CN103130415B - Medical glass with spodumene - Google Patents
Medical glass with spodumene Download PDFInfo
- Publication number
- CN103130415B CN103130415B CN201110376304.4A CN201110376304A CN103130415B CN 103130415 B CN103130415 B CN 103130415B CN 201110376304 A CN201110376304 A CN 201110376304A CN 103130415 B CN103130415 B CN 103130415B
- Authority
- CN
- China
- Prior art keywords
- glass
- parts
- oxide
- temperature
- spodumene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Glass Compositions (AREA)
Abstract
The invention relates to medical glass with spodumene. The glass material is especially suitable for making primary materials for the medical glass with high chemical stability or molded medical glass products and even glass materials for biological reagents. The medical glass with the spodumene is characterized by comprising the following raw materials of, by weight, 40-56 parts of quartz sand, 0.4-6.8 parts of the spodumene, 8-25 parts of feldspar powder; 0-3.5 parts of aluminum hydroxide; 15-25 parts of borax decahydrate; 1.5-4 parts of sodium nitrate, 0-5 parts of sodium carbonate, 0-3.5 parts of fluorite, 3-5 parts of calcite, 0-0.3 part of cerium oxide, 0-0.3 part of tin oxide, 0.05-1.0 part of ferric oxide, 0-3.5 parts of titanium oxide and 0-3 parts of manganese oxide. Due to the adoption and application of the spodumene, requirements for medical glass materials and biological reagent glass can be better met, and at the same time, the medical glass with the spodumene gains relatively good effect in economic benefits and social benefits.
Description
Technical field
The present invention relates to a kind of medical glass applying triphane, this glass material is specially adapted to make the primary material of high chemical stability medicine glass or molded medical glasswork, even biological reagent glass material.
Background technology
Medical packaging glass material is mainly used in pharmaceutical products packaging and uses, and can guarantee the stably stored of pharmaceutical products, keeps drug effect permanent.Because pharmaceutical products is constantly weeded out the old and bring forth the new in the world, the pH value range of liquid or medicament is constantly expanded, so need the medical glass packaging goods with more high chemical stability to meet the demands.
Glass material is the important component part in medical packaging material, it experienced by 100 years application and checkings, sufficient proof glass is the most reliable and the most stable wrapping material, because its have the good and chemical stability of resistance to air loss good etc. good characteristic, therefore, it is possible to be widely used in medical packaging field, such as ampoule, antibiotic bottle, infusion bottle, flask for medicinal preparations, storage blood bottle etc., medical packaging goods are related to human life's safety and health, concerning medicine storage, require that it has stability and security.Especially to storage neutrality, acidity and alkaline aqueous fusion injection or oil soluble injection, very high chemical stability must be had, comprise water-fast, acidproof, alkaline resistance properties, and special requirement have very high stability to hydrolysis resistance.
Glass in the fabrication process, need through high temperature melting technological process, therefore larger energy consumption can be caused, therefore, medicine glass not only will meet pharmaceutical products to while the requirement of the chemical stability of glass package, and more to meet energy-conserving and environment-protective and green manufacturing theory, realize energy-saving and emission-reduction object.
Summary of the invention
The object of the invention is, provide a kind of medical glass applying triphane, it has excellent chemical stability, can expand the stably stored needs of new pharmaceutical kind; Reduce glass melting temperature simultaneously, realize effects of energy saving and emission reduction better; Also to meet medical forming of glass requirement in addition, extend glass material property, improve Glass tubing forming accuracy; When energy growing tension and price higher, use the medical glass of triphane can significantly decline in temperature of fusion, thus can energy consumption be reduced, produce significant economic benefit; Moreover, in the reprocessing process of the elementary goods of glass (i.e. Glass tubing), significantly can reduce the generation of glass surface volatilization thing, meet the requirement of medical glass surface water resistant 1 grade of aspect, therefore by using and applying triphane, medical glass material and the requirement of biological reagent glass can be met better, in economic benefit and social benefit, also obtain good effect simultaneously.
Triphane is a kind of is main mineral products containing Lithium Oxide 98min, aluminum oxide, silicon oxide, and it is a kind of pyroxene race mineral, belongs to lithium aluminosilicate composition system, and its molecular formula is LiAl (SiO
3)
2.
Lithium Oxide 98min (the molecular formula Li contained in triphane
2o) monovalent base metal oxide is belonged to, Li
2o belongs to network modifying oxide in glass system, and it compares Na to the effect of glass
2o and K
2o has singularity.When O/Si ratio is less, namely glass structure very tight situation time, Lithium Oxide 98min is mainly scission of link effect, has strong effect of fluxing, and is a kind of strong fusing assistant, is conducive to the clarification of glass, introduces 0.05%-0.5%Li in glass
2o significantly can reduce the glass melting temperature 30 DEG C-50 DEG C of glass, is conducive to the production capacity and the quality that improve glass.In addition, because containing a large amount of aluminum oxide in triphane, Al
2o
3belong to intermediate oxide, as Na in glass
2o and Al
2o
3molecular ratio when being greater than 1, form aluminum-oxygen tetrahedron and also form continuous print structural network with silicon-oxy tetrahedron.Improve the chemical stability of glass, thermostability, physical strength, hardness and specific refractory power, alleviate the erosion of glass to refractory materials, in medical glass, usage quantity more than 8%, otherwise can not can improve glass viscosity and temperature of fusion.
The present inventor finds on the basis of a large amount of research work: the triphane of low iron content can be applied in transparent borosilicate medicine glass system preferably, and high Fe content triphane can be applied in brown borosilicate medicine glass system in addition.Not containing magnesium oxide in medical glass system of the present invention, glass flake phenomenon can be suppressed to produce, especially for injecting for class pharmaceutical prod, this is vital, otherwise slight flake situation can cause human muscle to be hardened, heavy then cause people's life danger; This glass system is not containing the heavy metal oxide such as barium, strontium in addition; Adopt environment-friendly type finings, as cerium oxide or stannic oxide, can avoid using the toxic element of arsenic oxide arsenoxide and weisspiessglanz on the harm of the person and impact; The present invention is also had not use sodium-chlor finings to avoid at glass, through heat processing and forming again, glass being caused to produce micro-bubble problem.
According to the action effect of the effective ingredients such as the Lithium Oxide 98min provided in triphane and aluminum oxide, according to theory of high packing and the mutual keying action relation of high field intensity minor diameter ion of glass structure, medical glass can be made at high chemical stability, reduce temperature of fusion, improve physical strength, suppress to obtain good result in surperficial volatile matter, the demand of medical glass and biological reagent glass can be met better.By triphane be raw material be incorporated into medical glass production manufacture in, than being used alone oxide containing lithium and salic industrial chemicals, as Quilonum Retard, aluminum oxide, aluminium hydroxide, can obtain and better melt effect, from the viewpoint of silicate reaction thermodynamics, reactions steps and endothermic heat of reaction process can be decreased, therefore can reach energy-conservation object and effect.
Glass tubing is the primary material of medical glass, and Glass tubing, through heat processing and forming process again, is manufactured vial, just can it can be used as the container containing of pharmaceutical products by general needs.The flame temperature of hot procedure will make Glass tubing viscosity reach 10
3dPas, temperature is now called for short T3 temperature, T3 temperature is lower, volatilization coagulum quantity on the Glass tubing surface that flame machining will be made to cause significantly reduces, volatilization coagulum is sodium oxide, water glass, Sodium Tetraborate, and these volatilization coagulums seriously restrict and perplex the realization of medical glass article surface water resistant 1 grade, therefore, also can obtain lower T3 temperature by applying triphane in medical glass, contributing to the raising of medical Glass tubing hot worked vial surface water repelling property.
The present invention apply the medical glass material of triphane, it is characterized in that: formed by containing following raw materials according, by mass percentage,
Further, it is characterized in that: be made up of following raw materials according, by mass percentage,
Further, it is characterized in that: be made up of following raw materials according, by mass percentage,
Further, it is characterized in that: be made up of following raw materials according, by mass percentage,
Further, it is characterized in that: be made up of following raw materials according, by mass percentage,
Further, it is characterized in that: be made up of following raw materials according, by mass percentage,
Further, it is characterized in that: be made up of following raw materials according, by mass percentage,
Further, it is characterized in that: be made up of following raw materials according, by mass percentage,
The present invention apply in the medical glass material of triphane, adopt cerium oxide or stannic oxide to be mainly used to realize glass clarifying effect, simultaneous oxidation cerium also has UV-preventing effect.Because cerium oxide or stannic oxide belong to oxidation-reduction type finings, therefore oxygen must be provided with the use of nitrate.Consider based on biological medicine glass safety, the present invention abandons the traditional As be harmful to
2o
3, Sb
2o
3, NaCl finings.
The present invention apply the medical glass material of triphane, its series of features viscosity points temperature is: T3 (η=10
3dPas) temperature is lower than 1330 DEG C; Tw (η=10
4dPas) temperature is lower than 1140 DEG C; Ts (η=10
76dPas) temperature is lower than being 785 DEG C; T
d(η=10
11.5dPas) temperature is lower than 638 DEG C.
Glass average coefficient of linear expansion is (46 ~ 72) × 10
-7/ DEG C scope, glass density is at 2.35 ~ 2.55g/cm
3.
Its chemical stability detects by relevant criterion, can reach water tolerance 1 grade respectively, acidproof 1 grade, alkaline-resisting 2 grades.
The present invention apply the medical glass formula composition of triphane and the reason of limited range is as described below.
Raw material in medical glass formula of the present invention is all domestic common commercially available frit except triphane.
The present invention's triphane used raw material is the triphane in the place of production, Australia of the neat Mining Limited Company agency and sales in sky, Sichuan, the triphane material characteristic in this place of production is that Lithium Oxide 98min content is high, iron oxides impurities is low, better can meet the ingredient requirement that glass production uses, its chemical composition range is (wt%): Li
2o 5.0-7.5, Fe
2o
30.10-0.25, Al
2o
319.41-26.91, SiO
264.16-74.35.
Quartz sand is used for providing silicon oxide (molecular formula SiO
2) composition, SiO
2be the composition of the necessity for forming glass skeleton, its content is higher, and chemical durability is better.On the other hand, put forward full-bodied tendency because it has, so, if use too much quartz sand to be just difficult to obtain the long glass of material property.Quartz sand content is more than 40%, is preferably more than 42%, and in addition, content, below 56%, is preferably less than 54%, is more preferably less than 52%, is preferably less than 50% further.Quartz sand is more than 42%, just can guarantee the chemical stability and the weather resistance that reach biological medicine requirement level.In addition, if quartz sand is less than 52%, then the melting of selected quartz raw material does not just need the longer time, then glass adhesion reduces.If quartz sand less than 50%, then the viscosity of glass reduces further, easily via Dan Na or can tie up the higher Glass tubing of network tube-pulling craft production dimensional precision.
Borax decahydrate is mainly used in providing boron oxide (molecular formula B
2o
3) sodium oxide (molecular formula Na
2o), B
2o
3be the neccessary composition for reducing glass viscosity and reinforcing glass chemical stability, its content is more, and glass just shows low viscosity characteristics; Na
2o plays fluxing action.Borax decahydrate content controls more than 15%, and be preferably more than 18%, in addition, borax decahydrate content is less than 25%, is preferably less than 23%, is more preferably less than 22%.
Triphane and Feldspar Powder are mainly used in providing aluminum oxide and necessary basic metal, and basic metal comprises Lithium Oxide 98min, sodium oxide, potassium oxide etc., and basic metal has characteristic of fluxing, and reduces glass viscosity, favourable energy-conservation.Aluminum oxide is the essential component greatly improving chemical durability of glass, devitrification of glass tendency can be reduced, also be the necessary composition improving glass hard (HRC65Yi Shang) and physical strength, it is the better composition improving modulus in tension, but it has the tendency improving glass viscosity simultaneously.
Feldspar Powder preferable range is 8%-25%; Triphane is except providing necessary aluminum oxide, more mainly to provide Lithium Oxide 98min, Lithium Oxide 98min can promote to melt effect consumingly, reduce temperature of fusion, suppress alkalimetal ion surface volatilization and coagulative generation in hot procedure, therefore the preferable range of triphane is 0.4%-6.8% is best.
SODIUMNITRATE and soda ash provide necessary sodium oxide, and sodium oxide is main alkalimetal oxide, and it is as flux composition, glass melting temperature is declined, there is the effect of the meltability improving glass, make glass low viscosity, viscosity characteristics is elongated, the stability of glass can be improved again.SODIUMNITRATE is also for finings provides necessary oxygen simultaneously, and therefore preferably SODIUMNITRATE scope is 1.5%-4%, and preferred soda ash scope is 0%-5%.
Fluorite and calcite are mainly for providing calcium oxide, and calcium oxide can make glass trend towards stabilization as alkali earths glass ingredient, suppress to occur crystallization in process of production at glass.There is the movement of the alkalimetal ion suppressed in glass simultaneously.Fluorite has effect of fluxing by force simultaneously, and preferred fluorite scope is 0%-3.5%, and calcite optimum range is 3%-5%.
Ferric oxide, titanium oxide, manganese oxide use as major colorants, and the ferric oxide of less than 0.20% mainly frit is brought into, if content is greater than 0.20% part by mainly by using raw iron oxide material to introduce.When titanium oxide, manganese oxide and ferric oxide use jointly, glass will be made to present brown, be conducive to glass to cover and cut-off effect ultraviolet, suppress the photochemical reaction of the pharmaceutical products in medical Glass Containers, promote the stable period of storage of pharmaceutical products.The best use range 0.05%-1.0% of the ferric oxide of brown medical glass, the best use range 0%-3.5% of titanium oxide, the best use range 0%-3% of manganese oxide.
Process of glass process is as follows:
First, the frit needed for selection, weighs, and becomes the glass formula with feature of the present invention, is mixed, melt in glass-melting furnace, and melting mode can adopt flame furnace, pure oxygen stove, all-electric melting furnace, electric booster flame stove.Adopt known glass forming method, comprise pellet and receive trombone slide, dimension network trombone slide, mold formed, then according to stress intensity in glass, carry out necessary annealing, form primary material (i.e. Glass tubing) or the finished product (i.e. Glass Containers or vial) of medical glass and biological reagent glass.
In order to the medical glass formula composition of the present invention's application triphane is described, and the acquired remarkable impact of performance, the mode adopting embodiment and comparative example to carry out contrasting is described, the category covered due to medical glass is relatively wide, emphasis of the present invention concentrates on two classes medicine glass kinds (i.e. the neutral boron silica glass said of industry and low borosilicate glass) and carries out emphasis statement, because these two kinds represent the market share of medical glass glass tube vial more than 80%, there is typical representative.Embodiment 1, embodiment 2, embodiment 3 are a series with comparative example 1, and wherein embodiment 3 appearance color is brown, belong to low borosilicate medicine glass kind; Embodiment 4, embodiment 5, embodiment 6 are a series with comparative example 2, and wherein embodiment 6 appearance color is brown, belong to neutral borosilicate medicine glass kind.
Embodiment
Embodiment 1
Based on embodiment, the present invention is described, table 1 is formula and the performance of embodiments of the invention and comparative example.
First, select raw material by table 1 glass formula, and, ingredient requirement, quartz sand (150 μm screen overflow be less than 1%, 45 μm of screen underflows be less than 30%); Aluminium hydroxide (median size 50 μm); Borax decahydrate (400 μm screen overflow be less than 10%, 63 μm of screen underflows be less than 10%); Fluorite and calcite, median size 200-500 μm; SODIUMNITRATE can not have conglomeration situation, as Feldspar Powder (median size 200 μm of screen underflows are less than 5%); Spodumene median size is 100 ~ 200 μm; Soda ash uses Soda Ash Danse, requires that median size is 200 ~ 500 μm; All the other raw materials should with commercially available powdery Chemicals, as cerium oxide, stannic oxide, ferric oxide, titanium oxide, manganese oxide, barium carbonate, sodium-chlor.
By the embodiment 1 glass formula composition (mass unit: g) in table 1, often prepare about 85g glass metal, need quartz sand 40g, triphane 5g, Feldspar Powder 25g, aluminium hydroxide 3.2g, borax decahydrate 15g, SODIUMNITRATE 3.5, soda ash 5g, calcite 3g, stannic oxide 0.25g, make it prepare burden to meet the glass formula of table 1 embodiment 1, wherein ferric oxide 0.05g is the impurity composition brought in raw material, first platinum crucible melting 24 hours at 1550 DEG C of temperature is used, secondly melten glass liquid is configured as the glass specimen goods of regulation, then anneal, require to test according to test event, the fundamental property of glass specimen is shown at table 1.
The evaluation application sink and float method of glass apparent density, this method is the liquid selecting Beta-bromo naphthalene and tetrabromoethane to be mixed to form different apparent density by a certain percentage, glass sample is suspended in mixing test solution top, along with the change of temperature, the density of test solution does corresponding change, and when the density of test solution is consistent with glass specimen, glass starts to sink, according to the temperature factor of sinking temperature and test solution, the density of glass just can be measured.
Expansion coefficient of glass thread evaluation application dilatometric method, this method is placed on silica glass support by sample, utilizes the different of the thermal expansivity of glass specimen and silica glass, the relative elongation of both mensuration in heat-processed.And the coefficient of expansion of quartz glass tube is known, therefore the total elongation of glass specimen should be the elongation sum of the isometric silica glass frame of digital sensor reading and sample.By its divided by intensification degree and sample length.The unit temperature of final expression glass at 20 DEG C to 300 DEG C and the increment of unit length.
Glass viscosity measure different viscosity value scope adopt measuring method and instrument carry out.10
2dPas, 10
3dPas and 10
4dPas viscosity measurement, with reference to ASTM C-965 standard, adopts and rotates high temperature viscosimeter; 10
7.6dPas viscosity measurement is with reference to ASTM C-338, adopt Littleton softening point apparatus, sample requires the glass yarn for Φ 0.65+0.1mm length 230mm, heat in process furnace by 5 DEG C/min temperature rise rate, make it temperature when extension speed reaches 1mm/min, be softening point temperature, it characterizes the softening unique point of glass in deadweight state; 10
11.5dPas viscosity measurement is with reference to ASTM E-228, and application horizontal expander coefficient measuring instrument, this viscosity number is characterized by the yield temperature point of sample under loading condition.
Chemical durability of glass evaluation method is:
Water tolerance H, adopts DIN ISO 719 standard, and represent the alkali equivalent that the acid of each sample beads consumes in table, unit adopts μ gNa
2o/g, the alkali equivalent weight maxima that the acid belonging to the beads of 1 grade of water resistant consumes is 31 μ gNa
2o/g; Belonging to 2 grades of water resistant alkali equivalent weight range is 31 ~ 62 μ gNa
2o/g; Belonging to 3 grades of alkali equivalent weight range is 62 ~ 260 μ gNa
2o/g.
Acid resistance S, adopts DIN ISO 12116 standard, represents each sample mg/cm in table
2acidproof weight loss amount.The weight loss maximum value belonging to 1 grade of acid-resistant glass is 0.70mg/cm
2; The weight loss scope belonging to 2 grades of acid-resistant glass is 0.70 ~ 1.50mg/cm
2; The weight loss belonging to 3 grades of acid-resistant glass is greater than 1.5mg/cm
2.
Alkali resistance L, adopts DIN ISO 695 standard, represents each sample mg/cm in table
2acidproof weight loss amount.The weight loss maximum value belonging to 1 grade of acid-resistant glass is 75mg/cm
2; The weight loss scope belonging to 2 grades of acid-resistant glass is 75 ~ 175mg/cm
2; The weight loss belonging to 3 grades of acid-resistant glass is greater than 175mg/cm
2.
Correlation performance parameters from table 1 embodiment 1, contrast with comparative example 1, Tm is temperature of fusion, and its temperature declines 36 DEG C, illustrates that adding more triphane significantly can reduce temperature of fusion, approximately can save energy about 5%-8%.T3 shows glass heat processing temperature, and its temperature declines 59 DEG C, achieves and significantly reduces, and can suppress the surface volatilization coagulum generation in the glass heat course of processing, be conducive to the realization of the surperficial water resistant 1 grade of glass glass tube vial.Tw is forming of glass feed temperature, and it declines 52 DEG C, illustrates and is conducive to forming of glass precision and reduces energy expenditure.Ts and Td homogeneous phase frequently more slightly declined, and for the profile adjustment of forming of glass provides grace time guarantee, slow down the heat radiation with surrounding environment, extends shaping regulation time, favourable acquisition high-accuracy glass goods.
For the chemical stability of embodiment 1, adopt water-fast, acidproof, alkaline-resisting evaluation respectively, its numerical value is as shown in table 1, evaluate by the grading of relevant criterion, it is water-fast and acidproofly reach 1 grade, alkaline-resistingly reaches 2 grades, compared with comparative example 1, every index improves 23%, 14%, 7% respectively, illustrates that chemical stability aspect is promoted by a relatively large margin.
Embodiment 2
By the embodiment 2 glass formula composition (mass unit: g) in table 1, often prepare about 85g glass metal, need quartz sand 48g, Spodumene 0.4g, Feldspar Powder 18.2g, borax decahydrate 25g, SODIUMNITRATE 4g, fluorite 1g, calcite 3g, stannic oxide 0.3g, make it prepare burden to meet the glass formula of table 1 embodiment 2, wherein ferric oxide 0.10g is the impurity composition brought in raw material, first platinum crucible melting 24 hours at 1550 DEG C of temperature is used, secondly melten glass liquid is configured as the glass specimen goods of regulation, then anneal, require to test according to test event, the fundamental property of glass specimen is shown at table 1.
Correlation performance parameters from table 1 embodiment 2, contrast with comparative example 1, Tm is temperature of fusion, and its temperature declines 16 DEG C, illustrates that adding a small amount of triphane can reduce temperature of fusion, approximately can save energy about 3-4%.T3 shows glass heat processing temperature, and its temperature declines 51 DEG C, achieves and significantly reduces, and can suppress the surface volatilization coagulum generation in the glass heat course of processing, be conducive to the realization of the surperficial water resistant 1 grade of glass glass tube vial.Tw is forming of glass feed temperature, and it declines 57 DEG C, illustrates and is conducive to forming of glass precision and reduces Power supply.Ts and Td homogeneous phase declines all to some extent than comparative example 1, for the profile adjustment of forming of glass provides grace time guarantee, slow down the heat radiation with surrounding environment, extends shaping regulation time, favourable acquisition high-accuracy glass goods.
For the chemical stability of embodiment 2, adopt water-fast, acidproof, alkaline-resisting evaluation respectively, its numerical value is as shown in table 1, evaluate by the grading of relevant criterion, water-fast and acidproofly reach 1 grade, alkaline-resistingly reach 2 grades, compared with comparative example 1, every index improves 31%, 29%, 20% respectively, illustrates that chemical stability aspect is promoted greatly.
Embodiment 3
By the embodiment 3 glass formula composition in table 1, (mass unit: g), often prepares about 85g glass metal, needs quartz sand 44g, Spodumene 1.5g, Feldspar Powder 19.0g, aluminium hydroxide 1g, borax decahydrate 16.9g, SODIUMNITRATE 3g, soda ash 2g, fluorite 3.5g, calcite 5g, cerium oxide 0.3g, ferric oxide 0.6g, manganese oxide 3g, brings ferric oxide 0.2g impurity in its Raw, make it prepare burden to meet the glass formula of table 1 embodiment 3.First platinum crucible melting 24 hours at 1550 DEG C of temperature is used, secondly melten glass liquid is configured as the glass specimen goods of regulation, then anneal, its appearance color is brown, require to test according to test event, show the fundamental property of glass specimen at table 1.
Correlation performance parameters from table 1 embodiment 3, contrast with comparative example 1, Tm is temperature of fusion, and its temperature declines 22 DEG C, illustrates that adding appropriate triphane can reduce temperature of fusion, approximately can save energy about 4-5%.T3 shows glass heat processing temperature, and its temperature declines 33 DEG C, achieves and reduces greatly, the surface in the glass heat course of processing can be suppressed to volatilize coagulative generation, be conducive to the realization of the surperficial water resistant 1 grade of glass glass tube vial.Tw is forming of glass feed temperature, and it declines 44 DEG C, illustrates and is conducive to forming of glass precision and reduces Power supply.Ts and Td homogeneous phase declines all to some extent than comparative example 1, for the profile adjustment of forming of glass provides grace time guarantee, slow down the heat radiation with surrounding environment, extends shaping regulation time, favourable acquisition high-accuracy glass goods.
For the chemical stability of embodiment 3, adopt water-fast, acidproof, alkaline-resisting evaluation respectively, its numerical value is as shown in table 1, evaluate by the grading of relevant criterion, water-fast and acidproofly reach 1 grade, alkaline-resistingly reach 2 grades, compared with comparative example 1, every index improves 34%, 29%, 25% respectively, illustrates that chemical stability aspect is promoted greatly.
Embodiment 4
By the embodiment 4 glass formula composition in table 1, (mass unit: g), often prepares about 85g glass metal, needs quartz sand 50g, Spodumene 6.8g, Feldspar Powder 9.0g, aluminium hydroxide 3.5g, borax decahydrate 21.9g, SODIUMNITRATE 1.5g, soda ash 1g, fluorite 2g, calcite 4g, cerium oxide 0.15g, makes it prepare burden to meet the glass formula of table 1 embodiment 4, and ferric oxide 0.15g wherein causes for impurity that raw material is brought into.First use platinum crucible melting 24 hours at 1600 DEG C of temperature, secondly melten glass liquid is configured as the glass specimen goods of regulation, then anneals, require to test according to test event, show the fundamental property of glass specimen at table 1.
Correlation performance parameters from table 1 embodiment 4, contrast with comparative example 2, Tm is temperature of fusion, and its temperature declines 44 DEG C, illustrates that adding more triphane significantly can reduce temperature of fusion, approximately can save energy about 6-8%.T3 shows glass heat processing temperature, and its temperature declines 85 DEG C, achieves and reduces greatly, the surface in the glass heat course of processing can be suppressed to volatilize coagulative generation, be conducive to the realization of the surperficial water resistant 1 grade of glass glass tube vial.Tw is forming of glass feed temperature, and it declines 68 DEG C, illustrates and is conducive to forming of glass precision and reduces Power supply.Ts and Td homogeneous phase declines all to some extent than comparative example 2, for the profile adjustment of forming of glass provides grace time guarantee, slow down the heat radiation with surrounding environment, extends shaping regulation time, favourable acquisition high-accuracy glass goods.
For the chemical stability of embodiment 4, adopt water-fast, acidproof, alkaline-resisting evaluation respectively, its numerical value is as shown in table 1, evaluate by the grading of relevant criterion, water-fast and acidproofly reach 1 grade, alkaline-resistingly reach 2 grades, compared with comparative example 1, every index improves 32%, 40%, 15% respectively, illustrates that chemical stability aspect is promoted greatly.
Embodiment 5
By the embodiment 5 glass formula composition in table 1, (mass unit: g), often prepares about 85g glass metal, needs quartz sand 56g, Spodumene 4g, Feldspar Powder 8g, aluminium hydroxide 0.5g, borax decahydrate 21.3g, SODIUMNITRATE 2g, fluorite 3g, calcite 4.5g, cerium oxide 0.20g, stannic oxide 0.30g, makes it prepare burden to meet the glass formula of table 1 embodiment 5, and ferric oxide 0.20g wherein causes for impurity that raw material is brought into.First use platinum crucible melting 24 hours at 1600 DEG C of temperature, secondly melten glass liquid is configured as the glass specimen goods of regulation, then anneals, require to test according to test event, show the fundamental property of glass specimen at table 1.
Correlation performance parameters from table 1 embodiment 5, contrast with comparative example 2, Tm is temperature of fusion, and its temperature declines 39 DEG C, illustrates that adding more triphane significantly can reduce temperature of fusion, approximately can save energy about 6-7%.T3 shows glass heat processing temperature, and its temperature declines 76 DEG C, achieves and reduces greatly, the surface in the glass heat course of processing can be suppressed to volatilize coagulative generation, be conducive to the realization of the surperficial water resistant 1 grade of glass glass tube vial.Tw is forming of glass feed temperature, and it declines 60 DEG C, illustrates and is conducive to forming of glass precision and reduces Power supply.Ts and Td homogeneous phase declines all to some extent than comparative example 2, for the profile adjustment of forming of glass provides grace time guarantee, slow down the heat radiation with surrounding environment, extends shaping regulation time, favourable acquisition high-accuracy glass goods.
For the chemical stability of embodiment 5, adopt water-fast, acidproof, alkaline-resisting evaluation respectively, its numerical value is as shown in table 1, evaluate by the grading of relevant criterion, water-fast and acidproofly reach 1 grade, alkaline-resistingly reach 2 grades, compared with comparative example 1, every index improves 35%, 40%, 18% respectively, illustrates that chemical stability aspect is promoted greatly.
Embodiment 6
By the embodiment 6 glass formula composition (mass unit: g) in table 1, often prepare about 85g glass metal, need quartz sand 52g, Spodumene 2.5g, Feldspar Powder 10g, aluminium hydroxide 2g, borax decahydrate 20.2g, SODIUMNITRATE 2g, soda ash 0.5g, fluorite 2g, calcite 4g, cerium oxide 0.3g, ferric oxide 0.8g, titanium oxide 3.5g, bring ferric oxide 0.2g impurity in its Raw, make it prepare burden to meet the glass formula of table 1 embodiment 6, ferric oxide 0.20g wherein causes for impurity that raw material is brought into.First platinum crucible melting 24 hours at 1600 DEG C of temperature is used, secondly melten glass liquid is configured as the glass specimen goods of regulation, then anneal, glasswork appearance color is brown, require to test according to test event, show the fundamental property of glass specimen at table 1.
Correlation performance parameters from table 1 embodiment 6, contrast with comparative example 2, Tm is temperature of fusion, and its temperature declines 27 DEG C, illustrates that adding more triphane significantly can reduce temperature of fusion, approximately can save energy about 4-6%.T3 shows glass heat processing temperature, and its temperature declines 80 DEG C, achieves and reduces greatly, the surface in the glass heat course of processing can be suppressed to volatilize coagulative generation, be conducive to the realization of the surperficial water resistant 1 grade of glass glass tube vial.Tw is forming of glass feed temperature, and it declines 52 DEG C, illustrates and is conducive to forming of glass precision and reduces Power supply.Ts and Td homogeneous phase declines all to some extent than comparative example 2, for the profile adjustment of forming of glass provides grace time guarantee, slow down the heat radiation with surrounding environment, extends shaping regulation time, favourable acquisition high-accuracy glass goods.
For the chemical stability of embodiment 6, adopt water-fast, acidproof, alkaline-resisting evaluation respectively, its numerical value is as shown in table 1, evaluate by the grading of relevant criterion, water-fast and acidproofly reach 1 grade, alkaline-resistingly reach 2 grades, compared with comparative example 1, every index improves 26%, 40%, 12% respectively, illustrates that chemical stability aspect is promoted greatly.
The formula composition and performance of [table 1] embodiment and comparative example
Note: 1 grade or 2 grades in H, S, L chemical stability data bracket is that standard described in by specification is carried out classification and determined.
Claims (6)
1. apply a medical glass material for triphane, it is characterized in that: be made up of following raw materials according, by mass percentage,
2. apply a medical glass material for triphane, it is characterized in that: be made up of following raw materials according, by mass percentage,
3. apply a medical glass material for triphane, it is characterized in that: be made up of following raw materials according, by mass percentage,
4. apply a medical glass material for triphane, it is characterized in that: be made up of following raw materials according, by mass percentage,
5. apply a medical glass material for triphane, it is characterized in that: be made up of following raw materials according, by mass percentage,
6. apply a medical glass material for triphane, it is characterized in that: be made up of following raw materials according, by mass percentage,
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110376304.4A CN103130415B (en) | 2011-11-23 | 2011-11-23 | Medical glass with spodumene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110376304.4A CN103130415B (en) | 2011-11-23 | 2011-11-23 | Medical glass with spodumene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103130415A CN103130415A (en) | 2013-06-05 |
| CN103130415B true CN103130415B (en) | 2015-06-17 |
Family
ID=48490929
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110376304.4A Active CN103130415B (en) | 2011-11-23 | 2011-11-23 | Medical glass with spodumene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103130415B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104926127A (en) * | 2015-06-17 | 2015-09-23 | 芮城县宏光医药包装业有限公司 | First grade water-fast pharmaceutical glass tube and preparation method |
| CN105036553A (en) * | 2015-08-04 | 2015-11-11 | 沧州四星玻璃股份有限公司 | Medicinal neutral borosilicate glass tube and preparing method thereof |
| CN105271743B (en) * | 2015-10-19 | 2018-07-27 | 山东康和医药包装材料科技有限公司 | A kind of formula and production method of the medicinal pipe of neutral boron silica glass |
| WO2017110906A1 (en) * | 2015-12-24 | 2017-06-29 | 日本電気硝子株式会社 | Production method for borosilicate glass |
| US20180354842A1 (en) * | 2015-12-25 | 2018-12-13 | Nippon Electric Glass Co., Ltd. | Mixed raw material for silicate glass and method for manufacturing tube glass using same |
| JPWO2017115728A1 (en) * | 2015-12-28 | 2018-10-18 | 日本電気硝子株式会社 | Method for producing aluminoborosilicate glass for pharmaceutical containers |
| CN106277765B (en) * | 2016-08-31 | 2019-01-04 | 山东省药用玻璃股份有限公司 | Brown pharmaceutical glass and preparation method thereof |
| CN106746638A (en) * | 2016-12-08 | 2017-05-31 | 姚均甫 | A kind of medical glass of application spodumene |
| CN108545934B (en) * | 2018-05-15 | 2021-01-12 | 张怀民 | Iron-titanium-carbon colored medical water-resistant glass |
| CN109206012B (en) * | 2018-11-06 | 2021-09-24 | 河南安彩高科股份有限公司 | Neutral borosilicate medicinal glass and preparation method thereof |
| CN110204180A (en) * | 2019-05-09 | 2019-09-06 | 山东乐和家日用品有限公司 | For producing the narrow slit device and technique of high alumina cell phone rear cover glass sheet |
| CN110282873B (en) * | 2019-07-05 | 2021-08-10 | 齐鲁工业大学 | Large bottle and can glass with long material property and preparation method thereof |
| CN117088612B (en) * | 2023-10-19 | 2024-01-05 | 山东金晶科技股份有限公司 | Neutral borosilicate glass medical tube and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1250755A (en) * | 1999-10-21 | 2000-04-19 | 哈尔滨医药股份有限公司制药三厂 | Tubular blue glass bottle for medicinal oral liquid and its making method |
| CN101148317A (en) * | 2007-08-22 | 2008-03-26 | 东营力诺玻璃制品有限责任公司 | Formula of medicinal neutral borosilicate glass |
| CN101343143A (en) * | 2008-08-18 | 2009-01-14 | 四川省阆中光明玻璃制品有限公司 | Neutral boron silex glass for mold-formed bottle for storing and freezing biotic product, and method of manufacturing the same |
| CN101462824A (en) * | 2007-12-20 | 2009-06-24 | 山东省药用玻璃股份有限公司 | Semi-neutral boron silica glass for medicinal tubed phial |
| CN101734856A (en) * | 2009-12-31 | 2010-06-16 | 山东省药用玻璃股份有限公司 | Glaucous medicinal glass bottle and manufacture method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3084772B2 (en) * | 1991-03-08 | 2000-09-04 | 日本電気硝子株式会社 | Borosilicate glass |
-
2011
- 2011-11-23 CN CN201110376304.4A patent/CN103130415B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1250755A (en) * | 1999-10-21 | 2000-04-19 | 哈尔滨医药股份有限公司制药三厂 | Tubular blue glass bottle for medicinal oral liquid and its making method |
| CN101148317A (en) * | 2007-08-22 | 2008-03-26 | 东营力诺玻璃制品有限责任公司 | Formula of medicinal neutral borosilicate glass |
| CN101462824A (en) * | 2007-12-20 | 2009-06-24 | 山东省药用玻璃股份有限公司 | Semi-neutral boron silica glass for medicinal tubed phial |
| CN101343143A (en) * | 2008-08-18 | 2009-01-14 | 四川省阆中光明玻璃制品有限公司 | Neutral boron silex glass for mold-formed bottle for storing and freezing biotic product, and method of manufacturing the same |
| CN101734856A (en) * | 2009-12-31 | 2010-06-16 | 山东省药用玻璃股份有限公司 | Glaucous medicinal glass bottle and manufacture method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 玻璃中引入锂辉石降低成本的实践经验;李鹏;《玻璃与搪瓷》;20010228;第29卷(第1期);第29页第2、4段，第30页第4段，第31页第2、7段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103130415A (en) | 2013-06-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103130415B (en) | Medical glass with spodumene | |
| JP6972207B2 (en) | Glass composition with improved chemical and mechanical durability | |
| CN101428969B (en) | Brown glass and uses thereof | |
| CN112811813B (en) | Borosilicate glass composition, borosilicate glass, and preparation method and application of borosilicate glass | |
| CN104261676B (en) | Neutral borosilicate glass and application thereof | |
| TW201412676A (en) | Ion exchangeable li-containing glass compositions for 3-D forming | |
| KR20140032379A (en) | High-strength alkali-aluminosilicate glass | |
| CN112694254A (en) | Medium borosilicate glass composition, medium borosilicate glass, and preparation method and application thereof | |
| WO2018121491A1 (en) | Borosilicate glass with high chemical resistance and application thereof | |
| CN104926127A (en) | First grade water-fast pharmaceutical glass tube and preparation method | |
| CN105384336B (en) | A kind of silicate glass composition and its ultra-thin glass made and preparation method and application | |
| CN106396371A (en) | Low-boron zirconium-free neutral glass having an optimized alkali metal ratio | |
| CN101428968B (en) | Blue glass for medical packaging and uses thereof | |
| JP2022526269A (en) | Chemically durable aluminosilicate glass composition and glass articles formed from it | |
| CN106746638A (en) | A kind of medical glass of application spodumene | |
| JPWO2017115728A1 (en) | Method for producing aluminoborosilicate glass for pharmaceutical containers | |
| WO2020153294A1 (en) | Glass for medicine container, and glass tube for medicine container and medicine container using same | |
| CN111372900A (en) | Ultraviolet-resistant alkali-resistant borosilicate glass and application thereof | |
| CN113896416A (en) | Glass and preparation method thereof | |
| JP3084772B2 (en) | Borosilicate glass | |
| CN110510873A (en) | Borosilicate glass and preparation method thereof | |
| TWI609849B (en) | Touch protection glass composition | |
| US2508070A (en) | Glass composition | |
| JP2021075453A (en) | Toughenable glass with high hydrolytic resistance and reduced color tinge | |
| CN117228953A (en) | Fireproof luminous glass with low aluminum content and high boron silicon content and preparation process thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: CHENGDU TIANQI LITHIUM INDUSTRIES INC. Free format text: FORMER OWNER: SICHUAN TIANQI MINING CO., LTD. Effective date: 20150527 |
|
| C14 | Grant of patent or utility model | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| GR01 | Patent grant | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20150527 Address after: Sichuan province Chengdu city Gaopeng road 610041 No. 10 Applicant after: Chengdu Tian Qili industry company limited Address before: High tech Zone Chengdu city Sichuan province 610041 Gaopeng Road No. 10 Applicant before: Sichuan Tianqi Mining Co., Ltd. |