WO2016135050A1 - Screening method for assessing the delamination propensity of glass - Google Patents
Screening method for assessing the delamination propensity of glass Download PDFInfo
- Publication number
- WO2016135050A1 WO2016135050A1 PCT/EP2016/053520 EP2016053520W WO2016135050A1 WO 2016135050 A1 WO2016135050 A1 WO 2016135050A1 EP 2016053520 W EP2016053520 W EP 2016053520W WO 2016135050 A1 WO2016135050 A1 WO 2016135050A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- glass material
- glass
- delamination
- extraction solution
- propensity
- Prior art date
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/38—Concrete; ceramics; glass; bricks
- G01N33/386—Glass
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N17/00—Investigating resistance of materials to the weather, to corrosion, or to light
Definitions
- the present invention refers to a screening method for assessing the delamination propensity of a glass material.
- Delamination is the result of a physicochemical process affecting the surface at the interface in the system glass/solution system in contact. It consists in the detachment, from the surface of the glass, of lanceolate, shiny and very thin particles of a length varying between 50 and 200 ⁇ , but that are rolled-up and they prove to be easily visible because they are reflective and floating in the contact liquid.
- Delamination takes place when the surface of the glass is altered as a result of interactions with moist environments subject to a wide temperature range or as the result of prolonged contact with extracting solutions of various types. In all cases, delamination is facilitated by surface leaching reactions that cause the formation of layers that are very rich in silica compared to the bulk glass.
- the mechanism of the formation of altered layers in a glass container is strongly influenced by the type of contact liquid (composition and pH) and by the forming conditions, typically the speed of conversion, the temperature of the flames enveloping the surface, and the annealing conditions, to name the most important factors.
- the delamination process can be accelerated by the particularly aggressive physicochemical characteristics of the filling liquid and by the presence of volatile elements, among which for example alkali and boron, in the specific composition of the glass of the container that trigger precisely those processes of volatilization that underlie the delamination process.
- the tests for screening delamination propensity are normally performed on whole containers so as to check the surface layer that has actually formed following the glass tube/container conversion process.
- the technical task proposed by the present invention is to realize a screening method for assessing the delamination propensity of a glass material.
- the screening method is realized prior to the conversion of the glass material into a container, and thus for glass materials of different compositions and origin, be they in the form of segments of tubes or sheets of flat glass.
- the qualitative analysis also comprises a visual assessment of the liquid extraction solution for turbidity.
- the qualitative analysis also comprises a microscopic assessment of the glass sample for pitting and corrosion.
- the liquid solution simulates a pharmaceutical drug intended to be contained therein.
- the glass material consists of a borosilicate glass.
- the glass material consists of a pharmaceutical glass with a hydrolytic resistance classified as Type 1.
- the immersion step continues for an interval of time ranging from 1 to 2 hours at a heating temperature ranging between 120 and 135°C, in an autoclave.
- a sample of this glass in the form of cylindrical tube is provided.
- the glass tube is subjected to a flaming process according to times and procedures that are perfectly reproducible at a temperature no lower, and preferably higher, than the softening point and monitored by suitable optical pyrometers.
- the flame conditions are selected in such a manner as to induce the processes of volatilization of volatile elements (alkali and boron) and enrichment in layers of different composition (phase separations, normally silica dissolved in borates, or borates dissolved in silica), which are typically realized during the process of converting the glass tube into a container.
- phase separations normally silica dissolved in borates, or borates dissolved in silica
- the flame temperatures and exposure times are suitably selected as a function of the type of glass being examined and they are monitored in progress by specific measurement instruments so as to ensure maximum possible reproducibility of the flaming process.
- the tube After the flaming process, the tube is immersed in a liquid extraction solution that simulates the final filling liquid.
- the ratio of the surface of the tube in contact with the liquid extraction solution to the volume of the liquid extraction solution is equal to the ratio of the internal surface of the container to be realized and in contact with filling liquid to the volume of the filling liquid intended for it.
- Extraction is carried out in an autoclave and it comprises heating to a given temperature and for a given time such as to reproduce conditions known in the literature to accelerate the delamination process (Guadagnino, E.; Zuccato D. Delamination propensity of pharmaceutical glass containers by accelerated testing with different extraction media. PDA j. Pharm. Set Technol 2012, 66 (1), 116- 125).
- Si, Al, and B are measured by ICP-OES, a visual assessment of the solution is made for turbidity, and the tube is coloured with methylene blue and analysed using SEM so as to indicate pitting and corrosion.
- a delamination propensity rating is then attributed to the glass material, correlated with the outcome of the quantitative and qualitative analysis.
- Composition material borosilicate glass for pharmaceutical use with a hydrolytic resistance classified as class 1.
- a sample of this glass in the form of a sheet of flat glass is provided.
- the flat glass sheet is subjected to a flaming process according to times and procedures that are perfectly reproducible at a temperature no lower, and preferably higher, than the softening point and monitored by suitable optical pyrometers.
- the flame conditions are selected in such a manner as to induce the processes of volatilization of volatile elements (alkali and boron) and enrichment in layers of different composition (phase separations, normally silica dissolved in borates, or borates dissolved in silica), which are typically realized during the process of converting the glass into a container.
- the flame temperatures and exposure times are suitably selected as a function of the type of glass being examined and they are monitored in progress by specific measurement instruments so as to ensure maximum possible reproducibility of the flaming process.
- the heat-treated flat glass sheet is then immersed in a liquid extraction solution that simulates the final filling liquid.
- the ratio of the surface of the flat sheet in contact with the liquid extraction solution to the volume of the liquid extraction solution is equal to the ratio of the internal surface of the container to be realized and in contact with filling liquid to the volume of the filling liquid.
- Extraction is carried out in an autoclave and it comprises heating to a given temperature and for a given time such as to reproduce conditions known in the literature to accelerate the delamination process.
- Si, Al, and B are measured by ICP-OES, a visual assessment of the solution is made for turbidity, and the glass sheet is coloured with methylene blue and analysed using SEM so as to indicate pitting and corrosion.
- a delamination propensity rating is then attributed to the glass sheet, correlated with the outcome of the quantitative and qualitative analysis.
- This version of the method is particularly advantageous because it makes it possible to investigate innovative compositions by simply pouring the newly- conceived glass, which has been melted in a laboratory, onto a plate.
- the exposure times are specially designed as a function of the thickness of the glass sheet and the composition of the glass at hand, so as to obtain surface alterations that are comparable to those realized upon forming the vial.
- This test on glass sheets is added to the tests already standardized for assessing surface hydrolytic resistance, thereby making it possible to complete the identity of a newly-conceived glass being proposed as a candidate to be subjected to thermoforming for producing a container, enabling an overall assessment thereof long before the pilot production phase.
- Composition material borosilicate glass for pharmaceutical use with a hydrolytic resistance classified as class 1.
Abstract
A screening method for assessing the delanimation propensity of a glass material, comprising the following steps: • selecting a glass material as a candidate for conversion into a container for a filling liquid • subjecting a sample of said glass material in the form of a flat sheet or tube to a flaming process for a given interval of time at a temperature no lower than the softening temperature thereof • after the flaming process, immersing the sample of glass material in a liquid extraction solution for a given interval of time, wherein the liquid extraction solution simulates at least the composition and/or the pH of the filling liquid, and wherein the ratio of the surface of the glass material in contact with the liquid extraction solution to the volume of the liquid extraction solution is equal to the ratio of the internal surface of the container in contact with the filling liquid to the volume of the filling liquid • subjecting the glass sample immersed in the liquid extraction solution to a cycle of thermal stress, so as to accelerate the extraction process • separating the glass sample from the liquid extraction solution and analysing quantitatively and qualitatively at least the extract dispersed in the liquid extraction solution • attributing a delamination propensity rating to the glass material, correlated with the outcome of the quantitative and qualitative analysis.
Description
SCREENING METHOD FOR ASSESSING THE DELAMINATION PROPENSITY OF GLASS
DESCRIPION
The present invention refers to a screening method for assessing the delamination propensity of a glass material.
Delamination is the result of a physicochemical process affecting the surface at the interface in the system glass/solution system in contact. It consists in the detachment, from the surface of the glass, of lanceolate, shiny and very thin particles of a length varying between 50 and 200 μιη, but that are rolled-up and they prove to be easily visible because they are reflective and floating in the contact liquid.
Delamination takes place when the surface of the glass is altered as a result of interactions with moist environments subject to a wide temperature range or as the result of prolonged contact with extracting solutions of various types. In all cases, delamination is facilitated by surface leaching reactions that cause the formation of layers that are very rich in silica compared to the bulk glass.
When the thickness of the altered layer exceeds a micron in thickness, absorption of water at the interface can become critical because it produces the expansion of layers that possess an expansion coefficient differing from that of the underlying glass. This can lead to the detachment of lamellar particles, generally known as "flakes", even in the case of events that involve slight stress such as simple agitation of the liquid.
The mechanism of the formation of altered layers in a glass container is strongly influenced by the type of contact liquid (composition and pH) and by the forming
conditions, typically the speed of conversion, the temperature of the flames enveloping the surface, and the annealing conditions, to name the most important factors.
Given that the detachment phenomenon takes some time before it manifests itself (normally during storage of the filled container), diagnostic techniques are needed to make it possible to predict the tendency of a container to delaminate, well before it is filled with the end product. For this purpose, accelerated extraction tests, normally for l-2h at 121 °C or for longer periods of time (of up to several days) at lower temperatures (50-80°) have been set up in various research centres and such tests comprise filling the manufactured article with liquids known to be highly corrosive to glass (potassium chloride, citric acid, glutaric acid, glycine, etc.). These tests are performed on the finished containers so as to check the surface state that has actually formed following the glass tube/container conversion process. Delamination is a problem of deep concern in the sector of pharmaceutical glass containers used for the distribution and storage of injectable drugs.
In this case, the delamination process can be accelerated by the particularly aggressive physicochemical characteristics of the filling liquid and by the presence of volatile elements, among which for example alkali and boron, in the specific composition of the glass of the container that trigger precisely those processes of volatilization that underlie the delamination process. The tests for screening delamination propensity are normally performed on whole containers so as to check the surface layer that has actually formed following the glass tube/container conversion process.
The technical task proposed by the present invention is to realize a screening method for assessing the delamination propensity of a glass material.
The technical task, as well as these and other aims, according to the present invention, are achieved by providing a screening method characterized in that it comprises the following steps:
• selecting a glass material as a candidate for conversion into a container for a filling liquid
• subjecting a sample of said glass material in the form of a flat sheet or tube to a flaming process for a given interval of time at a temperature no lower than the softening temperature thereof
• after the flaming process, immersing the sample of glass material in a liquid extraction solution for a given interval of time, wherein the liquid extraction solution simulates at least the composition and/or the pH of the filling liquid, and wherein the ratio of the surface of the glass material in contact with the liquid extraction solution to the volume of the liquid extraction solution is equal to the ratio of the internal surface of the container in contact with the filling liquid to the volume of the filling liquid
• subjecting the glass sample immersed in the liquid extraction solution to a cycle of thermal stress, so as to accelerate the extraction process
• separating the glass sample from the liquid extraction solution and analysing quantitatively and qualitatively at least the extract dispersed in the liquid extraction solution
• attributing a delamination propensity rating to the glass material,
correlated with the outcome of the quantitative and qualitative analysis • screening for the assessment of the delamination propensity of a glass material.
The screening method is realized prior to the conversion of the glass material into a container, and thus for glass materials of different compositions and origin, be they in the form of segments of tubes or sheets of flat glass.
In a preferred embodiment of the invention, the qualitative analysis also comprises a visual assessment of the liquid extraction solution for turbidity.
In a preferred embodiment of the invention, the qualitative analysis also comprises a microscopic assessment of the glass sample for pitting and corrosion.
In a preferred embodiment of the invention, the liquid solution simulates a pharmaceutical drug intended to be contained therein.
In a preferred embodiment of the invention, the glass material consists of a borosilicate glass.
In a preferred embodiment of the invention, the glass material consists of a pharmaceutical glass with a hydrolytic resistance classified as Type 1.
In a preferred embodiment of the invention, the immersion step continues for an interval of time ranging from 1 to 2 hours at a heating temperature ranging between 120 and 135°C, in an autoclave.
Further characteristics and advantages of the invention will become more apparent from the description of the screening method for assessing the delamination propensity of a glass material according to the invention, and they are illustrated by way of approximate and non-limiting example in the examples reported herein below and in the attached Figure 1 in which Graph 1 represents a comparative
analysis for tubular samples and Graph 2, a comparative analysis for plate-shaped samples.
EXAMPLE 1
Test of the delamination propensity of a glass material
A sample of this glass in the form of cylindrical tube is provided.
The glass tube is subjected to a flaming process according to times and procedures that are perfectly reproducible at a temperature no lower, and preferably higher, than the softening point and monitored by suitable optical pyrometers.
The flame conditions are selected in such a manner as to induce the processes of volatilization of volatile elements (alkali and boron) and enrichment in layers of different composition (phase separations, normally silica dissolved in borates, or borates dissolved in silica), which are typically realized during the process of converting the glass tube into a container. The flame temperatures and exposure times are suitably selected as a function of the type of glass being examined and they are monitored in progress by specific measurement instruments so as to ensure maximum possible reproducibility of the flaming process.
After the flaming process, the tube is immersed in a liquid extraction solution that simulates the final filling liquid. The ratio of the surface of the tube in contact with the liquid extraction solution to the volume of the liquid extraction solution is equal to the ratio of the internal surface of the container to be realized and in contact with filling liquid to the volume of the filling liquid intended for it.
Extraction is carried out in an autoclave and it comprises heating to a given temperature and for a given time such as to reproduce conditions known in the literature to accelerate the delamination process (Guadagnino, E.; Zuccato D.
Delamination propensity of pharmaceutical glass containers by accelerated testing with different extraction media. PDA j. Pharm. Set Technol 2012, 66 (1), 116- 125).
At the end of the extraction process, Si, Al, and B are measured by ICP-OES, a visual assessment of the solution is made for turbidity, and the tube is coloured with methylene blue and analysed using SEM so as to indicate pitting and corrosion.
A delamination propensity rating is then attributed to the glass material, correlated with the outcome of the quantitative and qualitative analysis.
A practical example is reported below.
Data on the glass sample (segment of glass tube'):
Composition material: borosilicate glass for pharmaceutical use with a hydrolytic resistance classified as class 1.
Chemical composition (example):
Dimensions: diameter of 26.50 mm, height of 52.00 mm
Data on the container obtained following conversion of the glass tube
Form: Vial
Dimensions: diameter 26,50 mm, height 52.00 mm
Filling volume: 19.0 mL total (17.1 mL at 90%)
Data on the flaming process for the glass sample:
Flame temperature: 780 ± 20°C
Flame application procedure: by means of adjustable burners
Type of flame: 02/air/CH4
Flame time: 5 ± 2 min
Data on the filling liquid:
Chemical composition: 0.9% NaCl
pH: 8
Extraction process data:
Extraction time in the autoclave: 1-2 h
Extraction temperature in the autoclave: 120-125°C
Volume of the extraction solution/surface of the glass
sample: comparable to the ratio of the volume of the filling liquid to the internal surface of the finished container
Analysis process:
analysis of the extraction solution by ICP-OES, determining the elements present in solution and the concentration of extracted Si02
Data on the process of attribution of the delamination propensity rating:
Comparison of the results obtained for the segment of tube sample and for the respective vial obtained following conversion of the glass tube (correlation between the delamination propensity rating of the finished container and the segment of tube).
With reference to Graph 1 attached hereto, three ranges of concentration of the extracted silica (Si02, ppm) are identifiable for vials of 17 mL ± 3mL produced with three types of borosilicate glass, the three ranges corresponding to a Low (0-5 ppm Si02), Medium (5-9 ppm Si02) and High (> 10 ppm Si02) delamination propensity, respectively.
The trend for the segments of glass tube representing the respective vials is perfectly matched.
EXAMPLE 2
Test of the delamination propensity of a glass material.
A sample of this glass in the form of a sheet of flat glass is provided.
The flat glass sheet is subjected to a flaming process according to times and procedures that are perfectly reproducible at a temperature no lower, and preferably higher, than the softening point and monitored by suitable optical pyrometers.
The flame conditions are selected in such a manner as to induce the processes of volatilization of volatile elements (alkali and boron) and enrichment in layers of different composition (phase separations, normally silica dissolved in borates, or borates dissolved in silica), which are typically realized during the process of converting the glass into a container. The flame temperatures and exposure times are suitably selected as a function of the type of glass being examined and they are monitored in progress by specific measurement instruments so as to ensure maximum possible reproducibility of the flaming process.
The heat-treated flat glass sheet is then immersed in a liquid extraction solution that simulates the final filling liquid. The ratio of the surface of the flat sheet in contact with the liquid extraction solution to the volume of the liquid extraction solution is equal to the ratio of the internal surface of the container to be realized and in contact with filling liquid to the volume of the filling liquid. Extraction is carried out in an autoclave and it comprises heating to a given temperature and for a given time such as to reproduce conditions known in the literature to accelerate the delamination process.
At the end of the extraction process, Si, Al, and B are measured by ICP-OES, a
visual assessment of the solution is made for turbidity, and the glass sheet is coloured with methylene blue and analysed using SEM so as to indicate pitting and corrosion.
A delamination propensity rating is then attributed to the glass sheet, correlated with the outcome of the quantitative and qualitative analysis.
This version of the method is particularly advantageous because it makes it possible to investigate innovative compositions by simply pouring the newly- conceived glass, which has been melted in a laboratory, onto a plate.
All thermal and glass sheet positioning parameters are entirely reproducible. The exposure times are specially designed as a function of the thickness of the glass sheet and the composition of the glass at hand, so as to obtain surface alterations that are comparable to those realized upon forming the vial.
This test on glass sheets is added to the tests already standardized for assessing surface hydrolytic resistance, thereby making it possible to complete the identity of a newly-conceived glass being proposed as a candidate to be subjected to thermoforming for producing a container, enabling an overall assessment thereof long before the pilot production phase.
A practical example is reported below.
Data on the glass sample (sheet of flat glass)
Composition material: borosilicate glass for pharmaceutical use with a hydrolytic resistance classified as class 1.
Chemical composition (example):
Form: sheet of flat glass
Dimensions: width of 12.00 mm, height of 50,00 mm
Data on the flaming process for the glass sample:
Flame temperature: 780 ± 20°C
Flame application procedure: by means of adjustable burners
Type of flame: 02/air/CH4
Flame time: 5 ± 2 min
Data on the filling liquid:
Chemical composition: 0.9% NaCl
pH: 8
Extraction process data:
Extraction time in the autoclave: 1-2 h
Extraction temperature in the autoclave: 120-125°C
Volume of the extraction solution/surface of the glass
sample: comparable to the ratio of the volume of the filling liquid to the internal surface of the finished container.
Analysis process:
analysis of the extraction solution by ICP-OES, determining the elements present in solution and the concentration of extracted Si02
Data on the process of attribution of the delamination propensity rating:
Comparison of the results obtained for the sample of the segment of tube and for the respective vial obtained following conversion of the glass tube (correlation between the delamination propensity rating of the finished container and the segment of tube).
With reference to Graph 2, three ranges of concentration of the extracted silica (Si02, ppm) are identifiable for vials of 17 mL ± 3mL produced with three types of borosilicate glass, the three ranges corresponding to a Low (0-5 ppm Si02), Medium (5-9 ppm Si02) and High (> 10 ppm Si02) delamination propensity, respectively.
The trend for the sheets of flat glass representing the respective vials is perfectly matched.
The method thus conceived can be utilized preferably but not necessarily in the field of glass containers for pharmaceutical use and it is susceptible to numerous modifications and variants, all of which falling within the scope of the inventive concept. Moreover, all details may be replaced with other technically equivalent elements.
Claims
1. A screening method for assessing the delamination propensity of a glass material, characterized in that it comprises the following steps:
• selecting a glass material as a candidate for conversion into a container for a filling liquid
• subjecting a sample of said glass material in the form of a flat sheet or tube to a flaming process for a given interval of time at a temperature no lower than the softening temperature thereof
• after the flaming process, immersing the sample of glass material in a liquid extraction solution for a given interval of time, wherein the liquid extraction solution simulates at least the composition and/or the pH of the filling liquid, and wherein the ratio of the surface of the glass material in contact with the liquid extraction solution to the volume of the liquid extraction solution is equal to the ratio of the internal surface of the container in contact with the filling liquid to the volume of the filling liquid
• subjecting the glass sample immersed in the liquid extraction solution to a cycle of thermal stress, so as to accelerate the extraction process
• separating the glass sample from the liquid extraction solution and analysing quantitatively and qualitatively at least the extract dispersed in the liquid extraction solution
• attributing a delamination propensity rating to the glass material, correlated with the outcome of the quantitative and qualitative analysis
2. The screening method for assessing the delamination propensity of a glass
material according to the preceding claim, characterized in that the qualitative analysis also comprises a visual assessment of the liquid extraction solution for turbidity.
3. The screening method for assessing the delamination propensity of a glass material according to any one of the preceding claims, characterized in that the qualitative analysis also comprises a microscopic assessment of the glass sample for pitting and corrosion.
4. The screening method for assessing the delamination propensity of a glass material according to any one of the preceding claims, characterized in that said liquid solution simulates a pharmaceutical drug.
5. The screening method for assessing the delamination propensity of a glass material according to any one of the preceding claims, characterized in that said glass material consists of a borosilicate glass.
6. The screening method for assessing the delamination propensity of a glass material according to any one of the preceding claims, characterized in that said glass material consists of a pharmaceutical glass with a hydrolytic resistance classified as Type 1.
7. The screening method for assessing the delamination propensity of a glass material according to any one of the preceding claims, characterized in that said immersion step continues for an interval of time ranging from 1 to 2 hours at a heating temperature ranging between 120 and 135°C, in an autoclave.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITMI20150266 | 2015-02-23 | ||
| ITMI2015A000266 | 2015-02-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2016135050A1 true WO2016135050A1 (en) | 2016-09-01 |
Family
ID=52781177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2016/053520 WO2016135050A1 (en) | 2015-02-23 | 2016-02-19 | Screening method for assessing the delamination propensity of glass |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2016135050A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110121648A (en) * | 2016-11-15 | 2019-08-13 | 贝克顿迪金森法国公司 | The evaluation method of the stability of biological products in prefilled syringe |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140034544A1 (en) * | 2012-11-30 | 2014-02-06 | Corning Incorporated | Strengthened borosilicate glass containers with improved damage tolerance |
| US20140240694A1 (en) * | 2011-10-27 | 2014-08-28 | Schott Ag | Rapid test method for evaluating the delamination tendency of glass packaging means |
-
2016
- 2016-02-19 WO PCT/EP2016/053520 patent/WO2016135050A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140240694A1 (en) * | 2011-10-27 | 2014-08-28 | Schott Ag | Rapid test method for evaluating the delamination tendency of glass packaging means |
| US20140034544A1 (en) * | 2012-11-30 | 2014-02-06 | Corning Incorporated | Strengthened borosilicate glass containers with improved damage tolerance |
Non-Patent Citations (3)
| Title |
|---|
| IACOCCA RONALD G ET AL: "Factors affecting the chemical durability of glass used in the pharmaceutical industry", AAPS PHARMSCITECH, SPRINGER NEW YORK LLC, US, vol. 11, no. 3, 1 September 2010 (2010-09-01), pages 1340 - 1349, XP008159537, ISSN: 1530-9932, [retrieved on 20100826], DOI: 10.1208/S12249-010-9506-9 * |
| PDA J. PHARM. SCI. TECHNOL., vol. 66, no. 1, 2012, pages 116 - 125 |
| ZHAO JIANXIU ET AL: "Glass Delamination: a Comparison of the Inner Surface Performance of Vials and Pre-filled Syringes", AAPS PHARMSCITECH, SPRINGER US, BOSTON, vol. 15, no. 6, 18 June 2014 (2014-06-18), pages 1398 - 1409, XP035376761, DOI: 10.1208/S12249-014-0167-Y * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110121648A (en) * | 2016-11-15 | 2019-08-13 | 贝克顿迪金森法国公司 | The evaluation method of the stability of biological products in prefilled syringe |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2684025B1 (en) | Breath ketone detector | |
| Kosarac et al. | A novel method for the quantitative determination of free and conjugated bisphenol A in human maternal and umbilical cord blood serum using a two-step solid phase extraction and gas chromatography/tandem mass spectrometry | |
| US10386351B2 (en) | Methods for detecting and quantifying analytes using gas species diffusion | |
| CN108398320B (en) | Method for measuring tensile stress corrosion of wrought aluminum alloy | |
| US20120142017A1 (en) | Biosensor device and manufacturing method thereof | |
| WO2016135050A1 (en) | Screening method for assessing the delamination propensity of glass | |
| Dong et al. | Migration model of toxic metals from ceramic food contact materials into acid food | |
| Plaisance et al. | Assessment of uncertainty of benzene measurements by Radiello diffusive sampler | |
| CN107356516A (en) | A kind of method of testing of asphalt with ultraviolet aging longitudinal direction depth | |
| DeRieux et al. | Effects of phase state and phase separation on dimethylamine uptake of ammonium sulfate and ammonium sulfate–sucrose mixed particles | |
| US10386365B2 (en) | Methods for detecting and quantifying analytes using ionic species diffusion | |
| CN103439397B (en) | Gas sensor towards olfactory analog instrument is selected, is changed and bearing calibration | |
| CN106485082B (en) | A kind of method for building up of the OPLS-DA diagnostic model based on refining metabolism group and its application | |
| Srinivasan et al. | Enhanced optical sensitivity of polyvinyl alcohol–reduced graphene oxide electrospun nanofiber coated etched fiber Bragg grating sensor for detection of myoglobin a cardiac biomarker | |
| CN105486890A (en) | Novel method for testing fluid inclusion in minerals | |
| Tamayo et al. | Analytical method for heavy metal determination in algae and turtle eggs from Guanahacabibes Protected Sea Park | |
| CN101290298A (en) | Cow milk freezing point checking method | |
| CN103289892B (en) | Biomaterial checkout gear | |
| EP3001184A1 (en) | Passive device for the detection and/or determination in situ of amines in gases | |
| CN104280333B (en) | Based on the method that glass column determines chemical durability of glass | |
| CN104928357A (en) | Polynucleotide, method and kit for detecting pathotype vibrio cholerae | |
| Rigaudier et al. | Hydrogen and oxygen isotope reference materials for the analysis of water inclusions in halite | |
| CN214584658U (en) | Device for measuring smokable substances in powder coating | |
| US20160291026A1 (en) | Biomarkers for detection of ovarian cancer | |
| Hafkenscheid et al. | A technical review of the feasibility of producing certified reference materials for the measurement of gaseous pollutants in ambient air |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 16708948 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 16708948 Country of ref document: EP Kind code of ref document: A1 |