Studies on thermal conductivity and durability of modified steel slag/rubber composites
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摘要: 利用自制鋼渣助磨改性劑處理熱悶渣、電爐渣與風淬渣，將改性后的鋼渣微粉與炭黑、橡膠基體等復合形成改性鋼渣/橡膠復合材料。采用導熱系數儀，測定三種改性鋼渣/橡膠復合材料熱氧老化1、3、5、7、9、11 d的導熱系數；根據Young’s與Flory方程計算出三種改性鋼渣/橡膠復合材料熱氧老化前后的接觸角θ與交聯密度；采用熱重分析儀（TGA）、場發射掃描電鏡（SEM）進行熱氧老化前后分析。未熱氧老化時，在三種改性鋼渣/橡膠復合材料中改性電爐鋼渣/橡膠復合材料的導熱系數最低，為0.187 W·m?1·K?1，是因為改性電爐渣粒中位徑（d50）最小，即3.49 μm，形成更致密的膠裹渣結構，不易形成導熱通路，使其導熱系數降低。熱氧老化時，破壞膠裹渣結構，改性電爐渣/橡膠復合材料形成的孔隙大，分散性最好，降低界面熱阻，更易形成導熱通路，使其導熱系數最高。熱氧老化后，橡膠復合材料表面粗糙度變大且存在較長裂紋與較深孔洞，導致橡膠復合材料吸水性增加，接觸角下降。由于改性熱悶渣的粒徑最大，在熱作用下氧氣更容易進入橡膠復合材料中與橡膠分子鏈（雙鍵）發生反應生成自由基，增加分子量，提高交聯密度；由于改性風淬渣的堿度最高，為3.3，不利于硫化過程，更易形成的不穩定碳層，使二次燃燒更加充分，導致交聯密度變小，在800 ℃時，熱氧老化后，改性風淬渣/橡膠復合材料殘余物炭渣質量分數僅為1.02%，耐久性最差。Abstract: Modified steel slag powder was used to create a modified steel slag/rubber composite material using self-made steel slag grinding modifier and combining it with carbon black and rubber matrix to treat hot braised steel slag, electric furnace steel slag, and air-quenched steel slag. Next, the thermal conductivity of the three types of modified steel slag/rubber composites was measured using a thermal conductivity instrument at 1, 3, 5, 7, 9, and 11 days. The surface contact angle θ and crosslinking density of the above composites were calculated using Young’s and Flory’s equations before and after thermal oxygen aging, and their changes were analyzed using thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). As a result, the thermal conductivity of the modified electric furnace slag/rubber composite material was the lowest [0.187 W·m?1·K?1]. Among them, the median diameter (d50) of the modified electric furnace slag particles was the smallest (3.49 μm) without thermal oxygen aging, easily forming a compact structure of rubber-wrapped slag, but more challenging to develop thermal conductivity paths that reduced thermal conductivity. In the process of thermal oxygen aging, the structure of rubber-wrapped slag was destroyed. While the modified electric furnace slag/rubber composite material had large pores and the best dispersibility, which reduced interface thermal resistance and easily formed thermal conductivity paths, its thermal conductivity was the highest. After thermal oxygen aging, it was found that long cracks, deep holes, and increased roughness lying on rubber composite material surface increase the water absorption and decrease the contact angle. Besides, due to the largest particle size of the modified hot braised slag, oxygen is more likely to enter the rubber composite material under the heat action to react with the rubber molecular chain (double bond) to generate free radicals, thus raising molecular weight and growing crosslinking density. The modified air-quenched slag had the highest basicity (3.3), was detrimental to the vulcanization process, and was prone to forming an unstable carbon layer, resulting in more secondary combustion and a lower crosslinking density. Moreover, the mass fraction of residual material called carbon residue was only 1.02% at 800 ℃ and it had the worst durability after thermal oxygen aging.
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Key words:
- modified steel slag /
- rubber /
- thermal oxygen aging /
- thermal conductivity /
- crosslinking density
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圖 1 改性鋼渣/橡膠復合材料導熱系數
Figure 1. Thermal conductivity of modified steel slag/rubber composite material
圖 2 改性鋼渣/橡膠復合材料熱氧老化前后表面接觸角. (a) 熱氧老化前；(b) 熱氧老化后
Figure 2. Surface contact angle of modified steel slag/rubber composite before and after thermal oxygen aging: (a) before thermal oxygen aging; (b) after thermal oxygen aging
圖 3 改性鋼渣/橡膠復合材料熱氧老化前后的SEM圖. (a) ZL0熱氧老化前；(b) ZL1熱氧老化前；(c) ZL2熱氧老化前；(d) ZL3熱氧老化前；(e) ZL0熱氧老化后；(f) ZL1熱氧老化后；(g) ZL2熱氧老化后；(h) ZL3熱氧老化后
Figure 3. Scanning electron microscopy image of modified steel slag/rubber composites before and after thermal oxygen aging: (a) ZL0 before thermal oxygen aging; (b) ZL1 before thermal oxygen aging; (c) ZL2 before thermal oxygen aging; (d) ZL3 before thermal oxygen aging; (e) ZL0 after thermal oxygen aging; (f) ZL1 after thermal oxygen aging; (g) ZL2 after thermal oxygen aging; (h) ZL3 after thermal oxygen aging
圖 4 改性鋼渣/橡膠復合材料熱氧老化后的交聯密度
Figure 4. Cross l linking density of modified steel slag/rubber composite material after thermal oxidation
圖 5 改性鋼渣/橡膠復合材料熱氧老化前后的質量變化率曲線. (a) 熱氧老化前；(b) 熱氧老化后
Figure 5. Weight loss curves of modified steel slag/rubber composite before and after thermal oxygen aging: (a) before thermal oxygen aging; (b) after thermal oxygen aging
圖 6 改性鋼渣/橡膠復合材料熱氧老化作用機理
Figure 6. Mechanism of thermal oxygen aging of modified steel slag/rubber composite
表 1 改性鋼渣/橡膠復合材料原料配比
Table 1. Raw material ratio of modified steel slag/rubber composite material
Sample Type of modified steel slag Modified steel slag/g Carbon black/g Rubber/g Stearic acid/g Zinc oxide/g Accelerator/g Sulfur/g ZL0 30 100 1 3 1 2 ZL1 Hot braised slag 20 30 100 1 3 1 2 ZL2 Air quenched slag 20 30 100 1 3 1 2 ZL3 Electric furnace slag 20 30 100 1 3 1 2 
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表 2 改性鋼渣微粉化學成分與粒徑
Table 2. Chemical composition and particle size of modified steel slag
Type of modified steel slag Chemical composition of modified steel slag（mass fraction）/% Particle size of modified steel slag/μm CaO Fe2O3 SiO2 MgO MnO P2O5 Al2O3 Others d90 d50 d10 Hot braised slag 46.16 25.21 13.06 4.51 2.78 2.47 2.95 2.648 20.90 7.59 2.86 Air quenched slag 46.68 28.14 10.71 4.81 2.32 2.47 3.38 1.49 9.90 3.82 1.06 Electric furnace slag 36.36 39.29 10.97 3.18 3.21 1.06 4.25 1.38 10.02 3.49 1.11
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表 3 改性鋼渣/橡膠復合材料熱氧老化的導熱系數
Table 3. Thermal conductivity of modified steel slag/rubber composites during thermal oxygen aging W·m?1·K?1
Sample Thermal conductivity corresponding to
thermal oxygen aging days0 d 1 d 3 d 5 d 7 d 9 d 11 d ZL1 0.192 0.234 0.223 0.219 0.210 0.199 0.184 ZL2 0.189 0.232 0.228 0.217 0.213 0.193 0.179 ZL3 0.187 0.253 0.230 0.229 0.221 0.209 0.187
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