AU715970B2 - Concrete compositions and processes for controlling alkali-silica reaction in same - Google Patents
Concrete compositions and processes for controlling alkali-silica reaction in same Download PDFInfo
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- AU715970B2 AU715970B2 AU71550/96A AU7155096A AU715970B2 AU 715970 B2 AU715970 B2 AU 715970B2 AU 71550/96 A AU71550/96 A AU 71550/96A AU 7155096 A AU7155096 A AU 7155096A AU 715970 B2 AU715970 B2 AU 715970B2
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- lithium
- concrete
- cement
- bearing ore
- asr
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- 239000004567 concrete Substances 0.000 title claims description 104
- 238000000034 method Methods 0.000 title claims description 39
- 239000000203 mixture Substances 0.000 title claims description 39
- 230000008569 process Effects 0.000 title claims description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 31
- 239000000377 silicon dioxide Substances 0.000 title claims description 19
- 238000006243 chemical reaction Methods 0.000 title description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 112
- 229910052744 lithium Inorganic materials 0.000 claims description 112
- 239000004568 cement Substances 0.000 claims description 62
- 239000003513 alkali Substances 0.000 claims description 27
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 claims description 18
- 229910052642 spodumene Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000012530 fluid Substances 0.000 claims description 15
- 238000006703 hydration reaction Methods 0.000 claims description 12
- 230000009257 reactivity Effects 0.000 claims description 12
- 230000036571 hydration Effects 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 230000000116 mitigating effect Effects 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 6
- 150000002642 lithium compounds Chemical class 0.000 claims description 6
- 239000012615 aggregate Substances 0.000 claims description 5
- -1 montebrasite Inorganic materials 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052822 amblygonite Inorganic materials 0.000 claims description 3
- 229910000174 eucryptite Inorganic materials 0.000 claims description 3
- 229910052629 lepidolite Inorganic materials 0.000 claims description 3
- 229910052670 petalite Inorganic materials 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 229910003002 lithium salt Inorganic materials 0.000 description 10
- 159000000002 lithium salts Chemical class 0.000 description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 5
- 239000011398 Portland cement Substances 0.000 description 5
- 235000011941 Tilia x europaea Nutrition 0.000 description 5
- 239000004571 lime Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000010881 fly ash Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910017119 AlPO Inorganic materials 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- DYKZEUFKJOSFSH-UHFFFAOYSA-K P([O-])([O-])([O-])=O.[Al+3].[Li+] Chemical compound P([O-])([O-])([O-])=O.[Al+3].[Li+] DYKZEUFKJOSFSH-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- 239000011405 expansive cement Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011396 hydraulic cement Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 1
- 239000011404 masonry cement Substances 0.000 description 1
- 239000011412 natural cement Substances 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 238000003359 percent control normalization Methods 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011150 reinforced concrete Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 229910052643 α-spodumene Inorganic materials 0.000 description 1
- 229910052644 β-spodumene Inorganic materials 0.000 description 1
Classifications
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- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
-
- 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
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/045—Alkali-metal containing silicates, e.g. petalite
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/603—Agents for controlling alkali-aggregate reactions
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/2023—Resistance against alkali-aggregate reaction
-
- 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
Description
WO 97/09282 PCT/US96/14326 -1- CONCRETE COMPOSITIONS AND PROCESSES FOR CONTROLLING ALKALI-SILICA REACTION IN SAME Cross-Reference to Related Applications This application is related to commonly owned copending Provisional Application Serial No.
60/003,475, filed September 8, 1995.
Field of the Invention This invention relates generally to concrete compositions and processes for controlling alkalisilica reaction in the same, and more particularly to the use of lithium bearing ores as components of concrete.
Background of the Invention Concrete is a conglomerate of aggregate (such as gravel, sand, and/or crushed stone), water, and hydraulic cement (such as portland cement), as well as other components and/or additives. Concrete is generally fluidic when it is first made, enabling it to be poured or placed into shapes, and then later hardens, and is never again fluidic, in the general sense. Typically, moisture present in normal concrete is basic (that is, has a high pH). Alkali materials can be supplied by the cement, aggregate, additives, and even from the environment in which the hardened concrete exists (such as salts placed on concrete to melt ice) Silica compounds are typically found in the aggregate components of concrete. Silica which is present in aggregates used to make concrete and mortars is subject to attack and dissolution by hydroxide ions present in basic solutions. Generally, the higher the pH the more basic the solution), the faster the attack.
WO 97/09282 PCTIUS96/14326 -2- Different forms of silica show varying degrees of susceptibility to this dissolution. If there is sufficient alkali metal ion also present in this solution (such as sodium or potassium ions), the alkali metal ions can react with the dissolved silica and form an alkali-silica gel. Under certain conditions, the resultant alkali-silica gel can absorb water and swell. The swelling can exert pressures greater than the tensile strength of the concrete and thus cause the concrete to swell and crack. This process (hydroxide attack of silica, followed by reaction with alkali such as sodium and potassium) is referred to generally in the art as an "alkali-silica reaction" or "ASR" ASR has caused the failure of concrete structures, although rarely. Further, ASR can weaken the ability of concrete to withstand other forms of attack. For example, concrete that is cracked due to this process can permit a greater degree of saturation and is therefore much more susceptible to damage as a result of "freeze-thaw" cycles. Similarly, cracks in the surfaces of steel reinforced concrete can compromise the ability of the concrete to keep out salts when subjected to de-icers, thus allowing corrosion of the steel it was designed to protect.
ASR is a common chemical process in many concretes around the world. As an indication of its importance to the concrete industry, by 1991 over 1,450 research articles had been published on the subject.
See S. Diamond, Alkali-aggregate reactions in concrete: an annotated bibliography 1939-1991, Washington,
D.C.:
National Research Council, Strategic Highway Research Program, SHRP-C/UWP-92-601:470 (1992) In 1987, Congress authorized a $150 million, five-year research program to be administered by the National Research Council to study and develop improvements in highway construction materials and -3construction practices. This program was called the Strategic Highway Research Program (SHRP). One of the areas addressed by this program was ASR mitigation.
Four recommendations resulted from the SHRP research for preventing ASR in concrete. D. Stark, et al., Eliminating or minimizing alkali-silica reactivity, Washington, D.C.:National Research Council, Strategic Highway Research Program, SHRP-C-343 (1993) (the "SHRP report").
One recommendation was the use a low alkali cement, which is defined as a cement with a sodium equivalent of 0.60% or less. The sodium equivalent of a cement is the weight percent of sodium, reported as sodium oxide, plus 0.658 times the weight percent of potassium, reported as potassium oxide. Sodium equivalent (Na20 can be represented generally by the formula Na20O 0.658 x K20 While the use of a low alkali cement can have some effectiveness, it is not a guarantee of ASR on a local basis, can have limited availability, and can be more expensive than high alkali cement; Further, if the raw feed for the cement-production I contains high levels of alkali, then the production of low alkali cement from such feed can generate much greater waste than would otherwise be the case.
Generally, "fines" are a waste product of cement production and are normally recirculated into the cement kiln. However, when the raw feed has a high alkali level, the fines must be removed from the process and constitute a waste material. These fines are called cement kiln dust.
Still further, using a low alkali cement is no guarantee of ASR control, as the cement is not the sole source of the alkalies in concrete that can -3acontribute to the problem. Alkalies also can be supplied by pozzolans that are either admixed in or
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WO 97/09282 PCT/US96/14326 -4part of the blended cement. Alkalies can be supplied by the mix water, admixtures used in the concrete, the aggregate itself, including recycled concrete used as aggregate, and/or deicers applied in snow and ice removal.
Another recommendation set forth by the SHRP report is the use a non-reactive aggregate. This, however, is not always possible. There are limited aggregates with no potential for reactivity, since all silica has some potential for reaction and most aggregates contain significant amounts of silica.
Recycled concrete when used as aggregate can also be reactive, particularly if it had already had ASR occurring before it was recycled. There are environmental reasons to use recycled glass as aggregate, but this is very reactive material. Also, transporting aggregates over long distances instead of using locally available materials adds significantly to the cost of concrete production.
Another recommendation is the use of appropriate levels of a suitable pozzolan. A pozzolan is a siliceous material that can combine with lime and water to harden, similar to a cement with just water.
Since the hydration of cement produces lime as a byproduct (resulting in its basic nature), pozzolans can work well with cements. The pozzolan may be added as a mineral admixture at the time of concrete production, blended with the cement, or interground with the cement during the final production step of cement. The end result is about the same, as neither the cement nor the pozzolan is substantially changed as a result of the blending.
However, sources of suitable pozzolans are not always available locally, and the supplies are limited. Also, many pozzolans used for this purpose are waste products, and thus are quite variable in WO 97/09282 PCT/US96/14326 composition. An example is fly ash, which is the end result of coal burned for electric generation.
Further, sufficient amounts of the pozzolan must be used, or the protection is short lived, or the ASR can actually be made worse. This is particularly true of pozzolans with significant lime contents, such as many fly ashes. In a cementitious system, the Ca:Si ratio is very important to its stability with regard to ASR. The higher the Ca:Si ratio, the less capable the system is of tying up alkali present, and there is more susceptibility to ASR. A low lime content pozzolan will reduce the ratio and give more protection from increased alkalies. However, a high lime content pozzolan will not give this protection, and further, since pozzolans carry their own alkalies into the system, this can easily make the situation worse.
Still another recommendation is the use a lithium-based admixture. Use of lithium was shown to be effective in ASR inhibition in 1951 (see W.J. McCoy and A.G. Caldwell, "New approach to inhibiting alkaliaggregate expansion," J.Amer.Concrete Institute, 22:693-706 (1951)). See also Y. Sakaguchi, et al., "The inhibiting effect of lithium compounds on alkalisilica reaction," Proceedings, 8th international conference, alkali aggregate reaction, Kyoto, Japan: 229-234 (1989), and the SHRP report.
For example, lithium salts, such as lithium hydroxide monohydrate, have been added to cement at the grinding stage of the cement production. J. Gajda, Development of a cement to inhibit alkali-silica reactivity, Skokie, IL, Portland Cement Association Research and Development Bulletin RD115T (1996). As with the pozzolan blended cements mentioned above, the net effect is basically the same as if the lithium salt were admixed into the concrete separately at the time the concrete was batched. That is, by adding the lithium salt to the cement at the time of grinding, WO 97/09282 PCT/US96/14326 -6neither the cement nor the lithium salt is changed during the process. Rather, the lithium salt and cement are merely blended.
Despite the effectiveness of cement produced in this manner to mitigate ASR, using relatively pure lithium compounds can result in substantial amounts of the lithium (about 50%, as reported in the SHRP Report) being "locked up" in the hydration products of the early hydration reactions of the cement. A substantial portion of the lithium ions, therefore, is unavailable for use in controlling ASR. This generally happens within the first few days of hydration. Still further, the concentration of hydroxyl ion can increase when lithium salts are admixed into concrete and mortars (see the SHRP Report). This can make the job of the lithium ion that much more difficult, and requires more lithium than would otherwise be the case.
In addition, lithium salts, such as lithium carbonate, lithium nitrate, lithium hydroxide and lithium fluoride, can be expensive relative to other concrete additives.
Summary of the Invention The present invention provides a process for producing concrete and mortars which are stabilized against alkali-silica reactivity from alkali containing components. In the invention, lithium bearing ores and ore concentrates are treated to impart lithium release properties thereto and added as a component of concrete. The use of treated lithium bearing ores can mitigate (minimize and/or substantially eliminate)
ASR
that can occur in the resultant concrete. This is turn can minimize and/or prevent deterioration of concrete from ASR.
Lithium is relatively slowly released initially upon addition of the treated lithium bearing ores to a fluidic concrete mixture of cement, aggregate -7and water. Preferably, the treated lithium bearing ores initially release less than 10 percent of the available lithium over the course of 14 days. This can prevent or minimize the ASR mitigating lithium compounds being bound in the hydration compounds, and thus loss of the ASR mitigating component, during cement hydration, which occurs early in the age of concrete. The majority of cement hydration typically occurs within twenty-four hours of initiating the process, and by one month, the bulk of the hydration that the concrete will experience has occurred. Since ASR is generally a relatively slow reaction that can develop over a period of months and even years, releasing lithium slowly after much of the hydration has occurred is a significant advantage.
Although lithium is initially slowly released into the concrete, over time, sufficient lithium is released to provide an ASR mitigating effect.
Preferably, after 60 days, 25 to 40% of the available lithium is released. This is contrast to the lithium release properties of untreated lithium bearing ores, o which, after 60 days, release essentially no lithium, or lithium salts, which immediately release lithium.
Further, lithium-bearing ores include s "siliceous materials which are pozzolanic by nature. In addition, lithium bearing ores are less expensive than lithium salts (which require extracting and purifying lithium from the ores). Still further, less lithium is required to inhibit ASR in the resultant concrete than purified forms of lithium because, as discussed above, the lithium is released slowly and after much of cement hydration has occurred.
The present invention also includes mineral admixtures, concrete and mortar which include the treated lithium bearing ore as a component.
-8- Detailed Description of the Tnvention Lithium bearing ores and ore concentrates useful in practicing the invention include, but are not limited to, lithium aluminum silicates, such as spodumene (Li20OAl 2 03-4SiO 2 petalite (Li20-Al 2 038SiO,), eucryptite (Li20-Al20-2SiO), lithium aluminum phosphate ores, such as amblygonite (LiF-AlPO 4 montebrasite, lepidolite, lithium-bearing clays, and mixtures thereof. As the skilled artisan will appreciate, the term "lithium bearing ore concentrate" refers to lithium bearing ores which have been treated (beneficiated) to concentrate the lithium bearing mineral. For ease of reference, as used herein the term "lithium bearing ores" refers to both beneficiated and non-beneficiated lithium bearing ores.
The lithium bearing ore is treated to impart lithium release properties to the ore when the ore is included as a component of concrete. In contrast, untreated lithium bearing ores do not exhibit lithium .release properties, as demonstrated by the examples below. Preferably, the lithium bearing ore is heated to effect a phase change in the structure of the ore, referred to generally in the art as "decrepitating." In this regard, naturally occurring lithium bearing ore generally exists in an "alpha" configuration (for example, "alpha-spodumene"). When heated, such ores undergo an irreversible phase change to a "beta" configuration ("beta-spodumene").
Lithium bearing ores can be decrepitated by heating the ore at a temperature sufficient and for a time sufficient to produce the phase change, for example, for spodumene, at a temperature of at least 900 0 C, preferably at least 1000°C, for at least an hour, or longer. As the skilled artisan will appreciate, the lithium bearing ore can be decrepitated -8aat varying temperatures and times, depending upon factors such as elements present in the a a..
a.
a.
a.
a.
a a a a *aaa.a -9ore other than lithium, the crystalline structure of the ore, and the like, and such conditions can be readily determined by the skilled artisan. Other techniques also can be used to treat the lithium bearing ore to impart lithium release properties thereto.
The inventors have found that addition of treated lithium bearing ore to a fluid concrete mixture or composition can result in the slow release of lithium into the concrete over time. Preferably, the treated lithium bearing ores initially release less than 10 percent of the available lithium (total amount of lithium present in the ore) over the course of 14 days. However, although lithium is initially slowly released into the concrete, over time, sufficient lithium is released to provide an ASR mitigating effect. Preferably, after 60 days, 25% to 40% of the available lithium is released.
The treated lithium bearing ores are added to the concrete mixture in an amount effective to mitigate the detrimental effects of ASR. Preferably, lithium "bearing ores are added to a concrete mixture in an amount from 0.1% to 60%, more preferably 1% to 40%, and most preferably 5% to 25%, by weight; based on the dry S"weight of the cement component of the concrete. Stated differently, the treated lithium bearing ores are added to the concrete mixture in an amount sufficient to provide molar ratios of lithium to sodium equivalent (Na20 O Na 2 O 0.658 x KO20) of 0.01:1 to 10:1 in the concrete mixture, preferably about 1:10 to 5:1, and more preferably 0.5:1 to 2:1.
The concrete compositions of the invention generally include cement, aggregate, water and treated lithium bearing ores. As used herein, the term "cement" refers to, but is not limited to, hydraulic and alite cements, such as Portland cement; blended cements, such as Portland cement blended with fly ash, blast-furnace slag, pozzolans, and the like, and mixtures thereof; masonry cement; oil well cement; natural cement; alumina cement; expansive cements, and the like, and mixtures thereof. The cement is present in the fluid concrete mixture in an amount between to 20% by weight based on the total weight of the concrete mixture.
Aggregates can include, but are not limited to natural and crushed quarried aggregate, sand, recycled concrete aggregate, glass, and the like, as well as mixtures thereof. Aggregate is present in the fluid concrete mixture in an amount between 75% to by weight, based on the total weight of the concrete mixture.
The fluid concrete mixture also includes water, in an amount ranging from 2% to 10% by weight based on the total weight of the mixture. The fluid 0*00 o concrete mixture also can include other materials as .00* known in the art for imparting various properties to concrete, including, but not limited to, air-entraining 'oo admixtures, water reducing admixtures, accelerating admixtures, pozzolans, such as, but not limited to, fly S"ash, metakaolin, and silica fume, and the like. These agents can be present in conventional amounts.
Although reference has been made to the ***components of concrete, it will be appreciated that the present invention also includes mortar compositions, which generally are similar in composition to concrete, except that mortar is typically made with sand as the sole aggregate, in contrast to concrete which includes larger aggregates. Sand in this sense is aggregate of about .95 cm and smaller in diameter.
Still further, although the process of making concrete has been described above with regard to the WO 97/09282 PCT/US96/14326 -11addition of treated lithium bearing ores to a fluid concrete mixture, the present invention also provides for the addition of such treated lithium bearing ores to cement, which is in turn mixed with other suitable components to form concrete. The treated lithium bearing ores can be added to the cement for example by blending or intergrinding the treated ore with cement.
The present invention will be further illustrated by the following non-limiting examples.
Example 1 To simulate what happens inside the pore solution in concrete, spodumene ore concentrate and decrepitated spodumene ore concentrate were placed in a simulated concrete pore solution at room temperature and samples analyzed for lithium for two months. The simulated pore solution was as follows (weight 0.2% Ca(OH) 2 1.0% NaOH, 2.45% KOH, and 96.35% deionized water. The following table gives the results in ppm lithium: Days Ore Concentrate Decrepitated Ore Concentrate 1 0.05 0.70 4 0.11 1.30 7 0.08 2.17 14 0.11 3.35 60 0.40 18.0 As can be seen from the table, about fifty times as much lithium was available from the decrepitated spodumene as from the untreated concentrate. The amounts used in the experiment were ten grams each of the untreated ore concentrate and the decrepitated material placed in four liters of solution. Both samples included 5% LiO by weight (about 58 ppm total lithium available, if all of the lithium were released). At the end of two months, about one third of the lithium from the decrepitated material had been released, whereas less than one WO 97/09282 PCT/US96/14326 -12percent of the lithium from the untreated ore concentrate was released.
Example 2 To demonstrate the release of lithium ion from these treated ores in cementitious systems, pastes with low and high alkali cement and 5% and decrepitated spodumene ore concentrate were made and the pore solutions extracted over time and analyzed for lithium. For the high alkali case (results are molarity of lithium): Age Control 5% 1 0 0.005 0.005 0 0.022 0.039 0 0.050 0.092 And for the low alkali case: Age Control 5% 1 0 0.004 0.004 0 0.012 0.024 0 0.045 0.086 In both cases, at all ages, the hydroxyl ion was near the original, but slightly less. Thus it was demonstrated that not only was there a slow but significant release, but that there was no extra demand placed on the system by an increase in pH, as would be the case for lithium salts tested under the SHRP program.
Example 3 As an example of more direct demonstration of the ability of the material to control ASR in concrete, concrete prisms were made according to Canadian Standards Association (CSA) A23.2-14A standard for alkali aggregate reactivity testing. Results for two highly reactive materials are given below. The first one from a quarry in New Mexico, is a reactive aggregate containing andesites and rhyollites, and has -13demonstrated severe reactivity even with low alkali cements. The second one from a quarry in Ontario, is a limestone with cherty inclusions, and also has an extensive and well documented history of severe reactions in the field. Results linear expansions) are shown for controls and for 10% replacement of the cement with decrepitated spodumene ore concentrate: Age NM SP (weeks) Control NM 10% Control SP 0 0 0 0 0 4 0.05 0.03 0.01 0 8 0.11 0.04 0.04 0.01 13 0.15 0.05 0.10 0.02 18 0.18 0.07 0.13 0.02 26 0.20 0.08 0.16 0.03 Significant reductions with highly reactive aggregates are thus demonstrated; greater dosages yield greater control of the ASR.
U.S. Patent No. 3,331,695 reports intergrinding spodumene with a portland cement to produce a cement that has accelerated strength gain.
The pozzolanic effect reported in the '695 patent is believed to result from.siliceous materials which are present in spodumene (about 60% silica), which are 9 known in the art to be pozzolanic by nature. Little lithium is released by this type of usage, and thus does not contribute to the pozzolanic effect. JP 62278151 reports reducing ASR by admixing lithium ores into concrete. Again, however, the effect is due to the pozzolanic nature of the material, not to its lithium release.
Neither U.S. Patent No. 3,331,695 nor JP 62278151 teach or recognize the importance of the delayed release of lithium into concrete systems with regard to ASR inhibition. As the above examples demonstrate, essentially none of the lithium from -13auntreated ores is actually released into the concrete.
Accordingly, the process of JP 62278151 is a pozzolanic **4~t
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0e4000 0 WO 97/09282 PCT/US96/14326 -14effect, which is second in effectiveness to a true lithium based control. More than an order of magnitude more lithium can be made to release by treatments such as decrepitation.
The foregoing examples are illustrative of the present invention and are not to be construed as limiting thereof.
Claims (26)
1. A process for making concrete stabilized against alkali-silica reactivity (ASR) from alkali containing components, the process including adding lithium bearing ore treated to release lithium over time into the concrete body and added to a fluid concrete mixture including cement, aggregate, and water in an amount sufficient to minimize ASR.
2. The process of Claim 1, wherein said lithium bearing ore is decrepitated lithium bearing ore.
3. The process of Claim 1, wherein said lithium bearing ore is selected from the group consisting of spodumene, petalite, eucryptite, amblygonite, montebrasite, lepidolite, lithium-bearing clays, and mixtures thereof. 9
4. The process of Claim 1, further comprising prior to said adding step the step of heating lithium bearing ore under conditions sufficient 99** 9 to impart lithium release properties thereto. The process of Claim 4, wherein said heating step includes heating lithium bearing ore under conditions sufficient to effect a phase change in the structure of the ore. 9
6. The process of Claim 4, wherein said heating step includes heating lithium bearing ore at a temperature of at least 900C for at least an hour. temperature of at least 900 0 C for at least an hour.
7. The process of Claim 1, wherein said adding step includes adding lithium bearing ore to the fluid concrete composition in an amount from o oo* *a 7 -16- 0.1% to 60% by weight based on the dry weight of the cement.
8. The process of Claim 1, wherein said adding step includes adding lithium bearing ore to the fluid concrete composition in an amount from 1% to by weight based on the dry weight of the cement.
9. .The process of Claim 1, wherein said adding step includes adding lithium bearing ore to the fluid concrete composition in an amount from 5% to by weight based on the dry weight of the cement. The process of Claim 1, wherein the treated lithium bearing ore releases less than percent of lithium present in the ore after 14 days.
11. The process of Claim 1, wherein the treated lithium bearing ore releases at least 25% of lithium present in the ore after 60 days.
12. A process for making concrete stabilized against alkali-silica reactivity (ASR) from alkali containing components, the process -including adding decrepitated spodumene to a fluid concrete mixture comprising cement, aggregate, and water.
13. The process of Claim 12, further including, prior to said adding stepthe step of heating naturally occurring spodumene at a temperature of at least 900 0 C for at least an hour. -17-
14. The ,process of Claim 12, wherein said adding step includes adding decrepitated spodumene to the fluid concrete composition in an amount from 0.1% to 60% by weight based on the dry weight of the cement. A process for making concrete stabilized against alkali-silica reactivity (ASR) from alkali containing components, the process including adding cement including lithium bearing ore treated to release lithium over time into the concrete body and added to a fluid concrete mixture including aggregate and water in an amount sufficient to minimize ASR.
16. The process of Claim 15, further including prior to said adding stepthe step of blending or intergrinding cement with treated lithium bearing ore.
17. The process of Claim 16, further including prior to said blending or intergrinding step the step of heating lithium bearing ore under conditions sufficient to impart lithium release properties thereto.
18. T.he process of Claim 17, wherein said -heating step includes heating the lithium bearing ore ata temperature of at least 900 0 C for at least an hour. i9. Concrete prepared according to the process of Claim 1. Concrete prepared according to the process of Claim 12. -18-
21. Concrete prepared according to the process of Claim
22. Concrete comprising cement, aggregate, and lithium bearing ore treated to release lithium over time into the concrete body and added to a fluid concrete mixture in an amount sufficient to minimize alkali-silica reactivity (ASR) from alkali containing components thereof.
23. The concrete of Claim 22, wherein said lithium bearing ore is decrepitated lithium bearing ore.
24. The concrete of Claim 22, wherein said lithium bearing ore is selected from the group consisting of spodumene, petalite, eucryptite, amblygonite, montebrasite, lepidolite, lithium-bearing clays, and mixtures thereof.
25. The concrete of Claim 22, wherein said .9 lithium bearing ore is decrepitated spodumene.
26. The concrete of Claim 22, wherein said treated lithium bearing ore is present in an amount from 0.1% to 60% by weight. .9
27. The concrete -of Claim 22, wherein said treated lithium bearing ore is present in an amount from 1% to 40% by weight.
28. The concrete of Claim 22, wherein said treated lithium bearing ore is present in an amount from 5% to 25% by weight. -19-
29. Concrete comprising cement, aggregate, and decrepitated spodumene in an amount sufficient to minimize alkali-silica reactivity (ASR) from alkali containing components thereof. A process for making concrete stabilized against alkali-silica reactivity (ASR), the process including' adding lithium compounds to a fluid concrete mixture including cement, aggregate, and water, said lithium compounds capable of releasing lithium into a concrete composition in ASR mitigating amounts after cement hydration is substantially complete.
31. Concrete prepared according to the process of Claim
32. Concrete.comprising cement, aggregate, and lithium compounds capable of releasing lithium in said concrete in ASR mitigating amounts after cement hydration is substantially complete. DATED this 10* day of NOVEMBER 1999 FMC CORPORATION WATERMARK PATENT AND TRADE MARK ATTORNEYS 4TH FLOOR, DURACK CENTRE 263 ADELAIDE TERRACE, PERTH WESTERN AUSTRALIA *oo
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US347595P | 1995-09-08 | 1995-09-08 | |
US60/003475 | 1995-09-08 | ||
US70955396A | 1996-09-06 | 1996-09-06 | |
US08/709553 | 1996-09-06 | ||
PCT/US1996/014326 WO1997009282A1 (en) | 1995-09-08 | 1996-09-06 | Concrete compositions and processes for controlling alkali-silica reaction in same |
Publications (2)
Publication Number | Publication Date |
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AU7155096A AU7155096A (en) | 1997-03-27 |
AU715970B2 true AU715970B2 (en) | 2000-02-10 |
Family
ID=26671800
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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AU71550/96A Ceased AU715970B2 (en) | 1995-09-08 | 1996-09-06 | Concrete compositions and processes for controlling alkali-silica reaction in same |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0848690A1 (en) |
AU (1) | AU715970B2 (en) |
CA (1) | CA2231183A1 (en) |
WO (1) | WO1997009282A1 (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5656075A (en) * | 1995-05-10 | 1997-08-12 | W. R. Grace & Co.-Conn. | Control of expansion in concrete due to alkali silica reaction |
US5803960A (en) * | 1997-01-17 | 1998-09-08 | The Trustees Of Columbia University In The City Of New York | Glass formula for avoiding ASR |
US5810921A (en) * | 1997-03-03 | 1998-09-22 | The Trustees Of Columbia University In The City Of New York | Use of waste glass in concrete |
JP4642177B2 (en) * | 2000-01-24 | 2011-03-02 | 電気化学工業株式会社 | Sludge reducing material, centrifugal molded body using the same, and manufacturing method thereof |
US6500254B1 (en) | 2000-06-30 | 2002-12-31 | Fmc Corporation | Cements including lithium glass compositions |
GB2444926A (en) * | 2006-12-18 | 2008-06-25 | Robert John Bracher | Coating material containing a lithium-containing silicate mineral |
EP2345626A1 (en) | 2010-01-15 | 2011-07-20 | Sika Technology AG | Coated additive for concrete production |
RU2513873C1 (en) * | 2013-01-15 | 2014-04-20 | Юлия Алексеевна Щепочкина | Mixture for making porous aggregate |
KR102625642B1 (en) * | 2019-03-27 | 2024-01-16 | 와커 헤미 아게 | How to reduce or prevent alkali-aggregate reaction in hardened concrete |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3331695A (en) * | 1964-06-23 | 1967-07-18 | Grace W R & Co | Spodumene accelerated portland cement |
WO1993012052A1 (en) * | 1991-12-19 | 1993-06-24 | Aston Material Services Limited | Improvements in and relating to treatments for concrete |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH0617254B2 (en) | 1986-05-28 | 1994-03-09 | 日産化学工業株式会社 | Method for preventing deterioration of curing concrete |
US5656075A (en) * | 1995-05-10 | 1997-08-12 | W. R. Grace & Co.-Conn. | Control of expansion in concrete due to alkali silica reaction |
-
1996
- 1996-09-06 CA CA002231183A patent/CA2231183A1/en not_active Abandoned
- 1996-09-06 WO PCT/US1996/014326 patent/WO1997009282A1/en not_active Application Discontinuation
- 1996-09-06 AU AU71550/96A patent/AU715970B2/en not_active Ceased
- 1996-09-06 EP EP96932965A patent/EP0848690A1/en not_active Withdrawn
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3331695A (en) * | 1964-06-23 | 1967-07-18 | Grace W R & Co | Spodumene accelerated portland cement |
WO1993012052A1 (en) * | 1991-12-19 | 1993-06-24 | Aston Material Services Limited | Improvements in and relating to treatments for concrete |
Also Published As
Publication number | Publication date |
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WO1997009282A1 (en) | 1997-03-13 |
EP0848690A1 (en) | 1998-06-24 |
AU7155096A (en) | 1997-03-27 |
CA2231183A1 (en) | 1997-03-13 |
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