GB2143809A - Rigid coherent gel for binding of refractories - Google Patents
Rigid coherent gel for binding of refractories Download PDFInfo
- Publication number
- GB2143809A GB2143809A GB08414078A GB8414078A GB2143809A GB 2143809 A GB2143809 A GB 2143809A GB 08414078 A GB08414078 A GB 08414078A GB 8414078 A GB8414078 A GB 8414078A GB 2143809 A GB2143809 A GB 2143809A
- Authority
- GB
- United Kingdom
- Prior art keywords
- gel
- double
- refractory
- grains
- chromium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 230000001427 coherent effect Effects 0.000 title claims description 6
- 239000011819 refractory material Substances 0.000 title description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 12
- 239000011651 chromium Substances 0.000 claims abstract description 12
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 10
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 9
- 230000007062 hydrolysis Effects 0.000 claims abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004411 aluminium Substances 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 20
- 238000001879 gelation Methods 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052596 spinel Inorganic materials 0.000 claims description 4
- 239000011029 spinel Substances 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 2
- 239000000413 hydrolysate Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims 2
- 150000001414 amino alcohols Chemical group 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 239000002002 slurry Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 230000001939 inductive effect Effects 0.000 abstract 1
- 229940102253 isopropanolamine Drugs 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 23
- 239000000203 mixture Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- QQHSIRTYSFLSRM-UHFFFAOYSA-N alumanylidynechromium Chemical compound [Al].[Cr] QQHSIRTYSFLSRM-UHFFFAOYSA-N 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 5
- 229910052566 spinel group Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011822 basic refractory Substances 0.000 description 1
- -1 chromium alkoxides Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
-
- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/03—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
- C04B35/04—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on magnesium oxide
- C04B35/043—Refractories from grain sized mixtures
-
- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/03—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
- C04B35/04—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on magnesium oxide
- C04B35/043—Refractories from grain sized mixtures
- C04B35/047—Refractories from grain sized mixtures containing chromium oxide or chrome ore
-
- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/6325—Organic additives based on organo-metallic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/069—Aluminium compounds without C-aluminium linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
A double alkoxide of chromium and aluminium, for example the isopropoxide is used to bind refractory grains. In an example magnesia grain is mixed into a slurry with the double hydroxide, water, isopropanol and triethanolamine being incorporated as hydrolysis and gellation inducing agents.
Description
SPECIFICATION
Improvements in the binding of refractories
This invention relates to the binding of refractories.
According to the present invention there is provided a method of forming a rigid coherent gel suitable for binding refractory grains such method comprising the step of causing or allowing a double alkoxide of chromium and aluminium to gel. The gelling sequence comprises an initial hydrolysis followed by a setting of the hydrolysate.
Chromium and aluminium form volatile double alkoxides which can be isoiated as pure compounds.
The double isopropoxide is soluble in isopropanol. When this solution is rendered aqueous for the hydrolysis and treated with triethanolamine, a strongly basic aminoalcohol, (preferably so as to give one bond per metal atom), a rigid coherent gel suitable for binding refractory grain is formed. This gel is especially suitable for binding alumina grain and basic refractory grains.
The addition of chrome to refractory compositions as a way of improving resistance to thermal shock and to erosion by slags is well known. However, if the composition contains silica in the bonding phase the advantages of adding chrome are minimised. Generally, for best results silica should be absent and the chromium present as a chromia- alumina solid solution, if the refractory composition is not basic.
This is achieved in accordance with the invention, as the use of a gel obtained from a chromium-aluminium double alkoxide to bind refractory grain, besides eliminating silica in the bonding phase, produces, after firing, a chromia-alumina solid solution. For best results the gel entraining the refractory grains should be fired under oxidising conditions.
When a chromium-aluminium double alkoxide is used to bind basic grain, e.g. magnesia grain, the oxide residues from the double alkoxide react to form spinels. The grain mixture should contain at least sufficient reactive magnesia to form the spinels. One way of achieving this is to include ball-milled magnesia fines in the grain mix. The formation of spinels is another important feature of the invention.
It should be noted that the simple chromium alkoxides are highly polymerised and therefore do not form useful gels.
The volatile double isopropoxide of chromium and aluminium may be synthesised (J.V.Singh, N.L.Jain and R.C.Mehrotra, Synth. React. Inorg. Met-Org. Chem., 1978, 979) according to equation (1).
CrC13.3THF + 3K [Al(OPri)4] < Cr [AI(OPr')4]3 + 3KCI + 3THF t This double isopropoxide of chromium and aluminium was prepared as described, on a tenfold scale.
The invention will now be described with reference to the following Examples:
Example I
Gelation conditions - procedure A
4g of the chromium-aluminium double isopropoxide are dissolved in 20 ml dry isopropanol and 0.85ml triethanolamine added. This corresponds to one bond per metal atom. This is the stock solution. As hydrolysis/gelation agent, a mixture of equal parts by volume of water and isopropanol is used. Table 1 gives gel times and gel characteristics.
TABLE 1
Gel characteristics of chromium aluminium double isopropoxide
Volume of stock Volume of hydrolysisl Gel time (min) and
solution (mI) gelation agent (mI) gel characteristics
10 0.1 No increase in viscosity
10 0.15 Ca.30 - rigid coherent gel
suitable for binding
refractory grain
10 0.2 Ca.1 - rigid coherent gel
Gelation conditions - procedure B
3.16g of the chromium-aluminium double isopropoxide Cr[Al(OPr)4]3 and 1.7ml triethanolamine are dissolved in 20 ml isopropanol. This is solution A. The hydrolysis/gelation agent, solution B, consists of water and isopropanol in equal volumes.
Table 2 gives gel times and gel characteristics.
TABLE 2
Gel characteristics of chromium aluminium double isopropoxide
Volume of solution A (ml) Volume of solution B rml) Gel characteristics
2 0.4 Hard brittle gel formed
very quickly
2 0.2 Hard brittle gel formed
very quickly
2 0.1 Gel formed in 1.5 min.
2 0.05 Gel formed in 2 min.
2 0.025 Gel formed in 13 min.
Example II
Preparation of refractory shape
To 10 ml stock solution there was added 0.15 ml of the hydrolysis and gelation agent. The resulting mixture was added to 90g Sardamag magnesia grain mix to give a slurry which was cast into a mould.
After about 30 minutes the casting was removed from the mould, then air-dried, baked and fired following standard procedures to give a refractory shape.
The Sardamag grain mix used had the following composition (Sardamag is a Registered Trade Mark).
B.S.410; 1976 sieve Percentage by weight
number and aperture
- 5 + 10 (-3.35mm + 1.70mm) 30
-10 + 25 (-1.70mm + 600 ,am) 20
-25 + 72 (-600 Fm + 212 Fm) 15
Ball-milled fines 35
The Sardamag grain used was Sardamag 251 SP grade.
The ball-milled fines had the following properties: Awl203 0.25% by weight
Fe203 0.22% by weight
CaO 1.62% by weight
SiO2 0.78% by weight
Residue MgO
BET surface area 2m2lg (approx.)
Surface area by Rigden method 0.25 - 0.30m2/g.
Sardamag 251 SP grain has the following typical analysis:
Mineral Weight percent
SiO2 0.7 - 0.9 AT203 0.2 - 0.4 Fe2O3 0.15 - 0.3 B203 0.02 - 0.4
CaO 1.8 - 2.3
MgO 95.5 - 96.5
Example III
A solution of the double alkoxide Cr [Al(OPr)4]3 in a mixture of triethanolamine and isopropanol was prepared by dissolving 3.16g of the double alkoxide and 1.7ml triethanolamine in 20ml isopropanol. This is solution A.
A mixture of water and isopropanol in equal volumes was also prepared. This is solution B.
0.15ml of solution B was added to 10ml of solution A. This mixture was added to 90g of magnesia grain mix, having the particle size distribution given below, to produce a slurry which was cast into a mould. After about 30 minutes the casting was removed from the mould, then air-dried, baked and fired at 1590 for about 4 hours. The refractory shape obtained had weil-bound grain and good surface characteristics. X-ray diffraction analysis showed the presence of substantial amounts of magnesia-alumina spinel and magnesia-chromia spinel.
Particle size distribution of magnesia grain
B.S. 410, 1976 sieve Aperture Percentage by weight
- S + 10 -3.55mm + 1.70mm 30
- 10 + 25 -1.70mm + 600 Am 20
- 25 + 72 -6001lm + 212 m 15
Ball-milled fines, BET 35
surface area approx. 2m2/g This Example demonstrates how substantial spinel formation can be induced by the use of a double alkoxide of chromium and aluminium to bind magnesia grain. This concept forms part of the subject of our copending Patent Application of today's date (Our Ref: MJD/JY/1264)
The invention can also be used in pressure moulding processes, for instance, the pressure moulding process which is described in British Patent Application No. 2,108,101A.
The procedure of the invention may be used to make the sliding-gate plate inserts described in British
Patent Application 2,113,806A.
Claims (11)
1. A method of forming a rigid coherent gel suitable for binding refractory grains such method comprising the step of causing or allowing to gel a double alkoxide of chromium and aluminium.
2. A method as claimed in Claim 1 wherein the double alkoxide is hydrolysed to a gellable hydrolysate by the addition of water.
3. A method as claimed in Claim 2 wherein a basic hydrolysis and gellation catalyst is added.
4. A method as claimed in Claim 3 in which the basic hydrolysis and gelation catalyst is an aminoalcohol.
5. A method as claimed in any of the preceding claims wherein the alkoxide is a double isopropoxide.
6. A method as claimed in either Claim 4 or Claim 5 wherein the double isopropoxide is dissolved in isopropanol and the solution is caused to gel by the addition of water and triethanolamine.
7. A method as claimed in Claim 3 wherein the refractory grains bound are alumina grains or magnesia grains.
8. A method as claimed in any of the preceding claims in which the refractory grains and the gel react on firing to produce at least one spinel.
9. A method as claimed in any of the preceding claims wherein the gel is fired ta form a refractory under oxidising conditions.
10. Methods according to Claim 1 and substantially as hereinbefore described.
11. Refractory shapes formed by a method according to any of the preceding claims.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08414078A GB2143809A (en) | 1983-06-21 | 1984-06-01 | Rigid coherent gel for binding of refractories |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB838316866A GB8316866D0 (en) | 1983-06-21 | 1983-06-21 | Binding of refractories |
| GB08414078A GB2143809A (en) | 1983-06-21 | 1984-06-01 | Rigid coherent gel for binding of refractories |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB8414078D0 GB8414078D0 (en) | 1984-07-04 |
| GB2143809A true GB2143809A (en) | 1985-02-20 |
Family
ID=26286442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08414078A Withdrawn GB2143809A (en) | 1983-06-21 | 1984-06-01 | Rigid coherent gel for binding of refractories |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2143809A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1988001991A1 (en) * | 1986-09-09 | 1988-03-24 | Manchem Limited | Binders for refractory grain |
| EP2060250A1 (en) * | 2007-11-16 | 2009-05-20 | KPSS Kao Professional Salon Services GmbH | Use of alkanolamines for thickening oxidative colouring emulsion |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB710427A (en) * | 1950-12-14 | 1954-06-09 | Socony Vacuum Oil Co Inc | Method of hydrogel preparation |
| GB996297A (en) * | 1960-11-15 | 1965-06-23 | Werner Hermann Kreidl | Improvements in refractory mortars |
| GB1003745A (en) * | 1961-06-07 | 1965-09-08 | Werner Hermann Kreidl | Improvements in refractory mortars |
| GB1350974A (en) * | 1970-05-26 | 1974-04-24 | Owens Illinois Inc | Double alkoxides and ultra-pure compounds prepared therefrom |
| GB2063848A (en) * | 1979-11-28 | 1981-06-10 | Zirconal Processes Ltd | Improvements in the binding of refractory powders |
| EP0063034A2 (en) * | 1981-04-10 | 1982-10-20 | Zirconal Processes Limited | Rigid coherent gel |
| GB2128604A (en) * | 1982-10-19 | 1984-05-02 | Harold Garton Emblem | Aluminium alkoxide derivates |
-
1984
- 1984-06-01 GB GB08414078A patent/GB2143809A/en not_active Withdrawn
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB710427A (en) * | 1950-12-14 | 1954-06-09 | Socony Vacuum Oil Co Inc | Method of hydrogel preparation |
| GB996297A (en) * | 1960-11-15 | 1965-06-23 | Werner Hermann Kreidl | Improvements in refractory mortars |
| GB1003745A (en) * | 1961-06-07 | 1965-09-08 | Werner Hermann Kreidl | Improvements in refractory mortars |
| GB1350974A (en) * | 1970-05-26 | 1974-04-24 | Owens Illinois Inc | Double alkoxides and ultra-pure compounds prepared therefrom |
| GB2063848A (en) * | 1979-11-28 | 1981-06-10 | Zirconal Processes Ltd | Improvements in the binding of refractory powders |
| EP0063034A2 (en) * | 1981-04-10 | 1982-10-20 | Zirconal Processes Limited | Rigid coherent gel |
| GB2128604A (en) * | 1982-10-19 | 1984-05-02 | Harold Garton Emblem | Aluminium alkoxide derivates |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1988001991A1 (en) * | 1986-09-09 | 1988-03-24 | Manchem Limited | Binders for refractory grain |
| EP2060250A1 (en) * | 2007-11-16 | 2009-05-20 | KPSS Kao Professional Salon Services GmbH | Use of alkanolamines for thickening oxidative colouring emulsion |
| WO2009062702A1 (en) * | 2007-11-16 | 2009-05-22 | Kpss-Kao Professional Salon Services Gmbh | Use of alkanolamines for thickening oxidative colouring emulsion |
| US8357209B2 (en) | 2007-11-16 | 2013-01-22 | Kpss-Kao Professional Salon Services Gmbh | Use of alkanolamines for thickening oxidative colouring emulsion |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8414078D0 (en) | 1984-07-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |