CN103130415A - Medical glass with spodumene - Google Patents
Medical glass with spodumene Download PDFInfo
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- CN103130415A CN103130415A CN2011103763044A CN201110376304A CN103130415A CN 103130415 A CN103130415 A CN 103130415A CN 2011103763044 A CN2011103763044 A CN 2011103763044A CN 201110376304 A CN201110376304 A CN 201110376304A CN 103130415 A CN103130415 A CN 103130415A
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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 of using triphane, this glass material is specially adapted to make primary material or molded medical glasswork, even the biological reagent glass material of high chemical stability medicine glass.
Background technology
The medical packaging glass material is mainly used in the pharmaceutical products packing and uses, and can guarantee the stably stored of pharmaceutical products, keeps drug effect permanent.Constantly weed out the old and bring forth the new due to pharmaceutical products in the world, the pH value scope of liquid or medicament is constantly expanded, and the medical glass packaging goods of high chemical stability meet the demands so need to have more.
Glass material is the important component part in the medical packaging material, it has experienced, and 100 years are used and checking, sufficient proof glass is the most reliable and the most stable wrapping material, because it has the good and good characteristic such as chemical stability is good of resistance to air loss, therefore can be widely used in the medical packaging field, such as ampoule, antibiotic bottle, infusion bottle, flask for medicinal preparations, storage blood bottle etc., the medical packaging goods are related to human life's safety and health, concerning medicine is stored, require it to have stability and security.Especially to storing neutrality, acidity and alkaline aqueous fusion injection or oil soluble injection, must have very high chemical stability, comprise water-fast, acidproof, alkaline resistance properties, and special requirement have very high stability to hydrolysis resistance.
Glass is in manufacturing processed, need through the high temperature melting technological process, therefore can cause larger energy consumption, therefore, when medicine glass not only will satisfy pharmaceutical products to the requirement of the chemical stability of glass package, and more to satisfy energy-conserving and environment-protective and green manufacturing theory, realize the energy-saving and emission-reduction purpose.
Summary of the invention
The object of the invention is, a kind of medical glass of using triphane is provided, and it has good chemical stability, can expand the stably stored needs of new pharmaceutical kind; Reduce simultaneously the glass melting temperature, realize better effects of energy saving and emission reduction; Also to satisfy in addition medical forming of glass requirement, extend the glass material property, improve the Glass tubing forming accuracy; In the situation that energy growing tension and price are higher, use the medical glass of triphane can significantly descend aspect temperature of fusion, thereby can reduce energy consumption, produce significant economic benefit; Moreover, in the reprocessing process of the elementary goods of glass (being Glass tubing), can significantly reduce the generation of glass surface volatilization thing, satisfy the requirement of 1 grade of aspect of medical glass surface water resistant, therefore by using and use triphane, can satisfy better medical glass material and the requirement of biological reagent glass, also obtain effect preferably aspect economic benefit and social benefit simultaneously.
Triphane is that a kind of Lithium Oxide 98min, aluminum oxide, silicon oxide of containing is main mineral products, and it is a kind of pyroxene family mineral, belongs to lithium aluminosilicate composition system, and its molecular formula is LiAl (SiO
3)
2
Lithium Oxide 98min (the molecular formula Li that contains in triphane
2O) belong to monovalent base metal oxide, Li
2O belongs to network modifying oxide in glass system, Na is compared in its effect to glass
2O and K
2O has singularity.When O/Si ratio hour, namely very during tight situation, Lithium Oxide 98min is mainly the scission of link effect to glass structure, has the 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 can significantly reduce by 30 ℃-50 ℃ of the glass melting temperatures of glass, is conducive to improve production capacity and the quality of glass.In addition, because contain a large amount of aluminum oxide, Al in triphane
2O
3Belong to intermediate oxide, Na in glass
2O and Al
2O
3Molecular ratio greater than 1 o'clock, form aluminum-oxygen tetrahedron and also form continuous structural network with silicon-oxy tetrahedron.Improve chemical stability, thermostability, physical strength, hardness and the specific refractory power of glass, alleviate glass to the erosion of refractory materials, usage quantity can not surpass 8% in medical glass, otherwise can improve glass viscosity and temperature of fusion.
The 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 the high Fe content triphane can be applied in brown borosilicate medicine glass system in addition.Do not contain magnesium oxide in medical glass system of the present invention, can suppress glass flake phenomenon and produce, especially for injection class pharmaceutical prod, this is vital, otherwise slight flake situation can cause the human muscle to be hardened, and is heavy cause people's life danger; This glass system does not contain the heavy metal oxides such as barium, strontium in addition; Adopt the environment-friendly type finings, as cerium oxide or stannic oxide, can avoid using the poisonous element of arsenic oxide arsenoxide and weisspiessglanz on harm and the impact of the person; Also have the present invention not use the sodium-chlor finings to avoid during through heat processing and forming again, can causing glass to produce the micro-bubble problem at glass.
Action effect according to effective ingredients such as the Lithium Oxide 98min that provides in triphane and aluminum oxide, theory of high packing and the mutual keying action relation of high field intensity minor diameter ion according to glass structure, can make medical glass obtaining good result aspect high chemical stability, reduction temperature of fusion, the physical strength that improves, the surperficial volatile matter of inhibition, can satisfy better the demand of medical glass and biological reagent glass.Be that raw material is incorporated in medical glass production manufacturing by triphane, than using separately oxide containing lithium and salic industrial chemicals, as Quilonum Retard, aluminum oxide, aluminium hydroxide, can obtain better to melt effect, from silicate reaction thermodynamics aspect, reactions steps and endothermic heat of reaction process can be reduced, therefore energy-conservation purpose and effect can be reached.
Glass tubing is the primary material of medical glass, generally need to made of glass tube be caused vial through heat processing and forming process again, could be with its container containing as pharmaceutical products.The flame temperature of hot procedure will make the Glass tubing viscosity reach 10
3DPas, the temperature of this moment is called for short the T3 temperature, the T3 temperature is lower, the lip-deep volatilization coagulum of the Glass tubing that flame machining is caused quantity significantly reduces, the volatilization coagulum is sodium oxide, water glass, Sodium Tetraborate, and these volatilization coagulums seriously restrict and perplex the realization of 1 grade of medical glass article surface water resistant, therefore, also can obtain lower T3 temperature by use triphane in medical glass, help the raising of the surperficial water repelling property of the hot worked vial of medical Glass tubing.
The medical glass material of triphane that the present invention uses is characterized in that: consisted of by containing following raw materials according, and by the quality percentage composition,
Further, it is characterized in that: consisted of by following raw materials according, by the quality percentage composition,
Further, it is characterized in that: consisted of by following raw materials according, by the quality percentage composition,
Further, it is characterized in that: consisted of by following raw materials according, by the quality percentage composition,
Further, it is characterized in that: consisted of by following raw materials according, by the quality percentage composition,
Further, it is characterized in that: consisted of by following raw materials according, by the quality percentage composition,
Further, it is characterized in that: consisted of by following raw materials according, by the quality percentage composition,
Further, it is characterized in that: consisted of by following raw materials according, by the quality percentage composition,
In the medical glass material of triphane that the present invention uses, adopt cerium oxide or stannic oxide to be mainly used to realize the glass clarifying effect, the simultaneous oxidation cerium also has the UV-preventing effect.Because cerium oxide or stannic oxide belong to the oxidation-reduction type finings, therefore must be used in conjunction with nitrate provides oxygen.Based on the consideration of biological medicine glass safety, traditional As that the present invention abandons being harmful to
2O
3, Sb
2O
3, the NaCl finings.
The medical glass material of triphane that the present invention uses, its serial intrinsic viscosity point temperature is: T3 (η=10
3DPas) temperature is lower than 1330 ℃; Tw (η=10
4DPas) temperature is lower than 1140 ℃; Ts (η=10
76DPas) temperature is lower than being 785 ℃; T
d(η=10
11.5DPas) temperature is lower than 638 ℃.
The glass average coefficient of linear expansion is (46～72) * 10
-7/ ℃ scope, glass density is at 2.35～2.55g/cm
3
Its chemical stability detects by relevant criterion, can reach respectively 1 grade of water tolerance, and acidproof 1 grade, alkaline-resisting 2 grades.
The medical glass formula of triphane that the present invention uses forms 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 raw material used 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, ferric oxide impurity is low, can better satisfy the ingredient requirement that glass production is used, 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 that its content is higher for the composition of the necessity that consists of the glass skeleton, chemical durability is better.On the other hand, because having, it puies forward full-bodied tendency, so, if use too much quartz sand just to be difficult to obtain the long glass of material property.Quartz sand content is more than 40%, and preferably more than 42%, in addition, content preferably below 54%, is more preferably below 52% below 56%, further preferably below 50%.Quartz sand is more than 42%, just can guarantee to reach chemical stability and the weather resistance of biological medicine requirement level.In addition, if quartz sand is below 52%, the melting of selected quartz raw material does not just need the longer time, and glass adhesion reduces.If quartz sand is below 50%, the viscosity of glass further reduces, and can be easy to by Dan Na or the higher Glass tubing of dimension 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 that its content is more for reducing the neccessary composition of glass viscosity and reinforcing glass chemical stability, glass just shows low viscosity characteristics; Na
2O plays fluxing action.Borax decahydrate content is controlled at more than 15%, is preferably more than 18%, and in addition, borax decahydrate content is below 25%, is preferably below 23%, is more preferably below 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 the characteristic of fluxing, and reduce the glass viscosity, and be favourable energy-conservation.Aluminum oxide is the essential component of greatly improving chemical durability of glass, can reduce the devitrification of glass tendency, simultaneously be also the necessary composition that improves glass hard (HRC65Yi Shang) and physical strength, it is the better composition that improves modulus in tension, but it has the tendency that improves glass viscosity.
The Feldspar Powder preferable range is 8%-25%; Triphane is except providing necessary aluminum oxide, more mainly for Lithium Oxide 98min is provided, Lithium Oxide 98min can promote to melt effect consumingly, reduce temperature of fusion, suppress alkalimetal ion surface volatilization and coagulative generation in hot procedure, so the preferable range of triphane is that 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 the flux composition, make the glass melting temperature descend, have the effect of the meltability of improving glass, make the glass low viscosity, viscosity characteristics is elongated, can improve again the stability of glass.SODIUMNITRATE is also for finings provides necessary oxygen simultaneously, and therefore preferred SODIUMNITRATE scope is 1.5%-4%, and preferred soda ash scope is 0%-5%.
Fluorite and calcite are mainly for calcium oxide is provided, and calcium oxide can make glass trend towards stabilization as the alkali earths glass ingredient, is suppressed at glass and crystallization occurs in process of production.Has simultaneously the movement that suppresses the alkalimetal ion in glass.Fluorite has the effect of fluxing by force simultaneously, and preferred fluorite scope is 0%-3.5%, and the calcite optimum range is 3%-5%.
Ferric oxide, titanium oxide, manganese oxide use as main tinting material, and the ferric oxide below 0.20% is mainly that frit is brought into, if content will be mainly by using raw iron oxide material to introduce greater than 0.20% part.When titanium oxide, manganese oxide and ferric oxide use jointly, glass is presented brown, be conducive to glass and cover and the 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.
The process of glass process is as follows:
At first, select required frit, carry out weighing, make it become the glass formula with feature of the present invention, it is mixed, melt in glass-melting furnace, the melting mode can adopt flame furnace, pure oxygen stove, all-electric melting furnace, electric booster flame stove.Adopt known glass forming method, comprise that pellet receives trombone slide, dimension network trombone slide, mold formed, then according to stress intensity in glass, carry out necessary annealing, form primary material (being Glass tubing) or the finished product (being Glass Containers or vial) of medical glass and biological reagent glass.
In order to illustrate that the present invention uses the medical glass formula composition of triphane, and the obtained remarkable impact of performance, the mode that adopts embodiment and comparative example to compare is described, because the category that medical glass covers is relatively wide, emphasis of the present invention concentrates on two class medicine glass kinds (being neutral boron silica glass and the low borosilicate glass that industry is said) and carries out the emphasis statement, because these two kinds represent the market share of medical made of glass tube bottle more than 80%, has Typical Representative.Embodiment 1, embodiment 2, embodiment 3 are a series with comparative example 1, and wherein embodiment 3 appearance colors are 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 colors are 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.
At first, press table 1 glass formula and select raw material, and, ingredient requirement, quartz sand (150 μ m screen overflows are below 1%, 45 μ m screen underflows be below 30%); Aluminium hydroxide (median size 50 μ m); Borax decahydrate (400 μ m screen overflows are below 10%, and 63 μ m screen underflows are below 10%); Fluorite and calcite, median size 200-500 μ m; SODIUMNITRATE can not have the conglomeration situation, as Feldspar Powder (median size 200 μ m screen underflows are below 5%); The Spodumene median size is 100～200 μ m; Soda ash uses Soda Ash Danse, and requiring median size is 200～500 μ m; All the other raw materials should be with commercially available powdery Chemicals, as cerium oxide, stannic oxide, ferric oxide, titanium oxide, manganese oxide, barium carbonate, sodium-chlor.
embodiment 1 glass formula of pressing in table 1 forms (mass unit: g), every preparation 85g left and right 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 its batching satisfy the glass formula of table 1 embodiment 1, wherein ferric oxide 0.05g is the impurity composition of bringing in raw material, at first use platinum crucible melting 24 hours at 1550 ℃ of temperature, 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 that has shown glass specimen at table 1.
Sink and float method is used in the evaluation of glass apparent density, this method is to select Beta-bromo naphthalene and tetrabromoethane to mix by a certain percentage the liquid that forms different apparent density, glass sample is suspended in mixes test solution top, variation along with temperature, the density of test solution is done corresponding the variation, and when the density of test solution was consistent with glass specimen, glass began sinking, according to the temperature factor of sinking temperature and test solution, just can measure the density of glass.
The dilatometer method is used in the expansion coefficient of glass thread evaluation, and this method is that sample is placed on the silica glass support, utilizes thermal expansivity different of glass specimen and silica glass, measures both relative elongations in heat-processed.And the coefficient of expansion of quartz glass tube is known, so the total elongation of glass specimen should be the elongation sum of the isometric silica glass frame of digital sensor reading and sample.With it divided by institute's intensification degree and sample length.Final expression glass is in the unit temperature of 20 ℃ to 300 ℃ and the increment of unit length.
Glass viscosity is measured the measuring method and the instrument that adopt in different viscosity value scope and is carried out.10
2DPas, 10
3DPas and 10
4The dPas viscosity measurement is adopted the rotation high temperature viscosimeter with reference to ASTM C-965 standard; 10
7.6The dPas viscosity measurement is with reference to ASTM C-338, adopt the Littleton softening point apparatus, sample requires to be the glass yarn of Φ 0.65+0.1mm length 230mm, heat in process furnace by 5 ℃/min temperature rise rate, temperature when making it extension speed and reaching 1mm/min, be softening point temperature, it characterizes glass in the softening unique point of deadweight state; 10
11.5The dPas viscosity measurement is used the horizontal expander coefficient measuring instrument with reference to ASTM E-228, and this viscosity number is characterized by the yield temperature point of sample under the loading condition.
The chemical durability of glass evaluation method is:
Water tolerance H adopts DIN ISO 719 standards, each sample of expression alkali equivalent that the acid of beads consumes in table, and unit adopts μ gNa
2O/g, belonging to the alkali equivalent maximum value that the acid of the beads of 1 grade of water resistant consumes is 31 μ gNa
2O/g; Belong to 2 grades of water resistant alkali when weight range be 31～62 μ gNa
2O/g; Belong to 3 grades of alkali when weight range be 62～260 μ gNa
2O/g.
Acid resistance S adopts DIN ISO 12116 standards, each sample mg/cm of expression in table
2Acidproof weight loss amount.The weight loss maximum value that belongs to 1 grade of acid-resistant glass is 0.70mg/cm
2The weight loss scope that belongs to 2 grades of acid-resistant glass is 0.70～1.50mg/cm
2Belong to the weight loss of 3 grades of acid-resistant glass greater than 1.5mg/cm
2
Alkali resistance L adopts DIN ISO 695 standards, each sample mg/cm of expression in table
2Acidproof weight loss amount.The weight loss maximum value that belongs to 1 grade of acid-resistant glass is 75mg/cm
2The weight loss scope that belongs to 2 grades of acid-resistant glass is 75～175mg/cm
2Belong to the weight loss of 3 grades of acid-resistant glass greater than 175mg/cm
2
Correlated performance parameter from table 1 embodiment 1 sees recently that with 1 pair of comparative example Tm is temperature of fusion, and its temperature descends 36 ℃, illustrates to add more triphane can significantly reduce temperature of fusion, approximately can save energy the 5%-8% left and right.T3 shows the glass heat processing temperature, and its temperature descends 59 ℃, has realized decrease, can suppress the surface volatilization coagulum generation in the glass heat course of processing, is conducive to the realization of 1 grade of the surperficial water resistant of made of glass tube bottle.Tw is the forming of glass feed temperature, and it descends 52 ℃, illustrates to be conducive to forming of glass precision and energy saving.Ts and Td homogeneous phase frequently descend more to some extent, for the profile adjustment of forming of glass provides the grace time guarantee, have slowed down the heat radiation with surrounding environment, have extended the shaping adjustment time, favourable acquisition high-accuracy glass goods.
Chemical stability for embodiment 1, adopt respectively water-fast, acidproof, the alkaline-resisting evaluation, its numerical value is as shown in table 1, grading by relevant criterion is estimated, it is water-fast and acidproofly reach 1 grade, alkaline-resistingly reaches 2 grades, compares with comparative example 1, every index has improved respectively 23%, 14%, 7%, illustrates that the chemical stability aspect is promoted by a relatively large margin.
Embodiment 2
embodiment 2 glass formulas of pressing in table 1 form (mass unit: g), every preparation 85g left and right 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 its batching satisfy the glass formula of table 1 embodiment 2, wherein ferric oxide 0.10g is the impurity composition of bringing in raw material, at first use platinum crucible melting 24 hours at 1550 ℃ of temperature, 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 that has shown glass specimen at table 1.
Correlated performance parameter from table 1 embodiment 2 sees recently that with 1 pair of comparative example Tm is temperature of fusion, and its temperature descends 16 ℃, illustrates to add a small amount of triphane can reduce temperature of fusion, approximately can save energy the 3-4% left and right.T3 shows the glass heat processing temperature, and its temperature descends 51 ℃, has realized decrease, can suppress the surface volatilization coagulum generation in the glass heat course of processing, is conducive to the realization of 1 grade of the surperficial water resistant of made of glass tube bottle.Tw is the forming of glass feed temperature, and it descends 57 ℃, illustrates to be conducive to the forming of glass precision and to reduce Power supply.Ts and Td homogeneous phase all descend to some extent than comparative example 1, for the profile adjustment of forming of glass provides the grace time guarantee, have slowed down the heat radiation with surrounding environment, have extended the shaping adjustment time, favourable acquisition high-accuracy glass goods.
Chemical stability for embodiment 2, adopt respectively water-fast, acidproof, the alkaline-resisting evaluation, its numerical value is as shown in table 1, grading by relevant criterion is estimated, water-fastly and acidproof reach 1 grade, alkaline-resistingly reach 2 grades, compare with comparative example 1, every index has improved respectively 31%, 29%, 20%, illustrates that the chemical stability aspect is promoted greatly.
Embodiment 3
Press embodiment 3 glass formulas in table 1 and form that (mass unit: g), every preparation 85g left and right 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 its batching satisfy the glass formula of table 1 embodiment 3.At first use platinum crucible melting 24 hours at 1550 ℃ of temperature, secondly melten glass liquid is configured as the glass specimen goods of regulation, then anneals, its appearance color is brown, require to test according to test event, shown the fundamental property of glass specimen at table 1.
Correlated performance parameter from table 1 embodiment 3 sees recently that with 1 pair of comparative example Tm is temperature of fusion, and its temperature descends 22 ℃, illustrates to add appropriate triphane can reduce temperature of fusion, approximately can save energy the 4-5% left and right.T3 shows the glass heat processing temperature, and its temperature descends 33 ℃, has realized reducing greatly, can suppress the coagulative generation of surface volatilization in the glass heat course of processing, is conducive to the realization of 1 grade of the surperficial water resistant of made of glass tube bottle.Tw is the forming of glass feed temperature, and it descends 44 ℃, illustrates to be conducive to the forming of glass precision and to reduce Power supply.Ts and Td homogeneous phase all descend to some extent than comparative example 1, for the profile adjustment of forming of glass provides the grace time guarantee, have slowed down the heat radiation with surrounding environment, have extended the shaping adjustment time, favourable acquisition high-accuracy glass goods.
Chemical stability for embodiment 3, adopt respectively water-fast, acidproof, the alkaline-resisting evaluation, its numerical value is as shown in table 1, grading by relevant criterion is estimated, water-fastly and acidproof reach 1 grade, alkaline-resistingly reach 2 grades, compare with comparative example 1, every index has improved respectively 34%, 29%, 25%, illustrates that the chemical stability aspect is promoted greatly.
Embodiment 4
Press embodiment 4 glass formulas in table 1 and form that (mass unit: g), every preparation 85g left and right 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 its batching satisfy the glass formula of table 1 embodiment 4, and ferric oxide 0.15g wherein is that the impurity that raw material is brought into causes.At first use platinum crucible melting 24 hours at 1600 ℃ of temperature, secondly melten glass liquid is configured as the glass specimen goods of regulation, then anneal, require to test according to test event, shown the fundamental property of glass specimen at table 1.
Correlated performance parameter from table 1 embodiment 4 sees recently that with 2 pairs of comparative examples Tm is temperature of fusion, and its temperature descends 44 ℃, illustrates to add more triphane can significantly reduce temperature of fusion, approximately can save energy the 6-8% left and right.T3 shows the glass heat processing temperature, and its temperature descends 85 ℃, has realized reducing greatly, can suppress the coagulative generation of surface volatilization in the glass heat course of processing, is conducive to the realization of 1 grade of the surperficial water resistant of made of glass tube bottle.Tw is the forming of glass feed temperature, and it descends 68 ℃, illustrates to be conducive to the forming of glass precision and to reduce Power supply.Ts and Td homogeneous phase all descend to some extent than comparative example 2, for the profile adjustment of forming of glass provides the grace time guarantee, have slowed down the heat radiation with surrounding environment, have extended the shaping adjustment time, favourable acquisition high-accuracy glass goods.
Chemical stability for embodiment 4, adopt respectively water-fast, acidproof, the alkaline-resisting evaluation, its numerical value is as shown in table 1, grading by relevant criterion is estimated, water-fastly and acidproof reach 1 grade, alkaline-resistingly reach 2 grades, compare with comparative example 1, every index has improved respectively 32%, 40%, 15%, illustrates that the chemical stability aspect is promoted greatly.
Embodiment 5
Press embodiment 5 glass formulas in table 1 and form that (mass unit: g), every preparation 85g left and right 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 its batching satisfy the glass formula of table 1 embodiment 5, and ferric oxide 0.20g wherein is that the impurity that raw material is brought into causes.At first use platinum crucible melting 24 hours at 1600 ℃ of temperature, secondly melten glass liquid is configured as the glass specimen goods of regulation, then anneal, require to test according to test event, shown the fundamental property of glass specimen at table 1.
Correlated performance parameter from table 1 embodiment 5 sees recently that with 2 pairs of comparative examples Tm is temperature of fusion, and its temperature descends 39 ℃, illustrates to add more triphane can significantly reduce temperature of fusion, approximately can save energy the 6-7% left and right.T3 shows the glass heat processing temperature, and its temperature descends 76 ℃, has realized reducing greatly, can suppress the coagulative generation of surface volatilization in the glass heat course of processing, is conducive to the realization of 1 grade of the surperficial water resistant of made of glass tube bottle.Tw is the forming of glass feed temperature, and it descends 60 ℃, illustrates to be conducive to the forming of glass precision and to reduce Power supply.Ts and Td homogeneous phase all descend to some extent than comparative example 2, for the profile adjustment of forming of glass provides the grace time guarantee, have slowed down the heat radiation with surrounding environment, have extended the shaping adjustment time, favourable acquisition high-accuracy glass goods.
Chemical stability for embodiment 5, adopt respectively water-fast, acidproof, the alkaline-resisting evaluation, its numerical value is as shown in table 1, grading by relevant criterion is estimated, water-fastly and acidproof reach 1 grade, alkaline-resistingly reach 2 grades, compare with comparative example 1, every index has improved respectively 35%, 40%, 18%, illustrates that the chemical stability aspect is promoted greatly.
Embodiment 6
Embodiment 6 glass formulas of pressing in table 1 form (mass unit: g), every preparation 85g left and right 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 brings ferric oxide 0.2g impurity in its Raw, make its batching satisfy the glass formula of table 1 embodiment 6, ferric oxide 0.20g wherein is that the impurity that raw material is brought into causes.At first use platinum crucible melting 24 hours at 1600 ℃ of temperature, secondly melten glass liquid is configured as the glass specimen goods of regulation, then anneals, the glasswork appearance color is brown, require to test according to test event, shown the fundamental property of glass specimen at table 1.
Correlated performance parameter from table 1 embodiment 6 sees recently that with 2 pairs of comparative examples Tm is temperature of fusion, and its temperature descends 27 ℃, illustrates to add more triphane can significantly reduce temperature of fusion, approximately can save energy the 4-6% left and right.T3 shows the glass heat processing temperature, and its temperature descends 80 ℃, has realized reducing greatly, can suppress the coagulative generation of surface volatilization in the glass heat course of processing, is conducive to the realization of 1 grade of the surperficial water resistant of made of glass tube bottle.Tw is the forming of glass feed temperature, and it descends 52 ℃, illustrates to be conducive to the forming of glass precision and to reduce Power supply.Ts and Td homogeneous phase all descend to some extent than comparative example 2, for the profile adjustment of forming of glass provides the grace time guarantee, have slowed down the heat radiation with surrounding environment, have extended the shaping adjustment time, favourable acquisition high-accuracy glass goods.
Chemical stability for embodiment 6, adopt respectively water-fast, acidproof, the alkaline-resisting evaluation, its numerical value is as shown in table 1, grading by relevant criterion is estimated, water-fastly and acidproof reach 1 grade, alkaline-resistingly reach 2 grades, compare with comparative example 1, every index has improved respectively 26%, 40%, 12%, illustrates that the chemical stability aspect is promoted greatly.
The formula composition and performance of [table 1] embodiment and comparative example
Annotate: in H, S, L chemical stability data bracket 1 grade or 2 grades is that standard described in by specification is carried out classification and determined.
Claims (8)
1. medical glass material of using triphane is characterized in that: consisted of by following raw materials according, and by the quality percentage composition,
2. claim 1 is used the medical glass material of triphane, it is characterized in that: consisted of by following raw materials according, and by the quality percentage composition,
3. claim 1 is used the medical glass material of triphane, it is characterized in that: consisted of by following raw materials according, and by the quality percentage composition,
4. claim 1 is used the medical glass material of triphane, it is characterized in that: consisted of by following raw materials according, and by the quality percentage composition,
5. claim 1 is used the medical glass material of triphane, it is characterized in that: consisted of by following raw materials according, and by the quality percentage composition,
6. claim 1 is used the medical glass material of triphane, it is characterized in that: consisted of by following raw materials according, and by the quality percentage composition,
7. claim 1 is used the medical glass material of triphane, it is characterized in that: consisted of by following raw materials according, and by the quality percentage composition,
8. claim 1 is used the medical glass material of triphane, it is characterized in that: consisted of by following raw materials according, and by the quality percentage composition,
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Cited By (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 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04280833A (en) * | 1991-03-08 | 1992-10-06 | Nippon Electric Glass Co Ltd | Borosilicate glass |
| 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 |
-
2011
- 2011-11-23 CN CN201110376304.4A patent/CN103130415B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04280833A (en) * | 1991-03-08 | 1992-10-06 | Nippon Electric Glass Co Ltd | Borosilicate glass |
| 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 |
|---|
| 李鹏: "玻璃中引入锂辉石降低成本的实践经验", 《玻璃与搪瓷》 * |
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