TW200815303A - Use of a pulverulent composition comprising titania and an inorganic binder to increase early strength - Google Patents

Abstract

Use of a pulverulent composition comprising an inorganic binder and, based on the binder, 0.25 to 5% by weight of finely divided titania for the preparation of products having high early strength.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the use of a powdery composition for enhancing the early strength of a product prepared by using the same, which comprises titanium dioxide and an inorganic binder. [Prior Art] • Photocatalytic properties of titanium dioxide are known in cement mixtures. In W098/0560 1, it is disclosed that titanium dioxide is used to obtain the color and brightness of a particular concrete. It specifically states that the compaction strength of concrete is not affected by titanium dioxide. A similar situation is revealed in wool /0054 1 which illustrates that the properties of the resulting concrete are unaffected. In JP2000 1 1 7 1 17, a mixture comprising 100 ® parts by weight of cement and 10 to 150 parts by weight of titanium dioxide is disclosed. In GB-A-8 49 1 75, it is disclosed that the coating composition for concrete is white cement and contains up to 3% by weight of titanium dioxide. In summary, it can be said that in the prior art, titanium dioxide was only revealed as a photocatalytic substance in a cement mixture. SUMMARY OF THE INVENTION It has now surprisingly been found that the early strength of a product comprising a hydraulic binder can be increased by a powdery composition comprising titanium dioxide and an inorganic binder. 200815303 The present invention relates to the use of a powdered composition for the manufacture of a product having a high early strength, the composition comprising an inorganic binder and 0.25 to 5% by weight of finely divided titanium dioxide based on the binder. More than 5% by weight of the titanium dioxide content in principle results in relatively poor processability of the water treated composition (e.g., a low dip in fresh concrete); while less than 0.25 wt% increases the early strength only slightly. Preferably, the titanium dioxide content is 〇 25 to 2% by weight, particularly preferably 0.25 to 1% by weight. A product having a high early strength and comprising an inorganic binder is herein understood to mean at least 30% higher than the reference enthalpy of the product containing no titanium dioxide at any desired point during the first 48 hours of product hardening. Strength 〇 Inorganic binder refers to an inorganic substance that can be processed in a plastic state, which hardens over a period of time while at the same time strongly bonding other substances (for example, coarse or relatively fine aggregates) to each other. The inorganic binder according to the present invention comprises a hydraulic binder (such as cement, hydraulic lime) which spontaneously hardens in the presence of water, and a latent hydraulic binder which exhibits a curing reaction only after pretreatment, in water and hydrogen. A non-hydraulic binder (such as gypsum powder, anhydrous binder, magnesium dioxide binder, non-hydraulic stucco) that reacts as a stable product of hardened materials (such as gangue dust) in the presence of calcium oxide. , phosphate binders and water glass). Preferably, a hydraulic binder such as cement and hydraulic lime can be used. The subdivision of titanium dioxide is understood to mean having 20 to 400 m ^ 2 / -6 - 200815303 ‘ 40 to 120 flat titanium is advantageous for flame hydrolysis to produce in principle suitable for hydrogen or inorganic substances. The surface is free, for example, t with Degussa can also be used as a very narrow distribution of titanium dioxide as the BET surface area of the aluminum (for example from February 23) or the patent application -A-1138632 By. Preferably, titanium dioxide having a BET surface area of a square meter per gram can be utilized. It has also been demonstrated that particles in the form of dioxins in the form of aggregated particles can be oxidized by, for example, flame oxidation. Here, the oxidizable and/or hydrolyzable starting material is oxidized or hydrolyzed in the oxygen flame. Suitable starting materials are. Due to its good availability, for example, titanium tetrachloride is a particularly obtained titanium dioxide powder which is as non-porous as possible and has a hydroxyl group. Highly suitable commercially available titanium dioxide powder A〇OXIDE® Ti02 P25 with a BET surface area of 5〇±15 m ^ 2 /g. Further, it is advantageous to have titanium dioxide having a first-order particle as disclosed in j W02005/0541.

It is also possible to use a mixed oxide powder which, in addition to the main components, also contains an additional metal oxide. For example, titanium monofluorene (for example from DE_A-423 5996), titanium_German Patent Application 102004062104.7, 2004] Titanium-niobium mixed oxide powder (for example from Germany 1 02004061 702.3, 2004-02-2 2 2 2 Doped titanium dioxide powder as disclosed in EP or EP. It is also possible to use a surface-modified titanium oxide or titanium mixed oxide powder. Preferably, the following decanes 200815303, alone or in a mixture, may be utilized for this purpose: z-organodecanes (R〇) 3Si (CnH2n + 1) and (RO) 3Si (CnH2n l), wherein R = alkyl, For example, methyl, ethyl, n-propyl, isopropyl, butyl and η = 1 - 2 0 〇 organic decanes R'X(R〇)ySi(CnH2n+1) and R'^RCOySKCnHh·!) Wherein R = alkyl, such as methyl, ethyl, n-propyl, isopropyl, butyl; R' = alkyl, such as methyl, ethyl, n-propyl, isopropyl, butyl; Cycloalkyl; and n = l-20; x + y = 3, X = 1, 2; y = 1, 2 〇 haloorgano-based decanes X3Si(CnH2n+1) and XsSiCCnH^-i), wherein X = C1, Bra n = l -20. Halogenyl organodecanes X2(R')Si(CnH2n+1)i XHROSUCnHh-i) wherein X = C1, Br; R' = alkyl, such as methyl, ethyl, n-propyl, isopropyl , butyl; R' = cycloalkyl; n = 1-20. Halogenyl organodecanes X(R')2Si(CnH2n+1) and XCR'hSKCnHh-), wherein X = C1, Br; R' = alkyl, such as methyl, ethyl, n-propyl, iso Propyl, butyl; R' = cycloalkyl and n = 1-20. Organic decanes (R〇hSi(CH2)m-R', wherein R = alkyl, such as methyl, ethyl or propyl; m = 0, 1-20; ΪΤ = methyl, aryl, for example one C6H5, substituted phenyl, C4H9, 〇CF2-CHF-CF3, C6F13, OCF2-CHF2, NH2, N3, SCN, ch = ch2, nh-ch2-ch2-nh2-, n-(ch2-ch2-nh2 2, ooc(ch3)c = ch2, och2-CH(0)CH2, NH-CO-N-CO-(CH2)5, NH-COO-CH3, NH-COO-CH2-CH3, NH-(CH2 3Si(OR)3, Sx-(CH2)3Si(OR)3 200815303, SH, NR'R,, R, '' (wherein R' = alkyl, aryl; R'' = H, alkyl, Aryl; R''' = H, alkyl, aryl, benzyl), C2H4NR''''R''' (wherein alkyl and s'''''''''''''' Organic decanes (R'') X(R〇)ySi(CH2)m-R', wherein R'' = alkyl, x + y = 3; ring-based, x = 1, 2' y = l , 2; m = 0, 1 to 20; R' = methyl, aryl, such as C6H5, substituted phenyl, C4H9, OCF2-CHF-CF3, C6Fi3, OCF2-CHF2, NH2, N3, SCN,

Ch=ch2, nh-ch2-ch2-nh2, n-( ch2- ch2- nh2)2, ooc(ch3)c = ch2, och2-ch(o)ch2, NH-CO-N-CO-(CH2) 5, NH-COO-CH3, NH-COO-CH2-CH3, NH-(CH2)3Si(OR)3, Sx-(CH2)3Si(OR)3, SH, NR'R,, R''' ( Wherein R, = alkyl, aryl; R'' = H, alkyl, aryl; R''' = H, alkyl, aryl, benzyl), C2H4NR''''R'''' '(wherein R''''=H, alkyl and R'', ''=H, alkyl). Haloorganyl decanes X3Si(CH2)m-R', wherein X = C1, Br; m = 0, 1-20; R' = methyl, aryl, for example C6H5, substituted phenyl 'C4H9' OCF2-CHF-CF3 ' C6F13 ' OCF2-CHF2 ' NH2 ' N3 ' SCN, ch = ch2, nh-ch2- ch2- nh2-, n-( ch2- ch2-NH2)2, -00C(CH3)C = CH2 , 0CH2-CH(0)CH2, NH-C0-N-CO-(CH2)5, -NH-COO-CH3, -NH-COO-CH2-CH3, -NH-(CH2)3Si(OR)3, -Sx-(CH2)3Si(OR)3 (wherein R = methyl, ethyl, propyl or butyl and x = 1 or 2), SH. Haloorganodecyl RX2Si(CH2)mR', wherein x = Ci, Br; m = 0, 1-20; R' = methyl, aryl, for example C6H5, substituted phenyl 200815303, C4H9, OCF2 -CHF-CF3, C6F13, OCF2-CHF2, NH2, N3, SCN, ch = ch2, nh-ch2-ch2-nh2-, n-(ch2-ch2-nh2)2, -OOC(CH3)C = CH2 Och2-ch(o)ch2, nh-co-n-CO-(CH2)5, -NH-COO-CH3, -NH-COO-CH2-CH3, -NH-(CH2)3Si(OR)3,- Sx-(CH2)3Si(OR)3 (wherein R = methyl, ethyl, propyl or butyl and x = 1 or 2), SH.

Haloorganodecyl R2XSi(CH2)mR', wherein X = C1, Br; m = 0, 1-20; R' = methyl, aryl, for example C6H5, substituted phenyl, C4H9, OCF2- CHF-CF3, C6F13, OCF2-CHF2, NH2, N3, SCN, CH = CH2, NH-CH2-CH2-NH2-, N-(CH2-CH2-nh2)2, -ooc(ch3)c = ch2, och2 -ch(o)ch2, nh-co-n-CO-(CH2)5, -NH-COO-CH3, -NH-COO-CH2-CH3, -NH-(CH2)3Si(〇R)3,- Sx-(CH2)3Si(OR)3 (wherein R = methyl, ethyl, propyl, butyl, and X = 1 or 2), SH. A taxane R'R2SiNHSiR2R, wherein R, R' = alkyl, alkenyl, aryl. Cyclopolysiloxanes D3, D4, D5. D3, D4, and D5 are understood to be cyclic polyoxyalkylenes having units of 3, 4, and 5-0-Si(CH3)2, such as octamethylcyclotetraoxane = D4 〇 10- 200815303

Me2

/〇—si\ Me2Si O

O

SiMe〇

•O

Me2 D4 Polyoxane or polydecane oil of the following form Y-( RI RT, -Sir-O- -Si—0- I R" 1 Υ where R = alkyl, aryl, (CH2)n-NH2 , Η R' = alkyl, aryl, (CH2)n-NH2, Η Rn = alkyl, aryl, (CH2)n-NH2, Η R"' = alkyl, aryl, (CH2)n- NH2, Η Y = CH3, Η, CzH2z+1, where ζ=1-20,

Si(CH3)3, Si(CH3)2H, Si(CH3)2OH, Si(CH3)2(OCH3), Si(CH3)2(CzH2z+1) wherein R| or R" or Rf" is (CH2) Z-NH2 and z= 1 -2 0, m = 0, 1, 2, 3, ..·°° , n = 0, 1 , 2, 3 , .·· 〇〇-11 - 200815303

u = 0, the following materials are preferably used as surface modifiers: octyltrimethoxydecane, octyltriethoxyphthalate, hexamethylacetamid, 3-methylpropoxypropyltrimethoxy Baseline, 3-methoxypropoxypropyltriethoxydecane, cetyltrimethoxydecane, cetyltriethoxydecane, dimethylpolyoxane, glycidyloxypropane Trimethoxy decane, condensed sugar # methoxy propyl triethoxy decane 'nonafluorohexyl trimethoxy decane, tridecafluorooctyl trimethoxy sand, trifluorooctyl triethoxy sand Aminopropyltriethoxysilane is particularly preferably used, and octyltrimethoxydecane, octyltriethoxydecane, and dimethylpolyoxane can be preferably used. Suitable surface modified titanium dioxide powders may be, for example, AEROXIDE® Ti02 T805 from Degussa having a BET surface area of 45 ± 10, m ^ 2 /g and a carbon content of 2.7 to 3.7% by weight. ® A powdery composition can also be used, in which titanium dioxide is sprayed on inorganic binders. In this case, it is advantageous if the water content of the composition is increased by up to 5%, particularly preferably at most 1.5%, as compared with the water content of the composition before being sprayed on the dispersion. For example, the inorganic binder may have a water content of 2% before spraying, and at most 7% after spraying, particularly preferably at most 3.5% water content. Due to the slight increase in water content, it is ensured that the composition is powdered even after spraying. The aqueous dispersion is atomized by spraying in accordance with methods known to those skilled in the art for spraying. -12- 200815303 Advantageously, the dispersion is a highly aqueous dispersion of small particle size. A titanium dioxide dispersion having a titanium dioxide content of at least 30% by weight based on the dispersion is particularly preferred. Further, those dispersions in which the average aggregate diameter of titanium oxide in the dispersion does not exceed 2 μm are preferable. Particularly preferably, it is possible to use a dispersion having an average aggregate diameter of less than 300 nm. The acidity and alkalinity of the dispersion is preferably 2 to 4 or 9 to 13. However, dispersions in the range of 4 to 9 can also be utilized. Adjust acid-base Φ 値 by adding acid or base. The dispersion may additionally contain additives which interfere with precipitation and re-agglomeration. The acid, base and/or additive should be chosen so as not to adversely interact with the hydraulic binder component. In principle, the liquid phase of the dispersion is aqueous. Table 1 illustrates suitable dispersions. Table 1: Titanium Dioxide Dispersion

Surface area Ti02 content Ti〇2 d 5 0 pH stability square meter / gram weight % micron 50 40 < 2 2-4 HN 〇 3 90 30 < 1.5 2-4 hno3 90 30 < 0.05 2-4 hno3 50 40 <0.10 2-4 hno3 50 30 <0.3 10-13 NaOH 90 30 <0.2 10-13 NaOH

The enthalpy (d5Q) in the particle size distribution was determined by dynamic light scattering using a Horiba measuring device (LB 500).

Commercially available titanium dioxide dispersions are, for example, VP Disp W -13- 200815303 740 X (40% by weight of Ti02, d5G < 0. 2 microns, pH 値6-9) and VP Disp W 2730 X (30 Weight% of Ti02, d5G < 0·1 micron). [Embodiment] Titanium dioxide used (a) AEROXIDE® Ti02 Ρ25 (Degussa AG), BET surface area 5 0 soil 1 5 m ^ 2 / g, drying loss S 1 · 5 wt%, acid-base 値 3.5-4.5. (b) Ti02-2: Titanium dioxide powder according to Example 0 of WO2005/054 1 3 6 with a BET surface area of 91 m ^ 2 /g. (c) Pigmented titanium dioxide: BET surface area < 10 m 2 /g. (d) 矽-titanium mixed oxide: According to Example 12 of DE-A-1 02004001 520, the BET surface area is 43 m ^ 2 /g, the titanium dioxide content is 49 wt%, and the vermiculite content is 51 wt%. (e) Ti02 dispersion 1 (aqueous): Ti02 surface area 90 m ^ 2 / g, Ti 〇 2 content 30 wt%, d5 〇 S 〇 2 μm, acid test 値 = 2 - 4, stabilization hno3. (f) Ti02 dispersion 2 (aqueous): Ti02 surface area 50 m ^ 2 / g, Ti 〇 2 content 30 wt%, d5 〇 S 0.3 μm, acid test 値 = 10-13, stabilization NaOH. Example 1 An inorganic binder (CEM I 52.5R HS/NA from Holcim) containing 1.5% by weight of AEROXIDE® Ti02 P25 cement was strongly mixed in a powder mixing -14-200815303 machine. Using this powder composition, a standard plaster (water-cement 値 0.45) was prepared in accordance with DIN 196 196. After 24 hours and 48 hours, the compaction strength of the plaster was measured on a scale of 1 X 1 x 4 cm following DIN 1 1 64. The experiment was repeated but titanium dioxide was not used. The comparison results are shown in Table 1. Table 1 · Early strength content after 24 hours and 48 hours After compressive strength compressive strength compressive strength Ti〇2 2 4 hour increase 4 8 hours weight % Newton / square mm % Newton / square mm 0 12.2 - 28.3 1.5 18.1 48 32.5 *) Based on cement

From Table 1, it is shown that the early strength of the mortar after 24 hours is almost 50% higher than that of the titanium dioxide-free one due to the addition of titanium dioxide. After 48 hours, the effect of titanium dioxide is stronger in the early stage of cement hydration than in the late stage. Measurements of the strength after 7 and 28 days showed that the increase in strength was not significant compared to the sample without titanium dioxide. Titanium dioxide therefore only works for early strength, but not for final strength. Example 2 A powdery composition of an inorganic binder (CEM I 42.5 R, Buderus) and different titanium dioxide (see Table 2) was prepared by intensive mixing in a powder mixer. All of the finished products contained titanium oxide of -15-200815303 in an amount of 0.5% by weight of the cement. Using this powdery composition, standard stucco (water-cement 値 0 · 4 5 ) was prepared in accordance with DIN 196 196. After 24 hours, the compaction strength of the plaster was measured on a prism measuring 1 x 1 x 4 cm following D IN 1 1 6 4 . Repeat the experiment without using dioxins. Table 2: Effect of different types of titanium dioxide on early strength Example Titanium dioxide compressive strength at 24 hours Compressive strength increased Newton/mm 2 % 2a (Comparative) Titanium dioxide free 12.16 • 2 b (Comparative) Pigment Ti02 12.37 2 2c AEROXIDE® Ti02 P25 17.72 46 2d Ti02-2 19.05 57 2e Si-Ti mixed oxide 15.85 30 *) Based on cement Table 2 shows that due to the use of finely divided titanium dioxide, an extremely significant increase in early strength can be achieved. The higher the specific surface area, the higher this becomes. However, due to the use of low surface area pigmented titanium dioxide, only a slight increase in early strength is achieved. Early strength can also be significantly increased by using a mixed oxide containing finely divided titanium dioxide. Example 3 By first spraying a different titanium dioxide dispersion (see Table 3) on a CEM I 42·5 R (Buderus) in an intensive mixer (15 liter volume, Maschinenfabrik Gustav Eirich GmbH & Co KG), the first titanium dioxide-containing 16-200815303 Powder composition. Using this powder composition, standard stucco (water-cement 値 〇 · 4 5 ) was prepared in accordance with DIN EN 196. After 24 hours, the compaction strength of the plaster was measured on a scale of 1 x 4 x 4 cm following d IN 1 164. The experiment was repeated without using titanium dioxide. Table 3: Examples of use of titanium dioxide dispersions Ti02 content of dispersions Compressive strength 2 4 hours of increase in compressive strength %" Newtons per square millimeter % 3 a (comparative) Λ /\\\ 12.16 - 3b$) 1.67 18.99 65 3c&) 1.67 17.55 88 $) Titanium Dioxide Dispersion; &) Titanium Dioxide Dispersion 2; *) Based on Cement; Table 3 shows that the use of a sprayed Dioxin dispersion can also significantly increase the strength of the early sweet phase. Example 4: Study of the strength increase of titanium dioxide addition in standard stucco samples. Starting materials: standard sand, CEM I 42.5 R (Buderus), Ti02P 25 (Degussa), water. Cement and Aeroxide Ti02 P25 were first strongly Mixing the ground. Then test the test object according to DIN EN 196 (water-cement 値: 0.45). Determine the strength of the mirror according to DIN 1164 on a 尺寸1·5χ1·5χ6.0 cm 稜鏡-17- 200815303 Table 4: Relationship between flexural/compressive strength (in Newtons per square millimeter) and titanium dioxide addition (in % by weight) Titanium dioxide addition 0.0 0.1 0.5 1.0 1.5 5.0 Id 3.67/ 3.76/ 4.56/ 4.77/ 6.64 / 4.52/ 12.16 12.48 17.72 18.23 18.25 16.41 2d 7.2 1/ 7.4 9/ 8.29/ 8.03/ 7.3 4/ 5.94/ 29.05 30.03 33.99 38.62 33.08 29.97

Table 4 shows that a very low concentration of 0.1% by weight of cement only caused a slight increase in early strength. However, a significant increase in the strength of the sample was observed by adding 5% by weight of titanium dioxide based on the binder. The intensity measured after 1 day in Table 4 also clearly shows that the early strength cannot always be further increased by the increase in the concentration of titanium dioxide. The intensity after 2 days (2d) was significantly lowered even at a concentration of 5%. In summary, it can be said that φ has an optimum enthalpy between the amount of non-active titanium dioxide and the amount of titanium dioxide which does not increase the early strength. Example 5: Reactivity of Titanium Dioxide in Cement Hydration Process

A 3.00 g of CEM I 42.5 R and a 3.00 g of CEM I 42·5 R and the added 2 wt% titanium dioxide powder composition were mixed in the test tube and uniformly compacted and required for hydration Distilled water (1.20 grams) was drawn into a syringe with a needle. Subsequently, the test tube and syringe were inserted into the sample space of a heat flow card meter for a constant temperature of 25 °C. When the temperature equilibrium is reached, water is sprayed into the powder bed and measurement begins. -18- 200815303

Figure 1 shows the hydration process of CEM 42·5 R I (curve a) and CEM 42.5 R I with the powdery composition of 2% by weight of titanium dioxide added (curve b). It can be seen that the thermal development of each of the initial peaks of the titanium dioxide added sample is significantly higher. In addition, the early increase and decrease of the heat release during the acceleration period due to the shorter induction time is seen, thereby illustrating the acceleration of the hydration of the cement due to the addition of titanium dioxide and the effect of the early strength increase.

Φ Figure 2 shows the hydration process of CEM 42.5 R I (curve a) and CEM 42.5 R I with the powdered composition of 2% by weight of titanium dioxide added (curve b). The amount of heat release after 24 hours was almost identical in the two samples. However, in the case of the addition of a sample of titanium dioxide, early thermal development during the acceleration period was also clearly seen. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows the hydration process of CEM 42.5 R I (curve a) and CEM 42·5 R 】 Φ with the powdery composition of 2% by weight of titanium dioxide added (curve b). Figure 2 shows the hydration process of CEM 42.5 R I (curve a) and CEM 42.5 R ] with 2% by weight of titanium dioxide added (curve b). -19-

Claims (1)

(1) 200815303 X. Patent Application No. 1 1. Use of a powdery composition for preparing a product having high early strength, the powdery composition comprising an inorganic binder and 0.25 to 5% by weight based on the binder Subdivided titanium dioxide. 2. The use of claim 1, wherein the titanium dioxide particles have a BET surface area of from 40 to 120 square meters per gram. 3. The use of claim 1 or 2, wherein the powder group comprises titanium dioxide sprayed on an inorganic binder. -20-