones for example which together are called an aggregate, whereby this aggregate is embedded in a matrix such as Portland cement or blast furnace cement. Concrete is one of the most important building materials and is used in great quantities.
Constructions which are made of high performance, durable, strong and highly fluid concrete are stronger, more stable, have a high workability and can be built more slim- lined. Such concrete offers a greater compressive strength, in the region of 80-120 Newton/mm2, and a greater durability compared to normal concrete.
At this moment most high performance, durable, strong and highly fluid concrete is produced with microsili- ca as filler material. A problem with this, is that such filler material is expensive however, the high performance, durable, strong and highly fluid concrete is in turn expen¬ sive, making it uneconomical to use for a lot of construc¬ tion work.
The present invention concerns the utilization of microminiaturized ash for the production of high perfor¬ mance, durable, strong and highly fluid concrete, which can be utilized on a much greater scale than presently.
Ash, such as fly ash and fuel ash, in particular coal fly ash, strongly resembles microsilica with respect to composition and qualities, with the exception of particle size. The particle size of coal fly ash lies mainly in the range of 10-300 μm, whilst the particle size of microsilica is mostly less than 1 μ.
Coal fly ash with a particle size within this range improves the characteristics of concrete and similar building materials when used as a filler. However for the ^utilization as filler for high performance, durable, strong and higly fluid concrete, it is desirable that the coal fly ash particles are reduced in size, because the particles are too coarse in order to realize an ideal stacking of the particles and dense cement structure such as occurs with microsilica. The utilization of fly ash in building materials is already known, for instance the GB patent specification GB 1 362 372 teaches a cement comprising a particulate mate¬ rial derived from pulverised fuel ash by attrition and/or fragmentation of the particles by mutual bombardment; Chemi- cal Abstracts volume 117 No. 4 teaches a steel bar reinfor¬ ced concrete with high strength and improved concrete steel adhesion, whereby the concrete contains fine sieved parti¬ cles of fly ash from coal combustion; and a report of the fourth CONMET/ACI International Conference on Fly Ash, Silica Fume, Slag and Natural Puzzolanes in Concrete (1992) May, Istanbul, Turkey, gives attention to concrete strength enhancement due to classified fly ash obtained by air sepa¬ ration methods.
The methods for obtaining fly ash particles detai- led in the prior art are however relatively inefficient and uneconomical.
According to a first aspect, the present invention provides a filler for concrete or similar building material, comprising physically comminuted ash particles, wherein the ash is, preferably, coal fly ash.
Coal fly ash is a fine powder which substantially consists of ball shaped glass like particles. The powder mainly consist of Si02 and A1203. Coal fly ash is obtained in great quantities by means of electrostatic or mechanical separation of material particles from the waste gas of furnaces stoked with coal powder. Such coal fly ash can be roughly 100 times cheaper produced than micro-silica which
is presently used as filler material for concrete and simi¬ lar building materials.
The grain size of coal fly ash thus obtained lies between 10-500 μm, with a D(50) of roughly 20-50 μm and a D(90) of roughly 80-300 μm. (This means that 50 % of the particles have a diameter smaller than 20-50 μm and that 90 % of the particles have a diameter smaller than 80-200 μm.) Coal fly ash has puzzolane qualities. This means that the material develops hydraulic qualities when it is activated in a basic environment (pH > 12) . Under hydraulic qualities is understood the ability of a material to react with water with the formation of insoluble in water stable compounds.
Coal fly ash also serves as filler material. This means that the material fills up the hollow cavities in the concrete (pores) . Besides this, coal fly ash improves the workability of concrete.
It appears from studies that the qualities of concrete improve, the finer the coal fly ash is. In practi- cal experiments, coal fly ash was physically comminuted, in order to yield a super fine product (reduced coal fly ash) . This physically comminuted coal fly ash preferably has a grain size of between 0-5 μm, and more preferably a D(50) of between 0.5-3 μm. This physically communited fly ash has the advan¬ tage that it is more reactive since its specific surface and the puzzolanity is greater. The filler qualities of the reduced coal fly ash are also improved, whereby the smaller pores in the concrete can now be filled. Accordingly a high performance, durable, strong and highly fluid concrete is yielded with a high initial strength which is easy to pro¬ cess and pour with little compaction energy. This yields the advantage that the construction time for a certain project, utilizing this concrete, is substantially shorter than with projects wherein such concrete is not used.
It is noted that the ash is preferably coal fly ash obtained from the waste gasses of an installation stoked with powder charcoal, but it will be obvious that ash can
also be obtained from other processes, such as ash collected with electrostatic filters from burning municipal waste and sludge, and other fuel ashes.
The present invention further provides, according to a second aspect, concrete or similar building material comprising as filler material, physically comminuted ash, particularly coal fly ash, particles, preferably with a diameter substantially of 5 μm or smaller; the use of physi¬ cally comminuted ash, particularly coal fly ash, as a filler for concrete and a method for production of concrete or similar building material comprising bringing together physically comminuted ash particles, particularly coal fly ash particles, with relatively small diameters with the basis composition of the concrete or similar building mate- rial.
According to a further aspect of the present invention, there is provided a method for the production of a filler material for concrete or similar building material. Micronization of ash can preferably occur with known mechanical mill methods, such as ball mills (dry or wet pulverization) , jet stream mills (dry pulverization) and vibration mills, and most preferably can be carried out in a pearl mill (wet pulverization) , for optimum results, in order to yield a product of physically, comminuted fly ash which can be supplied both in the form of a slurry and as a solid. This product is cheaper to produce than known concre¬ te filler materials, whereby high performance, durable, strong and highly fluid concrete, having physically comminu¬ ted ash as filler material, can be utilized on a larger scale than is at present.
Furthermore the present invention provides for the use of pulverizing mills for physically comminuting ash particles, particularly coal fly ash particles, and the use of concrete, or similar building materials with physically comminuted ash filler, particularly physically comminuted coal fly ash particles, in the construction industry.
The following experimental descriptions, results and examples air.; to clarify the present invention, but are not meant to limit its range.
Coal fly ash was selected from a low N0χ furnace from the Maasvlakte-centrale in the Netherlands. The chemi¬ cal and physical composition of this coal fly ash is given below in table 1.
Table 1
The particle size distribution of this start material is given in figure 1.
100 kg of coal fly ash start material was mechanically pulverized in a DRAIS pearl mill (PMC 5 TEX) .
The material was pulverized in an aqeous suspensi¬ on with a solid material content of 35 %. The average pulve- ration time for a loading of 30 kg was 5 hours. The particle size of the comminuted fly ash, is given in figure 2. The comminuted ultra fine fly ash particles so obtained, were characterized by the inventors in order to obtain an impression of their qualities with respect to microcilica.
In this comparison, the finest fraction of fly ash particles, separated out from the start material by means of air separation, the physically comminuted in the pearl mill fly ash particles and microsilica particles were taken, the results of which are shown in Table 2.
Table 2 start air physically micro¬ material separated comminuted silica
(SM) particles particles (MS)
(AS) (PC)
D(50) μm 21.6 9.9 1.6 0.2
D(90) μm 99.0 36.0 3.1 0.5
Grading 525 994 5390 modulus 1/mm specific 1.0 1.5 6.3 20.2 surface m2/g form round round broken round
Figure 3 shows an overview of the particle size distribution of these materials used for comparison.
The final result of this pulverization experiment yielded an end product with a D(50) = 1.6 μm and a D(90) = 3.1 μm.
Figures 4 and 5 show electron micrographs of the coal fly ash particles obtained after comminution with the pearl mill, taken at 10 μm and 3 μm respectively.
Figure 15 shows an electron micrograph of air separated fly ash particles taken at 10 μ for comparison. In order to further refine the pulverization process, a pre-pulverization step can be incorporated.
This comminuted, ultra fine coal fly ash, obtained via the pearl mill, was used for a laboratory research program carried out into mortar and concrete compositions.
Design, production and testing of mortar compositions
In order to obtain a better insight into the influence of comminuted, ultra fine fly ash on the hydration of cement, laboratory research was carried out, by the inventors, into the strength development and binding time development of mortar samples.
The mortar for the strength development was produ¬ ced according to DIN-IN 196 part 1, and had the following composition:
- cement type: 22 weight % ENCI Portland cement A - sand: 67 weight % Normen sand according to DIN
- water: 11 % water/cement ratio 0.50
- filler material: 5/10/15 weight %
- consistancy: Hagermann 170 ± 10 mm.
The filler material was added to the above compo¬ sition in a slurry form.
As filler material, the comminuted, ultra fine coal fly ash obtained by the pearl mill was used, and micro- silica, and a mixture of the comminuted, ultra fine coal fly ash obtained via the pearl mill and the microsilica were also used for comparison.
Compressive strength tests were carried out on the following four mortar mixtures: l) Portland cement A (Reference material)
2) Portland cement A 4- 5, 10, 15 weight % physi¬ cally comminuted, ultra fine coal fly ash particles.
3) Portland cement A + 5, 10, 15 weight % micro silica. 4) Portland cement A + 5, 10, 15 weight % of a mixture of 50 weight % microsilica and 50 weight % physi¬ cally comminuted ultra fine coal fly ash particles.
Table 3 gives the results of the compressive strength at intervals of 3, 7, 28 and 91 days of the mortar samples. In order to obtain the desired consistancy, a superplastifier was added to some of the samples.
Table 3 sample SP Hager- strength strength strength sσength density code (g) mann 3 days 7 days 28 days 91 days kg/mJ mm N/mm2 N/mm2 N/mm2 N/mm2
REF 0 174 27.6 373 51.2 65.9 2300
PC05 0 170 31.1 41.8 56.0 71.4 2280
PC10 0.5 173 33.2 44.3 603 77.2 2266
PC15 1.1 169 33.8 483 63.4 79.6 2263
MS05 1.7 173 31.0 40.8 59.2 70.5 2235
MS10 3.4 173 31.2 42.3 61.7 75.5 2214
MS 15 5.1 172 323 46.2 68.7 80.2 2221
PCMS05 0.9 174 30.6 41.9 593 70.2 2250
PCMS10 2.0 174 31.9 43.0 64.2 783 2242
PCMS15 3.0 173 32.8 42.4 66.9 81.7 2227
REF = reference ; MS = microsilica
PC = physically comminuted, ultra fine coal fly ash particles; SP = Superplastifier
PCMS = 50 weight % physically comminuted, ultra fine coal fly ash particles / 50 weight % microsilica
From these measurements it can be concluded that the compressive strength of the samples increases on the addition of physically comminuted ultra fine fly ash. The more physically comminuted, ultra fine fly ash is added, the greater the compressive strength becomes.
Figures 6 and 7 show graphically the compressive strength results.
Binding time development tests were carried out on ^the following three mortar mixtures: 1) Portland cement A (Reference)
2) Portland cement A plus 2-4-6-8-10-12-14 weight % air separated fly ash
3) Portland cement A plus 2-4-6-8-10-12-14 weight % physically comminuted fly ash obtained in the pearl mill. Table 4 gives an overview of the binding type measurements of the mortars.
Table 4 sample start end sample start end (h) binding binding binding binding
(time.hours) (time,hours) (time, hours) (time.hours)
AS-02 2.15 2.45 PC-02 2.15 3.00
AS-04 2.15 3.00 PC-04 2.15 3.00
AS-06 2.00 2.45 PC-06 2.15 3.00
AS-08 2.30 3.00 PC-08 2.15 3.00
AS-10 2.30 3.00 PC-10 1.45 2.45
AS-12 2.30 3.15 PC-12 1.45 2.30
AS-14 2.30 3.15 PC-14 1.45 2.30 reference 2.00 2.30
AS = air separated coal fly ash D(50) = 10 μm;
PC = physically comminuted ultra fine coal fly ash particles 02-14 = weight % filler; D(50) = 1,5 μm
From these measurements it can be concluded that air separated fly ash, at all the percentages (2-14) , had a slowing down effect on the hydration of cement.
With percentages of greater than 8 %, it can be seen that physically comminuted, ultra fine fly ash parti¬ cles had an accelerating effect on the hydration of cement. This shows the reactivity of physically comminuted, ultra fine fly ash particles as a filler material.
Design, production and testing of cement mixtures
Three concrete mixtures were designed and produ¬ ced, using physically comminuted (in the DRAIS Pearl mill) ultra fine fly ash particles.
These concrete mixtures were as follows:
1. Cement type : Portland cement A D max of tne mineral aggregates : 31,5 mm additional material : sand/river aggregate
2. Cement type : Portland cement A D max ° -ne mineral aggregates : 16 mm additional material : sand/river aggregate
3. Cement type : Portland cement C D max ° tne mineral aggregates : 16 mm additional material : sand/river aggregate
(this mixture having a composition equivalent to that of high strength concrete which has been practically tested in former research projects)
Comparison tests are also to be carried out by the inventors into the cement mixture composition used in the building of a construction from high quality concrete in Breda, the Netherlands.
A summary of the concrete mixture samples upon which tests were carried out is given in table 5.
Table 5 mixture 1 mixture 2 mixture 3 cement type PC-A PC-A PC-C content kg/πv5 360 360 450 addition sand/ sand/ sand/ aggregate aggregate aggregate
D- 313 16 16
WCF 032 032 032
WBF (k=0.2) 0.28-031 0.28-031 0.28-030
% filler matenal 1 (AS) 05/10/15 05/10/15 -
% filler matenal 2 (PC) 05/10/15/20 05/10/15/20 10/20
% filler matenal 3 (MS) 05/10/15 05/10/15 -
% filler matenal 4 (PC/MS) 05/10/15 05/10/15 -
% auxiliary substance (SP) 2.5 2.5 2.5 BV 80/20
AS = air separated fly ash particles D(50) = 10 μm;
PC = physically comminuted, ultra fine coal fly ash particles D(50) = 1.5 μm
MS = microsilica D(50) = 0.2 μm; PC/MS = 50/50 mixture air separated fly ash particles/physically comminuted, ultra fine coal fly ash particles
% filler matenal = weight % of the cement
% auxiliary substance = superplast weight % of the cement weight (Cugla)
WCF = water/cement ratio WBF = water/binder ratio k = 0.2 means that 20 % of the filler material weight is a binder
Concrete mixtures using air separated fly ash particles, microsilica and a mixture thereof were used for comparison.
Filler material was added as an aqueous slurry after the slurry had been well mixed five minutes before addition. 100 mm cubes were made from the three different concrete mixtures, which were stored, after form stripping in a "wet" room at 20°C ± 2°C at a relative humidity of > 95%.
Two reference mixtures were chosen for both mixtu¬ re 1 and mixture 2, namely REF1 with an equivalent water/ce¬ ment ratio and REF2 with a workability similar to the worka- bility of the mixtures with 5-10 weight % physically commi¬ nuted, ultra fine coal fly ash particles (pearl mill) .
In order to test whether physically comminuted, ultra fine coal fly ash particles could be used as a suit¬ able filler material in concrete, tests were carried out on both the concrete mortar and the hardened concrete. In order to do this, a number of aspects had to be taken into consi¬ deration, namely:
- the workability and stability of the concrete mortar,
- the compression strength development of the concrete, - the durability of the concrete.
In order to make a judgement on these, a number of tests were carried out, namely for:
1. workability and stability - slump
- flow measurement
- vibration measurement
- bleeding
2. compressive strength development
- the compression strength was measured after 1-2-3- 7-28-91 days
3. durability - water penetration after 28 days
- mercury porosimetry
- temperature development
All the tests were carried out according to the NEN, ISO or DIN regulations apart from the fluid measure¬ ment, mercury porσsimetry and temperature development.
Results of the concrete tests
1. Workability and stability
Tables 6 and 7 show the results of the slump, fluid measurement, vibration measurement and bleeding of the mixtures l and 2 respectively. The slump was determined according to NEN 5956, the vibration measurement according to NEN 5957 and the bleeding according to NEN-EN 480. The fluid measurement was determined substantially according to NEN 5957.
Table 6 sample slump flow vibration bleeding code mm measurement measurement % mm mm
REF1 170 320 420 < 1
REF2 220 470 540 9
AS05 190 330 420 < 1
AS10 230 430 520 < 1
AS15 250 500 570 < 1
PC05 230 420 520 < 1
PC10 240 540 600 < 1
PC15 270 610 700 < 1
PC20 250 510 610 < 1
MS05 220 400 500 < 1
MS10 220 350 470 < 1
MS15 190 320 440 < 1
PC/MS05 230 490 580 < 1
PC/MS10 260 600 700 < 1
PC/MS15 270 600 700 < 1
Filler material: AS = air separated fly ash particles; PC = physically comminuted, ultra fine coal fly ash particles; MS = microsilica; PC/MS = mixture 50 weight % / 50 weight % physically commi¬ nuted, ultra fine coal fly ash particles/microsilica REF1/2 = reference concretes; D max mineral aggregate = 31,5 mm
Conclusions from Table 6:
From the workability derived from the flow measu¬ rement, it can be concluded that the samples with a high percentage of physically comminuted ultra fine coal fly ash particles are highly fluid.
The fluidity of the microsilica samples, reduced when more filler material was added.
The samples with a mixture of microsilica and ultra fine coal fly ash particles had the same workability as samples with physically comminuted ultra fine coal fly ash particles alone.
All the samples with filler material showed virtu¬ ally no bleeding. Table 7 shows the workability and stability of mixture 2, maximum diameter (D^) of the mineral aggregates = 16 mm
Table 7 sample slump flow vibration bleeding code mm measurement measurement % mm mm
REF1 140 - - 2
REF2 170 330 490 8
AS05 < 10 - - < 1
AS10 180 370 450 < 1
AS15 195 400 480 3
PC05 160 340 480 8
PC10 210 390 530 < 1
PC15 220 400 610 < 1
PC20 250 380 610 < 1
MS05 200 400 490 4
MS10 200 380 490 < 1
MS15 200 380 510 < 1
PC/MS05 180 360 430 < 1
PC/MS10 230 430 530 < 1
PC/MS15 230 430 550 < 1
Filler material: AS = air separated fly ash particles; PC = physically comminuted, ultra fine coal fly ash particles MS = microsilica; PC/MS = mixture 50 weight % / 50 weight % physically commi¬ nuted, ultra fine coal fly ash particles/microsilica 05, 10, 15, 20 = weigth % filler D (mineral aggregates) = 16 mm
Conclusions from Table 7:
The mixtures with a D^ of 16 mm had a lower workability -* than the mixtures with a Dmma=>xv of 31.5 mm.
Figure 8 and 9 graphically represent the flow measurement, (an indication of workability) for mixtures l and 2.
2. Development of compressive strength The compression strength was measured according to
NEN 5968 and concerned an average of three compression tests. Tables 9, 10 and 11 show the compressive strength development for the mixtures 1, 2 and 3, carried out at 1, 2 , 3, 7, 28 and 91 days respectively.
Table 9 sample strength strength strength strength strength strength code 1 day 2 days 3 days 7 days 28 days 91 days (N/mm2) (N/mm2) (N/mm2) (N/mm2) (N/mm2) (N/mm2)
REF1 30.4 46.1 53.9 68.7 81.8 90.6
REF2 8.8 32.1 40.8 49.2 64.2 69.3
AS05 24.7 41.5 46.9 64.9 83.6 923
AS 10 23.6 42.1 49.7 64.9 81.6 93.7
AS15 20.4 43.0 50.1 623 79.8 92.4
PC05 31.4 45.90 50.5 653 80.0 85.9
PC10 36.0 50.4 58.9 66.2 86.2 96.0
PC15 22.5 45.4 53.2 69.6 95.8 105.9
PC20 26.0 47.6 53.5 - - -
MS05 323 49.1 57.5 69.4 94.0 953
MS10 35.1 49.0 55.9 70.6 96.6 103.9
MS 15 353 48.8 57.4 793 993 104.8
PC/MS05 28.6 45.0 54.2 66.7 86.5 92.9
PC/MS 10 28.0 47.6 54.8 71.4 93.2 993
PC/MS 15 32.0 50.7 59.2 73.9 97.1 103.4
Filler material: AS = air separated fly ash particles; PC = physically comminuted, ultra fine coal fly ash particles MS = microsilica; PC/MS = mixture 50 weight % / 50 weight % physically commi¬ nuted, ultra fine coal fly ash particles/microsilica 05, 10, 15, 20 = weight % filler D (mineral aggregates) = 31,5 mm
Table 10
sample strength strength strength strengdi strength code 1 day 3 days 7 days 28 days 91 days
(N/mm2) (N/mm2) (N/mm2) (N/mm2) (N/mm2)
REF1 17.7 49.7 61.8 75.1 84.4
REF2 12.2 43.1 55.0 68.5 783
AS05 213 58.2 70.0 84.4 95.5
AS 10 10.2 49.0 62.2 75.7 90.4
AS 15 9.8 47.4 593 74.9 91.1
PC05 7.1 503 62.1 78.1 89.2
PC10 15.9 51.0 633 58.0 96.9
PC15 26.4 60.7 753 100.2 113.5
PC20 26.9 58.4 73.9 100.8 113.9
MS05 27.7 57.4 73.6 96.0 107.5
MS 10 303 59.8 75.4 105.9 115.1
MS 15 30.7 58.9 76.7 106.0 114.9
PC/MS05 13.8 51.7 64.1 84.4 95.0
PC/MS 10 18.7 54.8 71.5 97.0 106.9
PC/MS 15 22.9 58.5 76.7 104.6 116.5
Filler material: AS = air separated fly ash particles; PC = physically comminuted, ultra fine coal fly ash particles MS = microsilica;
PC/MS = mixture 50 weight % / 50 weight % physically commi¬ nuted, ultra fine coal fly ash particles/microsilica 05, 10, 15, 20 = weight % filler D (mineral aggregates) = 16 mm
Table 11
sample strength strength strength strength strength code 1 day 3 days 7 days 28 days 91 days
(N/mm2) (N/mm2) (N/mm2) (N/mm2) (N/mm2)
PC10 613 82.1 89.4 1043 113.6
PC20 54.5 74.7 86.1 100.8 111.5
Filler material:
PC = physically comminuted, ultra fine coal fly ash particles;
Conclusions from Tables 9, 10, 11:
- The compressive strengths after 28 days of the mixtures with a Dmaχ of 31.5 mm and 15 % filler material PC, MS and PC/MS are 10 to 20 % higher than that of reference 1;
- The same mixtures with a Dm„.a-γx of 16 mm have com- pressive strengths 30 to 40 % higher than reference 1;
- The filler material function of AS does not yield any increase in compressive strength; - The optimum percentage of filler material for a
D max of 31.5 mm was for ultra fine fly ash, 15 %, microsilica 15 % and for PC/MS 15 %; and
- For Dmax - 16 mm, the optimal filler material percentage was 10 %; - The end strength, after 91 days of the mixture with a D-^j. = 16 mm is roughly 10 % higher than that of the mixtures with a D-m„a=xv of 31.5 mm.
The results of mixture 3 show that with a higher cement content, the filler material has a positive influence on the initial strength. The initial strength was twice as high as the comparable mixture 2. A filler material percen¬ tage of 20 % clearly yields lower compressive strength results than a filler material percentage of 10 %.
Figures 10, 11 and 12 show graphically the com- pressive strength results.
3. Durability
The durability of concrete is described as the resistance against environmental influence, whereby the concrete has a long life span. For a long life span of concrete, good design and a good realization are of great importance. The design of a concrete mixture begins with an optimal mixing of the different components in order to achieve concrete with a very closed structure. In order to predict life span and durability, a number of tests were carried out by the inventors, namely - the water penetration test for determining permeability,- mercury porosimetry for determining porosity and the pore distribution of the concrete, -petrography for visualizing the components after hardening and temperature development for predicting crack formation as a result of thermal stress.
Water penetration Water penetration was determined on cube samples of mixtures 1 and 2, after 28 days hardening according to DIN 1048 part 5, the results of which are reproduced in table 12.
Table 12 Water penetration in mm
sample code mixture 1 mixture 2
REF1 - 44
REF2 - 42
AS05 3 8
AS10 0 10
AS15 3 30
PC05 5 27
PC10 2 31
PC15 1 10
PC20 - 11
MS05 0 10
MS10 2 2
MS15 6 10
PC/MS05 3 21
PC/MS10 4 4
PC/MS15 5 6
Filler material: AS = air separated fly ash particles; PC = physically comminuted, ultra fine coal fly ash particles MS = microsilica; PC/MS = mixture 50 weight % / 50 weight % physically commi¬ nuted, ultra fine coal fly ash particles/microsilica 05, 10, 15, 20 = weight % filler D (mineral aggregates) = 16 mm
- Mercury porosimetry
Mercury porosimetry was used to determine total ^porosity, pore size and pore distribution of sawn off sample pieces, and was determined by means of the intrusion of mercury into the pores under a strength of 2000 bar. This yielded information about the total pore system of the sample and was therefore usefull in estimating durability. Porosimetry measurements were carried out on mixture 2, Ωmx = 16 mm, the results of which are given in table 13.
Table 13
samples pore pore pore porosity specific average volume volume volume ≤ 15 μm surface radius
≤ 15 μm > 15 μm total % pore pore run mπrVg m Vg mπvVg m2/g
REF2 193 0.9 20.2 4.7 2.10 19.9
AS15 15.8 0.9 16.8 3.9 1.85 19.9
PC15 20.8 0.5 213 5.0 2.64 15.7
MS 15 15.7 1.7 17.4 3.8 1.73 15.6
PC/MS 15 16.9 0.4 173 4.1 2.29 15.8
Filler material: AS = air separated fly ash particles;
PC = physically comminuted, ultra fine coal fly ash particles
MS = microsilica;
PC/MS = mixture 50 weight % / 50 weight % physically commi¬ nuted, ultra fine coal fly ash particles/microsilica
(where total pore volume = pore volume + pore volume) (< 15 μm) (> 15 μm)
15 = weight % filler material
From these measurements it can be concluded that the total porosity does not decrease after adding physically comminuted ultra fine fly ash particles. The size of the process became smaller.
Temperature development
Temperature development is a measurement of the amount of heat released from cement during hydration.
For a managable temperature gradient of the harde- ned concrete it was desirable that the heat release took place gradualy.
The temperature development of the mixtures was measured with thermo couples in sample cubes.
The results are quantified in table 14.
Table 14
Filler material: AS = air separated fly ash particles; PC = physically comminuted, ultra fine coal fly ash; MS = microsilica; PC/MS = mixture 50 weight % / 50 weight % physically commi¬ nuted, ultra fine coal fly ash particles/microsilica mixt.3-10/20 = mixture 3 10/20 weight % physically comminu¬ ted ultra fine coal fly ash particles
Conclusion from Table 14:
Ttotat yielded information about the total amount of released heat and is a quantification of the average tempe¬ rature per hour. The start temperature of Dmaχ 16 mm was higher than that of Dιnaχ 31.5 mm, because this measurement was taken in a period in which the environmental temperature was higher. The effect of this on the Ttotal was on average 10 %.
From the temperature measurements it appears that the heat development with mixture 2, D.^-. = 16 mm is greater than with mixture 1, Ωmx = 31.5 mm.
Mixture 3 had a higher temperature development and a higher heat development.
From these results, it can be seen that in general the heat development reduces as the filler material percen¬ tage is increased. On comparing the reference concrete without filler material, the heat development of the mixtu¬ res 1 and 2 with a filler material percentage of 15 % physi¬ cally comminuted, ultra fine fly ash particles (pearl mill) is more favourable, so that it can be concluded that a large temperature gradient of the designed mixtures is not to be expected.
Figures 13 and 14 graphically show the temperature development for the mixtures with a Drπaχ of 31.5 mm and a D of 16 mm.
The present invention is not limited by the above description, but is rather determined by the scope of the following claims.
Claims
1. Filler for concrete or similar building materi¬ al comprising:
- physically comminuted particles of ash, such as fly ash and or fuel ash.
2. Filler according to claim 1, wherein the fly ash is coal fly ash.
3. Filler according to claims 1 or 2, wherein the fly ash particles have a diameter of 5 μm or smaller.
4. Concrete or similar building material compri- sing as filler material physically comminuted particles of ash, such as fly ash and or fuel ash.
5. Concrete or similar building material according to claim 4, wherein the physically comminuted ash particles originate from coal fly ash, and have a diameter of 5 μm or smaller.
6. Concrete or similar building material according to claims 4 or 5 having a compressive strength of at least 80 N/mm2.
7. Method for producing filler for concrete or a similar building material comprising physically comminuting particles of ash, such as fly ash and or fuel ash.
8. Method according to claim 7, wherein the ash particles, in particular coal fly ash particles, are physi¬ cally comminuted by pulverization in a pearl mill.
9. Use of physically comminuted ash particles, such as fly ash and or fuel ash particles, as filler for concrete or a similar building material, wherein the parti¬ cles have a diameter of 5 μm or smaller.
10. Method for producing concrete or similar building material comprising bringing together ash parti¬ cles, such as fly ash and or fuel ash, physically comminuted according to claims 7 or 8, with a base composition of the concrete or similar building material.
11. Ash particles, such as fly ash and or fuel ash particles, characterized in that they have been physically comminuted by pulverization, in particular in a pearl mill.
12. Use of a pearl mill for comminuting ash parti¬ cles, in particular coal fly ash particles.
13. Use of concrete or similar building material obtained by the method according to claim 10, for building constructions.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL9400564A NL9400564A (en) | 1994-04-08 | 1994-04-08 | Filler for concrete and similar building material. |
NL9400564 | 1994-04-08 | ||
PCT/NL1995/000133 WO1995027685A1 (en) | 1994-04-08 | 1995-04-10 | Filler for concrete and similar building material |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0758308A1 true EP0758308A1 (en) | 1997-02-19 |
Family
ID=19864047
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19950913945 Withdrawn EP0758308A1 (en) | 1994-04-08 | 1995-04-10 | Filler for concrete and similar building material |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0758308A1 (en) |
JP (1) | JPH09511482A (en) |
CA (1) | CA2186248A1 (en) |
NL (1) | NL9400564A (en) |
WO (1) | WO1995027685A1 (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09118557A (en) * | 1995-10-25 | 1997-05-06 | Chichibu Onoda Cement Corp | Back-filling material |
FR2741062B1 (en) * | 1995-11-10 | 1998-05-07 | Electricite De France | GROUND INJECTION IN PARTICULAR UNDER LOW PRESSURE AND PRODUCT FOR ITS PREPARATION |
FR2744118B1 (en) * | 1996-01-31 | 1998-04-30 | Schlumberger Cie Dowell | FILTRATE CONTROL AGENT FOR OIL WELL CEMENT GROUT OR THE LIKE AND GROUT COMPOSITIONS COMPRISING SAID AGENT |
NO305896B1 (en) * | 1996-04-17 | 1999-08-16 | Elkem Materials | Method of treating silica-containing material |
US6242098B1 (en) * | 1999-02-17 | 2001-06-05 | Mineral Resources Technologies, Llc | Method of making mineral filler and pozzolan product from fly ash |
US6916863B2 (en) | 2000-11-14 | 2005-07-12 | Boral Material Technologies, Inc. | Filler comprising fly ash for use in polymer composites |
US6695902B2 (en) | 2000-11-14 | 2004-02-24 | Boral Material Technologies, Inc. | Asphalt composites including fly ash fillers or filler blends, methods of making same, and methods for selecting or modifying a fly ash filler for use in asphalt composites |
ITMI20010736A1 (en) * | 2001-04-05 | 2002-10-05 | Petracem Srl | ADDITIVES FOR BUILDING OBTAINED FROM BY-PRODUCTS OR RESIDUES OF PROCESSING AND PROCESS FOR THEIR PRODUCTION |
BR112021012604A2 (en) * | 2018-12-28 | 2021-10-05 | Universidade De São Paulo - Usp | MIXING OF FINES, FRESH OR HARDENED CONCRETE, PROCESS OF MIXING AND HOMOGENEIZING SAID MIXING OF FINES AND PRODUCTION PROCESS OF SAID FRESH CONCRETE |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US1466083A (en) * | 1921-05-11 | 1923-08-28 | Cinder Products Corp | Method of making plastic bodies from coal ashes and a plastic body made from such method |
FR2146699A5 (en) * | 1971-07-22 | 1973-03-02 | Corson G & W H | Quick setting hydraulic cementitious material - made by milling glassy fly ash and lime |
GB1362372A (en) * | 1972-09-07 | 1974-08-07 | Reid N G | Cement |
JPH0455350A (en) * | 1990-06-22 | 1992-02-24 | Shikoku Sogo Kenkyusho:Kk | Reinforced concrete |
FR2666576B1 (en) * | 1990-09-11 | 1993-04-02 | Armines | PROCESS FOR IMPROVING THE PERFORMANCE AND DURABILITY OF CONCRETE. |
JPH055350A (en) * | 1991-06-27 | 1993-01-14 | Doukou Sangyo:Kk | Wall structure for building |
-
1994
- 1994-04-08 NL NL9400564A patent/NL9400564A/en not_active Application Discontinuation
-
1995
- 1995-04-10 EP EP19950913945 patent/EP0758308A1/en not_active Withdrawn
- 1995-04-10 CA CA 2186248 patent/CA2186248A1/en not_active Abandoned
- 1995-04-10 JP JP52626295A patent/JPH09511482A/en active Pending
- 1995-04-10 WO PCT/NL1995/000133 patent/WO1995027685A1/en not_active Application Discontinuation
Non-Patent Citations (1)
Title |
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See references of WO9527685A1 * |
Also Published As
Publication number | Publication date |
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JPH09511482A (en) | 1997-11-18 |
NL9400564A (en) | 1995-11-01 |
WO1995027685A1 (en) | 1995-10-19 |
CA2186248A1 (en) | 1995-10-19 |
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