CN103131938B - 金属型稀土微合金化d型石墨铸铁玻璃模具及其制备方法 - Google Patents
金属型稀土微合金化d型石墨铸铁玻璃模具及其制备方法 Download PDFInfo
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- CN103131938B CN103131938B CN201310078992.5A CN201310078992A CN103131938B CN 103131938 B CN103131938 B CN 103131938B CN 201310078992 A CN201310078992 A CN 201310078992A CN 103131938 B CN103131938 B CN 103131938B
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- Prior art keywords
- iron
- mold
- rare earth
- type graphite
- microalloying
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- 239000011514 iron Substances 0.000 title claims abstract description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound 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[C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000010439 graphite Substances 0.000 title claims abstract description 50
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 50
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound data:image/svg+xml;base64,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 data:image/svg+xml;base64,PD94bWwgdmVyc2lvbj0nMS4wJyBlbmNvZGluZz0naXNvLTg4NTktMSc/Pgo8c3ZnIHZlcnNpb249JzEuMScgYmFzZVByb2ZpbGU9J2Z1bGwnCiAgICAgICAgICAgICAgeG1sbnM9J2h0dHA6Ly93d3cudzMub3JnLzIwMDAvc3ZnJwogICAgICAgICAgICAgICAgICAgICAgeG1sbnM6cmRraXQ9J2h0dHA6Ly93d3cucmRraXQub3JnL3htbCcKICAgICAgICAgICAgICAgICAgICAgIHhtbG5zOnhsaW5rPSdodHRwOi8vd3d3LnczLm9yZy8xOTk5L3hsaW5rJwogICAgICAgICAgICAgICAgICB4bWw6c3BhY2U9J3ByZXNlcnZlJwp3aWR0aD0nODVweCcgaGVpZ2h0PSc4NXB4JyB2aWV3Qm94PScwIDAgODUgODUnPgo8IS0tIEVORCBPRiBIRUFERVIgLS0+CjxyZWN0IHN0eWxlPSdvcGFjaXR5OjEuMDtmaWxsOiNGRkZGRkY7c3Ryb2tlOm5vbmUnIHdpZHRoPSc4NScgaGVpZ2h0PSc4NScgeD0nMCcgeT0nMCc+IDwvcmVjdD4KPHRleHQgZG9taW5hbnQtYmFzZWxpbmU9ImNlbnRyYWwiIHRleHQtYW5jaG9yPSJzdGFydCIgeD0nMTguNzk5NicgeT0nNDcuNzk1NScgc3R5bGU9J2ZvbnQtc2l6ZTozOHB4O2ZvbnQtc3R5bGU6bm9ybWFsO2ZvbnQtd2VpZ2h0Om5vcm1hbDtmaWxsLW9wYWNpdHk6MTtzdHJva2U6bm9uZTtmb250LWZhbWlseTpzYW5zLXNlcmlmO2ZpbGw6IzNCNDE0MycgPjx0c3Bhbj5GZTwvdHNwYW4+PC90ZXh0Pgo8L3N2Zz4K [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 46
- 239000011521 glasses Substances 0.000 title claims abstract description 26
- 229910052751 metals Inorganic materials 0.000 title claims abstract description 23
- 239000002184 metals Substances 0.000 title claims abstract description 23
- 229910052761 rare earth metals Inorganic materials 0.000 title claims abstract description 19
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 15
- 238000002360 preparation methods Methods 0.000 title claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- 239000010949 copper Substances 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 238000000137 annealing Methods 0.000 claims abstract description 11
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 10
- 239000000203 mixtures Substances 0.000 claims abstract description 8
- 229910000529 magnetic ferrites Inorganic materials 0.000 claims abstract description 7
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 7
- 241001081830 Degeneriaceae Species 0.000 claims description 26
- 239000011248 coating agents Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 239000002667 nucleating agents Substances 0.000 claims description 9
- 239000011901 water Chemical group 0.000 claims description 9
- 238000005266 casting Methods 0.000 claims description 8
- 229910018619 Si-Fe Inorganic materials 0.000 claims description 7
- 229910008289 Si—Fe Inorganic materials 0.000 claims description 7
- 238000000034 methods Methods 0.000 claims description 7
- VZJVWSHVAAUDKD-UHFFFAOYSA-N Potassium permanganate Chemical group 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[K+].[O-][Mn](=O)(=O)=O VZJVWSHVAAUDKD-UHFFFAOYSA-N 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000007788 liquids Substances 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- 239000010959 steel Substances 0.000 claims description 6
- RLQWHDODQVOVKU-UHFFFAOYSA-N tetrapotassium;silicate Chemical group 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- 108010038629 Molybdoferredoxin Proteins 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N Sodium silicate Chemical compound 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[Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 280000542077 Sprinkle companies 0.000 claims description 3
- HBELESVMOSDEOV-UHFFFAOYSA-N [Fe].[Mo] Chemical compound 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[Fe].[Mo] HBELESVMOSDEOV-UHFFFAOYSA-N 0.000 claims description 3
- PNXOJQQRXBVKEX-UHFFFAOYSA-N [Fe].[V] Chemical compound 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[Fe].[V] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound 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Abstract
Description
技术领域
[0001] 本发明涉及玻璃模具领域,特别是涉及一种金属型稀土微合金化D型石墨铸铁玻璃模具及其制备方法。
背景技术
[0002] 在玻璃制品成形过程中,玻璃模具频繁地接触1100°C以上的熔融玻璃,承受氧化、生长及热疲劳等作用。模腔热平衡温度一般在450~650°C,长期处于高温状态下工作而且反复的开模合模的过程中产生摩擦,因此需求玻璃模具组织致密均匀,应具有良好的耐热、耐磨、耐腐蚀、抗热疲劳、抗氧化、抗生长、导热性好、线性膨胀系数小、粘附温度高等特性。铸铁因为其具有良好的导热性、耐热性、铸造性和良好的加工性能并且原料充足价格低廉,而获得广泛的应用。铸铁中石墨的形态、数量及分布状况直接影响铸铁的基体强度、热传导能力、抗氧化能力、热膨胀系数等,从而影响热疲劳裂纹的萌生与扩展,其中石墨的形态最为重要。普通灰铸铁中石墨成片状,石墨片越粗大、连续,数量越多,氧化性气氛越易侵入模具内部,氧化也越严重。普通灰铸铁虽然具有良好的导热性能,但抗耐热疲劳性能、抗氧化生长性能、耐磨性能较差。同灰铸铁相比,球墨铸铁中的石墨为球状,减小了石墨对基体的切割作用,孕育作用使晶粒度比灰铸铁小,使球墨铸铁的综合性能提高。球墨铸铁虽然有较高的强度和韧性,并有良好的抗氧化性能,但由于其石墨呈孤立的球状,导热性较差,使玻璃制品在模腔中不能快速冷却,从而限制了成型速度的提高,不能适应目前市场上快速成型行列机的要求,在玻璃模具中的应用具有局限性。
发明内容
[0003] 本发明主要解决的技术问题是提供一种金属型稀土微合金化D型石墨铸铁玻璃模具及其制备方法,能够解决由于金属型冷却过快所产生的白口化倾向;完全石墨化的高温退火,使得最后得到铁素体基体组织;D型石墨铸铁各项综合性能指标大幅度地提尚,满足了玻璃模具所必须具备的要求,增加了模具的使用寿命。
[0004] 为解决上述技术问题,本发明采用的一个技术方案是:提供一种金属型稀土微合金化D型石墨铸铁玻璃模具,包括下列质量百分比的组合:
[0005] C 3.35-3.7%、Si 2-2.2%、Mn0.4-0.6%、Cr 0.3-0.4%、Mo 0.4-0.5%、Ni0.9-1.1%、V < 0.02%,Al < 0.02%、Cu < 0.02%、Ti 0.05-0.1%、RE 0.02-0.05%,其余为 Fe和不可避免的杂质。
[0006] 在本发明一个较佳实施例中,包括下列质量百分比的组合:C 3.55%、Si 2.1%、Mn0.5%、Cr 0.35%、Mo 0.5%、Ni 1.0%、V < 0.02%,Al < 0.02%、Cu < 0.02%、Ti 0.08%、RE0.04%,其余为Fe和不可避免的杂质。
[0007] 在本发明一个较佳实施例中,所述不可避免的杂质包括P < 0.05%、S < 0.01%。
[0008] 在本发明一个较佳实施例中,抗拉强度为350~380MPa,布氏硬度为150~170,金像组织为:85%铁素体+15%珠光体,石墨形态95%以上为D型石墨,内型腔15mm范围内全部为D型石墨,石墨等级为5~6级。
[0009] 本发明的另一个目的是提供一种金属型稀土微合金化D型石墨铸铁玻璃模具的制备方法,具体步骤包括:
[0010] (100)、按质量百分比配比其化学成分,C 3.35-3.7%, Si 2〜2.2%、Mn 0.4~0.6%、Cr 0.3-0.4%、Mo 0.4-0.5%、Ni 0.9-1.1%、V < 0.02%,Al < 0.02%、Cu < 0.02%、Ti
0.05-0.1%、RE 0.02-0.05%,其余为Fe和不可避免的杂质;
[0011 ] (200),熔炼:先将计算得出的按比例称量好的废钢、铸造生铁放入中频电炉中加热完全恪化后,再将按比例称量好的娃铁、猛铁、络铁、钥铁、I凡铁、钦铁、电解银、电解铜、纯铝加入加热完全融化后,调整铁水温度到1480°C -1500°C ;
[0012] (300)、净化和孕育:将占铁水总重量0.3%~0.5%稀土合金ReSiFe作为铁水的净化剂和占铁水总重量0.3%~0.5%含Ba的S1-Fe孕育剂,粒度为5mm左右,均匀混合,置于浇包底部,最后出炉温度不低于1480°C的铁水定量充入,进行孕育处理,孕育时间为6~10分钟,充分搅拌后,静置3~5分钟,扒渣,撒上覆盖剂;
[0013] (400)、浇注:金属铸型由HT200材料制成,铸型内腔与铁液接触的地方经涂料涂届IJ,涂料由耐火粘土,高锰酸钾、水玻璃和水组成其成份含量如下:耐火粘土 200 g,石墨60 g,水玻璃60 g,高锰酸钾0.5 g,水1000 g,经过涂料涂刷的金属铸型在浇注前,先预热,预热温度为300°C ~320°C,铁水浇注温度在1340°C ~1360°C之间;
[0014] (500)、热处理退火工艺:高温退火,850±50°C,保温6小时,随炉冷却至室温。
[0015] 在本发明一个较佳实施例中,所述S1-Fe孕育剂主要成分包括Si:65~ 70%,Al:4 〜6%,Ca 0.48%,Ba I 〜2%,Mn:8 〜10%。
[0016] 在本发明一个较佳实施例中,所述步骤(100)中按下列质量百分比的组合配比:C3.55%、Si 2.1%、Μη0.5%、Cr 0.35%、Mo 0.5%、Ni 1.0%、V < 0.02%, Al < 0.02%、Cu < 0.02%、Ti 0.08%、RE 0.04%,其余为Fe和不可避免的杂质。
[0017] 在本发明一个较佳实施例中,所述不可避免的杂质包括P < 0.05%、S < 0.01%。
[0018] 本发明的有益效果是:本发明金属型稀土微合金化D型石墨铸铁玻璃模具及其制备方法,具有以下优点:
[0019] (1)、使用稀土合金作为铁水的净化剂,在脱氧的同时还能细化奥氏体晶粒;
[0020] (2)、Cr、Mo等微合金化元素对液态铁液施行变质处理,其中Cr和Al也具有脱氧作用,这些脱氧产物可以作为石墨结晶核心,铁水形成的石墨片体细小且均匀。Mo又是提高奥氏体的稳定及扩大奥氏体相区的元素,使共析反应在更低的温度下进行,更有利于促进获得D型石墨,同时也使得珠光体数量增加且细化,而Cr在强烈促使合金渗碳体的形成的同时,也有效地减少了珠光体片间距,导致最终形成细小的珠光体组织,通过完全石墨化的高温退火,使得最后得到铁素体基体组织。
[0021] (3)、金属铸型的使用对D型石墨的形成具有关键作用,对金属型进行涂层和预热可以有效防止白口化倾向的发生,含Ba的S1-Fe孕育剂有利于D型石墨获得。
[0022] 总之,本发明金属型稀土微合金化D型石墨铸铁玻璃模具及其制备方法,能够解决由于金属型冷却过快所产生的白口化倾向;完全石墨化的高温退火,使得最后得到铁素体基体组织;D型石墨铸铁各项综合性能指标大幅度地提高,满足了玻璃模具所必须具备的要求,增加了模具的使用寿命。
具体实施方式
[0023] 下面对本发明的较佳实施例进行详细阐述,以使本发明的优点和特征能更易于被本领域技术人员理解,从而对本发明的保护范围做出更为清楚明确的界定。
[0024] 实施例一:
[0025] (I)、按质量百分比配比其化学成分,C 3.35%、Si 2%、Mn 0.4%、Cr 0.3%、Mo 0.4%、N1.9%、V < 0.02%,Al < 0.02%、Cu < 0.02%、T1.05%、RE0.02%,其余为 Fe 和不可避免的杂质,不可避免的杂质包括P < 0.05%、S < 0.01%。
[0026] ( 2 )、熔炼:先将计算得出的按比例称量好的废钢、铸造生铁放入中频电炉中加热完全恪化后,再将按比例称量好的娃铁、猛铁、络铁、钥铁、I凡铁、钦铁、电解银、电解铜、纯招加入加热完全融化后,调整铁水温度到1480°c ~1500°C。
[0027] (3)、净化和孕育:将占铁水总重量0.3%~0.5%稀土合金ReSiFe作为铁水的净化剂和占铁水总重量0.3%~0.5%含Ba的S1-Fe孕育剂(Si:65~ 70%,Al:4〜6%,Ca
0.48%, Ba I〜2%,Mn:8〜10% ),粒度为5mm左右,均匀混合,置于浇包底部。最后出炉温度不低于1480°C的铁水定量充入,进行孕育处理,孕育时间为8~10分钟,充分搅拌后,静置3~5分钟,扒渣,撒上覆盖剂。
[0028] (4)、浇注:金属铸型由HT200材料制成,铸型内腔与铁液接触的地方经涂料涂刷。涂料由耐火粘土,高锰酸钾、水玻璃和水组成其成份含量如下:耐火粘土 200 g,石墨60g,,水玻璃60 g,高锰酸钾0.5 g,水1000 go经过涂料涂刷的金属铸型在浇注前,先预热,预热温度为300°C ~320°C。铁水浇注温度在1340°C ~1360°C之间。
[0029] (5)、热处理退火工艺:高温退火,850±50°C,保温6小时,随炉冷却至室温。
[0030] 实施例二
[0031]按照下列质量百分比配比:C 3.55%、Si 2.1%、Mn0.5%、Cr 0.35%、Mo 0.5%、Ni
1.0%、V < 0.02%,Al < 0.02%、Cu < 0.02%、Ti 0.08%、RE 0.04%,其余为 Cu 和不可避免的杂质。制备方法与实施例一相同。成品需控制杂质中:P < 0.01%、S < 0.01%。
[0032] 实施例三
[0033]按照下列质量百分比配比:C 3.7%、Si 2.2%、Mn0.6%、Cr 0.4%、Mo 0.5%、Nil.1%、V < 0.02%,Al < 0.02%、Cu < 0.02%、T1.1%、RE0.05%,其余为 Cu 和不可避免的杂质。制备方法与实施例一相同。成品需控制杂质中:P < 0.01%、S < 0.01%。
[0034] D型石墨属于片状石墨的一种,在奥氏体树枝晶间生长,奥氏体的连续性割裂了石墨片的连续性,D型石墨与基体间的间隙比其他片状石墨与基体问的间隙小。D型石墨组织中的初生奥氏体具有骨架结构,而共晶奥氏体又像网络一样把初生奥氏体的各个枝干连接在一起,提高了骨架抵抗外力的能力。再加上D型石墨细小、卷曲、端部较钝的形态,决定它对基体的切割作用小,不易引起较大的应力集中,所以D型石墨铸铁特别适合应用于玻璃模具材料。
[0035] 利用微量元素Re对铁水的净化作用和强烈的脱氧功效,细化奥氏体晶粒。加之Cr,Mo等微合金化元素对铁液施行变质处理,其中Cr和Al也具有脱氧作用,脱氧产物可以作为石墨结晶核心。Mo又是提高奥氏体的稳定及扩大奥氏体相区的元素,使共析反应在更低的温度下进行,有利于促进获得D型石墨,同时也使得珠光体数量增加且细化,Cr在强烈促使合金渗碳体的形成的同时,有效地减少了珠光体片间距,最终形成细小的珠光体组织。因金属型具有导热性高,冷却速度快,可得到细小致密的组织,同时金属型铸造条件比较稳定,铸件有较高的精度和光洁度,铸件缺陷种类少,可提高成品率。铸型选取金属型更有利于D型石墨的形成。使用含Ba的S1-Fe孕育剂(S1:65~ 70%,Al:4〜6%,Ca 0.48%,Ba I〜2%,Mn:8〜10% )有利于D型石墨获得。金属型进行涂层和预热解决了由于金属型冷却过快所产生的白口化倾向。完全石墨化的高温退火,使得最后得到铁素体基体组织。其中孕育剂中的Ba和Ca等元素因为孕育剂加入量只有0.3-0.5%,而Ba和Ca又只占到孕育剂的1~2%和0.48%所以Ba和Ca分别只占总量的0.001%和0.00025%加上过程中的烧损,在成品的实际检测中是检测不出的,可忽略不计。
[0036] 本发明D型石墨铸铁各项综合性能指标大幅度地提高,满足了玻璃模具所必须具备的要求,增加了模具的使用寿命。
[0037] 以上所述仅为本发明的实施例,并非因此限制本发明的专利范围,凡是利用本发明说明书内容所作的等效结构或等效流程变换,或直接或间接运用在其他相关的技术领域,均同理包括在本发明的专利保护范围内。
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