WO2021026778A1 - 一种可提高注射针刚性韧性的不锈钢材料 - Google Patents
一种可提高注射针刚性韧性的不锈钢材料 Download PDFInfo
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- WO2021026778A1 WO2021026778A1 PCT/CN2019/100426 CN2019100426W WO2021026778A1 WO 2021026778 A1 WO2021026778 A1 WO 2021026778A1 CN 2019100426 W CN2019100426 W CN 2019100426W WO 2021026778 A1 WO2021026778 A1 WO 2021026778A1
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- stainless steel
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- the invention belongs to the technical field of stainless steel materials, and specifically relates to a stainless steel material that can improve the rigidity and toughness of an injection needle.
- austenitic stainless steel 304 or 316 the material used for injection needles is austenitic stainless steel 304 or 316.
- the advantages of austenitic 304 and 316 stainless steel are corrosion resistance and chemical resistance, so they are mostly used for injection needles.
- the biggest disadvantage of 304 and 316 is insufficient rigidity and strength.
- the Ni content of 316 is higher. 316 increases the Ni content and toughness, but it causes the deterioration of the rigidity of the stainless steel material.
- the needle tube is easier to bend during use.
- the injection has high requirements for the toughness and corrosion resistance of the steel.
- the rigidity can make the needle Sharper, toughness can make the needle tube not easy to break, corrosion resistance can prevent the material from being corroded by the injection syrup, or in other words, it will not be corroded during sterilization and storage.
- the purpose of this invention is to solve the problem that the injection needle stainless steel material in the prior art cannot meet the requirements of rigidity, toughness and corrosion resistance at the same time; to provide a stainless steel material that improves the strength of the injection needle, which has excellent combination of strength, toughness and rigidity and resistance Corrosive and relatively inexpensive.
- the present invention provides a stainless steel material, the chemical composition composition weight percentage is: chromium Cr 21-23, nitrogen N 0.08-0.2, nickel Ni 4.5-6.5, molybdenum Mo 2.5-3.5, carbon C ⁇ 0.03, silicon Si ⁇ 1.6, Manganese Mn ⁇ 2.6, sulfur S ⁇ 0.02, phosphorus P ⁇ 0.03, and the remaining iron Fe.
- the present invention surprisingly finds that under the premise of introducing the N component and combining and regulating the Cr and Ni components, the steel properties of the stainless steel can be improved and its toughness significantly improved, and the prepared stainless steel has a combination of strength and toughness and steel properties.
- chromium is a ferrite-forming element. Nevertheless, since it is the main corrosion-resistant element in stainless steel, it also improves the solubility of nitrogen, and the content should not be too high.
- the chromium content should be controlled within 21 ⁇ 23(wt)%, the solubility of nitrogen at atmospheric pressure is the highest content of nitrogen in steel. Even if nitrogen is added to the solubility, the solubility will decrease as the solidification progresses, and pore defects will occur, resulting in unqualified, and the nitrogen content The higher the higher, the higher the production process requirements and the higher the energy consumption, and the higher the finished product. In order to facilitate industrialized mass production, it is recommended that the nitrogen content be controlled at 0.08 ⁇ 0.2(wt)%, and nitrogen can also improve the pitting corrosion resistance of steel .
- Nickel is an element that stabilizes the austenite structure, which can promote the stability of the passive film of stainless steel, improve the thermodynamic stability of stainless steel, and strengthen the rust resistance and corrosion resistance of stainless steel.
- the nickel content is controlled within 4.5 ⁇ 6.5(wt)% .
- Carbon is also an important austenitizing element, but too much carbon will seriously affect the plasticity and corrosion resistance of steel. Therefore, the carbon content should be strictly controlled below 0.03 (wt)%. Too high will increase the difficulty of steel processing. The lower the better, the lower the higher the production cost.
- Manganese is a weak austenitizing element that can increase the solubility of nitrogen in steel. Therefore, at least but too much manganese should affect the performance of steel, so manganese should be controlled below 2.6 (wt)%.
- Chromium is a ferrite-forming element. However, since it is the main corrosion-resistant element in stainless steel and also improves the solubility of nitrogen, the content of chromium should be controlled at 21 to 23 (wt)%.
- molybdenum can increase the solubility of nitrogen, and the interaction with nitrogen can improve the corrosion resistance of steel, but too much content will reduce the toughness of steel, so it is controlled at 2.5-3.5 (wt)%.
- Silicon can promote the formation of ferrite, so the silicon content is controlled below 1.6 (wt)%, the lower the higher the production cost.
- the impurity elements sulfur and phosphorus should be controlled below 0.02 (wt)% and 0.03 (wt)%, respectively, to improve the overall performance of the steel, the lower the higher the production cost.
- the present invention provides a use of stainless steel material for preparing stainless steel injection needles. Because the stainless steel injection needle made of the stainless steel material of the present invention has good hot and cold work performance, compared with stainless steel 304 and stainless steel 316, the steel of the injection needle tube can be increased by 2 times under the same outer diameter and inner diameter. The toughness can be increased by 1.2 times, and the corrosivity has been significantly improved.
- the stainless steel injection needle is a stainless steel injection needle for animals or a stainless steel injection needle for humans, and the stainless steel injection needle for humans can be used for insulin, vaccine, and cosmetic injections.
- the stainless steel injection needle is a stainless steel injection needle for animals; generally speaking, the requirements for rigidity and toughness of the stainless steel injection needle for animals are higher than those for human injection needles, because the stainless steel material of the present invention is compared with the traditional stainless steel 304 and For stainless steel 316, under the same outer diameter and inner diameter, the rigidity can be increased by 2 times, the toughness can be increased by 1.2 times, and the corrosiveness is significantly improved; therefore, the stainless steel injection needle defined by the present invention can better meet the requirements of animal stainless steel injection For the requirements of rigidity and toughness.
- the present invention has the following advantages:
- the stainless steel material of the present invention has little change, it can be produced on the same line as the traditional stainless steel material and its stainless steel injection needle production line, without adjusting the production equipment.
- the stainless steel material for improving the strength of the injection needle of the present invention is mainly produced by the following processes:
- Press plate the stainless steel coil is squeezed to the required thickness of the steel coil through the roller press
- Welded pipe the steel strip with the slit width is entered into the pipe welding machine to be welded into a stainless steel tube coil;
- Sharpening The cut length of the needle tube is sharpened to the required angle of the needle tube through the sharpening machine, which meets the puncture standard of the injection needle.
- the stainless steel material for improving the strength of the injection needle of the present invention is made into an injection needle tube and the composition comparison of stainless steel 304 and stainless steel 316 is shown in Table 2.
- This material is stainless steel ⁇ 450 ⁇ 620 ⁇ 18 ⁇ 320 2.0B/2t 304 stainless steel ⁇ 205 ⁇ 520 ⁇ 40 ⁇ 200 2.0B/1.5t 316 stainless steel ⁇ 205 ⁇ 520 ⁇ 40 ⁇ 200 2.0B/1.5t
- the yield strength of this material is more than twice that of stainless steel 304 and stainless steel 316
- the tensile strength is 1.2 times that of stainless steel 304 and stainless steel 316
- the hardness is 1.6 times that of stainless steel 304 and stainless steel 316.
- the applicant has concluded that compared with stainless steel 304 and stainless steel 316, the rigidity of the injection needle tube made of the stainless steel material can be increased by 2 times and the toughness can be increased by 1.2 times under the same outer diameter and inner diameter. Corrosion has been significantly improved.
- the outer diameter is the same, the wall thickness is reduced, and the inner diameter is increased: using a stainless steel needle tube with the same outer diameter as 304 or 316, the inner diameter of our material can be larger, because the rigidity of the material of this patent is higher than that of 304 or 316 stainless steel 2 times, the toughness is increased by 1.2 times, so we can use a thinner wall thickness to increase the inner diameter, the outer diameter remains unchanged, the wall thickness is reduced, the inner diameter becomes larger, and the wall thickness of the needle tube is reduced, but it can also reach the injection needle Requirements for steel and toughness.
- the increase of the inner diameter can increase the injection flow, and the thinning of the wall thickness can also reduce the use of materials. At the same time, the sharpness can also be improved to reduce the pain of the patient's puncture.
- the above situation can be used for general injection or cosmetic injection.
- the inner diameter is the same, the wall thickness is reduced, and the outer diameter is reduced: using a stainless steel needle tube with the same inner hole as 304 or 316, the outer diameter of our material can be smaller, because the rigidity of the patented material is higher than that of 304 or 316 stainless steel
- the toughness is increased by 1.2 times, the outer diameter is reduced and the inner diameter is unchanged, and the rigidity and toughness requirements of the injection needle can also be met.
- the reduced outer diameter can improve the sharpness of the injection needle, reduce the pain of the patient's injection needle puncture, and also reduce the use of materials.
- the above conditions can be used for insulin, vaccines, and cosmetic injections.
- Same outer diameter, same wall thickness, same inner diameter use a needle tube with the same outer diameter and inner hole as 304 or 316 stainless steel, because the rigidity of the patented material is twice that of 304 or 316 stainless steel, and the toughness is increased by 1.2 Times, the use of our materials can greatly improve the rigidity and toughness of the injection needle, and ensure that the injection needle will not be bent or broken during the injection process.
- the above conditions are mainly used for animal injection needles.
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Abstract
一种不锈钢材料，化学成分组成重量百分比为：铬21～23，氮0.08～0.2，镍4.5～6.5，钼2.5～3.5，碳≤0.03，硅≤1.6，锰≤2.6，硫≤0.02，磷≤0.03，余量铁。该不锈钢材料可提高注射针的钢性、韧性及耐腐蚀性，且价格相对低廉。
Description
本发明属于不锈钢材料技术领域，具体涉及一种可提高注射针钢性、韧性的不锈钢材料。
目前注射针使用的材料为奥氏体不锈钢304或者316。奥氏体304和316不锈钢的优点是耐腐蚀、抗化学性，所以多用于注射针的使用，但304和316最大的缺点是钢性和强度不够，使用304和316作为注射针材料，注射针在使用过程中会出现弯曲断裂等现象。316相比304的耐腐蚀性更加好，但强度和钢性更差，从下面的化学成分表1看出：
表1市售不锈钢成分表
| C | Si | Mn | S | P | Cr | Ni | Mo | |
| 不锈钢304 | ≤0.07 | ≤1.6 | ≤2.6 | ≤0.03 | ≤0.035 | 17.0～19.0 | 0.6～11 | / |
| 不锈钢316 | ≤0.08 | ≤1.0 | ≤2.0 | ≤0.03 | ≤0.035 | 16.0～18.5 | 10.0～14.0 | 2.0～3.0 |
从以上元素表可看出，316的Ni含量更高。316提高了Ni的含量，提高了韧性，却引起了不锈钢材料的钢性变差，在使用过程中针管更加容易弯曲，注射针对钢性韧性抗腐蚀性有着很高的要求，钢性可以使针更加锋利，韧性可以使针管不容易断裂，抗腐蚀性可以使材料不被注射药水腐蚀，或者说在灭菌，存放期间不被腐蚀，针对以上出现的情况，我们研发了一种可提高注射针钢性韧性的不锈钢材料。
发明内容
本发的目的是解决现有技术中注射针不锈钢材料无法同时满足钢性、韧性及耐腐蚀性的要求；提供一种提高注射针强度的不锈钢材料，具有优良的强韧性和钢性组合以及抗腐蚀性，且价格相对低廉。
本发明提供了一种不锈钢材料，化学成分组成重量百分比为：铬Cr 21～23，氮N 0.08～0.2，镍Ni 4.5～6.5，钼Mo 2.5～3.5，碳C≤0.03， 硅Si≤1.6，锰Mn≤2.6，硫S≤0.02，磷P≤0.03，余量铁Fe。本发明惊奇的发现在引入N成分、并结合调控Cr和Ni成分的前提下，可以提高不锈钢的钢性并显著提高其韧性，制备出的不锈钢具有强韧性和钢性组合。
本发明所提供的不锈钢中，铬是铁素体形成元素，尽管如此，由于它是不锈钢中主要的耐蚀元素，而且也提高氮的溶解度，同时含量不宜过高，铬含量应控制在21～23(wt)％，大气压下氮的溶解度就是钢中氮的最高含量，即使将氮添加至溶解度，但随着凝固的进行溶解度会下降，就会发生气孔缺陷，导致不合格，同时氮的含量越高，生产工艺要求和能耗就越高，生产成品太高，为了方便工业化批量生产，建议氮含量控制在0.08～0.2(wt)％最佳，并且氮还可提高钢的耐点蚀性能。
镍元素是稳定奥氏体组织的元素，可促进不锈钢钝化膜的稳定性，提高不锈钢的热力学稳定性，强化不锈钢的不锈性和耐蚀性，镍含量控制在4.5～6.5(wt)％。
碳也是重要的奥氏体化元素，但过多的碳会严重影响钢的塑性和耐蚀性，因此碳含量应严格控制在0.03(wt)％以下，过高会增加钢的加工难度，越低越好，越低生产成本越高。
锰是一种弱的奥氏体化元素，可增加氮在钢中的溶解度，因此应至少但过多的锰元素影响钢的性能，所以锰应控制在2.6(wt)％以下。
铬是铁素体形成元素，尽管如此，由于它是不锈钢中主要的耐蚀元素，而且也提高氮的溶解度，铭含量应控制在21～23(wt)％。
钼的加入可以提高氮的溶解度，与氮相互作用可提高钢的耐腐蚀性能，但含量过多会降低钢的韧性，因此控制在2.5～3.5(wt)％。
硅可促使铁素体的形成，因此硅含量控制在低于1.6(wt)％，越低生产成本越高。
杂质元素硫和磷应分别控制在0.02(wt)％和0.03(wt)％以下，以提高钢的综合性能，越低生产成本越高。
根据本发明的另一个方面，本发明提供了一种不锈钢材料的用途，用于制备不锈钢注射针。由于本发明的不锈钢材料制备的不锈钢注射 针具有良好的热加工和冷加工性能，制作的注射针针管，与不锈钢304和不锈钢316相比，在相同外径和内径下，钢性可以提高2倍，韧性可以提高1.2倍，腐蚀性有着显著的提高。
优选的，所述不锈钢注射针为动物用不锈钢注射针或人用不锈钢注射针，所述人用不锈钢注射针可用于胰岛素、疫苗、美容注射。
优选的，所述不锈钢注射针为动物用不锈钢注射针；一般而言，动物用不锈钢注射针对刚性和韧性要求较人用注射针要求更高，由于本发明不锈钢材料相比于传统的不锈钢304和不锈钢316，在相同外径和内径下，钢性可以提高2倍，韧性可以提高1.2倍，腐蚀性有着显著的提高；所以，本发明所限定的不锈钢注射针可更好的满足动物用不锈钢注射针对刚性和韧性的要求。
与现有技术相比，本发明具有如下优点：
1)本发明在保持不锈钢材料成分基本不变的情况下，引入氮元素不仅可以显著提高不锈钢的钢性，并能提高韧性；使制备出的不锈钢具有强韧性和钢性组合；
2)适当增加铬元素，在含量不过高的同时以提高耐腐蚀性能；
3)由于本发明不锈钢材料改变小，所以可以与传统不锈钢材料及其不锈钢注射针的生产线共线生产，无需对生产设备做调整。
具体实施例方式
为使本发明的目的、技术方案和优点更加清楚明了，下面结合具体实施方式，对本发明进一步详细说明。应该理解，这些描述只是示例性的，而并非要限制本发明的范围。
一：生产工艺
本发明提高注射针强度的不锈钢材料制作成注射针管主要有以下工序：
1：冶炼：钢锭于1050～1150℃均匀化处理2～6小时，终锻温度不低于950℃，1100～1150℃固溶处理0.5～4小时。
2：压板：将不锈钢卷材通过辊压机挤压到所需要厚度的钢卷，
3：分切：合适厚度的不锈钢卷材通过分切机分切成所需要的宽度的钢卷，
4：焊管：将分切好宽度的钢带进入焊管机焊接成不锈钢管盘管；
5：定壁厚：焊接后的不锈钢盘管通过减壁厚机多次减壁，减到所要的钢管壁厚，减壁过程中需要多次回火保证材料的韧性。
6：定外径：减壁完成以后的不锈钢盘管通过拉管机多次拉拔，减小钢管外径，直至达到所需要的外径。减外径的过程中也需要多次回火处理。
7：钢管校直切断：将符合外径和壁厚要求的不锈钢盘管通过调直机调整到达标的直度，并且切成所需要的针管长度。
8：磨刃：将切好长度的针管通过磨刃机磨出针管所需要的角度，符合注射针的穿刺标准。
本发明提高注射针强度的不锈钢材料制作成注射针管和不锈钢304、不锈钢316的成分对比如表2。
表2化学成分表(wt％)
我们取了分别取了3炉本不锈钢材料各3个样本，其具体化学成分如表3所示，进行工艺试验，力学性能和相同规格的304和316样本对比如表4所示：
表3真空感应炉冶炼的本不锈钢的化学成分
| C | Si | Mn | S | P | Cr | Ni | Mo | N | |
| 本不锈钢材料样本1 | 0.018 | 1.3 | 2.2 | 0.018 | 0.028 | 22.28 | 4.56 | 2.55 | 0.2 |
| 本不锈钢材料样本2 | 0.025 | 1.4 | 2.3 | 0.015 | 0.022 | 22.19 | 4.55 | 2.58 | 0.1 |
| 本不锈钢材料样本3 | 0.029 | 1.5 | 2.4 | 0.013 | 0.023 | 22.21 | 4.53 | 2.54 | 0.08 |
表4物理性能测试表
| 材料 | Ys(Mpa) | Ts(Mpa) | El(％) | Hv | 备注 |
| 304不锈钢样本1 | 310 | 520 | 45 | 200 | 2.0B/1.5t |
| 304不锈钢样本2 | 205 | 580 | 40 | 185 | 2.0B/1.5t |
| 304不锈钢样本3 | 215 | 600 | 43 | 165 | 2.0B/1.5t |
| 316不锈钢样本1 | 289 | 584 | 52 | 200 | 2.0B/1.5t |
| 316不锈钢样本2 | 255 | 565 | 45 | 185 | 2.0B/1.5t |
| 316不锈钢样本3 | 205 | 520 | 40 | 177 | 2.0B/1.5t |
| 本材料不锈钢样本1 | 720 | 780 | 35 | 320 | 2.0B/2t |
| 本材料不锈钢样本2 | 550 | 680 | 28 | 288 | 2.0B/2t |
| 本材料不锈钢样本3 | 450 | 620 | 18 | 276 | 2.0B/2t |
工艺试验表明，该不锈钢材料，具有良好的热加工和冷加工性能，但是氮的含量过高硬度过大会影响加工，所以建议氮不能超过0.2(wt％)，综合以上表2-4和多次测试结果可以得出表5：
表5物理性能测试表
| 材料 | Ys(Mpa) | Ts(Mpa) | El(％) | Hv | 备注 |
| 本材料不锈钢 | ≥450 | ≥620 | ≥18 | ≤320 | 2.0B/2t |
| 304不锈钢 | ≥205 | ≥520 | ≥40 | ≤200 | 2.0B/1.5t |
| 316不锈钢 | ≥205 | ≥520 | ≥40 | ≤200 | 2.0B/1.5t |
可以看出，本材料的屈服强度是不锈钢304和不锈钢316的2倍多，抗拉强度是不锈钢304和不锈钢316的1.2倍，硬度是不锈钢304和不锈钢316的1.6倍。
申请人经过多次测试后得出，使用该不锈钢材料制作的注射针针管，与不锈钢304和不锈钢316相比，在相同外径和内径下，钢性可 以提高2倍，韧性可以提高1.2倍，腐蚀性有着显著的提高。
二：应用情况说明：
1：外径相同，壁厚减薄，内径增大：使用和304或者316同样外径的不锈钢针管，我们的材料内径可以更大，因为本专利的材料的钢性比304或者316不锈钢提高了2倍，韧性提高了1.2倍，所以我们可以使用更薄的壁厚来增大内径，外径不变，壁厚减薄，内径变大，减少了针管的壁厚，但同样可以达到注射针钢性、韧性的要求。内径增大可以提高注射流量，壁厚减薄也可以减少材料的使用，同时锋利度也可以提高，减少病人穿刺的痛苦。以上情况可以用于普通注射或者美容等注射。
2：内径相同，壁厚减薄，外径减小：使用和304或者316同样内孔的不锈钢针管，我们的材料外径可更小，因为本专利的材料的钢性比304或者316不锈钢提高了2倍，韧性提高了1.2倍，外径减小内径不变，同样可以达到注射针的钢性、韧性要求。外径减小可以提高注射针锋利度，减少病人注射针穿刺的痛苦，同时也可以减少材料的使用。以上情况可用于胰岛素、疫苗、美容注射。
3：外径相同，壁厚相同，内径相同：使用和304或者316不锈钢同样外径和内孔的针管，因为本专利的材料的钢性比304或者316不锈钢提高了2倍，韧性提高了1.2倍，使用我们的材料可以极大的提高注射针的钢性和韧性，确保注射针在注射过程中不被折弯或者折断，以上情况主要用于动物注射针。
尽管已经详细描述了本发明的实施方式，但是应该理解的是，在不偏离本发明的精神和范围的情况下，可以对本发明的实施方式做出各种改变、替换和变更。
Claims (7)
- 一种不锈钢材料，化学成分组成重量百分比为：铬Cr 21～23，氮N 0.08～0.2，镍Ni 4.5～6.5，钼Mo 2.5～3.5，碳C≤0.03，硅Si≤1.6，锰Mn≤2.6，硫S≤0.02，磷P≤0.03，余量铁Fe。
- 一种权利要求1所述不锈钢材料的用途，其特征在于：用于制备不锈钢注射针。
- 根据权利要求2所述的用途，其特征在于：所述不锈钢注射针为人用不锈钢注射针或者动物用不锈钢注射针。
- 根据权利要求3所述的用途，其特征在于：所述人用不锈钢注射针用于胰岛素、疫苗、美容注射。
- 根据权利要求3所述的用途，其特征在于：所述不锈钢注射针为动物用不锈钢注射针。
- 一种权利要求2所述的不锈钢注射针的制备方法，包括如下步骤：1)冶炼：钢锭于1050～1150℃均匀化处理2～6小时，终锻温度不低于950℃，1100～1150℃固溶处理0.5～4小时；2)压板：将不锈钢卷材通过辊压机挤压到所需要厚度的钢卷；3)分切：不锈钢卷材通过分切机分切成所需要的宽度的钢卷；4)焊管：将分切好宽度的钢带进入焊管机焊接成不锈钢管盘管；5)定壁厚：焊接后的不锈钢盘管通过减壁厚机多次减壁，减到所要的钢管壁厚；6)定外径：减壁完成以后的不锈钢盘管通过拉管机多次拉拔，减小钢管外径，直至达到所需要的外径；7)钢管校直切断：将符合外径和壁厚要求的不锈钢盘管通过调直机调整到达标的直度，并且切成所需要的针管长度；8)磨刃：将切好长度的针管通过磨刃机磨出针管所需要的角度，符合注射针的穿刺标准。
- 根据权利要求6所述的制备方法，其特征在于：步骤5)减壁过程中需要回火，步骤6)中减外径的过程中也需要回火处理。
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