GYPSUM BASED BUILDING MATERIAL

Abstract

A building material comprising an inorganic binder a reactive silicon source a reactive calcium source.

Claims

1. A building material comprising an inorganic binder a reactive silicon source a reactive calcium source.

2. The building material according to claim 1, wherein the inorganic binder comprises cementitious materials or calcium sulfate, wherein the calcium sulfate is selected from calcium sulfate dihydrate, stucco, α- and/or β-calcium sulfate hemihydrate, calcium sulfate anhydrite.

3. The building material according to claim 1, wherein the reactive silicon source is an amorphous silicon dioxide.

4. The building material according to claim 1, wherein (i) the particle size D50vol of the reactive silicon source is between 0.01 and 400 μm, or (ii) the particle size D50vol of the reactive calcium source is between 0.1 and 800 μm, or (iii) a combination of both.

5. The building material according to claim 1, wherein the amount of reactive silicon source is from 0.5 to 20% by weight with respect to the amount of inorganic binder in the building material.

6. The building material according to claim 1, wherein the reactive calcium source is selected from calcium oxide, calcium hydroxide, calcium carbonate and mixtures thereof.

7. The building material according to claim 1 wherein the amount of reactive calcium source is 0.5 to 40% by weight with respect to the amount of inorganic binder in the building material.

8. The building material according to claim 1, wherein the amount of the reactive calcium source relative to the amount of the reactive silicon source is from 2.5:1 to 1:1.

9. The building material according to claim 1, wherein the gypsum building product is a building board, a plaster, a putty, a joint compound, a screed, a fill, or a filler.

10. The building material according to claim 9, wherein the building board is a gypsum fiber board, a plasterboard, a cement board, or a building block.

11. The gypsum based building material according to claim 1, wherein the building product is able to form wollastonite upon heating above 600° C.

12. The building material according to claim 1 comprising auxiliary agents selected from retarding agents, accelerators, hydrophobic agents, liquifiers, strengthening agents, substances that liberates crystal water when heated (ATH), or thickening agents.

13. A method of making a building product comprising the steps of combining at least an inorganic binder reactive silicon source a reactive calcium source.

14. The method of claim 13 further comprising the step of forming a board.

15. Use of a mixture of a reactive silicon source and a reactive calcium source to form wollastonite in a building product in situ when the building product is exposed to fire.

16. The building material according to claim 1, wherein the inorganic binder comprises cement or concrete.

17. The building material according to claim 1, wherein the amorphous silicon dioxide is pyrogenic silicon dioxide, microsilica, or a mixture thereof.

18. The building material according to claim 1, wherein the amount of reactive silicon source is from 2 to 15% by weight with respect to the amount of inorganic binder in the building material.

19. The building material according to claim 1, wherein the amount of reactive calcium source is 2 to 30% by weight with respect to the amount of inorganic binder in the building material.

Description

FIGURES

[0030] FIG. 1: shrinkage of samples with differing compositions during heat application (embodiments according to the invention)

[0031] FIG. 2: shrinkage of samples with differing compositions during heat application (comparative examples)

[0032] The invention is further explained by the following, non-limiting examples.

EXAMPLE 1

[0033] Gypsum prisms the size of 120 mm×40 mm×20 mm for shrinkage measurements and 160 mm×40 mm×20 mm for stability measurements were prepared from a slurry containing the following materials: [0034] calcium sulfate: stucco (mainly calcium sulfate hemihydrate of the β form), Iphofen [0035] reactive silicon source: 50% suspension of microsilica (SiO.sub.2) in water, EMSAC 500, ELKEM, d50vol: 0.15 μm, specific surface according to Blaine: 15-30 m.sup.2/g [0036] reactive calcium source: limestone flour (CaCO.sub.3), Kalkstein-Füller KSF 60/3, Fels-Werke, d50vol: 8.4 μm, specific surface according to Blaine: 0.54 m.sup.2/g fibers: glass fibers, DuraCore® M300, Johns Manville

TABLE-US-00001 TABLE 1 Sample No. Unit 1 2 3 4 5 6 7* Stucco [%]-wt 84 76 68 84 76 68 100 EMSAC 500 [%]-wt 8 12 16 8 12 16 — limestone flour [%]-wt 8 12 16 8 12 16 — glass fibers [%]-wt — — — 0.3 0.3 0.3 0.3 WGV — 0.71 0.79 0.88 0.6 0.6 0.6 0.6 WGV—Water gypsum value: 100 divided by the weight in g of calcium sulfate per 100 g water *= comparative sample

[0037] Shrinkage measurements were carried out in a muffle furnace in which the samples were subjected to heating and their change in length was continually recorded. The measurement method and the necessary apparatus are thoroughly described in WO 2017/000972 A1. In short, the sample is moveably mounted on a sample holder in horizontal orientation. One end of the sample is abutted against a counter bearing. At the opposed end of the sample a detector rod exerts a pressure on the sample, always securing the abutment of the sample against the counter bearing. The detector rod measures the movement of the sample end against which it is pressed. This measurement, related to the original sample length before heated, is the length change in percent shown in FIGS. 1 and 2. The change in length of a specimen is measured while running through the standard temperature/time curve according to EN 1363-1. The comparative sample 7, which does not contain any wollastonite or its educts but only glass fibers, expands during the first about 20 min as all other samples do, see FIG. 1. During this time range the samples are heated and the crystal water comprised within the gypsum slowly becomes gaseous. As a result the sample body expands.

[0038] When the water vapor starts to gas out the sample body begins to shrink. After about 40 min all crystal water has evaporated and the sample starts to sinter. After two hours the body of the comparative sample lost more than 11% of its original length.

[0039] This shrinkage is considerable and results in severe problems if this material is used in firmly fixed drywall constructions, for example plasterboards. The plasterboards are usually fixed to metal studs via a multitude of screws. A 11% shrinkage in the length or breadth of the board, i.e. several centimeters in case of a plasterboard, causes the calcium sulfate material already brittle by volume-loss to break and/or rupture from its fixture and to at least partly fall into the room.

[0040] By contrast, sample 1 shows a shrinkage in length of only about 4%. According to XRD Rietveld analysis this sample contains 6 wt.-% of wollastonite which formed during heating from 8 wt.-% of microsilica-suspension and 8 wt.-% of limestone. Further, the period of low shrinkage after the expansion period is delayed by about 10 min. Slow shrinkage continues until 50 min after start and drops to moderate shrinkage afterwards. The drop in shrinkage between about 50 to 60 min is related to the end of the outgas sing of the crystal water. The calcium sulfate material now starts to sinter. The sintering process results in an additional strong volume reduction in the calcium sulfate material if no countermeasures are taken.

[0041] Without wanting to be bound by theory, the inventors presume that the addition of wollastonite educts results in the in situ formation of wollastonite while the sample body is heated. The reaction to wollastonite is endotherm and thus consumes energy which is otherwise acting on the evaporation of crystal water. The body is cooled as long as crystal water evaporates and wollastonite forms. Therefore, the time period (in the range of the first 50 to 60 min) in which the sample body first expands and then shrinks only slowly and remains close to the original volume is prolonged. This is a very important time period because in this time range evacuation of persons from a burning building is easily possible. The structure remains intact and temperatures do not rise uncontrollably. Thus, the longer this time period the better the chances to save people's lives. The wollastonite, once formed, has another positive effect on the shrinkage—it reduces the shrinkage which occurs due to the onset of the sinter process. The recent understanding of the inventors is that the wollastonite is not or only slightly affected by the sintering process, probably interferes with the sintering of the gypsum surface, and provides a rigid scaffold which reduces the overall sample shrinkage. In all samples containing educts of wollastonite, the shrinkage is lower than 4% as compared to the comparative sample 7 which shrinks about 11%. Thus, shrinkage is reduced to about ⅓.

[0042] Lowest shrinkage values were reached with sample 6 which contained the highest amount of wollastonite precursor materials (8 wt.-% microsilica and 16 wt.-% limestone flower) and additionally 0.3% of fibers. Shrinkage is in fact negligible (0.2%).

[0043] The composition of the samples 1 and 4 is identical. Sample 4 additionally contains glass fibers, which is the only difference to sample 1. The same is true for samples 2 and 5, and 3 and 6. In the samples containing glass fibers, i.e. samples 4, 5, and 6, shrinkage was additionally reduced by about 1% compared to the reference sample without glass fibers. Thus, the presence of glass fibers additionally reduces shrinkage.

[0044] The break and sag resistance of the samples according to Tab. 1 was measured in a muffle furnace heated to 930° C. The samples were placed on two supports such that their length ends rested on the supports and the supports were arranged in 11 cm distance from one another. The samples remained in the furnace for 60 min provided they did not break before. If the samples failed the measurement was aborted.

[0045] Table 2 shows the results of the measurements. The listed wollastonite content was determined after test on the specimens via XRD Rietveld analysis. The column “Break” lists the time of measurement elapsed until the break occurred. If no break occurred within the 60 min of total measurement the result is listed as “>60”. The column “Maximum Sag” contains the sag values due to heat treatment, i.e. the sag after heat treatment reduced by the sag before the heat treatment, if any.

TABLE-US-00002 TABLE 2 Analyzed amount of wollastonite Stability when heated (XRD Break Maximum Sag Rietveld) Density Test 1 Test 2 Test 1 Test 2 Sample [%] [kg/m.sup.3] [min] [mm] 1 6 1141 >60 >60 4 2 2 10 1109 >60 >60 2 <1 3 14 1086 >60 >60 <1 <1 4 7 1241 >60 >60 2 1 5 10 1304 >60 >60 1 <1 6 14 1342 >60 >60 <1 <1  7* 0 1166 >60 20-30 17 Break *= comparative sample

[0046] Two replicates were examined per sample, Test 1 and Test 2. One of the replicates of comparative sample 7 broke. The other one showed a sag of 17 mm. Sample 1, containing the lowest amounts of wollastonite precursor materials of all samples according to the invention, did not break but sagged for 2 and 4 mm, respectively. All other samples sagged only little, i.e. 2 mm and most even less than 1 mm. The formation of wollastonite thus enhances sag stability under heat.

EXAMPLE 2

Materials

[0047] calcium sulfate: stucco, Iphofen [0048] reactive silicon source: 50% suspension of microsilica (SiO.sub.2) in water, EMSAC 500, ELKEM [0049] glass flour, MWT Mineralwerk Thüringen [0050] reactive calcium source: limestone flour (CaCO.sub.3), Kalkstein-Füller KSF 60/3, Fels-Werke, burnt lime (CaO), max. 15%>90 μm according to DIN 4188 [0051] glass fibers: glass fibers, M300, Johns Manville [0052] wollastonite: Tremine 939-010, Quarzwerke Gruppe [0053] liquifier: Viscocrete G2, Sika

TABLE-US-00003 TABLE 3 Sample No. Unit 8* 9* 10* 11 12* 13* 14* Stucco [%]-wt 92 88 84 82 95 100 76 EMSAC 500 [%]-wt 8 12 16 12 — — — Glass flour [%]-wt — — — — — — 12 Limestone [%]-wt — — — — — — 12 flour Burnt lime [%]-wt — — — 6 — — — Wollastonite [%]-wt — — — — 5 — — Glass fiber [%]-wt 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Liquifier [%]-wt — — — 0.1 0.2 — 0.2 WGV — 0.57 0.56 0.55 0.6 0.65 0.6 0.6 *comparative

[0054] Described length measurements and sag and break measurements were made as described for example 1.

[0055] The samples listed in Tab. 3 are comparative examples except for sample 11. Sample 11 contains burnt lime (CaO) as reactive calcium source and microsilica as reactive silicon source. Sample 11 has the lowest shrinkage (about 1.3%) after heating of all samples tested in Tab. 3, see FIG. 2.

[0056] Next best are samples 10, 9, and 8 which exhibit a shrinkage in the range between 2% and 3% after heating. These samples were produced by adding only a reactive silicon source but no reactive calcium source. The silicon content increases from sample 8 to sample 10. The relatively low shrinkage is thought to be the result of calcium carbonate impurities within the used stucco. Natural gypsum is typically not a pure material but contains more or less impurities. Limestone is an abundant impurity in gypsum because it precipitates from hypersaline waters directly before gypsum precipitates as the salt load of the waters increases due to evaporation. Therefore, it is presumed that the low shrinkage of samples 8, 9, and 10 is due to the formation of wollastonite from added microsilica and impurity calcium carbonates. Since samples 9 and 10 are only slightly different in terms of shrinkage after heating, it is further presumed that the calcium carbonate impurities are almost completely reacted to wollastonite.

[0057] Sample 12 was tested to show that it matters if wollastonite is formed in situ in case of fire or if pre-formed wollastonite is used as additive. To sample 12 5 wt.-% of pre-formed wollastonite were added. After heating sample 12 shows a shrinkage of about 6%. The amount of added wollastonite to sample 12 is equal to the amount of wollastonite which was found to have formed in sample 8. However, sample 8 shows only about half the shrinkage (2.8%) of sample 12.

[0058] In sample 14 glass flour was used as silicon source together with limestone flour. Contents of the silicon and the calcium source were comparably high. Nevertheless, shrinkage after heating amounts to more than 7%. Therefore, it was concluded that it is not sufficient to provide any pulverized silicon source but that it has to be a reactive source, i.e. an amorphous silicon source to be really effective in terms of shrinkage due to heat exposure.

[0059] Sample 13 neither contains a reactive silicon nor a reactive calcium source and exhibits a shrinkage after heating of about 11%.

TABLE-US-00004 TABLE 4 Analyzed amount of Wollastonite Stability when heated (XRD Break Maximum sag Rietveld) Density Test 1 Test 2 Test 1 Test 2 Sample [%] [kg/m.sup.3] [min] [mm]  8* 5 1232 >60 >60 Break Break  9* 5 1259 >60 >60 Break <1 10* 5 1298 >60 >60 <1 <1 11  13 1243 >60 >60 <1 <1 12* 5 1158 >60 >60 5 3 13* 0 1164 10-20′ 20-30′ Break Break 14* 0 1261 30-40′ >60 Break 4

[0060] Table 4 lists the results of the break and sag measurements of the samples composed as shown in Tab. 3. The comparative samples 12 to 14 either broke or showed high sag values after temperature application, see Tab. 4. Also both replicates of sample 8 broke. Surprisingly, for sample 9 one specimen broke and one specimen exhibited a sag value of below 1 mm.

[0061] Sample 11, which is an embodiment according to the invention, showed very low sag values of below 1 mm after 60 min. of heating.