Preparation principles of low-cement refractory castables and analysis of core raw material properti
2025-09-16 11:07:09
I. Preparation principles of low-cement refractory castables
The preparation of low-cement refractory castables should take "reducing cement dosage, optimizing microstructure, and improving high-temperature performance" as the core goals, and strictly follow the following four principles to ensure that it has both workability and service stability:
1. Particle grading optimization principle
Particle grading is the basis for determining the bulk density, porosity and strength of castables. It must follow the "closest packing theory" and usually adopt a three-level or four-level grading design:
(1) Coarse aggregate (5-15mm): accounts for 30%-45%, mainly plays a skeleton support role, and raw materials with good chemical stability and low thermal expansion coefficient (such as high-alumina bauxite, corundum) must be selected to avoid structural cracking due to volume change at high temperature;
(2) Medium aggregate (1-5mm): accounts for 20%-30%, fills the gaps between coarse aggregates, improves material fluidity, and must match the composition of coarse aggregates to reduce interface reactions;
(3) Fine powder (0.074-1mm): accounts for 15%-25%, further filling the gaps between aggregates and improving density. The particle size of fine powder should be controlled within a reasonable range. Too coarse powder will easily lead to loose packing, while too fine powder will increase water demand. (4) Micro powder (<0.074mm): accounts for 5%-15%, including mineral micro powder (such as silica fume, alumina micro powder) and cement clinker micro powder. It is the key to achieving "low cement". Through the ball effect of micro powder and the reaction with volcanic ash, the cement dosage is reduced and the strength is improved. 2. Principles of precise control of cement dosage
The cement dosage (mainly aluminate cement) of low-cement castables is usually ≤8% (mass fraction). A balance must be struck between "reducing dosage" and "ensuring construction and early strength":
(1) Minimum effective dosage: Determine the cement dosage according to the purpose of the castable (e.g. 5%-7% for high-temperature kiln linings, 7%-8% for low-temperature pipelines), avoiding excessive dosage that may lead to the formation of low-melting-point calcium aluminates (e.g. CA6, C12A7) at high temperatures, which reduces refractoriness;
(2) Synergy with micropowders: Through the pozzolanic reaction of silica fume and alumina micropowders, they combine with cement hydration products (e.g. CAH10, C2AH8) to form stable C-A-S-H gel or columnar CA6 crystals, compensating for the strength loss caused by the reduction in cement dosage. 3. Principle of balance between water demand and fluidity
Water demand directly affects the density, porosity and workability of castables and needs to be controlled within a reasonable minimum range (usually 5%-8%):
(1) Reduce water demand: By adding high-efficiency water reducers (such as polycarboxylic acids and naphthalene series), the attraction between particles is reduced, high fluidity is achieved at low water content, and the formation of through pores after excessive water evaporation is avoided;
(2) Fluidity adaptation: Adjust fluidity according to the construction method (such as pumping and vibration). Pumped materials need to have an expansion of ≥250mm, and vibrated materials need to have an expansion of ≥200mm. At the same time, avoid excessive flow that causes aggregate stratification.
4. Volume stability control principle
Low-cement castables are prone to volume changes during heating due to phase change and decomposition of hydration products, which require raw material selection and additive control:
(1) Raw material expansion compensation: Add appropriate amount of expansion agent (such as kyanite and sillimanite, which are converted into mullite at high temperature and expand by 10%-15%) to offset the shrinkage caused by the decomposition of cement hydration products (such as CAH10 decomposing into C2AH8 at 100-200℃, with a volume shrinkage of about 10%);
(2) Microstructure optimization: Through micropowder filling and crystal directional growth (such as CA6 columnar crystal interweaving), the loose structure during heating is reduced and the volume stability is improved. It is usually required that the linear change rate after firing at 1100℃ is controlled within ±0.5%.
2. Key raw materials affecting the performance of low-cement refractory castables
The performance of low-cement castables (refractory, strength, thermal shock stability, corrosion resistance) is determined by the chemical composition, mineral structure and particle size distribution of the raw materials. The core raw materials can be divided into five categories:
1. Refractory aggregate: determines the refractory foundation and skeleton strength of the castable
Refractory aggregate accounts for 60%-75% and is the "skeleton" of the castable. Its performance directly determines the refractoriness and high-temperature bearing capacity of the castable:
(1) High-alumina aggregate (Al?O?≥70%):
- Composition and performance: The main components are corundum and mullite, with a refractoriness ≥1770℃, a compressive strength at room temperature ≥100MPa, and a compressive strength at high temperature (1400℃) ≥50MPa;
- Applicable scenarios: Medium and high temperature kiln linings (such as cement rotary kiln firing zone, metallurgical heating furnace), it is necessary to avoid excessive impurities (such as Fe?O?, TiO?) to prevent the formation of low melting point phase (such as FeO·Al?O?, melting point 1250℃);
(2) Corundum aggregate (Al?O?≥90%):
- Composition and performance: mainly α-corundum, dense structure, refractoriness ≥1850℃, corrosion resistance (such as resistance to molten steel and slag corrosion) is better than high aluminum aggregate;
- Applicable scenarios: Ultra-high temperature environment (such as steel blast furnace tapping channel, non-ferrous metal smelting furnace), it is necessary to control the aggregate particle size distribution to avoid excessive coarse aggregate leading to reduced thermal shock stability.
2. Refractory micropowder: the core of achieving “low cement” and performance improvement
Micropowder accounts for 5%-15% and is the key to distinguishing low-cement castables from ordinary castables. It mainly includes:
(1) Alumina micropowder (Al?O?≥99%, D50=1-5μm):
- Mechanism of action: reacts with cement hydration products to form CA6 crystals, improving high-temperature strength; fills aggregate gaps and reduces porosity (can reduce apparent porosity from 18% to below 12%);
- Performance impact: Increasing the amount of micropowder can improve refractoriness, but excessive amount (>15%) will increase water demand and needs to be used with water reducer;
(2) Silica fume (SiO?≥90%, D50=0.1-0.5μm):
- Mechanism of Action: It has high pozzolanic activity, reacting with Ca(OH)? produced by cement hydration to form a C-S-H gel, improving early strength. Its spherical particles reduce internal friction and enhance fluidity.
- Precautions: Silica fume dosage should be controlled (typically 3%-8%). Excessive use can lead to the formation of a large amount of low-melting-point glass (such as CaO-SiO?-Al?O? glass, melting point <1400°C) at high temperatures in the castable, reducing corrosion resistance.
3. Binder: The key to ensuring workability and strength development
The binder of low-cement castables is mainly aluminate cement, supplemented by chemical bonding of fine powder. Its performance affects the setting time and strength of the castable:
(1) Aluminate cement (CA-50, CA-70):
- Composition and characteristics: CA-50 contains 50%-60% CA (monocalcium aluminate), has a moderate setting time (initial setting ≥45min, final setting ≤10h), and high early strength (1d compressive strength ≥20MPa); CA-70 contains ≥70% CA, has higher early strength, but sets quickly and needs to be used with a retarder;
- Performance impact: The CaO content in cement directly affects the refractoriness. For every 1% increase in CaO, the refractoriness decreases by about 15-20℃. Therefore, cement with a low CaO content (CA-70 CaO≤22%) should be selected;
(2) Retarder/accelerator:
- Retarder (such as citric acid, tartaric acid, added at 0.05%-0.2%): Extends the setting time, suitable for long-distance transportation or large-volume pouring.
- Accelerator (such as Li?CO?, CaCl?, added at 0.01%-0.05%): Shortens the setting time and is suitable for low-temperature construction environments (such as winter construction). However, excessive use should be avoided, as it may reduce strength.
4. Water reducer: The core additive to balance water demand and fluidity
Water reducer is the key to achieving "low water and high flow" in low-cement castables. The addition amount is usually 0.1%-0.5%:
(1) Polycarboxylic acid water reducer:
- Advantages: High water reduction rate (up to 30%-40%), good slump retention (loss of expansion within 1 hour ≤ 20mm), and good compatibility with aluminate cement, which will not cause excessive retarding;
- Performance impact: It can reduce water demand by 2-3 percentage points, increase the compressive strength of the castable after firing at 1100℃ by 15%-20%, and reduce the apparent porosity by 3-5 percentage points;
(2) Naphthalene water reducer:
- Features: Medium water reduction rate (20%-25%), low price, suitable for scenes with low fluidity requirements;
- Note: The dosage must be controlled. Excessive dosage (>0.5%) will cause the castable to delaminate or lose strength.
5. Functional additives: regulating volume stability and special properties
(1) Expansion agent (kyanite, sillimanite):
- Function: At high temperature (1100-1400℃), it converts into mullite, expands by 10%-15%, offsets the shrinkage of the castable and prevents cracking;
- Dosage: Usually 3%-5%. Excessive dosage will cause excessive volume expansion and generate internal stress;
(2) Anti-explosion agent (metallic aluminum powder, addition amount 0.1%-0.3%):
- Function: During the heating process (200-600℃), it slowly oxidizes to generate Al?O?, releases a small amount of gas, and discharges the free water inside the castable, avoiding structural explosion caused by rapid evaporation of water at high temperature;
(3) Thermal shock stabilizer (silicon carbide, silicon nitride, addition amount 5%-10%):
- Function: Utilize the low expansion characteristics of silicon carbide (thermal expansion coefficient 4.5×10??/℃) and silicon nitride (thermal expansion coefficient 3.2×10??/℃) to reduce the thermal stress of the castable and improve the thermal shock stability (usually increasing the number of water-cooled thermal shocks from 10 to more than 20 times).
The preparation of low-cement refractory castables should take "reducing cement dosage, optimizing microstructure, and improving high-temperature performance" as the core goals, and strictly follow the following four principles to ensure that it has both workability and service stability:
1. Particle grading optimization principle
Particle grading is the basis for determining the bulk density, porosity and strength of castables. It must follow the "closest packing theory" and usually adopt a three-level or four-level grading design:
(1) Coarse aggregate (5-15mm): accounts for 30%-45%, mainly plays a skeleton support role, and raw materials with good chemical stability and low thermal expansion coefficient (such as high-alumina bauxite, corundum) must be selected to avoid structural cracking due to volume change at high temperature;
(2) Medium aggregate (1-5mm): accounts for 20%-30%, fills the gaps between coarse aggregates, improves material fluidity, and must match the composition of coarse aggregates to reduce interface reactions;
(3) Fine powder (0.074-1mm): accounts for 15%-25%, further filling the gaps between aggregates and improving density. The particle size of fine powder should be controlled within a reasonable range. Too coarse powder will easily lead to loose packing, while too fine powder will increase water demand. (4) Micro powder (<0.074mm): accounts for 5%-15%, including mineral micro powder (such as silica fume, alumina micro powder) and cement clinker micro powder. It is the key to achieving "low cement". Through the ball effect of micro powder and the reaction with volcanic ash, the cement dosage is reduced and the strength is improved. 2. Principles of precise control of cement dosage
The cement dosage (mainly aluminate cement) of low-cement castables is usually ≤8% (mass fraction). A balance must be struck between "reducing dosage" and "ensuring construction and early strength":
(1) Minimum effective dosage: Determine the cement dosage according to the purpose of the castable (e.g. 5%-7% for high-temperature kiln linings, 7%-8% for low-temperature pipelines), avoiding excessive dosage that may lead to the formation of low-melting-point calcium aluminates (e.g. CA6, C12A7) at high temperatures, which reduces refractoriness;
(2) Synergy with micropowders: Through the pozzolanic reaction of silica fume and alumina micropowders, they combine with cement hydration products (e.g. CAH10, C2AH8) to form stable C-A-S-H gel or columnar CA6 crystals, compensating for the strength loss caused by the reduction in cement dosage. 3. Principle of balance between water demand and fluidity
Water demand directly affects the density, porosity and workability of castables and needs to be controlled within a reasonable minimum range (usually 5%-8%):
(1) Reduce water demand: By adding high-efficiency water reducers (such as polycarboxylic acids and naphthalene series), the attraction between particles is reduced, high fluidity is achieved at low water content, and the formation of through pores after excessive water evaporation is avoided;
(2) Fluidity adaptation: Adjust fluidity according to the construction method (such as pumping and vibration). Pumped materials need to have an expansion of ≥250mm, and vibrated materials need to have an expansion of ≥200mm. At the same time, avoid excessive flow that causes aggregate stratification.
4. Volume stability control principle
Low-cement castables are prone to volume changes during heating due to phase change and decomposition of hydration products, which require raw material selection and additive control:
(1) Raw material expansion compensation: Add appropriate amount of expansion agent (such as kyanite and sillimanite, which are converted into mullite at high temperature and expand by 10%-15%) to offset the shrinkage caused by the decomposition of cement hydration products (such as CAH10 decomposing into C2AH8 at 100-200℃, with a volume shrinkage of about 10%);
(2) Microstructure optimization: Through micropowder filling and crystal directional growth (such as CA6 columnar crystal interweaving), the loose structure during heating is reduced and the volume stability is improved. It is usually required that the linear change rate after firing at 1100℃ is controlled within ±0.5%.
2. Key raw materials affecting the performance of low-cement refractory castables
The performance of low-cement castables (refractory, strength, thermal shock stability, corrosion resistance) is determined by the chemical composition, mineral structure and particle size distribution of the raw materials. The core raw materials can be divided into five categories:
1. Refractory aggregate: determines the refractory foundation and skeleton strength of the castable
Refractory aggregate accounts for 60%-75% and is the "skeleton" of the castable. Its performance directly determines the refractoriness and high-temperature bearing capacity of the castable:
(1) High-alumina aggregate (Al?O?≥70%):
- Composition and performance: The main components are corundum and mullite, with a refractoriness ≥1770℃, a compressive strength at room temperature ≥100MPa, and a compressive strength at high temperature (1400℃) ≥50MPa;
- Applicable scenarios: Medium and high temperature kiln linings (such as cement rotary kiln firing zone, metallurgical heating furnace), it is necessary to avoid excessive impurities (such as Fe?O?, TiO?) to prevent the formation of low melting point phase (such as FeO·Al?O?, melting point 1250℃);
(2) Corundum aggregate (Al?O?≥90%):
- Composition and performance: mainly α-corundum, dense structure, refractoriness ≥1850℃, corrosion resistance (such as resistance to molten steel and slag corrosion) is better than high aluminum aggregate;
- Applicable scenarios: Ultra-high temperature environment (such as steel blast furnace tapping channel, non-ferrous metal smelting furnace), it is necessary to control the aggregate particle size distribution to avoid excessive coarse aggregate leading to reduced thermal shock stability.
2. Refractory micropowder: the core of achieving “low cement” and performance improvement
Micropowder accounts for 5%-15% and is the key to distinguishing low-cement castables from ordinary castables. It mainly includes:
(1) Alumina micropowder (Al?O?≥99%, D50=1-5μm):
- Mechanism of action: reacts with cement hydration products to form CA6 crystals, improving high-temperature strength; fills aggregate gaps and reduces porosity (can reduce apparent porosity from 18% to below 12%);
- Performance impact: Increasing the amount of micropowder can improve refractoriness, but excessive amount (>15%) will increase water demand and needs to be used with water reducer;
(2) Silica fume (SiO?≥90%, D50=0.1-0.5μm):
- Mechanism of Action: It has high pozzolanic activity, reacting with Ca(OH)? produced by cement hydration to form a C-S-H gel, improving early strength. Its spherical particles reduce internal friction and enhance fluidity.
- Precautions: Silica fume dosage should be controlled (typically 3%-8%). Excessive use can lead to the formation of a large amount of low-melting-point glass (such as CaO-SiO?-Al?O? glass, melting point <1400°C) at high temperatures in the castable, reducing corrosion resistance.
3. Binder: The key to ensuring workability and strength development
The binder of low-cement castables is mainly aluminate cement, supplemented by chemical bonding of fine powder. Its performance affects the setting time and strength of the castable:
(1) Aluminate cement (CA-50, CA-70):
- Composition and characteristics: CA-50 contains 50%-60% CA (monocalcium aluminate), has a moderate setting time (initial setting ≥45min, final setting ≤10h), and high early strength (1d compressive strength ≥20MPa); CA-70 contains ≥70% CA, has higher early strength, but sets quickly and needs to be used with a retarder;
- Performance impact: The CaO content in cement directly affects the refractoriness. For every 1% increase in CaO, the refractoriness decreases by about 15-20℃. Therefore, cement with a low CaO content (CA-70 CaO≤22%) should be selected;
(2) Retarder/accelerator:
- Retarder (such as citric acid, tartaric acid, added at 0.05%-0.2%): Extends the setting time, suitable for long-distance transportation or large-volume pouring.
- Accelerator (such as Li?CO?, CaCl?, added at 0.01%-0.05%): Shortens the setting time and is suitable for low-temperature construction environments (such as winter construction). However, excessive use should be avoided, as it may reduce strength.
4. Water reducer: The core additive to balance water demand and fluidity
Water reducer is the key to achieving "low water and high flow" in low-cement castables. The addition amount is usually 0.1%-0.5%:
(1) Polycarboxylic acid water reducer:
- Advantages: High water reduction rate (up to 30%-40%), good slump retention (loss of expansion within 1 hour ≤ 20mm), and good compatibility with aluminate cement, which will not cause excessive retarding;
- Performance impact: It can reduce water demand by 2-3 percentage points, increase the compressive strength of the castable after firing at 1100℃ by 15%-20%, and reduce the apparent porosity by 3-5 percentage points;
(2) Naphthalene water reducer:
- Features: Medium water reduction rate (20%-25%), low price, suitable for scenes with low fluidity requirements;
- Note: The dosage must be controlled. Excessive dosage (>0.5%) will cause the castable to delaminate or lose strength.
5. Functional additives: regulating volume stability and special properties
(1) Expansion agent (kyanite, sillimanite):
- Function: At high temperature (1100-1400℃), it converts into mullite, expands by 10%-15%, offsets the shrinkage of the castable and prevents cracking;
- Dosage: Usually 3%-5%. Excessive dosage will cause excessive volume expansion and generate internal stress;
(2) Anti-explosion agent (metallic aluminum powder, addition amount 0.1%-0.3%):
- Function: During the heating process (200-600℃), it slowly oxidizes to generate Al?O?, releases a small amount of gas, and discharges the free water inside the castable, avoiding structural explosion caused by rapid evaporation of water at high temperature;
(3) Thermal shock stabilizer (silicon carbide, silicon nitride, addition amount 5%-10%):
- Function: Utilize the low expansion characteristics of silicon carbide (thermal expansion coefficient 4.5×10??/℃) and silicon nitride (thermal expansion coefficient 3.2×10??/℃) to reduce the thermal stress of the castable and improve the thermal shock stability (usually increasing the number of water-cooled thermal shocks from 10 to more than 20 times).