CN117018262A - Antibacterial and bacteriostatic copper alloy medical dressing and preparation method thereof - Google Patents
Antibacterial and bacteriostatic copper alloy medical dressing and preparation method thereof Download PDFInfo
- Publication number
- CN117018262A CN117018262A CN202311032076.8A CN202311032076A CN117018262A CN 117018262 A CN117018262 A CN 117018262A CN 202311032076 A CN202311032076 A CN 202311032076A CN 117018262 A CN117018262 A CN 117018262A
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- China
- Prior art keywords
- copper alloy
- antibacterial
- bacteriostatic
- medical dressing
- wire
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Classifications
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- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
- B22D11/004—Copper alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/16—Controlling or regulating processes or operations
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22D11/16—Controlling or regulating processes or operations
- B22D11/22—Controlling or regulating processes or operations for cooling cast stock or mould
- B22D11/225—Controlling or regulating processes or operations for cooling cast stock or mould for secondary cooling
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
- C21D9/525—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length for wire, for rods
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
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- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- C22C9/04—Alloys based on copper with zinc as the next major constituent
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- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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- C—CHEMISTRY; METALLURGY
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- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F3/00—Changing the physical structure of non-ferrous metals or alloys by special physical methods, e.g. treatment with neutrons
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- A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Animal Behavior & Ethology (AREA)
- Hematology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Life Sciences & Earth Sciences (AREA)
- Epidemiology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses an antibacterial and bacteriostatic copper alloy medical dressing and a preparation method thereof, wherein the preparation method comprises the following steps: raw materials are prepared according to the component design proportion of the copper alloy wire, a continuous directional solidification process is adopted to prepare a high-quality copper alloy bar blank, then the copper alloy bar blank is sequentially subjected to homogenizing annealing, rotary forging, electric pulse drawing, conventional drawing and aging treatment to prepare the copper alloy wire, and finally the copper alloy wire and cellulose are compounded and woven to obtain the antibacterial and bacteriostatic copper alloy medical dressing.
Description
Technical Field
The invention relates to the field of medical materials, in particular to an antibacterial and bacteriostatic copper alloy medical dressing and a preparation method thereof.
Background
Wounds refer to a break or injury of the skin and can be generally classified into acute and chronic types. The acute wound conforms to the normal healing process, and the healing time is less than 8 weeks. Whereas chronic wounds refer to abnormally healed wounds, the healing time is typically over 8 weeks. Wound healing is a very complex physiological process that can be divided into three overlapping phases: (1) inflammatory phase: at this stage, an inflammatory response occurs after wound injury. Blood clots form as immune cells enter the wound area to remove pathogens and damaged tissue. The inflammatory response also promotes constriction of the traumatic blood vessel to reduce bleeding and fluid loss. (2) cell proliferation phase: after the formation of a blood clot on the wound surface, the cell proliferation process begins. At this stage, the cells begin to proliferate, filling the wound cavity. New blood vessels (called capillaries) also begin to grow to supply nutrition and oxygen. At this time, red/pink tissue formation called granulation tissue was used as a marker of new tissue formation. (3) remodeling stage: once the wound is completely filled and granulation tissue is formed, the wound enters a remodelling phase. At this stage, the wound begins to reconstruct and remodel to restore the integrity of the skin. The scar tissue formed in the first stage gradually develops and strengthens, so that the structure of the wound becomes stronger and more stable. These three phases are critical phases in the wound healing process, each of which involves specific cellular and biological processes to promote repair and healing of the wound. If there are complications or interfering factors, it may cause the wound to evolve into a non-healing wound or a difficult-to-heal wound. Wound care is therefore very important for wound healing in patients. Wound care primarily applies medical dressings to the wound surface, common types of medical dressings include: silver ion dressing, propolis dressing, chemical medicine (such as iodine, chlorhexidine, etc.) containing coating dressing, antibacterial polypeptide enzyme dressing, antibiotic containing dressing, etc. These dressings have respective advantages depending on the use situation, but the disadvantages are also very obvious. The antibacterial effect of the silver ion dressing is obviously reduced after long-time use, and the antibacterial effect is unstable; propolis and chemical drug coating dressings are prone to cause allergic reactions; the cost of the antimicrobial polypeptide enzyme dressing is high and the antimicrobial effect of certain biosynthesis dressings is only effective for specific strains, possibly ineffective for other strains; antibiotic-containing dressings need to take into account issues such as resistance to drugs.
Copper metal has many advantages as a long-history metal antimicrobial agent, such as: copper has broad-spectrum antibacterial activity and has killing and inhibiting effects on various microorganisms such as bacteria, fungi and viruses. The copper alloy or copper-containing coating can maintain its antimicrobial activity for a long period of time. The antibacterial and sterilizing mechanisms of copper are various: when copper contacts a microorganism, copper ions are released into the microorganism cells, interfering with their metabolism and biochemical reactions, resulting in the death of the microorganism. In addition, copper can also interact directly with proteins and DNA on the surface of microorganisms, destroying its structure and function. Therefore, the corrosion rate (copper ion release rate) of the antibacterial copper alloy is controlled to have the antibacterial function, and meanwhile, the safety of the antibacterial copper alloy to a human body is ensured, so that the purpose of wound care can be achieved.
At present, most of researches on antibacterial copper relate to a preparation and processing method of copper alloy plates and strips, however, few researches and applications are carried out on preparing antibacterial medical dressings by weaving composite fibers such as wires, wires and cotton yarns of copper alloy. The application document with the application number of CN201810411598.1 discloses a preparation method of composite fiber antibacterial cloth of copper alloy wires, which comprises the steps of smelting to obtain copper alloy cast ingots, then carrying out repeated stretching processing forming, wiring, mutual spinning and braiding with polyester fibers, wherein the yield and the length of the copper alloy wires and wires prepared by the method are limited, and the copper alloy wires and wires do not relate to copper ion release regulation and control and antibacterial effect. The application document with the application number of CN 113174680A discloses an industrial deodorant and antibacterial fabric, which comprises 20-30% of copper fibers, 3-5% of flame-retardant elastic fibers, 50-60% of cotton yarns, 2-3% of silver fibers and 1-3% of modified fibers, and does not relate to regulation and control of properties such as component design, tissue structure, corrosion rate and the like of copper alloy wires and the effect of treating human wounds. The patent number CN103611366B discloses a bacteriostatic copper fiber air filter material and a preparation method thereof, copper-silver cast ingots (containing 99.99-99.97% of copper and 0.01-0.03% of silver in percentage by weight) are obtained through casting, then metal short fibers with the diameter of 22-60um and the length of 2-10mm are obtained through direct cutting by a machine tool, and finally a copper wire felt is obtained through non-woven spreading and high-temperature sintering, but the material is mainly used for the bacteriostasis in the air filtering process, and meanwhile, the method also has the problems of low production efficiency, high cost, poor quality and unstable performance.
Development of high-performance antibacterial medical dressing based on superfine copper wires and composite fiber braiding is an important way for solving the problem of safe and efficient repair and treatment of human wounds, especially chronic difficult-to-heal wounds. In order to improve the antibacterial and bacteriostatic properties and biocompatibility of the copper alloy, the copper alloy is generally added with other alloy elements for multi-element alloying, but the problems of poor casting blank quality, difficult processing of micron-sized superfine copper alloy wires, low yield, high cost and the like of the copper alloy prepared by adopting the traditional process are brought; in addition, the toughness of the superfine copper alloy wire needs to be regulated and controlled, and the superfine copper alloy wire is reasonably matched with the fiber performance so as to be woven with the fiber into the dressing. Therefore, the technical problems to be solved are: (1) Technology for improving antibacterial and bacteriostatic properties of copper alloy based on copper ion release regulation; (2) A technique for regulating and controlling the strength and toughness of copper alloy wires which are efficiently woven with fibers; (3) a low-cost preparation technology of the ultra-long high-toughness copper alloy wire.
Disclosure of Invention
In order to solve the problems that the dressing in the background is allergic to a human body, drug resistance, antibacterial effect and service life cannot be considered, and solve the problems that the traditional method for processing the antibacterial and bacteriostatic copper alloy wire material is difficult, the yield is low, the cost is high, the wire material is difficult to weave with fibers into the dressing, and the like, the first aim of the invention is to provide a preparation method of the antibacterial and bacteriostatic copper alloy medical dressing.
The second aim of the invention is to provide the antibacterial and bacteriostatic copper alloy medical dressing prepared by the preparation method.
In order to achieve the above purpose, the invention adopts the following technical scheme:
according to the preparation method of the antibacterial and bacteriostatic copper alloy medical dressing, raw materials are prepared according to the component design proportion of copper alloy wires, and are placed in a crucible of a directional solidification furnace to be smelted and directionally solidified to obtain a copper alloy bar blank; and then carrying out homogenizing annealing treatment on the copper alloy bar blank to obtain an annealed bar blank, carrying out rotary forging on the annealed bar blank to obtain a copper alloy wire, carrying out electric pulse drawing and conventional drawing on the copper alloy wire in sequence to obtain a drawing sample, carrying out aging treatment to obtain the copper alloy wire, and then compounding the copper alloy wire with cellulose to obtain the antibacterial and bacteriostatic copper alloy medical dressing.
In the present invention, conventional drawing refers to conventional drawing in which no electric pulse is applied during drawing.
The preparation method of the invention has the following steps:
(1) Firstly, according to the requirements for human body on antibiosis, bacteriostasis and biocompatibility, raw materials are prepared according to the component design proportion of the copper alloy wire, and a continuous directional solidification device is adopted to prepare a single crystal or columnar crystal structure copper alloy bar blank with high compactness, high surface quality and excellent cold processing performance.
(2) And carrying out homogenizing annealing treatment on the alloy rod blank to eliminate the phenomena of dendrite segregation of the rod blank and uneven components in the copper matrix.
(3) And (3) carrying out rotary forging processing on the bar subjected to the homogenizing annealing treatment to obtain a wire rod, and utilizing the characteristic of rotary forging high-frequency rotation local forging forming to enable the cross section of the alloy wire rod to form a certain degree of compressive stress, thereby being beneficial to improving the subsequent drawing processing forming performance.
(4) And processing the wire rod into the wire rod with large deformation by adopting an electric pulse drawing and conventional drawing combined process, and then performing conventional drawing on the wire rod. On one hand, the electric pulse drawing can greatly improve the dislocation multiplication capacity of the alloy and promote dislocation movement by utilizing the coupling effect of the joule heating effect and the non-heating effect generated by the electric pulse, and can obviously reduce the deformation resistance and the work hardening rate of the alloy so as to improve the processing forming capacity; on the other hand, by regulating and controlling pulse parameters and pass processing rates, dynamic recovery and dynamic recrystallization of the alloy are induced to different degrees, grains are refined, sub-crystals and recrystallized grains with different proportions are formed, the proportion of the large-angle grain boundaries and the small-angle grain boundaries and the connectivity parameters of the grain boundaries are regulated and controlled, and the precise control of the release of alloy copper ions based on the regulation and control of the grain boundaries is realized. The oxide skin, air holes and inclusions on the surface of the metal material can be eliminated by adopting conventional drawing, so that the surface of a drawing sample becomes flat and smooth, the surface quality of the drawing sample is improved, the toughness of the alloy wire can be improved, and the subsequent wiring, mutual spinning and braiding of the composite fiber into a dressing are facilitated.
(5) Aging treatment is carried out on the drawn alloy wire, so that a large number of second phase particles which are dispersed and distributed are separated out from the copper matrix, a primary cell pair is formed by utilizing the potential difference between the second phase particles and the copper matrix, and the corrosion rate of the alloy and the release of copper ions are further regulated and controlled.
(6) And (3) wiring, spinning and weaving the aged copper alloy wires and fibers into the antibacterial dressing.
Preferably, the copper alloy comprises the following components in percentage by mass: 0.1 to 10wt.% of Fe and 0.1 to 12 wt.% of X, wherein X is at least one selected from Zn, mg, ca, mn, ag, na and the balance is Cu.
The inventor finds that Fe is used as a first major element required by human body and is safe and friendly to human body. Fe participates in the synthesis of hemoglobin and the transportation of oxygen, and Fe element participates in the enzyme reaction in the cell respiration process, and Cu-Fe element balance in human body, so as to jointly maintain the immune system work of living body. In addition, for the copper alloy, fe can effectively improve the mechanical property of copper and is beneficial to the processing and forming of the copper alloy; in addition, by regulating and controlling the content of Fe element, a second phase rich in Fe can be formed in the copper matrix and a primary cell pair can be formed with the copper matrix, and the release rate of copper ions can be regulated and controlled. And other additive elements are safe and friendly to human bodies, and are dissolved into the copper matrix to regulate and control the electrode potential of the copper matrix, thereby being beneficial to further regulating and controlling the release rate of copper ions. As the second major element required for the human body, zn has various important roles in the normal physiological functions of the human body, such as: participating in protein, carbohydrate and fat metabolism; regulating immunity and enhancing matrix resistance; promoting DNA repair, preventing cell apoptosis, etc. Mn is used as trace element required by human body and participates in various enzyme reactions including skeleton development, fat and carbohydrate metabolism, antioxidation reaction and DNA synthesis. In addition, the addition of Mn can increase the hardness and strength of the copper alloy, improve the corrosion resistance, prolong the service time and slow down the release of copper ions. Mg is a trace element required for the human body, and is involved in the formation of bones, the normal operation of muscle and nerve functions, and also contributes to energy metabolism and enzyme activity in the human body. Ca is used as a trace element required by human body, is a main constituent element of bones and teeth, and also participates in various physiological processes such as neurotransmission, muscle contraction, cell communication and the like. In addition, the addition of Ca can remove S, O and other impurity elements in the alloy in the casting process, improve the processing performance and corrosion resistance of the alloy, and regulate the service time limit and the copper ion release rate as required. Ag and Cu can produce synergistic antibacterial effect. Moreover, as the electrode potential is low, ag can promote the release of copper ions, and plays a role in regulating and controlling the release of ions; secondly, the Ag element can promote cell growth, proliferation and differentiation, and is helpful for wound repair and healing. Na is used as an element required by human body, and can regulate a plurality of important physiological functions of the human body, such as body fluid balance, neurotransmitter transmission, muscle contraction and the like.
Preferably, when Zn is contained in the copper alloy, the mass fraction of Zn in the copper alloy is 0.1 to 15wt.%.
Preferably, when Mn is contained in the copper alloy, the mass fraction of Mn in the copper alloy is 0.1 to 5wt.%. .
Preferably, when Mg is contained in the copper alloy, the mass fraction of Mg in the copper alloy is 0.1 to 5wt.%.
Preferably, when Ca is contained in the copper alloy, the mass fraction of Ca in the copper alloy is 0.1 to 2wt.%.
Preferably, when Ag is contained in the copper alloy, the mass fraction of Ag in the copper alloy is 0.1 to 2wt.%.
Preferably, when Na is contained in the copper alloy, the mass fraction of Na in the copper alloy is 0.1 to 2wt.%.
Further preferably, the copper alloy comprises the following components in percentage by mass: 7.5 to 10wt.% of Fe and 1 to 11 wt.% of X, wherein X is at least one selected from Zn, mg and Ag, and the balance is Cu.
Still more preferably, the copper alloy comprises the following components in percentage by mass: 7.5 to 10wt.% of Fe and 1 to 2wt.% of Ag. The inventor finds that the preferable component can almost achieve the effect of completely inhibiting bacteria on the S.aureus strain.
Still more preferably, the copper alloy comprises the following components in percentage by mass: 7.5 to 10wt.% of Fe, 1 to 2wt.% of Mg and 1 to 2% of Ag. The inventor discovers that the preferable component has excellent antibacterial effect on various strains.
In a preferred scheme, the crucible is a corundum crucible or a graphite crucible, the crucible is cylindrical, and the diameter of the crucible is 10-15cm.
Preferably, the smelting temperature is 1300-1500 ℃ and the smelting vacuum degree is 10 -4 ～10 -2 Pa。
Preferably, the directional solidification process is as follows: the raw materials are placed in a crucible of directional solidification equipment to be smelted to obtain copper alloy melt, the copper alloy melt is continuously cast to obtain copper alloy bar blank, the continuous casting speed is controlled to be 0.5-5 mm/s during continuous casting, the primary cooling water flow of a crystallizer is 2-50L/min, and the secondary cooling water flow is 1-10L/min.
In the actual operation process, after the temperature of the copper alloy melt reaches a target value, a traction mechanism is started to perform continuous casting to obtain a copper alloy bar blank, and the inventor finds that the directional solidification process has obvious influence on the copper alloy structure, the processing performance and the antibacterial performance. When the temperature of the melt is too high, the traction speed is too high and the primary cooling water flow of the crystallizer is too low, the solid-liquid interface position of the copper alloy goes deep into the cooling section of the crystallizer, and the solid-liquid interface is in a larger meniscus degree, the prepared copper alloy rod blank is easy to crack and form a radial columnar crystal structure or a mixed crystal structure composed of columnar crystals and equiaxed crystals, so that the subsequent process of large deformation of the copper alloy rod blank is difficult to prepare wires. When the temperature of the melt is too low, the traction speed is too low and the primary cooling water flow of the crystallizer is too high, the solid-liquid interface position of the copper alloy is positioned at the outlet of the crucible, the copper alloy bar blank is easy to be scratched, hot cracked and even broken, and coarse grain structures are formed, so that the subsequent drawing processing is not facilitated. Only when the temperature of the melt, the traction speed and the primary cooling water flow of the crystallizer are controlled within the scope of the invention, the single crystal or columnar crystal structure copper alloy bar billet with high compactness, high surface quality and excellent cold processing performance can be prepared, and a high-quality billet is provided for the subsequent efficient preparation of superfine copper alloy wires.
The inventors have also found that the rate of continuous casting has an effect on the grains of the ingot formed, while the size of the grains has an important effect on the copper ion release rate and bacteriostatic properties. If the grains of the columnar crystals are too large, the corrosion process of the alloy can be regulated and controlled by the crystal penetration corrosion and the grain boundary corrosion together, and even is mainly controlled by the crystal penetration corrosion. At the moment, point defects such as vacancies or dislocation loops caused by vacancy collapse and the like have larger randomness, and the corrosion rate of the alloy cannot be regulated and controlled through grain boundaries and the like; the columnar crystal grains are too small, which means that the dislocation density is large, the processing difficulty of the alloy is increased, and when the grain size is lower than 100nm, the corrosion is mainly through crystal corrosion, so that the regulation and control of the corrosion rate of the alloy cannot be completed by regulating the grain boundary characteristics; when the directional solidification rate is controlled within the range of the invention, the refined grains are regulated and controlled in a short time by combining the electric pulse technology, so that the copper alloy wire with moderate grain size, narrow grain size distribution and uniform structure can be obtained, and the processability and antibacterial performance of the copper alloy can be regulated and controlled conveniently.
Further preferably, the continuous casting speed is 0.5-2 mm/min, preferably 0.8-0.9 mm/min, the primary cooling water flow of the crystallizer is 5-20L/h, and the secondary cooling water flow is 2-5L/min.
Preferably, the diameter of the copper alloy bar blank is 6-30 mm
Preferably, the temperature of the homogenizing annealing treatment is 800-1100 ℃, preferably 900-1000 ℃, and the time of the homogenizing annealing treatment is 4-12 h.
In the preferred scheme, the pass deformation of the rotary forging is 10-20%, the total deformation is 50-80%, the discharging speed is 1-3 m/min,
according to the invention, the antibacterial and bacteriostatic copper alloy medical dressing is prepared by compounding the copper alloy wire material and cellulose, so that the diameter of the required copper alloy wire material is thinner, the strength and toughness are better, the rotary forging processing is carried out after the homogenizing annealing treatment, the characteristics of rotary forging and high-frequency rotation local forging forming are utilized, the cross section of a sample can have certain compressive stress, namely axial strain, so that the material tends to be more isotropic, the rotary forging process introduces pre-pressing deformation for subsequent drawing, the subsequent drawing processing forming performance is improved, and the strength and toughness of the obtained copper alloy wire material are finally improved.
In a preferred scheme, the electric pulse parameters during the electric pulse drawing are as follows: the output voltage is: 2-15V; the output current is: 500-3000A; the pulse frequency is 100-3000 Hz; pulse width: 50-500 mu s.
In the actual operation process, the electric pulse parameters refer to parameters provided for the electrified processing area of the copper alloy wire rod after the rotary forging processing.
Further preferably, the electrical pulse parameters during the electrical pulse drawing are as follows: the output voltage is: 8-11V; the output current is: 1500-2000A; the pulse frequency is 200-1000 Hz; pulse width: 100-300 mu s.
Still further preferably, the electrical pulse parameters at the time of the electrical pulse drawing are: the output voltage is: 9-11V; the output current is: 1700-1800A; the pulse frequency is 500-700 Hz; pulse width: 100-200 mu s.
In a preferred scheme, during the electric pulse drawing, the single-pass deformation is 20-50%, the total deformation is more than 85.0%, and the drawing speed is 2-50 m/min.
Further preferably, the single-pass deformation amount is 25 to 35%, the total deformation amount is more than 95%, and the drawing speed is 5 to 20m/min, further preferably 10 to 15m/min.
According to the invention, the electric pulse drawing process is adopted to realize the processing of the copper alloy bar material into the superfine wire material by large deformation and the precise control of copper ion release based on grain boundary regulation, so as to control the antibacterial performance of the alloy. The electric pulse drawing process parameters have remarkable influence on the processing performance and grain boundary regulation and control of the copper alloy rod and wire, so that the optimization of the electric pulse drawing process parameters is very important. If the parameter settings are not within the scope of the present invention, there are two conditions for processing copper alloy rods and wires: (1) Parameters are lower than the range covered by the invention, such as output voltage, output current, pulse frequency and pulse width are too low, so that the joule heating effect and non-heating effect generated in the electric pulse processing process and the coupling effect are smaller, on the one hand, the degree of improving dislocation proliferation and movement is smaller, the processing hardening degree is larger, the wire breakage and wire breakage are easy to occur in the processing process, and the large-deformation drawing processing to the filament is difficult to realize; on the other hand, the method is also insufficient for inducing dynamic recovery and dynamic recrystallization of the alloy, sub-crystals and recrystallized grains with different proportions cannot be formed, the proportion of large-angle grain boundaries and small-angle grain boundaries and the regulation and control of connectivity parameters of the grain boundaries are difficult to realize, and further, the copper ion release and antibacterial performance of the alloy cannot be regulated and controlled through grain boundary corrosion. (2) The parameters are higher than the range covered by the invention, the electric pulse energy is too high, the joule heating effect and the temperature generated in the drawing process are also higher, the recrystallization of the alloy and the abnormal growth of crystal grains are induced, and the formed crystal boundaries are mostly large-angle crystal boundaries and are uneven in structure, so that the drawing processing of copper alloy filaments and the control of copper ion release and antibacterial performance of the alloy through the regulation and control of the crystal boundaries are not facilitated. Under the electric pulse processing conditions of the parameters, particularly the preferred parameters, the method not only can fully utilize the coupling effect of the electric pulse to generate the thermal effect and the non-thermal effect to improve the processing performance of the copper alloy, realize the drawing processing of the copper alloy with large deformation to ultra-fine wires, but also can refine grains and form sub-crystals and recrystallized grains with different proportions by inducing dynamic recovery and dynamic recrystallization of the alloy with different degrees, regulate and control the proportions of large-angle grain boundaries and small-angle grain boundaries and connectivity parameters of the grain boundaries, realize the precise control of the release of alloy copper ions based on the regulation and control of the grain boundaries, and simultaneously can improve the toughness and the antibacterial performance of the alloy wires, thereby being beneficial to subsequent and composite fiber wiring, mutual spinning and braiding into dressings.
In the preferred scheme, during conventional drawing, the single-pass deformation is 5-20%, the total deformation is 20-50%, and the drawing speed is 10-20 m/min.
The inventor finds that after the electric pulse drawing, the surface has the defects of oxide, air holes, inclusions and the like which influence the tissue performance of the wire, and through conventional drawing, the defects of oxide, air holes, inclusions and the like on the surface of the sample can be effectively eliminated, the dislocation density can be further increased, the grain boundary structure can be optimized, and the toughness of the wire can be regulated and controlled.
In a preferred scheme, the temperature of the aging treatment is 350-600 ℃, and the time of the aging treatment is 0.5-12 h.
The inventor finds that a large number of second phase particles which are dispersed and distributed can be formed in the copper alloy matrix through aging treatment, a primary cell pair is formed by utilizing the potential difference between the second phase particles and the copper matrix, the corrosion rate of the alloy and the release of copper ions can be further regulated and controlled, the antibacterial and bacteriostatic effects are improved, and meanwhile, the precipitated second phase particles are friendly and harmless to human bodies.
In a preferred scheme, the diameter of the copper alloy wire is 0.01-0.2 mm.
Further preferably, the diameter of the copper alloy wire is 10 to 50. Mu.m, preferably 20 to 30. Mu.m.
Preferably, the grain size of the crystal grains in the copper alloy wire is 0.2-50 μm.
In a preferred scheme, the mass ratio of the copper alloy wire to the cellulose is 10-90: 10 to 90 percent.
Preferably, the cellulose is at least one selected from cotton fiber, fibrilia and polyester fiber.
In a preferred scheme, the process of compounding the copper alloy wire with cellulose comprises the following steps: mixing, carding and needling the copper alloy wires with cellulose, or performing composite needling on the copper alloy wires and cellulose woven fabric, or carding the copper alloy wires into a net, and then performing composite needling on the copper alloy wires and cellulose spunlaced non-woven fabric.
Proper regulation of the strength and toughness of copper alloy wires is key to realize the dressing with composite fiber wiring, mutual spinning and braiding. If the strength and toughness of the copper alloy wire are too high, the fiber wires are easily broken in the weaving process, and if the strength and toughness of the copper alloy wire are too low, the copper alloy wires are easily broken in the weaving process. Only in the preparation process range of the application, the moderate-toughness copper alloy wire can be successfully distributed with the composite fiber and woven into the dressing.
The application also provides the antibacterial and bacteriostatic copper alloy medical dressing prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention provides a method for preparing a high-performance antibacterial and bacteriostatic copper alloy medical dressing, which comprises the steps of introducing a plurality of elements required by a human body into copper for multi-element microalloying, regulating and controlling the electrode potential of the copper by utilizing the synergistic effect of the alloy elements, forming a second phase which is friendly and harmless to the human body, forming a primary cell pair by utilizing the potential difference between second phase particles and a copper matrix, regulating and controlling the corrosion rate of the alloy and the release of copper ions, further improving the antibacterial and bacteriostatic properties of the copper alloy, and simultaneously, the alloy elements and the second phase can be absorbed by the human body and are safe and friendly, so that a key basic material is provided for preparing the high-performance antibacterial and bacteriostatic copper alloy medical dressing.
(2) The invention provides a novel technology for cooperatively regulating and controlling the grain boundary and the second phase of the copper alloy based on electric pulse drawing and heat treatment, realizes the accurate regulation and control of the release of copper alloy ions, and improves the antibacterial property and the toughness of the copper alloy wire. The coupling effect of the thermal effect and the non-thermal effect generated by the electric pulse is utilized to induce the dynamic recovery and the dynamic recrystallization of the alloy to different degrees, refine the crystal grains and form the sub-crystal and the recrystallized crystal grains with different proportions, regulate and control the proportion of the large-angle grain boundary and the small-angle grain boundary and the connectivity parameter of the grain boundary, and realize the accurate control of the release of the alloy copper ions based on the regulation and control of the grain boundary; in addition, by aging treatment of the copper alloy wire drawn by electric pulse, a large amount of second phase particles which are dispersed and distributed can be formed in the copper alloy matrix, and a galvanic cell pair is formed by utilizing the potential difference between the second phase particles and the copper matrix, so that the corrosion rate of the alloy and the release of copper ions can be further regulated and controlled. The antibacterial and bacteriostatic properties of the copper alloy wire can be obviously improved through the cooperative regulation and control of the electric pulse drawing and heat treatment process.
(3) Compared with the traditional copper alloy wire preparation process, the invention organically combines directional solidification, rotary forging and electric pulse drawing processes, provides a novel process for preparing and processing the high-performance medical copper alloy wire, and has the advantages of good comprehensive performance, low cost, high yield and large coiling length. Because the antibacterial and bacteriostatic copper alloy has more elements, the alloy blank prepared by the traditional casting method has poor quality, high work hardening degree, extremely easy wire breakage in the superfine wire drawing process, low yield, short length of coiled wire and high processing cost. Aiming at the problems, the invention adopts a directional solidification process to prepare a copper alloy bar blank with high compactness, high surface quality and monocrystal or columnar crystal structure, and has excellent cold processing performance; the rotary forging is adopted to process the alloy bar, and the characteristic of rotary forging high-frequency rotation local forging forming is utilized to enable the alloy cross section to form a certain degree of compressive stress, so that the subsequent drawing processing performance is improved; the processing performance of the copper alloy can be obviously improved by combining the electric pulse drawing process, the large-deformation drawing processing of the copper alloy into superfine wires is realized, and the problems of long flow, low yield, high cost, short coiling length (which is not beneficial to the subsequent braiding with fibers into dressing), poor quality and the like in the traditional process for preparing the superfine copper alloy wires are solved.
(4) The invention can prepare the high-performance antibacterial and bacteriostatic copper alloy microfilaments with the diameter of 0.01-0.2 mm with low cost and high efficiency through the integration of multi-element microalloying, directional solidification, rotary swaging, electric pulse drawing and heat treatment processes, and can be woven into antibacterial dressings with different copper alloy wires and cellulose mass ratios according to the requirements so as to meet the requirements of different application scenes.
Detailed Description
In order that the invention may be more readily understood, the invention will be further described with reference to the following examples. It should be understood that these examples are intended to illustrate the invention and not to limit the scope of the invention, and that the described embodiments are merely some, but not all, of the embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. Unless defined otherwise, the terms of art used hereinafter are consistent with the meanings understood by those skilled in the art; unless otherwise specified, the materials and equipment referred to herein may be purchased from the market or prepared by known methods.
Example 1
A novel antibacterial and bacteriostatic Cu-10wt.% Fe-10wt.% Zn alloy medical dressing and a preparation method thereof comprise the following steps:
(1) Directional solidification: opening a water cooling circulation system (the flow rate of circulating cooling water is 600L/h), putting prepared electrolytic copper sheets (the purity is 99.999%), cu-Fe intermediate alloy and Cu-Zn intermediate alloy into a corundum crucible in a directional solidification furnace according to the proportion (the Fe content is 10 wt%, the Zn content is 10 wt%, and the rest is Cu), closing a furnace door and an air inlet valve, opening a mechanical pump, a vacuum gauge and a molecular pump to reduce the vacuum degree (5 multiplied by 10) in the furnace -4 ) The corundum crucible is heated by induction coil, the smelting temperature is controlled at 1450 ℃, the temperature is kept for 20min, after the metal in the crucible is melted into liquid state, a mechanical turbine is started to drive a metal 145 connecting rod device to pull the crucible from the induction coil to a crystallizer (gallium-indium alloy cooling liquid at 16 ℃) at the continuous casting speed of 0.5mm/min for cooling and molding, the primary cooling water flow of the crystallizer is 10L/h, the secondary cooling water flow is 4L/min, and a cylindrical ingot with a columnar crystal structure with the diameter of 15mm is formed.
(2) Homogenizing annealing treatment: and (3) placing the cylindrical ingot casting of the single crystal or columnar crystal structure after directional solidification and cooling forming into a box-type resistance furnace for homogenizing annealing, wherein the heating temperature is 960 ℃, and the heat preservation time is 5 hours.
(3) And (3) carrying out rotary forging treatment on the homogenized annealed bar blank, controlling the pass deformation of rotary forging to be 10%, controlling the total deformation to be 50%, and controlling the discharging speed to be 2m/min to obtain the bar blank with the diameter of 7.5 mm.
(4) And (3) electric pulse drawing: putting the material subjected to the homogenizing annealing treatment into a drawing machine, connecting pulse power supplies at two ends, adjusting pulse power supply parameters, and outputting the voltage as follows: 10V; the output current is: 1800A; the pulse frequency is 600Hz; pulse width: 150 mus; the drawing speed was controlled at 15mm/min. The electric pulse drawing was started, the deformation amount of each time was controlled to 25%, the total deformation amount was 98.6%, and the ingot was drawn into a wire rod having a diameter of 0.1 mm.
(5) Conventional drawing: and carrying out conventional drawing on the test sample obtained by electric pulse drawing, wherein the pass deformation is 20%, the total deformation is 50%, and the drawing speed is 10mm/min, so as to obtain the wire with the diameter of 0.05 mm.
(6) Aging treatment: and (3) placing the wire material formed by the electric pulse drawing process into a box-type resistance furnace for aging heat preservation treatment, wherein the heat preservation temperature is 400 ℃, and the heat preservation time is 1h.
The grain size of the wire obtained in example 1 was examined to be in the range of 0.25 μm to 25. Mu.m.
(7) Preparing dressing by silk material and cellulose: and (2) mixing the aged silk material with cotton fiber according to the mass percentage of 50:50, mixing, carding and needling to prepare the dressing.
Example 2
A novel antibacterial and bacteriostatic Cu-7.5wt.% Fe-1wt.% Ag alloy medical dressing and a preparation method thereof comprise the following steps:
(1) Directional solidification: opening a water cooling circulation system (the flow rate of circulating cooling water is 600L/h), putting prepared electrolytic copper sheets (the purity is 99.999%), cu-Fe intermediate alloy and electrolytic silver sheets (the purity is 99.999%) into a corundum crucible in a directional solidification furnace according to the proportion (the Fe content is 7.5wt.%, the Ag content is 1wt.% and the rest is Cu), closing a furnace door and an air inlet valve, opening a mechanical pump, a vacuum gauge, a molecular pump to reduce the vacuum degree (5X 10-4) in the furnace, performing induction heating on the corundum crucible through an induction coil, controlling the smelting temperature to 1430 ℃ and preserving heat for 15min, after metal in the crucible is melted into a liquid state, starting a mechanical turbine to drive a metal 145 connecting rod device to pull the crucible from the induction coil into a crystallizer (gallium-indium alloy cooling liquid at 16 ℃) at a continuous casting speed of 0.8mm/min for cooling molding, and performing primary cooling water flow of the crystallizer for 10L/h, and secondary cooling water flow for 4L/min to form a cylindrical ingot with a columnar crystal structure with the diameter of 15 mm.
(2) Homogenizing annealing treatment: and (3) placing the cylindrical ingot casting of the single crystal or columnar crystal structure after directional solidification and cooling forming into a box-type resistance furnace for homogenizing annealing, wherein the heating temperature is 960 ℃, and the heat preservation time is 5 hours.
(3) And (3) carrying out rotary forging treatment on the homogenized annealed bar blank, controlling the pass deformation of rotary forging to be 10%, controlling the total deformation to be 50%, and controlling the discharging speed to be 2m/min to obtain the bar blank with the diameter of 7.5 mm. (4) electric pulse drawing: putting the material subjected to the homogenizing annealing treatment into a drawing machine, connecting pulse power supplies at two ends, adjusting pulse power supply parameters, and outputting the voltage as follows: 10V; the output current is: 1800A; the pulse frequency is 600Hz; pulse width: 150 mus; the drawing speed was controlled at 15mm/min. The electric pulse drawing was started, the deformation amount of each time was controlled to 25%, the total deformation amount was 98.6%, and the ingot was drawn into a wire rod having a diameter of 0.1 mm.
(5) Aging treatment: and (3) placing the wire material formed by the electric pulse drawing process into a box-type resistance furnace for aging heat preservation treatment, wherein the heat preservation temperature is 400 ℃, and the heat preservation time is 1h.
The grain size of the wire obtained in example 2 was examined to be in the range of 0.25 μm to 20. Mu.m.
(6) Preparing dressing by silk material and cellulose: and (2) mixing the aged silk material with cotton fiber according to the mass percentage of 50:50, mixing, carding and needling to prepare the dressing.
Example 3
A novel antibacterial and bacteriostatic Cu-7.5wt.% Fe-2wt.% Mg-1wt.% Ag alloy medical dressing and a preparation method thereof comprise the following steps:
(1) Directional solidification: opening a water cooling circulation system (the flow rate of circulating cooling water is 600L/h), putting prepared electrolytic copper sheets (with the purity of 99.999%), cu-Fe intermediate alloy, cu-Mg intermediate alloy and electrolytic silver sheets (with the purity of 99.999%) into a corundum crucible in a directional solidification furnace according to the proportion (7.5 wt.% of Fe, 2wt.% of Mg, 1wt.% of Ag and the balance Cu), closing a furnace door and an air inlet valve, opening a mechanical pump, a vacuum gauge and a molecular pump to reduce the vacuum degree (5 multiplied by 10) in the furnace -4 ) The corundum crucible is heated by induction through an induction coil, the smelting temperature is controlled to be 1410 ℃, and the temperature is kept for 10 minutes, so that the crucible is heated by inductionAfter metal in the crucible is melted into liquid, a mechanical turbine is started to drive a metal 145 connecting rod device to pull the crucible from an induction coil to a crystallizer (gallium-indium alloy cooling liquid at 16 ℃) at a continuous casting speed of 0.85mm/min for cooling and molding, and the primary cooling water flow of the crystallizer is 10L/h, and the secondary cooling water flow is 4L/min, so that a cylindrical cast ingot with a columnar crystal structure with the diameter of 15mm is formed.
(2) Homogenizing annealing treatment: and (3) placing the cylindrical ingot casting of the single crystal or columnar crystal structure after directional solidification and cooling forming into a box-type resistance furnace for homogenizing annealing, wherein the heating temperature is 960 ℃, and the heat preservation time is 5 hours.
(3) And (3) rotary forging: and (3) performing rotary forging treatment on the rod blank obtained through the homogenizing annealing treatment, controlling the pass deformation of rotary forging to be 10%, controlling the total deformation to be 50%, and controlling the discharging speed to be 2m/min to obtain the rod blank with the diameter of 7.5 mm.
(4) And (3) electric pulse drawing: putting the material subjected to the homogenizing annealing treatment into a drawing machine, connecting pulse power supplies at two ends, adjusting pulse power supply parameters, and outputting the voltage as follows: 10V; the output current is: 1700A; the pulse frequency is 600Hz; pulse width: 200 μs; the drawing speed was controlled at 15mm/min. The electric pulse drawing was started, the deformation amount of each time was controlled to 25%, the total deformation amount was 98.6%, and the ingot was drawn into a wire rod having a diameter of 0.1 mm.
(5) Aging treatment: and (3) placing the wire material formed by the electric pulse drawing process into a box-type resistance furnace for aging heat preservation treatment, wherein the heat preservation temperature is 400 ℃, and the heat preservation time is 1h.
The grain size of the wire obtained in example 3 was examined to be in the range of 0.2 μm to 30. Mu.m.
(6) Preparing dressing by silk material and cellulose: and (2) mixing the aged silk material with cotton fiber according to the mass percentage of 50:50, mixing, carding and needling to prepare the dressing.
Comparative example 1
The comparative example adopts a method for obtaining Cu-10wt.% Fe-10wt.% Zn alloy medical dressing without aging treatment and the preparation method thereof comprises the following steps:
(1) Directional solidification: the water-cooled circulation system was turned on (flow rate of circulating cooling water was 600L/h), and was readyThe method comprises the steps of (1) placing copper flakes (purity is 99.999%), cu-Fe intermediate alloy and Cu-Zn intermediate alloy in a corundum crucible in a directional solidification furnace according to a proportion (10 wt.% of Fe content, 10wt.% of Zn content and the balance of Cu), closing a furnace door and an air inlet valve, opening a mechanical pump, a vacuum gauge and a molecular pump to reduce the vacuum degree (5 multiplied by 10) in the furnace -4 ) The corundum crucible is heated by induction coil, the smelting temperature is controlled at 1450 ℃, the temperature is kept for 20min, after the metal in the crucible is melted into liquid state, a mechanical turbine is started to drive a metal 145 connecting rod device to pull the crucible from the induction coil to a crystallizer (gallium-indium alloy cooling liquid at 16 ℃) at the continuous casting speed of 0.5mm/min for cooling and molding, the primary cooling water flow of the crystallizer is 10L/h, the secondary cooling water flow is 4L/min, and a cylindrical ingot with a columnar crystal structure with the diameter of 15mm is formed.
(2) Homogenizing annealing treatment: and (3) placing the cylindrical ingot casting of the single crystal or columnar crystal structure after directional solidification and cooling forming into a box-type resistance furnace for homogenizing annealing, wherein the heating temperature is 960 ℃, and the heat preservation time is 5 hours.
(3) And (3) rotary forging: and (3) performing rotary forging treatment on the rod blank obtained through the homogenizing annealing treatment, controlling the pass deformation of rotary forging to be 10%, controlling the total deformation to be 50%, and controlling the discharging speed to be 2m/min to obtain the rod blank with the diameter of 7.5 mm.
(4) And (3) electric pulse drawing: putting the material subjected to the homogenizing annealing treatment into a drawing machine, connecting pulse power supplies at two ends, adjusting pulse power supply parameters, and outputting the voltage as follows: 10V; the output current is: 1800A; the pulse frequency is 600Hz; pulse width: 150 mus; the drawing speed was controlled at 15mm/min. The electric pulse drawing was started, the deformation amount of each time was controlled to 25%, the total deformation amount was 98.6%, and the ingot was drawn into a wire rod having a diameter of 0.1 mm.
(5) Conventional drawing: and carrying out conventional drawing on the test sample obtained by electric pulse drawing, wherein the pass deformation is 20%, the total deformation is 50%, and the drawing speed is 10mm/min, so as to obtain the wire with the diameter of 0.05 mm.
The grain size of the wire obtained in comparative example 1 was examined to be in the range of 0.1 μm to 45. Mu.m.
(6) Preparing dressing by silk material and cellulose: and (2) mixing the aged silk material with cotton fiber according to the mass percentage of 50:50, mixing, carding and needling to prepare the dressing.
Comparative example 2
The comparative example does not adopt a rotary forging process to prepare Cu-10wt.% Fe-10wt.% Zn alloy medical dressing and a preparation method thereof, and comprises the following steps:
(1) Directional solidification: opening a water cooling circulation system (the flow rate of circulating cooling water is 600L/h), putting prepared electrolytic copper sheets (the purity is 99.999%), cu-Fe intermediate alloy and Cu-Zn intermediate alloy into a corundum crucible in a directional solidification furnace according to the proportion (the Fe content is 10 wt%, the Zn content is 10 wt%, and the rest is Cu), closing a furnace door and an air inlet valve, opening a mechanical pump, a vacuum gauge and a molecular pump to reduce the vacuum degree (5 multiplied by 10) in the furnace -4 ) The corundum crucible is heated by induction coil, the smelting temperature is controlled at 1450 ℃, the temperature is kept for 20min, after the metal in the crucible is melted into liquid state, a mechanical turbine is started to drive a metal 145 connecting rod device to pull the crucible from the induction coil to a crystallizer (gallium-indium alloy cooling liquid at 16 ℃) at the continuous casting speed of 0.5mm/min for cooling and molding, the primary cooling water flow of the crystallizer is 10L/h, the secondary cooling water flow is 4L/min, and a cylindrical ingot with a columnar crystal structure with the diameter of 15mm is formed.
(2) Homogenizing annealing treatment: and (3) placing the cylindrical ingot casting of the single crystal or columnar crystal structure after directional solidification and cooling forming into a box-type resistance furnace for homogenizing annealing, wherein the heating temperature is 960 ℃, and the heat preservation time is 5 hours.
(3) And (3) electric pulse drawing: putting the material subjected to the homogenizing annealing treatment into a drawing machine, connecting pulse power supplies at two ends, adjusting pulse power supply parameters, and outputting the voltage as follows: 10V; the output current is: 1800A; the pulse frequency is 600Hz; pulse width: 150 mus; the drawing speed is controlled at 35mm/min. And (3) starting to perform electric pulse drawing, wherein the deformation amount of each time is controlled to be 50%, the total deformation amount is 99.6%, and the cast ingot is drawn into a wire rod with the diameter of 0.05 mm.
(4) Conventional drawing: and carrying out conventional drawing on the test sample obtained by electric pulse drawing, wherein the pass deformation is 20%, the total deformation is 50%, and the drawing speed is 10mm/min, so as to obtain the wire with the diameter of 0.05 mm.
(5) Aging treatment: and (3) placing the wire material formed by the electric pulse drawing process into a box-type resistance furnace for aging heat preservation treatment, wherein the heat preservation temperature is 400 ℃, and the heat preservation time is 1h.
The grain size of the wire obtained in comparative example 2 was examined to be in the range of 0.25 μm to 25. Mu.m.
(6) Preparing dressing by silk material and cellulose: and (2) mixing the aged silk material with cotton fiber according to the mass percentage of 50:50, mixing, carding and needling to prepare the dressing.
Comparative example 3
The comparative example adopts electric pulse drawing which is not in the parameter range of the patent, cu-10wt.% Fe-10wt.% Zn alloy medical dressing for aging treatment and the preparation method thereof, and comprises the following steps:
(1) Directional solidification: opening a water cooling circulation system (the flow rate of circulating cooling water is 600L/h), putting prepared electrolytic copper sheets (the purity is 99.999%), cu-Fe intermediate alloy and Cu-Zn intermediate alloy into a corundum crucible in a directional solidification furnace according to the proportion (the Fe content is 10 wt%, the Zn content is 10 wt%, and the rest is Cu), closing a furnace door and an air inlet valve, opening a mechanical pump and a vacuum gauge, enabling a molecular pump to reduce the vacuum degree (5X 10-4) in the furnace, performing induction heating on the corundum crucible through an induction coil, controlling the smelting temperature to 1450 ℃, preserving heat for 20min, enabling metal in the crucible to be molten, and starting a mechanical turbine to drive a metal 145 connecting rod device to pull the crucible from the induction coil to a condenser at the axial movement speed of 0.5mm/min
(gallium-indium alloy cooling liquid at 16 ℃) and forming into a cylindrical ingot with a columnar crystal structure with the diameter of 15 mm.
(2) Homogenizing annealing treatment: and (3) placing the cylindrical ingot casting of the single crystal or columnar crystal structure after directional solidification and cooling forming into a box-type resistance furnace for homogenizing annealing, wherein the heating temperature is 960 ℃, and the heat preservation time is 5 hours.
(3) And (3) rotary forging: and (3) performing rotary forging treatment on the rod blank obtained through the homogenizing annealing treatment, controlling the pass deformation of rotary forging to be 10%, controlling the total deformation to be 50%, and controlling the discharging speed to be 2m/min to obtain the rod blank with the diameter of 7.5 mm.
(4) And (3) electric pulse drawing: putting the material subjected to the homogenizing annealing treatment into a drawing machine, connecting pulse power supplies at two ends, adjusting pulse power supply parameters, and outputting the voltage as follows: 20V; the output current is: 3500A; the pulse frequency is 600Hz; pulse width: 150 mus; the drawing speed is controlled at 35mm/min. And (3) starting to perform electric pulse drawing, wherein the deformation amount of each time is controlled to be 50%, the total deformation amount is 99.6%, and the cast ingot is drawn into a wire rod with the diameter of 0.05 mm.
(5) Conventional drawing: and carrying out conventional drawing on the test sample obtained by electric pulse drawing, wherein the pass deformation is 20%, the total deformation is 50%, and the drawing speed is 10mm/min, so as to obtain the wire with the diameter of 0.05 mm.
(6) Aging treatment: and (3) placing the wire material formed by the electric pulse drawing process into a box-type resistance furnace for aging heat preservation treatment, wherein the heat preservation temperature is 400 ℃, and the heat preservation time is 1h.
The grain size of comparative example 3 was examined to be in the range of 1 μm to 100. Mu.m.
(7) Preparing dressing by silk material and cellulose: and (2) mixing the aged silk material with cotton fiber according to the mass percentage of 50:50, mixing, carding and needling to prepare the dressing.
Antibacterial property detection:
antibacterial performance detection is carried out on the antibacterial copper-based alloy functional composite dressing prepared in the embodiment according to related standard regulations of ' JISZ2801-2000 ' antibacterial processed product-antibacterial performance test method and antibacterial effect ', GB/T2591-2003 ' antibacterial Plastic antibacterial performance test method and antibacterial effect ', and the like, wherein the calculation formula of the antibacterial rate is as follows: antibacterial ratio (%) = [ (number of colonies of blank group-number of colonies of experiment group)/number of colonies of blank group ] ×100%.
The specific implementation method comprises the following steps: a flat coating method. The culture medium is Mueller-Hinton agar basal Medium (MH), the pH is 7.2-7.4, and the agar thickness is 4mm.
Resuscitating working strains: the frozen and recovered working strains E.coli (ATCC 25922) and staphylococcus aureus S.aureus (ATCC 25923) were inoculated on Columbia agar plates, cultured for 24 hours in an aerobic state at 37 ℃, stained with a smear, and morphologically observed as pure cultures, and were ready for use if no other impurities were present.
The concentration of the two bacterial liquids is determined to be 1.5X10 by a turbidimeter 6 Dropwise adding CFU/mL onto the dressing in the blank control and the dressing in the example and the comparative example in sequence, respectively covering the covering films on each sample by using a sterilizing forceps, enabling bacterial liquid to uniformly contact the samples, placing the samples in a sterilizing plate, and culturing for 24 hours in a constant-temperature incubator at 37 ℃ and a relative humidity of over 90%; taking out the cultured samples for 24 hours, respectively adding 10mL of eluent, repeatedly cleaning the samples and the cover film, fully shaking the samples, respectively taking 0.05mL of the samples to be dripped into a nutrient agar culture medium, making three parallel samples for each sample, uniformly coating the samples by using a sterilization triangle harrow, culturing the samples in a constant temperature oven at 37 ℃ for 24 hours, and then counting viable bacteria according to the method of GB/T4789.2, wherein the antibacterial rate detection result is shown in Table 1.
TABLE 1 antibacterial rate%
As can be seen from the comparison of the example 1 and the comparative example 1, compared with the ultra-fine wire Cu-10wt.% Fe-10wt.% Zn dressing which is subjected to aging treatment after electric pulse drawing and the ultra-fine wire Cu-10wt.% Fe-10wt.% Zn dressing which is not subjected to aging treatment after electric pulse drawing, the ultra-fine wire Cu-10wt.% Fe-10wt.% Zn dressing which is subjected to aging treatment after electric pulse drawing has higher antibacterial rate, because Fe phase and Cu matrix are separated out by aging to form a primary cell pair, copper ion release is promoted, antibacterial effect is promoted, and the recrystallization occurs in the annealing process in the example 1, grain refinement is more uniform in structure, the small-angle grain boundary ratio is further improved, and antibacterial performance is more stable; as can be seen from comparison of comparative example 2 and example 1, the ultra-fine wire Cu-10wt.% Fe-10wt.% Zn dressing prepared by the rotary swaging treatment has higher antibacterial rate compared with the rotary swaging treatment which is not performed, because the rotary swaging treatment introduces pre-deformation for subsequent drawing, the deformation resistance is reduced, the grain distribution is more uniform, and the copper ion release is more stable. As is clear from comparison of example 1 and comparative example 3, the electric pulse drawn ultrafine wire Cu-10wt.% Fe-10wt.% Zn dressing obtained within the parameter range of the present application was higher in antibacterial rate and smaller in grain size range. This is because the high-energy electric pulse can refine grains in a very short time within a reasonable parameter range, reduce texture, and improve structural uniformity, but if the parameter is not reasonable, grains are easily coarsened, causing overburning and the like. As can be seen from Table 1, the antibacterial rates of the medical dressings of the Cu-Fe-X alloy system of the ultra-thin filaments prepared by the short-process electric pulse drawing method for the medical dressings of the embodiment 1, the embodiment 2 and the embodiment 3 on the S.aureus strain and the E.coli strain are all more than 90%, and the medical dressings belong to the class I antibacterial effect. And example 1 was subjected to conventional drawing, whereas examples 2 and 3 were not subjected to conventional drawing. The reason is that the Fe content in example 1 is 10wt.%, greater than the Fe content in examples 2 and 3 by 7.5wt.%, and the higher Fe content may be oxidized by the influence of the high-energy electric pulse after the electric pulse pulling, affecting the surface quality of the finished product. At this time, conventional drawing is necessary to eliminate defects such as surface oxides, pores, inclusions, and the like. The conventional drawing described by the application is also embodied as a preferable scheme, so that the antibacterial performance of the product can be better regulated and controlled. And the killing efficiency of different embodiments is different for different strains, for example, for S.aureus strain, the bacteriostasis rate of the embodiment 2 is 99.9% greater than 97.5% of the embodiment 3 and greater than 95.9% of the embodiment 1; whereas for E.coli species, the 98.7% inhibition of example 1 was greater than 97.2% of example 3 and greater than 96.5% of example 2. The grain ranges of the three embodiments are moderate, which shows that the antibacterial effect is achieved in the component ranges, and the structural performance of the antibacterial copper alloy is uniform and uniform in the electric pulse drawing process parameters, and the antibacterial effect is achieved.
In conclusion, the novel antibacterial and bacteriostatic copper alloy medical dressing and the preparation method thereof can realize the inhibition effect on multiple strains and achieve level I antibacterial effect.
The foregoing is merely illustrative of the present application, and the present application is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the technical scope of the present application should be included in the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (10)
1. A preparation method of an antibacterial and bacteriostatic copper alloy medical dressing is characterized by comprising the following steps of: raw materials are prepared according to the component design proportion of the copper alloy wire, and are placed in a crucible of a directional solidification furnace to be smelted and directionally solidified to obtain a copper alloy bar blank; and then carrying out homogenizing annealing treatment on the copper alloy bar blank to obtain an annealed bar blank, carrying out rotary forging on the annealed bar blank to obtain a copper alloy wire, carrying out electric pulse drawing and conventional drawing on the copper alloy wire in sequence to obtain a drawing sample, carrying out aging treatment to obtain the copper alloy wire, and then compounding the copper alloy wire with cellulose to obtain the antibacterial and bacteriostatic copper alloy medical dressing.
2. The method for preparing the antibacterial and bacteriostatic copper alloy medical dressing according to claim 1, which is characterized in that: the copper alloy comprises the following components in percentage by mass: 0.1 to 10wt.% of Fe and 0.1 to 12 wt.% of X, wherein X is at least one selected from Zn, mg, ca, mn, ag, na and the balance is Cu.
3. The method for preparing the antibacterial and bacteriostatic copper alloy medical dressing according to claim 1 or 2, which is characterized in that: the crucible is a corundum crucible or a graphite crucible, the crucible is cylindrical, and the diameter of the crucible is 10-15mm;
the smelting temperature is 1300-1500 ℃, and the vacuum degree of smelting is 10 -4 ～10 -2 Pa；
The directional solidification process comprises the following steps: the raw materials are placed in a crucible of directional solidification equipment to be smelted to obtain copper alloy melt, the copper alloy melt is continuously cast to obtain copper alloy bar blank, the continuous casting speed is controlled to be 0.5-5 mm/s during continuous casting, the primary cooling water flow of a crystallizer is 2-50L/min, and the secondary cooling water flow is 1-10L/min.
4. The method for preparing the antibacterial and bacteriostatic copper alloy medical dressing according to claim 1 or 2, which is characterized in that: the temperature of the homogenizing annealing treatment is 800-1100 ℃, and the time of the homogenizing annealing treatment is 4-12 h;
The pass deformation of the rotary forging is 10-20%, the total deformation is 50-80%, and the discharging speed is 1-3 m/min.
5. The method for preparing the antibacterial and bacteriostatic copper alloy medical dressing according to claim 1 or 2, which is characterized in that: the electric pulse parameters during the electric pulse drawing are as follows: the output voltage is: 2-15V; the output current is: 500-3000A; the pulse frequency is 100-3000 Hz; pulse width: 50-500 mu s;
when the electric pulse is drawn, the single-pass deformation is 20-50%, the total deformation is more than 80.0%, and the drawing speed is 2-50 m/min;
during conventional drawing, the single-pass deformation is 5-20%, the total deformation is 20-50%, and the drawing speed is 10-20 m/min.
6. The method for preparing the antibacterial and bacteriostatic copper alloy medical dressing according to claim 1 or 2, which is characterized in that: the temperature of the aging treatment is 350-600 ℃, and the time of the aging treatment is 0.5-12 h.
7. The method for preparing the antibacterial and bacteriostatic copper alloy medical dressing according to claim 1 or 2, which is characterized in that: the diameter of the copper alloy wire is 0.01-0.2 mm;
the grain size of the crystal grains in the copper alloy wire is 0.2-50 mu m.
8. The method for preparing the antibacterial and bacteriostatic copper alloy medical dressing according to claim 1 or 2, which is characterized in that: the mass ratio of the copper alloy wire to the cellulose is 10-90: 10 to 90;
The cellulose is at least one selected from cotton fiber, fibrilia and polyester fiber.
9. The method for preparing the antibacterial and bacteriostatic copper alloy medical dressing according to claim 1 or 2, which is characterized in that: the process of compounding the copper alloy wire with cellulose comprises the following steps: mixing, carding and needling the copper alloy wires with cellulose, or performing composite needling on the copper alloy wires and cellulose woven fabric, or carding the copper alloy wires into a net, and then performing composite needling on the copper alloy wires and cellulose spunlaced non-woven fabric.
10. An antibacterial bacteriostatic copper alloy medical dressing prepared by the preparation method of any one of claims 1-9.
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