CN104093875B - 改进由金属和合金制成的产品的机械性能的方法 - Google Patents
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Abstract
本发明涉及冶金领域,更具体地涉及由金属主要是钢及其合金制成的产品的热化学表面处理,并且该方法可以用于为了增加产品的耐用性目的的产品硬化。一种改进由金属(主要是钢和在其基础上的合金)制成的产品的机械性能的方法包括在催化剂存在下在包含氮和/或其化合物的气氛中对产品渗氮。在观察气压和温度影响情况的同时,使所述产品和所述催化剂同时经历热等静压,所述气压和温度影响使得能够在所述产品的体积中获得下述位错密度:所述位错密度满足使所述产品物质的一部分转变为狄拉克物质的正电子状态的条件。
Description
技术领域
本发明涉及冶金领域,具体地涉及由金属(主要是钢及其合金)制成的产品的热化学表面处理。
背景技术
通过对产品表面层的硬化(例如,通过在氨或混合气体的气氛中在高温和高压下对产品渗氮的氮化物涂层)来改进金属和合金产品的机械性能的方法是已知的。通过产品表面预处理来获得硬化层的硬度和深度的增加,例如,借助于通过利用电子束技术(SU1707997,C23C14/48,1997)或借助于激光加热(RU2148676C1,C23C8/26,2000)使用成氮化物元素使产品表面合金化,并且在渗氮之后进行后续退火。通过在产品表面层中形成包含合金化元素的细分散氮化物的结构来实现硬化。通过氮化物沉积工艺的速度进而根据维持退火温度的精度和该过程的持续时间来确定硬化层的硬度和深度。
基于具体为通过对空气加压然后冷却然后在该温度下渗氮的初步热加工的方法(RU2133299C1,C23F17/00,1999)是已知的,该方法排除了在扩散通量沿垂直于形变方向取向时细部结构的再结晶。在扩散通量沿垂直于形变方向取向时,在存在热形变结构的材料中,氮扩散得更深入并且所形成的氮化物分布得更均匀且紧密。然而,该方法主要对于由低碳马氏体钢制成的产品的渗氮有效,而不适合低延展性的材料。
在改变化学反应动力学的催化剂(物质和化合物)存在下通过气体渗氮对金属和合金产品的硬化的方法是已知的。催化剂的结构以及其影响机理可以是各种各样的。
例如,在由RU2208659C1,C23C8/30,2003专利提出的方法中,为了表面氮处理的目的,使用高温球形催化剂用于饱和气体-空气混合物在工作空间内的受限流通以提供等温和扩散工艺的加速(所谓的“喷砂”效应)。
在由专利EP0408168,C23C8/02,1991和专利DE19652125,C23C8/24,1998提出的方法中,通过使用某些物质作为催化剂(该催化剂与表面氧化物相互作用并且有效地剥落工件表面并且有助于其塑化)来提供利用获得深硬化层来强化渗氮工艺。
当氨气的通量初步暴露于催化处理(RU2109080,C23C8/24,1998)时借助于各种化学组成的催化剂的方法是已知的,所述催化剂例如,基于氧化铝、氧化硅的化学组合物,或由在其组成中包含各种金属铂族的活性催化元素的金属及其合金制备。在由上述元素和化合物的催化处理下的含气体气氛获得关于氮化物对钢和合金产品的影响方面的特定活性,而对于本发明人的观点,不稳定的、高化学活性结构(氮自由基、氢自由基、氧化自由基、离子、离子自由基)为渗入到坚固金属基体并且与其反应的含气体介质中的活性组分。在渗氮过程期间引入特别影响气体反应物的转变的催化剂因子使得能够有目的的并且选择性地处理在这些工艺的过程中获得的最终产物和中间产物的所有光谱。上述方法能够改进钢和在其基础上获得的合金的低温表面浸渍(LTSI)的工艺(并且能够去除在LTSI工艺中产生的大量问题),这是因为该方法在最接近铁-氮二元相图的条件下提供通过氮的金属饱和的过程,因此在受限的温度范围内实现了催化剂作为渗氮工艺的活化剂的能力。
发明内容
本发明的目的是改进机械性能,特别为增加由金属(主要为钢和在其基础上的合金)制成的产品的硬度和冲击强度。
技术效果为通过强化气体渗氮工艺来增加高强度而非粘性层的深度和均匀性。通过设计影响产品材料的基本上为新的机制来提供强化,所述基本上为新的机制使得氮离子能够渗入到显著大于常规深度的深度处。
附加效果为工业处理耐火材料和低延展性材料的产品以及大尺寸产品和具有不规则形状的产品的可能性。
以下面的方式解决该问题:采用一种改进由金属制成的产品的机械性能的方法,所述金属主要为钢及钢基合金,该方法包括:在催化剂存在的情况下在含有氮和/或其化合物的气氛中进行渗氮,在观察气压和温度影响情况的同时,将所述产品和所述催化剂同时暴露于热等静压,所述气压和温度影响使得能够在所述产品的体积中获得下述位错密度:所述位错密度满足使所述产品物质的一部分转变为狄拉克物质的正电子状态的条件。
使用催化剂,使得在所述气氛中能够形成高活性介质和/或化合物,所述高活性介质和/或化合物在所述产品的体积中形成正电子素的条件下引发过渡相的出现。在气静压腔(gasostat)中执行热等静压,并且对中空产品的渗氮从其内表面执行,而热等静压在100MPa至300MPa的气压和1500℃至2500℃的温度限制下实施。使用周期系的第I族元素作为催化剂。在对中空产品渗氮时,将催化剂置于产品的内部,并且在通过利用产品设计的元素执行热等静压。
在渗氮工艺完成之后,通过退火实现产品的去杂质和产品杂质元素的纯化。
该方法的本质可以进行如下说明。
确定地是,在处理材料和饱和气氛的稳定相态中,渗氮是无效的,这是因为通过小的可塑性和高的金属变形阻力导致的低的氮扩散,而在相变的条件下出现由氮而导致的坚固金属基体的最强的饱和度。在这种情况下,氮扩散得更深入,同时出现氮化物分布得更规律且更密集。
通过由热等静压(在下文中称为HIP)影响产品和本催化剂来获得产品材料的相态不稳定性的条件。HIP的特征在于该工艺使得能够在不改变样品的形状的情况下设置大的塑性变形。
在塑性变形下,位错密度生长,该位错为晶体结构中主要类型的缺陷、晶体中内部压力的源。位错线,晶格的最大扭曲的位置。实际上,发生塑性变形是由于位错的运动和倍增而引起的。金属的可塑性和粘性是位错和在其上位错滑移的平面的充分性的结果,而变形硬化是通过位错密度和位错交互作用的强化而导致的。
与对于未扭曲晶体中的原子相比,靠近位错的原子从其平衡位置移出并且其移动到变形晶体中的新位置需要较少能量输入。位错无法仅呈现作为热运动的结果。晶体高温变形对于在晶体的形成期间已经出现的位错的滑移路径中位错的开始出现和增加是必要的。在高温变形的条件下,不仅位错密度增加,而且在晶体中的扩散速度也增加,同时晶体的化学稳定性降低。在位错附近扭曲的区域越大,用于通过原子间键合的能量确定的位错位移的能量势垒越小。在这点上,在位错线附近晶体结构变形,其中扭曲衰减与距离该线的距离成反比。当外部压力达到对于开始位错运动(在位错附近原子之间的键的断裂)所必需的值时,真正的晶体变形开始。
此外,已知的是,仅在外部压力的影响下,存在具有不为零的曲率的对称性的位错,在位错中,从本发明所解决的任务的能量部分的角度来看,大多数透视图为轴对称螺旋。
螺位错对应于在晶体中的螺旋结构的轴,其特征在于,扭曲与正常的平行面一起形成关于位错的连续螺旋斜面旋转。
基于已知的帕斯卡定律,HIP假定将产品放置在其上作用有一定压力的气体(或液体)介质中,结果为该压力在产品的表面上规则地分布,使得产品在多个方向被压缩。HIP的主要目的是增加产品具有封闭缺陷的密度。该技术使得产品的材料能够获得在许多情况下大大超过例如在热变形下可达到的水平的高强度和塑性。作为热等静压对产品的影响的结果,在其体积中,出现了导致违反在晶格中的二维周期性(导致位错密度的变化)的张力,沿着该张力存在在体积中的饱和剂的扩散。对于间隙原子容易移动到拉伸(变形)的晶格区域。扭曲的通道为易于扩散的通道。
对于金属的变形过程的数学描述,利用材料的弹性行为的各种模型。该模型的重要组成部分与弹性常数相关,并且在各向同性材料(金属为各向同性材料)的情况下,剪切模量G与热力学状态变量(压力和温度)相关。存在斯坦伯格(Steinberg)模型(Guinan M.W.和Steinberg D.J.,Pressure and temperature of the isotropic polycrystallineshear modulus for65elements.J.Phys.Chem.Solids,1974,第35卷,第1501至1512页)[1],其中剪切模量与温度和压力的相关性表示为以下公式:
G(P,T)=G0[1+AP/δ1/3-B(T-T0)]
其中:G为剪切模量
G0为在通常条件P=0,T=T0=300K下剪切模量的值,
A、B为取决于产品物质性能的常数,并且在分析试验信息的结果中获得,在Steinberg D.J.,Cohran S.G.,Guinan M.W.A constitutive model for metals athigh-strain rate.J.Appl.Phys.,1980,第51(3)卷,第1498至1504页,Steinberg D.J.,Equation of state and strength properties of selected materials.LLNL reportNo.URCL-MA-106439,1966[2]中提出,
δ=ρ/ρ0为在热力学状态的正常条件和当前条件下的产品材料的密度比。
在单位长度的范围内,位错的能量通过产生位错所必需的作用力来确定。
对于螺位错:
其中:G为剪切模量,
b为伯格矢量(Burgers vector),
r0,r1为在位错线附近的点的球面坐标。
因此,位错的内部能量的量正比于位错的长度和伯格矢量的平方。所有位错集合的能量(晶格变形的能量)通过位错的总长度和位错之间的距离限定,因此,通过位错的密度限定。
U∑=U螺Vη
其中η为位错的密度。
由此看出,产品材料内的螺位错的密度与外部影响的热力学参数的相关性是明显的。
施加影响以实现螺位错的所谓的“临界”密度,即,与在狄拉克物质的正电子态中(或者在物质的第五状态的中)产生的基层(substratum)中的位错密度的条件对应的密度。小部分所述物质转变为第五状态的过程(在遵守量子力学共振实现的一定条件下)伴随着促进增加产品体积中的饱和剂的扩散的速度和深度的显著量的能量的排放。该陈述是基于对以下的理解:狄拉克物质的第五状态的本质(在P.A.M.Dirac的“The Principles ofQuantum Mechanics”专论,第二版,Oxford,1935[3]中陈述)以及在将产品材料引入到具有物质的第五状态的量子力学共振中时在产品材料中发生的过程(在A.I.Ahiezer和V.V.Berestetsky的著作“Quantum electrodynamics”,Nauka,Moscow,1969[4]中提到)。
用于在物质的微体积中产生量子力学共振的条件是基于能量守恒定律和冲量矩(impulse moment)的。作为目的为将材料引入所述物质状态中的引发冲击,需要在单位体积的物质上产生一定的能量密度以及导致在狄拉克物质的正电子状态下的极化过程之后进行粒子和反粒子作用的所需的冲量矩或冲量的密度,其中在产品的物质分配必需附加能量的情况下,正电子反粒子湮灭。湮灭伴随着单独γ光子的产生,通过已知可利用的方法记录使得能够判断在产品的物质中的位错密度的临界值的达到。
鉴于以上所述,可以确定使得能够将小部分物质引入具有狄拉克物质的正电子状态的量子力学共振的热等静压的气压和温度条件。HIP操作条件的计算的数值区间被实验证实,在该数值区间下本发明的维护任务以最佳方式解决:
P=100MPa至300MPa
T=1500℃至2500℃
与大气相比,饱和气压的压力的增加促进了在正被处理的产品的表面上的吸收过程的强化,在该表面上存在饱和剂浓度的更密集的增加。这导致浓度梯度的增加,因此加速了扩散过程。除此(Sivert定律)之外,在压力增加下,氮在金属中的饱和环境溶解度增强,这防止了脆的氮化物相在硬化的产品表面上生长。
氮在产品材料的厚度中的扩散强化的效果的增强通过使用催化剂来获得,所述催化剂为与未转化为ε相的氮形成高活性连接物的物质。催化剂的特征为改变渗氮反应的动力学,即,增加反应进行的速度以促进氮分子分裂成原子,以增加包括氮的带正电的粒子/离子的浓度,催化剂阻止在产品的近表面层中形成的连接物的快速硬化,因此提高了在其体积内的氮扩散的梯度,这导致在产品中的饱和剂氮的浓度的增加。
通过催化剂的结构的选择实现最大效果,该催化剂提供了在作为活性还原剂的正电子素存在下在与在热等静压的条件中的饱和气氛相互作用下引发在产品体积中的相变的物质和连接物的产生。如所已知的,相似类型的反应(还原反应)伴随着大量能量的排放。这种情况以及晶格中的某些变化与在热等静压的影响下在产品的材料中开始的形成正电子素增强的效果有关。
可以应用周期系的第I族元素作为由于以下性能而能够提供上述过程的催化剂:
-最小离子半径(容易扩散),
-可利用的类氢光谱,
-提供所需磁场和轨道磁矩的接近量子数,
-促进正电子素产生所需的核结构,
-与伽马量子能量(2m0c2,其中m0为电子质量,c为光在真空中的速度)对应的所需的能级间距。
本发明的最佳实施方式
热等静压的工艺可以在气静压腔(gasostat)(用于气体静力处理的装置)中实施,在该装置中氮化气体为传递周围影响的工作介质。气静压腔设计,即在其结构内包括的高压容器,提供了对于现有方法的最有效的实施的气压(最高达300MPa)和温度(最高达2500℃)冲击的必要条件。例如,在USA(在Batter研究所)所研究和设计的大量设备符合这些要求。与可加工的产品一起将催化剂装载到气静压腔中。中空产品的渗氮通过影响其内部表面而有利地进行。在这种情况下,为了处理大尺寸中空产品,可以使用其构造作为气体静力装置的元件。例如,在两个连接端适当气密地密封的厚壁管的充分扩展部分的内腔可以用作高压罐(与气静压腔类似),并且可以通过氮化的气体和催化剂填充。
作为对由各种结构钢制成的产品的硬化所进行的大量试验的结果,在扩散层的显著深度处实现了材料的高显微硬度,其结果为产品的耐磨性增加了2倍至10倍。通过下面的曲线图示出了在样品产品材料的层的深度中的显微硬度的分布的试验数据。在温度T=1050℃并且相应地压力为55MPa、150MPa和300MPa下通过氮化气氛影响样品的条件下获得了数据。
工业实用性
本发明可以为了增加其耐用性的目的用于金属和金属合金产品的硬化,并且可以应用于冶金工业、石油提取、机械制造及其他工业。
Claims (6)
1.一种改进由金属制成的产品的机械性能的方法,所述方法包括在催化剂存在的情况下在含有氮和/或氮的化合物的气氛中进行产品渗氮,其特征在于在观察气压和温度影响情况的同时,将所述产品和所述催化剂同时暴露于热等静压,所述气压和温度影响使得能够在所述产品的体积中获得下述位错密度:所述位错密度满足使所述产品物质的一部分转变为正电子状态的条件。
2.根据权利要求1所述的方法,其中使用所述催化剂,使得在所述气氛中能够形成高活性介质和/或化合物,所述高活性介质和/或化合物在所述产品的体积中形成正电子素的条件下引发过渡相的出现。
3.根据权利要求1所述的方法,其中在气静压腔中执行所述热等静压。
4.根据权利要求1所述的方法,其中从中空产品的内表面执行对所述中空产品的渗氮。
5.根据权利要求1所述的方法,其中在100MPa至300MPa的气压和1500℃至2500℃的温度限值下实施所述热等静压。
6.根据权利要求4所述的方法,其中将所述催化剂置于产品的内腔中,并且所述产品的元素设计为适用于所述热等静压的条件。
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