SLAG-CONTAINING POLYMER CONCRETE AND GROUTING MORTAR

Abstract

A curable binder composition includes: a) at least one organic binder selected from the group made of a1) epoxy resins and curing agents for epoxy resins and a2) polyisocyanates and polyols, and b) at least 50% by weight of slag based on 100% by weight of the binder composition.

Claims

1. A curable binder composition comprising: a) at least one organic binder selected from the group consisting of a1) epoxy resins and curing agents for epoxy resins and a2) polyisocyanates and polyols, and b) at least 50% by weight of slag based on 100% by weight of the binder composition.

2. The binder composition as claimed in claim 1, wherein the binder composition contains 50% to 80% by weight, of slag, based on 100% by weight of the binder composition.

3. The binder composition as claimed in claim 1, wherein the slag is selected from the group consisting of blast furnace slags, steel slags, metallurgical slags, and slags from waste incineration.

4. The binder composition as claimed in claim 1, wherein the slag is an iron-containing slag containing at least 8% by weight, of iron, calculated as FeO.

5. The binder composition as claimed in claim 1, wherein the slag has a bulk density of at least 2.9 kg/l.

6. The binder composition as claimed in claim 1, the slag has a particle size of 0.05 to 16 mm.

7. The binder composition as claimed in claim 1, wherein the slag particles are irregularly shaped and/or have a rough surface.

8. The binder composition as claimed in claim 1, wherein at least one further mineral filler selected from the group consisting of limestone powder, chalk, quartz powder, silica dust, titanium dioxide, baryte powder, and alumina is additionally present.

9. The binder composition as claimed in claim 1, wherein at least one wetting agent and/or dispersant, is present.

10. The binder composition as claimed in claim 9, wherein the slag and optionally also the at least one further filler, if present, are coated with the wetting agent and/or dispersant.

11. A multicomponent system for producing a curable binder composition, comprising at least one resin component comprising at least one epoxy resin, and at least one curing agent component comprising at least one curing agent for epoxy resins, wherein slag and optionally further ingredients are present in the resin components, in the curing agent components and/or in any further components optionally present.

12. A multicomponent system for producing a curable binder composition, comprising at least one polyisocyanate component comprising at least one polyisocyanate, and at least one polyol component comprising at least one polyol, wherein slag and optionally further ingredients are present in the polyisocyanate components, in the polyol components and/or in any further components optionally present.

13. A method comprising bonding, coating or sealing substrates with the binder composition as claimed in claim 1 or with a multicomponent system for producing a curable binder composition, comprising at least one resin component comprising at least one epoxy resin, and at least one curing agent component comprising at least one curing agent for epoxy resins, wherein slag and optionally further ingredients are present in the resin components, in the curing agent components and/or in any further components optionally present for the filling of edges, holes or joints, as anchoring or injection resin, as a grouting or casting compound, as a floor covering and/or for production of moldings.

14. A method comprising producing materials having improved electrical conductivity at 20° C. with the binder composition as claimed in claim 1 or with a multicomponent system for producing a curable binder composition, comprising at least one resin component comprising at least one epoxy resin, and at least one curing agent component comprising at least one curing agent for epoxy resins, wherein slag and optionally further ingredients are present in the resin components, in the curing agent components and/or in any further components optionally present, wherein the slag in the binder composition is an iron-containing slag comprising at least 8% by weight of iron, calculated as FeO, based on the total weight of the slag, and/or a slag having a bulk density of at least 3.1 kg/l.

15. A cured binder composition obtained by curing of the binder composition as claimed in claim 1 or by mixing of the components and curing of a multicomponent system for producing a curable binder composition, comprising at least one resin component comprising at least one epoxy resin, and at least one curing agent component comprising at least one curing agent for epoxy resins, wherein slag and optionally further ingredients are present in the resin components, in the curing agent components and/or in any further components optionally present.

16. A method comprising bonding, coating or sealing substrates with the binder composition as claimed in claim 1 or with a multicomponent system for producing a curable binder composition, comprising at least one polyisocyanate component comprising at least one polyisocyanate, and at least one polyol component comprising at least one polyol, wherein slag and optionally further ingredients are present in the polyisocyanate components, in the polyol components and/or in any further components optionally present, for the filling of edges, holes or joints, as anchoring or injection resin, as a grouting or casting compound, as a floor covering and/or for production of moldings.

17. A method comprising producing materials having improved electrical conductivity at 20° C. with the binder composition as claimed in claim 1 or with a multicomponent system for producing a curable binder composition, comprising at least one polyisocyanate component comprising at least one polyisocyanate, and at least one polyol component comprising at least one polyol, wherein slag and optionally further ingredients are present in the polyisocyanate components, in the polyol components and/or in any further components optionally present, wherein the slag in the binder composition is an iron-containing slag comprising at least 8% by weight of iron, calculated as FeO, based on the total weight of the slag, and/or a slag having a bulk density of at least 3.1 kg/l.

18. A cured binder composition obtained by curing of the binder composition as claimed in claim 1 or by mixing of the components and curing of a multicomponent system for producing a curable binder composition, comprising at least one polyisocyanate component comprising at least one polyisocyanate, and at least one polyol component comprising at least one polyol, wherein slag and optionally further ingredients are present in the polyisocyanate components, in the polyol components and/or in any further components optionally present.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0218] FIG. 1 shows: a schematic representation of exemplary cross sections of irregularly shaped slag particles.

EXAMPLES

[0219] Working examples are presented hereinbelow, the purpose of which is to further elucidate the described invention. The invention is of course not limited to these described working examples.

[0220] “Ex.” stands for “example”.

[0221] “Ref.” stands for “reference example”.

[0222] Materials Used

[0223] The quartz sand and slags were dried before use and divided into grain fractions by sieving. The grain fractions were then mixed such that the grain size distribution of the sands used corresponded to a specified grain size distribution (grading curve).

[0224] EFS is an electric furnace slag from Stahl Gerlafingen, Switzerland. The material used had a bulk density of around 3.3 kg/l and an iron content, calculated as FeO, of about 19% by weight.

[0225] BFS is a blast furnace slag from Hüttenwerke Krupp Mannesmann, Germany, available from Hermann Rauen GmbH & Co., Germany. The material used had a bulk density of 2.9 kg/I and an iron content, calculated as FeO, of about 3% by weight.

[0226] Raulit® is a blast furnace slag from DK-Recycling and Roheisen GmbH, Germany, available under the brand name Raulit®-Mineralbaustoffgemisch from Hermann Rauen GmbH & Co., Germany. The material used had a bulk density of around 2.9 kg/I and an iron content, calculated as FeO, of about 1% by weight.

[0227] FS is a foundry sand from voestalpine AG, Austria. The material used had a bulk density of around 2.9 kg/I and an iron content, calculated as FeO, of less than 1% by weight.

[0228] CS is NAstra® iron silicate granules, a glassy copper slag available from Sibelco, Germany, having a bulk density of about 3.7 kg/I and an iron content, calculated as FeO, of about 51% by weight.

[0229] Sikadur®-42 HE is a three-component epoxy-resin-based grouting mortar available from Sika Schweiz AG.

[0230] The polycarboxylate ether (PCE) was a comb polymer with carboxylic acid groups and polyethylene glycol side chains.

[0231] Measurement Methods

[0232] The compressive strength and flexural strength were determined on 40×40×160 mm test specimens using testing machines in accordance with DIN EN 196-1.

[0233] For determination of the specific electrical volume resistance, the opposite 40×40 mm surfaces of the 40×40×160 mm test specimens were coated with electrically conductive gel and a steel electrode covering the entire surface was placed flush on both surfaces. The electrical volume resistance of the test specimens was determined by applying a voltage of 100 mV AC at a frequency of 1 kHz and 10 kHz to the two electrodes.

[0234] The thermal conductivity was determined in accordance with ASTM D5470-06 using the ZFW TIM tester from ZFW (Center for Thermal Management) Stuttgart, Germany, on test specimens 30 mm in diameter and 2 mm in height.

[0235] Production of the Test Specimens

[0236] Sikadur®-42 HE component A (comprising the epoxy resin; resin content 99.9% by weight) was mixed thoroughly with the associated component B (comprising the curing agent; curing agent content 70% by weight) in a weight ratio of 3:1 and then a self-produced solid component as per Table 1 was added and mixed in thoroughly. The weight ratio of component A to component B to solid component was 3:1:34.

[0237] To produce the test specimens, the mixed grouting mortar was poured into steel molds and stored in the formwork for 24 hours at 20° C. The test specimens were then removed from the formwork and stored further at 20° C. After 7 days of storage, the specific electrical resistance, strength, and thermal conductivity were determined.

TABLE-US-00001 TABLE 1 Composition of the solid component Constituent % by wt. Mixture of limestone powder and baryte powder, <0.1 mm 24.9 Sand (slag sand or quartz sand)*, 0.12-3.2 mm 74.6 Polycarboxylate ether solution (20% by weight of 0.5 polycarboxylate ether dissolved in 80% by weight of benzyl alcohol) *sand type: see the reference example and the examples.

[0238] For production of the solid component, the solid constituents were mixed dry and the polycarboxylate ether solution sprayed thereon while mixing.

[0239] Strength and Electrical Volume Resistance of Epoxy-Resin-Based Grouting Mortars

[0240] The type of sand used for epoxy resin compositions M-1 to M-7 and the properties thereof in the liquid state and cured state are shown in Table 2.

TABLE-US-00002 TABLE 2 Ref. 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 M-1 M-2 M-3 M-4 M-5 M-6 M-7 Sand Quartz EFS.sup.1) EFS BFS Raulit ® FS CS sand crystalline Consistency fluid.sup.2) viscous.sup.3) fluid fluid fluid fluid fluid after mixing Compressive 103.9 131.1 120.3 117.2 116.3 113.2 115.9 strength [MPa] Flexural 26.3 33.4 29.9 26.8 28.2 27.0 31.2 strength [MPa] Specific 175 n/a.sup.4) 40 121 137 187 27 electrical volume resistance [MΩ .Math. cm] at 1 kHz Factor.sup.5) 4.4 1.4 1.3 0.9 6.5 1 kHz Specific 17 n/a 5.2 12 14 21 3.1 electrical volume resistance [MΩ .Math. cm] at 10 kHz Factor 3.3 1.4 1.2 0.8 5.5 10 kHz .sup.1)without adding a polycarboxylate ether solution to the solid component .sup.2)fluid: self-flowing, could be poured into the mold .sup.3)viscous: mortar was not self-flowing, the mold had to be vibrated strongly in order to obtain a homogeneous test specimen .sup.4)n/a: no measured value available .sup.5)factor by which the specific electrical volume resistance of mortar M-2 to M-7 is reduced compared to the specific electrical volume resistance of the reference mortar M1, e.g. resistance M1/resistance M2

[0241] Thermal Conductivity of an Inventive Grouting Mortar M-8

Example 7

[0242] Sikadur®-42 HE component A (epoxy-resin-based resin component; resin content 99.9% by weight) was mixed thoroughly with the associated component B (curing agent component based on amine curing agent; curing agent content 70% by weight) in a weight ratio of 3:1. Into 40 g of this epoxy mixture was then mixed in thoroughly a solid component consisting of: [0243] 252 g of EFS sand having a particle size of 0.12-0.32 mm, [0244] 86 g of a mixture of limestone powder and baryte powder having a particle size of less than 0.1 mm, and [0245] 1.4 g of commercial wetting agent.

[0246] A test specimen having a diameter of 30 mm and a height of 2 mm was produced by pouring into appropriate molds and allowed to cure at 20° C. for 7 days.

[0247] The thermal conductivity of the sample was 2.06 W/(m.Math.K). This is significantly higher than the thermal conductivity of a commercial epoxy resin having typically 0.20 W/(m.Math.K).

[0248] Epoxy-Resin-Based Grouting Mortar Having Varying Amounts of Copper Slag

[0249] Sikadur®-42 HE component A (comprising the epoxy resin; resin content 99.9% by weight) was mixed thoroughly with the associated component B (comprising the curing agent; curing agent content 70% by weight) in a weight ratio of 3:1 and then a self-produced solid component having a composition as stated in Table 1 was added and mixed in thoroughly. The 0.12-3.2 mm sand in this measurement series was CS sand (copper slag). The weight ratio of component A to component B to solid component is stated in Table 3. The mixed grouting mortar was in each case poured into molds of 13×13×25 mm (width, height, length), shaken on a vibrating table for 1 minute, and stored in the formwork at 20° C. for 24 hours. After stripping, a virtually slag-free epoxy resin layer, assessed with the naked eye, was observed on the upper side of the test specimens and the thickness thereof was determined. The thickness of this layer and the content of fillers and slag in the grouting mortars are stated in Table 3.

TABLE-US-00003 TABLE 3 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12 M-9 M-10 M-11 M-12 M-13 Parts by weight in the grouting mortar Component A 3 3 3 3 3 Component B 1 1 1 1 1 Solid component 16 30 34 38 46 % by weight of solid component in the grouting mortar 80 88 89 90 92 % by weight of slag in the grouting mortar 59 65 66 67 68 Thickness of the slag-free epoxy resin layer on the upper side of the test specimen (in % of the total height of the test specimen) 28 15 11 5 3

[0250] Compressive Strength of Grouting Mortars Having Varying Proportions of Epoxy Resin and Curing Agent

[0251] Epoxy resin (produced from 60 parts by mass of Araldite GY 250, 20 parts by mass of F-resin, 15 parts by mass of 1,4-butane diglycidyl ether, 5 parts by mass of C12/C14 alkyl glycidyl ether) was mixed thoroughly with the curing agent (produced from 55 parts by mass of triethylenetetramine, 10 parts by mass of polyaminoamide adduct—having 115 g/equiv of H-active equivalents and approx. 270 mg KOH/g amine value—and 5 parts by mass of tris-2,4,6-dimethylaminomethylphenol) in the amounts stated in Tables 4 and 5. EFS and PCE were then added in the amounts shown in Tables 4 and 5 and mixed in thoroughly.

[0252] To produce the test specimens, the mixed grouting mortar was poured into steel molds. The flowability was assessed on a scale from 1 to 5, where 1 means not flowable and 5 means excellent flowability. The test specimens were stored in the formwork at 20° C. for 24 hours. The test specimens were then removed from the formwork and stored further at 20° C. After storage for 7 days, the compressive strength was determined.

TABLE-US-00004 TABLE 4 Ex 13 Ex 14 Ex 15 Ex 16 Ex 17 Ex 18 M-14 M-15 M-16 M-17 M-18 M-19 EFS 0.12-3.2 mm 29.88 29.88 29.88 29.88 29.88 29.88 PCE solution* 0.12 0.12 0.12 0.12 0.12 0.12 Epoxy resin 1.18 1.82 5.61 2.86 7.48 10.24 Curing agent 0.27 0.42 1.31 0.66 1.74 2.38 Flowability 1 1 4 2 5 5 Compressive 7.15 19.9 87.1 31.2 87.7 85.4 strength [MPa] *20% by weight of polycarboxylate ether dissolved in 80% by weight of benzyl alcohol

TABLE-US-00005 TABLE 5 Ref. Ex 19 Ex 20 Ex 21 Ex 22 Ex 23 24 M-20 M-21 M-22 M-23 M-24 M-25 CS 0.12-3.2 mm 29.88 29.88 29.88 29.88 29.88 29.88 PCE solution* 0.12 0.12 0.12 0.12 0.12 0.12 Epoxy resin 1.18 1.82 5.61 2.86 7.48 10.24 Curing agent 0.27 0.42 1.31 0.66 1.74 2.38 Flowability 1 1 5 2 5 5 Compressive 25.2 44.2 75.4 66.6 69.8 64.6 strength [MPa] *20% by weight of polycarboxylate ether dissolved in 80% by weight of benzyl alcohol

[0253] Compressive Strength of Grouting Mortars Having Varying Proportions of Polyurethane Resin

[0254] Polyurethane resin (PUR; produced by mixing 55 parts by mass of Setathane 1150, 3.5 parts by mass of Desmophen T 4011, 17.3 parts by mass of hydroxy-terminated polybutadiene polyol, 13.8 parts by mass of ethylhexane-1,3-diol, 10 parts by mass of Sylosiv A3, 0.1 parts by mass of Zr catalyst K-Kat A-209) was mixed thoroughly with Desmodur VL in the amounts stated in Tables 6 and 7. EFS, the mixture of limestone and baryte (see Table 1), and PCE were then added in the amounts shown in Tables 6 and 7 and mixed in thoroughly. To produce the test specimens, the mixed grouting mortar was poured into steel molds. The flowability was assessed on a scale from 1 to 5, where 1 means not flowable and 5 means excellent flowability. The test specimens were stored in the formwork at 20° C. for 24 hours. The test specimens were then removed from the formwork and stored further at 20° C. After storage for 7 days, the compressive strength was determined.

TABLE-US-00006 TABLE 6 Ex 25 Ex 26 Ex 27 Ex 28 M-26 M-27 M-28 M-29 EFS 0.12-3.2 mm 25.4 25.05 25.05 25.72 Mixture of limestone powder and 4.48 4.83 4.83 4.16 baryte powder, <0.1 mm PCE solution* 0.12 0.12 0.12 0.12 PUR 1.16 4.57 0.62 2.60 Desmodur VL 0.74 2.92 0.40 1.66 Flowability 1 3 2 2 Compressive strength [MPa] 18.3 31.9 38.3 33.8 *20% by weight of polycarboxylate ether dissolved in 80% by weight of benzyl alcohol

TABLE-US-00007 TABLE 7 Ex 29 Ex 30 Ex 31 Ex 32 M-26 M-27 M-28 M-29 CS 0.12-3.2 mm 25.4 25.05 25.05 25.72 Mixture of limestone powder and 4.48 4.83 4.83 4.16 baryte powder, <0.1 mm PCE solution* 0.12 0.12 0.12 0.12 PUR 1.16 4.57 0.62 2.60 Desmodur VL 0.74 2.92 0.40 1.66 Flowability 1 2 1 1 Compressive strength [MPa] 36.6 40.7 42.1 55.0 *20% by weight of polycarboxylate ether dissolved in 80% by weight of benzyl alcohol