WO2012170658A1 - Low molar, homogeneously substituted hec for use in cement-based systems - Google Patents
Low molar, homogeneously substituted hec for use in cement-based systems Download PDFInfo
- Publication number
- WO2012170658A1 WO2012170658A1 PCT/US2012/041293 US2012041293W WO2012170658A1 WO 2012170658 A1 WO2012170658 A1 WO 2012170658A1 US 2012041293 W US2012041293 W US 2012041293W WO 2012170658 A1 WO2012170658 A1 WO 2012170658A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cement
- hec
- mortar
- smooth
- based system
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/38—Polysaccharides or derivatives thereof
- C04B24/383—Cellulose or derivatives thereof
Definitions
- the present invention relates to cellulose ether compounds which are useful in cement-based systems, including mortars, for delivering long pot life as well as very high water retention capability at hot temperature while, providing better paste stability, optimized setting behavior for hot as well as cold temperature compared to typical, commercial cellulose ether compounds.
- cellulose ethers are typically used as water retention agents to achieve good water retention of the resulting wet mortar. Water retention is needed to control the water content for proper hydration of the mortar, including any binder, and to achieve good workability of the mortar. Secondary beneficial effects resulting from correct hydration performance of the mortar are proper strength development of the mortar and avoidance of cracks and sanding effects of the applied mortar layer.
- Typical cellulose ethers used for dry mortar application are methyl hydroxyethyl cellulose (MHEC) and methyl hydroxypropyl cellulose (MHPC).
- Mortars containing MHEC and/or MHPC exhibit the desired properties of strength development, avoidance of cracks and sanding effects.
- MHEC and MHPC typically do not afford mortars with hot temperature stability. Due to their hydrophobic character, they either do not properly dissolve at elevated temperatures or they precipitate and consequently become inactive upon temperature increase in the mortar.
- HEC hydroxyethyl cellulose
- HEC hydroxyethyl cellulose
- the present invention relates to a cement-based system, such as a mortar, having improved pot life and open time under hot weather conditions.
- the cement-based system of the present invention contains cement
- the cement-based system also contains sufficient water to provide appropriate consistency to the cement- based system, such as a mortar.
- the rheology control agent of the cement based system may include a second cellulose ether which is less hydrophilic than said smooth type HEC.
- the rheology control agent is present in an amount of about 0.10 % to about 1 % by weight, based on the weight of the cement- based system on a dry basis.
- the ratio of the second cellulose ether to hydroxyethylcellulose in the blend is in the range of about 10:90 to about 90: 10 by weight.
- the second cellular ether will be
- Figure 1 is a graph of the viscosity at 40°C of different MHEC/HEC blends (50:50) in EIFS.
- Figure 2 is a graph of the viscosity at 20°C of different CEs as well as MHEC/HEC blends (50:50) in EIFS.
- the present invention relates to a cellulose ether product for use in cement-based systems such as mortar applications under hot climate conditions.
- the cellulose ether product of the present invention improves various important application process-related parameters like water retention, pot life, and open time at high temperatures.
- “smooth-type” is characterized by a lower percent of released glucose compared to commercial HEC that correlates with lower percent of un-substituted AGUs and lower MS/DS ratio which is indicative or more homogeneous distribution of EO substitution along cellulose backbone in "smooth-type" substituted HEC than in standard commercial HEC.
- the low molar substitution smooth-type HEC of use in the present invention may be the water-soluble, low HE-MS HECs and modified HECs taught in US Application Publication No.
- the low MS, smooth-type, HEC of use in the present invention provides the hot temperature stability of standard commercial HECs while exhibiting improved wet mortar structure, higher aqueous viscosities and water retention capabilities. Moreover, due to its low, but more uniform, ethylene oxide substitution, the use of low MS, smooth-type, HEC results in cement-based mortars exhibiting acceptable setting behavior at room, as well as at elevated temperatures.
- the low MS, smooth-type HEC may also be blended with other cellulose ethers (CE) that are less hydrophilic, such as methylhydroxyethylcellulose (MHEC) or methylhydroxypropylcellulose (MHPC) for use in cement-based systems.
- CE cellulose ethers
- MHEC methylhydroxyethylcellulose
- MHPC methylhydroxypropylcellulose
- the CE/HEC-blends containing low MS, smooth-type, HEC provide advantages in comparison to blends containing standard commercial HECs. Since low MS, smooth-type, HEC provides improved air void stabilization and better mortar structure than standard commercial grade HECs, a higher percentage of HEC may be used in CE/HEC blends while still achieving acceptable mortar structure known for cement-based systems containing only MHEC or MHPC.
- the low MS, smooth-type, HEC results in cement-based systems exhibiting higher aqueous viscosities compared to HEC with higher MS.
- Use of low MS, smooth-type, HEC provides advantages of either achieving higher aqueous HEC viscosities and improved water retention capabilities or permitting the use of lower viscosity cellulose furnish to achieve similar viscosities HEC to standard commercial HEC grades.
- the cement-based systems contain various components including a cement, a filler/aggregate, a rheology control agent containing the low MS, smooth-type, HEC and may also include other CE as a blend including a blend of methylhydroxyethylcellulose and methylhydroxypropylcellulose, and sufficient water to provide appropriate consistency to the cement-based system.
- the rheology control agent may be present in an amount of about 0.1 % to about 1 % by weight, based on the weight of the cement-based mortar on a dry basis.
- cement is intended to include, but is not limited to: hydraulic cements, such as Portland Cement, Composite Cements, which are blended cements containing Portland Cement and other components like, e.g., fly ash, blast furnace slag, calcium carbonate, pozzolans, and the like, and mixtures thereof , or alumina cement, and the like, and mixtures thereof.
- suitable filler/aggregates such as silica sands, calcium carbonate, dolomite, as well as lightweight aggregates such as perlites, polystyrene beads,
- the proportion of filler/aggregate in the mortar is preferably between 50% and around 85%, more preferably between 60% and around 80%, and most preferably between 65% and around 75% by weight, based on the total dry ingredients.
- the rheology control agent of use in the cement-based system of the present invention may be the low MS, smooth-type, HEC or a blend of the low MS, smooth-type, HEC with another CE such as methylhydroxyethylcellulose (MHEC) or hydroxypropylcellulose (MHPC).
- the blend of MHEC and low MS, smooth-type, HEC as rheology control agent present in the cement-based system may be in a ratio of MHEC to low MS, smooth-type, HEC of about 10:90 to about 90: 10, preferably about 30:70 to about 70:30 or about 50:50.
- Typical cellulose ethers such as methylhydroxypropylcellulose (MHPC) or
- methylhydroxyethylcellulose perform well at temperatures up to 40°C, but at higher temperatures, water retention capability of cement-based systems, such as skim coats or EIFS mortars relying solely on these typical cellulose ethers suffers significantly. Crack formation and powdering effects observed in EIFS mortars are the consequences of insufficient water retention.
- a typical cement-based skim coat or EIFS mortar can contain some or all of the following components:
- sample is hydrolyzed to glucose and substituted glucose by treating with 3 milliliters of 72% sulfuric acid, diluting with water to 0.36 molar acid, and refluxing for five hours.
- the solution is analyzed by ion exchange chromatography with pulsed amperometric detection with a high pH eluent.
- concentration of unsubstituted anhydroglucose is quantified after calibration with a glucose standard.
- HEC Molar Substitution Analysis HE-MS by sealed tube Zeisel - gas chromatography
- the weight corrected for total volatiles and salt content is placed in a pressure tube 57% aqueous HI, and an o-xylene solution of the internal standard 2,5-dimethylhexane and heated at 185 degrees Celsius for 2 hours in an aluminum block.
- the ethyl iodide formed from the hydroxyethyl functional group is extracted into the xylene layer as it is formed.
- After cooling the xylene layer is analyzed by gas chromatography using a 30 m x 0.53 mm id column containing a 2.65 micrometer bonded methyl silicone stationary phase and a flame ionization detector.
- the percentage of ethyl iodide formed is calculated using its response relative to the 2,5-dimethylhexane internal standard, and the molecular substitution (MS) is calculated from that result.
- Aqueous 1 .0 wt% HEC solutions were prepared by dissolving about 2.5 grams of moisture corrected HEC powder for at least 16 hours. The viscosity of the sample solution is measured with a Brookfield viscometer with a LVT spindle number 4 at 30 rpm at 25 °C.
- Pot life is essential to ensure proper workability of the cement-based system, such as mortars, of a sufficient period of time. While having temperature stability, a user can avoid premature hardening of the cement-based system in the work bucket, complaints regarding the addition of too much water to the cement- based system, and undue waste of resulting from premature hardening of material.
- the benefits of increased pot life for cement-based systems include a longer period of time where the cement-based system remains workable and a higher application efficiency.
- Paste stability of the mortar was evaluated visual in the cup and on the plaster board after 90 minutes.
- Cellulose ethers are surface active additives which reduce mortar density. Cellulose ether entrains very small air pores into the mortar. It is essential to stabilize air pores as long as possible. Air pores of mortar with poor paste stability coagulates to greater voids. As a consequence workability of the mortar as well as its surface appearance suffers.
- Paste stability of regular HEC in cement-based skim coat is a critical issue.
- Table 5 illustrates that blends containing low MS, smooth-type HEC provide improved application performance to cement-based skim coat with respect to paste stability and workability.
- Cement-based skim coats containing the low MS, smooth-type HEC demonstrate the mentioned application advantages over standard commercial HEC while still having hot temperature stability.
- Pot life of a cement-based system is important to ensure proper workability over a long period of time (1 -4 hours).
- MHPC does not meet user requirements, especially at high temperatures.
- a blend of MHEC2 and HEC (50:50) improved pot life significantly.
- mortar consistency was maintained for a longer time period. While having temperature stability premature mortar hardening in the bucket was avoided (less loss of material due to premature hardening).
- the benefits of increased pot life for cement-based systems include a longer period of time where the cement-based system remains workable and higher application efficiency.
- Example 3 standard mixing for EIFS basic mixture was done. After maturing time 15sec, remixing on stepl with a hand mixer was done. Then, the mortar was filled into a metal ring, which was positioned on a piece of filter paper. Between the filter paper and the metal ring, a thin fiber fleece was placed while the filter paper was lying on a plastic plate. The weight of the arrangement was measured before and after the mortar was filled in. Thus, the weight of the wet mortar was calculated. Moreover, the weight of the filter paper was known. The complete filled system was placed in the heater at 70°C for a soaking time of 5 min. After soaking, the weight of the filter paper was measured again. Now, the water retention [%] was calculated.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12727079.1A EP2718242A1 (en) | 2011-06-09 | 2012-06-07 | Low molar, homogeneously substituted hec for use in cement-based systems |
BR112013031480A BR112013031480A2 (en) | 2011-06-09 | 2012-06-07 | homogeneously substituted low molar hec for use in cement-based systems |
MX2013013613A MX341940B (en) | 2011-06-09 | 2012-06-07 | Low molar, homogeneously substituted hec for use in cement-based systems. |
KR1020147000280A KR20140034897A (en) | 2011-06-09 | 2012-06-07 | Low molar, homogeneously substituted hec for use in cement-based systems |
JP2014514624A JP5922763B2 (en) | 2011-06-09 | 2012-06-07 | Low molar uniformly substituted HEC for use in cementitious systems |
CN201280028318.XA CN103596902B (en) | 2011-06-09 | 2012-06-07 | For the low mole of HEC evenly replaced of cement-based systems |
RU2013158815/03A RU2013158815A (en) | 2011-06-09 | 2012-06-07 | HYDROXYETHYL CELLULOSE WITH A LOW DEGREE OF MOLAR SUBSTITUTION AND UNIFORM DISTRIBUTION OF SUBSTITUTES IN THE MAIN CHAIN FOR APPLICATION IN CEMENT-BASED SYSTEMS |
ZA2014/00150A ZA201400150B (en) | 2011-06-09 | 2014-01-08 | Low molar, homogeneously substituted hec for use in cement-based systems |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201161520409P | 2011-06-09 | 2011-06-09 | |
US61/520,409 | 2011-06-09 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012170658A1 true WO2012170658A1 (en) | 2012-12-13 |
Family
ID=46246312
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2012/041293 WO2012170658A1 (en) | 2011-06-09 | 2012-06-07 | Low molar, homogeneously substituted hec for use in cement-based systems |
Country Status (11)
Country | Link |
---|---|
US (1) | US8430957B2 (en) |
EP (1) | EP2718242A1 (en) |
JP (1) | JP5922763B2 (en) |
KR (1) | KR20140034897A (en) |
CN (1) | CN103596902B (en) |
AR (1) | AR086888A1 (en) |
BR (1) | BR112013031480A2 (en) |
MX (1) | MX341940B (en) |
RU (1) | RU2013158815A (en) |
WO (1) | WO2012170658A1 (en) |
ZA (1) | ZA201400150B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10370459B2 (en) | 2013-03-15 | 2019-08-06 | Hercules Llc | Alkyl hydroxyalkyl cellulose ethers, methods of making, and use in cements and mortars |
WO2018130913A2 (en) | 2017-01-15 | 2018-07-19 | Butler Michael George | Apparatuses and systems for and methods of generating and placing zero-slump-pumpable concrete |
US11739026B2 (en) * | 2020-05-15 | 2023-08-29 | TPI Polene Public Company Limited | Lightweight fiber-reinforced cement material |
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US4470463A (en) * | 1983-01-27 | 1984-09-11 | The Dow Chemical Company | Well treating process and composition |
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US20060199742A1 (en) | 2005-03-02 | 2006-09-07 | Arisz Petrus Wilhelmus F | Water-soluble, low substitution hydroxyethylcellulose, derivatives thereof, process of making, and uses thereof |
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-
2012
- 2012-05-31 US US13/484,982 patent/US8430957B2/en active Active
- 2012-06-07 BR BR112013031480A patent/BR112013031480A2/en not_active IP Right Cessation
- 2012-06-07 MX MX2013013613A patent/MX341940B/en active IP Right Grant
- 2012-06-07 EP EP12727079.1A patent/EP2718242A1/en not_active Withdrawn
- 2012-06-07 KR KR1020147000280A patent/KR20140034897A/en not_active Application Discontinuation
- 2012-06-07 WO PCT/US2012/041293 patent/WO2012170658A1/en active Application Filing
- 2012-06-07 RU RU2013158815/03A patent/RU2013158815A/en not_active Application Discontinuation
- 2012-06-07 CN CN201280028318.XA patent/CN103596902B/en not_active Expired - Fee Related
- 2012-06-07 JP JP2014514624A patent/JP5922763B2/en active Active
- 2012-06-08 AR ARP120102054A patent/AR086888A1/en unknown
-
2014
- 2014-01-08 ZA ZA2014/00150A patent/ZA201400150B/en unknown
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US4470463A (en) * | 1983-01-27 | 1984-09-11 | The Dow Chemical Company | Well treating process and composition |
US4462836A (en) * | 1983-02-15 | 1984-07-31 | Gulf Oil Corporation | Cement composition and method of cement casing in a well |
US4687516A (en) * | 1984-12-11 | 1987-08-18 | Halliburton Company | Liquid fluid loss control additive for oil field cements |
EP0520413A2 (en) * | 1991-06-25 | 1992-12-30 | Jdc Corporation | Concrete composition |
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Also Published As
Publication number | Publication date |
---|---|
MX2013013613A (en) | 2014-01-08 |
CN103596902A (en) | 2014-02-19 |
US8430957B2 (en) | 2013-04-30 |
KR20140034897A (en) | 2014-03-20 |
AR086888A1 (en) | 2014-01-29 |
US20120312195A1 (en) | 2012-12-13 |
CN103596902B (en) | 2016-04-13 |
JP2014516022A (en) | 2014-07-07 |
EP2718242A1 (en) | 2014-04-16 |
JP5922763B2 (en) | 2016-05-24 |
MX341940B (en) | 2016-09-08 |
ZA201400150B (en) | 2015-09-30 |
RU2013158815A (en) | 2015-07-20 |
BR112013031480A2 (en) | 2016-12-13 |
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