CN117966163A - Enamel glass enamel based on calcium silicate improvement and preparation method thereof - Google Patents
Enamel glass enamel based on calcium silicate improvement and preparation method thereof Download PDFInfo
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- CN117966163A CN117966163A CN202410388441.7A CN202410388441A CN117966163A CN 117966163 A CN117966163 A CN 117966163A CN 202410388441 A CN202410388441 A CN 202410388441A CN 117966163 A CN117966163 A CN 117966163A
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- calcium silicate
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- enamel
- glass lining
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- 239000011521 glass Substances 0.000 title claims abstract description 205
- 239000000378 calcium silicate Substances 0.000 title claims abstract description 159
- 229910052918 calcium silicate Inorganic materials 0.000 title claims abstract description 159
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 title claims abstract description 159
- 210000003298 dental enamel Anatomy 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 230000006872 improvement Effects 0.000 title abstract description 4
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 78
- 239000010959 steel Substances 0.000 claims abstract description 78
- 238000010304 firing Methods 0.000 claims abstract description 38
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 38
- 238000001816 cooling Methods 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000005507 spraying Methods 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 238000005303 weighing Methods 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims description 49
- 239000011159 matrix material Substances 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000005520 cutting process Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000005488 sandblasting Methods 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 7
- 230000003746 surface roughness Effects 0.000 claims description 7
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 79
- 238000005260 corrosion Methods 0.000 abstract description 79
- 238000005452 bending Methods 0.000 abstract description 20
- 230000008569 process Effects 0.000 abstract description 14
- 239000007787 solid Substances 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 3
- 238000002474 experimental method Methods 0.000 description 34
- 239000002253 acid Substances 0.000 description 18
- 239000011148 porous material Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 238000007373 indentation Methods 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000919 ceramic Substances 0.000 description 15
- 238000001514 detection method Methods 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 238000004458 analytical method Methods 0.000 description 14
- 239000002131 composite material Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000003513 alkali Substances 0.000 description 11
- 230000004580 weight loss Effects 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- 238000006073 displacement reaction Methods 0.000 description 9
- 238000013001 point bending Methods 0.000 description 9
- 230000009471 action Effects 0.000 description 8
- 230000008859 change Effects 0.000 description 8
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- 239000000126 substance Substances 0.000 description 8
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- 230000001681 protective effect Effects 0.000 description 6
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 210000001787 dendrite Anatomy 0.000 description 5
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- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
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- 238000000227 grinding Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 235000009161 Espostoa lanata Nutrition 0.000 description 1
- 240000001624 Espostoa lanata Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910017061 Fe Co Inorganic materials 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
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- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical group [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
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- 235000013305 food Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Glass Compositions (AREA)
Abstract
The invention discloses a glass-lined enamel based on calcium silicate improvement and a preparation method thereof, comprising the following steps: s1, weighing; s2, glazing; s3, stirring; s4, spraying; s5, standing; s6, firing: placing the well-placed steel substrate into a Ma Fushi firing furnace for program heating and cooling, and firing to 30-40 min after the highest temperature is 880 ℃ to prepare the glass-lined porcelain glaze; the invention successfully prepares the high mechanical property enamel glass with high toughness, high bending strength and high hardness by adding a proper amount of calcium silicate solid powder in the enamel glass preparation process and strictly controlling the calcination process, and the enamel glass has the advantages of high corrosion resistance and low porosity, and has a certain guiding value for improving the existing enamel glass preparation process.
Description
Technical Field
The invention relates to the technical field of glass lining preparation, in particular to a glass lining enamel based on calcium silicate improvement and a preparation method thereof.
Background
Glass lining is a composite material composed of enamel and metal matrix, and has good corrosion resistance, heat resistance, impact resistance, wear resistance and other characteristics. In the chemical industry, the glass lining is widely applied to manufacturing of equipment such as a reaction kettle and a reaction kettle pipeline, and can effectively prevent materials and steam in the reaction kettle from leaking and avoid explosion or poisoning accidents. In addition, glass lining equipment is widely applied in the fields of construction, furniture, household appliances, automobiles, aerospace and the like, and can also be used for manufacturing various containers, pipe fittings, pipelines and the like. However, since glass lining exhibits so-called brittle fracture, also called "pop-porcelain", due to rapid propagation of cracks during use. Finally, the glass lining has the defects of high brittleness and poor fracture toughness.
At present, the phenomena of porcelain explosion of glass lining equipment mainly comprise the following steps: the quality problem of the glass lining product, improper manufacturing process and improper use cause porcelain explosion; high pressure in the glass lining equipment causes porcelain explosion; the enamel firing temperature is not well controlled, so that large-area porcelain explosion is caused; enamel glass aging and damage cause porcelain explosion and the like. The porcelain explosion phenomenon of the glass lining can bring potential safety hazards to users, and therefore, the attention is required.
Calcium silicate is an important glass-melting agent, which has good melting, thermal stability and thermal resistance properties. Calcium silicate is added as an adhesive in the production process of the glass lining, so that the bonding strength between a metal matrix and a glass lining coating can be changed, the mechanical strength and corrosion resistance of the glass lining are improved, and the chemical stability is improved.
In addition, the influence of calcium silicate on the mechanical property and corrosion resistance of the glass lining is researched, and reference can be provided for preparing other corrosion-resistant materials. For example, in the fields of chemical industry, food, medicine and the like, the requirement on corrosion-resistant materials is strict, so that the research of the influence of calcium silicate on the mechanical property and corrosion resistance of glass lining is of great importance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the improved enamel glass based on calcium silicate and the preparation method thereof.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the preparation method of the improved enamel glass based on calcium silicate comprises the following steps:
S1, weighing: weighing 0.03-0.15 part of calcium silicate particles and adding the calcium silicate particles into 28-30 parts of ground enamel;
S2, glaze preparation: preparing ground enamel treated in the step S1 and water into slurry according to the proportion of 1.5-2.5:1, and primarily stirring and mixing the ground enamel and the water by using a glass rod to prepare glass lining slurry;
S3, stirring: stirring the glass lining slurry by magnetic force for 20-30 min, and uniformly mixing the glass lining slurry;
S4, spraying: pouring the stirred glass lining slurry into a spray gun, connecting a compressed air source, and spraying the slurry on a steel substrate by adopting spraying pressure of 0.5-0.7 MPa;
s5, standing: placing the steel matrix sprayed with the slurry in a ventilated and cool place for standing for 24 h;
S6, firing: and (3) placing the well-placed steel substrate into a Ma Fushi firing furnace for program heating and cooling, and firing to 30-40 min after the highest temperature is 880 ℃ to obtain the glass-lined porcelain glaze.
Preferably, in step S1, the primer includes the following components in parts by mass: 65-75 parts of SiO 2, 8-12 parts of Na 2 O, 38-9 parts of Al2O, 3-5 parts of K2O, 2-4 parts of CaO, 1-3 parts of MnO, 30-2 parts of Co2O, 0-2 parts of NiO and 30-2 parts of Fe 2O.
Preferably, the ground coat specifically comprises the following components in parts by mass: siO 2 68.42.42 parts, na 2 O10.64 parts, al2O 3.74 parts, K2O3.42 parts, caO2.41 parts, mnO1.61 parts, co2O30.98 parts, niO0.84 parts, fe2O30.52 parts.
Preferably, the steel substrate in step S4 is Q235R steel.
Preferably, before step S4, the steel substrate needs to be pretreated, including the following steps:
S11, cutting an original steel plate into 60 mm multiplied by 30 multiplied by mm multiplied by 3 mm by using a metallographic cutting machine, then placing the cut steel plate into a Ma Fushi firing furnace, preserving heat for 30-40 min at 600-800 ℃, cooling and standing;
S12, carrying out sand blasting on the original steel plate treated in the step S11, removing rust, oxide and other impurities on the surface of the steel material, and increasing the surface roughness of the original steel plate.
Preferably, in step S6, the program temperature rise and drop includes the following steps:
s21, controlling the temperature rise time to be 30-40min, heating from 25 ℃ to 150 ℃, and preserving heat for 30-40min;
s22, controlling the temperature rise time to be 120-130min, heating from 150 ℃ to 650 ℃, and preserving heat for 30-40min;
S23, controlling the temperature rise time to be 40-50min, heating from 650 ℃ to 750 ℃, and preserving heat for 30-40min;
s24, controlling the temperature rise time to be 60-70min, heating from 750 ℃ to 880 ℃, and preserving heat for 30-40min;
S25, controlling the cooling time to be 120-130min, cooling from 880 ℃ to 600 ℃, and preserving heat for 30-40min;
s26, controlling the cooling time to be 130-140min, cooling from 600 ℃ to 25 ℃, and preserving heat for 30-40min.
A glass-lined enamel based on calcium silicate modification is prepared according to the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
According to the invention, a proper amount of calcium silicate solid powder is added in the glass lining preparation process, and the calcination process is strictly controlled, so that the glass lining with high mechanical properties of high toughness, high bending strength and high hardness is successfully prepared, wherein the maximum bending strength 544.597 MPa of a sample is enhanced by 13% when the sample is not added, the fracture toughness is enhanced by 204.55% when the sample is not added, the hardness is enhanced by 93.43% when the calcium silicate is not added, and meanwhile, the glass lining has the advantages of high corrosion resistance and low porosity, compared with the calcium silicate which is not added, the porosity is reduced by 88.68%, and the glass lining preparation process has a certain guiding value.
Drawings
FIG. 1 is a flow chart of the process for preparing the improved glass-lined enamel based on calcium silicate of the invention;
FIG. 2 is a graph of glass lining primer firing temperature versus time in accordance with the present invention;
FIG. 3 is a graph of the firing macromorphology of various calcium silicate content glass-lined base enamels of the present invention: (a) comparative example 1; (b) example 1; (c) example 2; (d) example 3; (e) example 4; (f) example 5;
FIG. 4 is a schematic diagram of a three-point bending experiment of enamel glass with different calcium silicate contents according to the invention;
FIG. 5 is a graph of crack microscopic morphology of the glass lining under-glaze with different calcium silicate contents after experiments;
FIG. 6 is a graph of glass lining flexural strength with varying calcium silicate content in accordance with the present invention;
FIG. 7 is a graph of three-point bending experiments for various glasses with different calcium silicate contents according to the present invention;
FIG. 8 is a graph of glass lining fracture toughness for various calcium silicate levels of the present invention;
FIG. 9 is a schematic diagram of the experiment of measuring the hardness of glass lining with different calcium silicate contents in the invention;
FIG. 10 is a graph of the microscopic morphology of surface indentations of various glass lining samples with different calcium silicate contents according to the present invention: (a) comparative example 1; (b) example 1; (c) example 2; (d) example 3; (e) example 4; (f) example 5;
FIG. 11 is a graph showing the variation of hardness of various glasses with different calcium silicate contents according to the present invention;
FIG. 12 is a graph of acid corrosion weight loss for various calcium silicate content composite glass lining of the present invention;
FIG. 13 is a graph showing the surface morphology of composite glass lining of the present invention with different calcium silicate contents after corrosion with 30vol% sulfuric acid: (a) comparative example 1; (b) example 1; (c) example 2; (d) example 3; (e) example 4; (f) example 5;
FIG. 14 is a plot of alkali corrosion weight loss for various calcium silicate content composite glass lining of the present invention;
FIG. 15 is a graph showing the surface morphology of composite glass lining with different calcium silicate contents after corrosion in 1mol/L sodium hydroxide solution: (a) comparative example 1; (b) example 1; (c) example 2; (d) example 3; (e) example 4; (f) example 5;
FIG. 16 is a chart of microscopic profiles of sections of glass lining samples of different calcium silicate contents according to the present invention: (a) comparative example 1; (b) example 1; (c) example 2; (d) example 3; (e) example 4; (f) example 5;
FIG. 17 is a chart of the microscopic morphology of the cross section of various calcium silicate composite glass lining according to the present invention: (a) comparative example 1; (b) example 1; (c) example 2; (d) example 3; (e) example 4; (f) example 5;
FIG. 18 is a graph showing the variation of the porosity of composite glass lining with different calcium silicate contents according to the present invention.
Detailed Description
The present invention now will be described more fully hereinafter with reference to the accompanying drawings, in which it is shown, however, to illustrate some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The specification parameters of the calcium silicate are shown in table 1:
TABLE 1 calcium silicate specification parameters
The components and mechanical properties of the Q235R steel are shown in tables 2 and 3:
Table 2. Composition (wt.%) of Q345R steel
TABLE 3 mechanical Properties of Q235 Steel
The components of the glass lining base enamel are shown in table 4:
table 4. Composition of glass lining base coat (wt.%)
Referring to fig. 1-18, the present invention provides a technical solution:
Example 1:
the preparation method of the improved enamel glass based on calcium silicate comprises the following steps:
S1, weighing: 0.03g of calcium silicate particles are weighed into 29.97g of ground coat;
S2, glaze preparation: preparing ground enamel treated in the step S1 and water into slurry according to the proportion of 2:1, and primarily stirring and mixing the ground enamel and the water by using a glass rod to prepare glass lining slurry;
s3, stirring: stirring the glass lining slurry by magnetic force for 30min, and uniformly mixing the glass lining slurry;
S4, spraying: pouring the stirred glass lining slurry into a spray gun, connecting a compressed air source, and spraying the slurry on a steel substrate by adopting a spraying pressure of 0.6 MPa;
s5, standing: placing the steel matrix sprayed with the slurry in a ventilated and cool place for standing for 24 h;
S6, firing: and (3) placing the well-placed steel substrate into a Ma Fushi firing furnace for program heating and cooling, and firing for 30min after the highest temperature is 880 ℃, so as to obtain the glass-lined porcelain glaze.
The experiment also requires pretreatment of the steel matrix, comprising the following steps:
S11, cutting an original steel plate into 60 mm multiplied by 30 multiplied by mm multiplied by 3 mm by using a metallographic cutting machine, then placing the cut steel plate into a Ma Fushi firing furnace, preserving heat for 30min at 600 ℃, cooling and standing;
S12, carrying out sand blasting on the original steel plate treated in the step S11, removing rust, oxide and other impurities on the surface of the steel material, and increasing the surface roughness of the original steel plate.
The process parameters of the program temperature rise and reduction are as follows:
example 2
The preparation method of the improved enamel glass based on calcium silicate comprises the following steps:
s1, weighing: 0.06g of calcium silicate particles are weighed into 29.94g of ground coat;
S2, glaze preparation: preparing ground enamel treated in the step S1 and water into slurry according to the proportion of 2:1, and primarily stirring and mixing the ground enamel and the water by using a glass rod to prepare glass lining slurry;
s3, stirring: stirring the glass lining slurry by magnetic force for 30min, and uniformly mixing the glass lining slurry;
S4, spraying: pouring the stirred glass lining slurry into a spray gun, connecting a compressed air source, and spraying the slurry on a steel substrate by adopting a spraying pressure of 0.6 MPa;
s5, standing: placing the steel matrix sprayed with the slurry in a ventilated and cool place for standing for 24 h;
S6, firing: and (3) placing the well-placed steel substrate into a Ma Fushi firing furnace for program heating and cooling, and firing for 30min after the highest temperature is 880 ℃, so as to obtain the glass-lined porcelain glaze.
The experiment also requires pretreatment of the steel matrix, comprising the following steps:
S11, cutting an original steel plate into 60 mm multiplied by 30 multiplied by mm multiplied by 3 mm by using a metallographic cutting machine, then placing the cut steel plate into a Ma Fushi firing furnace, preserving heat for 30min at 600 ℃, cooling and standing;
S12, carrying out sand blasting on the original steel plate treated in the step S11, removing rust, oxide and other impurities on the surface of the steel material, and increasing the surface roughness of the original steel plate.
The process parameters of the program temperature rise and reduction are as follows:
example 3
The preparation method of the improved enamel glass based on calcium silicate comprises the following steps:
s1, weighing: 0.09g of calcium silicate particles are weighed into 29.91g of ground coat;
S2, glaze preparation: preparing ground enamel treated in the step S1 and water into slurry according to the proportion of 2:1, and primarily stirring and mixing the ground enamel and the water by using a glass rod to prepare glass lining slurry;
s3, stirring: stirring the glass lining slurry by magnetic force for 30min, and uniformly mixing the glass lining slurry;
S4, spraying: pouring the stirred glass lining slurry into a spray gun, connecting a compressed air source, and spraying the slurry on a steel substrate by adopting a spraying pressure of 0.6 MPa;
s5, standing: placing the steel matrix sprayed with the slurry in a ventilated and cool place for standing for 24 h;
S6, firing: and (3) placing the well-placed steel substrate into a Ma Fushi firing furnace for program heating and cooling, and firing for 30min after the highest temperature is 880 ℃, so as to obtain the glass-lined porcelain glaze.
The experiment also requires pretreatment of the steel matrix, comprising the following steps:
S11, cutting an original steel plate into 60 mm multiplied by 30 multiplied by mm multiplied by 3 mm by using a metallographic cutting machine, then placing the cut steel plate into a Ma Fushi firing furnace, preserving heat for 30min at 600 ℃, cooling and standing;
S12, carrying out sand blasting on the original steel plate treated in the step S11, removing rust, oxide and other impurities on the surface of the steel material, and increasing the surface roughness of the original steel plate.
The process parameters of the program temperature rise and reduction are as follows:
Example 4
The preparation method of the improved enamel glass based on calcium silicate comprises the following steps:
s1, weighing: 0.12g of calcium silicate particles are weighed into 29.88g of ground coat;
S2, glaze preparation: preparing ground enamel treated in the step S1 and water into slurry according to the proportion of 2:1, and primarily stirring and mixing the ground enamel and the water by using a glass rod to prepare glass lining slurry;
s3, stirring: stirring the glass lining slurry by magnetic force for 30min, and uniformly mixing the glass lining slurry;
S4, spraying: pouring the stirred glass lining slurry into a spray gun, connecting a compressed air source, and spraying the slurry on a steel substrate by adopting a spraying pressure of 0.6 MPa;
s5, standing: placing the steel matrix sprayed with the slurry in a ventilated and cool place for standing for 24 h;
S6, firing: and (3) placing the well-placed steel substrate into a Ma Fushi firing furnace for program heating and cooling, and firing for 30min after the highest temperature is 880 ℃, so as to obtain the glass-lined porcelain glaze.
The experiment also requires pretreatment of the steel matrix, comprising the following steps:
S11, cutting an original steel plate into 60 mm multiplied by 30 multiplied by mm multiplied by 3 mm by using a metallographic cutting machine, then placing the cut steel plate into a Ma Fushi firing furnace, preserving heat for 30min at 600 ℃, cooling and standing;
S12, carrying out sand blasting on the original steel plate treated in the step S11, removing rust, oxide and other impurities on the surface of the steel material, and increasing the surface roughness of the original steel plate.
The process parameters of the program temperature rise and reduction are as follows:
example 5
The preparation method of the improved enamel glass based on calcium silicate comprises the following steps:
s1, weighing: 0.15g of calcium silicate particles are weighed into 29.85g of ground coat;
S2, glaze preparation: preparing ground enamel treated in the step S1 and water into slurry according to the proportion of 2:1, and primarily stirring and mixing the ground enamel and the water by using a glass rod to prepare glass lining slurry;
s3, stirring: stirring the glass lining slurry by magnetic force for 30min, and uniformly mixing the glass lining slurry;
S4, spraying: pouring the stirred glass lining slurry into a spray gun, connecting a compressed air source, and spraying the slurry on a steel substrate by adopting a spraying pressure of 0.6 MPa;
s5, standing: placing the steel matrix sprayed with the slurry in a ventilated and cool place for standing for 24 h;
S6, firing: and (3) placing the well-placed steel substrate into a Ma Fushi firing furnace for program heating and cooling, and firing for 30min after the highest temperature is 880 ℃, so as to obtain the glass-lined porcelain glaze.
The experiment also requires pretreatment of the steel matrix, comprising the following steps:
S11, cutting an original steel plate into 60 mm multiplied by 30 multiplied by mm multiplied by 3 mm by using a metallographic cutting machine, then placing the cut steel plate into a Ma Fushi firing furnace, preserving heat for 30min at 600 ℃, cooling and standing;
S12, carrying out sand blasting on the original steel plate treated in the step S11, removing rust, oxide and other impurities on the surface of the steel material, and increasing the surface roughness of the original steel plate.
The process parameters of the program temperature rise and reduction are as follows:
comparative example
Comparative example 1: comparative example 1 differs from example 1 only in that steps S1, S2 originally present in example 1 were omitted in comparative example 1, and thus the addition of calcium silicate particles was omitted, and the remaining steps were identical in comparative example 1 and example 1.
Performance testing and results analysis:
1. observing the macro morphology:
The macroscopical appearance of the enamel glass ground coat sintered with different calcium silicate contents is shown in figure 3, and the smoother the surface is, the black luster is presented and the texture similar to glass is realized along with the increase of the calcium silicate content. Wherein, at the content of 0.1 wt%, the surface is rough and has no bright black luster. When the mass fraction is increased to 0.4%, the surface is smoother, has obvious bright black luster, and has no bubbles and no cracks. However, the glass lining sample without calcium silicate has obvious concave-convex pits on the surface, no obvious blurring, roughening and mist, and no obvious texture and glossiness.
2. And (3) detecting bending strength of glass lining:
Carrying out a three-point bending experiment by adopting a hydraulic universal testing machine, arranging two fulcrums below two ends of the glass lining sample, and applying pressure above the middle points of the glass lining sample to enable cracks to appear on the lower surface of the glass lining sample to be tested; the three-point bending experimental principle is shown in figure 4;
the detection method comprises the following steps: before the experiment, glass lining samples with mass fractions of 0, 0.1%, 0.2%, 0.3%, 0.4% and 0.5% of calcium silicate are required to be pretreated, and the pretreatment steps are as follows:
(1) Selecting: and selecting two samples with similar ceramic layer thickness from all glass lining samples with each content obtained by firing, and determining the geometric center.
(2) Wiping: and wiping the surface of the porcelain layer of the glass lining sample by using an alcohol cotton ball to remove surface impurities.
(3) Polishing: the geometric center and surrounding area of the glass lined sample surface was sanded until the surface became rough.
And (3) sticking: and (3) sticking a resistance strain gauge on the geometric center of the surface of the glass lining sample by using glue, so as to ensure that the center of the strain gauge coincides with the geometric center of the sample, and accurately measuring the strain degree generated by the porcelain layer under the action of different stresses and the deformation degree generated by samples with different contents.
According to the national standard GB/T34171-2017 three-point bending method of thin and ultra-thin glass bending performance test method, the test uses a microcomputer controlled electrohydraulic servo universal tester with model WAW-600D, adopts a glass lining sample with size of 60 mm multiplied by 30mm multiplied by 3 mm, sets a test span (the distance between two roller type support rollers) of 50 mm and loading rate of 0.5 mm/min, carries out the three-point bending test, when the glass lining sample is placed, the porcelain layer surface of the glass lining sample is arranged below, the metal substrate surface is arranged above, and the external force load born by the sample is continuously increased along with the increase of time from the moment when the upper pressure head is contacted with the glass lining sample according to the set measurement distance and external force application rate. When the pressure is increased to a certain value, the porcelain layer can deform to a certain extent under the action of the three-point bending moment. When the pressure applied to the sample exceeds the maximum bearing force value of the porcelain layer, the glass lining surface is subjected to the action of tensile stress, radial force and circumferential force, so that cracks are generated, and the microcracks are continuously expanded under the action of the stress until the porcelain layer is completely broken.
After the experiment is finished, the peak value and the lowest value of the experimental force displayed by computer software connected with the instrument are recorded, and the displacement value and the deformation value respectively correspond to the peak value and the lowest value. Each glass lining sample comprises 2 parallel samples, the average value of the two measurement results is taken in the data processing process, the bending strength of the glass lining samples under different calcium silicate contents is calculated, and the microscopic appearance of the crack after the experiment is shown in figure 5;
The calculation formula of the maximum bending strength of the glass lining sample is as follows:
wherein:
P-MPa, maximum flexural Strength of sample
F-N, the maximum load at failure of fracture
L-mm being the span
B-mm, the width of the sample
H-mm, which is the thickness of the sample, and the thickness refers to the thickness of the glass lining layer and the steel plate;
According to the calculation formula, enamel glass bending strength values with different calcium silicate contents are calculated, two samples are tested on enamel glass samples with the same calcium silicate content, the average value of the two measurement results is taken in the data processing process, the average value is shown in table 5, and the maximum bending strength change curve is shown in fig. 6.
TABLE 5 glass lining flexural Strength Change with different calcium silicate content
As can be seen from fig. 6, the flexural strength of the glass lining samples increases and then decreases with increasing calcium silicate content. Wherein, when the calcium silicate addition content is 0.4 wt percent, the bending strength of the glass lining sample is enhanced to the greatest extent, and reaches 544.597 MPa, and the bending strength is improved by 13 percent compared with that of the glass lining sample when the glass lining sample is not added; when the calcium silicate addition content is 0.5 wt percent, the bending strength of the glass lining sample is the lowest and reaches 472.008 MPa, and compared with the bending strength when the glass lining sample is not added, the bending strength of the glass lining sample is reduced by 2.1 percent. When the calcium silicate addition content is more than 0.4 wt%, a micro crack source formed by a large number of defects exists inside due to poor sintering property of the calcium silicate particles. Under the disturbance of external force, local stress concentration is easy to generate at the crack source, so that the crack is rapidly expanded, and finally the bending strength resistance of the glass lining sample is reduced.
3. Fracture toughness analysis
Breakage is one of the common failure modes of glass lining materials in industrial applications, and does not generally have any sign, resulting in serious losses in the pharmaceutical, chemical, marine industries and the like. Therefore, the study of the fracture toughness of the glass lining is an extremely important mechanical property index.
The three-point bending experiment is carried out on samples with different calcium silicate addition contents, the obtained force and displacement relation curve is shown in fig. 7, the abscissa represents the displacement value, the ordinate represents the external load value, the M point is the highest point in the graph and represents the maximum load during fracture failure, at the moment, the surface of the glass lining sample is cracked and begins to fracture, and then the load value is continuously reduced along with the continuous expansion of the crack; the point N is the lowest point in the graph and represents the complete fracture failure of the porcelain layer of the glass lining sample. The test shows the fracture toughness of a glass lining sample by father for the force difference F and father for the displacement difference X between M, N points.
Before the ram is brought into contact with the glass lining sample, the software needs to be cleared. Once the two are in contact, the force applied to the sample increases from zero. In the beginning of the experiment, the metal matrix is subjected to increasing pressure, resulting in compressive deformation of the upper surface. However, since the metal matrix resists the external force, the interface between the metal matrix and the glass-lined ceramic layer will not bend, nor will the external force affect the glass-lined ceramic layer. When the external load increases beyond the resistance of the metal matrix, the steel matrix deforms. Under the action of interface stress, the glass-lined ceramic layer starts to bend and deform, and simultaneously the ceramic layer can resist external force so as to maintain the original state of the glass-lined ceramic layer. With the continuous increase of external load, when the strength limit of the porcelain layer is exceeded, microcracks are generated on the surface of the glass-lined porcelain layer, and the stress of the glass-lined sample reaches the maximum value. In the stage of microcrack expansion, the capability of the glass lining sample for resisting external force is reduced until the porcelain layer is completely broken and fails, and the external load born by the glass lining sample is minimum. Subsequently, the steel sheet undergoes different degrees of bending deformation under the action of external force.
To investigate the effect of different calcium silicate contents on the fracture toughness of glass lining samples, two glass lining samples of the same calcium silicate content were tested and the average of the two measurements was taken during the data processing. By calculating the force difference and displacement difference of the glass lining samples with different calcium silicate contents, the fracture toughness change of the samples with different calcium silicate contents can be accurately represented, as shown in table 6 and fig. 8.
TABLE 6 glass lining fracture toughness variation with varying calcium silicate content
Group of | Content/wt% | ∆F/kN | ∆X/mm |
Comparative example 1 | 0 | 0.110 | 0.101 |
Example 1 | 0.1 | 0.200 | 0.139 |
Example 2 | 0.2 | 0.215 | 0.142 |
Example 3 | 0.3 | 0.235 | 0.178 |
Example 4 | 0.4 | 0.335 | 0.232 |
Example 5 | 0.5 | 0.160 | 0.108 |
As can be seen from fig. 8, the fracture toughness of the glass lining samples tended to increase and decrease with increasing calcium silicate content, but increased to a different extent than when no calcium silicate was added. When the addition amount is 0.4 wt%, the fracture toughness of the glass lining reaches the highest value, the load force difference father is 0.335 KN, the displacement difference father is 0.232 and mm, compared with the glass lining sample without calcium silicate, the load force difference father is increased by 204.5%, and the displacement difference father is increased by 129.7%. When the calcium silicate addition content was 0.5 wt%, the fracture toughness of the glass lining sample was minimally improved, the load difference fatin was 0.16 KN, the displacement difference fatin was 0.108 and mm, and compared with the glass lining sample without calcium silicate, the load difference fatin was 45.5% and the displacement difference fatin was 6.93%. According to analysis, the addition of the calcium silicate can effectively improve the fracture toughness of the glass lining, because the calcium silicate can increase the resistance of the glass lining in the process of occurrence of cracks and crack propagation, and a proper amount of uniformly distributed calcium silicate can prevent the crack propagation, so that the consumption of crack energy is increased by prolonging the crack propagation path, and the fracture toughness of the glass lining is improved. However, if calcium silicate is added in excess, dispersion unevenness may be caused, and a microcrack source is formed, thereby reducing fracture toughness.
4. Hardness detection
The hardness test is a mechanical property test in which a material with known mechanical properties such as elastic modulus is pressed into the surface of a material to be tested to generate an indentation. The test adopts a Vickers pressure head, the pressure head applies load on a tested material, so that the material is subjected to permanent plastic deformation, namely, an indentation consistent with the shape of the pressure head is generated on the surface of the material, then the indentation area is observed and measured by a microscope, and the two diagonal measurement methods are used for calculating the indentation area.
In which d is the average length of the diagonal, mm
D1, d 2-diagonal length, mm
HV-Vickers hardness, GPa
F-apply pressure, N
S-indentation area, μm 2
P-indentation load, kg
The included angle of the opposite faces of the alpha-diamond regular rectangular pyramid pressure head is 136 degrees;
the test is carried out by measuring calcium silicate with sample size of 60 mm multiplied by 30 multiplied by mm multiplied by 3 mm, and the mass fractions of the composite glass lining samples are respectively 0, 0.1%, 0.2%, 0.3%, 0.4% and 0.5%, wherein the used instruments are a weighing sensor and a metallographic microscope.
The determination of the value of the applied load is particularly important because the experiment requires observation of the impression of the glass lining sample surface and accurate measurement of the length of the diagonal of the impression under the microscope. In order to ensure that the indentation position can be found quickly and accurately under a metallographic microscope, areas are predetermined on the surfaces of glass lining samples with different calcium silicate contents, and external force loads act on the areas through the pressure head. Before the diamond pressure head contacts with the sample, the symmetrical weighing sensor repeatedly carries out zero clearing operation, the porcelain layer begins to bear force, and the numerical value on the display panel of the weighing sensor is gradually increased from zero. If the applied pressure is too high, larger cracks and even breaks can be generated on the porcelain layer in the contact area of the sample and the pressure head; if the load is too small, the pressure head is pressed into the indentation of the sample to be too shallow, the shape of the indentation is not obvious under a microscope, and both are unfavorable for observation and measurement of the indentation, so that larger experimental errors can be caused. Through repeated attempts, the condition that the same sample generates the indentation under the action of different external force loads is observed, a proper external load value is determined to be about 4N, the dwell time is 8 s, then the pressure head is vertically separated from the surface of the sample, the subsequent observation of the indentation is prevented from being influenced, and all the samples are subjected to hardness detection under the condition.
The microscopic morphology of the surface indentation of the glass lining sample was observed under a metallographic microscope, as shown in fig. 10. As can be seen from the figure, the surfaces of glass lining samples with different calcium silicate contents are provided with quadrangular indentations under the same external force load, but the areas of the quadrilaterals are different.
The diagonal length of the surface indentations of samples with different contents is measured and accurately recorded by metallographic analysis software, and specific hardness values of the samples are obtained through theoretical calculation, as shown in table 7. Hardness change curves of various glass lining samples with different calcium silicate contents are drawn by using Origin software, and are shown in FIG. 11.
TABLE 7 composite glass lining hardness data sheet for different calcium silicate contents
As can be seen from fig. 11, the hardness of the glass lining samples showed a tendency to increase and decrease with increasing calcium silicate content, but increased to a different extent than when no calcium silicate was added. When the mass fraction reaches 0.3%, the hardness of the glass lining sample is enhanced to the greatest extent, namely 0.3120 GPa, and is 93.43% higher than that of a sample without calcium silicate. According to analysis, the experimental phenomenon is that under the condition of high temperature of 880 ℃, calcium silicate can undergo oxidative decomposition reaction to generate calcium oxide and silicon oxide, so that a more stable silicic acid network structure is formed, and the hardness of the porcelain layer is further improved. When the calcium silicate addition content is more than 0.3 wt%, the hardness of the glass lining sample is in a decreasing trend along with the increase of the calcium silicate content, and when the mass fraction reaches 0.5%, the hardness of the glass lining sample reaches the lowest, namely 0.0531 GPa, and compared with the sample without the calcium silicate, the hardness of the glass lining sample is reduced by 67.08%.
5. Acid corrosion resistance test
The acid resistance detection method comprises the following steps:
The corrosion resistance of the enamel glass is mainly determined by the components of the enamel layer, because the dense enamel layer can effectively isolate chemical substances from contacting with the surface of the enamel glass, thereby achieving the aim of corrosion resistance. The experiment adopts the ground coat with silicon dioxide as matrix agent, the mass fraction of the ground coat reaches 68.42%, the compactness of the porcelain layer can be effectively improved, and the corrosion resistance of the glass-lined porcelain glaze layer is enhanced. Calcium silicate particles with different contents are added into the original ground coat to form a more stable silicic acid network structure. The test adopts the tabletting with different calcium silicate contents, and the acid resistance test is carried out, so that the change condition of the quality of each tabletting sample along with time is obtained, and the influence of the calcium silicate on the corrosion resistance of the glass lining is evaluated through data processing and comprehensive analysis and discussion.
According to the national standard of GB/T7989-2013 determination of boiling acid resistance and vapor corrosion resistance of glass enamel, laboratory experiment conditions are considered, and a sulfuric acid solution with the volume fraction of 30% is selected as an acid detection reagent of a sample in the experiment. Tablets prepared with different calcium silicate contents were used as experimental raw materials, with contents of 0, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt% respectively. Three samples are selected for each content to carry out experiments, so that errors caused by experimental operation errors and other factors are reduced. The experimental procedure was as follows:
(1) Preparing: a solution of 100 ml volume percent sulfuric acid of 30% was prepared using laboratory existing 97 wt% concentrated sulfuric acid and deionized water, then poured evenly into two clean beakers, and sealed with a plastic wrap and rubber strips.
(2) And (3) drying: three tablets with different calcium silicate contents are obtained after firing, the tablets are placed under flowing water to be washed cleanly, the surface moisture is wiped off, and the tablets are placed in a baking oven at 120 ℃ to be baked for 5min, so that the residual moisture in the internal pore canal is removed.
(3) And (3) cooling: after the drying is finished, the mixture is naturally cooled to 25 ℃ in a ventilated shade.
(4) Weighing: the original mass of each sample before corrosion was measured by an electronic balance and recorded as m 0
(5) Experiment: the pressed samples were equally divided into two groups, placed in two beakers, and the time was recorded to begin the acid etch test. After 48 hours, each pellet was removed and placed in running water for washing. After cleaning, the mixture is put into a baking oven at 120 ℃ for 5 minutes. The samples were then allowed to cool naturally to 25 ℃ in a ventilated cool place, and the mass of each sample was measured again using an electronic balance and recorded as m 1. The mass of the sample was measured every 48 hours, m 2、m3、m4、m5、m6 and m 7 respectively, and the total duration of the experiment was 288 hours.
Corrosion weight loss: the raw data obtained by the experiment are processed to obtain the weightlessness weights of the samples after 48 h, 96 h, 144 h, 192 h, 240 h and 288 h, the corrosion conditions of the tablets with different calcium silicate contents are reflected, and the weightlessness weights of the tablets with different calcium silicate contents are shown in figure 12.
As can be seen from fig. 12, the addition of calcium silicate significantly improves the acid corrosion resistance of the glass-lined porcelain layer, wherein the acid corrosion resistance of the sample with the content of 0.5 wt% is better, the loss weight is 0.51: 0.51 mg, and the corrosion loss weight is reduced by 81% compared with the sample without calcium silicate. This is mainly because calcium silicate is a silicate and adheres to the surface of the sample to form a protective film that prevents further corrosion of the sample by the acid solution.
The surface morphology of the glass lining pressed samples after corrosion with sulfuric acid having a different calcium silicate content of 30 vol% is shown in fig. 13.
As can be seen from FIG. 13, corrosion holes with different degrees appear on the surfaces of glass lining pressed samples with different contents, wherein the corrosion condition without calcium silicate is the most serious, a large number of corrosion holes and corrosion cracks appear, and the ceramic layer structure is seriously damaged. At levels of 0.1 wt and 0.2 wt%, more severe corrosion conditions occur, and a large and large number of etch pits and circular pits appear on the surface, with the etch cracks being interlaced with each other throughout the surface. When the content was increased to 0.3 wt%, some relatively large and small number of etch pits and etch cracks appeared in the surface portion of the sample, the degree of corrosion was low, and the porcelain layer structure was slightly destroyed. At calcium silicate addition levels of 0.4 wt and 0.5 wt%, the surface etch pits become smaller and increased in number, and many tiny etch pits connect to each other forming relatively sharp etch cracks.
6. Alkali corrosion resistance test
The alkali resistance detection method comprises the following steps: glass-lined glazes are amorphous solids of random structure with silica as matrix forming the composition of silicate network structures, which are very similar to glass in corrosion form. Under alkaline conditions, the silicate network structure is destroyed and at the same time reacts strongly with the silica therein to form a water-soluble alkali silicate, also known as water glass, which finally results in a decrease in the chemical stability of the glass lining. The test adopts the tabletting with different calcium silicate contents, and the alkali-resistant test is adopted, so that the change condition of the quality of each tabletting sample along with time is obtained, and the influence of the calcium silicate on the alkali-resistant corrosion performance of the glass lining is evaluated through data processing and comprehensive analysis and discussion. According to the national standard of GB/T7989-2013 determination of boiling acid resistance and vapor corrosion resistance of glass enamel, and considering laboratory experimental conditions, the experiment adopts 1 mol/L sodium hydroxide solution as an experimental reagent, and the experimental raw materials and the experimental process are the same as those of an acid resistance detection experiment, and the total experimental duration is 336 h.
Corrosion weight loss: according to the original data obtained by the experiment, the weight loss of each sample after 48h, 96 h, 144 h, 192 h, 240 h, 288 h and 336 h is obtained, the corrosion condition of the tablets with different calcium silicate contents is reflected, and the alkaline corrosion weight loss of the tablets with different calcium silicate contents is shown in figure 14.
As shown in FIG. 14, the alkali resistance and corrosion resistance of the glass-lined porcelain layer are obviously improved along with the addition of calcium silicate, wherein the alkali resistance of glass-lined pressed sheets with the content of 0.4 wt percent and 0.5 wt percent are better and have little difference, the weight loss is respectively 0.44 mg and 0.40 mg, and compared with the sample corrosion weight loss without the addition of calcium silicate, the weight loss is respectively reduced by 76.84 percent and 78.95 percent, because the calcium silicate is attached to the surface of the sample to form a layer of protective film, the protective film is firstly reacted with sodium hydroxide to generate silicon dioxide, and then the decomposition rate of the protective film is gradually reduced along with the time, so that the further corrosion of the alkali solution is inhibited. When the content of calcium silicate is 0.1 wt to 0.3 wt percent, the corrosion rate of the sample gradually increases along with the increase of the number of corrosion days, because the addition amount of calcium silicate is relatively small, the silicon dioxide and sodium hydroxide undergo strong chemical reaction after the calcium silicate protective film is destroyed, the original silicate network structure is destroyed, an alkali silicate which is soluble in water is generated, and finally the chemical stability of the glass lining is reduced.
The surface morphology of the glass lining pressed sample after corrosion with sodium hydroxide solution with different calcium silicate content of 1 mol/L is shown in figure 15.
As can be seen from FIG. 15, various degrees of corrosion holes and corrosion cracks appear on the surfaces of the glass lining pressed sheet samples with different contents, wherein the corrosion of the glass lining pressed sheet samples without calcium silicate is most serious, the surfaces become very rough, and a large number of corrosion holes and pits appear. With the increase of the calcium silicate content, the corrosion condition of the glass lining pressed sample is gradually lightened. When the content is 0.1 wt%, a more serious corrosion condition occurs, and a large number of corrosion pits and circular pits appear on the surface, so that corrosion cracks are mutually staggered and connected on the surface. At a content of 0.2 wt%, the corrosion is relatively reduced, some small corrosion pits and round pits appear on the surface, and corrosion cracks are relatively few. At a content of 0.3 wt%, the degree of corrosion is lower, and some relatively large and small number of corrosion pits appear on the surface. When the addition content is 0.4 wt-0.5 wt%, the corrosion degree is the lowest, some corrosion pits and round pits with smaller and smaller quantity appear on the surface, and the length and the width of the corrosion cracks are obviously smaller than those of other samples.
7. Section adhesion performance detection
The detection method comprises the following steps: research shows that the enamel glass mainly consists of two parts of enamel and metal matrix, and the combination degree between the enamel glass and the metal matrix is one of the main indexes for measuring the quality of the enamel glass performance and is also a key factor for influencing the mechanical property and the corrosion resistance of the enamel glass. The research shows that the adhesive is cobalt oxide and nickel oxide, which can react with iron element in the steel matrix to obtain FeO through replacement, and Fe-Ni and Fe-Co alloy are formed, so that the adhesiveness between the metal matrix and the enamel is improved. In order to study the influence of calcium silicate on the adhesion performance between a matrix and enamel, section microscope observation is carried out on glass lining samples with different calcium silicate contents.
And (3) adopting a metallographic sample grinding and polishing machine and a metallographic microscope to treat glass lining samples with the raw materials of 0, 0.1 wt percent, 0.2. 0.2 wt percent, 0.3. 0.3 wt percent, 0.4. 0.4 wt percent and 0.5. 0.5 wt percent of calcium silicate by mass percent. The experimental procedure was as follows:
(1) Polishing: and (3) selecting each glass lining sample with different calcium silicate contents obtained by firing, placing the glass lining samples on a metallographic sample grinding and polishing machine, polishing the sections by using abrasive paper with 180 meshes, observing the appearance of the sections in the polishing process, and after the sections are polished to be smooth and bright, sequentially replacing the abrasive paper with 400 meshes, 1200 meshes, 2000 meshes and 4000 meshes to polish the sections until the sections are polished to be smooth and bright by using the abrasive paper with 4000 meshes.
(2) And (3) observation: adopting a metallographic microscope with the model of BMM-202E, setting the magnification to 100 times, adjusting the position, the visual field brightness and the definition until the microstructure at the interface of the steel plate substrate and the enamel can be clearly observed, and observing and shooting the microstructure at the sections of samples with different contents.
The microscopic appearance of the section of the glass lining sample with different calcium silicate contents is obtained by observation under a metallographic microscope, as shown in figure 16, wherein the upper layer is the glass lining enamel, and the lower layer is the metal matrix.
As can be seen from fig. 16, dendrite exists at the interface between the enamel and the metal substrate, forming a transition layer, and the more obvious the dendrite transition layer between the interfaces increases with increasing calcium silicate content, the higher the adhesion strength of the enamel. The dendrite body of the transition layer is firmly combined with the enamel and the metal matrix, and in the firing stage, a large number of complex chemical reactions are generated between the dendrite body and the metal matrix, and chemical bonds generated at the boundary enable the dendrite body and the metal matrix to be firmly and tightly combined together.
8. Enamel porosity analysis
Detection principle: porosity, which is the percentage of the volume of gas voids contained in a piece of material or structure, is the most common minor defect of glass lining, and is also an important material performance parameter that plays a critical role in the manufacturing and application of many materials. In general, the lower the porosity, the better the physical and mechanical properties of the material. As the porosity and pore size increase, the strength of the glass lining decreases, as pores exist inside the material, which can damage the overall mechanical microstructure of the material and make the material more fragile. Too high a porosity may increase the coefficient of thermal expansion of the glass lining, thereby creating thermal stress damage that affects the performance of the glass lining. The experiment is carried out by carrying out section microscopic observation on glass lining samples with different calcium silicate contents, observing and calculating the porosities with different contents, thereby researching the change of the added calcium silicate on the porosity of the glass lining, and determining the optimal added content.
The detection method comprises the following steps: the experiment is carried out by adopting the same method as the section adhesion performance detection experiment, placing a glass lining sample under a metallographic microscope with the magnification of 100 times, observing the pore morphology and the distribution of pores in the glass lining enamel at different positions of the same sample, storing a photo reflecting the distribution of the pores, and then calculating and analyzing the porosity of the sample by using software. The research shows that the porosity of the composite material can be measured and calculated by using the image processing software Photoshop and the image processing and analyzing software Lmage J, and the porosity values of different samples can be finally calculated, so that the method has the advantages of simplicity and applicability;
the microstructure of the calcium silicate composite glass lining is shown in figure 17, and the minimum pore diameter is about 13.35 mu m.
The porosities of the glass lining samples with different calcium silicate contents are shown in Table 8:
TABLE 8 porosities of different composite glass lining samples
Drawing a porosity change curve with different contents by using Origin software as shown in figure 18;
As can be seen from fig. 17 and 18, the pore sizes and the distribution characteristic states of the porcelain layers of the glass lining samples with different calcium silicate contents are different, and the pore sizes and the distribution characteristic states are mainly formed by retaining gases such as CO 2, CO and the like generated in the sintering process in the glass lining samples. As the calcium silicate content increases, the porosity tends to decrease and then increase. Wherein, the pore distribution of the glass lining sample without calcium silicate is dense and the number is more, the pore size is different and is approximately between 30 and 70 mu m, and the porosity is up to 24.56%. When the addition content of calcium silicate is 0.1 wt%, compared with the pure ground enamel, the ceramic layer of the glass lining sample has the advantages of reduced air hole number, increased spacing and reduced porosity. In the sample ceramic layer with the calcium silicate content of 0.3 wt percent, the number of air holes is obviously reduced, the diameter of the air holes is obviously reduced, the distance is increased, the number is less, and the porosity is lower than 11.06 percent. When the addition amount of calcium silicate is within the range of 0.3 wt to 0.4 wt%, the density of pores and the pore size are not greatly different, the density is reduced, the number is reduced, and the porosity is reduced. At a content of 0.4 wt%, the porosity reached a minimum of 2.78%, a 88.68% reduction compared to the glass lining sample without calcium silicate. However, when the calcium silicate content was increased to 0.5 wt%, the diameter of the pores was reduced but the degree of densification was significantly increased, and the porosity was increased by 2.25% compared to the pure ground coat. In summary, the sample with 0.4 wt% calcium silicate content had the best porosity among all samples tested by all experiments, and the sample was consistent with the results of mechanical experiments such as flexural strength and fracture toughness.
In summary, the experimental phenomena and results are summarized as follows:
(1) According to analysis of the three-point bending experimental result, the mechanical properties of the glass lining bending strength and the fracture toughness after the calcium silicate is added are tended to be increased and then decreased along with the increase of the content. When the calcium silicate content is within the range of 0.1 wt to 0.4 wt%, the flexural strength and fracture toughness of the sample tend to be continuously enhanced with increasing content, but the enhancement effect of various mechanical properties is not obvious because the calcium silicate is added in a small amount. When the content is 0.4 wt percent, the maximum bending strength of the experimental sample is 544.597 MPa, which is enhanced by 13 percent compared with the non-added sample; the fracture toughness is improved by 204.5 percent compared with that of the non-added material.
(2) According to the analysis of the hardness detection experiment result, the hardness of the glass lining sample tends to increase and then decrease with the increase of the content of calcium silicate. When the mass fraction reaches 0.3%, the hardness of the glass lining sample is enhanced to the greatest extent, namely 0.3120 GPa, and the hardness is improved by 93.43% compared with the hardness of the sample without calcium silicate.
(3) According to the analysis of acid resistance experiment results, the acid corrosion resistance of the glass-lined ceramic layer is obviously improved after calcium silicate is added. As can be seen from a metallographic microscope, the corrosion condition without calcium silicate is the most serious, a large number of corrosion holes and corrosion cracks appear, and the ceramic layer structure is seriously damaged. When the content is 0.5 wt percent, the glass lining pressed sheet sample has better acid corrosion resistance and loss weight of 0.51 mg, compared with the sample without calcium silicate, the glass lining pressed sheet sample has 81 percent lower corrosion loss weight, the surface corrosion pits are reduced and the number of the surface corrosion pits is smaller, and a plurality of tiny corrosion pits are connected with each other to form clear corrosion cracks. This is because calcium silicate, which is a silicate, adheres to the surface of the sample to form a protective film that prevents further corrosion of the sample by the acid.
(4) According to the analysis of acid resistance test results, the alkali resistance corrosion performance of porcelain layers of glass lining tabletting samples with different calcium silicate contents is superior to that of pure ground enamel samples, wherein the alkali resistance performance is not greatly different when the contents are 0.4 wt percent and 0.5 wt percent, the weight loss is respectively 0.44 mg and 0.40 mg, compared with the sample without calcium silicate, the corrosion weight loss is respectively reduced by 76.84 percent and 78.95 percent, the corrosion degree is lowest, a few corrosion pits and round pits with smaller number appear on the surface, and the length and the width of corrosion cracks are obviously smaller than those of other samples. Thus, when the calcium silicate addition content is 0.5 wt percent, the acid and alkali resistance of the porcelain layer is obviously improved.
(5) From the analysis of the observation phenomenon of the section adhesion detection, it is known that: the obvious branch-shaped transition layer exists at the interface of the steel substrate and the glass-lined ceramic layer, and the addition of a proper amount of calcium silicate can enhance the adhesion degree of branch-shaped crystals, so that the mechanical anchoring force between the steel substrate and the glass-lined ceramic layer is increased, and the adhesion is promoted.
(6) According to analysis of the pore detection phenomenon of the porcelain layer, the following steps are shown: overall, the porosity of the glass lining samples tended to decrease and then increase with increasing calcium silicate content. In the composite enamel glass sample ceramic layer with 0.4 wt percent, the pore diameter is obviously reduced, the density is reduced, the porosity reaches the lowest value of 2.78 percent, and compared with an enamel glass sample without calcium silicate, the porosity is reduced by 88.68 percent, which is consistent with the experimental result of mechanical properties. However, when the calcium silicate content was increased to 0.5 wt%, the diameter of the pores was reduced but the degree of densification was significantly increased, the porosity was 25.12%, and the porosity was increased by 2.25% compared to the pure base glaze. Comprehensive analysis shows that the addition of proper amount of calcium silicate can reduce the number of air holes in the ceramic layer effectively, and micro cracks produced by the material under the action of external force encounter small-diameter pores in the expansion process, so that the expansion direction is changed or expansion is stopped, the external force is consumed to a certain extent, and the mechanical properties of the material such as bending strength, fracture toughness and the like are enhanced.
The above-mentioned contents can prove that the invention successfully prepares the high mechanical property enamel glass with high toughness, high bending strength and high hardness by adding a proper amount of calcium silicate solid powder in the enamel glass preparation process and strictly controlling the calcination process, and simultaneously has the advantages of high corrosion resistance and low porosity. Thereby improving the existing glass lining preparation process and having a certain guiding value.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. The preparation method of the improved glass-lined porcelain glaze based on calcium silicate is characterized by comprising the following steps of:
S1, weighing: weighing 0.03-0.15 part of calcium silicate particles and adding the calcium silicate particles into 28-30 parts of ground enamel;
S2, glaze preparation: preparing ground enamel treated in the step S1 and water into slurry according to the proportion of 1.5-2.5:1, and primarily stirring and mixing the ground enamel and the water by using a glass rod to prepare glass lining slurry;
S3, stirring: stirring the glass lining slurry by magnetic force for 20-30 min, and uniformly mixing the glass lining slurry;
S4, spraying: pouring the stirred glass lining slurry into a spray gun, connecting a compressed air source, and spraying the slurry on a steel substrate by adopting spraying pressure of 0.5-0.7 MPa;
s5, standing: placing the steel matrix sprayed with the slurry in a ventilated and cool place for standing for 24 h;
S6, firing: and (3) placing the well-placed steel substrate into a Ma Fushi firing furnace for program heating and cooling, and firing to 30-40 min after the highest temperature is 880 ℃ to obtain the glass-lined porcelain glaze.
2. The method for preparing the improved glass-lined enamel based on calcium silicate according to claim 1, wherein in the step S1, the base enamel comprises the following components in parts by mass: 65-75 parts of SiO 2, 8-12 parts of Na 2 O, 38-9 parts of Al2O, 3-5 parts of K2O, 2-4 parts of CaO, 1-3 parts of MnO, 30-2 parts of Co2O, 0-2 parts of NiO and 30-2 parts of Fe 2O.
3. The preparation method of the improved glass-lined enamel based on calcium silicate according to claim 2, wherein the ground enamel comprises the following components in parts by mass: siO 2 68.42.42 parts, na 2 O10.64 parts, al2O 3.74 parts, K2O3.42 parts, caO2.41 parts, mnO1.61 parts, co2O30.98 parts, niO0.84 parts, fe2O30.52 parts.
4. The method for producing a glass-lined enamel modified with calcium silicate according to claim 1, wherein the steel substrate in step S4 is Q235R steel.
5. The method for preparing a glass-lined enamel modified on the basis of calcium silicate according to claim 4, characterized in that, before step S4, the steel substrate is subjected to a pretreatment comprising the following steps:
S11, cutting an original steel plate into 60 mm multiplied by 30 multiplied by mm multiplied by 3 mm by using a metallographic cutting machine, then placing the cut steel plate into a Ma Fushi firing furnace, preserving heat for 30-40 min at 600-800 ℃, cooling and standing;
S12, carrying out sand blasting on the original steel plate treated in the step S11, removing rust, oxide and other impurities on the surface of the steel material, and increasing the surface roughness of the original steel plate.
6. The method for preparing a glass-lined enamel based on calcium silicate modification according to claim 1, wherein in step S6, the procedure of heating and cooling comprises the steps of:
s21, controlling the temperature rise time to be 30-40min, heating from 25 ℃ to 150 ℃, and preserving heat for 30-40min;
s22, controlling the temperature rise time to be 120-130min, heating from 150 ℃ to 650 ℃, and preserving heat for 30-40min;
S23, controlling the temperature rise time to be 40-50min, heating from 650 ℃ to 750 ℃, and preserving heat for 30-40min;
s24, controlling the temperature rise time to be 60-70min, heating from 750 ℃ to 880 ℃, and preserving heat for 30-40min;
S25, controlling the cooling time to be 120-130min, cooling from 880 ℃ to 600 ℃, and preserving heat for 30-40min;
s26, controlling the cooling time to be 130-140min, cooling from 600 ℃ to 25 ℃, and preserving heat for 30-40min.
7. A glass-lined enamel modified on the basis of calcium silicate, characterized in that it is produced by a preparation method according to any one of claims 1 to 6.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105385934A (en) * | 2015-11-20 | 2016-03-09 | 平顶山市圣康炊具有限公司 | Enamel pan and manufacturing process thereof |
CN108409138A (en) * | 2018-04-11 | 2018-08-17 | 东北大学 | The enamel coating and its preparation process of a kind of resistance to sulfuric acid, salt acid dew piont corrosion |
CN110331407A (en) * | 2019-06-12 | 2019-10-15 | 毛军华 | A kind of preparation method of acid and alkali-resistance adherence board with enamel panel layer |
KR102057233B1 (en) * | 2018-12-18 | 2019-12-26 | 주식회사 코펙 | Enamel composition for preventing corrosion and anti-fouling of an element of a gas gas heater and a gas air heater for a heat exchanger and enamel coating method thereof |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN105385934A (en) * | 2015-11-20 | 2016-03-09 | 平顶山市圣康炊具有限公司 | Enamel pan and manufacturing process thereof |
CN108409138A (en) * | 2018-04-11 | 2018-08-17 | 东北大学 | The enamel coating and its preparation process of a kind of resistance to sulfuric acid, salt acid dew piont corrosion |
KR102057233B1 (en) * | 2018-12-18 | 2019-12-26 | 주식회사 코펙 | Enamel composition for preventing corrosion and anti-fouling of an element of a gas gas heater and a gas air heater for a heat exchanger and enamel coating method thereof |
CN110331407A (en) * | 2019-06-12 | 2019-10-15 | 毛军华 | A kind of preparation method of acid and alkali-resistance adherence board with enamel panel layer |
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