U.S. patent application number 16/485710 was filed with the patent office on 2020-02-20 for early strength enhancement of cements.
The applicant listed for this patent is GCP Applied Technologies Inc.. Invention is credited to Leslie J. Buzzell, Josephine H. Cheung, Byong-Wa Chun, Wee Fuk Lai, David F. Myers, Ernie Rocha, Denise A. Silva.
Application Number | 20200055775 16/485710 |
Document ID | / |
Family ID | 60480372 |
Filed Date | 2020-02-20 |
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United States Patent
Application |
20200055775 |
Kind Code |
A1 |
Silva; Denise A. ; et
al. |
February 20, 2020 |
EARLY STRENGTH ENHANCEMENT OF CEMENTS
Abstract
A method of making a cement composition, comprising grinding a
cement clinker and a strength-enhancing agent, thereby producing a
hydraulic cementitious powder, wherein the strength-enhancing agent
is present in the hydraulic cementitious powder in an amount of
from 0.001% to 0.09% based on dry weight of the hydraulic
cementitious powder. The strength-enhancing agent is a compound
represented by the following structural formula (I). The
definitions of variables R.sup.1, R.sup.2, and R.sup.3 as well as
R.sup.10, R.sup.20, and R.sup.30 are provided herein.
Inventors: |
Silva; Denise A.; (Los
Alamitos, CA) ; Cheung; Josephine H.; (Lexington,
MA) ; Myers; David F.; (Somerville, MA) ;
Chun; Byong-Wa; (Honolulu, HI) ; Rocha; Ernie;
(Merrimack, NH) ; Lai; Wee Fuk; (Singapore,
SG) ; Buzzell; Leslie J.; (Burlington, MA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
GCP Applied Technologies Inc. |
Cambridge |
MA |
US |
|
|
Family ID: |
60480372 |
Appl. No.: |
16/485710 |
Filed: |
October 25, 2017 |
PCT Filed: |
October 25, 2017 |
PCT NO: |
PCT/US2017/058226 |
371 Date: |
August 13, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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62508636 |
May 19, 2017 |
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62458380 |
Feb 13, 2017 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C09C 1/021 20130101;
C04B 28/04 20130101; Y02W 30/92 20150501; C04B 20/026 20130101;
C04B 2103/14 20130101; C04B 24/16 20130101; C04B 2103/52 20130101;
C04B 7/52 20130101; C04B 24/122 20130101; C04B 24/123 20130101;
C04B 24/38 20130101; C04B 24/121 20130101; C04B 2103/60 20130101;
B02C 23/18 20130101; C09C 1/02 20130101; B21B 27/027 20130101; C09C
3/08 20130101; Y02P 40/20 20151101; Y02W 30/94 20150501; C04B
24/005 20130101; C04B 24/10 20130101; C04B 24/02 20130101; C04B
40/0039 20130101; B02C 23/06 20130101; C09C 1/025 20130101; C04B
24/06 20130101; C04B 7/522 20130101; C09C 3/041 20130101; C04B
28/04 20130101; C04B 14/10 20130101; C04B 14/28 20130101; C04B
18/08 20130101; C04B 18/141 20130101; C04B 24/123 20130101; C04B
2103/0088 20130101; C04B 2103/12 20130101; C04B 2103/22 20130101;
C04B 2103/52 20130101; C04B 28/04 20130101; C04B 14/10 20130101;
C04B 14/28 20130101; C04B 18/08 20130101; C04B 18/141 20130101;
C04B 22/124 20130101; C04B 22/14 20130101; C04B 24/02 20130101;
C04B 24/04 20130101; C04B 24/06 20130101; C04B 24/10 20130101; C04B
24/122 20130101; C04B 24/123 20130101; C04B 2103/0088 20130101;
C04B 40/0039 20130101; C04B 22/10 20130101; C04B 22/14 20130101;
C04B 22/16 20130101; C04B 24/02 20130101; C04B 24/04 20130101; C04B
24/06 20130101; C04B 24/085 20130101; C04B 24/10 20130101; C04B
24/12 20130101; C04B 24/122 20130101; C04B 24/123 20130101; C04B
24/124 20130101; C04B 2103/302 20130101; C04B 2103/304 20130101;
C04B 20/026 20130101; C04B 14/28 20130101; C04B 20/026 20130101;
C04B 22/143 20130101 |
International
Class: |
C04B 7/52 20060101
C04B007/52; C04B 24/00 20060101 C04B024/00; C04B 24/38 20060101
C04B024/38; C04B 24/12 20060101 C04B024/12; C04B 24/06 20060101
C04B024/06 |
Claims
1. A method of making a cement composition, comprising: grinding a
cement clinker and a strength-enhancing agent, thereby producing a
hydraulic cementitious powder, wherein: the strength-enhancing
agent is present in the hydraulic cementitious powder in an amount
of from 0.001% to 0.09% based on dry weight of the hydraulic
cementitious powder, the strength-enhancing agent is a compound
represented by the following structural formula: ##STR00017##
wherein: R.sup.1 is (C.sub.1-C.sub.4)alkyl-OH; and R.sup.2 and
R.sup.3, each independently, is (C.sub.0-C.sub.3)alkyl-COOR*,
wherein R* is H, Na.sup.+, K.sup.+, or 1/2 Ca.sup.++.
2. The method of claim 1, further including adding to the cement
clinker at least one supplemental cementitious material selected
from the group consisting of: fly ash, granulated blast furnace
slag, limestone, calcined clay, natural pozzolan and artificial
pozzolan.
3. The method of claim 1, wherein the cement clinker includes
C.sub.3A in an amount of 0.3% to 9.0% based on dry weight of cement
clinker.
4. The method of claim 1, further comprising grinding with the
strength enhancement agent and the cement clinker at least one
supplemental component selected from a grinding aid, a set
retarding agent, or a set accelerating agent.
5. The method of claim 1, further comprising grinding with the
strength enhancement agent and the cement clinker at least one
grinding aid, and further wherein: the strength enhancement agent
is present in the amount of from 0.001% to 0.03% based on dry
weight of the hydraulic cementitious powder, and the at least one
grinding aid is added in the amount of from 0.001% to 0.06% based
on dry weight of the hydraulic cementitious powder.
6. The method of claim 1, further comprising grinding with the
strength enhancement agent and the cement clinker at least one
grinding aid and a set retarding agent, wherein: the strength
enhancement agent is present in the amount of 0.001-0.03% based on
dry weight of the hydraulic cementitious powder; the at least one
grinding aid is added in the amount of from 0.001% to 0.06% based
on dry weight of the hydraulic cementitious powder; the set
retarding agent is added in the amount of 0.001-0.03% based on dry
weight of the hydraulic cementitious powder.
7. The method of claim 1, further comprising grinding with the
strength enhancement agent and the cement clinker at least one
grinding aid and a set accelerating agent, wherein: the strength
enhancement agent is present in the amount of from 0.001% to 0.03%
based on dry weight of the hydraulic cementitious powder, the at
least one grinding aid is added in the amount of from 0.001 to
0.06% based on dry weight of the hydraulic cementitious powder, the
set accelerating agent is added in the amount of from 0.001% to
0.2% based on dry weight of the hydraulic cementitious powder.
8. The method of claim 1, further comprising grinding with the
strength enhancement agent and the cement clinker at least one
grinding aid, a set retarding agent, and a set accelerating agent,
wherein: the strength enhancement agent is present in the amount of
from 0.001% to 0.03% based on dry weight of the hydraulic
cementitious powder, the at least one grinding aid is added in the
amount of from 0.001% to 0.06% based on dry weight of the hydraulic
cementitious powder, the set retarding agent is added in the amount
of from 0.001% to 0.03% based on dry weight of the hydraulic
cementitious powder, and the set accelerating agent is added in the
amount of 0.001% to 0.2% based on dry weight of the hydraulic
cementitious powder.
9. The method of claim 5, wherein the grinding aid is one or more
of a glycol, glycerin, alkanolamine, acetic acid or an acetic acid
salt.
10. The method of claim 6, wherein the set retarding agent is one
or more of a gluconate salt, a molasses, sucrose, or a corn
syrup.
11. The method of claim 7, wherein the set accelerating agent is
one or more of a thiocyanate salt or a chloride salt.
12. (canceled)
13. The method of claim 4 wherein the strength enhancing agent is
EDG or a salt thereof, the grinding aid is the glycol, the set
retarding agent is sodium gluconate, and the set accelerating agent
is sodium thiocyanate.
14. The method of claim 1, further including grinding the cement
clinker and the strength-enhancing agent with an alkali
sulfate.
15. The method of claim 1, wherein the content of Na.sub.2O
equivalent in the hydraulic cementitious material is less than or
equal to 0.7% by weight of the hydraulic cementitious powder.
16. A composition prepared by the method of claim 1.
17. An additive composition, comprising: (A) a strength-enhancing
agent represented by the following structural formula: ##STR00018##
wherein: R.sup.1 is a (C.sub.1-C.sub.4)alkyl-OH; and R.sup.2 and
R.sup.3, each independently, is a (C.sub.0-C.sub.3)alkyl-COOR*,
wherein R* is H, Na.sup.+, K.sup.+, or 1/2 Ca.sup.++; and (B) at
least one grinding aid selected from one or more of a glycol,
glycerin, or acetic acid or an acetic acid salt, wherein the
additive composition is a liquid.
18. The additive composition of claim 17, wherein the weight ratio
of the strength enhancing agent to the grinding aid is from 1:9 to
9:1.
19. The additive composition of claim 17, further comprising a set
retarding agent, a set accelerating agent, or a mixture
thereof.
20. The additive composition of claim 17, wherein the strength
enhancing agent is N-(2-hydroxyethyl)iminodiacetic acid (EDG) or a
salt thereof.
21. The additive composition of claim 17, wherein the at least one
grinding aid is diethylene glycol.
22. The additive composition of claim 17, further comprising sodium
gluconate or sodium thiocyanate.
23. The additive composition of claim 17, further comprising an
alkali sulfate.
24. A cementitious composition comprising a cementitious binder
obtained by grinding a cement clinker with the additive composition
of claim 17.
25. A cement composition, comprising: a hydraulic cementitious
powder; a strength-enhancing agent, said strength-enhancing agent
being present in an amount of from 0.001% to 0.09% based on dry
weight of the hydraulic cementitious powder, wherein the
strength-enhancing agent is a compound represented by the following
structural formula: ##STR00019## wherein: R.sup.1 is a
(C.sub.1-C.sub.4)alkyl-OH; and R.sup.2 and R.sup.3, each
independently, is a (C.sub.0-C.sub.3)alkyl-COOR*, wherein R* is H,
Na.sup.+, K.sup.+, or 1/2 Ca.sup.++; and at least one grinding aid
selected from a glycol, glycerin, or acetic acid or an acetic acid
salt.
26. An additive composition for use in grinding with a cement
clinker, said composition comprising: (A) a strength-enhancing
agent represented by the following structural formula: ##STR00020##
wherein: R.sup.1 is a (C.sub.1-C.sub.4)alkyl-OH; and R.sup.2 and
R.sup.3, each independently, is a (C.sub.0-C.sub.3)alkyl-COOR*,
wherein R* is H, Na.sup.+, K.sup.+, or 1/2 Ca.sup.++; and (B) at
least one grinding aid selected from one or more of a glycol,
glycerin, or acetic acid or a salt thereof, wherein the additive
composition is a liquid.
27. A mixture of a cement clinker and the additive composition of
claim 17.
28. A method of claim 1, wherein the strength-enhancing agent is
made by a process comprising: reacting a monohaloacetic acid chosen
from monochloroacetic acid and monobromoacetic acid, or a salt
thereof, with a alkanolamine chosen from ethanolamine,
isopropanolamine, and isobutanolamine under alkaline conditions to
generate the strength-enhancing agent represented by the structural
formula ##STR00021## wherein: R.sup.1 is (C.sub.1-C.sub.4)alkyl-OH;
R.sup.2 and R.sup.3, each independently, represent
--CH.sub.2COO.sup.-R*, and R* is H, Na.sup.+, K.sup.+, or 1/2
Ca.sup.++.
29. The method of claim 28, wherein the haloacetic acid or its salt
is chloroacetic acid or its salt, and R.sup.1 is
--CH.sub.2CH.sub.2OH.
30. A method for making a strength-enhancing agent, comprising:
reacting a haloacetic acid chosen from one or more of a
chloroacetic acid and a bromoacetic acid, or a salt thereof, with
one or more alkanolamines of the structural formula (I)
##STR00022## under alkaline conditions, to generate the
strength-enhancing agent represented by structural formula (II)
##STR00023## wherein: each R.sup.10 is independently chosen from H,
(C.sub.1-C.sub.4)alkyl-OH, provided that in structural formula (I)
at least one group R.sup.10 is not H; R.sup.20 is chosen from
(C.sub.1-C.sub.4)alkyl-OH, and --C(R.sup.4).sub.2COO.sup.-M.sup.+;
and R.sup.30 is --C(R.sup.4).sub.2COO.sup.-M.sup.+; each R.sup.4 is
independently chosen from hydrogen, Br, and Cl; and M.sup.+ is
H.sup.+, Na.sup.+, K.sup.+, or 1/2 Ca.sup.++.
31. The method of claim 30, wherein: the chloroacetic acid is
monochloracetic acid or a salt thereof; the compound represented by
structural formula (I) is ethanolamine represented by the following
structural formula HO--CH.sub.2--CH.sub.2--NH.sub.2; and the
strength-enhancing agent represented by structural formula (II) is
sodium ethanol-diglycine ##STR00024## wherein the monochloracetic
acid or a salt thereof and the ethanolamine are reacted in the
presence of sodium hydroxide at above room temperature.
32. A strength-enhancing agent made by the methods according to
claim 28.
33. An additive composition, comprising: a first component; and a
cement additive component wherein: the cement additive component is
one or more agents chosen from a glycol, glycerol, acetic acid or a
salt thereof, an alkanolamine, an amine, a carbohydrate, a
water-reducing additive, an air-entraining agent, a chloride salt,
a nitrite salt, a nitrate salt, and a thiocyanate salt; and the
first component is prepared by reacting a haloacetic acid chosen
from one or more of a chloroacetic acid and a bromoacetic acid, or
a salt thereof, with one or more alkanolamines of the structural
formula (I) ##STR00025## under alkaline conditions, to generate the
first component represented by structural formula (II) ##STR00026##
wherein: each R.sup.10 is independently chosen from H,
(C.sub.1-C.sub.4)alkyl-OH, provided that in structural formula (I)
at least one group R.sup.10 is not H; R.sup.20 is chosen from
(C.sub.1-C.sub.4)alkyl-OH, and --C(R.sup.4).sub.2COO.sup.-M.sup.+;
and R.sup.30 is --C(R.sup.4).sub.2COO.sup.-M.sup.+; each R.sup.4 is
independently chosen from hydrogen, Br, and Cl; and M.sup.+ is
H.sup.+, Na.sup.+, 1/2 Ca.sup.++.
34. The additive composition of claim 33, wherein: the chloroacetic
acid is monochloracetic acid or a salt thereof; the compound
represented by structural formula (I) is ethanolamine represented
by the following structural formula
HO--CH.sub.2--CH.sub.2--NH.sub.2; and the strength-enhancing agent
represented by structural formula (II) is sodium ethanol-diglycine
##STR00027## wherein the monochloracetic acid or a salt thereof and
the ethanolamine are reacted in the presence of sodium hydroxide at
above room temperature.
35. The additive composition of claim 33, wherein the additive
composition is in liquid form.
36. A concrete composition, comprising: the additive composition of
claim 33, cement; a fine aggregate; a coarse aggregate, and at
least one supplemental cementitious material chosen from fly ash,
granulated blast furnace slag, limestone, calcined clay, natural
pozzolan, and artificial pozzolan.
37. A method of making a cement composition, comprising: reacting a
monohaloacetic acid chosen from monochloroacetic acid and
monobromoacetic acid, or a salt thereof, with a alkanolamine chosen
from ethanolamine, isopropanolamine, and isobutanolamine under
alkaline conditions to generate the strength-enhancing agent
represented by the structural formula ##STR00028## wherein: R.sup.1
is (C.sub.1-C.sub.4)alkyl-OH; and R.sup.2 and R.sup.3, each
independently, represent --CH.sub.2COO.sup.-R*, wherein R* is H,
Na.sup.+, K.sup.+, or 1/2 Ca.sup.++ thereby preparing a reaction
mixture; adding the reaction mixture without purification to a
cement clinker; and grinding the cement clinker and the reaction
mixture, thereby producing a hydraulic cementitious powder.
38. The method of claim 4, further comprising grinding with the
strength enhancement agent and the cement clinker at least one
grinding aid, and further wherein: the strength enhancement agent
is present in the amount of from 0.001% to 0.03% based on dry
weight of the hydraulic cementitious powder, and the at least one
grinding aid is added in the amount of from 0.001% to 0.1% based on
dry weight of the hydraulic cementitious powder.
39. The method of claim 4, further comprising grinding with the
strength enhancement agent and the cement clinker at least one
grinding aid and a set retarding agent, wherein: the strength
enhancement agent is present in the amount of 0.001-0.03% based on
dry weight of the hydraulic cementitious powder; the at least one
grinding aid is added in the amount of from 0.001% to 0.1% based on
dry weight of the hydraulic cementitious powder; the set retarding
agent is added in the amount of 0.001-0.03% based on dry weight of
the hydraulic cementitious powder.
40. The method of claim 4, further comprising grinding with the
strength enhancement agent and the cement clinker at least one
grinding aid and a set accelerating agent, wherein: the strength
enhancement agent is present in the amount of from 0.001% to 0.03%
based on dry weight of the hydraulic cementitious powder, the at
least one grinding aid is added in the amount of from 0.001 to 0.1%
based on dry weight of the hydraulic cementitious powder, the set
accelerating agent is added in the amount of from 0.001% to 0.2%
based on dry weight of the hydraulic cementitious powder.
41. The method of claim 4, further comprising grinding with the
strength enhancement agent and the cement clinker at least one
grinding aid, a set retarding agent, and a set accelerating agent,
wherein: the strength enhancement agent is present in the amount of
from 0.001% to 0.03% based on dry weight of the hydraulic
cementitious powder, the at least one grinding aid is added in the
amount of from 0.001% to 0.1% based on dry weight of the hydraulic
cementitious powder, the set retarding agent is added in the amount
of from 0.001% to 0.03% based on dry weight of the hydraulic
cementitious powder, and the set accelerating agent is added in the
amount of 0.001% to 0.2% based on dry weight of the hydraulic
cementitious powder.
42. The method of claim 1, further including grinding the cement
clinker and the strength-enhancing agent with an alkali sulfate
and/or an alkali carbonate.
43. (canceled)
44. (canceled)
45. (canceled)
46. (canceled)
47. (canceled)
48. (canceled)
49. (canceled)
50. (canceled)
51. (canceled)
52. (canceled)
Description
RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional
Application No. 62/458,380, filed on Feb. 13, 2017 and U.S.
Provisional Application No. 62/508,636, filed on May 19, 2017. The
entire teachings of the above applications are incorporated herein
by reference.
BACKGROUND OF THE INVENTION
[0002] For cementitious compositions such as ready-mix, precast, or
prestress concrete, for which it is desired to expedite manufacture
or to obtain a concrete that can be subjected quickly to foot or
car traffic, the concrete industry has prized the ability to obtain
early compressive strength. Early strength is also important for
applications that use bagged cements because it allows the users to
obtain a minimum strength. The industry typically refers to early
strength in terms of the compressive strength of the mortar and
concrete within 1-3 days after mixing the cementitious material
with water to initiate the curing reaction by which the composition
hardens into a structure. Optimizing the compressive strength of
hydraulic cementitious materials through the use of chemical
admixtures has been studied in the engineering and chemical arts.
While early strength cements are available, they are not always
suitable for a particular task. Furthermore, certain chemical
additives can impart undesirable characteristics to the cement. As
such, there is a need for a chemical additive for hydraulic
cementitious materials that can increase early compressive
strength.
SUMMARY OF THE INVENTION
[0003] It has now been discovered that certain amino acid
derivatives that include a carboxyl group (in either acid or salt
form) and an alcohol group, such as ethanol diglycinate (EDG),
surprisingly imparts early strength to certain cement compositions
comprising hydraulic cementitious materials. In example
embodiments, the hydraulic cementitious materials are preferably
characterized by having not more than 9% tricalcium aluminate
(C.sub.3A) content.
[0004] In the first example embodiment, the present invention is a
method of making a cement composition. The method comprises
grinding a cement clinker and a strength-enhancing agent, thereby
producing a hydraulic cementitious powder. The strength-enhancing
agent is present in the hydraulic cementitious powder in an amount
of from 0.001% to 0.09% based on dry weight of the hydraulic
cementitious powder. The strength-enhancing agent is a compound
represented by the following structural formula:
##STR00001##
wherein R.sup.1 is (C.sub.1-C.sub.4)alkyl-OH; and R.sup.2 and
R.sup.3, each independently, is (C.sub.0-C.sub.3)alkyl-COOR*,
wherein R* is H, Na.sup.+, or K.sup.+. In one example embodiment,
R* is H, Na.sup.+, K.sup.+, or 1/2 Ca.sup.++.
[0005] In a further aspect of the first example embodiment, the
cement clinker includes tricalcium aluminate (C.sub.3A) in an
amount of 0.3% to 9.0% based on dry weight of cement clinker. The
content of the total aluminate phase (C.sub.3A) can be determined
by quantitative X-ray diffraction using the Rietveld refinement
method.
[0006] In another example embodiment, the present invention is an
additive composition, comprising (A) a strength-enhancing agent
described above with reference to the first embodiment; and (B) at
least one grinding aid selected from one or more of a glycol,
glycerin, or acetic acid or an acetic acid salt. In one aspect, the
additive composition is a liquid.
[0007] In another example embodiment, the present invention is a
cement composition, comprising a hydraulic cementitious powder that
includes tricalcium aluminate (C.sub.3A) in an amount of from 0.3%
to 9.0% based on dry weight of the hydraulic cementitious powder; a
strength-enhancing agent present in an amount of from 0.001% to
0.09% based on dry weight of the hydraulic cementitious powder; at
least one grinding aid selected from a glycol, glycerin, or acetic
acid or a salt thereof. The strength-enhancing agent is a compound
described above with reference to the first example embodiment.
[0008] The strength-enhancing agents described herein possess
important advantages in addition to early strength enhancement. For
example, while some strength-enhancing agents will cause iron
staining in finished cementitious products due to iron chelation in
the cement pore water, the cement compositions described herein do
not cause iron staining. The agents described herein can also be
used as grinding aids in the cement manufacturing process,
resulting in cements having a higher specific surface area.
[0009] In another example embodiment, the strength-enhancing agent
suitable for use with the methods and compositions of the present
invention is made by a process comprising: reacting a
monohaloacetic acid chosen from monochloroacetic acid and
monobromoacetic acid, or a salt thereof, with a alkanolamine chosen
from ethanolamine, isopropanolamine, and isobutanolamine under
alkaline conditions to generate the strength-enhancing agent
represented by the structural formula
##STR00002##
[0010] wherein R.sup.1 is (C.sub.1-C.sub.4)alkyl-OH; and R.sup.2
and R.sup.3, each independently, represent --CH.sub.2COOR* wherein
R* is H, Na.sup.+, K.sup.+, or 1/2 Ca.sup.++
[0011] In another example embodiment, the present invention is a
method of making a strength-enhancing agent and a
strength-enhancing agent made by the method, comprising: reacting a
haloacetic acid chosen from one or more of a chloroacetic acid and
a bromoacetic acid, or a salt thereof, with one or more
alkanolamines of the structural formula (I)
##STR00003##
[0012] under alkaline conditions, to generate the
strength-enhancing agent represented by structural formula (II)
##STR00004##
[0013] wherein:
[0014] each R.sup.10 is independently chosen from H,
(C.sub.1-C.sub.4)alkyl-OH, provided that in structural formula (I)
at least one group R.sup.10 is not H;
[0015] R.sup.20 is chosen from (C.sub.1-C.sub.4)alkyl-OH, and
--C(R.sup.4).sub.2COO.sup.-M.sup.+; and R.sup.30 is
--C(R.sup.4).sub.2COO.sup.-M.sup.+; each R.sup.4 is independently
chosen from hydrogen, Br, and Cl; and M.sup.+ is H.sup.+, Na.sup.+,
K.sup.+, or 1/2 Ca.sup.++.
[0016] In another example embodiment, the present invention is an
additive composition, comprising: a first component; and a cement
additive component. The cement additive component is one or more
agent chosen from a glycol, glycerol, acetic acid or a salt
thereof, an alkanolamine, an amine, a carbohydrate, a
water-reducing additive, an air-entraining agent, a chloride salt,
a nitrite salt, a nitrate salt, and a thiocyanate salt; and the
first component is prepared by reacting a haloacetic acid chosen
from one or more of a chloroacetic acid and a bromoacetic acid, or
a salt thereof, with one or more alkanolamines of the structural
formula (I)
##STR00005##
[0017] under alkaline conditions, to generate the first component
represented by structural formula (II)
##STR00006##
[0018] wherein each R.sup.10 is independently chosen from H,
(C.sub.1-C.sub.4)alkyl-OH, provided that in structural formula (I)
at least one group R.sup.10 is not H; R.sup.20 is chosen from
(C.sub.1-C.sub.4)alkyl-OH, and --C(R.sup.4).sub.2COO.sup.-M.sup.+;
and R.sup.30 is --C(R.sup.4).sub.2COO.sup.-M.sup.+; each R.sup.4 is
independently chosen from hydrogen, Br, and Cl; and M.sup.+is
H.sup.+, Na.sup.+, K.sup.+, or 1/2 Ca.sup.++.
[0019] In another example embodiment, the present invention is a
concrete composition, comprising the additive composition described
above; cement; a fine aggregate; a coarse aggregate, and at least
one supplemental cementitious material chosen from fly ash,
granulated blast furnace slag, limestone, calcined clay, natural
pozzolan, and artificial pozzolan.
[0020] In another example embodiment, the present invention is a
method of making a cement composition, comprising reacting a
monohaloacetic acid chosen from monochloroacetic acid and
monobromoacetic acid, or a salt thereof, with a alkanolamine chosen
from ethanolamine, isopropanolamine, and isobutanolamine under
alkaline conditions to generate the strength-enhancing agent
represented by the structural formula
##STR00007##
[0021] wherein:
[0022] R.sup.1 is (C.sub.1-C.sub.4)alkyl-OH; and R.sup.2 and
R.sup.3, each independently, represent --CH.sub.2COO.sup.-R*,
thereby preparing a reaction mixture; adding the reaction mixture
without purification to a cement clinker; and grinding the cement
clinker and the reaction mixture, thereby producing a hydraulic
cementitious powder.
[0023] The strength-enhancing agents described above, including the
compounds manufactured by the above-described reaction of a
haloacetic acid or a salt thereof with one or more alkanolamines,
enhance early strength in cement, particularly when used as a
grinding additive. The additive composition that include such
strength-enhancing agents can be combined with one or more
conventional grinding additive components, such as may be chosen
from glycols, glycerols, acetic acid or salt thereof (e.g., sodium
acetate), alkanolamines (e.g., triethanolamine,
triisopropanolamine, diethanolisopropanolamine), amines (e.g.,
tetrahydroxylethylene diamine), carbohydrates, polycarboxylate
ethers, air entraining agents, chlorides, nitrites, nitrates,
thiocyanates, alkali sulfates, alkali carbonates, or mixture
thereof, to provide an additive grinding composition providing
value and flexibility to cement manufacturers.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] The foregoing will be apparent from the following more
particular description of example embodiments of the invention, as
illustrated in the accompanying drawings in which like reference
characters refer to the same parts throughout the different views.
The drawings are not necessarily to scale, emphasis instead being
placed upon illustrating embodiments of the present invention.
[0025] FIG. 1 is a plot of a change (in percent relative to a
control) of compressive strength of a cement sample at Day 1 post
mortar preparation as a function of C.sub.3A content. Na.sub.2-EDG
was added to the samples at 0.02% by weight of the cementitious
material.
[0026] FIG. 2A is a plot of compressive strength (in MPa) of a
cement A sample at Day 1 post mortar preparation as a function of
the carboxyl functionality (COO--) content (expressed in
parts-per-million relative to cement weight). The carboxyl
functionality is provided by the listed additives.
[0027] FIG. 2B is a plot of compressive strength (in MPa) of a
cement B sample at Day 1 post mortar preparation as a function of
the content of the additive (in weight percent).
[0028] FIG. 3 is a plot of "volume fraction" of the particles in a
ground cement sample as a function of particle size in micrometers.
Filled circles indicate cement compositions that include 0.02% by
weight Na.sub.2-EDG additive; white squares--cement compositions
without an additive.
[0029] FIG. 4A and FIG. 4B, collectively, represent Table 1 of
Example 1.
[0030] FIG. 5, panel A, shows the NMR spectrum of Sample A,
described in Example 6. FIG. 5, panel B, shows the NMR spectrum of
Sample B, described in Example 6.
DETAILED DESCRIPTION OF THE INVENTION
[0031] A description of example embodiments of the invention
follows.
[0032] The conventional cement chemist's notation uses the
following abbreviations:
[0033] CaO.dbd.C
[0034] SiO.sub.2.dbd.S
[0035] Al.sub.2O.sub.3=A
[0036] Fe.sub.2O.sub.3.dbd.F
[0037] Under this notation, the following abbreviations are
used:
[0038] tricalcium silicate=C.sub.3S
[0039] dicalcium silicate=C.sub.2S
[0040] tricalcium aluminate=C.sub.3A
[0041] tetracalcium aluminoferrite=C.sub.4AF
[0042] As used herein, "alkyl" means an optionally substituted
saturated aliphatic branched or straight-chain monovalent
hydrocarbon radical having the specified number of carbon atoms.
Thus, "(C.sub.1-C.sub.4) alkyl" means a radical having from 1-4
carbon atoms in a linear or branched arrangement.
"(C.sub.1-C.sub.4)alkyl" includes methyl, ethyl, propyl, isopropyl,
n-butyl and tert-butyl.
[0043] As used herein, "alkanolamine" means an alkyl, typically a
C1-C6 alkyl, functionalized with at least one amino group and at
least one hydroxyl group. Examples of alkanolamines include
triethanolamine or TEA, diethanol isopropanolamine or DEIPA, and
tri-isopropanolamine or TIPA (typically used as conventional
grinding aids in cement production).
[0044] As used herein, the term "amino acid" refers to a compound
having both an amino --NH.sub.2 and a carboxy --CO.sub.2H
functionalities. The term includes both a naturally occurring amino
acid and a non-natural amino acid. The term "amino acid," unless
otherwise indicated, includes both isolated amino acid molecules
(i.e. molecules that include both, an amino-attached hydrogen and a
carbonyl carbon-attached hydroxyl) and residues of amino acids
(i.e. molecules in which either one or both an amino-attached
hydrogen or a carbonyl carbon-attached hydroxyl are removed). The
amino group can be alpha-amino group, beta-amino group, etc. For
example, the term "amino acid alanine" can refer either to an
isolated alanine H-Ala-OH or to any one of the alanine residues
H-Gly-, -Gly-OH, or -Gly-. Unless otherwise indicated, all amino
acids found in the compounds described herein can be either in D or
L configuration or a mixture. The term "amino acid" includes salts
thereof.
[0045] An amino acid can be modified with additional functional
groups. Examples of the additional functional groups include
additional amino groups, additional carboxyl groups, and hydroxyl
groups. Such modified amino acids can be referred to as "amino acid
derivatives." Examples of such amino acid derivatives include amino
acids that include two carboxyl groups and one alcohol group, such
as ethanol diglycinate (EDG).
[0046] As used herein, "glycol" refers to any one of an alkyl
polyol compounds formed by oligomerization or polymerization of an
alkyl diol via an ether bond formation. In example embodiments, a
glycol is a polymer or an oligomer of a C2-C4 alkyl diol. For
example, a glycol suitable to be used in this invention includes
diethylene glycol, polyethylene glycol, monopropylene glycol,
dipropylene glycol, tripropylene glycol, tetrapropylene glycol, or
mixtures thereof. The term "glycol," as used herein, can also refer
to "glycol bottoms," i.e. mixed glycols typically comprised of
ethylene glycol, diethylene glycol, triethylene glycol, and
tetraethylene glycol, often with color and other impurities.
[0047] As used herein, the term "glycerin" refers to
propane-1,2,3-triol, both in purified and in crude form. For
example, "glycerin," as used herein, can refer to a crude glycerin,
such as a byproduct obtained in the manufacture of biodiesel.
[0048] As used herein, "acetic acid" refers to a compound having
the structural formula CH.sub.3COOH. Salts of acetic acid (acetate
salts) include salts of the alkali metals (Group I of the periodic
table, such as sodium and potassium), and salts of alkali-earth
metals (Group II of the periodic table, such as Ca.sup.2+).
Preferred among these are sodium, potassium, and calcium
acetate.
[0049] As used herein, "gluconic acid" refers to the compound
having the following structural formula:
##STR00008##
[0050] Salts of gluconic acid include ammonium salts, alkali metal
salts (sodium and potassium), alkali-earth metal salts (calcium),
and salts of iron, zinc, and aluminum.
[0051] As used herein, "sucrose" refers to a disaccharide
combination of the monosaccharides glucose and fructose with the
formula C.sub.12H.sub.22O.sub.11.
[0052] As used herein, "corn syrup" refers to syrup made from
cornstarch, consisting of dextrose, maltose, and dextrins.
[0053] As used herein, "molasses" refers to thick, dark brown syrup
obtained from raw sugar during the refining process.
[0054] As used herein, a "chloride salt" refers to an alkali metal
(Group I of the periodic table, e.g., sodium or potassium) or an
alkali-earth (Group II of the periodic table, e.g., calcium) salts
of hydrochloric acid.
[0055] As used herein, a "thiocyanate salts" refers to an alkali
metal (Group I of the periodic table, e.g., sodium or potassium) or
an alkali-earth (Group II of the periodic table, e.g., calcium)
salts of thiocyanic acid.
[0056] As used herein, a "nitrite salt" refers to an alkali metal
(Group I of the periodic table, e.g., sodium or potassium) or an
alkali-earth (Group II of the periodic table, e.g., calcium) salts
of nitrous acid (HNO.sub.2).
[0057] As used herein, a "nitrate salt" refers to an alkali metal
(Group I of the periodic table, e.g., sodium or potassium) or an
alkali-earth (Group II of the periodic table, e.g., calcium) salts
of nitric acid (HNO.sub.3).
[0058] As used herein, an "alkali sulfate" refers to an alkali
metal (Group I of the periodic table, e.g., sodium or potassium) or
an alkali-earth (Group II of the periodic table, e.g., calcium)
salts of sulfuric acid (H.sub.2SO.sub.4).
[0059] As used herein, an "alkali carbonate" refers to an alkali
metal (Group I of the periodic table, e.g., sodium or potassium) or
an alkali-earth (Group II of the periodic table, e.g., calcium)
salts of carbonic acid (H.sub.2CO.sub.3).
[0060] The term "amine," as used herein, means an "NH.sub.3," an
"NH.sub.2R.sub.p," an "NHR.sub.pR.sub.q," or an
"NR.sub.pR.sub.qR.sub.s" group. The term "amino", as used herein,
refers to a mono-, bi-, or trivalent radical of the amine. In
either the amine or amino groups, R.sub.p, R.sub.q, R.sub.q can
each be a C1-C6 alkyl, optionally substituted with the one or more
hydroxyl groups or amino groups. Examples of an amine include
tetrahydroxylethylene diamine (THEED).
[0061] As used herein, the term "alkanolamine" refers to an amine
or an amine in which one of the alkyl groups is substituted with
the hydroxyl. Examples of alkanolamines include triethanolamine,
triisopropanolamine, and diethanolisopropanolamine.
[0062] As used herein, the term "carbohydrate" refers to
polysaccharide cement additives, usually used as cement retarders.
Examples include celluloses, exemplified by carboxymethylated
hydroxyethylated celluloses, gum arabic and guar gum. Gum arabic is
a product of an acacia tree of tropical Africa and is entirely
soluble in water. Guar gum is derived from the seed of an annual
plant which is cultivated in India. These products consist mainly
of a polysaccharide of galactose and mannose.
[0063] As used herein, the term "a haloacetic acid," unless
specifically indicated, refers to any one of mono-, di-, or
tri-substituted acetic acid analogs, or a mixture thereof. For
example, the "chloroacetic acid" refers to any one of the following
compounds or a mixture thereof: Cl--CH.sub.2--COOH,
Cl.sub.2CH--COOH, or Cl.sub.3C--COOH.
[0064] As used herein, the phrase "under alkaline condition" refers
to the reaction conditions where the pH of the reaction mixture is
greater than 7.
[0065] As used herein, the phrase "room temperature" refers to the
temperature of about 21 to 25.degree. C.
[0066] The content of all components in the compositions described
below is indicated relative to the dry weight of the
composition.
[0067] The terms "cement composition" or "cementitious powder" is
used herein to designate a binder or an adhesive that includes a
material that will solidify upon addition of water (hydraulic
cementitious material), and an optional additive. Most cementitious
materials are produced by high-temperature processing of calcined
lime and a clay. When mixed with water, hydraulic cementitious
materials form mortar or, mixed with sand, gravel, and water, make
concrete. The terms "cementitious material," "cementitious powder,"
and "cement" can be used interchangeably.
[0068] Cement compositions includes mortar and concrete
compositions comprising a hydraulic cement. Cement compositions can
be mixtures composed of a cementitious material, for example,
Portland cement, either alone or in combination with other
components such as fly ash, silica fume, blast furnace slag,
limestone, natural pozzolans or artificial pozzolans, and water;
mortars are pastes additionally including fine aggregate, and
concretes are mortars additionally including coarse aggregate. The
cement compositions of this invention are formed by mixing certain
amounts of required materials, e.g., a hydraulic cement, water, and
fine or coarse aggregate, as may be applicable for the particular
cement composition being formed.
[0069] As used herein, the term "clinker" refers to a material made
by heating limestone (calcium carbonate) with other materials (such
as clay) to about 1450.degree. C. in a kiln, in a process known as
calcination, whereby a molecule of carbon dioxide is liberated from
the calcium carbonate to form calcium oxide, or quicklime, which is
then blended with the other materials that have been included in
the mix to form calcium silicates and other cementitious
compounds.
[0070] As used herein, the term "Portland cement" include all
cementitious compositions which meet either the requirements of the
ASTM (as designated by ASTM Specification C150), or the established
standards of other countries. Portland cement is prepared by
sintering a mixture of components including calcium carbonate (as
limestone), aluminum silicate (as clay or shale), silicon dioxide
(as sand), and miscellaneous iron oxides. During the sintering
process, chemical reactions take place wherein hardened nodules,
commonly called clinkers, are formed. Portland cement clinker is
formed by the reaction of calcium oxide with acidic components to
give, primarily tricalcium silicate, dicalcium silicate, tricalcium
aluminate, and a ferrite solid solution phase approximating
tetracalcium aluminoferrite.
[0071] After the clinker has cooled, it is pulverized together with
a small amount of gypsum (calcium sulfate) in a finish grinding
mill to provide a fine, homogeneous powdery product known as
Portland cement. Due to the extreme hardness of the clinkers, a
large amount of energy is required to properly mill them into a
suitable powder form. Energy requirements for finish grinding can
vary from about 33 to 77 kWh/ton, depending upon the nature of the
clinker. Several materials such as glycols, alkanolamines, aromatic
acetates, etc., have been shown to reduce the amount of energy
required and thereby improve the efficiency of the grinding of the
hard clinkers. These materials, commonly known as grinding aids,
are processing additives which are introduced into the mill in
small dosages and interground with the clinker to attain a uniform
powdery mixture. In addition to reducing grinding energy, the
commonly used processing additives are frequently used to improve
the ability of the powder to flow easily and reduce its tendency to
form lumps during storage.
[0072] Clinker production involves the release of CO.sub.2 from the
calcination of limestone. It is estimated that for each ton of
clinker produced, up to one ton of CO.sub.2 is released to the
atmosphere. The utilization of fillers such as limestone or clinker
substitutes such as granulated blast furnace slags, natural or
artificial pozzolans, pulverized fuel ash, and the like, for a
portion of the clinker allow a reduction on the emitted CO.sub.2
levels per ton of finished cement. As used herein, the term filler
refers to an inert material that has no later age strength
enhancing attributes; the term "clinker substitute" refers to a
material that may contribute to long term compressive strength
enhancement beyond 28 days. The addition of these fillers or
clinker substitutes to form "blended cements" is limited in
practice by the fact that such addition usually results in a
diminution in the physical strength properties of the resultant
cement. For example, when a filler, such as limestone, is blended
in amounts greater than 5%, the resultant cement exhibits a marked
reduction in strength, particularly with respect to the strength
attained after 28 days of moist curing (28-day strength). As used
herein, the term "blended cements" refers to hydraulic cement
compositions containing between 2 and 90%, more conventionally
between 5 and 70%, fillers or clinker substitute materials.
[0073] As used herein, the term "fine aggregate" refers to
particulate material used in construction whose size is less than
4.75 mm. The term "coarse aggregate" refers to particulate material
used in construction that is larger than about 2/16 inch.
[0074] In a first example embodiment, the present invention is a
method of making a cement composition. The method comprises
grinding a cement clinker and a strength-enhancing agent, thereby
producing a hydraulic cementitious powder.
[0075] In a first aspect of the first example embodiment, the
strength-enhancing agent is present in the hydraulic cementitious
powder in an amount of from 0.001% to 0.09% based on dry weight of
the hydraulic cementitious powder. The strength-enhancing agent is
a compound represented by the following structural formula:
##STR00009##
wherein R.sup.1 is (C.sub.1-C.sub.4)alkyl-OH; and R.sup.2 and
R.sup.3, each independently, is (C.sub.0-C.sub.3)alkyl-COOR*,
wherein R* is H, Na.sup.+, and K.sup.+. In an example embodiment,
R* is Na.sup.+, K.sup.+, or 1/2 Ca.sup.++.
[0076] In a second aspect of the first example embodiment, the
method of the first example embodiment further includes adding to
the cement clinker at least one supplemental cementitious material
selected from the group consisting of: fly ash, granulated blast
furnace slag, limestone, calcined clay, natural pozzolans and
artificial pozzolans.
[0077] In a third aspect of the first example embodiment, the
cement clinker includes C.sub.3A in the amount of 0.3% to 9.0%, for
example, 0.3% to 7.0% based on dry weight of cement clinker. The
content of the total aluminate phase (C.sub.3A) can be determined
by quantitative X-ray diffraction using the Rietveld refinement
method.
[0078] In a fourth aspect of the first example embodiment, the
method further includes grinding with the strength enhancement
agent and the cement clinker at least one supplemental component
selected from a grinding aid, a set retarding agent, or a set
accelerating agent.
[0079] In a fifth aspect of the first example embodiment, the
method is as described above with respect to the first through the
fourth aspects of the first example embodiments, further comprising
grinding with the strength enhancement agent and the cement clinker
at least one grinding aid. In various aspects, the strength
enhancement agent is present in the amount of from 0.001% to 0.03%
based on dry weight of the hydraulic cementitious powder, and the
at least one grinding aid is added in the amount of from 0.001% to
0.06% based on dry weight of the hydraulic cementitious powder. In
one aspect, the strength enhancement agent is present in the amount
of from 0.001% to 0.03% based on dry weight of the hydraulic
cementitious powder, and the at least one grinding aid is added in
the amount of from 0.001% to 0.1% based on dry weight of the
hydraulic cementitious powder.
[0080] In a sixth aspect of the first example embodiment, the
method is as described above with respect to the first through the
fourth aspects of the first example embodiments, further comprising
grinding with the strength enhancement agent and the cement clinker
at least one grinding aid and a set retarding agent. In various
aspects, the strength enhancement agent is present in the amount of
0.001-0.03% based on dry weight of the hydraulic cementitious
powder; the at least one grinding aid is added in the amount of
from 0.001% to 0.06% based on dry weight of the hydraulic
cementitious powder; the set retarding agent is added in the amount
of 0.001-0.03% based on dry weight of the hydraulic cementitious
powder. In other aspects, the strength enhancement agent is present
in the amount of 0.001-0.03% based on dry weight of the hydraulic
cementitious powder; the at least one grinding aid is added in the
amount of from 0.001% to 0.1% based on dry weight of the hydraulic
cementitious powder; the set retarding agent is added in the amount
of 0.001-0.03% based on dry weight of the hydraulic cementitious
powder.
[0081] In a seventh aspect of the first example embodiment, the
method is as described above with respect to the first through the
fourth aspects of the first example embodiments, further comprising
grinding with the strength enhancement agent and the cement clinker
at least one grinding aid and a set accelerating agent. In various
aspects, the strength enhancement agent is present in the amount of
from 0.001% to 0.03% based on dry weight of the hydraulic
cementitious powder, the at least one grinding aid is added in the
amount of from 0.001 to 0.06% based on dry weight of the hydraulic
cementitious powder, the set accelerating agent is added in the
amount of from 0.001% to 0.2% based on dry weight of the hydraulic
cementitious powder. In other aspects, the strength enhancement
agent is present in the amount of from 0.001% to 0.03% based on dry
weight of the hydraulic cementitious powder, the at least one
grinding aid is added in the amount of from 0.001 to 0.1% based on
dry weight of the hydraulic cementitious powder, the set
accelerating agent is added in the amount of from 0.001% to 0.2%
based on dry weight of the hydraulic cementitious powder.
[0082] In an eighth aspect of the first example embodiment, the
method is as described above with respect to the first through the
fourth aspects of the first example embodiments, further comprising
grinding with the strength enhancement agent and the cement clinker
at least one grinding aid, a set retarding agent, and a set
accelerating agent. In various aspects, the strength enhancement
agent is present in the amount of from 0.001% to 0.03% based on dry
weight of the hydraulic cementitious powder, the at least one
grinding aid is added in the amount of from 0.001% to 0.06% based
on dry weight of the hydraulic cementitious powder, the set
retarding agent is added in the amount of from 0.001% to 0.03%
based on dry weight of the hydraulic cementitious powder, and the
set accelerating agent is added in the amount of 0.001% to 0.2%
based on dry weight of the hydraulic cementitious powder. In other
aspects, the strength enhancement agent is present in the amount of
from 0.001% to 0.03% based on dry weight of the hydraulic
cementitious powder, the at least one grinding aid is added in the
amount of from 0.001% to 0.1% based on dry weight of the hydraulic
cementitious powder, the set retarding agent is added in the amount
of from 0.001% to 0.03% based on dry weight of the hydraulic
cementitious powder, and the set accelerating agent is added in the
amount of 0.001% to 0.2% based on dry weight of the hydraulic
cementitious powder.
[0083] In a ninth aspect of the first example embodiment, the
method is as described above with respect to any of the first
through eighth aspects, and further the strength enhancing agent is
N-(2-hydroxyethyl)iminodiacetic acid (EDG) or a salt thereof (e.g.
sodium, potassium).
[0084] In a tenth aspect of the first example embodiment, the
method is as described above with respect to any of the fourth
through ninth aspects, and further the grinding aid is one or more
of a glycol (e.g., diethylene glycol, polyethylene glycol,
monopropylene glycol, dipropylene glycol, tripropylene glycol,
tetra propylene glycol), glycerin, a C1-C6 alkanolamine (e.g., TEA,
DEIPA, and TIPA), acetic acid or an acetic acid salt (e.g., sodium
acetate).
[0085] In an eleventh aspect of the first example embodiment, the
method is as described above with respect to the fourth through
sixth and eighth and ninth aspects, and further the set retarding
agent is one or more of a gluconate salt (e.g. sodium gluconate), a
molasses, sucrose, or a corn syrup.
[0086] In a twelfth aspect of the first example embodiment, the
method is as described above with respect to the fourth, fifth,
seventh, eighth, and ninth aspects, and further the set
accelerating agent is one or more of a thiocyanate salt (e.g.
sodium, potassium, calcium) or a chloride salt (sodium, potassium,
calcium).
[0087] In a thirteenth aspect of the first example embodiment, the
method is as described above with respect to the fourth embodiment,
and further the strength enhancing agent is EDG or a salt thereof
(e.g. sodium, potassium), the grinding aid is the glycol (e.g.,
diethylene glycol, DEG), the set retarding agent is sodium
gluconate, and the set accelerating agent is sodium
thiocyanate.
[0088] In a fourteenth aspect of the first example embodiment, the
method is as described above with respect to any of the aspects of
the first example embodiment, further including grinding the cement
clinker and the strength-enhancing agent with an alkali sulfate
(e.g., sodium sulfate). In an additional aspect of the first
example embodiment, the method is as described above with respect
to any of the aspects of the first example embodiment, further
including grinding the cement clinker and the strength-enhancing
agent with an alkali sulfate and/or an alkali carbonate (e.g.,
sodium sulfate, sodium carbonate, sodium bicarbonate).
[0089] In a fifteenth aspect of the first example embodiment, the
strength-enhancing agent is made by a process comprising: reacting
a monohaloacetic acid chosen from monochloroacetic acid and
monobromoacetic acid, or a salt thereof, with a alkanolamine chosen
from ethanolamine, isopropanolamine, and isobutanolamine under
alkaline conditions to generate the strength-enhancing agent
represented by the structural formula
##STR00010##
[0090] wherein: R.sup.1 is (C.sub.1-C.sub.4)alkyl-OH; and R.sup.2
and R.sup.3, each independently, represent --CH.sub.2COOR*, where
R* is defined above with respect to the first aspect of the first
example embodiment. For example, the haloacetic acid or its salt is
chloroacetic acid or its salt, and R.sup.1 is
--CH.sub.2CH.sub.2OH.
[0091] In any of aspects of the first example embodiment, the
content of Na.sub.2O equivalent in the hydraulic cementitious
material is less than or equal to 0.7% by weight of the hydraulic
cementitious powder. The content of Na.sub.2O equivalents in cement
is determined as follows, in weight percent: % Na.sub.2O
equivalent=% Na.sub.2O+0.658*% K.sub.2O, where the values of %
Na.sub.2O and % K.sub.2O in cement can be determined using either
X-ray fluorescence (XRF) or inductively coupled plasma mass
spectroscopy (ICP-MS).
[0092] In a second example embodiment, the present invention is a
composition prepared by the method of any one aspect of the first
example embodiment.
[0093] In a third example embodiment, the present invention is an
additive composition, comprising (A) a strength-enhancing agent
represented by the following structural formula:
##STR00011##
and (B) at least one grinding aid selected from one or more of a
glycol (e.g., diethylene glycol, polyethylene glycol, monopropylene
glycol, dipropylene glycol, tripropylene glycol, tetra propylene
glycol), glycerin, or acetic acid or a salt thereof, wherein the
additive composition is a liquid.
[0094] The strength-enhancing agent of the third example embodiment
is described above with respect to the first example
embodiment.
[0095] In a first aspect of the third example embodiment, the
weight ratio of the strength enhancing agent to the grinding aid in
the additive composition is from 1:9 to 9:1. In another aspect of
the third example embodiment, the weight ratio of the strength
enhancing agent to the grinding aid in the additive composition is
from 1:19 to 19:1.
[0096] In the second aspect of the third example embodiment, the
additive composition is as described above with respect to any of
the aspects of the second example embodiment, further comprising a
set retarding agent, a set accelerating agent, or a mixture
thereof.
[0097] In the third aspect of the third example embodiment, the
additive composition is as described above with respect to any of
the aspects of the second example embodiment, and further the
strength enhancing agent is N-(2-hydroxyethyl)iminodiacetic acid
(EDG) or a salt thereof (e.g. sodium, potassium).
[0098] In the fourth aspect of the third example embodiment, the
additive composition is as described above with respect to any of
the aspects of the second example embodiment, and further the at
least one grinding aid is diethylene glycol.
[0099] In the fifth aspect of the third example embodiment, the
additive composition is as described above with respect to any of
the aspects of the second example embodiment, further comprising
sodium gluconate or sodium thiocyanate.
[0100] In the sixth aspect of the third example embodiment, the
additive composition is as described above with respect to any of
the aspects of the second example embodiment, further comprising an
alkali sulfate (e.g., sodium sulfate). In the another aspect of the
third example embodiment, the additive composition is as described
above with respect to any of the aspects of the second example
embodiment, further comprising an alkali sulfate and/or an alkali
carbonate (e.g., sodium sulfate, sodium carbonate, sodium
bicarbonate).
[0101] In a fourth example embodiment, the present invention is a
cementitious composition comprising a cementitious binder obtained
by grinding a cement clinker with the additive composition of any
aspect of the third example embodiment.
[0102] In a fifth example embodiment, the present invention is a
cement composition, comprising a hydraulic cementitious powder,
said hydraulic cementitious powder including tricalcium aluminate
(C.sub.3A) in an amount of from 0.3% to 9.0% based on dry weight of
the hydraulic cementitious powder; a strength-enhancing agent, said
strength-enhancing agent being present in an amount of from 0.001%
to 0.09% based on dry weight of the hydraulic cementitious powder,
and at least one grinding aid selected from a glycol (e.g.,
diethylene glycol, polyethylene glycol, monopropylene glycol,
dipropylene glycol, tripropylene glycol, tetra propylene glycol),
glycerin, or acetic acid or an acetate salt (e.g., sodium or
potassium acetate).
[0103] The strength-enhancing agent of the fifth example embodiment
is described above with respect to the first example
embodiment.
[0104] In a sixth example embodiment, the present invention is an
additive composition for use in grinding with a cement clinker,
said composition comprising (A) a strength-enhancing agent and (B)
at least one grinding aid selected from one or more of a glycol,
glycerin, or acetic acid or an acetate salt, wherein the additive
composition is a liquid. The strength-enhancing agent of the sixth
example embodiment is described above with respect to the first
example embodiment.
[0105] In a seventh example embodiment, the present invention is a
mixture of a cement clinker and the additive composition of any
aspect of the third example embodiment.
[0106] In an eighth example embodiment, the present invention is a
method for making a strength-enhancing agent, comprising reacting a
haloacetic acid chosen from one or more of a chloroacetic acid and
a bromoacetic acid, or a salt thereof, with one or more
alkanolamines of the structural formula (I)
##STR00012##
[0107] under alkaline conditions, to generate the
strength-enhancing agent represented by structural formula (II)
##STR00013##
[0108] wherein each R.sup.10 is independently chosen from H,
(C.sub.1-C.sub.4)alkyl-OH, provided that in structural formula (I)
at least one group R.sup.10 is not H; R.sup.20 is chosen from
(C.sub.1-C.sub.4)alkyl-OH, and --C(R.sup.4).sub.2COO.sup.-M.sup.+;
and R.sup.30 is --C(R.sup.4).sub.2COO.sup.-M.sup.+; each R.sup.4 is
independently chosen from hydrogen, Br, and Cl; and M.sup.+is
H.sup.+, Na.sup.+, K.sup.+, or 1/2 Ca.sup.++.
[0109] In a first aspect of the eighth example embodiment, the
chloroacetic acid is monochloracetic acid or a salt thereof; the
compound represented by structural formula (I) is ethanolamine
represented by the following structural formula
HO--CH.sub.2--CH.sub.2--NH.sub.2; and the strength-enhancing agent
represented by structural formula (II) is sodium ethanol-diglycine
(EDG)
##STR00014##
[0110] wherein the monochloracetic acid or a salt thereof and the
ethanolamine are reacted in the presence of sodium hydroxide at
above room temperature.
[0111] In another aspect, the monochloracetic acid or a salt
thereof and the ethanolamine are reacted in the presence of sodium
hydroxide at any temperature at which the reaction process can be
carried out, for example at or above room temperature. The
temperature of reaction can be chosen depending on a particular
condition to reduce the process of the present invention to
practice. For example, when the higher productivity of the process
is desirable, higher temperature, such as at above the room
temperature can be chosen, whereas the higher EDG content is
desired, the lower temperature, such as at the room temperature or
below, is preferably applied. The temperature of the manufacturing
process is suitably controlled depending on the preferences of the
product and the production process. It is noted that the
neutralization of chloroacetic acid with alkali generates heat that
can either be used or controlled as the reaction temperature chosen
above.
[0112] In a ninth example embodiment, the present invention is a
strength-enhancing agent made by the methods according to the any
aspect of the eighth example embodiment. It is contemplated that
the strength enhancing agent according to the ninth example
embodiment can be used in the methods and compositions according to
any aspects of the first to the seventh example embodiments.
[0113] In a tenth example embodiment, the present invention is an
additive composition, comprising a first component; and a cement
additive component, wherein the cement additive component is one or
more agent chosen from a glycol, glycerol, acetic acid or a salt
thereof, an alkanolamine, an amine, a carbohydrate, a
water-reducing additive, an air-entraining agent, a chloride salt,
a nitrite salt, a nitrate salt, and a thiocyanate salt; and the
first component is prepared according to the eighth example
embodiment and any aspect thereof.
[0114] In a first aspect of the tenth example embodiment, the
additive composition is in liquid form.
[0115] In an eleventh example embodiment, the present invention is
a concrete composition, comprising the additive composition
according to the tenth example embodiment and any aspect thereof;
cement; a fine aggregate; a coarse aggregate, and at least one
supplemental cementitious material chosen from fly ash, granulated
blast furnace slag, limestone, calcined clay, natural pozzolan, and
artificial pozzolan.
[0116] In a twelfth example embodiment, the present invention is a
method of making a concrete composition, comprising preparing a
reaction mixture according to the fifteenth aspect of the first
example embodiment or the eight example embodiment and any aspect
thereof, adding the reaction mixture without purification to a
cement clinker; and grinding the cement clinker and the reaction
mixture, thereby producing a hydraulic cementitious powder.
[0117] It has now been discovered that, unlike traditional
strength-enhancers (e.g., TEA, DEIPA, TIPA), the strength-enhancing
agents described herein (e.g., ethanol diglycinate in acid or salt
form) do not involve increasing the solubility of iron in the
hydrated cement, and, therefore do not cause yellow staining on
finished products.
[0118] Other strength enhancing agents, such as TEA, DEIPA, and
TIPA, while improving strength, tend to increase the amount of air
entrained in the cement. In some instances, adding such agents can
lead to set cement compositions with large porosity and poor
finished surfaces. Although incorporation of air detraining agents
(ADA), such as those illustrated in U.S. Pat. No. 5,156,679,
incorporated herein by reference in its entirety, enable reduction
in the air content, the formation and release of bubbles from the
cement compositions cannot be eliminated.
[0119] The amino acid derivatives described herein can
simultaneously improve early strength, without entraining large air
voids. This is desirable as it can lead to cement compositions,
such as Portland cement concrete, with lower porosities and better
finished surfaces.
[0120] A particular advantage of the additive of the invention is
that it may be either interground or intermixed with the cement. As
used herein, the terms "interground" and "intermixed" refer to the
particular stage of the cement processing in which the amino acid
derivatives described herein, for example EDG, are added. They may
be added to the clinker during the finish grinding stage and thus
interground to help reduce the energy requirements and provide a
uniform free flowing cement powder with reduced tendency to form
lumps during storage. It is also possible to add the subject
additives as an admixture to powdered cement either prior to, in
conjunction with, or after the addition of water when effecting the
hydraulic setting of the cement. Further, the amino acid
derivatives of this invention may be supplied in a pure
concentrated form, or diluted in aqueous or organic solvents, and
may also be used in combination with other chemical admixtures,
including but not limited to: accelerating admixtures, air
entrainers, air detrainers, water-reducing admixtures, retarding
admixtures (as defined in ASTM C494) and the like, and mixtures
thereof. The additive according to the invention may be used with
ordinary cement or with blended cements.
[0121] Example embodiments of the invention, including the
strength-enhancing agents made by reacting a haloacetic acid or a
salt thereof with an alkanolamine, provide additive compositions
for facilitating cement grinding, and provide early cement strength
enhancement, without generating the attendant disadvantages of
producing hazardous products as would be expected from current
commercial processes that involve monoethanolamine, formaldehyde,
and sodium cyanide starting materials.
[0122] One skilled in the art, using the preceding detailed
description, can utilize the present invention to its fullest
extent. The following examples are provided to illustrate the
invention, but should not be construed as limiting the invention in
any way except as indicated in the appended claims. All parts and
percentages are by weight unless otherwise indicated and additives
are expressed as percent active ingredient as solids based weight
of dry cement (% s/c). Compressive strengths of the cement samples
were determined in accordance with EN method 196-1. The following
examples were prepared using commercially available cements and
clinkers.
EXEMPLIFICATION
Example 1: Ethanoldiglycine Disodium Salt (Na.sub.2-EDG) Enhances
Early Strength of Cements
[0123] Table 1, presented in FIG. 4A and FIG. 4B, describes cement
samples tested in this example.
[0124] A variety of cements (i.e. cementitious material) have been
tested in mortars (i.e. the cement composition), and the impact of
0.02% Na2-EDG by weight of the cementitious material on compressive
strength has been assessed. The content of the total crystalline
phases has been determined by quantitative X-ray diffraction using
Rietveld refinement method. The content of sulfur element,
expressed as SO.sub.3, was determined by X-ray fluorescence (XRF).
The total alkali content or the content of Na.sub.2O equivalent in
cement is determined as follows, in weight percent: % Na.sub.2O
equivalent=% Na.sub.2O+0.658*% K.sub.2O, where the values of %
Na.sub.2O and % K.sub.2O in cement are determined using XRF. The
description of the tested cements and the results of the
compressive strength measurements are provided in Table 1 (see
FIGS. 4A and 4B).
[0125] Mortars were prepared following the EN 196-1 testing
protocol, where 450 grams of cement are mixed with 225 grams of
water and 1350 grams of a graded sand. Additives were added to the
water before mortar mixing. The mortar prepared this way was used
to cast 40.times.40.times.160 mm prismatic specimens that were
submitted to compression until rupture after 1 day of curing in a
moist room at 20.6.degree. C. and more than 95% relative humidity.
The rupture load was converted to compressive strength (in
MPa).
[0126] The results of this experiment indicate that Na.sub.2-EDG
can increase the strength of cements.
[0127] To visualize the results, the value of percent early
strength increase as a function of the C.sub.3A content was
plotted. FIG. 1 represents such a plot for Na.sub.2-EDG added at
0.02% by weight of the cementitious material.
Example 2: Na.sub.2-EDG Enhances Early Strength
[0128] The performance of Na.sub.2-EDG was compared to that of
other additives--Na-glycine, sarcosine, and Na.sub.2-EDTA--using
Cement A.
[0129] The structures of these additives are reproduced below:
##STR00015##
[0130] The mortars were prepared using Cement A as described above
in Example 1. The additives (Sarcosine, glycine, sodium salt, EDTA,
disodium salt, and EDG disodium salt) were added in varying amounts
expressed as parts-per-million of the carboxylic groups (COO--),
and the compressive strength of samples at Day 1 was measured. The
results, presented as a plot of Day 1 compressive strength as a
function of COO-- content, are shown in FIG. 2A.
[0131] FIG. 2A shows that EDG is a superior enhancer of early
strength when compared to the other additives.
[0132] The performance of EDG was further compared to that of
bicine and TEA using Cement B. The structural formulas of bicine
and TEA are reproduced below:
##STR00016##
[0133] Mortars were prepared using Cement B as described above. The
mortar mixes were used to prepare 40.times.40.times.160 mm
prismatic specimens that were tested under compression load until
rupture after 24 hours of storage at 20.6.degree. C. and greater
than 95% relative humidity.
[0134] FIG. 2B is a plot of Day 1 compressive strength (in MPa) of
Cement B as a function of the content of the additive (in weight
percent). FIG. 2B shows that 0.005%, 0.01% and 0.02% Na.sub.2-EDG
increased the 1-day strength of the cement by 0.8 MPa, 1.6 MPa, and
2.0 MPa, respectively. Bicine, added at 0.002% to 0.0075%, enhanced
1 day strength by 1.2 to 2.1 MPa, respectively. TEA added at
0.0075% and 0.015% enhanced 1 day strength by 1.9 MPa and 1.5 MPa,
respectively. It is surprising that EDG had similar to superior
performance to bicine and TEA, even though it contains two carboxyl
groups.
Example 3: Na.sub.2-EDG Improves Grinding Efficiency of Cements
[0135] The effect of Na.sub.2-EDG additive on grinding efficiency
of cementitious material was investigated in a laboratory scale
ball mill. For this investigation, 3325 grams of a commercial
clinker were ground in with 63.5 grams gypsum and 39.4 grams
basanite (calcium sulfate hemi-hydrate) at 88-95.degree. C. The
grindings were periodically interrupted to evaluate the fineness of
the cements using the Blaine air permeability apparatus, which
allows assessing the specific surface area (SSA) of powders. Table
2, below, shows the Blaine SSA values for samples containing either
no chemical additive or for samples containing 0.02% Na.sub.2-EDG
(% weight of solids on cement). In this experiment, 0.05% water (%
of cement weight) was added to the control cementitious material
(no chemical additive) to account for the presence of water in the
EDG additive.
TABLE-US-00001 TABLE 2 Blaine specific surface area values of
laboratory ground cements Blaine SSA Dosage (cm.sup.2/g) for each
grinding time (minutes) Additive (% s/c) 120 150 210 250 295 325
347 None 0.00 2173 n/a 2474 n/a 2838 n/a 2958 EDG 0.02 2333 2562
2799 2893 3017 3050 n/a n/a: result not available
[0136] The data in Table 2 demonstrates that addition of
Na.sub.2-EDG increased the specific surface area of the ground
material at all grinding times comparing to the sample with no
chemical additives.
[0137] The particle size distributions (PSD) of the sample of the
cementitious material to which 0.02% by weight Na.sub.2-EDG was
added, ground for 325 minutes, and of the sample containing no
chemical additives, ground for 347 minutes, was determined using
laser diffraction. This technique measures the particle size
distribution by measuring the angular variation in intensity of
light scattered as a laser beam passes through the dispersed
powders. The data is presented in FIG. 3, which is a plot of
"percent volume fraction" as a function of particle size in
micrometers (i.e. the curve indicates the accumulated percent by
volume at a given size in the sample). The tests were performed in
a Malvern Mastersize 3000 particle size analyzer coupled with an
Aero S dry dispersion unit in 1-3 grams cement samples.
[0138] It is seen that, even though ground for less time than the
sample with no chemical admixtures, the curve representing the EDG
sample is slightly shifted to lower particle sizes, indicating a
finer distribution as compared to the sample with no chemical
additives.
Example 4: Formulations with EDG Provide Higher Early Strength
[0139] Table 3 shows the impact of Na.sub.2-EDG and combinations of
Na.sub.2-EDG with sodium thiocyanate, sodium gluconate, and/or
diethylene glycol on the early strength of mortars prepared
according to the protocol described in Example 1. Cement I was used
to prepare the mortars. Table 3 shows that the combination of
Na.sub.2-EDG with other components allow a further increase of
1-day strength.
TABLE-US-00002 TABLE 3 Na- EDG NaSCN gluconate DEG 1 d % (% s/c) (%
s/c) (% s/c) (% s/c) blank 0 0 0 0 100.0% 0.01 0 0 0 106.3% 0.02 0
0 0 108.4% 0.01 0.02 0.0075 0 111.3% 0.02 0.04 0 0 113.2% 0.02 0.04
0.015 0 122.1% 0.01 0 0 0.03 103.6% 0.02 0 0.015 0 103.4% 0.0077
0.02 0.0039 0.015 118.8% 0.0116 0.03 0.058 0.0225 124.8% 0.0155
0.04 0.078 0.03 126.5%
[0140] Table 4 shows the impact of Na.sub.2-EDG and combinations
with calcium chloride on the 1-day strength of mortars prepared
according to the same protocol, using Cement E. The combination of
Na.sub.2-EDG with calcium chloride allows a further increase of
1-day compressive strength.
TABLE-US-00003 TABLE 4 EDG CaCl2 1 d % (% s/c) (% s/c) blank 0 0
100.0% 0 0.03 108.8% 0 0.06 122.8% 0.01 0 112.7% 0.01 0.03 123.2%
0.02 0 118.2% 0.02 0.06 127.6%
Example 5: Addition of EDG Causes No Iron Staining
[0141] A test to evaluate iron staining of mortars was
conducted.
[0142] Cement W was weighed (259 g) and deposited in a plastic
cylinder; sand was then added (1350 g) and the cylinder was
manually and vigorously shaken for 30 seconds to allow the two
components to blend. For mixes requiring the use of EDG, previously
prepared mix water solutions were added to the Hobart mortar mixing
bowl at this time; otherwise, the necessary amount of water (192 g)
was weighed and added to the bowl. All samples had the same
water-to-cement weight ratio of 0.74. The cement and sand blend was
poured onto the water (or additive-containing water) in the bowl.
The mixer was turned on and mixed at its lowest speed for 30
seconds, and then it was switched to its second lowest speed and
allowed to mix for an additional 30 seconds. After this time, the
mixer was stopped, the paddle and bowl were removed, and the mortar
was stirred slightly in two revolutions with a spoon before being
deposited (approximately 400 g) in a pre-labeled plastic bag. This
bag was closed in such a way that all possible air was squished
out. The bag was transported to an environmentally controlled room
(54% relative humidity, 24.degree. C.) with minimal traffic and
allowed to sit for 7 days. After this time, a razor was used to
make a slit in the bag (approximately 2 cm) near each corner, and
the bag was allowed to sit for an additional 21 days in the
controlled environment. At the end of this aging period, the region
where the slits were cut were visually analyzed and photographed to
document the findings related to iron staining. Yellow staining is
defined as a yellow to orange shade to the mortar surface in the
immediate vicinity of the cut slits. Samples containing no chemical
admixtures (reference) and 0.02% Na.sub.2-EDG (% cement weight)
were prepared according to the above protocol, and no difference in
color between the two samples were noticed, indicating that EDG
does not cause yellow staining in finished products.
Example 6: Process for Making New Additive Compositions
[0143] This example describes the synthesis of ethylene-diglycine
(EDG) by reacting mono-ethanolamine (MEA) with monochloracetic acid
(MCA) in the presence of a sodium hydroxide (NaOH) and heat, to
generate EDG and sodium chloride (NaCl).
[0144] The reaction products reported in Examples 6 through 18
included NaCl, a known strength enhancer, at 55-95% by weight of
Na.sub.2-EDG. The content of NaCl can be reduced to 0% by
purification.
[0145] The reaction products reported in Examples 6 through 18
included impurities (i.e. compounds other than EDG and NaCl) at up
to 12% of sample weight. The content of solid impurities was up to
40% of total solids in the reaction product mixture. The content of
impurities can be reduced by optimizing the manufacturing
process.
[0146] The synthesis was conducted by the following procedure:
10.91 g ethanolamine (0.175 moles), 56.01 g of 50% NaOH solution
(0.700 moles) and 100 g of distilled water were charged into a 250
ml four neck round bottom flask. The flask was equipped with a
condenser, a mechanical stirrer and a dropping funnel. Chloroacetic
acid 33.08 g (0.350 moles) was dissolved in 24 grams of water and
charged into the dropping funnel. Chloroacetic acid was slowly
added to the flask over a period of 7 minutes. The reaction was
then heated to a temperature of 90 degrees centigrade and held at
that temperature for 5 hours. Additional 28.06 grams of 50% NaOH
solution was added to complete the conversion of chloroacetic acid
over the course of the reaction. The pH of the final product was
12.6.
[0147] Table 5 shows the early strengths (at Day 1) of mortars
prepared with cements E, F, and I, described in FIG. 4A and FIG.
4B, in the presence of the informed percentages (% weight of solids
and % weight of Na.sub.2-EDG on cement weight or % s/c) of a
commercial Na.sub.2-EDG-based product manufactured by the process
that involves monoethanolamine, formaldehyde, and sodium cyanide
starting materials (named `commercial`) and of a product
manufactured in the laboratory by combining MEA with MCA in the
presence of NaOH. Table 5 shows the similar performance of the
Example 6 sample compared to the `commercial` sample.
TABLE-US-00004 TABLE 5 Dosage of solid reaction products
Na.sub.2--EDG Cement Source of EDG (% s/c) (% s/c) 1 d % blank E --
0 100.0% E Commercial 0.005 0.005 106.0% E Commercial 0.01 0.01
119.6% E Commercial 0.02 0.02 107.8% E Example 6 0.009 0.0059
112.1% E Example 6 0.017 0.0118 119.0% E Example 6 0.035 0.0236
117.0% F -- 0 0 100.0% F Commercial 0.005 0.005 115.0% F Commercial
0.01 0.01 117.8% F Commercial 0.02 0.02 118.2% F Example 6 0.007
0.0044 113.6% F Example 6 0.015 0.0088 120.0% F Example 6 0.029
0.0177 126.1% I -- 0 0 100.0% I Commercial 0.005 0.005 105.3% I
Commercial 0.01 0.01 107.7% I Commercial 0.02 0.02 107.3% I Example
6 0.007 0.0044 114.4% I Example 6 0.015 0.0088 109.8% I Example 6
0.029 0.0177 110.2%
[0148] Table 6 shows the characterization of these two sources of
EDG (`commercial` or Sample A, and `Example 6` or Sample B). Total
solids was calculated by a standard oven method by determining the
weight difference after drying the sample at 125.+-.1.degree. C.
for 25.+-.1 minutes, run in triplicates. EDG material was tested
for its chloride content by Ion Chromatography with the column for
anions analysis with autosupressor and electrochemical detection
(Dionex DX-500).
[0149] Structure analysis of EDG material was performed by H1
liquid-state Nuclear Magnetic Resonance Spectroscopy (Varian Unity
INOVA 400 High resolution). FIG. 5 shows the NMR spectra of the two
samples. NMR assignments (in ppm) are as follows: 2.71 (A), 2.74
(B) --NCH2-groups; 3.21 (A), 3.24 (B) Glycine --CH2-groups; 3.63
(A), 3.62 (B) --OCH2-groups.
[0150] The small differences in chemical shift between the two
samples are due to differences in pH. Both samples show the major
component is Na.sub.2-EDG. Minor components are disodium ethanol
monoglycinate and unidentified components.
TABLE-US-00005 TABLE 6 Commercial EDG or Example 6 EDG or
Characteristic Sample A Sample B Total solids (%) 30.41 .+-. 0.07
27.56 .+-. 0.09 pH 12.97 12.60 Chloride (% of sample) 1.006
5.230
Examples 7-11--Synthesis of Na.sub.2-EDG
[0151] The MCA-MEA adducts were prepared by the same process as
described in Example 6. Table 7 shows the amounts of MCA, MEA and
alkali used for the reactions. The final products pH values are
also shown.
TABLE-US-00006 TABLE 7 Chloroacetic acid Ethanolamine Product (MCA)
(MEA) Alkali addition pH Example 7 0.225 mol 0.113 mol
Na.sub.2CO.sub.3 powder 9.8 (19553-186) (21.3 grams) (7.02 grams)
0.676 mol (71.67 grams) Example 8 0.350 mol 0.175 mol 50% NaOH
solution 12.9 (19553-188) (33.08 grams) (10.91 grams) 1.61 mol NaOH
(90.01 grams solution)* Example 9 0.350 mol 0.175 mol 50% NaOH
solution 10.8 (19553-189) (33.08 grams) (10.91 grams) 0.7 mol NaOH
(56.01 grams solution) Example 10 0.350 mol 0.175 mol NaOH pellet
3.3 (19553-190) (33.08 grams) (10.91 grams) 0.35 mol NaOH (14.00
grams solution) Example 11 0.350 mol 0.183 mol NaOH pellet NA
(19553-191) (33.08 grams) (11.43 grams) 0.7 mol NaOH (28.01 grams
solution) *0.7 mol (56.01 grams of 50% solution) of NaOH is added
first, then 34 grams of 50% NaOH solution was added during the
course of the reaction. NA: not available
Example 12-18--Synthesis and Performance of Na.sub.2-EDG
[0152] The MCA-MEA adducts shown in Table 8 were prepared by
similar process as described in Example 6 but under different
temperatures and reaction times. Total solids was calculated by a
standard oven as described in Example 6, and EDG content was
determined by Ion Chromatography (IC). Set up for IC is Dionex
DX-500 with column for anions analysis with auto-suppressor. EDG
standard (acid form) at different concentrations was run to acquire
calibration curve and, based on that, the amount of EDG (acid form)
in the sample was calculated and recalculated to sodium salt
form.
[0153] Table 9 shows the strength performance at 1 day of age of
Examples 12-18 when tested in EN-196 mortars prepared with Cement
F. Examples 12-18 show similar to superior performance compared to
the `commercial` sample.
TABLE-US-00007 TABLE 8 Theoretical Na.sub.2-EDG Yield (mass %,
Nominal Molar based on Na2- EDG Yield Ratio Reaction Reaction
reactor EDG (% of (MCA:MEA:NaOH) T (.degree. C.) time (h) charges)
(%) theoretical) Example 2:1:4 60 1 19.0% 14.60 77 12 0060-27
Example 2:1:6 60 0.5 15.5% 10.38 67 13 0060-33 Example 2:1:6 50 1
15.5% 12.34 80 14 0060-39 Example 2:1:6 40 4 15.5% 9.87 64 15
0060-41 Example 2:1:4 40 4 19.0% 12.49 66 16 0060-43 Example 2:1:4
50 2 16.6% 14.70 89 17 0060-45 Example 2:1:4 25 n/a 19.0% 15.42 81
18 0060-49
TABLE-US-00008 TABLE 9 Dosage of solid reaction products 1 d %
Source of EDG (% s/c) blank -- 0 100.00% Commercial 0.01 114.9%
Commercial 0.02 116.3% Example 12 0.01 115.6% Example 12 0.02
124.4% Example 13 0.01 113.8% Example 13 0.02 118.5% Example 14
0.01 113.6% Example 14 0.02 116.7% Example 15 0.01 115.6% Example
15 0.02 119.4% Example 16 0.01 125.0% Example 16 0.02 121.7%
Example 17 0.01 113.9% Example 17 0.02 118.2% Example 18 0.01
127.3% Example 18 0.02 126.9%
Example 19: Formulation with EDG and Diethanolisopropanolamine
(DEIPA) Provides Higher Early Strength than Formulations with Just
One of these Amines
[0154] A combination of EDG, diethanolisopropanolamine (DEIPA), and
calcium chloride was evaluated for its ability to enhance either
early strength, or late strength, or both of a cement. The Example
19 Cement was used to prepare the mortars. The results of the QXRD
and XRF analyses of the Example 19 cement are presented below in
Tables 10 and 11.
TABLE-US-00009 TABLE 10 QXRD analysis of Example 19 Cement Phase
determined by % QXRD weight Alite 66.2 Belite 9.9 C4AF 11.0 C3A 4.3
CaO 0.1 MgO 1.0 Ca(OH)2 0.6 Calcite 0.9 Gypsum 2.6 Hemihydrate 0.0
Anhydrite 2.5
TABLE-US-00010 TABLE 11 XRF analysis of Example 19 Cement Analyte
determined by XRF Weight % Total SO.sub.3 2.71 Total Alkali
0.47
[0155] The mortars were prepared according to the protocol
described in Example 1 using the Example 19 Cement, and the results
of strength measurements were expressed as a change in MPa compared
to a reference cement (DMPa). The results are presented in Table
12.
TABLE-US-00011 TABLE 12 Strength of Example 19 Cement EDG DEIPA
CaCl.sub.2 DMPa DMPa DMPa Total Run ppm ppm ppm 1 day 3 day 7 day
DMPa Avg DMPa 1 118 0 293 0.6 1 0.7 2.3 0.76 2 0 100 293 1.2 0.5
-0.7 1.0 0.33 3 50 58 293 1.0 1.0 1.5 3.5 1.17
[0156] Runs 1 and 2 reported in Table 12 were done with either EDG
or DEIPA alone, and resulted in the average strength increase ("Avg
DMPa") of 0.76 and 0.33 MPa, respectively. Run 3 was done using a
blend of EDG and DEIPA at similar total dosage. The average
strength increase was 1.17 MPa.
[0157] While this invention has been particularly shown and
described with references to example embodiments thereof, it will
be understood by those skilled in the art that various changes in
form and details may be made therein without departing from the
scope of the invention encompassed by the appended claims.
* * * * *