CN109233037A - A kind of modification ferrochrome slag for fire-retardant reinforced rubber filler - Google Patents
A kind of modification ferrochrome slag for fire-retardant reinforced rubber filler Download PDFInfo
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- CN109233037A CN109233037A CN201811195175.7A CN201811195175A CN109233037A CN 109233037 A CN109233037 A CN 109233037A CN 201811195175 A CN201811195175 A CN 201811195175A CN 109233037 A CN109233037 A CN 109233037A
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- ferrochrome slag
- ferrochrome
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention discloses a kind of modification ferrochrome slags for fire-retardant reinforced rubber filler, belong to resource circulation utilization field.The modification ferrochrome cinder ladle includes two oxalic acid hydrate solution, silane coupling agent KH560, acetone and ferrochrome slag；The mass fraction of the two oxalic acid hydrates solution is 80%~95%；The partial size of the ferrochrome slag is 4.2 μm~113.8 μm；The silane coupling agent KH560 is technical pure；The acetone is that analysis is pure.The price that the present invention solves existing rubber industry main stuffing carbon black and white carbon black is higher and performance is single, only there is reinforcing property, ferrochrome slag, which is directly added into rubber, easily reunites, and the problem that the inorganic interface of ferrochrome slag is poor with the compatibility of rubber organic interface, the high added value for realizing industrial waste recycles, promote smelter to increase benefit, rubber product industry cost declining, meets the industry development requirement of current energy conservation and environmental protection, circular economy.
Description
Technical field
The invention belongs to resource circulation utilization fields, and in particular to a kind of modification ferrochrome for fire-retardant reinforced rubber filler
Slag and preparation method thereof.
Background technique
Ferrochrome slag is the pyrometallurgical smelting generated chromium residue of when containing ferrochrome, mainly mineral hot furnace method smelting high carbon chromium
It is generated when iron, main chemical compositions SiO2、Fe2O3、Al2O3、CaO、MgO、Cr2O3、SO3、P2O5Deng wherein Al2O3With MgO
Content it is higher.Ferrochrome slag is mainly used as cement raw material at present, and production process pollutes ambient enviroment and added value is low,
Therefore, it how efficiently with the utilization ferrochrome slag of high added value, realizes the purpose of environment Reduction of Students' Study Load, reducing enterprise cost, is one and compels to be essential
It solves the problems, such as.
Rubber needs largely using filler in preparation process to improve as widely applied polymer material
Its mechanical property, processing performance and filling increase-volume.Currently used gum filler mainly includes carbon black, white carbon black etc., still
The production of carbon black and white carbon black not only cumbersome, but also need to consume mass energy and resource, lead to higher cost and performance
It is single, i.e., only there is reinforcing property.In face of the above problem, ferrochrome slag is a kind of potential as a kind of high magnesium substance of Silicon-rich high alumina
Fire-retardant reinforced filling, utilize the SiO contained2, CaO play reinforcing effect, utilize MgO, the Al contained2O3Fire retardation is played,
It realizes that the high added value of industrial waste recycles, promotes smelter synergy, rubber product industry cost declining.
Summary of the invention
Price in order to solve existing rubber industry main stuffing carbon black and white carbon black is higher and performance is single, i.e., only has
Reinforcing property, ferrochrome slag is directly added into easily reunites and the inorganic interface of ferrochrome slag and rubber organic interface in rubber
The poor problem of compatibility, the present invention provides a kind of modification ferrochrome slag for fire-retardant reinforced rubber filler, to solve with
Upper problem.
The present invention is achieved by the following technical programs.
The present invention provides a kind of modification ferrochrome slag for fire-retardant reinforced rubber filler, the modification ferrochrome slags by weight hundred
Divide as follows than being formulated:
The mass fraction of the two oxalic acid hydrates solution is 80%~95%；The silane coupling agent KH560 is technical pure；
The acetone is that analysis is pure；The partial size of the ferrochrome slag is 4.2 μm~113.8 μm, and chemical component (mass fraction) is SiO2
(3.96%~35.62%), Fe2O3(5.63%~7.26%), Al2O3(22.54%~24.32%), CaO (0.30%~
0.41%), MgO (23.68%~26.78%), Cr2O3(6.89%~8.32%), SO3(0.061%~0.092%), P2O5
(0.022%~0.037%) and other (1.008%~2.387%).
Invention also provides the preparation method of above-mentioned modified ferrochrome slag, which includes the following steps:
Two oxalic acid hydrate solution are mixed with ferrochrome slag first, using constant temperature blender with magnetic force at 55 DEG C of whipping temp
~75 DEG C, 7h~10h is stirred to it under mixing speed 650r/min~950r/min, be then added into said mixture
Silane coupling agent KH560, acetone, using constant temperature blender with magnetic force in 35 DEG C~65 DEG C of whipping temp, mixing speed 450r/min
Under~850r/min, 1h~3h is stirred, obtains modified ferrochrome slag.
The principles of science of the invention:
On the one hand, it is reacted using two oxalic acid hydrate solution with part CaO in ferrochrome slag, to be conducive to improve ferrochrome
Specific surface area, pore volume and the aperture of slag achieve the purpose that abundant pore structure, improve the contact area of ferrochrome slag and rubber, with
And ferrochrome slag achievees the effect that reinforcing rubber the adsorption capacity of carbon black or white carbon black.
On the other hand, the ferrochrome slag with good pore structure will cause moisture pick-up properties enhancing, further result in ferrochrome slag group
The generation of poly- phenomenon aggravates ferrochrome slag dispersibility in rubber and is deteriorated, so using silane coupling agent KH560 and acetone to having
The ferrochrome slag surface of good pore structure is modified processing, forms modified ferrochrome slag, it is easy to reunite not only to can solve ferrochrome slag
Problem, and can be further improved the compatibility of modified ferrochrome slag and rubber, further achieve the effect that reinforcing rubber.
In addition, containing a large amount of Al in ferrochrome slag2O3With MgO, wherein Al2O3It is the compound of high rigidity, fusing point 2054
DEG C, boiling point is 2980 DEG C；MgO is typical alkaline earth oxide, and fusing point is 2852 DEG C, and boiling point is 3600 DEG C.Therefore Al2O3
It is good refractory material with MgO, a large amount of Al will be contained2O3It is added in rubber, can substantially mention with the modification ferrochrome slag of MgO
The flame retardant property of high rubber, achievees the effect that rubber flame-retarded.
Compared with prior art, the present invention has following technical effect that
1, the present invention solve existing rubber industry main stuffing carbon black and white carbon black price it is higher and only there is reinforcement
Performance, ferrochrome slag, which are directly added into rubber, easily reunites and the inorganic interface of ferrochrome slag is compatible with rubber organic interface
The poor problem of property.
2, the present invention is fire-retardant reinforced rubber filler using modified ferrochrome slag, and realizes the high added value of industrial waste
It recycles, promotes smelter synergy, rubber product industry cost declining, meet the production of current energy conservation and environmental protection, circular economy
Industry demand for development.
Specific embodiment
The present invention is described in detail below in conjunction with specific embodiment, but the present invention is not limited to following embodiments.
One, a kind of preparation method of the modification ferrochrome slag for fire-retardant reinforced rubber filler of the present invention
Embodiment 1
Component and its quality proportioning used for preparing product of the present invention 100g are as follows:
The mass fraction of the two oxalic acid hydrates solution is 80%；The silane coupling agent KH560 is technical pure；Described third
Ketone is that analysis is pure；The partial size of the ferrochrome slag is 4.8 μm~110.7 μm, and chemical component (mass fraction) is SiO2
(34.54%), Fe2O3(5.95%), Al2O3(23.88%), CaO (0.33%), MgO (25.43%), Cr2O3(7.64%),
SO3(0.069%), P2O5(0.024%) and other (2.137%).
Two oxalic acid hydrate solution are mixed with ferrochrome slag first, using constant temperature blender with magnetic force in whipping temp 65
DEG C, 10h is stirred to it under mixing speed 650r/min, silane coupling agent KH560, third are then added into said mixture
Ketone stirs 2h using constant temperature blender with magnetic force at 45 DEG C of whipping temp, mixing speed 850r/min, obtains modified ferrochrome slag.
Embodiment 2
Component and its quality proportioning used for preparing product of the present invention 100g are as follows:
The mass fraction of the two oxalic acid hydrates solution is 95%；The silane coupling agent KH560 is technical pure；Described third
Ketone is that analysis is pure；The partial size of the ferrochrome slag is 5.2 μm~110.3 μm, and chemical component (mass fraction) is SiO2
(35.27%), Fe2O3(7.26%), Al2O3(24.03%), CaO (0.38%), MgO (23.68%), Cr2O3(6.89%),
SO3(0.092%), P2O5(0.037%) and other (2.361%).
Two oxalic acid hydrate solution are mixed with ferrochrome slag first, using constant temperature blender with magnetic force in whipping temp 75
DEG C, 9h is stirred to it under mixing speed 850r/min, silane coupling agent KH560, third are then added into said mixture
Ketone stirs 1h using constant temperature blender with magnetic force at 35 DEG C of whipping temp, mixing speed 550r/min, obtains modified ferrochrome slag.
Embodiment 3
Component and its quality proportioning used for preparing product of the present invention 100g are as follows:
The mass fraction of the two oxalic acid hydrates solution is 85%；The silane coupling agent KH560 is technical pure；Described third
Ketone is that analysis is pure；The partial size of the ferrochrome slag is 5.0 μm~100.9 μm, and chemical component (mass fraction) is SiO2
(35.62%), Fe2O3(6.53%), Al2O3(24.32%), CaO (0.41%), MgO (24.95%), Cr2O3(7.05%),
SO3(0.081%), P2O5(0.031%) and other (1.008%).
Two oxalic acid hydrate solution are mixed with ferrochrome slag first, using constant temperature blender with magnetic force in whipping temp 55
DEG C, 9h is stirred to it under mixing speed 950r/min, silane coupling agent KH560, third are then added into said mixture
Ketone stirs 1.5h using constant temperature blender with magnetic force at 65 DEG C of whipping temp, mixing speed 650r/min, obtains modified ferrochrome
Slag.
Embodiment 4
Component and its quality proportioning used for preparing product of the present invention 100g are as follows:
The mass fraction of the two oxalic acid hydrates solution is 90%；The silane coupling agent KH560 is technical pure；Described third
Ketone is that analysis is pure；The partial size of the ferrochrome slag is 4.2 μm~112.5 μm, and chemical component (mass fraction) is SiO2
(35.14%), Fe2O3(6.58%), Al2O3(24.08%), CaO (0.37%), MgO (24.69%), Cr2O3(7.19%),
SO3(0.080%), P2O5(0.029%) and other (1.841%).
Two oxalic acid hydrate solution are mixed with ferrochrome slag first, using constant temperature blender with magnetic force in whipping temp 60
DEG C, 8h is stirred to it under mixing speed 750r/min, silane coupling agent KH560, third are then added into said mixture
Ketone stirs 3h using constant temperature blender with magnetic force at 55 DEG C of whipping temp, mixing speed 450r/min, obtains modified ferrochrome slag.
Embodiment 5
Component and its quality proportioning used for preparing product of the present invention 100g are as follows:
The mass fraction of the two oxalic acid hydrates solution is 80%；The silane coupling agent KH560 is technical pure；Described third
Ketone is that analysis is pure；The partial size of the ferrochrome slag is 4.7 μm~113.8 μm, and chemical component (mass fraction) is SiO2
(33.96%), Fe2O3(5.63%), Al2O3(22.54%), CaO (0.30%), MgO (26.78%), Cr2O3(8.32%),
SO3(0.061%), P2O5(0.022%) and other (2.387%).
Two oxalic acid hydrate solution are mixed with ferrochrome slag first, using constant temperature blender with magnetic force in whipping temp 70
DEG C, 7h is stirred to it under mixing speed 950r/min, silane coupling agent KH560, third are then added into said mixture
Ketone stirs 2.5h using constant temperature blender with magnetic force at 45 DEG C of whipping temp, mixing speed 750r/min, obtains modified ferrochrome
Slag.
Embodiment 6
Component and its quality proportioning used for preparing product of the present invention 100g are as follows:
The mass fraction of the two oxalic acid hydrates solution is 95%；The silane coupling agent KH560 is technical pure；Described third
Ketone is that analysis is pure；The partial size of the ferrochrome slag is 5.5 μm~98.6 μm, and chemical component (mass fraction) is SiO2(34.91%),
Fe2O3(6.39%), Al2O3(23.77%), CaO (0.38%), MgO (25.12%), Cr2O3(7.42%), SO3
(0.077%), P2O5(0.028%) and other (1.905%).
Two oxalic acid hydrate solution are mixed with ferrochrome slag first, using constant temperature blender with magnetic force in whipping temp 55
DEG C, 9h is stirred to it under mixing speed 850r/min, silane coupling agent KH560, third are then added into said mixture
Ketone stirs 1.5h using constant temperature blender with magnetic force at 55 DEG C of whipping temp, mixing speed 850r/min, obtains modified ferrochrome
Slag.
Comparative example 1
Component and its quality proportioning used for preparing product of the present invention 100g are as follows:
The mass fraction of the two oxalic acid hydrates solution is 95%；The silane coupling agent KH560 is technical pure；Described third
Ketone is that analysis is pure；The partial size of the ferrochrome slag is 5.5 μm~98.6 μm, and chemical component (mass fraction) is SiO2(34.91%),
Fe2O3(6.39%), Al2O3(23.77%), CaO (0.38%), MgO (25.12%), Cr2O3(7.42%), SO3
(0.077%), P2O5(0.028%) and other (1.905%).
Two oxalic acid hydrate solution are mixed with ferrochrome slag first, using constant temperature blender with magnetic force in whipping temp 55
DEG C, 9h is stirred to it under mixing speed 850r/min, silane coupling agent KH560, third are then added into said mixture
Ketone stirs 1.5h using constant temperature blender with magnetic force at 55 DEG C of whipping temp, mixing speed 850r/min, obtains modified ferrochrome
Slag.
Comparative example 2
Component and its quality proportioning used for preparing product of the present invention 100g are as follows:
The mass fraction of the two oxalic acid hydrates solution is 95%；The silane coupling agent KH560 is technical pure；Described third
Ketone is that analysis is pure；The partial size of the ferrochrome slag is 5.5 μm~98.6 μm, and chemical component (mass fraction) is SiO2(34.91%),
Fe2O3(6.39%), Al2O3(23.77%), CaO (0.38%), MgO (25.12%), Cr2O3(7.42%), SO3
(0.077%), P2O5(0.028%) and other (1.905%).
Two oxalic acid hydrate solution are mixed with ferrochrome slag first, using constant temperature blender with magnetic force in whipping temp 55
DEG C, 9h is stirred to it under mixing speed 850r/min, silane coupling agent KH560, third are then added into said mixture
Ketone stirs 1.5h using constant temperature blender with magnetic force at 55 DEG C of whipping temp, mixing speed 850r/min, obtains modified ferrochrome
Slag.
Comparative example 3
Component and its quality proportioning used for preparing product of the present invention 100g are as follows:
The mass fraction of the two oxalic acid hydrates solution is 95%；The silane coupling agent KH560 is technical pure；Described third
Ketone is that analysis is pure；The partial size of the ferrochrome slag is 5.5 μm~98.6 μm, and chemical component (mass fraction) is SiO2(34.91%),
Fe2O3(6.39%), Al2O3(23.77%), CaO (0.38%), MgO (25.12%), Cr2O3(7.42%), SO3
(0.077%), P2O5(0.028%) and other (1.905%).
Two oxalic acid hydrate solution are mixed with ferrochrome slag first, using constant temperature blender with magnetic force in whipping temp 55
DEG C, 9h is stirred to it under mixing speed 850r/min, silane coupling agent KH560, third are then added into said mixture
Ketone stirs 1.5h using constant temperature blender with magnetic force at 55 DEG C of whipping temp, mixing speed 850r/min, obtains modified ferrochrome
Slag.
Comparative example 4
Component and its quality proportioning used for preparing product of the present invention 100g are as follows:
The mass fraction of the two oxalic acid hydrates solution is 95%；The silane coupling agent KH560 is technical pure；Described third
Ketone is that analysis is pure.
Utilize constant temperature blender with magnetic force in 55 DEG C of whipping temp, mixing speed 850r/min two oxalic acid hydrate solution first
Under 9h is stirred to it, then into said mixture be added silane coupling agent KH560, acetone, utilize temperature constant magnetic stirring
Device stirs 1.5h at 55 DEG C of whipping temp, mixing speed 850r/min, obtains modified solution.
Two, the Mechanics Performance Testing after rubber is added in the modified ferrochrome slag of the present invention
Examples 1 to 6 and comparative example 1~4 are prepared, performance testing process is as follows:
After natural rubber (100 parts) is put into open mill thin logical 3~5 times, mixer (smelting temperature is added in natural rubber
70 DEG C) it is kneaded 3min, it sequentially adds zinc oxide (2.5 parts) aggregate sample and is kneaded 1min, carbon black (30 parts) is added and modified ferrochrome slag
(20 parts) aggregate sample takes out spare, i.e. mixing after being kneaded 1min, addition promotor (1.0 parts) and (1.5 parts) mixing 1min of sulphur
Glue；It is logical 6~8 times thin that mixing glue is put into open mill, after parking 12h after beating triangle bag 5 times, the mixing glue of 60g is weighed, using four
Pillar vulcanizing press is vulcanized, and curing temperature is 145 DEG C, and vulcanization is placed for 24 hours after a certain period of time, obtains modified ferrochrome slag day
Right rubber.
" measurement of vulcanized rubber or thermoplastic elastomer tensile stress-strain performance " (GB/T528-2009) tests modified chromium
The tensile property of scum natural rubber；" measurement of vulcanized rubber or thermoplastic elastomer tearing strength is (pants type, square, crescent
Sample) " (GB/T529-2008) test the tearing strength of modified ferrochrome slag natural rubber；" vulcanized rubber or thermoplastic elastomer pressure
Enter hardness test method part 1: Shore durometer method (Shao Er hardness) " test the hardness for being modified ferrochrome slag natural rubber；" modeling
Expect combustibility test method oxygen index method " (GB/T2406-1993) test the limit oxygen index of modified ferrochrome slag natural rubber
(LOI)；" equipment and device plastic material combustibility test method UL94 " (ISBN 0-7629-0082-2) tests modified chromium
The vertical combustion rank of scum natural rubber.
The mechanical property and flame retardant property of the modified ferrochrome slag natural rubber of table 1.
Claims (2)
1. a kind of modification ferrochrome slag for fire-retardant reinforced rubber filler, which is characterized in that by weight percentage, described in preparation
Modified ferrochrome slag raw material is as follows:
The mass fraction of the two oxalic acid hydrates solution is 80%~95%；
The silane coupling agent KH560 is technical pure；
The acetone is that analysis is pure；
The partial size of the ferrochrome slag is 4.2 μm~113.8 μm, chemical component, by weight percent than being calculated as:
2. a kind of preparation method for the modification ferrochrome slag of fire-retardant reinforced rubber filler, feature as described in claim 1 exist
In including the following steps:
Two oxalic acid hydrate solution are mixed with ferrochrome slag first, using constant temperature blender with magnetic force in whipping temp 55 DEG C~75
DEG C, 7h~10h is stirred to it under mixing speed 650r/min~950r/min, silane is then added into said mixture
Coupling agent KH560, acetone, using constant temperature blender with magnetic force 35 DEG C~65 DEG C of whipping temp, mixing speed 450r/min~
Under 850r/min, 1h~3h is stirred, obtains modified ferrochrome slag.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811195175.7A CN109233037A (en) | 2018-10-15 | 2018-10-15 | A kind of modification ferrochrome slag for fire-retardant reinforced rubber filler |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811195175.7A CN109233037A (en) | 2018-10-15 | 2018-10-15 | A kind of modification ferrochrome slag for fire-retardant reinforced rubber filler |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109233037A true CN109233037A (en) | 2019-01-18 |
Family
ID=65052964
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| Application Number | Title | Priority Date | Filing Date |
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| CN201811195175.7A Withdrawn CN109233037A (en) | 2018-10-15 | 2018-10-15 | A kind of modification ferrochrome slag for fire-retardant reinforced rubber filler |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114292026A (en) * | 2022-01-20 | 2022-04-08 | 广东永航新材料实业股份有限公司 | Satin glaze suitable for quick firing and having special crystallization effect and preparation method thereof |
-
2018
- 2018-10-15 CN CN201811195175.7A patent/CN109233037A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114292026A (en) * | 2022-01-20 | 2022-04-08 | 广东永航新材料实业股份有限公司 | Satin glaze suitable for quick firing and having special crystallization effect and preparation method thereof |
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Application publication date: 20190118 |